JPH0654377B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for processing a silver halide color photographic reflective light-sensitive material, and in particular, the stability and color developability of a color developer are improved and continuous processing is performed. The present invention relates to a processing method in which the rise of fog at time is remarkably reduced.

(Prior Art) A color developing solution containing an aromatic primary amine color developing agent has been used for a long time for forming a color image, and now plays a central role in an image forming method for color photography. Is playing. However, the color developer has a problem that it is very easily oxidized by air or metal, and when a color image is formed using the oxidized developer, fog is increased, sensitivity and gradation are changed. It is well known that the desired photographic characteristics cannot be obtained due to such problems.

Therefore, various means for improving the preservative property of such a color developer have been studied so far, and among them, the method of using hydroxylamine and sulfite ion in combination is the most general. However, hydroxylamine acids, JP-A-56-9734
7, Japanese Patent Publication No. 56-39359 and West German Patent 2227.
Organic phosphonic acids described in 639, JP-A-52-102
No. 726, No. 53-42730, No. 54-12112.
No. 7, No. 55-126241 and No. 55-65956.
And other phosphonocarboxylic acids, and others
Examples thereof include compounds described in JP-A Nos. 8-195845, 58-203440, and JP-B-53-40900.

(Problems to be Solved by the Invention) However, even if these techniques are used alone or in combination, the fog density of a color image obtained by using a developer after aging due to insufficient preserving performance. However, satisfactory results have not been obtained because of adverse effects on photographic characteristics, such as an increase in image quality and fluctuations in photographic performance, and a competitive effect with a developing agent to inhibit color development.

Further, benzyl alcohol, which is very effective as a color-developing accelerator for color developing agents, has been widely used in the developing solutions of color photographic reflective light-sensitive materials as an almost essential component, but benzyl alcohol is harmful to the environment and hygiene. In addition, since there are problems such as difficulty in liquid preparation, there is a demand for a technique capable of obtaining sufficient color development even when benzyl alcohol is removed. However, since many of the known compounds as a preservative of the developing solution act competitively with the developing agent to cause color development inhibition as described above, it is difficult to be compatible with the technology for removing benzyl alcohol as a color development accelerator. It was a thing.

In particular, a color photographic light-sensitive material paper containing a silver chlorobromide emulsion having a high chlorine content is liable to be disturbed in color development, and fog is apt to occur during color development (for example, JP-A-58-95345).
No. 59 and No. 232342), a satisfactory compound has been found as a preservative which enables the removal of benzyl alcohol and has excellent preservative performance when such an emulsion is used. Absent.

Therefore, an object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material which is excellent in stability of a color developer which does not substantially contain benzyl alcohol and in which a rise in fog during continuous processing is remarkably reduced. Especially.

Another object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material which is excellent in color forming property even though it is processed with a color developing solution which does not substantially contain benzyl alcohol.

(Means for Solving the Problems) The above object is to provide a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a reflective support, with an aromatic group represented by the following general formula (A). A method for processing a silver halide color photographic light-sensitive material, which comprises processing with a color developing solution containing a primary amine color developing agent and at least one saccharide and containing substantially no benzyl alcohol. Was found.

General formula (A) (In the formula, X represents a counter ion of a primary amine) By using the above-mentioned specific developing agent in combination with a saccharide in a developing solution, the saccharide not only exhibits a very excellent preservative action, Surprisingly, it was found that the removal of benzyl alcohol still achieved sufficient color development.

As mentioned above, some saccharides are already known as preservatives (JP-A-52-102727), but when combined with the above-mentioned specific developing agent, the photographic light-sensitive material on the reflective support, in other words, color. There has been no suggestion that the stability is remarkably improved in a benzyl alcohol-free system in the processing of photographic paper, fog generation can be effectively prevented, and sufficient color development is achieved.

Further, in the above-mentioned document, it is disclosed that a certain stability effect can be obtained by incorporating a saccharide into a developing solution containing no benzyl alcohol in the development processing of a color negative film. However, in general, benzyl alcohol has been widely used in the processing of color photographic paper in the past, and a certain result can be obtained even if it is not substantially contained in the development processing of the color negative film. Therefore, the processing liquid components of the color photographic paper and the color negative film are different from each other, and even if the system useful in the development processing of the color negative film is directly applied to the color photographic paper, the same result cannot be obtained. Since the useful developing system cannot be used as it is for the formulation of a color negative film, it does not suggest the present invention at all.

Hereinafter, the above-mentioned saccharides will be described in detail.

Sugars (also called carbohydrates) consist of monosaccharides and polysaccharides,
Most of them are represented by the general formula C _n H _2m O _m (n and m are natural numbers)
With. The monosaccharides are generally referred to as aldehydes or ketones of polyhydric alcohols (referred to as aldose and ketose, respectively) and their reduced derivatives, oxidized derivatives, dehydrated derivatives, and a wider range of derivatives such as amino sugars and thio sugars. In addition, the polysaccharide refers to a product obtained by dehydration condensation of two or more of the above-mentioned monosaccharides.

Among these sugars, more preferable ones are aldoses having a reducing aldehyde group, and derivatives thereof, and particularly preferable ones are those corresponding to monosaccharides.

Specific examples of saccharides that can be used in the present invention are shown below, but the present invention is not limited thereto. (These optical isomers can be similarly used.) (1) D-xylose (2) L-arabinose (3) D-ribose (4) D-deoxyribose (5) D-glucose (6) D-galactose (7) D-mannose (8) D-fructose (9) L-sorbose (10) D-tagatose (11) L-fucose (12) L-rhamnose (13) D-mannoheptulose (14) Sedoheptulose (15) D-erythrose (16) Glycosan <1,5> α <1,2> (17) Glycocene-1,2 (18) D-glycal (19) D-sorbit (sorbitol) (20) D-gluconic acid (21) Glucosamine (22) Galactosamine (23) Chitin (24) 6-amino-6-deoxy-D-glucose (25) 3-amino-3-deoxy-D-ribose (26) Picrosin (27) D-apiose (28) 3-deoxyapiose (29) D-thioglucose (30) Thiomethylribose (31) α-lactose (32) α-maltose (33) D-trehalose (34) Maltotriose Sugars are widely found in nature, and commercial products are easily available. Further, various derivatives can be easily synthesized by carrying out reduction, oxidation, dehydration reaction or the like.

The amount of saccharide added to the color developing solution is preferably 0.05 to 30 g, and particularly preferably 0.1 to 1 color developing solution.
g to 15 g. Further, two or more kinds of sugars can be used together.

Next, the color developing agent used in the present invention will be described.

The color developing agent used in the present invention is represented by the following general formula (A).
It is represented by.

General formula (A) In the formula, X is a compound that forms a salt with a primary amine,
Examples thereof include sulfates, hydrochlorides, oxalates, phosphates, p-toluenesulfonates, nitrates, etc., but are not limited thereto.

The amount of the color developing agent used is preferably 0.1 g to about 20 g per color developing solution, particularly preferably 0.5 to.
It has a concentration of about 10 g.

Further, benzyl alcohol is not substantially contained in the developing solution. The term "substantially free from" means that the amount per color developer is 2 ml or less, preferably 0 ml.

Further, as other preservatives of saccharides used in the present invention, sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, sulfite salts such as potassium metasulfite, and carbonyl sulfite adduct as necessary. Can be added. The amount added to these color developers is 1.0 g / or less, preferably 0.5 g /
It is the following, and the smaller one is preferable. Especially homeostasis and /
Alternatively, from the viewpoint of photographic characteristics, it is preferable that the amount of sulfite ion added is small.

As other preservatives, hydroxyacetones described in U.S. Pat. No. 3,615,503 and British Patent 1,306,176, JP-A-52-143020 and 53-8.
9425, α-aminocarbonyl compounds, various metals described in JP-A-57-44148 and 57-53749, hydroxamic acids described in JP-A-52-27638, and 59-160141. α, α'-
Dicarbonyl compounds, salicylic acids described in No. 59-180588, alkanolamines described in No. 54-3532, poly (alkyleneimines) described in No. 56-94349, gluconic acid derivatives described in No. 56-75647, etc. Can be raised. Two or more kinds of these preservatives may be used in combination, if necessary.

In particular, addition of alkanolamines (triethanolasine, diethanolasine, etc.) and / or aromatic polyhydroxy compound is preferable.

The color developing solution used in the present invention preferably has a pH of 9 to 10.
12, more preferably 9 to 11.0, and the color developing solution may contain other known developing solution component compounds.

In order to maintain the above pH, it is preferable to use various buffers.

As the buffering agent, carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycine salt, 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 salt,
Trishydroxyaminomethane salt, lysine salt and the like can be used. Especially carbonates, phosphates, tetraborate,
Hydroxybenzoate is soluble and has a high pH of 9.0 or higher.
It is particularly preferable to use these buffering agents, because they have excellent buffering ability in the range, have no adverse effects on the photographic performance (fogging, etc.) even when added to the color developing solution, and are inexpensive, and these buffering agents are used.

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

The amount of the buffer added to the color developer is 0.1 mol /
It is preferably not less than 0.1 mol./mol.
It is particularly preferably 4 mol / mol.

In addition, various chelating agents can be used in the color developing solution as a precipitation preventing agent for calcium and magnesium, or for improving the stability of the color developing solution.

As the chelating agent, organic acid compounds are preferable, for example, aminopolycarboxylic acids described in JP-B Nos. 48-30496 and 44-30232, and JP-A-56-97347.
No. 5, Japanese Patent Publication No. 56-39359 and West German Patent No. 2,22.
Organic phosphonic acids described in 7,639, JP-A-52-1
02726, 53-42730, 54-121.
127, 55-126241 and 55-659.
Examples thereof include phosphonocarboxylic acids described in JP-A No. 506 and the like, and other compounds described in JP-A Nos. 58-195845, 58-203440 and 53-40900. Specific examples are shown below, but the present invention is not limited thereto.

-Nitrilotriacetic acid-Diethylenetriaminepentaacetic acid-Ethylenediaminetetraacetic acid-Triethylenetetraminehexaacetic acid-N, N, N-trimethylenephosphonic acid-Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid-1,3 -Diamino-2-propanoltetraacetic acid-Transcyclohexanediaminetetraacetic acid-Nitrilotripropionic acid- 1,2-diaminopropanetetraacetic acid-Hydroxyethyliminodiacetic acid-Glycol ether diaminetetraacetic acid-Hydroxyethylenediaminetriacetic acid-Ethylenediamineorthohydroxyphenyl Acetic acid 2-phosphonobutane-1,2,4-tricarboxylic acid 1-hydroxyethylidene-1,1-diphosphonic acid N, N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid Chelating agents may be used in combination of two or more if necessary.

The amount of these chelating agents added may be an amount sufficient to block the metal ions in the color developing solution. Eg 1
The amount is about 0.1 g to 10 g.

If necessary, any development accelerator can be added to the color developing solution. As a development accelerator, Japanese Patent Publication No. 37-
16088, 37-5987, 38-7826
Nos. 44-12380, 45-9019 and U.S. Pat. No. 3,813,247, thioether compounds, JP-A-52-49829 and 50-.
No. 15554, p-phenylenediamine compounds, JP-A-50-137726, JP-B-44-30
074, JP-A-56-156826 and JP-A-52-4.
No. 3429, etc., quaternary ammonium salts, US Pat. Nos. 2,610,122 and 4,119,46.
No. 2, p-aminophenols, US Pat. No. 2,4
94,903, 3,128,182, 4,23
0,796, 3,253,919, Japanese Patent Publication No. 41-
11431, U.S. Pat. Nos. 2,482,546, 2,596,926 and 3,582,346, and the like amine compounds, JP-B-37-16088, 42-25201, and US Patent No. 3,128,183
No. 4, Japanese Patent Publication Nos. 41-11431 and 42-23883, and U.S. Pat. No. 3,532,501, and other polyalkylene oxides, 1-phenyl-3-pyrazolidones, hydrazines, mesoionic compounds, and ions. Type compounds, imidazoles, etc. can be added as necessary.

If desired, any antifoggant can be added to the color developer used in the present invention. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide, and organic antifoggants can be used. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-
Nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, hydroxyazaindolizine, 5-nitroindazole, mercaptotriazoles As a typical example, a nitrogen-containing heterocyclic compound such as

The color developer used in the present invention preferably contains a fluorescent whitening agent. Fluorescent brighteners include 4,4'-
Diamino-2,2'-disulfostilbene compounds are preferred. The addition amount is 0 to 5 g / preferably 0.1 g to 4
It is g /.

If necessary, various surfactants such as alkyl sulfonic acid, aryl phosphonic acid, aliphatic carboxylic acid and aromatic carboxylic acid may be added.

The processing temperature of the color developing solution of the present invention is 20 to 50 ° C, preferably 30 to 40 ° C. The processing time is 20 seconds to 5 minutes, preferably 30 seconds to 2 minutes. The amount of replenishment is preferably small, but ^{20 to} 600 ml, preferably 50, per 1 m ^{2 of} the light-sensitive material.
~ 300 ml. More preferably 100 ml to 200 ml
Is.

Next, the bleaching solution, the bleach-fixing solution and the fixing solution used in the present invention will be described.

As the bleaching agent used in the bleaching solution or the bleach-fixing solution used in the present invention, any bleaching agent can be used. Carboxylic acids, aminopolyphosphonic acids, complex salts such as phosphonocarboxylic acids and organic phosphonic acids) or organic acids such as citric acid, tartaric acid, malic acid; persulfates; hydrogen peroxide and the like are preferable.

Of these, organic complex salts of iron (III) are particularly preferable from the viewpoint of rapid processing and prevention of environmental pollution. The aminopolycarboxylic acids, aminopolyphosphonic acids, or organic phosphonic acids or salts thereof useful for forming organic complex salts of iron (III) are listed: ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N- (β -Oxyethyl) -N,
N ', N'-triacetic acid, 1,3-diaminopropanetetraacetic acid, triethylenetetraminehexaacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, cyclohexanediaminetetraacetic acid, 1,3-diamino-2- Propanol tetraacetic acid, methyliminodiacetic acid, iminodiacetic acid, hydroxyliminodiacetic acid, dihydroxyethylglycine ethyl ether diamine tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine tetrapropionic acid, ethylenediamine dipropionacetic acid, phenylenediamine tetraacetic acid, 2-phosphonobutane -1,2,4-triacetic acid, 1,3-diaminopropanol-N, N, N ', N'-
Tetramethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, 1,3-propylenediamine-N, N, N', N'-tetramethylenephosphonic acid, 1-hydroxyethylidene-1 , 1, -diphosphonic acid, and the like.

These compounds may be sodium, potassium, lithium or ammonium salts. Among these compounds, the iron (III) complex salts of ethylenediaminetetraacetic acid, 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, and 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 or phosphonocarboxylic acid may be used to form a ferric ion complex salt in a solution. When used in the form of a complex salt, one type Complex salt may be used, or two or more kinds of complex salts may be used. On the other hand, when a complex salt is formed in a solution using a ferric iron salt and a chelating agent, one kind of ferric salt or You may use 2 or more types. Furthermore, one or more chelating agents may be used. Further, in any case, the chelating agent may be used in an amount more than that for forming the ferric ion complex salt. Among the iron complexes, aminopolycarboxylic acid iron complexes are preferable, and the addition amount thereof is 0.01 to 1.0.
Mol / preferably 0.05 to 0.50 mol /.

Further, a bleaching accelerator can be used in the bleaching solution or the bleach-fixing solution, if necessary. Specific examples of useful bleaching accelerators include U.S. Pat. No. 3,893,858, West German Patents 1,290,812 and 2,059,988,
JP-A-53-32736, JP-A-53-57831, JP-A-53-37418, JP-A-53-65732, and JP-A-53-53.
No. 72623, No. 53-95630, No. 53-956
No. 31, No. 53-104232, No. 53-12442
No. 4, No. 53-141623, No. 53-28426.
No., Research Disclosure No. 17129 (1
Compounds having a mercapto group or a disulfide group as described in, for example, July 1978); thiazolidine derivatives as described in JP-A-50-140129; JP-B-45.
-8506, JP-A-52-20832, 53-3
2735, thiourea derivatives described in U.S. Pat. No. 3,706,561; West German Patent 1,127,715, iodide described in JP-A-58-16235; West German Patent 9
66,410 and 2,748,430; polyethylene oxides; polyamine compounds described in JP-B-45-8836; other JP-A-49-42434
No. 49, No. 49-59644, No. 53-94927, No. 54-35727, No. 55-26506 and No. 5
Examples thereof include compounds described in JP-A No. 8-163940, iodine, bromide ion and the like. Of these, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of large accelerated curing, and in particular, US Pat. No. 3,893,858,
West German Patent No. 1,290,812, JP-A-53-956
The compounds described in No. 30 are preferable.

In addition, the bleaching solution or bleach-fixing solution used in the present invention contains a bromide (for example, potassium bromide, sodium bromide,
Rehalogenating agents such as ammonium bromide) or chlorides (eg potassium chloride, sodium chloride, ammonium chloride) or iodides (eg ammonium iodide) can be included. Boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, if necessary.
Has a pH buffering capacity for sodium citrate, tartaric acid, etc. 1
It is possible to add more than one kind of inorganic acid, organic acid and their alkali metal or ammonium salts, or corrosion inhibitors such as ammonium nitrate and guanidine.

The bleach-fixing solution or the fixing agent used in the fixing solution according to the present invention includes known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylene. Bisthioglycolic acid, 3,6-dithia-
It is a water-soluble silver halide solubilizer such as thioether compounds such as 1,8-octanediol and thioureas, and these can be used alone or in combination of two or more. Further, a special bleach-fixing solution containing 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, it is preferable to use thiosulfate, particularly ammonium thiosulfate.

The amount of the fixing agent per 1 is preferably 0.3 to 2 mol, more preferably 0.5 to 1.0 mol.

The pH range of the bleach-fixing solution or the fixing solution in the present invention is 3 to 1
0 is preferable, and 5 to 9 is particularly preferable. When the pH is lower than this, desilvering property is improved, but deterioration of the liquid and leuco conversion of the cyan dye are promoted. On the other hand, if the pH is higher than this, desilvering is delayed and stain is likely to occur.

To adjust the pH, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate and the like can be added as necessary.

Further, the bleach-fixing solution may contain various other fluorescent whitening agents, defoaming agents or surfactants, polyvinylpyrrolidone, organic solvents such as methanol.

The bleach-fixing solution and fixing solution in the present invention include sulfites (eg, sodium sulfite, potassium sulfite, ammonium sulfite, etc.), bisulfites (eg, ammonium bisulfite, sodium bisulfite, bisulfite) as preservatives. Potassium, etc.), metabisulfite (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.) and the like, and a sulfite ion-releasing compound. These compounds are converted to sulphite ion and the amount is about 0.0
The content is preferably 2 to 0.50 mol / mol, more preferably 0.04 to 0.40 mol / mol.

As a preservative, it is common to add sulfite, but in addition, ascorbic acid and carbonyl bisulfite adduct,
Alternatively, a carbonyl compound or the like may be added.

Further, a buffering agent, a fluorescent whitening agent, a chelating agent, an antifungal agent and the like may be added if necessary.

Next, the water washing step in the present invention will be described. In the present invention, a simple treatment method such as performing only a so-called "stabilization treatment" may be used without providing a substantial water washing step in place of the usual "water washing treatment". As described above, the “water washing treatment” in the present invention is used in a broad sense as described above. In addition, the term “rinsing treatment” as used herein includes rinsing treatment and other alternative washing treatments.

The amount of washing water in the present invention is difficult to define because it depends on the number of multi-stage countercurrent washing baths and the carry-in amount of the pre-bath component of the light-sensitive material, but in the present invention, bleaching and fixing in the final washing bath are performed. The liquid component should be 1 × 10 ⁻⁴ . For example, in the case of washing in countercurrent with 3 tanks, about 100 per 1 m ² of light-sensitive material
It is preferable to use 0 ml or more, more preferably 500
It is 0 ml or more. In the case of water-saving treatment, the photosensitive material is 1 m ²
It is recommended to use 100 to 1000 ml per one.

The washing temperature is 15 ° C to 45 ° C, more preferably 20 ° C to 3
It is 5 ° C.

In the washing process, for the purpose of preventing precipitation and stabilizing the washing water,
Various known compounds may be added. For example, chelating agents such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphonic acid, bactericides and antifungal agents that prevent the generation of various bacteria, algae, and molds (for example, "Journal of Antibacterial And Anti-Fungal Agents "(J.Antibact.Antifung.Agents), Vol. 11,
No. 5, p207 to 223 (1983) and compounds described in Hiroshi Horiguchi "Chemistry of Antibacterial and Antifungal Agents", metal salts represented by magnesium salts and aluminum salts, alkali metal and ammonium salts, or If necessary, a surfactant or the like for preventing a drying load and unevenness can be added. Or West, “Photographic Signence and Engineering Magazine (Ph
ot.Sci.Eng.), Volume 6, pages 344-359 (19)
65) and the like may be added.

Add chelating agents, bactericides and anti-bacterial agents to the wash water,
The present invention is particularly effective in the case where the amount of washing water is greatly reduced by multi-stage countercurrent washing with two or more tanks. It is also particularly effective when a multi-stage countercurrent stabilization treatment step (so-called stabilization treatment) as described in JP-A-57-8543 is carried out instead of the usual water washing step. In these cases, the bleaching and fixing components in the final bath are 5 × 10 ^-2 or less, preferably 1 ×
It should be 10 ^-2 or less.

Various compounds are added to the stabilizing bath for the purpose of stabilizing the image. For example, adjust membrane pH (eg pH 3-8)
Various buffers for (eg borate, metaborate,
Borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid,
Typical examples include aldehydes such as polycarboxylic acid used in combination) and formalin.
In addition, chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), bactericidal agents (thiazole-based, isothiazole-based, halogenated phenol, sulfanilamide,
Benzotriazole etc.), surfactant, fluorescent brightener,
Various additives such as a hardener may be used, and two or more kinds of the same or different target compounds may be used in combination.

Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate as a film pH adjusting agent for the processor in order to improve the image storability.

When the amount of washing water as described above is significantly reduced, it is preferable to allow a part or all of the overflow water of washing water to flow into the bleach-fixing bath or the fixing bath which is a pre-bath for the purpose of reducing the amount of drainage.

In this treatment step, a constant finish can be obtained by using a replenisher of each treatment solution to prevent the composition of the solution from changing during continuous processing. The replenishment amount can be reduced to half or less than the standard replenishment amount for cost reduction.

If necessary, a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, various floating pigs, various squeegees, nitrogen stirring, air stirring and the like may be provided in each treatment bath.

The method of the present invention is a process using a color developing solution,
It can be applied to any processing step. For example, it can be applied to the processing of color paper, color reversal paper, and the like.

The silver halide emulsion of the light-sensitive material used in the present invention may have any halogen composition such as silver iodobromide, silver bromide, silver chlorobromide and silver chloride, but in the case of performing rapid processing or low replenishment processing. In particular, a silver chlorobromide emulsion or a silver chloride emulsion containing 60 mol% or more of silver chloride is preferable, and a silver chloride content of 80 to 100 mol% is particularly preferable. The processing method of the present invention is further characterized in that fog generation is sufficiently suppressed even when an emulsion having a high silver chloride content is used, and that color development is not inhibited. When high sensitivity is required and capry during production, storage, and / or processing is required to be particularly low, a silver chlorobromide emulsion or odor containing 50 mol% or more of silver bromide is used. A silver halide emulsion is preferable, and 70 mol% or more is more preferable. When the silver bromide content is 90 mol% or more, rapid processing becomes difficult, but means for accelerating development, for example, means for causing a development accelerator such as a silver halide liquid agent, a fogging agent, or a developer described below to act during processing. The use of is capable of speeding up the development to some extent without being limited by the content of silver bromide, which is preferable in some cases. In any case, it is not preferable to contain a large amount of silver iodide, and the amount may be 3 mol% or less. These silver halide emulsions are preferably used mainly for color paper and the like. Silver iodobromide and silver chloroiodobromide are preferable for the color light-sensitive material for photographing (negative film, reversal film, etc.), and the silver iodide content is preferably 3 to 15 mol%.

The silver halide grains used in the present invention may have different phases in the inside and the surface layer, may have a multi-phase structure having a junction structure, or may have a uniform phase as a whole. Moreover, they may be mixed.

The average grain size of the silver halide grains used in the present invention is represented by the grain diameter (in the case of spherical grains or grains close to spheres) and the ridge length in the case of cubic grains, which is the average based on the projected area. In the above case, the value is also expressed in terms of spheres) is preferably 2 μm or less and 0.1 μm or more, and particularly preferably 1.5 μm or less and 0.15 μm or more. The grain size distribution may be narrow or wide, but the value (variation rate) obtained by dividing the standard deviation value in the grain size distribution curve of the silver halide emulsion by the average grain size is 20%.
It is preferable to use a so-called monodisperse silver halide emulsion within the range of 15%, particularly preferably within the range of 15%. Further, in order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodisperse silver halide emulsions having different grain sizes in the emulsion layers having substantially the same color sensitivity (the above-mentioned monodispersity is the same). Those having a variation rate are preferable) can be mixed in the same layer or multilayer-coated in different layers. 2 more
It is also possible to use a mixture of two or more kinds of polydisperse silver halide emulsions or a combination of monodisperse emulsions and polydisperse emulsions or to form multiple layers.

The silver halide grains used in the present invention may have a regular crystal such as a cube, an octahedron, a rhodohedron, and a tetradecahedron, or may have a coexisting form thereof. It may have an irregular crystal form such as a spherical shape, or may have a composite form of these crystal forms. Further, tabular grains may be used, and an emulsion in which tabular grains having a length / thickness ratio value of 5 or more, particularly 8 or more account for 50% or more of the total projected area of the grains may be used. It may be an emulsion composed of a mixture of these various crystal forms. These various emulsions may be either a surface latent image type which forms a latent image mainly on the surface or an internal latent image type which is formed inside the grain.

The photographic emulsions used in the present invention are those described in Graphide, "Chemistry and Physics of Photography" [P. Glafkides, Chimie et Physique Photo.
graphique, Paul Montel, 1967], Duffin, "Photoemulsion Chemistry" [GF Duffin, Photograhic Emul
sion Chemistry, Focal Press, 1966], "Manufacturing and coating of photographic emulsions" by Zelikman et al. [VL Zelikman eta]
l, Making and Coating Potographic 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 a method of reacting a soluble silver salt and a soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, a combination thereof or the like. Good. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

Further, an emulsion prepared by a so-called conversion method, which includes a step of converting already formed silver halide into a silver halide having a smaller solubility product until the completion of the silver halide grain formation step, and a halogenated Emulsions which have undergone similar halogen conversion after the completion of the silver grain formation process can also be used.

In the process of silver halide grain formation or physical ripening,
Cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or iron complex salt may coexist.

The silver halide emulsion is usually used for coating after physical ripening, desalting and chemical ripening after grain formation.

Known silver halide solvents (e.g., ammonia, Rhodan potassium or U.S. Pat. No. 3,271,157;
1-12360, JP-A-53-82408, JP-A-53-144319, JP-A-54-100717, JP-A-54-155828, and the like. It can be used in aging and chemical aging. In order to remove the soluble silver salt from the emulsion after physical ripening, a Nudel water washing, a flocculation sedimentation method, an ultrafiltration method or the like is used.

The silver halide emulsion used in the present invention is a compound containing sulfur capable of reacting with active gelatin or silver (for example, thiosulfate,
Sulfur sensitization method using thioureas, mercapto compounds, rhodanins); Reduction sensitization method using reducing substances (eg, primary tin salts, amines, hydrazine derivatives, formamidinesulfinic acid, silane compounds); metals Compounds (eg, gold complex salts, Pt, Ir, Pd, Rh, F
A noble metal sensitization method using a complex salt of a metal of Group VIII of the periodic table such as e) can be used alone or in combination.

Each of the blue-sensitive, green-sensitive and red-sensitive emulsions used in the present invention is spectrally sensitized with a methine dye or the like so as to have color sensitivity. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. These dyes can be applied to any of the nuclei commonly used for cyanine dyes as a basic heterocyclic nucleus.
That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these Nucleus of fused aromatic hydrocarbon ring, namely, indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus A nucleus, a quinoline nucleus, etc. can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, 2-thiooxazolidine-
2,4-dione nucleus, thiazolidine-2,4-dione nucleus,
A 5 to 6-membered heterocyclic nucleus such as a rhodanine nucleus or a thiobarbituric acid nucleus can be applied.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for the purpose of supersensitization. Typical examples thereof are U.S. Pat. Nos. 2,688,545, 2,977,229, 3,397,060, 3,522,052, 3,527,641, and 3,617. 293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703,377, 3,769,301. No. 3,814,609, No. 3,837,862, No. 4,026,707, and US Pat. No. 1,344,281.
No. 1,507,803, Japanese Patent Publication No. 43-4936
No. 53-12375, JP-A No. 52-110618.
No. 52-109925.

A dye that does not itself have a spectral sensitizing effect or a substance that does not substantially absorb visible light together with a sensitizing dye,
A substance exhibiting supersensitization may be included in the emulsion.

These sensitizing dyes may be added during grain formation, before or after chemical sensitization, during chemical sensitization, or during coating. Addition at the time of grain formation is effective not only for enhancing adsorption but also for controlling the crystal shape and the grain internal structure. Further, addition during chemical sensitization is effective not only for enhancing adsorption but also for controlling chemical sensitization sites and preventing crystal deformation. In the case of an emulsion containing a high content of silver chloride, these addition methods are particularly effective, and it is particularly useful to apply them to grains having a high silver bromide or silver iodide content on the grain surface. is there.

The color coupler incorporated in the light-sensitive material preferably has a ballast group or is polymerized to be diffusion resistant. The amount of coated silver can be reduced in the case of a two-equivalent color coupler in which a coupling active position is substituted by a leaving group, rather than a four-equivalent color coupler in which a hydrogen atom is present. It is also possible to use a coupler in which the color-forming dye has an appropriate diffusibility, a non-color-forming coupler, or a DIR coupler which releases a development inhibitor upon coupling reaction or a coupler which releases a development accelerator.

A typical example of the yellow coupler that can be used in the present invention is an oil protect type acylacetamide coupler. A specific example is US Pat. No. 2,40.
No. 7,210, No. 2,875,057 and No. 3,265,506. In the present invention, it is preferable to use a two-equivalent yellow coupler, and US Pat. Nos. 3,408,194 and 3,447,928 are preferred.
No. 3,933,501 and No. 4,022.
No. 620 and the like, which are oxygen atom-releasing yellow couplers, or JP-B-55-10739, U.S. Pat. Nos. 4,401,752, 4,326,024, R
D18053 (April 1979), British Patent No. 1,42
No. 5,020, West German Application Publication No. 2,219,917,
Typical examples thereof include nitrogen atom releasing yellow couplers described in Nos. 2,261,361, 2,329,587 and 2,433,812. The α-pivaloyl acetanilide type coupler is excellent in the fastness of the color forming dye, especially the light fastness, while
The benzoylacetanilide coupler provides high color density.

Examples of the magenta coupler which can be used in the present invention include oil-protection type indazolone type or cyanoacetyl type, preferably 5-pyrazolone type and pyrazoloazole type couplers such as pyrazolotriazoles. The 5-pyrazolone-based coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group, from the viewpoint of the hue and color density of the color forming dye, and a typical example thereof is U.S. Pat. No. 2,311,082. Same number 2,
343,703, 2,600,788, 2,908,573, 3,062,653, 3,152,896 and 3,936,015.
No. etc. As a leaving group for a 2-equivalent 5-pyrazolone-based coupler, US Pat. No. 4,310,619
Nitrogen atom leaving group described in U.S. Pat.
The arylthio groups described in 51,897 are preferred. Further, the 5-pyrazolone-based coupler having a ballast group described in EP 73,636 provides a high color density.

As the pyrazoloazole type coupler, pyrazolobenzimidazoles described in US Pat. No. 3,369,879, preferably pyrazolo [5,1-c] [described in US Pat. No. 3,725,067] are used. 1,2,4] triazoles, Research Disclosure 24220
(June 1984) and piazolotetrazoles and Research Disclosure 24230 (198).
Pyrazolopyrazoles described in June, 4). The imidazo [1,2-b] pyrazoles described in European Patent No. 119,741 are preferable from the viewpoint of low yellow sub-absorption of the color forming dye and light fastness, and European Patent No. 1
Pyrazolo [1,5-b] [1, described in 19,860.
2,4] triazole is particularly preferred.

Cyan couplers that can be used in the present invention include oil-protection type naphthol type and phenol type couplers. The naphthol type couplers described in US Pat. No. 2,474,293, preferably US Pat. No. 4,05.
No. 2,212, No. 4,146,396, No. 4,2
Representative examples thereof include oxygen atom desorption type two-equivalent naphthol couplers described in Nos. 28,233 and 4,296,200. Further, specific examples of the phenol-based coupler are described in U.S. Pat. No. 2,369,929 and U.S. Pat.
801,171, 2,772,162, 2,895,826 and the like. Cyan couplers that are robust to humidity and temperature are preferably used in the present invention, of which typical examples are US Pat.
No. 72,002, a phenolic cyan coupler having an alkyl group of ethyl group or more at the meta position of the phenol nucleus, US Pat. Nos. 2,772,162, and 3,
758,308, 4,126,396, 4,334,011, 4,327,173, West German Patent Publication 3,329,729 and Japanese Patent Application No. 58-.
2,5-diacylamino-substituted phenol-based couplers described in US Pat.
No. 6,622, No. 4,333,999, No. 4,4
51,559 and 4,427,767, which have a phenylureido group at the 2-position and 5-
Examples thereof include phenolic couplers having an acylamino group at the position.

Particularly, in the treatment method of the present invention, the following general formula (C-
By using at least one of the cyan couplers represented by I) and (C-II), fog is further reduced and good photographic properties can be obtained. Such an effect is remarkable. General formulas (C-I) and (C-II)
Will be described in detail below.

General formula (C-I) (In the formula, R ₁₁ represents an alkyl group, a cycloalkyl group, an aryl group, an amino group or a heterocyclic group. R ₁₂ represents an alkyl group or an aryl group. R ₁₃ represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. And R ₁₃
May combine with R ₁₂ to form a ring. Z ₁₁ represents a hydrogen atom, a halogen atom, or a group capable of splitting off upon reaction with an oxidation product of an aromatic primary amine type color developing agent. ) General formula (C-II) (In the formula, R ₁₄ represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. R ₁₅ represents an alkyl group having 2 or more carbon atoms. R ₁₆ represents a hydrogen atom, a halogen atom or an alkyl group. Z ₁₂ represents a hydrogen atom, a halogen atom or a group capable of splitting off upon reaction with an oxidized product of an aromatic primary amine type color developing agent.) Cyan couplers represented by the general formulas (C-I) and (C-II) In R ₁₁ , R ₁₂ and R ₁₄ , the alkyl group having 1 to 32 carbon atoms includes, for example, a methyl group, a butyl group, a tridecyl group, a cyclohexyl group, an allyl group and the like, and the aryl group includes, for example, a phenyl group, Examples thereof include a naphthyl group, and examples of the heterocyclic group include a 2-pyridyl group and 2
-Imidazolyl group, 2-furyl group, 6-quinolyl group and the like. These groups further include an alkyl group, an aryl group, a heterocyclic group, an alkoxy group (for example, a methoxy group, a 2-methoxyethoxy group, etc.), an aryloxy group (for example, a 2,4-di-tert-aluminphenoxy group, Two
-Chlorophenoxy group, 4-dianophenoxy group etc.), alkenyloxy group (eg 2-propenyloxy group etc.), acyl group (eg acetyl group, benzoyl group etc.), ester group (eg butoxycarbonyl group, Phenoxycarbonyl group, acetoxy group, benzoyloxy group, butoxysulfonyl group, toluenesulfonyloxy group etc.), amide group (eg acetylamino group, methanesulfonamide group, dipropylsulfamoylamino group etc.), carbamoyl group (eg dimethyl) Carbamoyl group, ethylcarbamoyl group, etc.), sulfamoyl group (eg, butylsulfamoyl group, etc.),
Imido group (eg, succinimide group, hydantoinyl group, etc.), ureido group (eg, phenylureido group, dimethylureido group, etc.), aliphatic or aromatic sulfonyl group (eg, methanesulfonyl group, phenylsulfonyl group, etc.), fat Group or aromatic thio group (for example, ethylthio group, phenylthio group, etc.), hydroxy group, cyano group, carboxy group, nitro group, sulfo group,
It may be substituted with a group selected from a halogen atom and the like.

In the general formula (CI), when R ₁₃ is a substitutable substituent, it may be substituted with the optionally substituted substituent described for R ₁₁ .

The amino group of R ₁₁ may be substituted or unsubstituted. Examples of the substituent in the case of substituting here include those mentioned above. Examples of the substituted amino group for R ₁₁ include an anilino group and a benzothiazolylamino group.

The carbon number of R _{15 in} the general formula (C-II) is at least 2
As the alkyl group which may be substituted, for example,
Ethyl group, propyl group, butyl group, pentadecyl group, t
Examples thereof include an ert-butyl group, a cyclohexyl group, a cyclohexylmethyl group, a phenylthiomethyl group, a dodecyloxyphenylthiomethyl group, a butanamidomethyl group and a methoxymethyl group.

In the general formula (CI) and general formula (C-II), Z ₁₁
And Z ₁₂ each represent a hydrogen atom or a coupling-off group (including a coupling-off atom; the same applies hereinafter), and examples thereof include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), alkoxy. Group (for example, ethoxy group, dodecyloxy group, methoxyethylcarbamoylmethoxy group, carboxypropyloxy group,
Methylsulfonylethoxy group etc.), aryloxy group (eg 4-chlorophenoxy group, 4-methoxyphenoxy group, 4-carboxyphenoxy group etc.), acyloxy group (eg acetoxy group, tetradecanoyloxy group, benzoyloxy group) Etc.), sulfonyloxy group (eg, methanesulfonyloxy group, toluenesulfonyloxy group, etc.), amide group (eg, dichloroacetylamino group, heptafluorobutylamino group, methanesulfonylamino group, toluenesulfonylamino group, etc.), alkoxy Carbonyloxy group (eg, ethoxycarbonyloxy group, benzyloxycarbonyloxy group, etc.), aryloxycarbonyloxy group (eg, phenoxycarbonyloxy group, etc.), aliphatic or aromatic thio group For example, an ethylthio group, a phenylthio group, etc. tetrazolylthio group), an imido group (e.g.,
Succinimide group, hydantoinyl group, etc.), aromatic azo group (eg, phenylazo group, etc.) and the like. These leaving groups may include groups useful for photography.

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

In formula (C-I), preferred R ₁₁ is an aryl group,
A heterocyclic group, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group,
A carbamoyl group, a sulfonamide group, a sulfamoyl group, a sulfonyl group, a sulfamide group, an oxycarbonyl group, and an aryl group substituted with a cyano group are more preferable.

In the general formula (CI), when R ₁₃ and R ₁₂ do not form a group, R ₁₂ is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group. , R ₁₃ is preferably a hydrogen atom.

In formula (C-II), R ₁₄ is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group.

In formula (C-II), preferred R ₁₅ has 2 to 1 carbon atoms.
5 is a methyl group having an alkyl group of 5 and 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 formula (C-II), R ₁₅ is more preferably an alkyl group having 2 to ₁₅ carbon atoms, and particularly preferably an alkyl group having 2 to 4 carbon atoms.

Preferred R ₁₆ in formula (C-II) is a hydrogen atom or a halogen atom, and a chlorine atom and a fluorine atom are particularly preferred.

Preferred Z in the general formulas (C-I) and (C-II)
₁₁ and Z ₁₂ are a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group and a sulfonamide group, respectively.

In formula (CI), Z ₁₂ is more preferably a halogen atom, and particularly preferably a chlorine atom or a fluorine atom.

In formula (CI), Z ₁₁ is more preferably a halogen atom, particularly preferably a chlorine atom or a fluorine atom.

Specific examples of the cyan couplers represented by the general formulas (C-I) and (C-II) are shown below, but the present invention is not limited thereto.

The graininess can be improved by using a coupler in which the color forming dye has an appropriate diffusibility. Such dye-diffusing couplers are exemplified by magenta couplers in U.S. Pat. No. 4,366,237 and British Patent No. 2,125,570, and also in European Patent No. 96,570 and West German Application No. No. 234,533, specific examples of yellow, magenta or cyan couplers are described.

The dye-forming coupler and the above-mentioned special coupler may form a dimer or higher polymer. Typical examples of polymerized dye forming couplers are found in US Pat. No. 3,451,82.
0 and 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and US Patent No. 4,367,
282.

The various couplers used in the present invention can be used in combination of two or more kinds in the same layer of the light-sensitive layer in order to satisfy the properties required for the light-sensitive material, and the same compound can be used in two or more different layers. Can also be introduced.

The coupler used in the present invention can be introduced into the light-sensitive material by an oil-in-water dispersion method. In the oil-in-water dispersion method, the boiling point is 175.
After being dissolved in either a single solution of a high-boiling point organic solvent having a temperature of not lower than 0 ° C. or a so-called auxiliary solvent having a low boiling point, or a mixed solution thereof, it is finely dispersed in an aqueous medium such as water or an aqueous gelatin solution in the presence of a surfactant. Examples of high boiling point organic solvents are described in US Pat. No. 2,322,027 and the like. The dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, rinsing with water, ultrafiltration or the like before being used for coating.

Specific examples of the high boiling point organic solvent include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate,
Di-2-ethylhexyl phthalate, decyl phthalate, etc.), esters of phosphoric acid or phosphonic acid (triphenyl phosphate, tricresyl phosphate, 2-
Ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenylphosphonate, etc.), benzoic acid esters (2-ethylhexylbenzoate,
Dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (diethyldodecane amide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-aminophenol, etc.) ),
Aliphatic carboxylic acid esters (dioctyl azelate,
Glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc., aniline derivatives (N, N-dibutyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) ) And the like. 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. Typical examples are ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2- Examples include ethoxyethyl acetate and dimethylformamide.

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

The standard amount of the color coupler used is in the range of 0.001 to 1 mol per mol of the light-sensitive silver halide, preferably 0.01 to 0.5 mol for the yellow coupler and 0.003 for the magenta coupler. In the cyan coupler, it is 0.002 to 0.3 mol.

The light-sensitive material used in the present invention is, as a color antifoggant or a color mixture inhibitor, a hydroquinone derivative, an aminophenol derivative, an amine, a gallic acid derivative, a catechol derivative, an ascorbic acid derivative, a colorless coupler, a sulfonamidephenol derivative, etc. May be included.

A known anti-fading agent can be used in the light-sensitive material used in the present invention. Organic fading inhibitors include hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols, hindered phenols centering on bisphenols, gallic acid derivatives, methylenedioxybenzene. Typical examples thereof include ethers or ester derivatives in which the phenolic hydroxyl groups of these compounds, aminophenols, hindered amines and these compounds are silylated or alkylated. Also (bissalicylaldoximate)
A metal complex represented by a nickel complex and a (bis-N, N-dialkyldithiocarbamate) nickel complex can also be used.

To prevent deterioration of the yellow dye image due to heat, humidity and light,
As described in US Pat. No. 4,268,593,
A compound having both partial structures of hindered amine and hindered phenol in the same molecule gives good results. Further, in order to prevent the deterioration of the magenta dye image, particularly the deterioration by light, substitution of spiroindanes described in JP-A-56-159644 and hydroquinone diether or monoether described in JP-A-55-89835. The chromans given give favorable results.

In order to improve the storability of cyan images, particularly the light fastness, it is preferable to use a benzotriazole-based ultraviolet absorber in combination. This UV absorber may be coemulsified with a cyan coupler.

The amount of the ultraviolet absorber and the coating amount may be an amount sufficient to impart light stability to the cyan dye image, but if used in an excessively large amount, it may cause yellowing in the unexposed portion (white background portion) of the color photographic light-sensitive material. Therefore, it is usually preferably 1 × 10 ^-4 mol /
m ^{2 to} 2 × 10 ⁻³ mol / m ² , particularly 5 × 10 ⁻⁴ mol / m ² to
It is set in the range of 1.5 × 10 ⁻³ mol / m ² .

In a light-sensitive material layer structure of a normal color paper, either one layer on both sides adjacent to the cyan coupler-containing red-sensitive emulsion layer,
An ultraviolet absorber is preferably contained in both layers.
When the ultraviolet absorber is added to the intermediate layer between the green-sensitive layer and the red-sensitive layer, it may be co-emulsified with the color mixing inhibitor. When the ultraviolet absorber is added to the protective layer, another protective layer may be coated as the outermost layer. The protective layer may contain a matting agent having an arbitrary particle size.

In the light-sensitive material used in the present invention, an ultraviolet absorber can be added to the hydrophilic colloid layer.

The light-sensitive material used in the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as prevention of irradiation or halation. Oxonol-based, anthraquinone-based, or azo-based dyes are preferred. Oxonol dyes that absorb green light and red light are preferable.

In the photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material used in the present invention, stilbene-based, triazine-based,
A whitening agent such as an oxazole type or a coumarin type may be included. Water-soluble ones may be used, and water-insoluble whitening agents may be used in the form of dispersion.

The present invention is applicable to multilayer multicolor photographic materials having at least two different spectral sensitivities on the support. Multilayer natural color photographic materials usually have at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on a support.
The order of these layers can be arbitrarily selected as required. Further, each of the above emulsion layers may be composed of two or more emulsion layers having different sensitivities, and a non-photosensitive layer may be present between two or more emulsion layers having the same photosensitivity.

It is preferable that the light-sensitive material used in the present invention is appropriately provided with auxiliary layers such as a protective layer, an intermediate layer, a filter layer, an antihalation layer and a back layer in addition to the silver halide emulsion layer.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material used in the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein;
Cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives;
Various synthetic hydrophilic polymer substances such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. are used. be able to. The use of acrylic acid modified polyvinyl alcohol in the protective layer is particularly useful, and more useful for rapid processing with silver chloride emulsions.

Examples of gelatin include lime-processed gelatin, acid-processed gelatin and Bull.Soc.Sci.Phot.Japan., No. 16, p. 30, (196
The enzyme-treated gelatin as described in 6) may be used, or a hydrolyzed product or an enzymatically decomposed product of gelatin can also be used.

In the light-sensitive material used in the present invention, in addition to the above-mentioned additives, various stabilizers, stain inhibitors, developing agents or precursors thereof, development accelerators or precursors thereof as described above, lubricants and mordants are further added. , Matting agents, antistatic agents, plasticizers,
Alternatively, various additives useful for photographic light-sensitive materials may be added. Representative examples of these additives are described in Research Disclosure 17643 (December 1978) and 18716 (November 1979).

These additives are very important in rapid printing, rapid processing, and further in relation to the saccharides of the present invention. Further, particularly when the halogen composition of the emulsion used contains a high content of silver chloride, it is useful in the present invention in combination with a mercaptoazole-based, mercaptothiadiazole-based, and mercaptobenzazole-based compound for color forming and fog generation. is there.

The "reflective support" that can be used in the present invention is one that enhances the reflectivity and makes the dye image formed on the silver halide emulsion layer clear, and such a reflective support has an oxidation property on the support. Examples include those coated with a hydrophobic resin containing a light reflecting substance such as titanium, zinc oxide, calcium carbonate and calcium sulfate dispersed therein, and those using a hydrophobic resin containing a light reflecting substance dispersed therein as a support. For example, baryta paper, polyethylene-coated paper, polypropylene-based synthetic paper, a transparent support provided with a reflective layer or in combination with a reflective material, such as a glass plate, polyethylene terephthalate, a polyester film such as cellulose triacetate or cellulose nitrate, Polyamide film, Polycarbonate film,
There are polystyrene films and the like, and these supports can be appropriately selected depending on the purpose of use.

(Example) Below, the effect of this invention is demonstrated in an Example.

Example 1 Table A on a paper support laminated on both sides with polyethylene
A multi-layer color photographic paper having the layer constitution shown in was prepared. The coating liquid was prepared as follows.

Preparation of coating liquid for the first layer: 19.1 g of a yellow coupler (a), 4.4 g of a color image stabilizer (b), 27.2 ml of ethyl acetate and a solvent (c).
7.9 ml was added and dissolved, and this solution was emulsified and dispersed in 185 ml of a 10% gelatin aqueous solution containing 8 ml of 10% sodium dodecylbenzenesulfonate. On the other hand, the following blue-sensitive sensitizing dye was added to a silver chlorobromide emulsion (containing 1 mol% of silver bromide and 70 g / kg of Ag) at 5.0 × 10 ⁻⁴ mol per mol of silver chlorobromide to give a blue-sensitive emulsion. 90 g of the product was prepared. The emulsified dispersion and the emulsion were mixed and dissolved, the gelatin concentration was adjusted so that the composition shown in Table A was obtained, and the coating solution for the first layer was prepared.

The coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer.

As a gelatin hardening agent for each layer, 1-oxy-3,5-
Dichloro-s-triazine sodium salt was used.

The following were used as the spectral sensitizer for each emulsion.

Blue-sensitive emulsion layer (5.0 × 10 ⁻⁴ mol added per mol of silver halide) Green sensitive emulsion layer (Adding 4.0 × 10 ⁻⁴ mol per mol of silver halide) (7.0 × 10 ⁻⁴ mol added per mol of silver halide) Red-sensitive emulsion layer (Addition of 1.0 × 10 ⁻⁴ mol per mol of silver halide) The following dye was used as an anti-irradiation dye in each emulsion layer.

Green sensitive emulsion layer Red-sensitive emulsion layer Structural formulas of compounds such as couplers used in this example are as follows.

(j) Solvent (iso C ₉ H ₁₉ O ₃ P = 0 The obtained color photographic paper was processed in the following processing steps in which the composition of the color developing solution was changed.

Treatment process Temperature Time Color development 35 ° C 45 seconds Bleach fixing 35 ° C 45 seconds Rinse 1 35 ° C 20 seconds Rinse 2 35 ° C 20 seconds Rinse 3 35 ° C 20 seconds Dry 80 ° C 60 seconds Rinse 3 to rinse 1 tank It was washed with countercurrent water. The treatment liquids used are as follows.

Color developer Additive See Table 1 Benzyl alcohol See Table 1 Diethylene glycol See Table 1 Sodium sulfite 0.2g Potassium carbonate 30g EDTA ・ 2Na 1g Sodium chloride 1.5g Color developing agent (See Table 1) 0.012 mol Whitening agent ( 4,4'-diamino-stilbene) 3.0 g water to make 1000 ml pH 10.05 bleach-fixing solution _{EDTAFe (III) NH 4 · 2H} 2 O 60g EDTA · 2Na · 2H 2 O 4g ammonium thiosulfate (70%) 120 ml sodium sulfite 16g Glacial acetic acid 7g Water added 1000ml pH 5.5 Rinse solution Formalin (37%) 0.1ml 1-Hydroxyethylidene-1,1-diphosphonic acid (60%) 1.6ml Bismuth chloride 0.35g Ammonia water (26%) 2.5ml Nitrilotan Acetic acid ・ 3Na 1.0 g EDTA ・ 4H 0.5 g Sodium sulfite 1.0 g 5-chloro-2 -Methyl-4 50 mg Isothiazolin-3-one Water was added to 1000 ml. For each color developer, immediately after preparation (fresh solution) and after standing for 14 days at 40 ° C (prepared solution), 2 Used the type.

Table 1 shows the photographic characteristics of the obtained fresh liquid and aged liquid.

The photographic property is represented by two points, that is, Dmin at magenta density and gradation.

Dmin represents the minimum density, and gradation represents the density change from the point where the density is 0.5 to the density point on the high exposure side of 0.3 for logE.

If there is no preservative or if it is hydroxylamine, fog will occur over time, gradation will change (No. 1, 2, 3), and color developing agents other than the present invention will be used. When used, it also causes fog and changes in photographic properties. (No. 4, 5, 6). Further, it can be seen that hydroxylamine cannot remove benzyl alcohol because the gradation is close and color development is inhibited in a system where benzyl alcohol does not exist. (No. 1).

On the other hand, when saccharides are used as the preservative, it can be seen that a constant high gradation can be obtained regardless of the removal of benzyl alcohol, and the removal of benzyl alcohol does not hinder the color development. (No. 7-17). Furthermore, the benzyl alcohol-free developer solution according to the present invention has a higher Dmin.
It can be seen that the temporal stability is excellent from both the viewpoints of gradation and gradation (Nos. 7, 10, 12, 14 and 16).

Example 2 In Example 1, the bromine ion content of the green-sensitive layer emulsion was 8
When the photographic property change with the passage of time was evaluated in the same manner as in Example 1 with 0 mol% or more, good results were obtained with little increase in fog in the constitution of the present invention.

Example 3 As described in Table B, the first layer (bottom layer) to the seventh layer (top layer) were applied to double-sided polyethylene laminated paper that had been subjected to corona discharge machining to prepare a sample.

The coating liquid for the first layer was prepared as follows. A mixture of 200 g of a yellow coupler, 93.3 g of an anti-fading agent, 10 g of a high boiling point solvent (p) and 5 g of (q) and 600 ml of ethyl acetate as an auxiliary solvent was dissolved by heating at 60 ° C., and then alkanol B (alkylnaphthalene sulfonate, A coupler dispersion was prepared by mixing 3300 ml of a 5% gelatin aqueous solution containing 330 ml of a 5% aqueous solution of DuPont) and emulsifying using a colloid mill. Ethyl acetate was distilled off from this dispersion under reduced pressure to obtain a sensitizing dye for blue-sensitive emulsion layer and 1-methyl-2-mercapto-5-acetylamino-
1,400 g of emulsion containing 1,3,4-triazole (A
(including 96.7 g and 170 g of gelatin) and further added 2600 g of 10% gelatin aqueous solution to prepare a coating liquid. The coating solutions for the second to seventh layers were prepared according to the first layer.

The following substances were used as sensitizing dyes in each emulsion layer.

Blue-sensitive emulsion layer; Anhydro-5-methoxy-5'-methyl-3,3'-disulfopropylselenacyanine hydroxide Green-sensitive emulsion layer; Anhydro-9-ethyl-5,5'-diphenyl-3,3 ' -Disulfoethyloxacarbocyanine hydroxide red-sensitive emulsion layer; 3,3'-diethyl-5-methoxy-
9,9 '-(2,2-dimethyl-1,3
-Propano) thiadicarbocyanine iodoside The following substances were used as stabilizers for each emulsion layer.

1-methyl-2-mercapto-5-acetylamino-
1,3,4-Triazole The following substances were used as anti-irradiation dyes.

4- (3-carboxy-5-hydroxy-4- (3-
(3-Carboxy-5-oxo-1- (4-sulfonatophenyl) -2-pyrazolin-4-ylidene) -1-propenyl) -1-pyrazolyl) benzenesulfonate-
Di-potassium salt N, N '-(4,8-dihydroxy-9,10-dioxo-3,7-disulfonatoanthracene-1,5-diyl) bis (aminomethanesulfonate) -tetrasodium salt 1,2-bis (vinylsulfonyl) ethane was used as a hardener.

The couplers used are as follows.

Yellow coupler Magenta coupler The cyan coupler was modified as shown in Table 2.

The compounds used in this example are as follows.

UV absorber (n): 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole UV absorber (o): 2- (2-hydroxy-3,5-di-tert-butyl) Phenyl) benzotriazole Solvent (p): Di (2-ethylhexyl) phthalate Solvent (q): Dibutylphthalate Antifade agent (r): 2,5-di-tert-amylphenyl-3,5-di-tert
-Butylhydroxybenzoate Anti-fading agent (s): 2,5-di-tert-octylhydroquinone Anti-fading agent (t): 1,4-di-tert-amyl-2,5-dioctyloxybenzene Anti-fading agent (u ): 2,2′-Methylenebis- (4-methyl-6-tert-butylphenol) The multilayer color photographic paper obtained as described above was subjected to wedge-shaped exposure and then processed in the following processing steps.

Processing time Temperature Color development 3 minutes 30 seconds 33 ° C. Bleach-fixing 1 minute 30 seconds 33 ° C. Rinse (3 tanks 2 minutes 30 ° C. cascade) Drying 1 minute 80 ° C. The processing solutions used are as follows.

Color developer water 800 ml triethanolamine 10 ml 5,6-dihydroxy-1,2,4-benzene sodium trisulfonate 300 mg N, N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid 0.1 g Nitrilo-N, N-trimethylenephosphonic acid (40%) 1.0 g Potassium bromide 0.6 g Additives Table 2 Sodium sulfite Table 2 Potassium carbonate 30 g N-ethyl-N- (β-methanesulfonamide) Ethyl) -3-methyl-4-aminoaniline sulfate 5.5 g Fluorescent brightener (4,4'-diaminostilbene type) 1.0 g Water was added to 1000 ml KOH pH 10.10 Bleach-fixing solution Ammonium thiosulfate (70%) 150 ml Sodium sulfite 15 g Ethylenediamineiron (III) ammonium 60 g Ethi Diamine tetraacetic acid 10 g Fluorescent whitening agent (4,4'-diaminostilbene type) 1.0 g 2-Mercapto-5-amino-3,4-thiadiazole 1.0 g Water was added and 1000 ml pH 7.0 with ammonia water. Rinsing solution 5-chloro-2-methyl-4-isothiazolin-3-one 40 mg 2-methyl-4-isothiazolin-3-one 10 mg 2-octyl-4-isothiazolin-3-one 10 mg Bismuth chloride (40%) 0 0.5 g nitrilo-N, N, N-trimethylene phosphonic acid (40%) 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid (60%) 2.5 g Fluorescent brightener (4,4'-diaminostye) Ruben system) 1.0g Ammonia water (26%) 2.0ml Add water and 1000ml with KOH pH 7.5 Color developer There are, solution preparation immediately (fresh solution) and liquid preparation after 38 ° C., using two kinds of after one month aging (aging solution).

The Dmin and gradation of cyan in the fresh liquid and the aged liquid were determined, and the difference between the results obtained with the aged liquid and the fresh liquid is shown in Table 2.

As is clear from Table 2, when the treatment liquid of the present invention is used in a system containing no benzyl alcohol, the fog increase is small and the gradation change is small even when the aged liquid is used. Recognize. Further, this effect is more remarkable when the concentration of sulfite ion in the treatment liquid is low.

On the other hand, in the case of processing with a processing solution to which hydroxylamine is added, there is a large increase in fog with the passage of time of the color developing solution and a large change in gradation.

When a light-sensitive material containing a cyan coupler represented by the general formula (C-I) or (C-II) is processed with the processing solution of the present invention, the general formulas (C-I) and (C-II) are used. )
It can be seen that, compared with the case of processing a light-sensitive material containing a cyan coupler other than the above, the increase in fog with time of the color developing solution is small and the gradation change is small. Further, this effect is more remarkable when the concentration of sulfite ion in the treatment liquid is low.

Example 4 Using the color printing paper obtained in Example 1, a running test was carried out until the tank capacity (60) of the color developing solution was replenished by 3 times in the following processing steps.

However, the composition of the color developing solution was changed as shown in Table 3.

The rinse was a three-tank countercurrent system from rinse to rinse.

The composition of each treatment liquid used is as follows.

Bleach-fixing solution (tank solution and replenisher are the _{same) EDTAFe (III) NH 4 ·} 2H 2 O 60g EDTA · 2Na · 2H 2 O 4g Ammonium thiosulfate (70%) was added to 120ml sodium sulfite 16g glacial acetic 7g water 1000 ml pH 5.5 Rinse solution (tank solution and replenisher are the same) EDTA ・ 2Na ・ 2H ₂ O 0.4 g Water was added to 1000 ml pH 7.0 Treatment was performed according to the above treatment method, and the water was not added at the start of running and at the end of running. The B (blue), G (green), and R (red) densities of the exposed areas were measured with a Fuji-type densitometer. 60 samples at the end of running
After being left at 70 ° C. and 70% RH for 2 months, the B, G and R densities of the unexposed area were measured again.

The results obtained are shown in Table 3.

In the system using sugar as the developing solution, the increase in stain with running was significantly reduced when hydroxylamine was added, and at the same time, the increase in stain with forced aging of the color photographic paper after processing was also significantly reduced ( No. 38
.About.44) together with superior performance in the absence of the benzyl alcohol according to the invention. (No.3
8, 40, 42, 43, 44).

In the system using hydroxylamine, the presence or absence of benzyl alcohol has little effect on the increase of Dmin, whereas in the system using saccharides, the system containing no benzyl alcohol according to the present invention contains It is characteristic that the increase in the stain is remarkably reduced.

(Effects of the Invention) According to the present invention, the stability and color developability of the color developing solution are significantly improved in the color developing solution which does not substantially contain benzyl alcohol, which has a high pollution load, and as a result, the color developing solution after use is used. Even in the processing method described above, the increase of fog and the change in gradation were significantly suppressed, and a color image having excellent photographic characteristics was obtained.

Further, such an effect of the present invention was more remarkable when the concentration of sulfite ion in the treatment liquid was low. Furthermore, the effect of the present invention was remarkable when a light-sensitive material containing a specific cyan coupler was processed. Furthermore, even in continuous processing,
The rise of fog was remarkably reduced, and the stability of the obtained color image with time was excellent.

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a reflective support, and an aromatic primary amine color developing agent represented by the following general formula (A) and at least one of them. A method of processing a silver halide color photographic light-sensitive material, which comprises processing with a color developer containing a saccharide and substantially not containing benzyl alcohol. General formula (A) (In the formula, X represents a counter ion of a primary amine)