JP2946263B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a silver halide color photographic material (hereinafter referred to as a color photographic material) after imagewise exposure.
The present invention relates to a method for processing by a development process having a color development process, a desilvering process, and a stabilization process.

[0002]

2. Description of the Related Art Generally, color development of a color negative photographic light-sensitive material for photographing represented by a photographic light-sensitive material in which silver halide contains silver iodide includes a color development step, a desilvering step, and a washing step. A process and a stabilization process are sequentially performed. In the color reversal photographic light-sensitive material, after the black-and-white development step and the reversal processing step are performed, the above-described color development processing is performed, but instead of the stabilization processing in the final processing, the color development step and the desilvering step are performed. Between them, a process that can be called an adjustment stabilization process may be performed. As described above, in the color light-sensitive material for photography, a stabilizing process for inactivating an unreacted coupler is performed in any of the processes. However, despite such processing, there is a problem that yellow stain is generated, particularly when stored under dry conditions after the processing. This is considered to be due to the decomposition of the unreacted residual coupler.

In the development processing of color photographic light-sensitive materials such as color negative photographic light-sensitive materials and color reversal photographic light-sensitive materials, formalin (formaldehyde) has been used as a stabilizing solution in order to prevent fading of magenta dyes. Was. Since formalin is harmful to the human body, efforts have been made to reduce the concentration of formalin in the stabilizing solution and to convert to a formalin substitute (for example, a formalin precursor such as an N-methylol compound). However, it was found that when the formalin concentration in the stabilizing solution was reduced, the yellow stain increased instead. Further, formalin substitutes such as N-methylol compounds reduce the formalin concentration in the liquid by an equilibrium reaction in the stable liquid and reduce the adverse effect on the human body. It was found that when the value of was decreased, the yellow stain increased in the same manner as described above. Therefore, there has been a demand for development of a developing method of a photographic color light-sensitive material capable of effectively preventing the occurrence of yellow stain even if the formalin concentration in the stabilizing solution is reduced.

[0004]

Accordingly, the first aspect of the present invention is as follows.
An object of the present invention is to provide a method for processing a color light-sensitive material having good image storability by preventing the occurrence of yellow stain after development processing. A second object of the present invention is to provide a method for processing a color light-sensitive material in which the occurrence of yellow stain is prevented even when the concentration of formalin harmful to the human body in a stabilizing solution is reduced.

[0005]

The above object has been achieved by the following method for processing a silver halide color photographic light-sensitive material. That is, in a method of processing an imagewise exposed silver halide color photographic light-sensitive material by a development process having a color development step, a desilvering step and a stabilization step, the light-sensitive material contains 1 to 30 mol of silver iodide. % Of the silver halide emulsion layer, the bleaching solution used in the desilvering step contains a ferric complex salt of a compound represented by the following general formula (I), and the pH of the bleaching solution is Is 3.
0 to 5.0, the fixing solution contains thiosulfate,
A method for processing a silver halide color photographic material, wherein the pH of the solution is 6.5 to 8.0 and the processing solution used in the stabilizing step contains substantially no formaldehyde. General formula (I)

[0006]

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In the formula (I), R ₁ , R ₂ , R ₃ , R ₄ , R
₅ and R ₆ each independently represent a hydrogen atom, an aliphatic group, an aromatic group or a hydroxy group. W represents a linking group represented by the following general formula (W). M ₁ , M ₂ , M ₃ and M ₄ are
Each independently represents a hydrogen atom or a cation. Formula (W)-(W ₁ -Z) _n -W ₂ -In the formula (W), W ₁ represents an alkylene group or a single bond. W
₂ represents an alkylene group or -CO-. Z is a single bond,-
O -, - S -, - CO-, or -N (R _W) - represents the (R _W represents a hydrogen atom or an optionally substituted alkyl group.). However, Z and W ₁ are not simultaneously a single bond. n represents an integer of 1 to 3.

Hereinafter, the present invention will be described in detail. The developing step of the present invention comprises a color developing step, a desilvering step, and a stabilizing step. Other steps may be inserted before and after these steps, or the stabilizing step may be a color developing step and a desilvering step. It may be between the processing steps. However, the stabilizing step is a step for stabilizing a dye image obtained by color development, and therefore, the stabilizing step is performed after the color developing step.

In the present invention, the treatment solution used in the stabilization step substantially does not contain formaldehyde means that the concentration of free formaldehyde in the treatment solution is 0.01 mol / l or less, preferably 0.005 mol / l. The content is particularly preferably 0.001 mol / liter or less, and most preferably it does not contain any. Instead of formalin, the processing solution used in the stabilization step of the present invention may be a compound that stabilizes a dye image, for example, benzaldehydes such as m-hydroxybenzaldehyde, formaldehyde bisulfite adduct, hexamethylenetetramine and its derivatives, Hydrotriazine and its derivatives, N-methylol compounds such as dimethylol urea and N-methylol pyrazole, azolyl methylamine compounds such as 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine, organic acids and It is preferable to include a pH buffer or the like. The following are specific examples.

[0010]

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[0011]

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The preferable addition amount of these compounds is 0.001 to 0.02 mol per liter of the processing solution.
It is preferable that the concentration of free formaldehyde in the treatment liquid is lower because the scattering of formaldehyde gas is reduced. From such a point, as the dye image stabilizer, m-hydroxybenzaldehyde, hexamethylenetetramine, N-
N-methylolazoles described in JP-A-4-270344 such as methylolpyrazole, 1,4-bis (1,
Azolylmethylamines described in European Patent Publication No. 0,504,609A2, such as (2,4-triazol-1-ylmethyl) piperazine, are preferred.

Hereinafter, the compound of the formula (I) of the present invention will be described in more detail. R ₁ , R ₂ , R ₃ , R ₄ , R ₅
And an aliphatic group represented by R ₆ is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group;
Those having 1 to 10 carbon atoms are preferred. The aliphatic group is more preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group and an ethyl group. The aromatic group represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ is a monocyclic or bicyclic aryl group, such as a phenyl group and a naphthyl group,
A phenyl group is more preferred. R ₁ , R ₂ , R ₃ , R ₄ ,
The aliphatic group and the aromatic group represented by R ₅ and R ₆ may have a substituent, for example, an alkyl group (eg, methyl,
Ethyl), an aralkyl group (eg, phenylmethyl), an alkenyl group (eg, allyl), an alkynyl group, an alkoxy group (eg, methoxy, ethoxy), an aryl group (eg, phenyl, p-methylphenyl), an amino group (eg, dimethylamino), Acylamino group (eg, acetylamino), sulfonylamino group (eg, methanesulfonylamino), ureido group, urethane group, aryloxy group (eg, phenyloxy), sulfamoyl (eg, methylsulfamoyl), carbamoyl group (eg, carbamoyl, methylcarbamoyl) ), An alkylthio group (eg, methylthio), an arylthio group (eg, phenylthio), a sulfonyl group (eg, methanesulfonyl), a sulfinyl group (eg, methanesulfinyl), a hydroxy group, a halogen atom ( For example, chlorine atom, bromine atom, fluorine atom, cyano group, sulfo group, carboxy group, phosphono group, aryloxycarbonyl group (eg, phenyloxycarbonyl), acyl group (eg, acetyl, benzoyl), alkoxycarbonyl group (eg, methoxycarbonyl) ), An acyloxy group (for example, acetoxy), a carbonamido group, a sulfonamido group, a nitro group, a hydroxamic acid group, and the like. When the substituent has a carbon atom, it preferably has 1 to 4 carbon atoms. R ₁ ,
R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are preferably a hydrogen atom or a hydroxy group, and more preferably a hydrogen atom.

The linking group represented by W is represented by the following general formula (W). Formula (W)-(W ₁ -Z) _n -W ₂ -W ₁ represents an alkylene group or a single bond. The alkylene group represented by W ₁ is preferably a linear or branched alkylene group having 1 to 8 carbon atoms (for example, methylene, ethylene, propylene) or a cycloalkylene group having 5 to 10 carbon atoms (for example, 1,2-cyclohexyl). Shiren). W ₂ represents an alkylene group or -CO-. The alkylene group represented by W ₂ has the same meaning as the alkylene group represented by W ₁ . The alkylene groups represented by W ₁ and W ₂ may be the same or different from each other, or may have a substituent. As the substituent, those exemplified as the substituent of R ₁ can be applied, and preferably an alkyl group, a hydroxy group or a carboxy group. W ₁ and W ₂ are more preferably an alkylene group having 1 to 3 carbon atoms, and particularly preferably a methylene group or an ethylene group. Z is a single bond, -O-, -S-, -C
_{O -, - N (R W} ) - represents a. R _W represents a hydrogen atom or an optionally substituted alkyl group. As the substituent, those exemplified as the substituent of R ₁ can be applied, but preferably,
It is a carboxy group, a phosphono group, a sulfo group, a hydroxy group or an amino group. Z is preferably a single bond.
n is preferably 1 or 2, more preferably 1
It is. Specific examples of the linking group represented by W include, for example, the following.

[0015]

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Examples of the cation represented by M ₁ , M ₂ , M ₃ and M ₄ include alkali metals (eg, lithium, sodium, potassium), ammonium (eg, ammonium, tetraethylammonium) and pyridinium. it can.

In the present invention, specific examples of the compound represented by the above general formula (I) are shown below, but the present invention is not limited thereto.

[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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In the compounds of the general formula (I), I-1 and I-
Compounds of 2, I-3, I-15, I-16 and I-17 are particularly preferred. The compounds represented by the general formula (I) of the present invention are disclosed in JP-A-63-199295 and JP-A-3-17-17.
It can be synthesized according to the description in, for example, 3857 gazette. As described in these documents, the compounds represented by the general formula (I) of the present invention include optical isomers ([R, R], [S, S], [S, R] , [R, S])
Exists. For example, three optical isomers ([R, R], [S, S] and [S, R]) are present in the exemplary compound (I-1) of the compound represented by the general formula (I) of the present invention. And they can be synthesized individually or as a mixture. It goes without saying that the present invention includes these individual optical isomers and mixtures thereof. In the present invention, a compound synthesized from an L-form amino acid such as [S, S] -form as a raw material is more preferable than other optical isomers. These compounds are from Springer and Copekka's Chem. Z.
vesti., 20 (6): 414-422 (1966) and JP-A-3-173857.

The iron (III) complex salt of the compound represented by the general formula (I) of the present invention can be prepared by mixing a trivalent iron ion with the compound of the general formula (I). Of course, you may isolate and use as an iron (III) complex salt. In this case, it can be isolated, for example, as an ammonium salt, a sodium salt, or a potassium salt. The amount of the iron (III) complex salt of the compound represented by the general formula (I) of the present invention is as follows:
0.02 mol per liter of processing solution having bleaching ability
1.0 mol, preferably about 0.04 mol to about 0.5 mol. Such an amount effectively acts as a bleaching agent. Also, besides the iron (III) complex, the free form is 10 to 20
It is preferable to make it exist by about% in excess.

The desilvering step of the present invention is carried out by a combination of a bleaching step, a fixing step, and a bleach-fixing step, representative examples of which are shown below. Bleaching-Fixing Bleaching-Bleaching-Fixing Bleaching-Bleaching-Fixing Bleaching-Washing-Fixing Bleaching-Fixing Fixing-Bleaching-Fixing Particularly preferred in the present invention.

Hereinafter, a processing solution having a bleaching ability in the desilvering step (generically referring to a bleaching solution or a bleach-fixing solution) will be described. As the bleaching agent used in the processing solution having bleaching ability, in addition to the bleaching agent of the present invention (a ferric complex salt of the compound of the general formula (I)), the following compounds Fe (II)
I), Co (III) or Mn (III) chelating bleaches or persulfates (eg peroxodisulfate);
Hydrogen peroxide, bromate and the like can be used in combination. Compounds that form the chelating bleach include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N- (β-oxyethyl) -N, N ′, N′-triacetic acid, 1,2-diaminopropanetetraacetic acid, 1,3-diaminopropanetetraacetic acid, nitrilotriacetic acid, nitrilo-N-2
-Carboxy-N, N-diacetic acid, N- (2-acetamido) iminodiacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, dihydroxyethylglycine, ethyletherdiaminetetraacetic acid, glycoletherdiaminetetraacetic acid, ethylenediaminetetrapropionic acid , Phenylenediaminetetraacetic acid, 1,3-diaminopropanol-N,
N, N ', N'-tetramethylenephosphonic acid, ethylenediamine-N, N, N', N'-tetramethylenephosphonic acid,
Examples thereof include 1,3-propylenediamine-N, N, N ', N'-tetramethylenephosphonic acid and their sodium and ammonium salts. Of the above, 1,3-
Diaminopropanetetraacetic acid, nitrilo-N-2-carboxy-N, N-diacetic acid, N- (2-acetamido) iminodiacetic acid are particularly preferred.

It is preferable to add a halide such as chloride, bromide and iodide as a rehalogenating agent for accelerating the oxidation of silver to the processing solution having bleaching ability. Further, an organic ligand which forms a sparingly soluble silver salt may be added instead of the halide. The halide is added as an alkali metal salt or ammonium salt, or a salt such as guanidine or amine. Specific examples include potassium bromide, sodium bromide, ammonium bromide, potassium chloride, guanidine hydrochloride, and the like, and preferably potassium bromide or sodium bromide. The amount of rehalogenating agent in the bleaching solution is 2
A mole / liter or less is appropriate. It is preferably from 0.01 to 2.0 mol / liter, more preferably from 0.1 to 1.
7 mol / l. The bleach-fixing solution contains a fixing agent (described later), and may further contain all other compounds contained in the fixing solution described later. If necessary, the rehalogenating agent may be contained. When the rehalogenating agent is used in the bleach-fix solution, the amount is 0.001 to 2.
0 mol / l, preferably 0.001 to 1.0 mol / l.

The bleaching solution or bleach-fixing solution according to the present invention further comprises a bleaching accelerator, a corrosion inhibitor for preventing the corrosion of the processing bath, a buffer for maintaining the pH of the solution, a fluorescent whitening agent, an antifoaming agent and the like. It is added as needed. Examples of the bleaching accelerator include, for example, US Pat. No. 3,893,858, German Patent 1,290,812, and US Pat. No. 1,138,8.
No. 42, JP-A-53-95630, and compounds having a mercapto group or disulfide group described in Research Disclosure No. 17129 (1978), thiazolidine derivatives described in JP-A-50-140129, U.S. Pat. Thiourea derivatives, polyethylene oxides described in German Patent 2,748,430, polyamine compounds described in JP-B-45-8836, and imidazole compounds described in JP-A-49-40493. Etc. can be used. Among them, the mercapto compounds described in U.S. Pat. No. 1,138,842 are preferred. As the corrosion inhibitor, a nitrate is preferably used, and ammonium nitrate, sodium nitrate, potassium nitrate and the like are used. The addition amount is 0.01 to 2.0 mol / l, preferably 0.1 to 2.0 mol / l.
05 to 0.5 mol / l. In the bleaching solution or the bleach-fixing solution according to the present invention, the total ammonium ion concentration is preferably not more than 0.3 g ion / liter. This embodiment is preferable from the viewpoint of image storability and environmental preservation, and in the present invention, it is more preferably 0.1 mol / liter or less.

The pH of the bleaching solution according to the present invention is from 3.0 to 5.
0 . When performing after color development immediately Bleaching is suppressed bleaching fog also unstable metal chelate according to the present invention
In order not to do so, a pH of 3.0 to 5.0 is preferable. For this purpose, any pH buffering agent can be used as long as it is not easily oxidized by the bleaching agent and has a buffering action in the above pH range. For example, organic acids such as acetic acid, glycolic acid, lactic acid, propionic acid, butyric acid, malic acid, chloroacetic acid, levulinic acid, ureidopropionic acid, pyridine, dimethylpyrazole, 2-methyl-o
-Organic bases such as oxazoline and aminoacetonitrile. These buffers may be used in combination of two or more. In the present invention, an organic acid having a pKa of 2.0 to 5.5 is preferred, and acetic acid and glycolic acid alone or in combination are particularly preferred. The total amount of these buffers used is suitably 3.0 mol or less, preferably 0.5 to 2.0 mol, per liter of processing solution having bleaching ability. To adjust the pH of the processing solution having bleaching ability to the above range, the acid and the alkali agent (for example, aqueous ammonia,
KOH, NaOH, imidazole, monoethanolamine, diethanolamine) may be used in combination. Among them, KOH is preferred.

The bleaching or bleach-fixing step is carried out at 30 ° C. to 6 ° C.
Although it can be performed in a temperature range of 0 ° C, preferably 35 ° C to 50 ° C
It is. The bleaching and / or bleach-fixing process time is 1
It is used in a range of 0 second to 2 minutes, preferably 10 seconds to 1 minute. More preferably, it is 15 seconds to 45 seconds. Under these preferred processing conditions, good results are obtained which are fast and without stain increase.

A thiosulfate is used for the fixing solution. For example <br/> If, ammonium thiosulfate, sodium thiosulfate, potassium thiosulfate, and thiosulfate guanidine down like. Of these, thiosulfates, particularly ammonium thiosulfate, are preferred for quick fixing. Furthermore, by using two or more types of fixing agents in combination, it is possible to perform quicker fixing.
For example, in addition to ammonium thiosulfate, ammonium Ji Ossian acid, imidazole, thiourea, also preferably used in combination thioether, in this case, the second fixing agent in the range of 0.01 to 100 mol% relative ammonium thiosulfate It is preferred to add. The amount of the fixing agent is 0.1 to 0.3 mol, preferably 0.5 to 2.0 mol, per liter of the bleach-fixing solution or the fixing solution. The pH of the fixer is
6.5 to 8.0 are preferable in order to obtain stable fixing performance.

A preservative is added to the bleach-fixing solution or the fixing solution,
The temporal stability of the liquid can also be improved. In the case of a bleach-fixing solution or a fixing solution containing a thiosulfate, a sulfite and / or a bisulfite adduct of hydroxylamine, hydrazine or aldehyde (for example, a bisulfite adduct of acetaldehyde, particularly preferably Is effective to use an aromatic aldehyde bisulfite adduct described in JP-A-1-298935. Also, Japanese Patent Application Laid-Open No. 62-14304
It is also preferable to use the sulfinic acid compound described in No. 8.
It is also preferable to add a buffer to the bleach-fixing solution or the fixing solution in order to keep the pH of the solution constant. For example, phosphates or imidazoles such as imidazole, 1-methyl-imidazole, 2-methyl-imidazole, 1-ethyl-imidazole, triethanolamine,
N-allylmorpholine, N-benzoylpiperazine and the like can be mentioned. Further, in the fixing solution, by adding various chelating agents, iron ions brought in from the bleaching solution can be concealed and the stability of the solution can be improved. Such preferred chelating agents include 1-hydroxyethylidene-
1,1-diphosphonic acid, ethylenediamine-N, N,
N ', N'-tetramethylenephosphonic acid, nitrilotrimethylenephosphonic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,2-propanediaminetetraacetic acid and the like. The fixing step can be performed at a temperature in the range of 30 ° C to 60 ° C, preferably 35 ° C to 50 ° C. The time of the fixing process is 5 seconds to 2 minutes, preferably 10 seconds to 1 minute and 40 seconds, and more preferably 10 seconds to 45 seconds.

When the stabilizing step is performed after the desilvering step in the present invention, the stabilizing step may be performed after the washing step, or the stabilizing step according to the present invention may be performed without substantial washing. Can also be performed. Tap water can be used as the water used in the water washing treatment step, but water deionized by ion exchange resin or the like to a Ca or Mg ion concentration of 5 mg / liter or less, water sterilized by halogen, an ultraviolet germicidal lamp, or the like. It is preferred to use In addition, tap water may be used as water for correcting the amount of evaporation of each processing solution, but it is preferable to use deionized water or sterilized water which is preferably used in the above-mentioned washing step.

The washing water and the stabilizing solution of the present invention preferably contain various surfactants in order to prevent unevenness of water droplets when the processed photosensitive material is dried. These surfactants include polyethylene glycol type nonionic surfactant, polyhydric alcohol type nonionic surfactant, alkylbenzene sulfonate type anionic surfactant, higher alcohol sulfate ester type anionic surfactant Agent, alkyl naphthalene sulfonate type anionic surfactant, quaternary ammonium salt type cationic surfactant, amine salt type cationic surfactant, amino salt type amphoteric surfactant, betaine type amphoteric surfactant However, it is preferable to use a nonionic surfactant, and an alkylphenol ethylene oxide adduct is particularly preferable. Octyl, nonyl, dodecyl, and dinonylphenol are particularly preferred as the alkylphenol, and the number of moles of ethylene oxide added is particularly preferably 8 to 14. It is also preferable to use a silicon surfactant having a high defoaming effect.

The washing water and the stabilizing solution of the present invention preferably contain various antibacterial agents and antifungal agents in order to prevent generation of water rust and mold generated on the photosensitive material after processing. . Examples of these antibacterial agents and antifungal agents are described in JP-A-57-157244 and JP-A-58-105.
No. 145, thiazolyl benzimidazole compounds, isothiazolone compounds as disclosed in JP-A-57-8542, chlorophenol compounds represented by trichlorophenol, bromophenol compounds, organic compounds Tin, organic zinc compounds, acid amide compounds, diazine and triazine compounds, thiourea compounds, benzotriazole compounds, alkylguanidine compounds, quaternary ammonium salts such as benzammonium chloride, and penicillins. Such as antibiotics, journal Antibacterial
And Antifungus Agent (J. Antib
act. Antifung.Agents), Vol.1, No.5, p.207-223 (1
983). These may be used in combination of two or more. Also, JP-A-48-8382
Various fungicides described in No. 0 can also be used.

It is preferable that the washing water and the stabilizer of the present invention contain various chelating agents. Preferred chelating agents include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N, N
-Trimethylene phosphonic acid, diethylene triamine-
Organic phosphonic acids such as N, N, N ', N'-tetramethylenephosphonic acid or EP 345,172A
The hydrolyzate of the maleic anhydride polymer described in No. 1 can be used.

The stabilizer of the present invention may further contain, if necessary, an ammonium compound such as ammonium chloride or ammonium sulfite, a metal compound such as Bi or Al, a fluorescent whitening agent, a hardening agent, US Pat. It is also preferable to include an alkanolamine described in No. 583 or a preservative that can be contained in the above-mentioned fixing solution or bleach-fixing solution.
Of these, sulfinic acid compounds (for example, benzenesulfinic acid, toluenesulfinic acid, and salts thereof such as sodium and potassium) described in JP-A-1-231051 are preferred. 1 × 10 ⁻⁵ to 1 × 10 ⁻³ mol per 1 mol, particularly 3 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol per mol.
The pH of the stabilizer is usually in the range of 4 to 10, but preferably 6 to 9. The processing temperature of the stabilizer is 3
0-45 ° C is preferred. Further, when the processing time is short, the effect of the present invention becomes remarkable and 10 seconds to 2 minutes, particularly 10 seconds.
~ 60 seconds is preferred. Further, the effect is most remarkable in 10 seconds to 25 seconds, which is preferable, and processing can be performed in a short time without deteriorating image storability.

The color developing agent used in the color developing solution in the color developing step may be any known aromatic primary amine developing agent. Representative examples of the color developing agent are shown below, but are not limited thereto. P-1 N, N-diethyl-p-phenylenediamine P-2 2-amino-5- (N, N-diethylamino)
Toluene P-3 2-Amino-5- (N-ethyl-N-laurylamino) toluene P-4 4-Amino-3-methyl-N-ethyl-N-
[Β- (methanesulfonamido) ethyl] aniline P-5 N- (2-amino-5-N, N-diethylaminophenylethyl) methanesulfonamide P-6 N, N-dimethyl-p-phenylenediamine P-7 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline P-8 4-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline P-9 4-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline P-10 4-amino-3-methyl-N-ethyl-N-
(2-hydroxyethyl) -aniline

Among the above-mentioned p-phenylenediamine derivatives, particularly preferred are compounds P-4 and P-10.
These p-phenylenediamine derivatives are generally used as salts such as sulfates, hydrochlorides, sulfites, p-toluenesulfonates, nitrates, and naphthalene-1,5-disulfonates. . The amount of the color developing agent is preferably from about 0.003 mol to 1 liter of the color developing solution.
About 0.1 mol, more preferably 0.01 mol to 0.05
Is a mole.

If necessary, a sulfite such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, or a carbonyl sulfite adduct may be used as a preservative in the color developing solution. Although it can be added, the concentration of the sulfite compound is preferably smaller in the present invention, and the preferable addition amount thereof is 0.005 mol or less, more preferably 0.001 mol or less per liter of the color developing solution. ,
It may not be included at all. Carbonyl bisulfite adducts are preferred because they can substantially reduce the concentration of sulfite or bisulfite compounds. Also in this case, it is preferable to control the concentration of sulfurous acid or bisulfite, which is advantageous, within the above range. Further, as compounds for directly preserving the aromatic primary amine color developing agent, various hydroxylamines described in JP-A-63-5341 and JP-A-63-106655 (among others having a sulfo group or a carboxy group). Compounds are preferred.), Hydroxamic acids described in JP-A-63-43138, hydrazines and hydrazides described in JP-A-63-146041, phenols described in JP-A-63-44657 and JP-A-63-58443, Id 63-
Examples thereof include α-hydroxyketones and α-aminoketones described in No. 44656, and various saccharides described in 63-36244. Further, in combination with the above compounds, JP-A-63-4235, JP-A-63-24254,
No. 63-21647, No. 63-146040, No. 6
Monoamines described in JP-A-3-27841 and JP-A-63-25654, JP-A-63-30845, JP-A-63-14
Nos. 6040, 63-43139, polyamines described in 63-21647, 63-26655 and 63-44555, 63
Nitroxyl radicals described in JP-A-53551, 63
Alcohols described in -43140 and 63-53549, oximes described in 63-56654 and tertiary amines described in 63-239647 can be used. Other preservatives are disclosed in
Various metals described in Nos. 44148 and 57-53749, salicylic acids described in 59-180588, alkanolamines described in 54-3582, and polyethyleneimines described in 56-94349. And an aromatic polyhydroxy compound described in U.S. Pat. No. 3,746,544, if necessary.
Particularly, addition of an aromatic polyhydroxy compound is preferred.

The color developing solution used in the present invention preferably has a pH of 9 to 12, more preferably 9 to 11.0. In order to maintain the above pH, it is preferable to use various buffers. Specific examples of the buffer include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, Sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), 5-sulfo-2
Potassium-hydroxybenzoate (potassium 5-sulfosalicylate); The amount of the buffer added is preferably 0.1 mol or more per liter of the color developing solution, and particularly preferably 0.1 to 0.4 mol.

In addition, it is preferable to use various chelating agents in the color developing solution as an agent for preventing precipitation of calcium and magnesium or for improving the stability of the color developing solution. Organic acid compounds are preferred as the chelating agent,
Examples include aminopolycarboxylic acids, organic phosphonic acids, and phosphonocarboxylic acids. Representative examples of these are diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid,
Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diaminetetraacetic acid,
Ethylenediamine orthohydroxyphenylacetic acid, 2-
Phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N '
-Bis (2-hydroxybenzyl) ethylenediamine-
N, N'-diacetic acid and the like can be mentioned. These chelating agents may be used in combination of two or more as necessary. The chelating agent may be added in an amount sufficient to block metal ions in the color developing solution, for example, about 0.1 g to 10 g per liter of the color developing solution.

An optional development accelerator can be added to the color developer if necessary. However, it is preferable that the color developing solution of the present invention does not substantially contain benzyl alcohol from the viewpoints of pollution, liquid preparation and prevention of color contamination. Here, "substantially" means that the color developer contains no more than 2 ml, preferably no color developer per liter. Other development accelerators are described in
No. 16088, No. 37-5987, No. 38-7826
And thioether compounds described in U.S. Pat. No. 3,818,247, JP-A-52-49829 and JP-A-50-1515.
No. 554, p-phenylenediamine compounds described in JP-A-50-137726, JP-B-44-30074.
And JP-A-56-156826 and JP-A-52-43429.
Quaternary ammonium salts described in US Pat.
94,903, 3,128,182, 4,23
Nos. 0,796 and 3,253,919,
No. 11431, U.S. Pat. Nos. 2,482,546, 2,596,926, and 3,582,346, and the like.
No. 2-25201, U.S. Pat. No. 3,128,183,
Polyalkylene oxides described in JP-B-41-11431, JP-B-42-23883, U.S. Pat. be able to. The addition amount of the development accelerator is about 0.01 g to 5 g per liter of the color developing solution.

In the present invention, if necessary,
Optional antifoggants can be added. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-
Nitrogen-containing compounds such as nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine Heterocyclic compounds can be mentioned as typical examples. The amount of the antifoggant added is about 0.001 g to 1 g per liter of the color developing solution. The color developer used in the present invention may contain a fluorescent whitening agent. As the fluorescent whitening agent, a 4,4'-diamino-2,2'-disulfostilbene compound is preferable. The amount of the fluorescent whitening agent is from 0 to 5 g, preferably from 0.1 g to 4 g, per liter of the color developing solution. Further, various surfactants such as alkylsulfonic acid, arylsulfonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added as necessary.

The processing temperature in the color developing solution is suitably from 20 to 50 ° C, preferably from 30 to 45 ° C. The processing time is suitably from 20 seconds to 4 minutes, preferably from 20 seconds to 2 minutes, and more preferably from 20 seconds to 1 minute. In the present invention, in order to speed up the processing, it is preferable to provide an alkaline processing bath (hereinafter referred to as a pre-development bath) before the color developing step. In this case, the pre-development bath may contain a compound that can be contained in all color developing solutions other than the color developing agent. The processing time of the pre-development bath is preferably 10 to 60 seconds, more preferably 10 to 30 seconds.

The processing method of the present invention can be preferably used for color reversal processing. In the reversal process, after the black and white development, the reversal process is performed as necessary, and then the color development is performed. The black-and-white developing solution used at this time is a so-called black first developing solution which is generally used in a reversal process of a color photosensitive material, and is a black-and-white developing solution used in a processing solution of a black-and-white silver halide photosensitive material. Various well-known additives used in addition to the liquid can be contained. Typical additives include developing agents such as 1-phenyl-3-pyrazolidone, methol and hydroquinone, preservatives such as sulfites, accelerators such as sodium hydroxide, sodium carbonate and potassium carbonate. And inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole and methylbenzthiazole, water softeners such as polyphosphates, and development inhibitors consisting of trace amounts of iodides and mercapto compounds. Can be.

The processing method of the present invention is used when performing continuous processing using an automatic developing machine. The replenisher for each processing solution compensates for the consumption and deterioration of the processing solution components due to the processing of the photosensitive material and the aging in the automatic processor, and also suppresses the accumulation of undesired components eluted from the photosensitive material in the processing solution. In order to maintain the performance at a constant level, it is preferable to add it according to the amount of the processed photographic material. Therefore, the compound for compensating for the consumption and deterioration of the processing solution components due to the processing of the photosensitive material and the aging in the automatic developing machine has a higher concentration than the tank solution, and the processing solution of the undesired components eluted from the photosensitive material into the processing solution. The compound that suppresses accumulation has a lower concentration than the tank liquid. Further, each processing step may be provided with two or more processing baths, and in that case, it is preferable to adopt a countercurrent system in which the replenisher is poured from the rear bath to the front bath. In particular, a cascade of two to four stages is preferably used in the washing step and the stabilizing step. Further, the color developing bath may be divided into two or more baths as necessary, and a color developing replenisher may be replenished from the first or last bath to shorten the developing time and further reduce the replenishing amount. Further, Japanese Patent Application Laid-Open No. 2-675
Using a processing tank having a small cross-sectional area in the form of a slit as described in No. 56, replenish from the side near the post-bath and replenish from the opposite side so that the developer flows in the direction opposite to the direction of travel of the photosensitive material. The overflow method is also preferable. Conversely, replenishment may be performed so that the developing solution flows in the same direction as the direction of travel of the photosensitive material. The replenishment amount of each processing solution is preferably reduced as long as the composition change in each processing solution does not cause photographic performance problems or inconvenience of contamination of other solutions.

The color developing replenisher contains compounds contained in the color developing solution. Compounds for compensating for the consumption and deterioration of the processing solution components due to the processing of the photosensitive material and the aging in the automatic developing machine are color developing agents and preservatives. Includes twice the amount. Compounds that suppress the accumulation of undesirable components eluted from the light-sensitive material in the processing solution are development inhibitors represented by halides (for example, potassium bromide). 0.6 times. The concentration of the halide in the replenisher is usually 0.006 mol / l or less, but the lower the replenishment, the lower the concentration needs to be. Compounds that hardly change in concentration due to processing or aging are usually contained at approximately the same concentration as the color developing tank solution. Examples of this are chelating agents and buffers. Further, the pH of the color developing replenisher is set higher than the tank liquid by about 0.1 to 1.0 in order to prevent the pH of the tank liquid from decreasing due to the processing. This difference in pH also needs to increase with decreasing replenishment.

The replenishment amount of the color developing solution is 3000 ml or less per 1 m ² of the light-sensitive material, and is preferably 50 to 600 ml, more preferably 50 to 300 ml. The replenishment amount of the bleaching solution is 20 to 90 per m ² of the light-sensitive material.
0 ml, preferably 50-550 ml, more preferably 50-250 ml. The replenishment amount of the bleach-fixing solution is ^{20 to} 1500 ml, preferably 30 to 6 ml per m ² of the light-sensitive material.
00 ml, more preferably 50-200 ml.
The bleach-fixing solution may be replenished as a single solution, or may be separately replenished as a bleaching composition and a fixing composition, or may be mixed with an overflow solution from a bleaching bath and / or a fixing bath. And may be used as a bleach-fix replenisher. The replenishment amount of the fixing solution is ^{20 to} 1500 m per 1 m ² of the photosensitive material.
l, preferably 30-600 ml, more preferably 50-200 ml. The replenishment amount of the washing water and the stabilizing solution is preferably from 200 to 1500 ml, more preferably from 300 to 600 ml, per m ^{2 of the} photographic material to be processed. The water washing step and the stabilization step are preferably performed in a multi-stage countercurrent system, and the number of stages is preferably two to four. The replenishment amount is 1 to 50 times, preferably 2 to 30 times, more preferably 2 to 15 times the amount brought in from the previous bath per unit area.

It is preferable to use a method in which the overflow liquid in the washing step or the stabilization step is flowed into a bath having a fixing ability, which is a pre-bath, since the amount of waste liquid can be reduced.

When processing with an automatic developing machine using the above black-and-white developer or color developing solution, the area (opening area) where the developing solution (color developing solution and black-and-white developing solution) comes into contact with air should be as small as possible. preferable. For example, opening area (cm ² )
Is divided by the volume of the developing solution (cm ³ ), and the opening ratio is preferably 0.01 (cm ⁻¹ ) or less.
005 or less is more preferable.

In order to further reduce the amount of the replenisher for environmental protection, it is preferable to use a combination of various regeneration methods. Regeneration may be performed while circulating the processing solution in the automatic developing machine, or after once removing it from the processing tank, subjecting it to an appropriate regeneration processing, and then returning it to the processing tank again as a replenisher. Is also good. In particular, the developer can be regenerated and used. Regeneration of the developing solution means that the used developing solution is subjected to anion exchange resin or electrodialysis, or the activity of the developing solution is increased by adding a processing chemical called a regenerating agent, and used again as a processing solution. . In this case, the regeneration rate (the ratio of the overflow solution in the replenisher)
Is preferably 50% or more, particularly preferably 70% or more. In the process using the developer regeneration, the overflow of the developer is regenerated and then used as a replenisher. As a regeneration method, it is preferable to use an anion exchange resin. Particularly preferred examples of the composition of the anion exchange resin and the method for regenerating the resin include those described in Diaion Manual (I) (14th edition, 1986) issued by Mitsubishi Kasei Kogyo. Further, among the anion exchange resins, resins having the composition described in JP-A-2-952 and JP-A-1-281152 are preferable.

The metal chelate bleach in the bleaching solution and / or the bleach-fixing solution is reduced in accordance with the bleaching process. It is preferably taken. In particular,
It is preferable that air is blown into the bleaching solution and / or the bleach-fixing solution by an air pump, and the metal chelate in a reduced state is re-oxidized with oxygen, so-called aeration. In addition, regeneration can be performed by adding an oxidizing agent such as hydrogen peroxide, persulfate, or bromate. The regeneration of the fixing solution and the bleach-fixing solution is carried out by electrolytic reduction of accumulated silver ions. In addition, it is also preferable to remove the accumulated halogen ions with an anion exchange resin in order to maintain the fixing performance. In order to reduce the amount of washing water used, ion exchange or ultrafiltration is used, and it is particularly preferable to use ultrafiltration.

In the present invention, a processing solution having a fixing ability can be subjected to silver recovery by a known method, and a regenerating solution subjected to such silver recovery can be used. Examples of the silver recovery method include an electrolysis method (described in French Patent No. 2,299,667), a precipitation method (described in JP-A-52-73037, and German Patent No. 2,331,220), and an ion exchange method. (JP-A-51-17114, German Patent No. 2,548,237) and a metal substitution method (UK Patent No. 1,353,805).
No.) is effective. These silver recovery methods are preferably performed in-line from the tank liquid because the rapid processing suitability is further improved.

The processing method of the present invention is performed using an automatic developing machine. The automatic developing machine preferred for the present invention is described below. In the present invention, in order to perform processing quickly, the air time when the photosensitive material moves between processing solutions, that is, the crossover time is preferably as short as possible, preferably 10 seconds or less, more preferably 7 seconds or less, More preferably, it is 5 seconds or less. In order to achieve the above-mentioned short-time crossover, the present invention preferably employs a cine-type automatic developing machine, and particularly preferably employs a leader transport system. Such a system is developed by Fuji Photo Film Co., Ltd. automatic developing machine FP-56.
0B. The linear velocity of conveyance is preferably higher, but is generally 30 cm to 2 m per minute, preferably 50 cm to 1.5 m. JP-A-60-191257, 6
No. 0-191258 and No. 60-191259 are preferable. Particularly, as a conveying mechanism,
It is preferable to adopt each system described in JP-A-3-126944, JP-A-3-127061, and JP-A-3-127062. Further, in order to shorten the crossover time and prevent the mixing of the processing solution, the crossover rack preferably has a mixing prevention plate described in JP-A-3-126943.

In the present invention, it is preferable that the agitation of each processing solution is as strong as possible in order to more effectively exert the effects of the present invention. Specific methods of strengthening the stirring are described in JP-A-62-183460 and JP-A-62-183.
No. 461, namely, a color negative film processor FP-56 manufactured by Fuji Photo Film Co., Ltd.
A method in which a jet of a processing solution impinges on the emulsion surface of a light-sensitive material, such as that employed in OB 0B, a method of increasing the stirring effect by using a rotating means disclosed in Japanese Patent Application Laid-Open No. 62-183461, and a method provided in the solution. A method of moving the photosensitive material (film) while bringing the wiper blade into contact with the emulsion surface to turbulence the emulsion surface to improve the stirring effect, and a method of increasing the circulation flow rate of the entire processing solution. Of these, the method of colliding the jet of the processing liquid is most preferable, and it is preferable that all the processing tanks adopt this method. In particular, when processing with a processing solution having a fixing ability, the effect of the present invention is greatly improved by causing a jet to collide within 15 seconds after the photosensitive material comes into contact with the processing solution having the fixing ability. More preferably 1
It is within 0 seconds, more preferably within 5 seconds.

The method of jet collision in each processing solution is described more specifically in the emulsion surface described in Examples of the Invention in JP-A-62-183460, page 3, lower right column to page 4, lower right column. It is preferable to discharge a liquid pumped by a pump from a nozzle provided opposite to the nozzle. As a pump, Iwaki's magnet pump MD-10, MD-15, MD-
20 etc. can be used. The hole diameter of the nozzle is 0.5 to 2 mm, preferably 0.8 to 1.5 mm. Further, the nozzle is preferably opened in a direction perpendicular to the chamber plate surface and the film surface as much as possible, and in a circular shape.
The shape may be a rectangle or a slit. The number of nozzles is 1 to 50, preferably 10 to 30, per liter of tank capacity. In addition, if the jet is applied to a part of the film, unevenness in development or residual color occurs,
It is preferable that the nozzle positions are sequentially shifted so that the nozzles are not located on the same place, and are not on a straight line parallel to the transport direction. The preferred arrangement of the nozzles is such that about 4 to 8 rows of holes are perpendicular to the conveying direction, and the positions are gradually changed at appropriate intervals. If the distance from the nozzle to the film is too short, the above-mentioned unevenness is likely to occur, and if it is too far, the stirring effect is weakened, so it is preferably 1 to 12 mm, more preferably 3 to 9 mm. Similarly, the flow rate of the liquid discharged from each nozzle has an optimum range, preferably 0.5 to 5 m / sec, particularly preferably 1 to 3 m / sec. Circulation of the entire processing liquid may be performed only through the nozzle, or a separate circulation system may be provided. The total circulation flow rate is 0.2 to 5 liters, preferably 0.5 to 4 liters per minute per liter of tank capacity in each processing tank. It is better that the circulation flow rate is relatively high, and a preferable range is 1.5 to 4 liters.

The automatic developing machine used in the processing of the present invention preferably has an apparatus for aeration of the bleaching solution. By aeration, it is possible to prevent a decrease in bleaching speed due to the formation of a divalent iron complex during continuous processing and the formation of a cyan leuco dye called poor color reversion. Aeration is described in JP-A-2-176746 and 2-17.
As described in No. 6747, it is preferable to supply a flow rate of 0.01 liter or more per liter of the processing tank by using a porous nozzle having a pore diameter of 300 μm or less. Processing the photosensitive material continuously or intermittently while replenishing the replenisher is called running processing.Bleach during the running processing is extremely foamed by the surfactant eluted from the processed photosensitive material. It will be easier. Therefore, when aeration is performed, a very large number of bubbles are generated and may overflow from the processing tank. In order to prevent this, it is preferable to provide defoaming means.
No. 1, 2-165367 and 2-165368 are effective.

It is preferable to perform so-called evaporation correction, in which water corresponding to the amount of evaporation of the processing liquid is supplied to each processing liquid in the present invention. Particularly, it is preferable in a color developing solution, a bleaching solution or a bleach-fixing solution. The specific method for replenishing such water is not particularly limited. Among them, a monitor water tank different from the bleaching tank described in JP-A Nos. 1-254959 and 1-254960 is installed. The amount of evaporation of water in the inside is obtained, the amount of evaporation of water in the bleaching tank is calculated from the amount of evaporation of water, and a method of replenishing water to the bleaching tank in proportion to the amount of evaporation is disclosed in Japanese Patent Application No. 2-46743. 2-4
No. 7777, No. 2-47778, No. 2-47779
And an evaporation correction method using a liquid level sensor or an overflow sensor described in JP-A-2-117972. The most preferable evaporation correction method is to predict and add water corresponding to the amount of evaporation. As described in Japanese Patent Application No. 2-103894, information on the operation time, stop time, and temperature control time of the automatic developing machine is provided. Is added by the amount of water calculated by a coefficient obtained in advance based on the above.

It is also necessary to take measures to reduce the amount of evaporation, and it is necessary to reduce the opening area and adjust the air volume of the exhaust fan. For example, the preferable aperture ratio of the color developing solution is as described above, but it is preferable to similarly reduce the opening area in other processing solutions. The exhaust fan is installed to prevent condensation during temperature control.
Preferred emissions, per minute 0.1 m ³ to 1 m ^3, a particularly preferred displacement volume, 0.2 m ³ to 0.4
m is ^3. The drying conditions of the photosensitive material also affect the evaporation of the processing liquid. As the drying method, it is preferable to use a ceramic hot air heater, and the supply air volume is 4 m ^{3 /} min.
To 20 m ³ are preferred, particularly 6 m ³ through 10m ³ preferred. The thermostat for preventing heating of the ceramic hot air heater is preferably operated by heat transfer, and the mounting position is preferably mounted on the leeward or upwind side through a radiation fin or a heat transfer portion. The drying temperature is preferably adjusted according to the water content of the photosensitive material to be processed.
The optimum temperature is 45 to 55 ° C for a film having a width and 55 to 65 ° C for a brownie film. The drying time is preferably 30 seconds to 2 minutes, more preferably 40 seconds to 80 seconds. A replenishing pump is used for replenishing the processing solution, and a bellows type replenishing pump is preferable. Further, as a method of improving the replenishment accuracy, it is effective to reduce the diameter of the liquid feeding tube to the replenishment nozzle in order to prevent backflow when the pump is stopped. A preferred inner diameter is 1 to 8 mm, and a particularly preferred inner diameter is 2 to 5 mm.

Although various component materials are used in the automatic developing machine, preferred materials are described below. The tank material such as the treatment tank and the temperature control tank is preferably a modified PPO (modified polyphenylene oxide) or a modified PPE (modified polyphenylene ether) resin. The modified PPO includes "Noryl" manufactured by Nippon GE Plastics Co., Ltd., and the modified PPE includes "Zylon" manufactured by Asahi Kasei Kogyo Co., Ltd. and "Iupiece" manufactured by Mitsubishi Gas Chemical. In addition, these materials are suitable for parts that may come into contact with the processing liquid, such as processing racks and crossovers. As a material of the roller of the processing section, a resin such as PVC (polyvinyl chloride), PP (polypropylene), PE (polyethylene), and TPX (polymethylpentene) is suitable. These materials can also be used for other treatment liquid contact parts. Incidentally, PE resin is also preferable for the material of the replenishment tank formed by blow molding. Materials for processing parts, gears, sprockets, bearings, etc. include PA (polyamide), PBT (polybutylene terephthalate), UH
Resins such as MPE (ultra high molecular weight polyethylene), PPS (polyphenylene sulfide), and LCP (fully aromatic polyester resin, liquid crystal polymer) are suitable. The PA resin is a polyamide resin such as 66 nylon, 12 nylon, 6 nylon, and the like, and a resin containing glass fiber, carbon fiber, or the like is strong against swelling due to the treatment liquid and can be used.
Also, high molecular weight products such as MC nylon and compression molded products can be used without fiber reinforcement. As the UHMPE resin, an unreinforced product is suitable, and “Lyubuma” and “HiZEX Million” manufactured by Mitsui Petrochemical Co., Ltd., “New Light” manufactured by Sakushin Kogyo Co., Ltd., and “Sun Fine” manufactured by Asahi Kasei Kogyo Co., Ltd. Are suitable. The molecular weight is preferably 1,000,000 or more, more preferably 1,000,000 to 5,000,000. The PPS resin is preferably glass fiber or carbon fiber reinforced. The LCP resin includes “Victrex” manufactured by ICI Japan Co., Ltd., “Econol” manufactured by Sumitomo Chemical Co., Ltd., “Zyder” manufactured by Nippon Oil Co., Ltd., and “Vectra” manufactured by Polyplastics Co., Ltd. Particularly, as the material of the conveyor belt, an ultra-high-strength polyethylene fiber or polyvinylidene fluoride resin described in Japanese Patent Application No. 2-276886 is preferable. As a soft material such as a squeeze roller, a foamed vinyl chloride resin, a foamed silicone resin, and a foamed urethane resin are suitable. Examples of the urethane foam resin include “Rubicel” manufactured by Toyo Polymer Co., Ltd. As a rubber material such as a pipe joint, an agitation jet pipe joint, or a sealing material, EPDM rubber, silicon rubber, viton rubber, or the like is preferable.

Although the continuous processing by the replenishment method has been mainly described above, in the present invention, the processing is performed without replenishment with a fixed amount of the processing liquid, and then the whole or a part of the processing liquid is replaced with a new liquid. A batch processing method for performing the processing again can also be preferably used.

The light-sensitive material of the present invention has a coated silver amount of 2
g / m ² or more, and the dry film thickness is preferably 18 μm or less, particularly preferably 16 μm or less. The silver halide color photographic light-sensitive material generally has at least one layer of a silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer on a support. In the present invention, the number and order of the silver halide emulsion layers and the non-light-sensitive layers are not particularly limited. A typical example is a light-sensitive material having a light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support,
The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light and red light. From the red color sensitive layer, the green color sensitive layer, and the blue color sensitive layer in this order. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different color-sensitive layers are sandwiched between the same color-sensitive layers. Non-photosensitive layers such as various intermediate layers may be provided between the silver halide photosensitive layers and as the uppermost layer and the lowermost layer. For the intermediate layer, JP-A-61-43748, JP-A-59-113438, and JP-A-5-113438
Nos. 9-113440, 61-20037, 61-
A coupler or the like described in No. 20038 may be contained, and a color mixture inhibitor, an ultraviolet absorber, a stain inhibitor or the like may be contained as usually used.

As described in West German Patent 1,121,470 or British Patent 923,045, a plurality of silver halide emulsion layers constituting each unit photosensitive layer may be composed of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer. A two-layer structure of layers can be preferably used. Usually, it is preferable to arrange them so that the light sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the respective halogen emulsion layers. Also, JP-A-57-112751, JP-A-62-200350,
As described in JP-A-62-206541 and JP-A-62-206543, a low-sensitivity emulsion layer may be provided on the side remote from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.
As a specific example, from the side farthest from the support, a low-sensitivity blue-sensitive layer (BL) / a high-sensitivity blue-sensitive layer (BH) / a high-sensitivity green-sensitive layer (GH) / a low-sensitivity green-sensitive layer (GL) / High-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL) /
Alternatively, they can be installed in the order of BH / BL / GL / GH / RH / RL, or in the order of BH / BL / GH / GL / RL / RH. Further, as described in JP-B-55-34932, the layers can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. JP-A-56-25738 and JP-A-62-63.
As described in JP-A-936, the blue-sensitive layer / GL / RL / GH / RH may be arranged in this order from the farthest side from the support. As described in JP-B-46-15495, the upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is more than the middle layer. An example is an arrangement in which a silver halide emulsion layer having a low sensitivity is arranged and three layers having different sensitivities are sequentially reduced in sensitivity toward a support. Even when such three layers having different sensitivities are used, as described in JP-A-59-202264, a medium-speed emulsion layer / They may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer. As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive material.

The dried film thickness of all the constituent layers except the support and the undercoat layer and the back layer of the light-sensitive material is from 12.0 to 20.0 μm from the viewpoint of bleaching fog, stain over time and the like.
It is preferred that More preferably, 12.0 to 1
It is 8.0 μm.

The film thickness of the photosensitive material is determined by measuring the thickness of the photosensitive material by 2
After storage of the photographic material under conditions of 5 ° C. and 50% RH, the photographic material was stored for 7 days. First, the total thickness of the photographic material was measured. The film thickness of all coating layers excluding the support of the above-mentioned photosensitive material is determined by the difference. The thickness is measured, for example, using a contact-type piezoelectric transducer (Anritus Electric Co.
Ltd., K-402B Stand.). The removal of the coating layer on the support can be performed using an aqueous solution of sodium hypochlorite. Also,
Using a scanning electron microscope, a cross-sectional photograph of the photosensitive material is taken (preferably at a magnification of 3,000 or more), and the total thickness on the support can be measured.

The swelling ratio of the photosensitive material in the present invention [(25
Equilibrium swelling film thickness in H ₂ O at 25 ° C., dry film thickness at 25 ° C., 55% RH) ÷ (total film thickness dried at 25 ° C., 55% RH) × 100] is 50 to 200%. Preferably, 70-1
50% is more preferred. If the swelling ratio deviates from the above value, the remaining amount of the color developing agent increases, and photographic performance,
This has an adverse effect on image quality such as desilvering properties and film physical properties such as film strength.

Further, the film swelling speed of the light-sensitive material in the present invention is determined by setting a saturated swelling film thickness to 90% of the maximum swelling film thickness reached when processing in a color developing solution (38 ° C., 3 minutes 15 seconds). When the time required to reach the half film thickness is defined as the swelling speed T _1/2 , T _1/2 is preferably 15 seconds or less, more preferably 9 seconds or less.

The silver halide contained in the photographic emulsion layer of the light-sensitive material used in the present invention may be any of silver iodobromide, silver iodochlorobromide, silver chlorobromide, silver bromide and silver chloride. Good.
Preferred silver halides are silver iodobromide, silver iodochloride or silver iodochlorobromide containing about 1 to 30 mol% of silver iodide. Particularly preferred is silver iodobromide containing 2 to 25 mol% iodide.

The silver halide grains of the photographic emulsion are cubic,
Those having regular crystals such as octahedron and tetrahedron,
Those having an irregular crystal form such as a sphere or a plate, those having a crystal defect such as a twin plane, or a composite form thereof may be used. The silver halide may be fine grains having a grain size of about 0.2 μm or less or large grains having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion usable in the present invention is, for example, Research Disclosure (RD) No. 1
7643 (December 1978), pp. 22-23, "I. Emulsion Production (Emulsio
n preparation and types) ”and No. 18716 (1979
Nov., 648, Grafkid, "Physics and Chemistry of Photography",
Published by Paul Montell (P. Glafkides, Chimie et Physiq)
ue Photographique (Paul Montel, 1967)), "Photographic Emulsion Chemistry" by Duffin, Focal Press (GF Duff
in, Photographic Emulsion Chemistry (Focal Press,
1966)), "Manufacture and coating of photographic emulsions", by Zerikman et al.,
Published by Focal Press (VL Zelikman et al., Makin
g and Coating Photographic Emulsion (Focal Press, 1
964)) and the like. U.S. Pat. Nos. 3,574,628 and 3,653
Monodisperse emulsions described in US Pat. No. 5,394 and British Patent No. 1,413,748 are also preferable. Tabular grains having an aspect ratio of about 5 or more can also be used in the present invention. Tabular grains are described in Photographic Science and Engineering by Gatov (Gutoff, Photogr
aphic Science and Engineering), Vol. 14, 248
257 (1970); U.S. Patent No. 4,434,2.
No. 26, No. 4,414,310, No. 4,430,04
8 and 4,439,520 and British Patent 2,1
12,157 and the like.

The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, or may have a phase structure. Further, silver halides having different compositions may be joined by epitaxial joining,
Further, it may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide. Also, a mixture of particles of various crystal forms may be used.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. Additives used in such a process are described in Research Disclosure Nos. 17643 (December 1978) and 18716 (December 1978).
(November 1979) and No. 307105 (November 1989), and the relevant locations are summarized in the table below. Known photographic additives that can be used in the present invention are also described in the above three Research Disclosures (RD),
The relevant places are shown in the table below.

Types of Additives [RD 17643] [RD 18716] [RD 307105] 1. Chemical sensitizer page 23, page 648, right column, page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, 23 -24 pages 648 right column 866-868 supersensitizers 649 page right column 4. Brightener 24 pages 647 page right column 868 5. Fogging prevention 24-25 page 649 right column 868-870 Agents, stabilizers 6.Light absorbers, pages 25-26, page 649, right column, page 873, filters, page 650, left column Dyes, ultraviolet absorbers 7.Stain protection 7.Page 25, right column, page 650, left column, page 872 Column 8. Dye image image page 25 Page 650 Left column 872 Fixative 9. Hardening agent 26 Page 651 Left column 874-875 10. Binder 26 Page 651 Left column 873-874 11. Plasticizer, 27 Page 650 Right column Page 876 Lubricant 12. Coating aid, 26-27 Page 650 Right column 875-876 Surfactant 13. Static 27 Page 650 Right column 876-877 Inhibitor 14.Mat agent 878 ~ 879 pages

In the present invention, various color couplers can be used in combination.
17643, VII-CG and RD No. 307105,
It is described in the patents described in VII-CG. As a yellow coupler, for example, U.S. Pat.
No. 501, No. 4,022,620, No. 4,326,0
No. 24, No. 4,401,752, No. 4,248,96
No. 1, Japanese Patent Publication No. 58-10739, British Patent No. 1,42
5,020, 1,476,760; U.S. Pat. Nos. 3,973,968; 4,314,023; 4,511,649; and EP 249,473A.
, Japanese Unexamined Patent Application Publication No. 3-212548, Japanese Patent Application No. 3-63680.
No., Japanese Patent Application No. 3-157480, Japanese Patent Application No. 3-10179
8, U.S. Pat. No. 5,118,599;
No. 18042, EP 501,306 and the like are preferred.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferred, and US Pat. Nos. 4,310,619 and 4,351,897,
European Patent No. 73,636, US Patent No. 3,061,4
No. 32, 3,725,064, RD No. 24220
(June 1984), JP-A-60-33552, RD
No. 24230 (June 1984), JP-A-60-43
No. 659, No. 61-72238, No. 60-35730
No. 55-118034, No. 60-185951
No. 4,500,630, U.S. Pat.
654, 4,556,630, WO (PCT) 8
What is described in 8/04795 etc. is preferable.

Examples of the cyan coupler include phenol-based and naphthol-based couplers.
052,212, 4,146,396, 4,2
No. 28,233, No. 4,296,200, No. 2,36
9,929, 2,801,171, 2,77
2,162, 2,895,826, 3,77
2,002, 3,758,308, 4,33
4,011, 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121,365A.
No. 249,453A, U.S. Pat.
No. 22, 4,333, 999, 4, 753, 87
No. 1, No. 4,451,559, No. 4,427,767
Nos. 4,690,889 and 4,254,212
No. 4,296,199, JP-A-61-42658.
, European Patent Nos. 484,909 and 456,226
And those described in JP-A Nos. 491,197 and 488,248 are preferable.

A colored coupler for correcting unnecessary absorption of a coloring dye is described in RD No. Section VII-G of 17643,
U.S. Pat. No. 4,163,670, JP-B-57-394.
No. 13, U.S. Pat. Nos. 4,004,929 and 4,13
No. 8,258, British Patent No. 1,146,368, JP-A-3-251843 and JP-A-4-212149 are preferred. No. 4,774,181.
Couplers that correct unnecessary absorption of color-forming dyes by fluorescent dyes released during the coupling described in JP-A No. 4177/1988, and dye precursor groups capable of forming dyes by reacting with developing agents described in U.S. Pat. No. 4,777,120. It is also preferable to use a coupler having a as a leaving group.

Examples of couplers in which a coloring dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent No. 2,125,570, and European Patent No. 96,570.
Those described in West German Patent (Published) No. 3,234,533 are preferred.

Typical examples of polymerized dye-forming couplers are described in US Pat. Nos. 3,451,820 and 4,082.
0,211, 4,367,282, 4,40
Nos. 9,320, 4,576,910 and British Patent No. 2,102,173.

Couplers which release a photographically useful residue upon coupling can also be preferably used. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent Nos. 2,097,140 and 2,13.
1,188, JP-A-59-157638 and JP-A-59-57638.
170,840 and JP-A-4-21248 are preferred.

Other couplers that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,42.
No. 7, etc., EP 173,30
No. 2A, couplers capable of releasing dyes that recolor after release, RD No. No. 11449, ibid. 24241, JP-A-6
Bleach accelerator releasing couplers described in JP-A 1-2201247, ligand releasing couplers described in U.S. Pat. No. 4,553,477, leuco dye releasing couplers described in JP-A-63-75747, U.S. Pat. 4,774,
No. 181 which emits a fluorescent dye.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of high boiling solvents used in the oil-in-water dispersion method are described in US Pat.
No. 027, etc., specific examples of the high boiling organic solvent having a boiling point at normal pressure of 175 ° C. or higher used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-cyclohexyl phthalate). 2-ethylhexyl phthalate, decyl phthalate, bis (2,4-
Di-t-amylphenyl) phthalate, bis (2,4-
Di-t-amylphenyl) isophthalate, bis (1,
Esters of phosphoric acid or phosphonic acid (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxy) Ethyl phosphate,
Trichloropropyl phosphate, di-2-ethylhexylphenylphosphonate, etc.), benzoic esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N, N-diethyldodecaneamide, N , N-diethyllaurylamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-
Amyl phenols, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl-2) -Butoxy-5-t
tert-octylaniline and the like, and hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene and the like) 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 thereof include acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, Ethoxyethyl acetate, dimethylformamide and the like can be mentioned.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,3.
No. 63, West German Patent Application (OLS) No. 2,541,274
No. 2,541,230 and the like.

These couplers may be impregnated with a loadable latex polymer (for example, described in US Pat. No. 4,203,716) in the presence or absence of the high-boiling organic solvent, or may be insoluble in water. It can be dissolved in a polymer soluble in an organic solvent and emulsified and dispersed in a hydrophilic colloid aqueous solution. Preferably, the international publication number WO8
Homopolymers or copolymers described on pages 12 to 30 of 08/00723 are used. In particular, use of an acrylamide-based polymer is preferred for stabilizing a color image.

Suitable supports which can be used in the present invention are described, for example, in RD No. No. 17643, p. 18
716 at page 647 right column to page 648 left column.

The support of the color negative film used in the present invention includes a support having a conductive layer and a transparent magnetic material layer on one side, as described in JP-A-4-62543.
International Patent Publication WO90 / 04205, FIG.
A having a magnetic recording layer described in A.
No. 124628, which has a stripe magnetic recording layer,
In addition, those having a transparent magnetic recording layer adjacent to the stripe magnetic recording layer are also preferable. It is preferable to provide a protective layer described in JP-A-4-73737 on these magnetic recording layers.

The thickness of the support is preferably from 70 μm to 120 μm.
No. 6, page 5, upper right column, line 1 to page 6, upper right column, line 5 can be used, and preferred are cellulose derivatives (eg, diacetyl-, triacetyl-, propionyl-, butanoyl). -, Acetylpropionyl-acetate) and JP-B-48-4041.
No. 4 (for example, polyethylene terephthalate, poly-1,4-cyclohexane dimethylene terephthalate, polyethylene naphthalate). It is preferable to use polyester for the support of the film used in the present invention since a higher draining effect can be obtained.

The package (patrone) for accommodating the color negative film of the present invention may be of any type currently used or known, and in particular, US Pat. No. 4,834,30.
No. 6, FIG. 1 to FIG. 3 or
U.S. Pat. No. 4,846,418, FIG. 1-FI
G. FIG. Those described in No. 3 are preferred. In addition, a color negative film used in the present invention is disclosed in JP-A-4-125558.
No. 1, page 14, upper left column, line 1 to page 18, lower left column, line 11 are preferable.

The present invention can be applied to various photosensitive materials. In particular, it is preferably used for color negative films for general use or movies, and reversal films for slides or televisions.

[0091]

【Example】

Example On a subbed cellulose triacetate film support,
Sample 101, which is a multilayer color photographic material composed of each layer having the following composition, was prepared. (Composition of photosensitive layer) The main materials used for each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow coupler H: Gelatin hardener ExS: sensitizing dye The coating amount is g / g for silver halide and colloidal silver.
The amount of silver expressed in m ² units, the amount expressed in g / m ² for couplers, additives and gelatin, and the number of moles per mole of silver halide in the same layer for sensitizing dyes Indicated by

First layer: Antihalation layer Black colloidal silver Silver coating amount 0.20 Gelatin 2.20 UV-1 0.11 UV-2 0.20 Cpd-1 4.0 × 10 ^-2 Cpd-2 1.9 × 10 ^-2 HBS-1 0.30 HBS-2 1.2 × 10 ^-2

Second layer: Intermediate layer Fine grain silver iodobromide (AgI 1.0 mol%, equivalent sphere diameter 0.07 μm)
m) Silver coating amount 0.15 Gelatin 1.00 ExC-4 6.0 × 10 ^-2 Cpd-3 2.0 × 10 ^-2

Third layer: low-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion A silver coating amount 0.42 silver iodobromide emulsion B silver coating amount 0.40 gelatin 1.90 ExS-1 6.8 × 10 ^-4 mol ExS-2 2.2 × 10 ^-4 mol ExS-3 6.0 × 10 ^-5 mol ExC-1 0.65 ExC-3 1.0 × 10 ^-2 ExC-4 2.3 × 10 ^-2 HBS-1 0.32

Fourth layer: middle-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion C Silver coating amount 0.85 Gelatin 0.91 ExS-1 4.5 × 10 ^-4 mol ExS-2 1.5 × 10 ^-4 mol ExS-3 4.5 × 10 ^{− 5} mol ExC-1 0.13 ExC-2 6.2 × 10 ^-2 ExC-4 4.0 × 10 ^-2 ExC-6 3.0 × 10 ^-2 HBS-1 0.10

Fifth layer: High-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion D Silver coating amount 1.50 Gelatin 1.20 ExS-1 3.0 × 10 ^-4 mol ExS-2 9.0 × 10 ^-5 mol ExS-3 3.0 × 10 ^{− 5} mol ExC-2 8.5 × 10 ^-2 ExC-5 3.6 × 10 ^-2 ExC-6 1.0 × 10 ^-2 ExC-7 3.7 × 10 ^-2 HBS-1 0.12 HBS-2 0.12

Sixth layer: Intermediate layer Gelatin 1.00 Cpd-4 8.0 × 10 ^-2 HBS-1 8.0 × 10 ^-2

Seventh layer: low-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion E Silver coating amount 0.28 Silver iodobromide emulsion F Silver coating amount 0.16 Gelatin 1.20 ExS-4 7.5 × 10 ^-4 mol ExS-5 3.0 × 10 ^-4 mol ExS-6 1.5 × 10 ^-4 mol ExM-1 0.50 ExM-2 0.10 ExM-5 3.5 × 10 ^-2 HBS-1 0.20 HBS-3 3.0 × 10 ^-2

[0099] Eighth layer: middle sensitivity green-sensitive emulsion layer Silver iodobromide emulsion G silver laydown 0.57 Gelatin 0.45 ExS-4 5.2 × 10 ^-4 mol ExS-5 2.1 × 10 ^-4 mol ExS-6 1.1 × 10 ^{- 4} mol ExM-1 0.12 ExM-2 7.1 × 10 ^-3 ExM-3 3.5 × 10 ^-2 HBS-1 0.15 HBS-3 1.0 × 10 ^-2

Ninth layer: Intermediate layer Gelatin 0.50 HBS-1 2.0 × 10 ^-2

Tenth layer: High-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion H Silver coating amount 1.30 Gelatin 1.20 ExS-4 3.0 × 10 ^-4 mol ExS-5 1.2 × 10 ^-4 mol ExS-6 1.2 × 10 ^{− 4} mol ExM-4 5.8 × 10 ^-2 ExM-6 5.0 × 10 ^-3 ExC-2 4.5 × 10 ^-3 Cpd-5 1.0 × 10 ^-2 HBS-1 0.25

Eleventh layer: Yellow filter layer Gelatin 0.50 Cpd-6 5.2 × 10 ^-2 HBS-1 0.12

12th layer: Intermediate layer Gelatin 0.45 Cpd-3 0.10

13th layer: Low-sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion I Silver coating amount 0.20 Gelatin 1.00 ExS-7 3.0 × 10 ^-4 mol ExY-1 0.60 ExY-2 2.3 × 10 ^-2 HBS-1 0.15

Fourteenth layer: Medium-sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion J Silver coating amount 0.19 Gelatin 0.35 ExS-7 3.0 × 10 ^-4 mol ExY-1 0.22 HBS-1 7.0 × 10 ^-2

Fifteenth layer: Intermediate layer Fine grain silver iodobromide (AgI 2 mol%, uniform AgI type, equivalent sphere diameter 0.13 μm) Silver coating amount 0.20 Gelatin 0.36

Sixteenth layer: High-sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion K Silver coating amount 1.55 Gelatin 1.00 ExS-8 2.2 × 10 ^-4 mol ExY-1 0.21 HBS-1 7.0 × 10 ^-2

17th layer: 1st protective layer Gelatin 1.80 UV-1 0.13 UV-2 0.21 HBS-1 1.0 × 10 ^-2 HBS-1 1.0 × 10 ^-2

18th layer: 2nd protective layer Fine grain silver chloride (equivalent sphere diameter 0.07 μm) Silver coating amount 0.36 gelatin 0.70 B-1 (1.5 μm diameter) 2.0 × 10 ^-2 B-2 (1.5 μm diameter) 0.15 B-3 3.0 × 10 ^-2 W-1 2.0 × 10 ^-2 H-1 0.35 Cpd-7 1.00

[0110] In addition to the above,
1,2-Benzisothiazolin-3-one (average 200 ppm based on gelatin), n-butyl-p-hydroxybenzoate (about 1,000 ppm) and 2-phenoxyethanol (about 10,000 ppm) were added. Furthermore, B-
4 to B-6, W-2, W-3, F-1 to F-1
5, contains iron salts, lead salts, gold salts, platinum salts, iridium salts, rhodium salts and palladium salts.

[0111]

[Table 1]

In Table A, (1) Each emulsion was reduced and sensitized at the time of preparation of grains using thiourea dioxide and thiosulfonic acid according to the examples in JP-A-2-191938. (2) Each emulsion was subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. I have. (3) For preparing tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. (4) Dislocation lines as described in JP-A-3-237450 are observed in tabular grains and normal crystal grains having a grain structure using a high-pressure electron microscope.

[0113]

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[0118]

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[0119]

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[0120]

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[0121]

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[0122]

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[0124]

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[0126]

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The sample 101 prepared as described above was used for 35 samples.
The film was cut to a length of 2 m with a width of mm, and the film was processed under the following conditions using an automatic developing machine without exposure. In addition, the bleaching agent of the bleaching solution and the image stabilizer of the stabilizing solution were sequentially replaced as shown in Table B, and the other processes were performed under the same conditions. And The processing steps and the composition of the processing solution are shown.

(Processing step) Process Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 38.0 ° C 400 ml 17 liter Bleaching 50 seconds 38.0 ° C 140 ml 5 liters Fixing (1) 50 seconds 38.0 ° C -5 Liter Fixing (2) 50 seconds 38.0 ℃ 420 ml 5 liter Washing water 30 seconds 38.0 ℃ 980 ml 3 liter Stable (1) 20 seconds 38.0 ℃-3 liter Stable (2) 20 seconds 38.0 ℃ 560 ml 3 liter drying 1 the amount of min 60 ° C. * the replenishing amount is per photosensitive material 1 m ²

The fixing solution and the stabilizing solution were of the countercurrent type from (2) to (1), and the overflow of the washing water was all introduced into the fixing bath. The amount of the developer brought into the bleaching step, the amount of the bleaching liquid brought into the fixing step, and the amount of the fixing liquid brought into the washing step were 65 ml, 50 ml and 1 m ² of the light-sensitive material, respectively.
ml and 50 ml. The crossover time is 6 seconds in each case, and this time is included in the processing time of the previous step. Further, each replenisher was replenished with the same liquid as the respective tank liquid.

The composition of the processing solution is shown below. (Color developing solution) Unit (g) Diethylenetriaminepentaacetic acid 2.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.3 Sodium sulfite 3.9 Potassium carbonate 37.5 Potassium bromide 1.4 Potassium iodide 1.3 mg Hydroxylamine sulfate 2.4 2-Methyl-4 -[N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 4.5 Add water and add 1.0 liter pH 10.05

(Bleaching solution) Unit (g) Ferric ammonium salt of each compound described in Table-B 0.33 mol Ammonium bromide 80 Ammonium nitrate 15 Hydroxyacetic acid 50 Acetic acid 40 Add water and add 1.0 liter pH (prepared with aqueous ammonia) 4.2

(Fixing solution) Unit (g) Ammonium sulfite 19 Ammonium thiosulfate (700 g / L) 280 mL Imidazole 15 Ethylenediaminetetraacetic acid 15 Add water to 1.0 L pH (prepared with aqueous ammonia and acetic acid) 7.4

(Washing water) Tap water was replaced with H-type strongly acidic cation exchange resin (Amberlite IR- manufactured by Rohm and Haas Company).
120B) and a mixed bed column packed with an OH type strongly basic anion exchange resin (Amberlite IR-400) to reduce the calcium and magnesium ion concentration to 3 m.
g / liter or less, followed by sodium diisocyanurate 20 mg / liter and sodium sulfate 1
50 mg / liter was added. The pH of this solution is 6.5
〜7.5.

(Stabilizing solution) Unit (g) Sodium p-toluenesulfinate 0.1 Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.2 Disodium ethylenediaminetetraacetate 0.05 Image stabilization described in Table-B Preparation (described in Table B) 1.0 liter with water, pH 7.2

[Evaluation of Image Preservation] Each sample after the above-mentioned processing was subjected to a photographic densitometer FSD10 manufactured by Fuji Photo Film Co., Ltd.
After measuring the yellow density at 3, a 25 ° C. relative humidity 25
%, And the same concentration was measured again for 2 months. The increase in yellow density was measured in this way, and the occurrence of yellow stain was evaluated. The results are shown in Table-B.

[0136]

[Table 2]

[0137]

[Table 3]

[0138]

[Table 4]

From the results in Table-B, it can be seen from the general formula (I) of the present invention.
By using a ferric complex salt of the compound represented by the formula (1) as a bleaching agent and making the concentration of free formaldehyde in the stabilizing solution 0.01 mol / liter or less, generation of yellow stain can be effectively prevented. In particular, lowering the concentration of free formaldehyde in the stabilizing solution tends to more effectively prevent the generation of yellow stain. However, when a known bleaching agent such as PDTA, EDTA or ferric diethylenetriaminetetraacetate is used, the generation of yellow stain cannot be effectively prevented, and the concentration of free formaldehyde in the stabilizing solution is reduced to 0.03. Even if it is increased to mol / liter, the generation of yellow stain cannot be effectively prevented.

Example 2 In place of the undercoated cellulose triacetate film support used for the sample 101 prepared in Example 1, a film having a thickness of 10
A sample 201 was prepared in the same manner as in Example 1 except that a polyethylene naphthalate of 0 μm was used as a support, and the back surface was coated with a stripe magnetic recording layer described in Example 1 of JP-A-4-124628. Produced. When a test similar to that of Example 1 was performed using this sample 201, the effect of the present invention was obtained as in Example 1. Further, instead of the support used for the sample 101 of Example 1,
The support and the backing layer were replaced with the same one as the sample No. I-3 of Example 1 of JP-A-4-62543,
C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) CH ₂ COOK is applied to the protective layer.
A sample 202 was prepared in the same manner as in Example 1 except that the application was performed so as to be 5 mg / m ² . This sample 202 was processed into the format shown in FIG. 5 of JP-A-4-62543, and the same test as in Example 1 was performed.
The effect of the present invention was obtained in the same manner as described above.

[0141]

According to the treatment method of the present invention, the compound represented by the general formula (I)
By using a ferric complex salt of the compound represented by the formula (1) as a bleaching agent and treating it with a stable solution containing substantially no formaldehyde, yellow stain is generated even after long-term storage under dry conditions after development processing. Was effectively prevented.

Continuation of front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G03C 7/42 G03C 11/00 501

Claims (1)

(57) [Claims] 1. A method of processing a silver halide color photographic light-sensitive material which has been imagewise exposed to light by a development process comprising a color development step, a desilvering step and a stabilization step. A bleaching solution used in the desilvering step contains a ferric complex salt of a compound represented by the following general formula (I): PH of the liquid is 3.0 to 5.0
The fixing solution contains thiosulfate , and the pH of the fixing solution is
A processing method for a silver halide color photographic light-sensitive material, wherein the processing solution is 6.5 to 8.0 and the processing solution used in the stabilizing step contains substantially no formaldehyde. General formula (I) In the formula (I), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R
₆ each independently represents a hydrogen atom, an aliphatic group, an aromatic group or a hydroxy group. W represents a linking group represented by the following general formula (W). M ₁ , M ₂ , M ₃ and M ₄ each independently represent a hydrogen atom or a cation. Formula (W)-(W ₁ -Z) _n -W ₂ -In the formula (W), W ₁ represents an alkylene group or a single bond. W
₂ represents an alkylene group or -CO-. Z is a single bond,-
O -, - S -, - CO-, or -N (R _W) - represents the (R _W represents a hydrogen atom or an optionally substituted alkyl group.). However, Z and W ₁ are not simultaneously a single bond. n represents an integer of 1 to 3.