JPH0827520B2 - 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 light-sensitive material, and in particular, the stability and color-forming property of a color developer are improved and continuous processing is performed. The present invention relates to a processing method using a color photographic developer in which the increase in fog at time is significantly reduced.

(Prior Art) A color photographic developing solution using an aromatic primary amine color developing agent (hereinafter simply referred to as a color developing solution) has been used for a long time in a color image forming method, and nowadays a color photographic image forming method is used. It plays a central role in the method. However, the above color developing solution is very easily oxidized by the presence of air and metal, and when a color image is formed using such a time-dependent developing solution, fog is increased, and sensitivity and gradation are changed. Or
It is well known that photographic characteristics can be different than desired.

Therefore, various means for improving the preservability of color developing solutions have been studied, and the method of using hydroxylamine and sulfite ion in combination is the most general method. However, when hydroxylamine is decomposed, ammonia is generated to cause fog, and sulfite ion has a drawback that it acts as a competing compound of a developing agent and inhibits color development. It is hard to call it a drug.

In addition, various preservatives and chelating agents have been studied in order to improve the stability of color developers. For example, as preservatives, there are JP-A Nos. 52-49828 and 59-16014.
2, No. 56-47038, and aromatic polyhydroxy compounds described in U.S. Pat.No. 3,746,544, U.S. Pat.
Hydroxylcarbonyl compounds described in No. 3 and British Patent No. 1,306,176, α-aminocarbonyl compounds described in JP-A Nos. 52-143020 and 53-89425, alkanolamines described in JP-A-54-3532, and JP-A No. 54-3532. 57-44148 and 57-537
Examples thereof include metal salts described in No. 49, and the like. Further, as the chelating agent, aminopolycarboxylic acids described in JP-B-48-30496 and 44-30232, JP-A-56-97347, JP-B-56-39359 and West German Patent 2,227,639 described organic phosphones Acids, JP-A Nos. 52-102726, 53-42730, 5
4-121127, 55-126241 and phosphonocarboxylic acids described in 55-65956 and the like, other JP-A-58-195845,
Examples thereof include the compounds described in JP-A-58-2-3440 and JP-B-53-40900.

(Problems to be Solved by the Invention) However, even if these conventional techniques are used, satisfactory results cannot be obtained due to insufficient preserving performance, adverse effects on photographic characteristics, and merits and demerits. .

In particular, in the color developer from which benzyl alcohol has been removed, which is problematic in terms of pollution prevention and liquid preparation, it is inevitable that the color developing performance will deteriorate, but in such a system, the preservative acting as a competing compound remarkably develops color. In many cases, the above-mentioned conventional techniques cannot be satisfied because they impair the sex.

Further, the color photographic light-sensitive material containing a silver chlorobromide emulsion having a high chlorine content is apt to cause fog during color development as described in JP-A-58-95345 and 59-232342. When such an emulsion is used, a preservative having a low emulsion solubility and a superior preservative performance is indispensable. In this sense, development of a new developing solution is desired.

Therefore, an object of the present invention is to provide a developer composition for a silver halide color photographic light-sensitive material, which is excellent in stability and color developability and in which a rise in fog during continuous processing is remarkably reduced.

A further object of the present invention is to provide a color developer composition having excellent stability without lowering the color density even when it does not substantially contain benzyl alcohol.

It is another object of the present invention to provide a method for processing a silver halide color photographic light-sensitive material in which the stability of a color developing solution is improved, the change with time during continuous processing or the like is significantly reduced, and the rise of fog is prevented. And

(Means for Solving Problems) The above object of the present invention is to treat a silver halide color photographic light-sensitive material with a developer containing a p-phenylenediamine derivative color developing agent and a compound represented by the following general formula. And a method for processing a silver halide color photographic light-sensitive material.

(In the formula, R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group when n is 1, and a hydrogen atom from an alkyl group, an aryl group, or a heterocyclic group when n is 2 or more.
Represents a group having a valency or higher. These alkyl group, aryl group or heterocyclic group may have a substituent. Substituents for these groups include hydroxy group, alkoxy group, acyloxy group, acylamino group, sulfonylamino group,
Examples thereof include alkoxycarbonyl group, cyano group, nitro group, halogen atom, sulfo group, carboxy group, ureido group, carbamoyl group and sulfamoyl group. Preferably, R is a hydrogen atom or a substituted or unsubstituted alkyl group. More preferably, R is an alkyl group substituted with a hydrophilic functional group such as a hydroxy group, a sulfo group, a sulfonylamino group and a sulfamoyl group. When R is an alkyl group, it preferably has 1 to 10 carbon atoms. R
Is not limited to a monovalent group. That is, R is an n-valent group, and when n is 2 or more, R is preferably an n-valent group corresponding to the above-exemplified groups.

A is an organic group composed of an atom selected from a carbon atom, an oxygen atom and a sulfur atom, and represents a saturated or unsaturated 3- to 8-membered ring. A may have a substituent, and may have a condensed benzene ring or heterocycle.
A is a substituent such as a hydroxyalkyl group, an alkyl group,
It may have a carboxy group or a hydroxy group.

As a preferable example, A is saturated or unsaturated 5 to
It represents a 6-membered ring. n represents an integer of 1 or more. The upper limit of n is not particularly limited and may be high as long as the compound is water-soluble. Usually, n is preferably in the range of 1 to 3.

Specific examples of the compound represented by formula (I) are shown below, but the invention is not limited thereto.

Next, specific synthesis examples of the compound represented by the general formula (I) are shown below.

Synthesis of Compound I- (2) Piperidine (8.5 g) and sodium hydroxide (6 g) were dissolved in water (50 ml), dimethylsulfate (18.9 g) was added dropwise, and the mixture was heated under reflux for 2 hr. The mixture was allowed to cool, extracted with ethyl acetate, and distilled under reduced pressure to obtain compound I- (2). Yield 5.5 g (55%) Synthesis of compound I- (3) 8.5 g piperidine and 6 g sodium hydroxide were dissolved in 50 ml water, 12 g ethylene chlorohydrin was added dropwise, and the mixture was heated under reflux for 4 hours. The mixture was allowed to cool, extracted with ethyl acetate, and distilled under reduced pressure to obtain compound I- (3). Yield 5.8 g (45%) The content of the compound represented by the general formula (I) is 0.01 to 50 g, preferably 0.1 to 20 g, per 1 color developing solution.

 Hereinafter, the color developer of the present invention will be described.

The color developing solution of the present invention contains a known p-phenylenediamine derivative color developing agent. Representative examples are shown below, but the invention is not limited thereto.

Further, these p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, sulfites and p-toluenesulfonates. The amount of the p-phenylenediamine derivative developing agent used is about 0.1 g to about 20 g per developing solution,
More preferably, the concentration is about 0.5 g to about 10 g.

The color developer of the present invention preferably contains hydroxylamines represented by the following general formula (II).

General formula (II) In the formula, R ¹ and R ² represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, or an unsubstituted or substituted aryl group.

It is preferable that R ¹ and R ² are alkyl groups or alkenyl groups, and it is more preferable that at least one of them has a substituent. R ¹ and R ² may be linked to form a heterocycle together with the nitrogen atom.

The alkyl group and alkenyl group may be linear, branched or cyclic, and the substituents are halogen atoms (F, Cl,
Br, etc.), aryl groups (phenyl group, p-chlorophenyl group, etc.), alkoxy groups (methoxy group, ethoxy group,
Methoxyethoxy group, etc.), aryloxy group (phenoxy group, etc.), sulfonyl group (methanesulfonyl group, p
-Toluenesulfonyl group, etc.), sulfonamide group (methanesulfonamide group, benzenesulfonamide group, etc.), sulfamoyl group (diethylsulfamoyl group,
Unsubstituted sulfamoyl group), carbamoyl group (unsubstituted carbamoyl group, diethylcarbamoyl group, etc.), amide group (acetamide group, benzamide group, etc.), ureido group (methylureido group, phenylureido group, etc.), alkoxycarbonylamino group ( Methoxycarbonylamino group), allyloxycarbonylamino group (phenoxycarbonylamino group, etc.), alkoxycarbonyl group (methoxycarbonyl group, etc.), aryloxycarbonyl group (phenoxycarbonyl group, etc.), cyano group, hydroxy group, carboxy group, Sulfo group, nitro group, amino group (unsubstituted amino group, diethylamino group, etc.), alkylthio group (methylthio group, etc.), arylthio group (phenylthio group, etc.), and heterocyclic group (morpholyl group, pyridyl group, etc.) ) Can be mentioned. Here, R ¹ and R ² may be the same or different from each other, and the substituents of R ¹ and R ² may be the same or different.

The carbon number of R ¹ and R ² is preferably 1-10, and especially 1-5.
Is preferred. Examples of the nitrogen-containing heterocycle formed by connecting R ¹ and R ² include a piperidyl group, a pyrrolidylyl group, an N-alkylpiperazyl group, a morpholyl group, an indolinyl group, and a benztriazolyl group.

Preferred substituents for R ¹ and R ² are a hydroxy group, an alkoxy group, an alkyl or aryl sulfonyl group, an amide group,
A carboxy group, a cyano group, a sulfo group, a nitro group and an amino group.

Specific examples of the compound represented by formula (II) used in the present invention are shown below, but the scope of the present invention is not limited to this compound.

II- (34) NH ₂ OH The compound represented by the general formula (II) can be synthesized by the known method shown below.

U.S. Pat.Nos. 3,661,996, 3,362,961 and 3,293,03
4, Japanese Patent Publication No. 42-2794, U.S. Pat.
3,655,764, 3,467,711, 3,455,916, and
No. 3,287,125 and No. 3,287,124 These compounds may form salts with various acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid and acetic acid.

The amount of the compound represented by the general formula (II) added to the color developing solution is preferably 0.1 g to 20 g per color developing solution.
It is 0.5g-10g.

The color developer of the present invention preferably contains substantially no benzyl alcohol from the viewpoints of pollution prevention, solution preparation and fog prevention. Substantially free means that benzyl alcohol is not more than 2 ml, preferably not at all, per color developer.

Further, as a preservative, a sulfite salt such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, or a carbonyl sulfite adduct may be added if necessary. The addition amount of these is 0 g to 20 g / l, preferably 0 g to 5 g / l,
If the stability of the color developing solution is maintained, it is preferably as small as possible.

Other preservatives include hydroxyacetones described in U.S. Pat. No. 3,615,503 and British Patent 1,306,176;
Α-aminocarbonyl compounds described in 2-143020 and 53-89425, various metals described in JP-A-57-44148 and 57-53749, various sugars described in JP-A-52-102727 , 5
Hydroxamic acids described in 2-27638, α, α'-dicarbonyl compounds described in 59-160141, salicylic acids described in 59-180588, alkanolamines described in 54-3532, 56-94349 No. poly (alkyleneimine)
, Gluconic acid derivatives described in JP-A-56-75647, etc. may be contained if necessary, and these preservatives may be added as needed.
You may use together 1 or more types.

 It is also preferable to add an aromatic polyhydroxy compound.

The color developing solution of the present invention preferably has a pH of 9 to 12, more preferably 9 to 11.0, and the color developing solution can contain compounds of other known developing solution components.

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

As the buffer, carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycine salt, N, N dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4-dihydroxy salt Phenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1,3-
Propanediol salt, valine salt, proline salt, trishydrocyaminomethane salt, lysine salt and the like can be used. Particularly, carbonate, phosphate, tetraborate, and hydroxybenzoate are excellent in solubility and buffer capacity in a high pH range of pH 9.0 or more, and even when added to a color developing solution, they are effective for photographic performance. It is particularly preferable to use these buffers, since they have the advantages of being free from adverse effects (fogging, etc.) and being inexpensive.

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

The amount of the buffer added to the color developing solution is preferably 0.1 mol / l or more, and particularly preferably 0.1 mol / l to 0.4 mol / l.

In addition, various chelating agents can be used as a precipitation inhibitor of calcium or magnesium in the color developing solution 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-48-30496 and 44-30232, JP-A-56-97347, JP-B-56-39359, and West German Patent 2,227,639. Organic phosphonic acids, JP-A-5
2-102726, 53-42730, 54-121127, 55-1262
Examples thereof include phosphonocarboxylic acids described in JP-A Nos. 41 and 55-65956, and 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 Diethylenetriamine pentaacetic acid Ethylenediaminetetraacetic acid Triethylenetetramine hexaacetic acid N, N, N-trimethylenephosphonic acid Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid 1,3-diamino-2-propanol- Tetraacetic acid transcyclohexanediaminetetraacetic acid nitrilotriapropionic acid 1,2-diaminopropanetetraacetic acid hydroxyethyliminodiacetic acid glycol ether diaminetetraacetic acid hydroxyethylenediamine triacetic acid ethylenediamine orthohydroxyphenylacetic acid 2-phosphonobutane-1,2,4-tricarboxylic acid 1-Hydroxyethylidene-1,1-diphosphonic acid N, N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid These 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
It is about 0.1g to 10g per unit.

If necessary, any development accelerator can be added to the color developing solution. As a development accelerator, Japanese Patent Publication No. 37-1
No. 6088, No. 37-5987, No. 38-7826, No. 44-12380, No.
Thioether compounds represented by 45-9019 and U.S. Pat. No. 3,813,247, JP-A-52-49829, and JP-A-50-15554.
P-phenylenediamine compounds represented by JP-A Nos. 50-137726, JP-B-44-30074, JP-A-56-156826 and JP-A-52-43429, and quaternary ammonium salts,
P-Aminophenols described in U.S. Pat. Nos. 2,610,122 and 4,119,462, U.S. Pat. Nos. 2,494,903 and 3,128,182
No. 4,230,796, 3,253,919, Japanese Patent Publication No. 41-11431
U.S. Pat.Nos. 2,482,546, 2,596,926 and 3,582,
Amine compounds described in No. 346, Japanese Examined Patent Publication No. 37-16088,
No. 42-25201, U.S. Patent No. 3,128,183, Japanese Patent Publication No. 41-11431
No. 42-23883 and U.S. Pat. No. 3,532,501, and other polyalkylene oxides, and other 1-phenyl-
If necessary, 3-pyrazolidones, hydrazines, mesoionic compounds, ionic compounds, imidazoles and the like can be added.

In the present invention, any antifoggant can be added if necessary. 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 and 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, indazoles, and hydroxyazaindolizine adenine.

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

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

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

Next, the bleaching solution, the bleach-fixing solution and the fixing solution used in the processing method of 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, but in particular, an organic complex salt of iron (III) (for example, aminopolycarboxylic acid such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid). Acids, complex salts such as aminopolyphosphonic acid, phosphonocarboxylic acid and organic phosphonic acid) or organic acids such as citric acid, tartaric acid and malic acid; persulfates; hydrogen peroxide and the like are preferable. Of these, iron (II
The organic complex salt of I) is particularly preferable from the viewpoint of rapid treatment and prevention of environmental pollution. Enumerating aminopolycarboxylic acids, aminopolyphosphonic acids, or organic phosphonic acids or salts thereof useful for forming organic complex salts of iron (III),
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 ethyletherdiaminetetraacetic acid, glycoletherdiaminetetraacetic acid, ethylenediaminetetrapropionic acid, ethylenediaminedipropionacetic acid, phenylenediaminetetraacetic 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,
Examples thereof include N ', N'-tetramethylenephosphonic acid and 1-hydroxyethylidene-1,1-diphosphonic acid.

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, or ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium nitrate, 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 of complex salt may be used, or two or more types of complex salt may be used. On the other hand, when a complex salt is formed in a solution by using a ferric salt and a chelating agent, one or more ferric salts may be used. Furthermore, one or more chelating agents may be used. In any case, the chelating agent may be used in excess of the amount of forming the ferric ion complex salt. Among the iron complexes, aminopolycarboxylic acid iron complexes are preferable, and the addition amount is 0.01 to 1.
It is 0 mol / l, preferably 0.05 to 0.50 mol / l.

In the bleaching solution or the bleach-fixing solution, a bleaching accelerator can be used if necessary. Specific examples of useful bleaching accelerators include U.S. Patent No. 3,893,858 and West German Patent No.
1,290,812, 2,059,988, JP-A-53-32736, the same
53-57831, 53-37418, 53-65732, 53-72623
No. 53, No. 53-95630, No. 53-95631, No. 53-104232, No. 5
3-124424, 53-141623, 53-28426, Research Disclosure No. 17129 (July 1978), and other compounds having a mercapto group or a disulfide group; JP-A-50-140129 Thiazolidine derivatives as described in JP-B-45-8506, JP-A-52-20832 and JP-A-5-20832.
3-32735, thiourea derivatives described in U.S. Pat. No. 3,706,561; West German Patent 1,127,715, iodide described in JP-A-58-16235; polyethylene described in West German Patents 966,410 and 2,748,430. Oxides; polyamine compounds described in JP-B-45-8836; other JP-A-49-42434,
49-59644, 53-94927, 54-35727, 55-26506
And the compounds described in JP-A No. 58-163940, iodine, bromide ion and the like. Of these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large accelerating effect, and particularly preferred are the compounds described in U.S. Patent No. 3,893,858, West German Patent No. 1,290,812, and JP-A-53-95630.

In addition, the bleaching solution or the bleach-fixing solution of the present invention may contain bromide (eg, potassium bromide, sodium bromide, ammonium bromide) or chloride (eg, potassium chloride, sodium chloride, ammonium chloride) or iodide (eg, iodide). Ammonium) rehalogenating agents.
Boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, sodium phosphate, citric acid, sodium citrate, if necessary.
It is possible to add one or more kinds of inorganic acids having pH buffering ability such as tartaric acid, organic acids 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 in the present invention is a known fixing agent, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylenebis. Thioglycolic acid, thioether compounds such as 3,6-dithia-1.8-octanediol, and water-soluble silver halide solubilizers such as thioureas, which may be used alone or in admixture of two or more. I can. Further, a special bleach-fixing solution comprising a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can be used. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred.

The amount of the fixing agent per 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 10 are preferable, and 5 to 9 are particularly preferable. pH
If it is lower than this, desilvering property is improved but deterioration of the liquid and leuco conversion of the cyan dye are promoted. On the contrary, 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 and the like.

In the present invention, the bleach-fixing solution or the fixing solution is a sulfite as a preservative (for example, sodium sulfite, potassium sulfite,
Sulfite ion such as ammonium sulfite), bisulfite (eg, ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.), metabisulfite (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.) Contains a release compound. These compounds are about 0.02-0.50 mol in terms of sulfite ion.
/ l is preferably contained, more preferably 0.04 ~
It is 0.40 mol / l.

As a preservative, it is common to add sulfite,
In addition, ascorbic acid and carbonyl bisulfite addition products,
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 as required.

Next, the washing step of the present invention will be described. In the present invention, a simple treatment method such as performing only a so-called "stabilization treatment" without providing a substantial water washing step in place of the usual "water washing treatment" can be used. As described above, the “water-washing treatment” in the present invention is used in a broad sense as described above.

The rinsing water amount of the present invention is difficult to define because it varies depending on the number of multi-stage countercurrent rinsing baths and the amount of the pre-bath component of the light-sensitive material introduced, but in the present invention, the bleaching and fixing solution components in the final rinsing bath are Is 1 × 10 ⁻⁴ or less. For example, in the case of washing with countercurrent flow in 3 tanks, about 1000 ml per 1 m ² of light-sensitive material
It is preferably used above, more preferably 5000 ml or more. In the case of water-saving treatment, 100 to 1m ² of light-sensitive material
It is recommended to use 1000 ml.

The washing temperature is 15 ° C to 45 ° C, more preferably 20 ° C to 35 ° C.

Various known compounds may be added to the washing treatment step for the purpose of preventing precipitation and stabilizing the washing water. 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's "Chemistry of antibacterial and antifungal", metal salts represented by magnesium salts and aluminum salts, alkali metal and ammonium salts, or dry load and unevenness. If necessary, a surfactant or the like for preventing the above can be added.
Alternatively, compounds described in West, "Photographic Science and Engineering Magazine (Phot.Sci.Eng.), Volume 6, pp. 344-359 (1965) and the like may be added.

Furthermore, the present invention is particularly effective in the case of adding a chelating agent, a bactericidal agent, and an antibacterial agent to the washing water to significantly reduce the amount of washing water by multistage countercurrent washing with two or more tanks. Also,
It is also particularly effective when a multistage countercurrent stabilization treatment step (so-called stabilization treatment) as described in JP-A-57-8543 is carried out instead of the ordinary 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 an image. For example, adjust the membrane pH (eg pH 3 ~
8) various buffering agents (for example, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc. Are used in combination) and aldehydes such as formalin. Other 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.) ), Various additives such as surfactants, optical brighteners and hardeners may be used, and two or more kinds of the same or different target compounds may be used in combination.

Also, ammonium chloride as a membrane pH adjuster for the processor,
It is preferable to add various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate in order to improve the image storability.

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

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 agitation, air agitation and the like may be provided in each treatment bath.

The method of the present invention can be applied to any processing step using a color developer. For example, it can be applied to processing of color paper, color reversal paper, color positive film, color negative film, color reversal film, and the like.

The silver halide emulsion of the light-sensitive material to which the processing method of the present invention is applied can be of any halogen composition such as silver iodobromide, silver bromide, silver chlorobromide, and silver chloride, but rapid processing and low replenishment processing are possible. In the case of carrying out, the silver chlorobromide emulsion or silver chloride emulsion containing 60 mol% or more of silver chloride is preferable, and the case where the content of silver chloride is 80 to 100 mol% is particularly preferable. When high sensitivity is required and fog 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 promoting development, such as means for causing a development accelerator such as a silver halide solvent, 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.

In the present invention, the silver halide grains of the silver halide emulsion may have different phases in the inside and surface layers, 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 (the grain diameter is shown for spherical or near-sphere grains, and the edge length is given for cubic grains, and the average is based on the projected area. Expressed in conversion.)
Is preferably 2 μ or less and 0.1 μ or more, particularly preferably 1.5 μ or less and 0.15 μ 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 within 20%, particularly preferably 15 It is preferred to use so-called monodisperse silver halide emulsions within the range of% in the present invention. 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. Further, two or more kinds of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion can be used as a mixture or as a mixture.

The silver halide grains used in the present invention have a regular shape such as a cube, an octahedron, a rhodohedron and a tetrahedron.
r) crystallites or their coexistence, and irregular (irregula) shapes such as spherical shapes.
r) It may have a crystalline form or a composite form of these crystalline 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 as a seed on the surface or an internal latent image type which forms inside a grain.

The photographic emulsion used in the present invention is described in "Graphkide's Chemistry and Physics" [P. Glafkides, Chimieet Physique Phot].
ographique (Paul Motel, 1967)], Duffin's "Photoemulsion Chemistry" [GFDuffin.Photograhic Emulsion
Chemistry (Focal Press, 1966)], Zelikman et al., "Manufacturing and Coating of Photographic Emulsions" [VL Zelikman et al. "M
aking and Coating Photographic Emulsion (Focal Pre
ss, 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 constant in a liquid phase in which silver halide is produced, 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 silver halide Emulsions which have undergone a similar halogen conversion after the completion of the grain formation process can also be used.

In the process of silver halide grain formation or physical ripening, cadmium salt, zinc salt, lead salt, copper salt, thallium salt,
An iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt may be present together.

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

Known silver halide solvents (e.g., ammonia, rodancali or U.S. Pat. No. 3,271,157, JP-A-51-12360).
JP-A-53-82408, JP-A-53-144319, JP-A-54-
The thioethers and thione compounds described in 100717 or JP-A-54-155828 can be used for precipitation, physical 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 (eg, thiosulfates, thioureas, mercapto compounds, rhodanins).
Sulfur sensitization method using a reducing substance (for example, stannous salt,
Reduction sensitization method using amines, hydrazine derivatives, formamidinesulfinic acid, silane compounds); metal compounds (eg, gold complex salts, Pt, Ir, Pd, Rh, Fe and other metals of Group VIII) A noble metal sensitizing method using a complex salt) can be used alone or in combination.

Each of the blue-sensitive, green-sensitive and red-sensitive emulsions of the present invention is spectrally sensitized with a methine dye or the like so as to have color sensitivity. The dye used is a cyanine dye,
It includes 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.

Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. 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, etc .; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these Nucleus fused with an aromatic hydrocarbon ring, that is, indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus,
A benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus and the like 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-
A 5- or 6-membered heterocyclic nucleus such as 2,4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, or 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 supersensitization. Typical examples thereof are U.S. Pat.Nos. 2,688,545, 2,977,229, and 3,397,060.
No. 3,522,052, No. 3,527,641, No. 3,617,293
No. 3, No. 3,628,964, No. 3,666,480, No. 3,672,89
No. 8, No. 3,679,428, No. 3,703,377, No. 3,769,3
No. 01, No. 3,814,609, No. 3,837,862, No. 4,026,
No. 707, British Patent Nos. 1,344,281, 1,507,803, Japanese Patent Publication Nos. 43-4936, 53-12375, and JP-A Nos. 52-110618 and 52.
-109925.

Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization.

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 also particularly useful to apply them to grains having an increased content of silver bromide or silver iodide 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. A coupler in which the color-forming dye has a suitable diffusibility, a colorless coupler, or a DIR coupler which releases a development inhibitor upon coupling reaction or a coupler which releases a development accelerator can also be used.

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 U.S. Pat.
No. 210, No. 2,875,057 and No. 3,265,506. In the present invention, the use of a 2-equivalent yellow coupler is preferable, and U.S. Pat. Nos. 3,408,194 and 3,44 are used.
No. 7,928, No. 3,933,501 and No. 4,022,620 oxygen atom desorption type yellow couplers described in JP-B-58-10739, U.S. Pat.Nos. 4,401,752, 4,3
26,024, RD18053 (April 1979), UK Patent 1,425,0
No. 20, West German Application Publication No. 2,219,917, No. 2,261,361,
Typical examples thereof include nitrogen atom-releasing yellow couplers described in JP-A-2,329,587 and JP-A-2,433,812. The α-pivaloyl acetanilide type coupler is excellent in the fastness, especially the light fastness, of the color forming dye, while the α-benzoyl acetanilide type coupler can obtain a high coloring density.

Examples of the magenta coupler that can be used in the present invention include oil-protection type indazolone type or cyanoacetyl type couplers, 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 typical examples thereof are U.S. Pat.Nos. 2,311,082 and 2,343,703. ,
No. 2,600,788, No. 2,908,573, No. 3,062,653
No. 3,152,896 and No. 3,936,015. As the leaving group of the 2-equivalent 5-pyrazolone-based coupler, the nitrogen atom leaving group described in US Pat. No. 4,310,619 or the arylthio group described in US Pat. No. 4,351,897 is preferable. Further, the 5-pyrazolone-based coupler having a ballast group described in EP 73,636 provides a high color density.

As the pyrazoloazole-based coupler, US Pat.
369,879 pyrazolobenzimidazoles, preferably pyrazolo [5,1-c] [1,2,4] triazoles described in US Pat. No. 3,725,067, Research Disclosure 24220 (June 1984). Pyrazolotetrazoles described and Research Disclosure 2423
0 (June 1984). The imidazo [1,2] described in European Patent No. 119,741 has a small yellow sub-absorption of the coloring dye and the light fastness.
-b] pyrazoles are preferred, and the pyrazolo [5,1-b] [1,2,4] triazoles described in EP 119,860 are particularly preferred.

Cyan couplers that can be used in the present invention include oil-protection type naphthol-based and phenol-based couplers, naphthol-based couplers described in U.S. Pat.No. 2,474,293, preferably U.S. Pat.Nos. 4,052,212, 4,146,396, and No. 4,228,233 and No. 4,296,200
As a representative example, the oxygen atom-releasing two-equivalent naphthol-based couplers described in JP-A No. 1994-242242 can be mentioned. Further, specific examples of the phenol-based coupler are described in U.S. Patents 2,369,929 and 2,80.
1,171, 2,772,162, 2,895,826 and the like. Cyan couplers that are fast against humidity and temperature are preferably used in the present invention, and typical examples thereof include a phenol having an alkyl group of ethyl group or higher at the meta 1-position of the phenol nucleus described in U.S. Pat.No. 3,772,002. Cyan couplers, U.S. Pat.Nos. 2,772,162, 3,758,308, 4,126,396, 4,334,011,
No. 4,327,173, West German Patent Publication No. 3,329,729 and Japanese Patent Application No. 58-42671, and 2,5-diacylamino-substituted phenol-based couplers and U.S. Pat.No. 3,446,622.
Nos. 4,333,999, 4,451,559 and 4,42
Phenol couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position described in 7,767 and the like.

The graininess can be improved by using a coupler in which the color forming dye has an appropriate diffusibility. Such dye-diffusing couplers are described in U.S. Pat.No. 4,366,237 and British Patent 2,1.
Specific examples of magenta couplers are described in 25,570, and specific examples of yellow, magenta or cyan couplers are described in EP 96,570 and West German Patent Application Publication No. 3,234,533.

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 described in US Pat. Nos. 3,451,820 and 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and U.S. 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. The above can be introduced.

The coupler used in the present invention can be introduced into a light-sensitive material by an oil-in-water dispersion method. In the oil-in-water dispersion method, the boiling point is
After being dissolved in either a single liquid of a high boiling point organic solvent having a boiling point of 175 ° C or higher and a so-called auxiliary solvent having a low boiling point or a mixed liquid of both, finely dispersed in an aqueous medium such as water or a gelatin aqueous solution in the presence of a surfactant. . Examples of high boiling 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, noodle washing, or ultrafiltration, and then 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.), phosphoric acid or phosphonic acid esters (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-ethyl-hexyl) Bezoate, dodecylbenzoate, 2-ethylhexyl-
p-hydroxybenzoate etc.), amides (diethyldodecane amide, N-tetradecylpyrrolidone etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol 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 (balafine, Dodecylbenzene, diisopropylnaphthalene, etc.) and the like. The auxiliary solvent has a boiling point of about 30 ° C or higher,
Preferably, an organic solvent having a temperature of 50 ° C. or higher and about 160 ° C. or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like.

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, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

The standard amount of the color coupler used is in the range of 0.001 to 1 mol per mol of the photosensitive silver halide,
Preferably 0.01 to 0.5 moles for yellow couplers,
It is 0.003 to 0.3 mol for the magenta coupler and 0.002 to 0.3 mol for the cyan coupler.

The light-sensitive material to which the method of the present invention can be applied is 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 as a color fog inhibitor or color mixture inhibitor Etc. may be contained.

A known anticorrosive agent can be used in the light-sensitive material to which the method of the present invention is applied. Examples of organic anti-corrosion agents include hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols, hindered phenols centering on bisphenols, gallic acid derivatives, methylenedioxy. Silylation of phenolic hydroxyl groups of benzenes, aminophenols, hindered amines and these compounds,
Representative examples are alkylated ether or ester derivatives. Further, a metal complex represented by (bissalicylaldoximate) nickel complex and (bis-N, N-dialkyldithiocarbamate) nickel complex can also be used.

To prevent the deterioration of the yellow dye image by heat, humidity and light, a compound having both partial structures of hindered amine and hindered phenol in the same molecule as described in US Pat. No. 4,268,593 gives good results. Further, in order to prevent deterioration of the magenta dye image, particularly deterioration by light, spiroindanes described in JP-A-56-159644 and hydroquinone diethers or monoethers described in JP-A-55-89835 are substituted. Chromans 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 coating amount of the ultraviolet absorber 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 , especially 5 × 10 ⁻⁴ mol / m ^{2 to} 1.5 × 1
It is set in the range of 0 ^-3 mol / m ² .

In the light-sensitive material layer structure of a normal color paper, either one of both sides adjacent to the cyan coupler-containing red-sensitive emulsion layer,
Preferably, the layers on both sides contain an ultraviolet absorber.
When an ultraviolet absorber is added to the intermediate layer between the green-sensitive layer and the red-sensitive layer, it may be co-emulsified with a 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 to which the present invention is applied, an ultraviolet absorber can be added to the hydrophilic colloid layer.

The light-sensitive material to which the present invention is applied may contain a water-soluble dye in a 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 particularly preferable.

In the photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material to which the present invention is applied, 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, as described above. 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. Each of the above emulsion layers may be composed of two or more emulsion layers having different sensitivities, and two emulsion layers having the same sensitivity.
A non-light sensitive layer may be present between two or more emulsion layers.

The light-sensitive material to which the present invention is applied is preferably provided with an auxiliary layer 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.

Gelatin is advantageously used as the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material to which the present invention is applied, 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, cellulose sulfates, etc., sugar derivatives such as sodium alginate and starch derivatives; polyvinyl. Use various synthetic hydrophilic polymer substances such as alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and other single or copolymers. be able to. The use of acrylic acid-modified polyvinyl alcohol in the protective layer is particularly useful, and even more useful for rapid processing with high silver chloride content emulsions.

As gelatin, in addition to lime-processed gelatin, acid-processed gelatin and Bull.Soc.Soi.Phot.Japan.No.16, p.30 (196
Oxygen-treated gelatin as described in 6) may be used, and a hydrolyzed product or an enzymatically decomposed product of gelatin may also be used.

The light-sensitive material to which the present invention is applied, in addition to the above-mentioned additives, further various stabilizers, stain inhibitors, developing agents or precursors thereof, development accelerators or precursors thereof as described above, lubricants, mordants, A matting agent, an antistatic agent, a plasticizer or other various additives useful for photographic light-sensitive materials may be added. Representative examples of these additives are Research Disclosure 17643 (December 1978) and 18716 (19).
(November 1979).

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

The "reflective support" that can be used for the light-sensitive material to which the present invention is applied is to increase the reflectivity to make the dye image formed on the silver halide emulsion layer clearer. A support coated with a hydrophobic resin containing a light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate or calcium sulfate, or a support using a hydrophobic resin containing a light-reflecting substance dispersed therein. Is included. 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, polyester film of cellulose triacetate or cellulose nitrate, polyamide film , A polycarbonate film, a polystyrene film and the like, and these supports can be appropriately selected depending on the purpose of use.

(Effect of the Invention) According to the method of the present invention, the developer is excellent in stability and color developability, and it is possible to remarkably reduce the increase of fog during continuous processing of the silver halide color photographic light-sensitive material.

Further, in the method of the present invention, the above effect is further enhanced by using the developing solution as a system containing substantially no benzyl alcohol.

By using the developer of the present invention, stability can be enhanced and deterioration of color development can be prevented without using a substance that acts as a competitive compound of a developing agent such as sulfite ion.

(Example) The present invention will be described in more detail based on an example.

Example 1 On a paper support laminated on both sides with polyethylene,
A multilayer color photographic paper was created. The coating liquid was prepared as follows.

Preparation of first layer coating solution 19.1 g of yellow coupler (a) and color image stabilizer (b)
To 4.4 g, 27.2 ml of ethyl acetate and 7.9 ml of the solvent (c) were 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 dyes were added to a silver chlorobromide emulsion (containing 1.0 mol% of silver bromide and 70 g / kg of Ag) per mol of silver chlorobromide.
90 g of a blue-sensitive emulsion was prepared by adding 0 × 10 ⁻⁴ mol.
The emulsified dispersion and the emulsion were mixed and dissolved, the gelatin concentration was adjusted so that the composition shown in Table B 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 the 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.

(5.0 × 10 ^-4 mol added per mol of silver halide) (4.0 × 10 ^-4 mol added per mol of silver halide) (7.0 × 10 ^-4 mol added per mol of silver halide) (Addition of 0.9 × 10 ⁻⁴ mol per mol of silver halide) The following dye was used as an anti-irradiation dye for each emulsion layer.

Structural formulas of compounds such as couplers used in this example are as follows.

The color photographic paper thus obtained was subjected to wedge-shaped exposure and then processed in the following processing steps.

Treatment process Temperature Time Color development 35 ℃ 45 seconds Bleach-fixing 35 ℃ 45 seconds Rinse 1 35 ℃ 20 seconds Rinse 2 35 ℃ 20 seconds Rinse 3 35 ℃ 20 seconds Dry 80 ℃ 60 seconds Each liquid used is as follows. .

Color developer N, N-diethyl hydroxylamine 4g Potassium carbonate 30g EDTA ・ 2Na ・ 2H ₂ O 2g Sodium chloride 1.0g 4-Amino-3-methyl-N-ethyl-N- [β- (methanesulfonamido) ethyl]- p-Phenylenediamine sulphate 5.0g Fluorescent brightener (4,4'-diamino-stilbene type) 3.0g Compound of general formula (I) Table 1 Add water to 1000ml pH 10.10 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 to make 1000 ml pH 5.5 rinse solution 1-hydroxyethylidene-1,1 '- diphosphonic acid (60 %) 1.6 ml Bismuth chloride 0.35 g Polyvinylpyrrolidone 0.25 g Ammonia water (26%) 2.5 ml Nitrilotriacetic acid ・ 3Na 1.0 g EDTA ・ 4H 0.5 g Sodium sulfite 1.0 g 5-Chloro-2-methyl-4-isothiazoline-3- on 50 mg formalin (37%) 0.1 ml Water was added to 1000 ml pH 7.0 1 part of the color developer obtained as above
The beaker was left in an open system at 40 ° C. for 20 days and then treated again in the above treatment step.

The treatment using the color developing solution left for 20 days was used as a aging solution test, and the treatment using the color developing solution before standing was used as a fresh solution test.

Table 1 shows the photographic properties of the obtained fresh liquid and the photographic properties in the aged liquid test.

The photographic characteristics are 3 in terms of Dmin at yellow density, sensitivity and gradation.
Expressed by dots.

Sensitivity points are represented by density values at a constant exposure amount (100 CMS), and gradations are represented by 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.

According to the present invention, even if the developer is stored in an open system for a long period of time, the photographic property hardly changes, and stable performance can be obtained. On the other hand, when sodium sulfite or triethanolamine is used, it changes over time, and the fog in the photographic image rises or the gradation changes.

Example 2 As described in Table C, double-sided polyethylene laminated paper treated with corona discharge was coated with the first layer (bottom layer) to the seventh layer (top layer) to prepare a sample.

The coating liquid for the first layer was prepared as follows. That is, 200 g of yellow coupler shown in the table, anti-fading agent 9
A mixture of 3.3 g, 10 g of the high boiling point solvent (p) and 5 g of (q) and 600 ml of ethyl acetate as an auxiliary solvent was heated and dissolved at 60 ° C., and then a 5% aqueous solution of alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont) was added. The mixture was mixed with 3,300 ml of a 5% aqueous gelatin solution containing 330 ml, and emulsified using a colloid mill to prepare a coupler dispersion. Ethyl acetate was distilled off from this dispersion under reduced pressure, and the sensitizing dye for blue-sensitive emulsion layer and 1
-Methyl-2-mercapto-5-acetylamino-1,3,
1,400 g of emulsion containing 4-triazole (96.7 g as Ag.
(Including 170 g of gelatin), and 2600 g of 10% gelatin aqueous solution were further added to prepare a coating solution. The coating solutions for the second to seventh layers were prepared according to the first layer.

n2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole o2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazole p di (2-ethylhexyl) phthalate q dibutyl phthalate r 2,5-di-tert-amylphenyl-3,5-di-tert-butylhydroxybenzoate s 2,5-di-tert-octylhydroquinone t 1,4-di-tert-amyl-2, 5-Dioctyloxybenzene u 2,2'-methylenebis (4-methyl-6-tert-butylphenol) 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) thiazicarbocyanine iodide The following compounds 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 Also, 1,2-bis (vinylsulfonyl) ethane was used as a hardening agent.

 The couplers used are as follows.

Cyan coupler [C-1; C-2 = 50:50 mixture (molar ratio)] The multilayer color photographic paper obtained as described below was subjected to wedge-shaped exposure and then processed in the following processing steps.

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

Color developer Water 800 ml Benzyl alcohol Table 2 Diethylene glycol Table 2 Diethylenetriamine pentaacetic acid 1.0 g N, N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid 0.1 g Nitrilo-N, N, N- Trimethylenephosphonic acid (40%) 1.0 g Potassium bromide 1.0 g Compound of general formula (I) Table 2 Hydroxyamines Table 2 Potassium carbonate 30 g N-ethyl-N- (β-methanesulfonamidoethyl) -3- Methyl-4-aminoaniline sulphate 5.5g Fluorescent brightener (4,4'-diaminostilbene type) 1.0g Add water and 1000ml KOH pH 10.10 Bleach-fix solution Ammonium thiosulfate (70%) 150ml Sodium sulfite 15g Ethylenediamineiron (III) ammonium 60g Ethylenediaminetetraacetic acid 10g Optical brightener (4,4'-diaminostilbene type) 1.0g 2-Mercapto-5-a No-3,4-thiadiazole 1.0 g Water was added and 1000 ml with ammonium water pH 7.0 Rinsing solution 5-chloro-2-methyl-4-isothiazolin-3-one 40 mg 2-Methyl-4-isothiazoline-3- On 10 mg 2-octyl-4-isothiazolin-3-one 10 mg Bismuth chloride (40%) 0.5 g Nitrilo-N, N, N-trimethylenephosphonic acid (40%) 1.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid (60%) 2.5g Optical brightener (4,4'-diaminostilbene type) 1.0g Ammonium water (26%) 2.0ml Add water and 1000ml with KOH pH7.5 The Dmin, sensitivity, and gradation of magenta in the solution and the storage solution were determined, and the change value of each photographic performance based on the photographic property in the fresh solution is shown in Table 2.

From the results in the above table, the developer composition of the present invention exhibits excellent effects in a system containing benzyl alcohol,
In particular, it was found that photographic performance was significantly stabilized when used in a system containing no benzyl alcohol (Experiment N
o.15,16,17,18,21,22,23,24,25). on the other hand,
When the hydroxylamines are used alone, the storage solution changes with time and the photographic properties change greatly.

Example 3 The silver halide emulsion composition of the third layer of the sample printing paper was changed to silver bromide.
A photographic printing paper was prepared in the same manner as in Example 2 except that the amount was 80 mol%, and was stored in the same manner as in Experiment Nos. 12 to 25 to test for changes in photographic properties. As in Example 2, hydroxylamines alone were used. While the photographic properties changed significantly with the aging of the storage solution, the developer composition of the present invention showed remarkable stability, especially in a system containing no benzyl alcohol.

Example 4 The photographic properties of a fresh solution and an aged solution were tested in the same manner as in Example 1 except that the compound of the general formula (I) in the color developing solution was replaced with the compounds shown in Table 3 below. The results are shown in Table 3. From the results in the table, it can be seen that according to the method of the present invention, there is almost no change in photographic property even with the developer after long-term storage.

Example 5 A photographic property in an aged solution was carried out in the same manner as in Example 2 except that the compounds of the general formula (I), the hydroxylamines and the benzyl alcohol / diethylene glycol ratio in the color developer were set as shown in Table 4. The change was tested. The results are shown in Table 4. From the results in the table, it can be seen that the photographic performance is remarkably stabilized by the method of the present invention.

Claims (2)

[Claims] 1. A silver halide color photographic light-sensitive material comprising p-
A method of processing a silver halide color photographic light-sensitive material, which comprises processing with a developer containing a phenylenediamine derivative color developing agent and a compound represented by the following general formula. (In the formula, R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group when n is 1, and a hydrogen atom is taken from the alkyl group, the aryl group, or the heterocyclic group when n is 2 or more. Represents a divalent or higher valent group A is an organic group composed of an atom selected from a carbon atom, an oxygen atom and a sulfur atom, and is a saturated or unsaturated 3
~ Represents a 8-membered ring. A may have a hydroxyalkyl group, an alkyl group, a carboxy group, or a hydroxy group as a substituent, and A may have a condensed benzene ring or heterocycle. n represents an integer of 1 or more. ) 2. The method of processing a silver halide color photographic light-sensitive material according to claim 1, wherein the developer contains substantially no benzyl alcohol.