JP2568916B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a method for processing a silver halide color photographic light-sensitive material. More specifically, the present invention relates to an improved color developer and a desilvering step following a color developing step. The present invention relates to a processing method in which rapid processing is carried out with a bleaching solution improved in the above, and the image storability after processing is not impaired.

(Prior Art) Generally, the basic steps of processing a color light-sensitive material are a color development step and a desilvering step. In the color developing step, the silver halide exposed by the color developing agent is reduced to form silver, and the oxidized color developing agent reacts with a color forming agent (coupler) to give a dye image. In the subsequent desilvering step, silver produced in the color developing step is oxidized by the action of an oxidizing agent (commonly called a bleaching agent), and then dissolved by a silver ion complexing agent commonly called a fixing agent. You. Through this desilvering step, only a dye image is formed on the color photographic material.

The above desilvering step is performed in two baths, a bleach bath containing a bleaching agent and a fixing bath containing a fixing agent, and in a single bath using a bleach-fixing bath in which a bleaching agent and a fixing agent coexist. There is.

The actual development process includes various auxiliary steps such as to maintain the photographic and physical quality of an image or to improve the storability of an image, in addition to the above basic steps. For example, there are a dura bath, a stop bath, an image stabilizing bath, and a washing bath.

In recent years, with the spread of small in-store processing service systems called mini-labs, there has been a strong demand for shortening the time required for the processing in order to quickly respond to processing requests from customers.

In particular, the shortening of the desilvering step, which conventionally occupies most of the processing time, has been the most requested.

However, ferric acetic acid ethylenediaminetetraacetate, which is a main bleaching agent used in bleaching solutions and bleach-fixing solutions, has a basic defect of weak oxidizing power.
Despite various improvements such as the combined use of bleaching accelerators, the above requirements have not been met.

On the other hand, red blood salts, dichromates, ferric chloride, persulfates, bromates, etc. are known as strong oxidizing bleaching agents. In view of the above, each of them has many disadvantages and cannot be widely used for in-store processing.

Under these circumstances, the 1,3-method described in JP-A-62-222252 is disclosed.
A bleaching solution containing a ferric diaminopropanetetraacetate complex at a pH of about 6 has a higher oxidizing power than a bleaching solution containing a ferric ethylenediaminetetraacetate complex salt, and enables more rapid silver bleaching. It has the disadvantage of generating color fogging, which is particularly bad when it is directly bleached without any intermediate bath after color development.

On the other hand, to speed up processing, there is a reduction in color development time. One way to reduce the time is to increase the pH of the developer, but this impairs the stability of the solution. Another is to raise the developing temperature, but this also impairs the stability of the solution. The other is to use a development accelerator, but the current technology changes the photographic characteristics. Another is to increase the concentration of the developing agent. However, when the concentration of the active ingredient is high, the stain after the treatment becomes a problem.

(Problems to be Solved by the Invention) Accordingly, a first object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material capable of obtaining high color developability with a reduced development time. A second object of the present invention is to provide an improved bleaching bath in the desilvering step and to provide a method for processing a silver halide color photographic light-sensitive material having a reduced processing time. A third object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material in which the image storability after processing, in particular, the generation of stains of unexposed portions is small.

(Means for Solving the Problems) In order to solve the problems, the present inventor made various studies, and as a result, could be achieved by the method described below.
That is, after imagewise exposing a silver halide color photographic light-sensitive material, it is developed with a color developing solution containing 1.2 × 10 ^-2 mol / or more of a color developing agent, followed by ferric 1,3-diaminopropanetetraacetate. Contains 0.2 mol / or more of a complex salt (hereinafter abbreviated as DPTA · Fe) and has an acid dissociation constant of 2.5 to
5.5 acid containing 0.5 to 1.5 mol / or more, pH 2.5 to 4.0
By treating with a bleaching solution.

 Hereinafter, the present invention will be described in detail.

The color developer used in the present invention contains an aromatic primary amine color developing agent known as a color developing agent. Preferred examples are p-phenylenediamine derivatives. Representative examples are shown below, but are not limited thereto.

D-1 N, N-diethyl-p-phenylenediamine D-2 2-amino-5-diethylaminotoluene 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 4-amino-3-methyl -N-ethyl-N-
[Β- (methanesulfonamido) ethyl] -aniline D-7 N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide D-8 N, N-dimethyl-p-phenylenediamine D-9 4-amino -3-Methyl-N-ethyl-N-methoxyethylaniline D-10 4-Amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-11 4-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline Among the above p-phenylenediamine derivatives, particularly preferred is Exemplified Compound D-5.

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 1.2 × 10 ⁻² mol / or more per developer.

In the present invention, it is preferable to use a sulfate of D-5 as a color developing agent in order to speed up color development processing.

When the concentration of the color developing agent is 1.2 × 10 ^-2 mol / or less, a long development processing time is required, and speeding up cannot be achieved. Conversely, if the concentration of the developing agent is too high, the concentration of the main agent incorporated in the light-sensitive material will be high, affecting the stability of the processing solution in the subsequent processing step, or the remaining main agent will be lost during storage of the processed light-sensitive material It adversely affects the color image and causes stain.

However, the use of the bleaching solution of the present invention described below makes it possible to widen the upper limit of the conventional main agent concentration range, that is, in the present invention, the color developing agent concentration is 1.2 × 10 ^−2.
Mol / or more, preferably in the range of 1.9 × 10 ^{-2 to} 6.0 × 10 ^-2 mol /, more preferably in the range of 2.4 × 10 ^{-2 to} 6.0 × 10 ^-2 .
The most preferable range of × 10 ^-2 mol / 3.1 × 10 ^{-2 to} 6.0 ×
10 ^-2 mol /.

Further, as a preservative, a sulfite such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, or a carbonyl sulfite adduct is added to the color developer as necessary. be able to.

The preferred addition amount is 0.5 g to 10 g per color developer.
More preferably, it is 1 g to 5 g.

Examples of compounds which directly preserve the color developing agent include various hydroxylamines, hydroxamic acids described in Japanese Patent Application No. 61-186559, hydrazines described in JP-A-61-170756, hydrazides, and hydrazides described in JP-A-61-188742. No. 61-2032
Phenols described in No. 53, α-hydroxyketones and α-aminoketones described in No. 61-188741, and / or
It is preferable to add various sugars described in JP-A-61-180616. Also, in combination with the above compound, Japanese Patent Application No. 61-147823,
Nos. 61-166674, 61-165621, 61-164515,
Monoamines described in 61-170789, 61-168159, etc., 61-173595, 61-164515, 61-186560
No. 61-165621 and No. 61-165621.
Polyamines described in 169789, polyamines described in 61-1888619, nitroxy radicals described in 61-197760, alcohols described in 61-186561 and 61-197419, 61-198987 The oximes described therein, and 61-26 of the same.
It is preferable to use tertiary amines described in No. 5149.

Other preservatives include JP-A Nos. 57-44148 and 57-5.
Various metals 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 may be contained as necessary. Particularly, addition of an aromatic polyhydroxy compound is preferred.

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.

Specific examples of the buffer include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate,
Sodium tetraborate (borax), potassium tetraborate, o
-Sodium hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-sulfo-
Examples thereof include sodium 2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate). 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.

As the chelating agent, an organic acid compound is preferable, and examples thereof include aminopolycarboxylic acids, organic phosphonic acids, and phosphonocarboxylic acids. Specific examples are shown below, but the present invention is not limited thereto.

Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid,
1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphone Acid, N, N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid,
These chelating agents may be used in combination of two or more as necessary. Preferred are aminopolycarboxylic acids, and hydroxyethyliminodiacetic acid is particularly preferred.

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. However, it is preferred that the color developer of the present invention does not substantially contain benzyl alcohol from the viewpoints of pollution, liquid preparation and prevention of color contamination. Here, “substantially” means that the developer does not contain 2 ml or less, preferably no developer, at all.

Other development accelerators include JP-B-37-16088,
7-5987, 38-7826, 44-12380, 45-9919
Thioether compounds disclosed in U.S. Pat. No. 3,813,247 and US Pat. No. 3,813,247; p-phenylenediamine compounds disclosed in JP-A-52-49829 and JP-A-50-15554;
-137726, JP-B-44-30074, JP-A-56-156826 and JP-A-52-43429, etc., quaternary ammonium salts, U.S. Pat.Nos. 2,494,903, 3,128,182, 4,23
Nos. 0,796, 3,253,919, JP-B-41-11431, U.S. Patent Nos. 2,482,546, 2,596,926 and 3,582,346, etc., and the amine compounds described in JP-B-37-16088, 42-2.
No. 5201, U.S. Pat.No. 3,128,183, JP-B-41-11431,
No. 42-23883 and U.S. Pat.No. 3,532,501, polyalkylene oxides and other 1-phenyl-3
-Pyrazolidones, imidazoles and the like can be added as needed.

In the present invention, an optional antifoggant can be added as required. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and organic antifoggants 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, indazole, hydroxyazaindolizine, and adenine.

The color developer used in the present invention may contain a fluorescent whitening agent. As the fluorescent brightening agent, a 4,4'-diamino-2,2'-disulfostilbene compound is preferable.
The addition amount is 0 to 5 g / preferably 0.1 g to 4 g /.

Further, various surfactants such as alkylsulfonic acid, arylphosphonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added as needed.

The processing temperature of the color developer of the present invention is from 20 to 50C, preferably from 30 to 45C. Processing time is 20 seconds to 5 minutes, preferably 30
Seconds to 3 minutes. The replenishment amount is preferably smaller, but is preferably 100 to 1500 ml, preferably 100 to 800 ml, per m ^{2 of} the light-sensitive material.
More preferably, it is 100 ml to 400 ml.

Also, the color developing bath is divided into two or more baths as necessary,
Replenish the color developer replenisher from the last bath or the last bath,
The development time and the replenishment amount may be reduced.

The processing method of the present invention can also be used for color reversal processing. In the present invention, a so-called black-and-white first developing solution used for reversal processing of a color photographic light-sensitive material which is generally known as a black-and-white developing solution used at this time, or a solution used for processing a black-and-white photosensitive material can be used. In addition, various well-known additives generally added to a black-and-white developer can be contained.

Typical additives include developing agents such as 1-phenyl-3-pyrazolidone, methol and hydroquinone, preservatives such as sulfites, and accelerators composed of alkalis such as sodium hydroxide, sodium carbonate and potassium carbonate. , Potassium bromide, 2-methylbenzimidazole,
Examples thereof include inorganic or organic inhibitors such as methylbenzthiazole, water softeners such as polyphosphate, and a development inhibitor comprising a small amount of iodide or a mercapto compound.

In the bleaching solution of the present invention, a ferric complex of 1,3-diaminopropanetetraacetic acid is used.
Mol or more, and preferably 0.25 mol or more, particularly preferably 0.3 mol or more for speeding up. However, excessive use adversely inhibits the bleaching reaction, and the upper limit is 0.5 mol.

Ferric complex salt of 1,3-diaminopropanetetraacetic acid can be used as a salt of ammonium, sodium, potassium or the like.
Ammonium salts are preferred because of the fastest bleaching. If the amount of the ferric complex salt of 1,3-diaminopropanetetraacetic acid is less than 0.2 mol, bleaching is rapidly delayed, and the stain after treatment increases, so that the present invention contains 0.2 mol or more. It is a condition.

 Next, the pH of the bleaching solution of the present invention will be described.

A bleaching solution having a pH of 6 and containing a ferric complex of 1,3-diaminopropanetetraacetic acid is known from JP-A-62-222252.
Conventionally, the pH of a bleaching solution containing an aminopolycarboxylic acid ferric complex salt has been optimized widely around pH 6 from both the viewpoints of securing the bleaching speed and preventing the failure of cyan dye recoloration. In other words, although the bleaching speed is improved by lowering the pH, the poor recoloring of the cyan dye occurs, so that the optimum balance is around pH 6.

On the other hand, the present invention has a feature that the effect is exhibited by adjusting the pH of the bleaching solution to 2.5 to 4.0, and it is said that it is a conventional trade-off that rapid desilvering and improvement of poor recoloring of cyan dye can be achieved. To solve problems. The preferred range of the pH of the bleaching solution of the present invention is 2.5 to 4.0. To adjust the pH to this range, organic acids such as acetic acid, citric acid, and malonic acid, and inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid can be used.
Acids having an acid dissociation constant (Pka) in the range of 2.5 to 5.5 are preferred in terms of imparting buffering properties to the region of the present invention. In addition to the acetic acid, citric acid and malonic acid, benzoic acid, formic acid, butyric acid, malic acid, Various organic acids such as tartaric acid, oxalic acid, propionic acid and phthalic acid can be mentioned. Of these, acetic acid is particularly preferred.

The amount of these acids to be used is preferably 0.1 to 2 mol, and particularly preferably 0.5 to 1.5 mol, per bleaching solution.

It is preferable that 1,3-diaminopropanetetraacetic acid is added to the bleaching solution in a slightly excessive amount, which is necessary for complex formation with ferric ion, and usually in an amount of 1 to 10%. preferable.

The bleaching solution of the present invention may contain a ferric complex of aminopolycarboxylic acid other than a ferric complex of 1,3-diaminopropanetetraacetic acid, and specifically, ethylenediaminetetraacetic acid and diethylenetriaminepentaferric acid. Acetic acid and a ferric complex salt of cyclohexanediaminetetraacetic acid can be given.

Various bleaching accelerators can be added to the bleaching solution of the present invention.

For such bleaching accelerators, for example, U.S. Patent No. 3,893,858, German Patent No. 1,290,812, British Patent No. 1,138,842, JP-A-53-95630, Research Disclosure No. 17129 (1978
A compound having a mercapto group or a disulfide group, a thiazolidine derivative described in JP-A-50-140129, a thiourea derivative described in U.S. Pat. No. 3,706,561; The iodides described in 16235, the polyethylene oxides described in German Patent No. 2,748,430, the polyamine compounds described in JP-B-45-8836, and the like can be used. Particularly preferred are mercapto compounds as described in GB 1,138,842.

The bleaching solution constituting the present invention contains, in addition to the bleaching agent and the above compound, a bromide such as potassium bromide, sodium bromide, ammonium bromide or a chloride such as potassium chloride, sodium chloride or ammonium chloride. Silver halide can be included. The concentration of the silver rehalide is 0.1 to 5 mol, preferably 0.5 to 3 mol, per bleaching solution.

Further, it is preferable to use ammonium sulfate as a metal corrosion inhibitor.

The replenishment rate of the bleaching solution of the present invention the photosensitive material 1 m ² per 50ml~200
ml, preferably 100 ml to 1000 ml.

In the bleaching solution, it is preferable to oxidize the ferrous 1,3-diaminopropanetetraacetic acid salt formed by the treatment by aeration.

 The light-sensitive material after bleaching is subsequently subjected to a fixing process.

As a fixing agent, thiosulfates such as sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate, and potassium thiosulfate; thiocyanates such as sodium thiocyanate, ammonium thiocyanate, and potassium thiocyanate; thiourea; thioether; it can.

Among them, it is preferable to use ammonium thiosulfate, and the amount thereof is 0.3 to 3 mol per 1 fixer, preferably
0.5 to 2 mol.

From the viewpoint of promoting fixing, it is also preferable to use the above-mentioned ammonium thiocyanate (rhodanammonium), thiourea, and thioether (for example, 3,6-dithia-1,8-octanediol) in combination. Is generally about 0.01 mol to 0.1 mol per fixing solution, but the use of 1 to 3 mol may greatly enhance the fixing promoting effect.

The fixing solution may contain a sulfite as a preservative, for example, sodium sulfite, potassium sulfite, ammonium sulfite, and a bisulfite adduct of hydroxylamine, hydrazine, and an aldehyde compound, for example, sodium acetaldehyde bisulfite. . Further, various fluorescent whitening agents, antifoaming agents or surfactants, polyvinylpyrrolidone, organic solvents such as methanol can be contained, and particularly as preservatives are described in Japanese Patent Application No. 60-283831. It is preferable to use a sulfinic acid compound of

From 300ml per photosensitive material 1 m ² as the replenishing amount of the fixing solution
3000 ml is preferred, more preferably 300 ml to 1000 ml
It is.

Further, it is preferable to add various aminopolycarboxylic acids or organic phosphonic acids to the fixing solution of the present invention for the purpose of stabilizing the solution.

 The fixing solution may be a bleach-fixing solution having bleaching ability.

The shorter the total time of the desilvering step of the present invention, the more remarkable the effect of the present invention can be obtained. The preferred time is 1 minute to 4 minutes, more preferably 1 minute 30 seconds to 3 minutes. The processing temperature is from 25 ° C to 50 ° C, preferably from 35 ° C to 45 ° C. In a preferable temperature range, the desilvering speed is improved, and generation of stain after processing is effectively prevented.

In the desilvering step of the present invention, it is preferable that stirring is strengthened as much as possible in order to more effectively exert the effects of the present invention.

As a specific method of strengthening stirring, JP-A-62-183460,
JP-A-62-183461 describes a method of impinging a jet of a processing solution on an emulsion surface of a light-sensitive material, a method of increasing a stirring effect by using a rotating means disclosed in JP-A-62-183461, and further, a method of immersion in a liquid. There are a method of improving the stirring effect by moving the photosensitive material while bringing the wiper plate and the emulsion surface into contact with each other to make the emulsion surface turbulent, and a method of increasing the circulation flow rate of the entire processing solution. Such a stirring improving means is effective in any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the stabilizer into the emulsion film, and consequently increases the desilvering speed.

Further, the means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or eliminate the fixing inhibition effect of the bleaching accelerator.

The automatic developing machine used in the present invention is disclosed in JP-A-60-191257.
It is preferable to have the photosensitive material conveying means described in JP-A Nos. 191258 and 191259. As described in Japanese Patent Application Laid-Open No. 60-191257, such a transport means can significantly reduce the carry-in of the processing solution from the pre-bath to the post-bath, and is highly effective in preventing the performance of the processing solution from deteriorating. Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution.

The effect of the present invention is remarkable when the total processing time not including the drying time is short. Specifically, the effect is clearly exhibited when the total processing time is 8 minutes or less. The difference from the processing method becomes significant. Therefore, in the present invention, the total processing time is preferably 8 minutes or less, particularly preferably 7 minutes or less.

The processing method of the present invention comprises the above-described processing steps such as color development, bleaching, bleach-fixing and fixing. here,
After the bleach-fixing or fixing step, processing steps such as washing and stabilization are generally performed. However, after a bath having a fixing ability, a simple stabilization treatment without substantial washing is performed. Processing methods can also be used.

Known additives can be added to the washing water used in the washing step, if necessary. For example, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphoric acid, bactericides and deterrents that prevent the growth of various bacteria and algae (eg, isothiazolone, organochlorine bactericides, benzotriazole, etc.) , A drying load, and a surfactant for preventing unevenness can be used. Or LE
West, “Water Quality Criteria”, Phot.Sci.and Eng., V
ol. 9, No. 6, pages 344 to 359 (1965) and the like can also be used.

As the stabilizing solution used in the stabilizing step, a processing solution that stabilizes the dye image is used. For example, a liquid having a buffer capacity of pH 3 to 6, a liquid containing an aldehyde (for example, formalin), or the like can be used. The stabilizing solution may contain, as necessary, a metal compound such as an ammonium compound, Bi, or Al, a fluorescent brightener, a chelating agent (eg, 1-hydroxyethylidene-1,1-diphosphonic acid), a bactericide, and a deodorant. , A hardener, a surfactant and the like can be used.

In the washing step and the stabilizing step, a multi-stage countercurrent system is preferable, and the number of stages is preferably two to four. The replenishing amount is 1 to 50 times, preferably 2 to 30 times, more preferably 2 to 15 times the amount brought in from the previous bath per unit area.

Water used in these washing or stabilizing steps is not limited to tap water, and may be C
a, It is preferable to use water deionized to an Mg concentration of 5 mg / or less, water that has been sterilized by halogen, an ultraviolet germicidal lamp, or the like.

In the above-described processing steps of the photosensitive material, when the continuous processing is performed by the automatic developing machine, the processing solution may be concentrated due to evaporation, particularly when the processing amount is small or the opening area of the processing solution is large. Becomes In order to correct such concentration of the processing solution, it is preferable to replenish an appropriate amount of water or a correction solution.

In addition, the amount of waste liquid can also be reduced by using a method in which the overflow solution in the washing step or the stabilization step is flowed into a bath having a fixing ability, which is a pre-bath.

The light-sensitive material of the present invention comprises at least one of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer of a silver halide emulsion layer on a support.
The number of layers and the order of the silver halide emulsion layer and the non-photosensitive layer are not particularly limited as long as the layers are provided. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. The light-sensitive layer is a unit light-sensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic light-sensitive material, generally, The arrangement is such that a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are arranged in this order from the support side. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity.

Non-photosensitive layers such as various intermediate layers may be provided between the silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

The intermediate layer is described in JP-A-61-43748 and JP-A-59-113438.
No. 59-113440, No. 61-20037, couplers as described in the specification of JP 61-20038, DIR compounds and the like may be contained, and contains a color mixing inhibitor as usually used. You may go out.

The plurality of silver halide emulsion layers constituting each unit photosensitive layer are described in West German Patent No. 1,121,470 or British Patent No. 923,045.
No. 2 of the high-speed emulsion layer and the low-speed emulsion layer
A layer configuration can be preferably used. Usually, it is preferable to arrange them so that the light sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the respective halogen emulsion layers. Also, JP-A-57-112751, 62-127
As described in 200350, 62-206541, 62-206543, etc., a low-speed emulsion layer may be provided on the side remote from the support and a high-speed emulsion layer may be provided on the side near the support.

As specific examples, from the farthest side from the support, a low-sensitivity blue-sensitive layer (BL) / a high-sensitivity blue-sensitive layer (BH) / a high-sensitivity green-sensitive layer (GH) / a low-sensitivity green-sensitive layer (GL) / High-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL) or BH / BL /
They can be installed in the order of GL / GH / RH / RL or BH / BL / GH / GL / RL / RH.

Also, as described in JP-B-55-34932, the blue-sensitive layer / GH / RH / GL / RL is selected from the side farthest from the support.
Can be arranged in this order. JP-A-56-25738
As described in JP-A-62-63936, the layers may be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

As described in JP-B-49-15495, the upper layer is the most sensitive silver halide emulsion layer, the middle layer is the less sensitive silver halide emulsion layer, and the lower layer is more sensitive than the middle layer. A silver halide emulsion layer having a low degree is arranged,
There is an array composed of three layers having different sensitivities in which the sensitivities are sequentially decreased toward the support. Even in the case of three layers having different sensitivities, Japanese Patent Application Laid-Open No.
As described in JP-A-202464, a medium-speed emulsion layer / a high-speed emulsion layer / a low-speed emulsion layer may be arranged in the same color-sensitive layer from the side remote from the support.

As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive material.

Preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing about 30 mol% or less of silver iodide. . Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 25 mol% silver iodide.

Silver halide grains in photographic emulsions are cubic, octahedral,
It may be one having regular crystals such as tetradecahedron, one having irregular crystal forms such as spherical or plate-like, one having crystal defects such as twin planes, or a complex form thereof.

The silver halide may be fine grains having a grain size of about 0.2 μm or less or large grains having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion that can be used in the present invention is described in, for example, Research Disclosure (RD) No. 17643 (1978).
December), p. 22-23, "I. Emulsion preparati
on and types) ”and No. 18716 (November 1979),
Page 648, Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (P. Glafkides, Chemic et Phisique Photogr
aphique, Paul Montel, 1967), Photographic Emulsion Chemistry by Duffin, GFDuffin, Photographi, Focal Press
c Emulsion Chemistry (Focal Press, 1966)), "Manufacture and coating of photographic emulsions" by Zerikman et al., Published by Focal Press (VLZelikman et al., Making and Coating Photo).
graphic Emulsion, Focal Press, 1964).

Monodisperse emulsions described in U.S. Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable.

Tabular grains having an aspect ratio of about 5 or more can also be used in the present invention. Tabular grains are provided by Gaft, Photographic Science and Engineerin
g), Vol. 14, pp. 248-257 (1970); U.S. Patent No. 4,434,2
No. 26, 4,414,310, 4,433,048, 4,439,520 and British Patent No. 2,112,157 can be easily prepared.

The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, may have a layered structure, and even if silver halides having different compositions are joined by epitaxial junction. Also, it may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide.

 Also, a mixture of particles of various crystal forms may be used.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. The additive used in such a process is Research Disclosure No. 1
7643 and No. 18716, and the relevant portions are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant portions are shown in the following table.

Also, in order to prevent deterioration of photographic performance due to formaldehyde gas, U.S. Patent Nos. 4,411,987 and 4,435,503
It is preferable to add a compound capable of being fixed by reacting with formaldehyde described in (1) to the photosensitive material.

Various color couplers can be used in the present invention, and specific examples thereof are described in the patents described in the aforementioned Research Disclosure (RD) No. 17643, VII-CG.

As a yellow coupler, for example, U.S. Pat.
No. 501, No. 4,022,620, No. 4,326,024, No. 4,40
No. 1,752, No. 4,248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020, No. 1,476,760, U.S. Pat.
Preferred are those described in 3,968, 4,314,023, 4,511,649, and EP 249,473A.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable, and US Patent No. 4,310,
No. 619, No. 4,351,897, European Patent No. 73,636, U.S. Pat. No. 3,061,432, No. 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-3355
No. 2, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, JP-A-61-72238, and JP-A-60-35
No. 730, No. 51-118034, No. 60-185951, U.S. Pat.
No. 4,500,630, No. 4,540,654, No. 4,556,630, WO
(PCT) 88/04795 and the like are particularly preferred.

Cyan couplers include phenolic and naphthol couplers, U.S. Pat.Nos. 4,052,212, 4,146,396, 4,228,233, 4,296,200,
No. 2,369.929, No. 2,801,171, No. 2,772,162
No. 2,895,826, No. 3,772,002, No. 3,758,30
No. 8, No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121,365A, No. 249,453
A, U.S. Pat.Nos. 3,446,622, 4,333,999,
No. 4,753,871, No. 4,451,559, No. 4,427,767, No. 4,690,889, No. 4,254,212, No. 4,296,199,
Preferred are those described in JP-A-61-42658.

Colored couplers for correcting unwanted absorption of coloring dyes are described in Research Disclosure No.17643 VII.
Section G, U.S. Pat.No. 4,163,670, JP-B-57-39413,
U.S. Pat.Nos. 4,004,929 and 4,138,258; British Patent No.
Those described in 1,146,368 are preferred.

As a coupler in which the coloring dye has an appropriate diffusivity,
Preferred are those described in U.S. Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent No. 96,570, and West German Patent (Published) No. 3,234,533.

Typical examples of polymerized dye-shaped couplers are U.S. Patent Nos. 3,451,820, 4,080,211 and 4,367,282.
No. 4,409,320, No. 4,576,910, British Patent 2,10
No. 2,173.

Couplers that release a photographically useful residue upon coupling can also be preferably used in the present invention. DIR couplers that release development inhibitors are described in RD17643, VII-F above.
Patents, JP-A-57-151944 and JP-A-57-1542
No. 3, 60-184248, 63-37346, U.S. Pat.
Those described in JP 8,962 are preferred.

Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include UK Patent Nos. 2,097,140 and 2,1
No. 31,188, JP-A Nos. 59-157638 and 59-170840 are preferred.

In addition, as couplers that can be used in the light-sensitive material of the present invention, competitive couplers described in U.S. Pat.No. 4,130,427, U.S. Pat.Nos. 4,283,472 and 4,338,393,
No. 4,310,618 and the like, multi-equivalent couplers described in
185950, DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR described in JP-A-62-24252 and the like.
Coupler-releasing redox compound or DIR redox-releasing redox compound, coupler releasing a dye that recolors after release as described in EP 173,302A, RD No. 1144
9, 24241, bleach accelerator releasing couplers described in JP-A-61-201247, ligand releasing couplers described in U.S. Pat.No. 4,553,477, etc., and leuco dyes described in JP-A-63-75747 are released. Couplers and the like.

The coupler used in the present invention can be introduced into a light-sensitive material by various known dispersion methods.

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027.

Specific examples of the high boiling point organic solvent having a boiling point at normal pressure of 175 ° C. or higher used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2,4-di-t-aluminphenyl) phthalate, bis (2,4-di-t-aluminphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate, etc., phosphoric acid or phosphonic acid ester (Triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-
2-ethylhexylphenylphosphonate, etc.), benzoates (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N, N-diethyldodecaneamide, N, N-diethyllaurylamide) , N-tetradecylpyrrolidone), alcohols or phenols (isostearyl alcohol, 2,4-di-tert)
-Amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl- 2-butoxy-5-ter
t-octylaniline, etc.), and hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.). As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, and 2-hexane. Ethoxyethyl acetate, dimethylformamide and the like can be mentioned.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in U.S. Pat. No. 4,199,363 and West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films, and color reversal papers.

Suitable supports that can be used in the present invention include, for example, those described above.
From page 28 of RD.No.17643, and from the right column of page 647 of No.18716
It is described in the left column on page 648.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 20 μm or less, and the film swelling speed T _1/2 is preferably 10 seconds or less. Film thickness is 25 ° C and relative humidity is 55
% Means the film thickness measured under humidity control (2 days), and the film swelling rate T _1/2 can be measured according to a method known in the art. For example, A.Gree
n) et al. Photographic Science and Engineering (Pho.Sci.Eng.), Vol. 19, No. 2, 124
Can be measured by using a type of Swellometer described (swelling meter) pp to 129, T _1/2 is 30 ° C. with a color developer,
90% of the maximum swollen film thickness reached when the treatment is performed for 3 minutes and 15 seconds is defined as a saturated film thickness, and is defined as the time required to reach a film thickness which is 1/2 of the saturated film thickness.

The film swelling speed T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging conditions after coating.

The swelling ratio is preferably from 150 to 400%. The swelling ratio can be calculated from the maximum swelling film thickness under the conditions described above according to the following formula (maximum swelling film thickness-film thickness) / film thickness.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.

Example 1 Example 1 On a cellulose triacetate film support having an undercoat, Sample 01, which is a multilayered color light-sensitive material comprising the following layers, was prepared.

The amount coated amount (Composition of photosensitive layer) is represented in units of g / m ² of silver for silver halide and colloidal silver, also couplers, the amount for the additives and gelatin, expressed in units of g / m ^2, The sensitizing dyes are shown in terms of moles per mole of silver halide in the same layer.

First layer (anti-halation layer) Black colloidal silver 0.2 Gelatin 1.3 ExM-8 0.06 UV-1 0.1 UV-2 0.2 Solv-1 0.01 Solv-2 0.01 Layer (intermediate layer) Fine grain silver bromide (average particle size 0.07 μm) ... 0.10 Gelatin 1.5 UV-1 ... 0.06 UV-2 ... 0.03 ExC-2 ... 0.02 ExF-1 ... 0.004 Solv-1 ... 0.1 Solv-2 ...... 0.09 Third layer (first red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 2 mol%, internal high AgI type, equivalent sphere diameter of 0.
3 μm, coefficient of variation of equivalent sphere diameter 29%, normal crystal, twin mixed particles, diameter / thickness ratio 2.5) Silver coating amount ...... 0.4 Gelatin ...... 0.6 ExS-1 ...... 1.0 × 10 ^-4 ExS-2 ...... 3.0 × 10 ^-4 ExS-3… 1 × 10 ^-5 ExC-3… 0.06 ExC-4… 0.06 ExC-7… 0.04 ExC-2… 0.03 Solv-1 …… 0.03 Solv-3 …… 0.012 4th layer (2nd red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 5 mol%, internal high AgI type, equivalent sphere diameter 0.
7 μm, sphere equivalent diameter variation coefficient 25%, normal crystal, twin mixed particles, diameter / thickness ratio 4) Coating silver amount: 0.7 Gelatin: 0.5 ExS-1: 1 × 10 ^-4 ExS-2: 3 x 10 ^-4 ExS-3 ... 1 x 10 ^-5 ExC-3 ... 0.24 ExC-4 ... 0.24 ExC-7 ... 0.04 ExC-2 ... 0.04 Solv-1 ... 0.15 Solv-3 ... 0.02 Fifth layer (third red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, equivalent sphere diameter)
0.8 μm, coefficient of variation of equivalent sphere diameter 16%, normal crystal, twin mixed particles, diameter / thickness ratio 1.3) Silver coating amount 1.0 gelatin 1.0 ExS-1 1 × 10 ^-4 ExS-2 … 3 × 10 ^-4 ExS-3… 1 × 10 ^-5 ExC-5… 0.05 ExC-6… 0.1 Solv-1… 0.01 Solv-2… 0.05 0.05 6th layer (intermediate layer) gelatin …… 1.0 Cpd-1... 0.03 Solv-1... 0.05 Seventh layer (first green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 2 mol%, high internal AgI type, equivalent sphere diameter of 0,0)
3 μm, coefficient of variation of equivalent sphere diameter 28%, normal crystal, twin mixed particles, diameter / thickness ratio 2.5) Silver coating amount 0.30 ExS-4 5 × 10 ^-4 ExS-6 0.3 × 10 ^{− 4} ExS-5 ... 2 x 10 ^-4 gelatin ... 1.0 ExM-9 ... 0.2 ExY-14 ... 0.03 ExM-8 ... 0.03 Solv-1 0.5 Eighth layer (second green-sensitive emulsion layer) Silver halide emulsion (AgI 4 mol%, internal high AgI type, equivalent sphere diameter 0.
6 μm, variation coefficient of sphere equivalent diameter 38%, normal crystal, twin mixed particles, diameter / thickness ratio 4) Coating amount of silver: 0.4 Gelatin: 0.5 ExS-4: 5 × 10 ^-4 ExS-5: 2 × 10 ^-4 ExS-6 ...... 0.3 × 10 ^-4 ExM-9 ...... 0.25 ExM-8 ...... 0.03 ExM-10 ...... 0.015 ExY-14 ...... 0.01 Solv-1 ...... 0.2 3 green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 6 mol%, internal high AgI type, equivalent sphere diameter 1.
0 μm, coefficient of variation of sphere equivalent diameter 80%, normal crystal, twin mixed particles, diameter / thickness ratio 1.2) Silver coating amount 0.85 gelatin 1.0 ExS-7 3.5 x ^10-4 ExS-8 1.4 × 10 ^-4 ExM-11 ...... 0.01 ExM-12 ...... 0.03 ExM-13 ...... 0.20 ExM-8 ...... 0.02 ExY-15 ...... 0.02 Solv-1 ...... 0.20 Solv-2 ...... 0.05 Layer 10 (Yellow filter layer) Gelatin ... 1.2 Yellow colloidal silver ... 0.08 Cpd-2 ... 0.1 Solv-1 ... 0.3 Layer 11 (first blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, internal High AgI type, ball equivalent diameter 0.
5 μm, coefficient of variation of sphere equivalent diameter: 15%, octahedral particles) Silver coating amount: 0.4 Gelatin: 1.0 ExS-9: 2 × 10 ^-4 ExY-16: 0.9 ExY-14: 0.07 Solv-1 0.2 Layer 12 (second blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, equivalent sphere diameter)
1.3 μm, coefficient of variation of equivalent sphere diameter 25%, normal crystal, twin mixed particles, diameter / thickness ratio 4.5) Silver coating amount 0.5 gelatin 0.6 ExS-9 1 × 10 ^-4 ExY-16 ... 0.25 Solv-1 ... 0.07 13th layer (first protective layer) Gelatin ... 0.8 UV-1 ... 0.1 UV-2 ... 0.2 Solv-1 ... 0.01 Solv-2 ... 0.01 Layer 14 (first layer) (2 protective layer) Fine particle silver bromide (average particle size 0.07 μm)… 0.5 Gelatin… 0.45 Polymethyl methacrylate particles (1.5 μm diameter)… 0.2
H-1... 0.4 Cpd-3... 0.5 Cpd-4... 0.5 In addition to the above components, a surfactant was added to each layer as a coating aid. The sample prepared as described above was
And

Next, the chemical structural formulas or chemical names of the compounds used in the present invention are shown below.

Solv-1: Tricresyl phosphate Solv-2: Dibutyl phthalate Solv-3: Bis (2-ethylhexyl) phthalate The color photosensitive material sample 01 prepared as described above
The following treatment was carried out under two conditions after exposure for 0.1 second at 20 lux using a light source having a color temperature of 00 ° K.

(Color developing solution) Unit (g) △ Hydroxyethyliminodiacetic acid 5.0 △ Sodium sulfite 4.0 △ Potassium carbonate 30.0 △ Potassium bromide 1.3 △ Potassium iodide 1.2mg △ Hydroxyamine sulfate 2.0 △ 4- (N-ethyl-N -Β-hydroxyethylamino) -2-methylaniline sulfate (color developing agent) 1.6 × 10 ^-2 mol △ 1-hydroxyethylidene-1,1-diphosphonic acid 3.0 △ Add water 1.0 pH 10.05 (Bleaching solution ) Unit (g) △ Ferric complex of ethylenediaminetetraacetic acid (EDTA / Fe) 0.3 mol △ 1,3-Diaminopropanetetraacetic acid 3.0 △ Ammonium bromide 100 △ Acetic acid 50 △ Ammonium nitrate 30 △ Add water and add 1.0 acetic acid and ammonia PH 6.0 (fixing solution) Mother liquor (g) △ 1-hydroxyethylidene-1,1-diphosphonic acid 7.0 △ Ethylenediaminetetraacetic acid disodium salt 7.0 △ Ammonium sulfite 1 6.0 △ ammonium thiosulfate solution (700g /) 240ml △ 3,6-dithia-1,8-octanediol 5.0 △ Add water and pH 1.0 with 1.0 acetic acid and ammonia (washing water) Tap water is H-type strongly acidic cation exchange resin (Rohm and Haas Amberlite IR-120B) and OH type anion exchange resin (Amberlite IRA-400) packed in a mixed-bed column filled with water to reduce the calcium and magnesium ion concentration to 3 mg / or less. Subsequently, 20 mg / sodium dichloride isocyanurate and 0.15 g / sodium sulfate were added. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizing solution) Unit (g) △ Formalin (37%) 2.0 ml △ Polyoxyethylene-p-monononyl phenyl ether (average degree of polymerization 10) 0.3 △ Disodium ethylenediaminetetraacetate 0.05 △ Add water 1.0 pH 5.0- 8.0 After completion of the processing, the density of the sample was measured, and the appropriate development time and stain over time were evaluated by the following methods.

Appropriate development time (Table-1-b) The density of the processed sample was measured with a Macbeth densitometer. At this time, the magenta density was 1.5.

The color developing agent concentration of the color developing solution is changed as shown in Table 1, and the color developing time is variously changed, and the processing is carried out. I asked.

 The results are shown in Table 1-b.

Aging stain (Table-1-a) The pH of the bleaching solution and the concentration of EDTA / Fe in the bleaching solution at each development processing time in Table-1-b are shown in Table 1-a.
The unexposed sample 01 was processed by changing the TA / Fe concentration and the pH and setting the bleaching time to 45 seconds.

Measure the magenta concentration of the treated samples and measure each sample for 60 minutes.
After storing for 30 days at 70 ° C. and a relative humidity of 70%, the magenta concentration was measured again. The concentration increase due to storage at this time was defined as stain with time.

 The results are shown in Table-1-a.

As can be seen from Table 1, the development time can be reduced by increasing the concentration of the developing agent. However, when EDTA / Fe, which has been commonly used, is used as a bleaching agent, or when DPTA / Fe is used in a small amount (1.5 mol /)
When used, the stain over time deteriorates as the concentration of the color developing agent increases, which is unacceptable.
Within the range of the Fe concentration and the pH, stain with time is effectively suppressed, and rapid processing can be performed without deteriorating image storability.

The acetic acid used for the pH adjustment has an acid dissociation constant of 4.56.

Example 2 The sample 01 prepared in Example 1 was cut into a 35 mm width, photographed with a camera under the sensitivity condition of ISO 100, and treated continuously for 30 days at 30 m / day for 15 days with the following processing steps and processing liquid. Was performed.

The bleaching solution obtained as described above was adjusted to each pH shown in Table 2 using aqueous ammonia or acetic acid.

In each pH condition, using a sample obtained by subjecting sample 01 to white light exposure at 200 lux for 0.1 second using a light source having a color temperature of 4800 ° K, and changing the bleaching time to 20, 35, 45 and 60 seconds, 1
Was performed.

After the treatment, the amount of silver remaining in the sample was determined by fluorescent X-ray analysis. Table 2 shows the obtained results.

From the results in the above table, if the pH of the bleaching solution is within the range of the present invention, the amount of residual silver in the sample is clearly small even if the bleaching time is shortened, and rapid desilvering becomes possible.

Example 3 Each experiment of Example 1 and Example 2 was performed using the following samples 02 and 03 in place of the sample 01, and similar results were obtained.

Sample 02 Sample 02 was prepared as a multilayer color photosensitive material comprising the following layers on a cellulose triacetate film support having an undercoat.

The amount coated amount (Composition of photosensitive layer) is represented in units of g / m ² of silver for silver halide and colloidal silver, also couplers, the amount for the additives and gelatin, expressed in units of g / m ^2, The sensitizing dyes are shown in terms of moles per mole of silver halide in the same layer. The symbols indicating the additives have the following meanings. However, when it has a plurality of effects, only one of them is represented.

UV; UV absorber, Solv; High boiling organic solvent, ExF; Dye, Ex
S; sensitizing dye, ExC; cyan coupler, ExM; magenta coupler, ExY; yellow coupler, Cpd; additive First layer (anti-halation layer) Black colloidal silver 0.15 gelatin 2.9 UV-1 0.03 UV-2 0.06 UV-3 0.07 Solv-2 0.08 ExF-1 0.01 ExF-2 0.01 Second layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, uniform AgI type, equivalent spherical diameter 0.4)
[mu] m, spherical coefficient of variation of 37% equivalent diameter, the plate-like particles, diameter / thickness ratio 3.0) coating silver amount 0.4 Gelatin ^{0.8 ExS-1 2.3 × 10 -4} ExS-2 1.4 × 10 -4 ExS-5 2.3 × 10 - ⁴ ExS-7 8.0 × 10 ^-6 ExC-1 0.17 ExC-2 0.03 ExC-3 0.13 Third layer (medium-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 6 mol%, core-shell ratio 2: 1) High
AgI type, sphere equivalent diameter 0.65μm, sphere equivalent diameter variation coefficient 25%,
Plate-like grains, diameter / thickness ratio 2.0) Silver coating amount 0.65 Silver iodobromide emulsion (AgI 4 mol%, uniform AgI type, equivalent sphere diameter 0.4)
[mu] m, spherical coefficient of variation of 37% equivalent diameter, the plate-like particles, diameter / thickness ratio 3.0) coating silver amount 0.1 Gelatin ^{1.0 ExS-1 2 × 10 -4} ExS-2 1.2 × 10 -4 ExS-5 2 × 10 - ⁴ ExS-7 7 × 10 ^-6 ExC-1 0.31 ExC-2 0.01 ExC-3 0.06 4th layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 6 mol%, core-shell ratio 2: 1 internal) High
AgI type, equivalent spherical diameter 0.7 μm, coefficient of variation of equivalent spherical diameter 25%, plate-like particle, diameter / thickness ratio 2.5) Coating silver amount 0.9 Gelatin 0.8 ExS-1 1.6 × 10 ^-4 ExS-2 1.6 × 10 ^-4 ExS-5 1.6 × 10 ^-4 ExS-7 6 × 10 ^-4 ExC-1 0.07 ExC-4 0.05 Solv-1 0.07 Solv-2 0.20 Cpd-7 4.6 × 10 ^-4 Fifth layer (intermediate layer) Gelatin 0.6 UV -4 0.03 UV-5 0.04 Cpd-1 0.1 Polyethyl acrylate latex 0.08 Solv-1 0.05 6th layer (low sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, uniform AgI type, equivalent sphere diameter 0.4)
μm, coefficient of variation of sphere equivalent diameter 37%, plate-like particles, diameter / thickness ratio 2.0) Silver coating 0.18 gelatin 0.4 ExS-3 2 × 10 ^-4 ExS-4 7 × 10 ^-4 ExS-5 1 × 10 ^{− 4} ExM-5 0.11 ExM-7 0.03 ExY-8 0.01 Solv-1 0.09 Solv-4 0.01 7th layer (medium speed green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, surface of core-shell ratio 1: 1) High
AgI type, equivalent sphere diameter 0.5 μm, coefficient of variation of equivalent sphere diameter 20%, plate-like particles, diameter / thickness ratio 4.0) Coating silver amount 0.27 Gelatin 0.6 ExS-3 2 × 10 ^-4 ExS-4 7 × 10 ^-4 ExS-5 1 × 10 ^-4 ExM-5 0.17 ExM-7 0.04 ExY-8 0.02 Solv-1 0.14 Solv-4 0.02 Eighth layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 8.7 mol%, Multilayer structure particles having a silver content ratio of 3: 4: 2, 24 mol, 0 mol, 3 mol% from the inside of the AgI content,
Equivalent sphere diameter 0.7 μm, Coefficient of variation of sphere equivalent diameter 25%, plate-like particles, diameter / thickness ratio 1.6) Coating silver amount 0.7 Gelatin 0.8 ExS-4 5.2 × 10 ^-4 ExS-5 1 × 10 ^-4 ExS-8 0.3 × 10 ^-4 ExM-5 0.1 ExM-6 0.03 ExY-8 0.02 ExC-1 0.02 ExC-4 0.01 Solv-1 0.25 Solv-2 0.06 Solv-4 0.01 Cpd-7 1 × 10 ^-4 9th layer (middle Layer) Gelatin 0.6 Cpd-1 0.04 Polyethyl acrylate latex 0.12 Solv-1 0.02 10th layer (donor layer of multilayer effect on red-sensitive layer) Silver iodobromide emulsion (AgI 6 mol%, core-shell ratio 2: 1 internal height)
AgI type, equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 25%, plate-like grains, diameter / thickness ratio 2.0) Silver coating amount 0.68 Silver iodobromide emulsion (AgI 4 mol%, uniform AgI type, equivalent sphere diameter) 0.4
μm, coefficient of variation of equivalent sphere diameter 37%, plate-like particles, diameter / thickness ratio 3.0) Silver coating 0.19 gelatin 1.0 ExS-3 6 × 10 ^-4 ExM-10 0.19 Solv-1 0.20 Layer 11 (yellow filter layer) Yellow colloidal silver 0.06 gelatin 0.8 Cpd-2 0.13 Solv-1 0.13 Cpd-1 0.07 Cpd-6 0.002 H-1 0.13 12th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4.5 mol%, uniform) AgI type, ball equivalent diameter 0.
7 μm, coefficient of variation of sphere equivalent diameter 15%, tabular grains, diameter / thickness ratio 7.0) Silver coating amount 0.3 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, sphere equivalent diameter 0.3)
μm, coefficient of variation of sphere equivalent diameter 30%, plate-like particles, diameter / thickness ratio 7.0) Silver coating 0.15 gelatin 1.8 ExS-6 9 × 10 ^-4 ExC-1 0.06 ExC-4 0.03 ExY-9 0.14 ExY-11 0.89 Solv-1 0.42 Layer 13 (intermediate layer) Gelatin 0.7 ExY-12 0.20 Solv-1 0.34 Layer 14 (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, spherical) Equivalent diameter
1.0 μm, coefficient of variation of equivalent sphere diameter 25%, multiple twin plate-like grains, diameter / thickness ratio 2.0) Silver coating amount 0.5 Gelatin 0.5 ExS-6 1 × 10 ^-4 ExY-9 0.01 ExY-11 0.20 ExC-1 0.02 Solv-1 0.10 15th layer (first protective layer) Fine grain silver iodobromide emulsion (AgI 2 mol%, uniform AgI type, equivalent sphere diameter 0.07 μm) Paint silver amount 0.12 Gelatin 0.9 UV-4 0.11 UV-5 0.16 Solv-5 0.02 H-1 0.13 Cpd-5 0.10 Polyethyl acrylate latex 0.09 16th layer (2nd protective layer) Fine grain silver iodobromide emulsion (AgI 2 mol%, uniform AgI type, equivalent sphere diameter 0.07 μm) Paint silver Amount 0.36 Gelatin 0.55 Polymethyl methacrylate particles (1.5 μm in diameter) 0.2 H-1 0.17 In addition to the above components, an emulsion stabilizer Cpd-3 was added to each layer.
(0.07 g / m ² ) and a surfactant Cpd-4 (0.03 g / m ² ) were added as coating aids.

Solv-1 Tricresyl phosphate Solv-2 Dibutyl phthalate Solv-5 Trihexyl phosphate Sample 03 On a cellulose triacetate film support having an undercoat, each layer having the following composition was applied in multiple layers to prepare Sample 03 as a multilayer color photosensitive material.

(Composition of photosensitive layer) The number corresponding to each component indicates the coating amount expressed in g / m ² , and for silver halide, the coating amount is expressed in terms of silver. However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer.

1st layer (antihalation layer) Black colloidal silver silver 0.18 gelatin 0.40 2nd layer (intermediate layer) 2,5-di-t-pentadecylhydroquinone 0.18 EX-1 0.07 EX-3 0.02 EX-12 0.002 U-1 0.06 U-2 0.08 U-3 0.10 HBS-1 0.10 HBS-2 0.02 Gelatin 1.04 Third layer (first red-sensitive emulsion layer) Emulsion A silver 0.25 Emulsion B silver 0.25 Sensitizing dye I 6.9 × 10 ^-5 Sensitizing dye II 1.8 × 10 ^-5 sensitizing dye III 3.1 × 10 ^-4 EX-2 0.335 EX-10 0.020 gelatin 0.87 4th layer (second red-sensitive emulsion layer) Emulsion C silver 1.0 sensitizing dye I 5.1 × 10 ^-5 sensitization Dye II 1.4 × 10 ^-5 Sensitizing dye III 2.3 × 10 ^-4 EX-2 0.400 EX-3 0.050 EX-10 0.015 Gelatin 1.30 Fifth layer (third red-sensitive emulsion layer) Emulsion D Silver 1.60 Sensitizing dye I 5.4 × 10 ^-5 sensitizing dye II 1.4 × 10 ^-5 sensitizing dye III 2.4 × 10 ^-4 EX-3 0.010 EX-4 0.080 EX-2 0.097 HSB-1 0.22 HSB-2 0.10 Gelatin 1.63 6th layer (intermediate layer) ) EX-5 0.040 HBS-1 0.020 Gelatin 0.80 7th layer (first green-sensitive emulsion layer) Emulsion A silver 0.15 Emulsion B silver 0.15 sensitizing dye V 3.0 × 10 ^-5 sensitizing dye VI 1.0 × 10 ^-4 sensitizing dye VII 3.8 × 10 ^-4 EX-6 0.260 EX-1 0.021 EX-7 0.030 EX-8 0.025 HBS-1 0.100 HBS-3 0.010 Gelatin 0.63 Eighth layer (second green-sensitive emulsion layer) Emulsion C Silver 0.45 Sensitizing dye V 2.1 × 10 ^-5 Sensitizing dye VI 7.0 × 10 ^-5 sensitizing dye VII 2.6 × 10 ^-4 EX-6 0.094 EX-8 0.018 EX-7 0.026 HBS-1 0.160 HBS-3 0.008 Gelatin 0.50 Ninth layer (third green-sensitive emulsion layer) Emulsion E Silver 1.2 Sensitizing dye V 3.5 × 10 ^-5 Sensitizing dye VI 8.0 × 10 ^-5 Sensitizing dye VII 3.0 × 10 ^-4 EX-13 0.015 EX-11 0.100 EX-1 0.025 HBS-1 0.25 HBS-2 0.10 Gelatin 1.54 10th layer (yellow filter layer) Yellow colloidal silver silver 0.05 EX-5 0.08 HBS-1 0.03 gelatin 0.95 11th layer (first blue-sensitive emulsion layer) Emulsion A silver 0.08 Emulsion B silver 0.07 Emulsion F silver 0.07 sensitizing dye VIII 3.5 × 10 ^-4 EX-9 0.721 EX-8 0.042 HBS-1 0. 28 Gelatin 1.10 12th layer (2nd blue-sensitive emulsion layer) Emulsion G silver 0.45 sensitizing dye VIII 2.1 × 10 ^-4 EX-9 0.154 EX-10 0.007 HBS-1 0.05 Gelatin 0.78 13th layer (3rd blue-sensitive emulsion Layer) Emulsion H silver 0.77 Sensitizing dye VIII 2.2 × 10 ^-4 EX-9 0.20 HBS-1 0.07 Gelatin 0.69 14th layer (first protective layer) Emulsion I silver 0.5 U-4 0.11 U-5 0.17 HBS-1 0.05 Gelatin 1.00 15th layer (2nd protective layer) Polymethyl acrylate particles (about 1.5 μm in diameter) 0.54 S-1 0.20 Gelatin 1.20 In addition to the above components, gelatin hardener H-1 and surfactant are added did.

HBS-1 Tricresyl phosphate HBS-2 Di-n-butyl phthalate Example-4 The same processing as in Example 2 was carried out except that the processing steps and the processing solution were changed as follows, and the processing was performed in exactly the same manner. Was confirmed.

(Color developing solution and bleaching solution) Same as in Example 2. (Stabilizing solution) Common for mother liquor and replenisher Formalin (37%) 1.2 ml 5-Chloro-2-methyl-4-isothiazolin-3-one 6.0 mg 2-Methyl-4-isothiazolin-3-one 3.0 mg Surfactant 0.4 [C ₁₀ H ₂₁ -OCH ₂ CH ₂ O ₁₀ H] Ethylene glycol 1.0 Add water 1.0 pH 5.0-7.0 (Effect of the Invention) By carrying out the present invention, rapid processing with excellent image storability after processing Was completed.

Claims (1)

(57) [Claims] (1) After imagewise exposing a silver halide color photographic light-sensitive material, it is developed with a color developing solution containing at least 1.2.times.10.sup.- ² mol / mol of a color developing agent, followed by 1,3-diaminopropanetetraacetic acid. Containing 0.2 mol / or more of a ferric complex salt,
A method for processing a silver halide color photographic light-sensitive material, wherein the processing is carried out with a bleaching solution containing an acid having an acid dissociation constant of 2.5 to 5.5 at 0.5 to 1.5 mol / or more and a pH of 2.5 to 4.0.