JPH04130432A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To lessen the replenishing rate of a processing soln. by confining the replenishing amt. of a color development replenishing liquid to <=650ml per 1m<2> photosensitive material and incorporating >=0.1mol/l imidazole compd. into the processing liquid having fixability. CONSTITUTION:The replenishing amt. of the color developer is <=650ml, preferably 200 to 600ml, more preferably 200 to 550ml, and more particularly preferably 300 to 450ml per 1m<2> photosensitive material. Stains known as after colors are more generated as the replenishing amt. is smaller when the processing with such low replenishing is executed. The imidazole compd. is, thereupon, incorporated at >=0.1mol/l into the liquid having the fixability at the time of the fixing processing after the color development. The content of the imidazole compd. in the liquid having the fixability is preferably 0.1 to 1mol, more preferably 0.2 to 0.8mol, more particularly preferably 0.25 to 0.4mol per 1l processing liquid. The lower replenishing of the processing liquid is executed in this way.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a method for processing silver halide color photographic light-sensitive materials (hereinafter also simply referred to as light-sensitive materials), and in particular to a method for processing silver halide color photographic materials (hereinafter simply referred to as light-sensitive materials), in particular, by reducing the amount of replenishment in the color development step. , relates to a processing method that provides excellent photographic properties while reducing the amount of environmental waste.

(Prior Art) In a method for processing silver halide color photographic materials,
The used processing liquid is generally disposed of as overflow liquid.

However, these used processing liquids, which are recovered and processed as waste liquids, have a large pollution load value and are not preferable in terms of environmental conservation, and the collection and delivery costs for their recovery cannot be ignored. Therefore, if these used processing liquids (overflow liquids) can be used again as replenishing liquids, that is, if they can be recycled, it will be effective in saving resources, reducing pollution, and reducing costs. In particular, many proposals have been made regarding methods for regenerating color developing solutions. For example, JP-A-54-37731, JP-A No. 54-37731;
No. 6-1048, No. 56-1049, No. 56-271
No. 42, No. 56-33644, No. 56-149036
Regeneration method by electrodialysis described in No. 1, etc., 1986-15
71, the regeneration method using activated carbon described in JP-A No. 58-14831, the ion exchange membrane method described in JP-A-52-105820, JP-A-53-132343, and JP-A-55-144.
No. 240, No. 57-146249, U.S. Patent No. 4.34
Examples include the regeneration method using an ion exchange resin described in No. 8.475 and the like.

Such recycling has conventionally been carried out in large-scale photofinishing laboratories (so-called large laboratories).

However, regeneration treatment requires work to remove unnecessary substances from the waste liquid and work to add missing chemicals to use as a replenisher, which not only incurs labor costs but also requires technology to control these processes. It takes.

In particular, it is technically difficult to regenerate color developing solutions, and it has been impossible in small and medium-sized laboratories without technicians or in-store processing laboratories called minilabs.

Therefore, recently, research has been conducted on methods of reducing the amount of replenishment as much as possible.

However, in color development processing, if low replenishment processing is performed, photographic characteristics such as sensitivity, minimum density, or gradation may vary greatly, and performance may not be stable. This tendency is particularly strong in high-sensitivity photosensitive materials such as color negative films and color reversal films. As a method for solving these problems, methods have been proposed in which various compounds or specific couplers are incorporated into light-sensitive materials. For example, JP-A-61
-282841, 62-148951, 63-
No. 144353, No. 63-236037, No. 63-2
No. 96041 and JP-A No. 1-180542. In addition, a method for reducing the bromide concentration in a color developer replenisher in the processing of photosensitive materials containing silver iodide emulsions is disclosed in Japanese Patent Application Laid-open Nos. 61243453 and 61-25185.
No. 1, No. 61-251852, No. 61-261741
No. 292638, No. 62-99750, No. 62
-1) Described in No. 3143, No. 63-144352, etc.

(Problems to be Solved by the Present Invention) However, although some effects can be obtained by using the above method, 650y per rrf of photosensitive material
d! If you wish to further reduce replenishment as shown below,
It has not been possible to solve the problem that colored substances such as sensitizing dyes and dyes remain (residual color) in the photographic material after processing, resulting in an increase in so-called stain.

This residual color was particularly noticeable when the processing time of the water washing and stabilization steps was shortened or when the amount of replenishment was reduced.

Therefore, the first object of the present invention is to achieve low replenishment of processing liquid, thereby preserving the environment and reducing costs.

A second object of the present invention is to provide a processing method that does not cause an increase in staining due to residual color even when the amount of replenishment of color developer is reduced.

(Means for solving problems) The above object of the present invention was achieved by the following method.

That is, in a method in which a silver halide color photographic light-sensitive material is subjected to color development while being replenished with a color developer replenisher, and then processed with a processing solution having fixing ability, the replenishment amount of the color developer replenisher is equal to The hit is less than 650,
and the processing liquid having the fixing ability contains 0 imidazole compound.
．． This was achieved by a treatment characterized by containing 1 mol/l or more. Furthermore, in the above processing method, it has been found that even greater effects can be obtained by processing the silver halide color photographic light-sensitive material with a processing solution containing glycolic acid and/or lactic acid that has bleaching ability after color development. It is.

The present invention is particularly effective in processing silver halide color photographic materials containing silver iodobromide emulsions with a silver iodide content of 0.1 to 30 mol, and is particularly effective when used in processing color negative films. .

In the present invention, the color development step is carried out without being replenished with a color development replenisher.

The amount of replenishment of the color developing solution is 650-ml or less, preferably 200-600ml, more preferably 200-550ml, particularly preferably 300-450ml per 1m of light-sensitive material.

When such low replenishment processing is performed, the more the replenishment amount decreases, the more stains called residual color occur. This stain may be due to colored substances such as sensitizing dyes or dyes contained in the light-sensitive material, or may remain after processing due to poor cleaning, and can be removed by performing sufficient water washing again.

However, in the current situation where faster processing is desired, it is sometimes undesirable to carry out long water washing or stabilization treatments.

The present inventors conducted studies to achieve both rapid processing and prevention of residual color, and as a result, they arrived at the present invention.

That is, the inventors have found that the above-mentioned problem can be solved by containing an imidazole compound of 0.1 mol/l or more in a solution having fixing ability during the fixing process after color development.

In the present invention, the liquid having fixing ability refers to a fixing liquid or a bleach-fixing liquid.

The preferred content of the imidazole compound in the solution having fixing ability is 0.1 to 1 mol, preferably 0.2 to 0.8 mol, particularly preferably 0.2 mol, per processing solution 1).
It is 5 to 0.4 mol.

Among the imidazole compounds, preferred are the following formulas (
This is a compound represented by I).

- Formula (I) In the above - Formula (I), R,, R,, R8 and R
4 represents a hydrogen atom, an alkyl group or an alkenyl group, respectively.

The alkyl group may have a substituent and preferably has 1 to 5 carbon atoms, particularly 1 to 2 carbon atoms.
It is preferable that

Among these, unsubstituted ones are preferred, such as methyl and ethyl.

The alkenyl group may have a substituent and preferably has 2 to 5 carbon atoms, particularly 2 to 5 carbon atoms.
It is preferable that it is 3.

Among these, unsubstituted ones are preferred, such as vinyl and allyl.

Furthermore, examples of the substituent when the alkyl group or alkenyl group has a substituent include a hydroxy group, an amino group, a nitro group, and the like.

Among the above, in the present invention, it is preferable that RI to R4 are a hydrogen atom or an unsubstituted alkyl group having 1 to 2 carbon atoms, and when an alkyl group is present, any one of R1 to R4 is an alkyl group. It is preferable that R1
It is most preferred that -R4 are all hydrogen atoms.

Specific examples of the compound represented by formula (1) are listed below, but the invention is not limited thereto.

(1) Imidazole (2) 1-methylimidazole (3) 2-methylimidazole (4) 4-methylimidazole (5) 4-hydroxymethylimidazole (6) 1-ethylimidazole (7) l-vinylimidazole (8) 4-aminomethylimidazole (9) 2,4-dimethylimidazole (10) 2,4.5-)dimethylimidazole (1))
2-aminoethylimidazole (12) 2-nitroethylimidazole Among the compounds exemplified above,
Particularly preferred are (1), (2), (3), (4), and (6), with (1) being the most preferred.

Note that these compounds have an acid dissociation constant (pKa) of 6 to 10.
, particularly preferably 6.5 to 8.5.

The compound (imidazole compound) represented by -a formula CI) is commercially available, and can be used as is in the present invention.

In the method for processing a photosensitive material of the present invention, the photosensitive material after imagewise exposure is 650 ml per rrr of photosensitive material as described above.
After replenishment, color development processing is performed.

The color developing solution used in the present invention contains a known aromatic primary amine color developing agent.

Preferred examples are p-phenylenediamine derivatives, and representative examples are shown below, but the invention is not limited to these.

D-IN, N-diethyl-p-phenylenediamine D-22-amino-5-diethylaminotoluene D-32-amino-5-(N-ethyl-N-laurylamino)toluene D-44-[N-ethyl- N-(β-hydroxyethyl)aminocoaniline D-52-Methyl-4-[N~ethyl-N-(β-hydroxyethyl)aminocoaniline 4-amino-3-methyl-N-ethyl N-[β -(methanesulfonamide)ethylcoaniline N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide N,N-dimethyl-p-phenylenecyamine 4-amino-3-methyl-N-ethyl N-methoxy Ethylaniline 4-amino-3-methyl-N-ethyl-N-β-ethoxyethylaniline 4-amino-3-methyl-N-ethyl-N-β-butoxyethylaniline Particularly preferred among the above p-phenylenediamine derivatives is exemplified compound D-5.

Further, these p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, sulfites, and p-toluenesulfonates. The amount of the aromatic primary amine color developing agent used is preferably a concentration of 0.001 to 0.1 mol per color developer 1), more preferably 0.01 to 0.0 mol.
The concentration is 6 molar.

In addition, the color developer contains sodium sulfite as a preservative.
Sulfites such as potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, and carbonyl sulfite adducts may be added as necessary.

The preferred amount of preservative added is 0.5 per 1) color developer.
~log, more preferably 1 to 5 g.

Alternatively, the aromatic primary amine color developing agent may be directly applied to
Various hydroxylamines (for example, JP-A-63-5341 and JP-A-63-106655)
Among the compounds described in the above, compounds having a sulfo group or a carboxy group 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, JP-A-63-146041;
It is preferable to add α-hydroxyketones and α-aminoketones described in No. 44656 and/or various saccharides described in No. 6336244. In addition, in combination with the above compounds, JP-A-63-4235, JP-A-63-2425
4, monoamines described in No. 63-21647, No. 63-146040, No. 63-27841, No. 63-25654, etc., No. 63-30845, No. 63
-14640, diamines described in No. 63-43139, etc.; polyamines described in No. 63-21647, No. 63-26655, and No. 63-44655;
Nitroxy radicals described in No. 3-53551, No. 63
It is preferable to use the alcohols described in No. 43140 and No. 63-53549, the oximes described in No. 63-56654, and the tertiary amines described in No. 63-239447.

Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
- Salicylic acids described in No. 180588, JP-A-54-3
Alkanolamines described in No. 582, JP-A-56-9
Polyethyleneimines described in No. 4349, U.S. Patent No. 3
, 746,544, etc., may be contained as necessary. Particularly preferred is the addition of an aromatic polyhydroxy compound.

The color developing solution used in the present invention preferably has a pH of 9 to
12, more preferably 9-1). 0, and the color developer may contain other known developer component compounds.

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

Specific examples of buffering agents include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, trisodium phosphate, dipotassium phosphate, sodium borate, potassium borate, Sodium tetraborate (borax), potassium tetraborate, O-
Sodium hydroxybenzoate (sodium salicylate), potassium 0-hydroxybenzoate, sodium 5-sulfo-2hydroquinebenzoate (sodium 5-sulfosalicylate), 5-sulfo-2-hydroxybenzoate, potassium arzoate (5-sulfosalicylic acid) Potassium), etc. However, the present invention is not limited to these compounds.

The amount of buffering agent added to the color developing solution is preferably 01 mol/β or more, particularly preferably 0.01 to 0.4 mol/l.

In addition, various caloric acid agents can be used in the color developer as agents for preventing precipitation of calcium and magnesium, or to improve the stability of the color developer. The chelating agent is preferably an organic acid compound, such as aminopolycarphonic acids, organic phosphonic acids, and phosphonocarphonic acids.

Typical examples of these are nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenecyaminetetraacetic acid, N, N, N
-trimethylenephosphonic acid, ethylenediamine-N,N
, N', N'-tetramethylenephosphonic acid, trans-nochlorohexaneaminetetraacetic acid, l,2-aminopropanetetraacetic acid, hydroquinethyliminodiacetic acid, glycol ethercyaminetetraacetic acid, ethylenecyamine orthohydro Quinphenylacetic acid, 2-phosphonobutane-1゜2.4-tricarboxylic acid, 1-hydroxyethylidene-
Examples include 1,1-diphosphonic acid and N,N'-his(2-hydroquinobenzyl)ethylenediamine NN'-diacetic acid. Two or more of these chelating agents may be used in combination, if necessary.

The amount of these chelating agents added may be sufficient to sequester metal ions in the color developer, for example, II!
It is about 1 g to 10 g of O per serving.

Any development accelerator can be added to the color developing solution if necessary. However, it is preferable that the color developing solution in the present invention does not substantially contain benzyl alcohol from the viewpoints of pollution, liquid preparation properties, and prevention of color staining.

Here, "substantially" means developer II! 2mj7 or less, preferably not at all.

Other development accelerators include: Japanese Patent Publication No. 37-16088
No. 37-5987, No. 38-7826, No. 44
-12380, 45-9019, U.S. Patent No. 3,
818,247, etc.; p-phenylenediamine compounds described in JP-A-52-49829 and JP-A-50-15554;
No. 137726, Japanese Patent Publication No. 44-30074, Japanese Patent Publication No. 1977
4 described in No. 6156826, No. 52-43429, etc.
class ammonium salts, U.S. Patent No. 2,494.903, U.S. Patent No. 3,128,182, U.S. Patent No. 4 230.796
No. 3.253.919, Special Publication No. 41-1) 43
No. 1, U.S. Patent No. 2.482.546, U.S. Patent No. 2,59
6,926, amine compounds described in Japanese Patent Publication No. 3,582,346, etc., Japanese Patent Publication No. 37-16088, Japanese Patent Publication No. 42-2
5201, U.S. Pat. No. 3,128,183, Japanese Patent Publication No. 41-1) No. 431, No. 42-23883, U.S. Pat. 3-Vyrazolidones,
Imidazole and the like can be added as necessary.

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

The color developing solution used in the present invention may contain a fluorescent whitening agent. As the fluorescent whitening agent, 4゜4゛-diamino-2,2゜-disulfostilbene type compounds are preferred. The amount added is 0 to 5 g/z, preferably O, Ig to 4 g/I
! It is.

Furthermore, various surfactants such as alkylsulfonic acids, arylsulfonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added as necessary.

The color developer replenisher contains compounds contained in the color developer. The role of the color developer replenisher is to replenish the color developer with compounds that decrease due to processing of the photosensitive material and deterioration over time in an automatic processor, and conversely to control the concentration of compounds eluted from the photosensitive material during processing. This is to keep developing performance constant. Therefore, the former compound has a higher concentration than the color developing tank liquid, and the latter compound has a lower concentration. The former compounds are color developing agents and preservatives, and the replenisher contains 1.
Contains t~2 times the amount. Further, the latter compound is a development inhibitor represented by a halide (for example, potassium bromide), and is contained in the replenisher solution 0 to 0.6 times as much as the tank solution. The halide concentration in the replenisher is usually 0006
It may be less than mol/l, or it may be necessary to reduce the concentration as the replenishment level decreases, or it may not be contained at all.

In addition, compounds whose concentration does not easily change due to processing or aging are usually contained at approximately the same concentration as in the color developing tank solution.

Examples of this are chelating agents and buffering agents.

Further, the pH of the color developing replenisher is set to be about 0.05 to 0.5 higher than that of the tank solution in order to prevent the pH of the tank solution from decreasing due to processing. This pH difference also needs to increase as the amount of replenishment decreases.

The processing temperature with the color developer in the present invention is 20 to 50°
C1 is preferably 30 to 45°C. Processing time is 20
The time is from seconds to 5 minutes, preferably from 30 seconds to 3 minutes and 20 seconds, and more preferably from 1 minute to 2 minutes and 30 seconds.

Further, the color developing bath may be divided into two or more baths as necessary, and the color developing replenisher may be replenished from the first bath or the last bath, thereby shortening the developing time and further reducing the amount of replenishment.

The processing method of the present invention can also be used for color reversal processing. The black-and-white developer used at this time is a so-called black-and-white first developer, which is commonly used in the reversal processing of color photosensitive materials. Various well-known additives used in liquids can be included.

Typical additives include l-phenyl-3-virapritone, developing agents such as metol and hydroquinone, preservatives such as sulfites, and accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate, and potassium carbonate. ,
Inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole, methylbenzthiazole,
Examples include water softeners such as polyphosphates, and development inhibitors consisting of trace amounts of iodides and mercapto compounds.

When processing with an automatic processor using the above developer, it is preferable that the area (opening area) where the developer comes into contact with air be as small as possible. For example, if the aperture ratio is the value obtained by dividing the aperture area (aXr) by the volume of the developer (Cal'), the aperture ratio is 0. It is preferably O1 or less, and more preferably o, oos or less.

Further, in order to correct concentration of the developer due to evaporation, it is preferable to add water corresponding to the amount of evaporation.

The present invention is also effective when the developer is recycled and used.

Recycling of a developer is to increase the activity of the used developer by subjecting it to anion exchange resin, electrodialysis, or adding a processing chemical called a regenerant, and then using it again as a processing solution. .

In this case, the regeneration rate (ratio of overflow liquid in the replenisher) is preferably 50% or more, particularly preferably 70% or more.

As a regeneration method, it is preferable to use an anion exchange resin. Particularly preferred compositions of anion exchange resins and resin regeneration methods include those described in Diaion Manual (I) (14th edition, 1986) published by Mitsubishi Kasei Corporation.

In addition, among anion exchange resins, patent application No. 63-472
Preferred are resins having the compositions described in No. 69 and Japanese Patent Application No. 63-1)0054.

In processing using developer regeneration, the overflow liquid of the developer is regenerated and then used as a replenisher.

In the present invention, the color-developed photosensitive material is processed with a processing solution having bleaching ability. The processing liquid having bleaching ability as used herein refers to a bleaching liquid and a bleach-fixing liquid.

Typical desilvering treatment steps including treatment with such a treatment solution include the following.

■ Bleach-fixing ■ Bleach → Bleach-fixing ■ Bleach → Washing → Fixing ■ Bleach → Bleach-fixing → Fixing ■ Bleach-fixing ■ Fixing → Bleach-fixing Among the above steps, steps ■, ■, and ■ are particularly preferred, and steps ■ For example, JP-A-61-75352
Disclosed in the issue. For process ■, see JP-A-61-1
43755 and Japanese Patent Application No. 2216389.

In addition, the treatment baths such as bleaching baths and fixing baths used in the above steps may have one tank or two or more tanks (for example, 2 to 4 tanks, in which case a countercurrent type is preferable). good.

The above steps may be carried out after color development via a rinsing bath, water washing bath, stop bath, etc., or preferably carried out immediately after color development.

The oxidizing agent contained as a main component in the treatment solution having bleaching ability of the present invention includes inorganic compounds such as red blood salt, ferric chloride, dichromate, persulfate, and bromate, and aminopolycarbonate. Partially organic compounds of acid iron (I[[) complex salts can be mentioned.

In the present invention, aminopolycarphonic acid iron (I[[) complex salt is preferably used from the viewpoint of environmental protection, handling safety, metal corrosivity, etc.

Below, aminopolycarboxylic acid iron (II) in the present invention will be described.
I) Specific examples of complex salts will be given, but the invention is not limited to these. In addition, the oxidation-reduction potential is recorded.

Floor Compound Redox potential (mV
vs, NHE, pH=6) 1, N-(2-acetamide) Iron(I) iminodiacetate complex 180 Iron(III) methyliminodiacetate complex 200 Iron(I) iminodiacetate complex 210 1.4-Butylenediaminetetraacetic acid Iron (I[[) complex salt 230 diethylenethioethernaminetetraacetate iron<II[) complex salt 230
Glycol etherine amine iron tetraacetate (I[) complex salt 24013-Propylene diamine iron tetraacetate (DI) complex salt 250 Ethylenecyamine iron tetraacetate (I) complex salt 1)0 Noethylenetriamine iron pentaacetate (I[[) complex salt 8010 , trans-1,2-cyclohexanediaminetetraacetic acid iron (III) salt 80 In the present invention, the Wlton of rapid processing and the 3゜6゜5゜4゜7゜9゜8゜ effect are effectively exhibited. The redox potential is 150 m from the viewpoint of
An oxidizing agent having a redox potential of V or more (hereinafter referred to as a high potential oxidizing agent) is preferable, more preferably an oxidizing agent having a redox potential of 180 mV or more, most preferably 200 mV or more. If the redox potential is too high, bleaching and fogging will occur, so the upper limit is 700 mV or less, preferably 500 mV or less.

The redox potential of the oxidizing agent in the above is determined by the Transactions Co., Ltd.
actions of the Faraday
5ociety), vol. 55 (1959), 1312~
It is defined by the redox potential measured by the method described on page 1313.

The oxidation-reduction potential in this case was obtained by the method described above under the condition of pH 6.0, and the potential determined at pH 6.0 is used because the color development process has been completed and the bleaching ability has been achieved. When a photosensitive material enters the processing solution, the pH in the film of the photosensitive material decreases, and if the pH decreases quickly, the bleaching fog will be small. This is because if the pH is high, the bleaching blade smudge will be large, so a pH around 6.0 is an indication of the occurrence of bleaching smudge.

Among these, particularly preferred is the 1,3-propylenezaminetetraacetic acid iron (■) complex salt of compound Nα7 (hereinafter abbreviated as 1,3-PDTA-Fe (III)) (this is a particularly preferred 1986-222252, JP-A-64-
It is the same compound as the 1,3-diaminopropanetetraacetic acid iron(II) complex salt disclosed in No.

Aminopolycarphonic acid iron (II) complex salt contains sodium,
Salts such as potassium and ammonium are used, and ammonium salt is preferred because it bleaches the fastest.

The amount of the oxidizing agent used in the processing liquid having bleaching ability in the present invention is preferably 0.17 mol or more per processing liquid 1), and is 0.017 mol or more in order to speed up the processing and reduce bleaching blade blur and stain.
It is preferably 25 moles or more. Particularly preferred is 0.30 mol or more.

However, since the use of an excessively high concentration solution will inhibit the bleaching reaction, the upper limit of the concentration should be about 0.7 mol.

Further, in the present invention, the oxidizing agent may be used alone or in combination of two or more.

When two or more types are used together, the total concentration may be within the above range.

In addition, when using an aminopolycarboxylic acid iron (III) complex salt in a treatment solution having bleaching ability, it can be added in the form of a complex salt as described above, or it can be added in the form of a complex-forming compound, aminopolycarboxylic acid, and iron(III) complex salt. A complex salt may be formed in the bleaching solution by coexisting with a ferric salt (for example, ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate).

In the case of this complex formation, the aminopolycarboxylic acid may be added in a slightly excess amount compared to the amount required for complex formation with ferric ions, and when added in excess, it is usually 0.01.
It is preferable to use an excess in the range of 10% to 10%.

The processing solution that develops the bleaching ability as described above has a numerically pH of -2
-8 are used. To speed up processing, the pH
25 to 50, preferably 30 to 48, particularly preferably 35 to 4.5, and the replenisher is usually 2.0
It may be used as ~42.

In the present invention, the pH is adjusted to the above range (for this, known acids can be used).

As such an acid, an acid having a pKa of 2 to 55 is preferable. In the present invention, pKa represents the logarithm of the reciprocal of the acid dissociation constant, and indicates a value determined at an ionic strength of 01.25°C.

In the present invention, an acid having a pKa of 20 to 5.5 is used at 0.5 mol/f! It is preferable to use a processing solution containing the above-mentioned bleaching ability or to eliminate the bleaching turnip IJ, and to improve the increase in staining in uncolored areas over time after processing.

The acid with a pKa of 2.0 to 55 may be an inorganic acid such as phosphoric acid, an organic acid such as acetic acid, malonic acid, citric acid, etc. The organic acid is an acid having a molecular weight of .0 to 5.5.Among the organic acids, organic acids having a carboxyl group are particularly preferred.

The organic acid having a pKa of 20 to 55 may be a monobasic acid or a polybasic acid. In the case of polybasic acids, their pK
If a is in the above range of 20 to 55, it can be used as a metal salt (for example, sodium or potassium salt) or ammonium salt. Further, two or more kinds of organic acids having a pKa of 2.0 to 5.5 can be used in combination. However, the term acid here excludes aminopolycarboxylic acids, their salts, and their Fe complex salts.

Preferred specific examples of organic acids with a pKa of 2.0 to 55 that can be used in the present invention include formic acid, acetic acid, monochloroacetic acid, monobromoacetic acid, glycolic acid, propionic acid, monochloropropionic acid, lactic acid, pyruvic acid, Aliphatic-basic acids such as acrylic acid, butyric acid, isobutyric acid, pivalic acid, aminobutyric acid, valeric acid, isovaleric acid, asparagine, alanine, arginine, ethionine, glycidi, glutamine, stein, serine, methionine, leucine, etc. Amino acid-based compounds with: benzoic acid and monosubstituted benzoic acids such as chloro and hydroquine, and aromatic compounds such as nicotinic acid.
Basic acids: Aliphatic tribasic acids such as oxalic acid, malonic acid, succinic acid, tartaric acid, malic acid, maleic acid, fumaric acid, oxaloacetic acid, glutaric acid, ampic acid, aspartic acid, glutamic acid, glutaric acid, Various organic acids can be listed, including amino acid tribasic acids such as cystine and ascorbic acid; aromatic tribasic acids such as phthalic acid and terephthalic acid; and polybasic acids such as citric acid.

In the present invention, among these, monobasic acids having a hydroxyl group and a carboxyl group are preferred, and glycolic acid and lactic acid are particularly preferred.

The amount of glycolic acid and lactic acid used is 0.2 to 2 mol, preferably 0.5 to 1.5 mol, per 1) of the bleaching solution. These acids are preferable because they exhibit the effects of the present invention more markedly, are odorless, and inhibit bleaching blade blemish.

Further, in the present invention, it is preferable to use acetic acid and glycolic acid or lactic acid in combination because the effect of simultaneously solving the problem of residual color and bleaching blade blur becomes significant.

The combined ratio of acetic acid and glycolic acid or lactic acid is 1:2.
~2 liters is preferred.

In the present invention, the total amount of these acids used is suitably 0.5 mole or more per 1β in a processing solution having bleaching ability. Preferably 12 to 25 mol/I! It is. More preferably 15 to 2°0 mol/! It is.

When adjusting the pH of the processing solution having bleaching ability to the above range,
The above acids and alkaline agents (e.g. aqueous ammonia, KOH
, NaOH, imidazole, monoethanolamine, jetanolamine) may be used in combination. Among these, ammonia water is preferred.

Further, as the alkaline agent used in the bleach starter when adjusting the starting solution of the processing solution having bleaching ability from the replenisher, it is preferable to use imidazole, monoethanolamine or jetanolamine.

In the present invention, various bleaching accelerators may be added to the processing solution having bleaching ability or its pre-bath. Such bleach accelerators are described, for example, in U.S. Pat.
93.858, German Patent No. 1,290.82
Specification No. 1, British Patent No. 1,138,842,
Compounds that grow mercapto groups or disulfide groups as described in JP-A No. 53-95630 and Research Disclosure No. 17129 (July 1978 issue), 1,000 azolidine derivatives as described in JP-A-50-140129; Thiourea derivatives described in U.S. Patent No. 3,706,561, iodides described in JP-A-58-16235, polyethylene oxides described in German Patent No. 2,748,430, 45-8836
Polyamine compounds described in the above publication can be used. Particularly preferred are mercapto compounds as described in British Patent No. 1,138.842 and Japanese Patent Application No. 1-1-256.

In addition to the oxidizing agent (bleaching agent) and the above-mentioned compounds, the processing solution having bleaching ability in the present invention includes bromides such as potassium bromide, sodium bromide, ammonium bromide, or chlorides such as potassium chloride, sodium chloride, Rehalokenizing agents such as ammonium chloride may be included. The concentration of the rehalogenating agent is 0.0.
The amount is 1 to 5 mol, preferably 0.5 to 3 mol.

Further, it is preferable to use ammonium nitrate as a metal corrosion prevention agent.

In the present invention, it is preferable to adopt a replenishment method, and the amount of replenishment of bleaching solution is 600 m 1 per 1rd photosensitive material.
It is preferably 100 to 500 m1 or less, and more preferably 100 to 500 m1.

Further, the bleaching treatment time is 120 seconds or less, preferably 50 seconds or less, and more preferably 40 seconds or less. The present invention is effective in such a shortened processing time.

In addition, during the treatment, it is preferable that the treatment solution having bleaching ability using the aminopolycarboxylic acid iron (In) complex salt is subjected to aeration to oxidize the produced aminopolycarboxylic acid iron (II) complex salt.

This regenerates the oxidizing agent and maintains extremely stable page printing performance.

In the treatment with a treatment liquid having bleaching ability in the present invention, it is preferable to perform so-called evaporation correction, in which water corresponding to the evaporated amount of the treatment liquid is supplied. Particularly preferred is a bleaching solution containing a high potential oxidizing agent as an oxidizing agent.

There are no particular restrictions on the specific method for replenishing water; for example, methods (1) to (4) below may be used.

(1) Install a monitor tank separate from the bleach tank, calculate the evaporation amount of water in the monitor tank, calculate the evaporation amount of water in the bleach tank from this water evaporation amount, and calculate the amount of water evaporation in proportion to this evaporation amount. Method of replenishing water in a bleaching tank (Japanese Patent Application Laid-open No. 1-254959,
(See Publication No. 1-254960). At this time, it is preferable to replenish water at regular intervals.

(2) A method of controlling the specific gravity of the bleach solution in the bleach tank and replenishing a certain amount of water when the specific gravity exceeds a certain value.

(3) A method of replenishing water when the level of the bleach solution in the bleach tank drops by a predetermined amount due to evaporation.

(4) A method of estimating the amount of evaporation from the treatment equipment, environmental conditions, etc. and replenishing a fixed amount of water equivalent to the estimated amount.

These methods are performed once or several times a day.

Among the methods (1) to (4) above, (3) and (4)
The method described above is preferable because it can effectively prevent changes in the composition of the treatment liquid with a simple configuration.

In the case of (3), it is preferable that the liquid level is detected by a level sensor, and when the liquid level drops to a certain level, water is replenished to compensate for the drop.

In the present invention, the photosensitive material that has been processed with a processing liquid having bleaching ability is then processed with a processing liquid having fixing ability.

The processing liquid that improves the fixing ability mentioned here specifically includes a fixing liquid and a bleach-fixing liquid.

When the treatment is carried out with a bleaching ability or a bleach-fixing solution, it may also serve as a treatment that increases the fixing ability, as in step (2) above. The bleach-fix solution as a processing solution with bleaching ability is substantially the same as the bleach-fix solution as a processing solution with fixing ability, or the above-mentioned method (2) or In step (2), the bleaching solution and the bleach-fixing solution may use different oxidizing agents.

The processing liquid having fixing ability of the present invention contains not only the above-mentioned imidazole compound but also a fixing agent.

As fixing agents, thiosulfates such as sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate, potassium thiosulfate, thiocyanates (rodan salts) such as sodium thiocyanate, ammonium thioneanate, potassium thiocyanate, thiourea, Thioethers etc. can be given. Among these, it is preferable to use ammonium thiosulfate. The amount of fixing agent is 0.3 to 3 mol per fixer or bleach-fixer 1), preferably 0.
It is 5 to 2 moles.

In addition, from the viewpoint of promoting fixation, the above-mentioned ammonium thiocyanate (rhodan ammonium), thiourea, thioether (for example, 3,6-cythia, 8-octanediol)
It is also preferable to use them together.

The amount of these compounds used in combination is 0.01 to 1 mol, preferably 0.01 to 0.5 mol per fixer or bleach-fixer 1).
It may be used in moles, but depending on the case, using 1 to 3 moles can greatly enhance the fixing promoting effect.

As the fixing agent in the fixing solution or bleach-fixing solution, it is preferable to use a thiosulfate and a thionoanate in combination in order to speed up the processing. In particular, a combination of ammonium thiosulfate and ammonium thiocyanate is preferred. When used together, thiosulfate is added in the amount of 043 to 3 mol/
1 and thiocyanate at 1 to 3 mol/l, preferably 1 to 25 mol/l.

The fixer or bleach-fixer contains sulfites as preservatives (e.g. sodium sulfite, potassium sulfite, ammonium sulfite) and hydroxylamine, hydrazine,
Bisulfite adducts of aldehyde compounds (e.g. acetaldehyde sodium bisulfite, particularly preferably
-298935) and the like can be included. Furthermore, it is possible to contain various optical brighteners, antifoaming agents, surfactants, polyvinylpyrrolidone, organic solvents such as methanol, etc. In particular, as a preservative, the It is preferable to use a sulfinic acid compound.

Furthermore, it is preferable to add various aminopolycarboxylic acids and organic phosphonic acids to the fixer and bleach-fixer for the purpose of stabilizing the solution. Preferred compounds include 1-hydroxyethylidene-1,1-diphosphonic acid and ethylenediamine-1,1-diphosphonic acid.
N, N, N', N' Tetramethylenephosphonic acid, nitrilotrimethylenephosphonic acid, ethylenecyaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, and 1,2-propylenediaminetetraacetic acid can be mentioned. Among these, -hydroxyethylidene-1,1-diphosphonic acid and ethylenediaminetetraacetic acid are particularly preferred.

The amount of these compounds to be added is 0.00% per 1 liter of treatment solution.
OI ~ 0.3 mol, preferably 01-02 mol.

The bleach-fix solution may contain compounds that can be contained in the bleach solution described above.

In the bleach-fix solution, the amount of bleach per 1 i' of bleach-fix solution is 0. O1 to 05 mol, preferably 0.015 to 0.05 mol
The amount is 0.3 mol, particularly preferably 0.02 to 0.2 mol.

The pH of the fixer is preferably 5 to 9, more preferably 7.
~8 is preferred. In addition, the pH of the bleach-fix solution is 6.
-85 is preferable, and 6°5-8.0 is more preferable.

In the present invention, the bleach-fix solution (start solution) at the start of processing is prepared by dissolving the above-mentioned compounds used in the bleach-fix solution in water. It may also be prepared by

When using the replenishment method, the amount of replenishment of the fixer or bleach-fixer is 100 to 300 per 1rrl' of the photosensitive material.
0mj7 is preferred, more preferably 3OO~180
It is 0ml. The bleach-fix solution may be replenished as a bleach-fix replenisher, or may be carried out using an overflow solution of the bleach solution and the fix solution as described in Japanese Patent Application No. 2-216'389.

Further, as in the above bleaching process, it is preferable to perform the bleach-fixing process while replenishing the processing solution and replenishing water corresponding to the evaporated amount.

Further, in the present invention, the total processing time of the processing having fixing ability is preferably 0.5 to 2 minutes, particularly 0.5 to 1 minute.

In the present invention, the shorter the total processing time of the desilvering step consisting of a combination of bleaching, bleach-fixing, and fixing, the more remarkable the effects of the present invention can be obtained. The preferred time is 45 seconds to 4 minutes, more preferably 1 minute to 2 minutes.

In addition, the treatment temperature is 25-50°C, preferably 35-40°C.
It is 5°C. In a preferred temperature range, the desilvering rate is improved and the occurrence of staining after processing is effectively prevented.

The processing liquid having the fixing ability of the present invention can be subjected to silver recovery by a known method, and a recycled liquid after such silver recovery can be used. As a silver recovery method, electrolysis method (
French Patent No. 2,299,667), precipitation method (Japanese Patent Application Laid-Open No. 52-73037, German Patent No. 2,331,220)
No. 4), ion exchange method (JP-A-51-171) No. 4,
Effective methods include the method described in German Patent No. 2,548,237) and the metal substitution method (described in British Patent No. 1,353,805). It is preferable to carry out these silver recovery methods in-line from the tank liquid, since the suitability for rapid processing becomes even better.

In the present invention, after the treatment step with fixing ability, treatment steps such as washing with water and stabilization are performed. It is also possible to use a simple processing method in which after processing with a processing liquid having fixing ability, stabilization processing is performed without substantial washing with water.

The washing water used in the washing step can contain various surfactants in order to prevent uneven water droplets when drying the photosensitive material after processing. These surfactants include polyethylene glycol type nonionic surfactants, polyhydric alcohol type nonionic surfactants, alkylbenzene sulfonate type anionic surfactants, and higher alcohol sulfate ester salt type anionic surfactants. agent, alkylnaphthalene 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, since ionic surfactants may combine with various ions mixed in during processing to form insoluble substances, it is preferable to use nonionic surfactants, especially alkylphenol ethylene oxide adducts. Or preferable. As the alkylphenol, octyl, nonyl, dodecyl, and dinonylphenol are particularly preferred, and the number of moles of ethylene oxide added is particularly preferably 8 to 14. Furthermore, it is also preferable to use a silicone surfactant that has a high antifoaming effect.

In addition, various antibacterial agents,
It may also contain a fungicide. Examples of these antibacterial and antifungal agents are disclosed in Japanese Patent Application Laid-open No. 15724-1983.
4 and No. 58-105145, isothiazolone compounds as shown in JP-A-57-8542, or tetrachlorophenol as represented by trichlorophenol. Phenolic compounds, bromophenol compounds, organotin and organozinc compounds, thiocyanic acid and isothiocyanic acid compounds,
Alternatively, an acid amide compound, a diazino or triazine compound, a thiourea compound, a penbutriazole alkylguaninone compound, or
Quaternary ammonium salts such as benzalkonium chloride, antibiotics such as penicillin, etc.
tibact, Antifung, Agents)
Vol 1. No, 5. p, 207-223 (
One or more of the general-purpose anti-spill agents described in (1983) may be used in combination. Furthermore, various fungicides described in JP-A-48-83820 can also be used.

It is also preferable to contain various chelating agents. Preferred compounds for the chelating agent include aminopolycarphonic acids such as ethylenediaminetetraacetic acid and soethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenenoaminetetraacetic acid, diethylenetriamine-N, NN', N'-tetramethylenephosphonic acid and other organic phosphonic acids, or European Patent No. 3451
Examples include hydrolysates of maleic anhydride polymers described in 72AI.

Further, it is preferable that the washing water contains a preservative that can be contained in the above-mentioned fixing solution or bleach-fixing solution.

The stabilizing solution used in the stabilization step includes a processing solution that stabilizes the dye image, such as a solution containing a residual acid, a solution having a buffering capacity of pH 3 to 6, and a solution containing an aldehyde (for example, formalin or glutaraldehyde). It can be used. The stabilizing liquid may contain all the compounds that can be added to the washing water, and may also contain ammonium compounds such as ammonium chloride and ammonium sulfite, B1, AA, etc.
Nato metal compound, optical brightener, JP-A-2-15334
No. 8, JP-A No. 63-244036 and U.S. Patent No. 485
N-methylol compounds described in No. 9574 etc. (for example,
Dimethylol urea), hexamethylenetetramine and its derivatives, hexahydrotriazine and its derivatives, various dye stabilizers and stabilization methods using these, hardening agents, alkanolamines described in U.S. Pat. No. 4,786,583, etc. I can do it.

Further, the water washing step and the stabilization step are preferably carried out using a multistage countercurrent method, and the number of stages is preferably 2 to 4 stages.

The replenishment amount is 1 to 5 of the amount brought in from the previous bath per unit area.
0 times, preferably 2 to 30 times, more preferably 2 to 15 times
It's double.

The water used in these washing steps and stabilization steps can be tap water, or water that has been deionized with an ion exchange resin to reduce the Ca5Mg concentration to 5 μ/l or less,
It is preferable to use water that has been sterilized using halogen or ultraviolet germicidal lamps.

In addition, the water used to correct the evaporation content of each treatment liquid may be tap water, or deionized water or sterilized water that is preferably used in the above-mentioned washing or stabilization process. It's beautiful.

In the present invention, it is preferable to replenish not only the bleaching solution, bleach-fixing solution, and fixing solution but also other processing solutions with an appropriate amount of water, a correction solution, or a processing replenisher in order to correct concentration due to evaporation.

Further, it is preferable to use a method in which the overflow liquid from the water washing step or the stabilization step is allowed to flow into a bath having a fixing ability, which is a pre-bath, because the amount of waste liquid can be reduced.

In the present invention, the effect is particularly effectively exhibited when the total treatment time with the treatment liquid after bleaching treatment, that is, the total treatment time before entering the drying step, is 1 minute to 3 minutes. Preferably, the time is 1 minute 20 seconds to 2 minutes.

The processing method of the present invention is usually carried out using an automatic processor. An automatic processor preferred for the present invention will be described below.

In the present invention, the air time during which the photosensitive material moves between each processing solution, that is, the crossover time, is preferably as short as possible, preferably 10 seconds or less, more preferably 7 seconds or less, and still more preferably 5 seconds or less. .

In order to achieve the above-mentioned short-time crossover, it is preferable to use a cine type automatic developing machine in the present invention, and a leader conveyance type is particularly preferable. Such a system is used in the automatic processor FP-550B manufactured by Fuji Photo Film. Also, is the linear speed of conveyance higher or preferable?
The above leader system generally has a speed of 30an to 2m per minute, preferably 50cm to 1.5m.

As a means of conveying readers and photosensitive materials,
No. 191257, No. 60-191258, No. 60-1
The belt conveyance system described in Japanese Patent Application No. 91259 is preferred, and in particular, as the conveyance mechanism, Japanese Patent Application No. 1-265794 and Japanese Patent Application No. 1-265794,
It is preferable to employ the methods described in No. 266915 and No. 1-266916.

Further, in order to shorten the crossover time and prevent mixing of the processing liquid, it is preferable that the structure of the crossover rack has a mixing prevention plate as described in Japanese Patent Application No. 1-265795.

In the present invention, it is preferable that the stirring of each treatment liquid be as strong as possible in order to more effectively exhibit the effects of the present invention.

A specific method for strengthening stirring is disclosed in Japanese Patent Application Laid-open No. 62-1834.
No. 60, JP-A No. 62-183461, in which a jet of processing liquid impinges on the emulsion surface of a light-sensitive material such as that used in the color negative film processor FP-230B manufactured by Fuji Photo Film ■. There is also a method of increasing the stirring effect using a rotating means as disclosed in JP-A No. 62-183461, and a method of moving the photosensitive material (film) while bringing the emulsion surface into contact with a wiper blade provided in the liquid to improve the emulsion surface. Examples include a method of improving the stirring effect by creating turbulent flow, and a method of increasing the circulation flow rate of the entire treatment liquid. Among these, the method of colliding jets of the processing liquid is most preferred, and it is preferable that this method is adopted for all processing tanks.

In particular, when processing with a processing liquid having a fixing ability, the effects of the present invention can be greatly improved by colliding the jet stream within 15 seconds after the photosensitive material comes into contact with the processing liquid having a fixing ability. More preferably within 10 seconds, still more preferably within 5 seconds.

The reason why such an effect is obtained is currently unknown, or if the agitation is too weak immediately after contact with the photosensitive material or the liquid with fixing ability, a factor that causes residual color may occur, causing the jet to collide strongly. It is thought that this factor can be removed by

More specifically, the jet impingement method for each processing liquid is described in the section of Examples of the invention on page 3, lower right column to page 4, lower right column of JP-A-62-183460. It is preferable to use a method in which the liquid is discharged under pressure by a pump from nozzles provided facing each other.

The pump is Ikki's magnetic pump MD-1.
0, MD-15, MD-20, etc. can be used. The hole diameter of the nozzle is 0.5 to 2, preferably 0.8
It is 1.5 mm from In addition, it is preferable that the nozzle opens in a circular direction as perpendicular to the chamber plate surface and the film surface as possible, but the angle may be 60 degrees to 120 degrees from the conveyance direction side, and the shape may be rectangular or slit-like. . The number of nozzles is 1 per tank capacity If.
The number is 50, preferably 10 to 30. In addition, if the jet stream hits a part of the film unevenly, uneven development or residual color will occur, so make sure to position the nozzle so that it does not hit only the same place and on a straight line parallel to the transport direction. It is preferable to shift them sequentially. A preferred arrangement of these nozzles is, for example, as shown in FIG. 3, in which about 4 to 8 large nozzles are arranged perpendicularly to the conveying direction, and their 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 fast, the stirring effect will be weakened, so it is preferably 1 to 12 mm, more preferably 3 to 9 mm.

The flow rate of the liquid discharged from each nozzle similarly exists in an optimum range, preferably 05 to 5 m/sec, particularly preferably 1 to 5 m/sec.
It is 3m/sec.

The entire treatment liquid may be circulated only through the nozzle, or a separate circulation system may be provided. The total circulation flow rate is 0.2 to 51 per minute, preferably 0 per tank capacity of each treatment tank.
5 to 41, or the circulation flow rate in each desilvering step of bleaching, bleach-fixing, and fixing should be relatively large, and the preferable range is 1.5 to 41.

The automatic processor used in the process of the present invention preferably has a device for aerating the bleaching solution.

Aeration can prevent a reduction in bleaching speed due to the formation of divalent iron complexes during continuous processing and the formation of cyan leuco dyes, which are known as poor color recovery.

Air lanes are disclosed in Japanese Unexamined Patent Application Publication No. 2-176746 and No. 2-176746.
- Pore diameter 300 μm as described in No. 176747
0.014 per liter of treatment tank using the following porous nozzle
? It is preferable to supply a flow rate higher than that.

Processing the photosensitive material continuously or intermittently without replenishing the replenisher is called running processing, or the bleaching solution used during running processing is extremely degraded by the surfactant eluted from the processed photosensitive material. It becomes easier to foam. Therefore, when aeration is performed, so many bubbles are generated that the treatment tank may overflow. In order to prevent this, it is preferable to provide a defoaming means.
No. 04731, No. 2-165367, No. 2-1653
The method described in No. 68 is effective.

In the process of the present invention, it is preferable to correct the evaporative concentration of the process liquid that occurs during the running process.

The most preferable evaporation correction method is to predict and add water equivalent to the amount of water that evaporates.As described in Japanese Patent Application No. 1-103894, information on the operating time, stop time, and temperature control time of the automatic developing machine is used. The amount of water added is calculated based on a coefficient determined in advance.

In addition, Japanese Patent Application Nos. 2-46743 and 2-47777
No. 2-47778, No. 2-47779, No. 2-
1) An evaporation correction method using a liquid level sensor as described in No. 7972 is also preferred.

In addition, it is necessary to take measures to reduce the amount of evaporation, such as reducing the opening area or adjusting the air volume of the exhaust fan.

For example, it is preferable that the aperture ratio of the color developing solution is as described above, or that the aperture area of other processing solutions is similarly reduced.

The exhaust fan is installed to prevent condensation during temperature control, but the preferred exhaust rate is 0.1rn' to 0.1rn' per minute.
lrn', and a particularly preferable displacement is 0.2
m'~0.4rn'.

Furthermore, the drying conditions of the photosensitive material also affect the evaporation of the processing liquid.

As a drying method, it is preferable to use a ceramic hot air heater, and the supply air volume is 4 rn' 12 to 12 rn' per minute.
20 rn' is preferred, and 6 rn' to 10 rn' is particularly preferred.

The thermostat for preventing heating of the ceramic hot air heater is preferably operated by heat transfer, and the thermostat is preferably mounted on the leeward or upwind side through heat radiation fins or heat transfer parts.

The drying temperature is preferably adjusted depending on the moisture content of the photosensitive material to be processed, and for a film with a width of 35, the drying temperature is 45 to 5.
The optimum temperature is 5°C, and 55 to 65°C for brownie film.

When replenishing the processing solution, a replenishment pump is used, or preferably a bellows type replenishment pump. Furthermore, an effective method for improving replenishment accuracy is 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 squares, and a particularly preferred inner diameter is 2 to 5 squares.

The various component materials used and preferred materials for automatic processors are described below.

The material for tanks such as the processing tank and the temperature control tank is preferably modified PP0 (modified polyphenylene oxide) or modified PPE (modified polyphenylene ether) resin. Examples of modified PPO include "Noryl" manufactured by Japan GE Plastics Co., Ltd., and examples of modified PPE include "Zylon" manufactured by Asahi Kasei Corporation and "Iupiace" manufactured by Mitsubishi Gas Chemical. Furthermore, these materials are suitable for parts such as processing racks and crossovers that may come into contact with processing liquids.

The roller material of the processing section is PVC (polyvinyl chloride), PP (polypropylene), PE (polyethylene), or TP.
Resins such as X (polymethylpentene) are suitable. Furthermore, these materials can also be used for other processing liquid contact parts.

Incidentally, PE resin is also preferable as a material for a replenishment tank formed by blow molding.

The material of processing parts, gears, sprockets, bearings etc. is P.
A (polyamide), PBT (polybutylene terephthalate), UHMPE (ultra high molecular weight polyethylene), P
Resins such as PS (polyphenylene sulfide) and LCP (wholly aromatic polyester resin, liquid crystal polymer) are suitable.

The PA resin is a polyamide resin such as nylon 66, nylon 12, or nylon 6, and those containing glass fibers, carbon fibers, etc. can be used because they are resistant to swelling by the processing liquid.

Furthermore, single polymer products such as MC nylon and compression molded products can be used without fiber reinforcement. Unreinforced UHMPE resins are suitable, such as Mitsui Petrochemical's ``Luvma'' and HIZEX Million''.
Sakushin Kogyo's ``New Light'' and Asahi Kasei's ``Sunfine'' are suitable. The molecular weight is preferably 100
1,000,000 or more, more preferably 1,000,000 to 5,000,000.

The PPS resin is preferably one reinforced with glass fiber or carbon fiber. Examples of LCP resins include ICI Japan's ``Pictrex,'' Sumitomo Chemical's ``C-Econol'', Nippon Oil's ``Zyder,'' and Polyplastics'``Vectra.''

Suitable soft materials for squeeze rollers and the like include foamed vinyl chloride resin, foamed silicone resin, and foamed urethane resin. Examples of foamed urethane resins include "Rubicell" manufactured by Toyo Polymer ■.

As the rubber material for piping joints, adhesion jet pipe joints, and sealing materials, EPDM rubber, silicone rubber, pyton rubber, etc. are preferable.

The light-sensitive material in the present invention may be provided with at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on a support. There are no particular limitations on the number and order of the emulsion layers and non-photosensitive layers. A typical example is a silver halide color photographic light-sensitive material having a light-sensitive layer on a support, which is composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different light sensitivities. Yes, the photosensitive layer is a unit photosensitive layer that is sensitive to blue light, green light, or red light,
In a multilayer silver halide color photographic light-sensitive material, generally unit photosensitive layers are arranged, or a red-sensitive layer, a green-sensitive layer and a blue-sensitive layer are provided in this order from the support side. but,
Depending on the purpose, the above-mentioned installation order may be reversed, or the installation order may be such that different color-sensitive layers are sandwiched within the same color-sensitive layer.

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

For the middle class, Japanese Patent Application Laid-open Nos. 61-43748 and 59-1)
No. 3438, No. 59-1) No. 3440, No. 61-200
No. 37, No. 61-20038, etc. may be included, and the color mixture inhibitor, ultraviolet absorber, stain inhibitor, etc., which are commonly used, may also be included.

The plurality of silver halide emulsion layers constituting each unit photosensitive layer are
West German Patent No. 1,121,470 or British Patent No. 9
As described in No. 23,045, a two-layer structure consisting of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer can be preferably used. Usually, it is preferable to arrange the layers so that the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also, JP-A-57-1
) No. 2751, No. 62-200350, No. 62-20
As described in No. 6541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side far 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, low sensitivity blue sensitive layer (BL) / high sensitivity blue sensitive layer (BH) / high sensitivity green sensitive layer (GH) / low sensitivity green sensitive layer (GL) /high-sensitivity red-sensitive layer (RH)/low-sensitivity red-sensitive layer (RL)/in order,
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 Japanese Patent Publication No. 55-34932, from the side farthest from the support, the blue-sensitive layer/GH/R
They can also be arranged in the order of H/GL/RL. Furthermore, as described in JP-A-56-25738 and JP-A-62-63936, it is also possible to arrange the blue-sensitive layer/GL/RL/GH/RH in this order from the farthest side from the support. Ru.

Further, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a /SS rosin silver emulsion layer with a lower sensitivity,
An arrangement may be made in which a silver halide emulsion layer having lower photosensitivity than the middle layer is arranged as the lower layer, and three layers having different photosensitivity are successively lowered toward the support. Even when it is composed of three layers with different photosensitivity,
As described in Japanese Patent Application Laid-Open No. 59-202464,
In the same color-sensitive layer, medium-sensitivity emulsion layer/high-sensitivity emulsion layer/low-sensitivity emulsion layer may be arranged in this order from the side remote from the support.

As mentioned above, various layer structures and arrangements can be selected depending on the purpose of each photosensitive material.

Any of these layer arrangements can be used in the photosensitive material of the present invention, but in the present invention, the dry film thickness of all constituent layers of the photosensitive material excluding the support and the undercoat layer and backing layer of the support is 20.0μ or less. This is particularly preferable in achieving the object of the present invention.

More preferably, it is 18.0μ or less.

These film thickness regulations are determined by the color developing agents that are incorporated into these layers of the photosensitive material during and after processing.
This is because the amount of remaining color developing agent has a large effect on bleaching fog and staining that occurs during image storage after processing. Note that it is desirable that the lower limit value in the film thickness regulation be reduced within a range that does not significantly impair the performance of the photosensitive material based on the above regulation. The lower limit of the total dry film thickness of the constituent layers of the photosensitive material excluding the support and the undercoat layer of the support is 12.0μ, and the lower limit of the total dry film thickness of the constituent layers excluding the support and the undercoat layer of the support is 12.0 μm. The lower limit of the total dry film thickness of the constituent layers is 1.0μ.

The film thickness may be reduced in either the photosensitive layer or the non-photosensitive layer.

The film thickness of the multilayer color photosensitive material in the present invention is determined by storing the photosensitive material to be measured at 25°C and 150% RH for 7 days after its preparation, and first measuring the total thickness of the photosensitive material. After removing the coated layer on the support, the thickness is measured again, and the difference is used as the thickness of the entire coated layer of the photosensitive material excluding the support. This thickness measurement is
For example, a film thickness measuring device (Anr
itusElectric Co, Ltd., K-
402B 5tand, ). Note that the coating layer on the support can be removed using an aqueous sodium hypochlorite solution.

It is also possible to take a cross-sectional photograph of the photosensitive material using a scanning electron microscope (magnification is preferably 3,000 times or more) and measure the total thickness on the support.

Swelling rate of the photosensitive material in the present invention [(25°C1H2O
Equilibrium swelling film thickness in -25°C, 155%RH dry total film thickness/25°C, 55%RH dry total film thickness)X100]
is preferably 50 to 200%, more preferably 70 to 150%. If the swelling ratio deviates from the above-mentioned value, the amount of color developing agent remaining will increase, and this will have an adverse effect on photographic performance, image quality such as desilvering properties, and film properties such as film strength.

Furthermore, the film swelling rate of the photosensitive material in the present invention is defined as the saturated swelling film thickness, which is 90% of the maximum swelling film thickness reached when processed in a color developing solution (38°C, 3 minutes 15 seconds). When the time required to reach the film thickness is defined as the swelling rate T%, it is preferable that 1% is 15 seconds or less. More preferably, it is 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. Preferred silver halides are silver iodobromide, silver iodochloride, or silver iodochlorobromide, containing about 0.1 to 30 mole percent silver iodide. Particularly preferred is silver iodobromide containing from about 2 to about 25 mole percent iodide.

Silver halide grains in photographic emulsions include those with regular crystal shapes such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. It may be one that grows crystal defects or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 microns or less, or large grains with a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD) Ni1) 7643
(December 1978) 1. pp. 22-23, “I.

Emulsion production CEmuls1on preparat4on
andtypes)' and N1) 18716 (
January 1979), 648 pages, Glafkide [Physics and Chemistry of Photography], published by Paul Montell (P, Glafk)
ides, Chimie et Physique
Photographique Paul
Montel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F,
Duffin, PhotographicEmul
sion Chemistry (Focal Pres.
s, I 966)), “Manufacture and Coating of Photographic Emulsions” by Zelikman et al., published by Focal Press (V, L, Ze
likman et alMakingand Co
Ating Photographic Emul
sion.

Focal Press, 1964).

U.S. Patent No. 3,574,628, U.S. Patent No. 3,655.3
Monodisperse emulsions such as those described in No. 94 and British Patent No. 1.413,748 are also preferred.

Tabular grains having an aspect ratio of about 5 or more can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Science and Engineering.
ence and Engineerjng), 14th
Vol. 248-257 (1970): U.S. Patent No. 4,
434゜226, same No. 4,414,310, same No. 4
No. 430.048, No. 4,439,520 and British Patent No. 2,1) No. 2.157.

The crystal structure may be --like, the inside and outside may have different halogen compositions, or it may have a phase structure. Further, silver halides having different compositions may be bonded by epitaxial bonding, or compounds other than silver halide such as silver rhodan or lead oxide may be bonded.

Also, mixtures of particles of various crystal forms may be used.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are subject to Research Disclosure N1
) 17643 (December 1978), same Na1871
6 (January 1979)) and NQ307105
(January 1989)), and the relevant sections are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the three Research Disclosures (RD) mentioned above, and the relevant descriptions are shown in the table below.

Additives (Class 74 RD 17643 RD 1871
6 RD 3071051, chemical sensitizer page 23
Page 648 right column Page 866 2. Sensitivity enhancer
Page 648 right column 3, spectral sensitizer, pages 23-24 6
Page 48 right column Pages 866-868 Supersensitizer
~Page 649 Right column 4, Brightener Page 24 647
Page right page right page 868 page 5, anti-fogging page 24-25 page 649 right column page 868-870 agent, stabilizer 8° dye image stabilizer page 25 page 650 page left side page 872 page 9 degree hardener page 26 page 651 left Column 874-875 pages 1)゜Binder plasticizer, lubricant Page 26 651 page left 1t 873-874 page 27 650 page right m876 page 12゜Coating aid, surfactant 26-27 page 650 page right column 875~ Page 876 13° Static prevention side Page 27 Page 650 Right column Pages 876-877 14° Matting agent Pages 878-879 Various color couplers can be used in combination with the present invention, and typical examples thereof are as described above. RDNtl17643
, ■-C-G and RD Fish 307105, ■-C-G.

As a yellow coupler, for example, U.S. Patent No. 3.93
No. 3,501, No. 4,022,620, No. 4,32
No. 6,024, No. 4,401.752, No. 4,2
48,961, Japanese Patent Publication No. 58-10739, British Patent No. 1.425,020, British Patent No. 1,476.760,
U.S. Patent No. 3973.968, U.S. Patent No. 4,314,0
23, 4,51), 649, European Patent No. 249
The one described in No. 473A is preferred.

As the magenta coupler, 5-pyrazolone and pyrazoloazole compounds are preferred, and U.S. Patent No. 4,31
0,619, European Patent No. 4,351°897, European Patent No. 73,636, US Patent No. 3,061,432, US Patent No. 3,725,064, RD Chu 24220 (198
June 4), JP-A No. 60-33552, RD Nao 242
30 (June 1984), JP-A No. 60-43659,
No. 61-72238, No. 60-35730, No. 55
-1) No. 8034, No. 60-185951, U.S. Patent No. 4,500,630, U.S. Patent No. 4,540.654,
No. 4,556.630, WO (PCT) 8 B1
Particularly preferred are those described in No. 04795 and the like.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Pat. No. 4.052.21.
No. 2, No. 4,146,396, No. 4,228,2
No. 33, No. 4,296,200, No. 2.369,
No. 929, No. 2,801.171, No. 2,772
．． No. 162, No. 2,895,826, No. 3.77
No. 2,002, No. 3,758.308, No. 4,3
34.01), No. 4,327,173, West German Patent Publication No. 3.329,729, European Patent No. 121.36
No. 5A, No. 249,453A, U.S. Patent No. 3,44
No. 6,622, No. 4.333゜999, No. 4,7
53.871, same No. 4゜451.559, same No. 4,
No. 427,767, No. 4,690,889, No. 4
．． Preferred are those described in No. 254.212, No. 4,296,199, JP-A-61-42658, and the like.

Colored couplers for correcting unnecessary absorption of color-forming dyes are disclosed in RDN 1) 17643, Section ■-G, U.S. Patent No. 4.
, 163,670, Japanese Patent Publication No. 57-39413, U.S. Patent No. 4,004,929, U.S. Patent No. 4,138,258
Preferred are those described in British Patent No. 1,146.368. Additionally, there are couplers that correct unnecessary absorption of coloring dyes using fluorescent dyes released during coupling as described in U.S. Pat. No. 4,774.181, and U.S. Pat.
It is also preferred to use a coupler having as a leaving group a dye precursor group which reacts with a developing agent to form a dye as described in No. 7.120.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4.366.237 and British Patent No. 2.125.
, 570, European Patent No. 96,570, and West German Patent Publication No. 3,234,533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat. Nos. 3,451,820 and 4,08021;
British Patent No. 4,367.282, British Patent No. 4,409,320, British Patent No. 4,576.910, British Patent No. 2,102,
It is described in No. 173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent Nos. 2,097.140 and 2,1.
No. 31,188, JP-A-59-157638, JP-A No. 59
-170840 is preferred.

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat. Coupler, RD Demon 1)
449, No. 24241, bleach accelerator releasing couplers described in JP-A-61-201247, etc., U.S. Pat. No. 4,5
Examples include the Gantt-emitting coupler described in JP-A No. 53-477, the leuco dye-emitting coupler described in JP-A-63-75747, the fluorescent dye-emitting coupler described in U.S. Pat. No. 4,774,181, etc. It will be done.

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

Examples of high-boiling point solvents used in the oil-in-water dispersion method are described in U.S. Patent No. 2,322,027, etc.; Specific examples of boiling point organic solvents include phthalate esters (dibutyl phthalate, dicyclohexyl phthalate,
Di-2-ethylhexyl phthalate, decyl phthalate, bis(2゜4-di-t-amylphenyl) phthalate, bis(2,4-di-t-amylphenyl) isophthalate, bis(1,1-diethylpropyl) ) Phthalate, etc.), esters of phosphoric or phosphonic acids (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyldiphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, Trichloropropyl phosphate, di-2-ethylhexylphenylphosphonate, etc.), benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N,N-diethyl Dodecanamide, N, N diethyl laurylamide,
N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2.4-
di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N- dibutyl-2-butoxy-5-tertoctylaniline, etc.), hydrocarbons (varafine, todenorhensen, diisopropylnaphthalene, etc.). Further, as the auxiliary solvent, a solvent having a boiling point of about 30°C or higher, preferably 50°C or higher and about 160°C or lower can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, Examples include cyclohexanone, 2-nitoxyethyl acetate, dimethylformamide, and the like.

The steps and effects of latex dispersion methods and specific examples of latex for impregnation are described in U.S. Pat.
1,230, etc.

These couplers can also be impregnated into rhodapuru latex polymers (e.g., U.S. Pat. No. 4,203,716) in the presence or absence of the high-boiling organic solvents described above.
Alternatively, it can be dissolved in a water-insoluble but organic solvent-soluble polymer and emulsified and dispersed in a hydrophilic colloid aqueous solution.

Preferably, the homopolymers or copolymers described on pages 12 to 30 of International Publication No. WO88100723 are used. In particular, the use of acrylamide-based polymers is preferred from the viewpoint of color image stabilization.

In the present invention, particularly preferred compounds, couplers or silver norogenide emulsions contained in the photographic material to be processed are shown below. With these, the effects of the present invention can be significantly obtained.

As a coupler, 2 shown in the general formula (1) from the lower right column on page 17 to the upper left column on page 24 of JP-A-1-210956.
Equivalent yellow coupler, JP-A-1-21) No. 756 20
Magenta coupler shown by general formula (M-1) from the upper left column of the page to the upper left column of page 30, JP-A-1-210955 No. 3
Phenol-type cyan couplers having a ureido group at the 2-position represented by the general formula (1) from the lower left column on page 9 to the upper left column on page 18 of JP-A-1-210954. ) Naphthol type cyan coupler having an amide group at the 5-position, JP-A-1-210953
From the upper left column on page 4 of the issue to the upper left column on page 22, hydrolyzable development inhibitor-releasing couplers represented by the general formula (I) are shown in JP-A-1-
Development inhibitor releasing couplers described in No. 213654, page 3, lower left column to page 10, upper left column, and JP-A-1-214849, page 3, page 3, lower left column to page 18, upper right column, JP-A-1-21
Preferred are the polymer couplers described in No. 3649, page 16, lower left column to pages 34, and the water-soluble polymer couplers described in JP-A-1-239553, page 2, lower left column to pages 27.

Also, combinations of magenta couplers of general formula (I) and compounds of general formula (II) described in JP-A-1-213656, page 4, upper right column to page 15, upper left column, JP-A-1-2136
Bleach accelerator-releasing compounds described in No. 50, page 3, upper right column to page 15, upper left column, and formalin scavengers represented by formulas ■ to ■, described in JP-A-216354, page 20, page 20, lower right column to page 25, upper right column. -1 JP-A-1-21) No. 752 19
Yellow dye represented by general formula (I) from the upper left column of page 26 to the upper right column of page 26, and yellow dye represented by general formula (H) from the upper right column of page 3 to the lower left column of page 6 of JP-A-1-21) 754 Hardener, JP-A-1-21) 755, page 3, upper right column to page 6, upper left column, surfactants represented by general formulas (I) and (II), JP-A-1-21) 755, page 6, upper left column. -21) General formulas (I) to (■) described in the lower left column on page 3 of No. 751 to the upper left column on page 10, and JP-A-1-2136
No. 46, page 3, upper left column to page 6, upper left column, are preferred preservatives represented by the general formula (I).

Furthermore, as a silver halide emulsion, JP-A-1-2217
46 No. 46, page 2, lower left column to page 4, upper left column,
Preferred are the tabular emulsions described in JP-A-227153, pages 2, upper left column to 61, upper left column, and the multi-structure grain emulsions described in JP-A-1-227154, pages 2, upper left column to 61, upper right column.

As the sensitizing dye, compounds of the general formula (A) and their addition methods described in JP-A-1-21)753, page 5, upper left column to page 16, upper right column are preferred.

In the present invention, particularly preferred couplers to be contained in the light-sensitive material include yellow colored cyan couplers represented by the general formulas (CI) to (CIV) shown in Japanese Patent Application No. 2-50137, pages 9 to 1) 2; 2-101) No. 60, p. 8 -
Page 47 shows a hydrolyzable development inhibitor-releasing coupler represented by the general formula (I) and a pyrazoloazole magenta coupler described in Japanese Patent Application No. 1-334534.

The present invention can be applied to various color photosensitive materials. Color negative film, especially for general use or motion pictures,
It is preferably applied to color reversal films for slides or televisions.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
DN1) 17843 page 28 and NcL18716
It is described from the right column on page 647 to the left column on page 648.

(Example) The present invention will be described in detail below with reference to Examples, but the present invention is not limited thereto.

Example 1 On a subbed cellulose triacetate film support,
Sample 101, which is a multilayer color light-sensitive material consisting of each layer having the composition shown below, was prepared.

(Composition of photosensitive layer) The coating amount is gl for silver halide and colloidal silver.
The amount of silver in rd units, for coupler additives and gelatin in g/rd units, and for sensitizing dyes in moles per mole of silver genide in the same layer. Indicated.

1st layer: antihalation layer black colloidal silver silver coating amount 0.20 gelatin 2.20UV-10,
1) UV-20,20 Cp d -14,0X10-" CI) d -21,9X 1O-2 Solv-10,30 S o l v -21,2xlO-2 2nd layer co-intermediate layer fine particle iodobromide Silver (Ag1).0 mol%, equivalent sphere diameter 0.0
7 μm) Silver coating amount 0.15 gelatin
1.00E X C-46,OX
10-' Cpd-32,0xlO-2 3rd layer 1st red-sensitive emulsion layer Silver iodobromide emulsion (Ag 15.0 mol%, surface height Agl type, equivalent sphere diameter 0.9 μm, coefficient of variation of equivalent sphere diameter 21%, tabular grains, diameter/thickness ratio 7.5) Silver coating amount 0.42 Silver iodobromide emulsion (Ag 14.0 mol%, internal high Agl type, equivalent sphere diameter 0.4 μm, coefficient of variation of one sphere equivalent diameter 18%, dodecahedral particles) Silver coating amount 0.40 Gelatin 1.90ExS-14,
5XlO-'Mole Ex S -21,5x 10"'Mole Ex S
-34,Ox 10-'mol ExC-10,65 ExC-31,OX 1O-2 ExC-42,3xlO-2 Solv-10,32 4th layer: 2nd red-sensitive emulsion layer Silver iodobromide emulsion (Ag 18.5 mol%, internal high Agl type, equivalent sphere diameter 1.0 μm.

Coefficient of variation of equivalent sphere diameter 25%, plate-shaped particles, diameter/thickness ratio 3. o) Silver coating amount 0.85 Gelatin 0.91E
S-13,OX 10-'%/I.

EXS -21,OX 10-'molExS 3
3.0XlO-'%leExC-1
0.13ExC-26,2
X10-"ExC-44,0xlO-" 5olv-10,10 5th layer 3rd red-sensitive emulsion layer Silver iodobromide emulsion (Ag1 1). 3 mol%, internal high Agl
Mold, equivalent sphere diameter 1.4μm, coefficient of variation of one sphere equivalent diameter 28%, plate-shaped particles, diameter/thickness ratio 6.0) Silver coating amount 1,50 Gelatin 1.20ExS
-12,0xlO-' mole ExS-26,0xlO-5 mole ExS-32,0xlO bow mole ExC-28,5xlCr2 ExC-57,3X10-2 Solv-10,12 Solv-20,12 6th layer: Intermediate layer Seratin 1.00Cp
d -48,0X10-2 S o 1 v -18,0XIO-" 7th layer: First green-sensitive emulsion layer Silver iodobromide emulsion (Ag 15.0 mol%, surface height AgT 1, sphere equivalent diameter 09 μm, sphere Coefficient of variation of equivalent diameter 21%, tabular grain, diameter/thickness ratio 7.0) Silver coating amount Silver iodobromide emulsion (AgI 4.0 mol%, internal high AgI type, equivalent sphere diameter 0.4 μm, equivalent sphere diameter Coefficient of variation of 18%, dodecahedral grains) Silver coating amount Gelatin xS-4 xS-5 xS-6 xM-1 xM-2 xM-5 olv-1 olv-3 8th layer: 2nd green-sensitive emulsion layer Silver iodobromide emulsion (Ag 18.5 mol%, internal high AgI type, equivalent sphere diameter 1.0 μm, 0, [6 1,20 5, OX 10-' mol 2, OX 10-' mol 1, OX 10- 'mol 0.50 0.10 3.5X 10-'' 0.20 3.0X10-2 Coefficient of variation of equivalent sphere diameter 25%, plate-shaped particles, diameter/thickness ratio 3
．． 0) Silver coating amount 057 gelatin
. , 45ExS-43,5xlO-'
Mol Ex S -51,,4x 10-' Mol Ex S
-67, Ox 10-5 mol ExM-10,12 ExM -27,1 Gelatin 0.5゜So
I v -12, (lxlO-' 10th layer/3rd green-sensitive emulsion layer Silver iodobromide emulsion (Ag1 1).3 mol%, internal height AgI
Type, equivalent sphere diameter 1.4 μm, coefficient of variation of equivalent sphere diameter 28%,
Plate-shaped particles, diameter/thickness ratio 6.0) Silver coating amount 1
,3゜gelatin 1.20
xS-4 xS-5 xS-6 xM-4 xM-6 xC-2 pd-5 olv-1 1st) layer, yellow filter layer gelatin pd-6 olv-1 12th layer: middle layer gelatin pd-3 Layer 13: First blue-sensitive emulsion layer Silver iodobromide emulsion (Ag 12 mol%, average-AgT type, equivalent sphere diameter 0.55 μm, coefficient of variation of equivalent sphere diameter 25%, tabular grains, diameter/thickness ratio 7. 0) 5.2X10 2.0XIF' mol 8, OX 10-' mol 8.0xlO-s mol 4.5X to-' 1, OX 10-2 4.5 0.50 0.12 0.45 0, I0 Silver coating amount 0.20 Gelatin 1.00E
X S -73,0XlO-' mol ExY-10,60 ExY-22,3 High Ag
L type, equivalent sphere diameter 1.0μm, coefficient of variation of equivalent sphere diameter 16%
, octahedral particles) Silver coating amount 0.19 Gelatin 0.35E X S −
72,OX 10-'%leExY-1
0.22S o 1 v -17,0xlO
-2 15th layer, intermediate layer fine grain silver iodobromide (AgI 2 mol%, uniform-Agl type, equivalent sphere diameter 0.13 μm) Silver coating amount
0.20 Gelatin 0.36 No. 16
Layer: Third blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 14.0 mol%, internal high Ag
L type, equivalent sphere diameter 1.7 μm, coefficient of variation of equivalent sphere diameter 28%
, plate-shaped particles, diameter/thickness ratio 5.0) Silver coating amount
1.55 gelatin 1.0
0E X S -81,5X 10-'mol EXY-1
0,21 S o 1 v -17,0xlO-2 17th layer: 1st
Protective layer gelatin 1.80UV-
10,13 UV-20,21 S o l v -1), 0xlO-”S o l v
-21,0xlO-” 18th layer: 2nd protective layer fine grain silver chloride (equivalent sphere diameter 0.07 μm) Silver coating amount
0.36 Gelatin 0.70B-1
(Diameter 1.5μm) 2.0xlO-'B-
2 (diameter 1.5μm) 0.15B -3
3,Ox to-" W -12,Ox 10-" H-10,35 Cpd-71,00 This sample contained l,2-benzisothiaprin-3-one (average 200 ppm relative to gelatin), n-butyl-p-hydroxybenzoate (approximately 1.000
ppm), and 2-phenoxyethanol (approximately 1
o, ooo ppm) were added. Furthermore, B-4, B
-5, W-2, W-3, F~1, F-2, F-3, F-
4, F-5, F-6, F-7, F-8, F-9, F-1
0, F-1) Contains F-12, F-13 and iron salts, lead salts, gold salts, platinum salts, iridium salts, and rhodium salts.

V-1 x/y=7/3 (weight ratio) V-2 xC-1 C xC-2 H xC xC H xC-5 xM xM-2 xM-3 Shil xM-4 CI-1゜ Shil xM-5 Shil xM xY-1 xY Cpd-] Cpd-3 nH Cpd-4 Cpd-5 0M Cpd-6 Cpd-7 rM.

olv-1 olv-2 olv-3 xS-1 xS-2 xS-3 xS-4 xS-5 xS-6 xS-7 xS-8 W-1 n=2-4 Crystal except for the support of sample 101 The dry film thickness was 22 μm, and the swelling rate T1/, was 9 seconds.

After cutting the sample 101 prepared as described above into a width of 35 mm and processing it into +35 size, 24-exposure film,
I packed it into a patrone and took a picture with my camera. Then the first
As shown in the figure, the tongue portion of the film was cut and processed using an automatic developing machine as described below. Each treatment was carried out under the conditions shown in Table 1, and the above samples were treated for 20 minutes at a distance of 100 m per day.
I did it in between (running process).

The treatment steps and treatment liquid composition are shown below.

Processing process Processing time Processing temperature Replenishment amount 1 Tank capacity Color development 3 minutes 05 seconds 38.0°C Table-1) 71
Bleaching 50 seconds 38.0℃ 1
40d 5f bleach fixing 50 seconds 38.
0°C 51 fixation 5
0 seconds 38.0 °C 420d
5A' water washing 30 seconds 38.0 °C
980t/317 stable (1)
20 seconds 38.0°C 31 stable (2+ 20 seconds 38.0°C 560d
3I! Drying 1 minute at 50℃
The amount of replenishment was determined per 1 i of photosensitive material.The water submergence was carried out in a countercurrent manner from (2) to (1), and all the overflow of the washing water was introduced into the fixing bath. To replenish the bleach-fix bath, make a cut at the top of the bleach tank and the top of the fix tank of the automatic processor, and make sure that all the overflow liquid generated by supplying replenisher to the bleach tank and fix tank goes into the bleach-fix bath. I made it possible for the influx to occur. The amount of developer carried into the bleaching process, the amount of bleaching solution carried into the bleach-fixing process, the amount of bleach-fixing solution carried into the fixing process, and the amount of fixing solution carried into the washing process are each 6 per rri of photosensitive material.
5ml, 50xl', 50-150-. Also,
The crossover time is 6 seconds in each case, and this time is included in the processing time of the previous step.

The composition of the treatment liquid is shown below.

(Color developer) Start solution (g) Replenisher (
g) Diethylenetriaminepentaacetic acid 2.0 2.
21-Hydroxyethylidene-3,33,31,1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide (KBr) Potassium iodide Hydroxylamine sulfate 2-Methyl-4-[N-ethyl-N-(β-hydroxyethyl ) Aminocoaniline sulfate (CD) Add water and H 3,9 37,5 1,4 1,3 ■ 2.4 4.5 1.0! ! 10.05 Table-1 3,3 Table-1 1, Oj' Table-1 (Bleach Replenisher) 1.3-Propylene diamine Tetraacetic acid Ferric ammonium monohydrate Ammonium bromide Ammonium nitrate Hydroxyacetic acid Acetic acid (g) 195 .0 120.0 24.0 80.0 60.0 Add water 1901pH
(Adjusted with aqueous ammonia) 3.80 The above bleach replenisher was used as a 1-liquid working solution kit, which had been stored in 21-unit polyethylene bottles in advance.

(Bleach start solution) Bleach replenisher solution 4! Water to 21! A mixture of 82g of jetanolamine and 82g of jetanolamine was used as a bleaching solution starter. (
pH 4,2) (Bleach-fixing start solution) 15:85 of the above bleaching start solution and the following fixing start solution
mixture of. (pH 6,9) (Fixer replenisher) Ammonium sulfite ammonium thiosulfate aqueous solution (700 g/I riimidazole (g) 57.0 40rd table Ethylenediaminetetraacetic acid 40.0 Add water to 1.0 fpH [adjusted with aqueous ammonia and acetic acid: 1 7.45 The above fixing replenisher was used as a 1-liquid working solution kit, which was stored in 21 bottles each in polyethylene bottles.

(Fixing start liquid) Fixer replenisher 2I! Water to 41! A mixture was used.

(pH 7,4) (Washing water) Start solution and replenisher common tap water was mixed with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type strongly basic anion exchange resin (Amberlite IR-120B manufactured by Rohm and Haas). Light IRA-4
Water was passed through a mixed bed column packed with 00) to reduce the concentration of calcium and magnesium ions to 3 mg/1 or less, followed by 20 m of sodium isocyanurate dichloride.
g// and 150 mg/l of sodium sulfate were added.

The pH of this solution is 65-7 It was in the range of 5.

(Stabilizing solution) Common formalin for starting solution and replenisher solution (37%) Sodium p-1-luenesulfinate polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) Ethylenediaminetetraacetic acid disodium salt (g) 1. 2rnI! Add 3 g water and enjoy! H The automatic developing machine used for the above processing has a structure as shown in FIG. This automatic developing machine has a two-course processing line and can process two films in parallel at the same time.

The processing procedure and the structure of the automatic processor will be described below.

The cut film 42 as shown in Figure 1 is attached to a special tape 5.
1) is attached to a leader 48 made of polyethylene terephthalate and set in the supply section 1).

When the drive starts, it is pulled by the leader and the patrone 46
More film is pulled out. When the film is completely pulled out, it detects the distance that the table that fixes the cartridge has moved and automatically cuts the end of the film. The conveyance method of the leader is a belt conveyance similar to that of FP-230B manufactured by Fuji Photo Film Co., Ltd.

The leader and film are sequentially bleached, bleach-fixed, fixed, washed with water, stabilized (1), and stabilized (2) starting with a color developer, and are then dried through a drying section.

There are 2 racks for color development only, and 1 rack for each other process. The period between two racks of color development is a submerged turn.

The linear speed of the automatic processor is 60 alI/min. Each rack from color development to stabilization (2) is the same as the above FP-230B.
It has a jet agitation system similar to that of the color development rack, and a jet of processing liquid hits the film emulsion surface. The jet of each processing solution hits the emulsion film surface 5 seconds after contacting the film with the processing solution.The nozzle is circular with a diameter of 1.2M, and the number of nozzles is 250 for color development, 250 for bleaching, 100 pieces each for bleach-fixing and fixing, and 60 pieces for each bath for washing and stabilizing. The arrangement of the nozzles is as shown in FIG. The pumps that pump the processing solution to the nozzles are Iwaki magnetic bombs: two MD 15s for color development, one MD20 each for bleaching, bleach-fixing, and fixing, and one MD 20 for each bath for washing and stabilization. There is one 10 in total. The distance from the nozzle to the film surface was about 5 degrees. Furthermore, the flow rate of the processing liquid discharged from the nozzle is 1 to 1.2 m/m/m for color development.
seconds, and the others were 1.5 to 2 m/second.

The circulation line for the jet agitation of the color developer is equipped with a flow meter equipped with an electronic signal output to monitor the jet flow rate and circulation amount.If the flow rate reaches a level that causes development defects, an alarm will be issued. It has the function of emitting

The bleach solution is equipped with an air pump device. The structure of the air pump device is described in Japanese Patent Application No. 2-104731.

Air pump air flow rate is 2I per minute! The nozzle is made of polypropylene resin and is a porous nozzle with a pore diameter of about 100 μm. In addition, a separate air pump is used to introduce outside air into the upper part of the aeration device for defoaming.

The processing solution opening area of the above automatic developing machine is 100% for color development.
al, and 70ai for other baths.

There is an exhaust fan on the top of the stable (1), which blows air at 0.5 m/min during temperature control and processing. It is exhausted at a flow rate of 3rn'.

The drying section has the structure shown in Japanese Patent Application No. 2-94628. The air flow rate during drying was 8 rrl' per minute.

Each replenishment tank has a capacity of 121 and is a blow molded piece of polyethylene resin. Each replenishment tank has a float type liquid level sensor.

The replenishment pump is a bellows type, and the poppet valve and O-ring are made of Viton rubber.

The material of the treatment tank is "Noril FN-215JJ", the rack is "Zylon 220v", the rollers are polyvinyl chloride, and the gears, sprockets, and bearings are made of glass fiber-containing 66
Nylon and PBT.

A hard squeeze roller made of polyvinyl chloride and a soft squeeze roller made of Rubicel are placed between the stabilizing section (2) and the drying section to squeeze the film surface.

The above-mentioned automatic developing machine performs the water addition method described in Japanese Patent Application No. 2-103894, and replenishes each tank with a calculated amount of washing water replenisher at the time of startup every day.

During running treatment, temperature was controlled for 10 hours a day. Only the heater for the color developing solution was made of stainless steel, and the other tanks used ceramic heaters.

The crossover rack has the structure described in Japanese Patent Application No. 1-265795. This crossover rack has a snap fit that fits tightly to the rack, making it easy to install and remove. Therefore, in order to withstand repeated fatigue, we used Noryl 731JJ, which has excellent chemical and fatigue resistance.

At the end of each of the above running processes, the unexposed sample 101
A film prepared from the above was processed and residual color was evaluated according to the following method.

(Residual Color Evaluation Method) The G density of the unexposed area of the processed film is measured using a photographic densitometer FSD 103 manufactured by Fuji Photo Film ■. After re-rinsing with warm water at 38°C for 10 minutes and drying, the same area of the film is measured in the same manner, and the decrease in concentration due to re-rinsing is regarded as residual color.

The results of residual color = G concentration before re-washing - G concentration after re-washing are shown in Table 1.

As can be seen from Table 1, in a processing solution that does not contain imidazole and has a fixing ability, when the color developer is replenished at a low level, residual color increases significantly.

However, by incorporating 0.1 mol/l or more of imidazole into the processing solution having fixing ability, no residual color sensitivity occurs even if the color developer is refilled at a low level.

Example 2 In Process 7 of Example 1, the same test as Process 7 of Example 1 was conducted except that the concentrations of glycolic acid and acetic acid in the bleach replenisher were changed as shown in Table 2.

The results of residual color are shown in Table 2.

Further, since each of the treatments No. 7 to IO was performed under the same color development conditions, the degree of bleaching fog can be determined based on the density after rewashing, which removes residual color. The G concentration after this re-washing is also shown in Table 3.

Table 2 The concentrations of acetic acid and glycolic acid in the bleach tank solution at the end of the running process are 6 times lower than the concentration in the bleach replenisher.
It was 6%.

As can be seen from Table 2, when glycolic acid was included in the bleaching solution, residual color and bleaching blade blemish were reduced, and especially when glycolic acid and acetic acid were used together, better results were obtained.

Example 3 Similar results were obtained when the glycolic acid in the bleach replenisher in Process 7 in Example 2 was replaced with 1.2 mol/l lactic acid.

Example 4 When the following photosensitive materials were processed after the running process in the processing of NO34 in Example-1, good performance was obtained with little residual color as in Example-1.

JP-A No. 2-90151 Sample 201 of Example 2 (Dry film thickness of photographic constituent layer 17 μm N T,...=9 seconds) JP-A No. 2-90151
-93641 Sensitive material 9 of Example 3 JP-A-2-9364
1 Sensitive material of Example 1 Example 5 After the running treatment in the processing of N007 of Example-1, the amount of gelatin in each layer of sample 201 of JP-A-2-90151 was adjusted to form a dry film of the photographic constituent layer. 16μ thick
When the light-sensitive material was processed with a grade of m, even better performance was obtained with less residual color.

(Effects of the Present Invention) By using the present invention, it is possible to reduce the amount of color developer replenishment and to perform rapid processing without causing deterioration of photographic properties such as residual color.

[Brief explanation of drawings]

FIG. 1 shows a state in which a film is attached to a leader used in the processing of an automatic processor shown in an example of the present invention. FIG. 2 shows the structure of an automatic processor, and the two-dot chain line indicates the leader and the path of the film. FIG. 3 shows the arrangement of jet nozzles for jet agitation that are fixed to the rack of the developing processing tank, and the small circles represent the nozzles. 42... Film 46... Patrone reader, square hole, adhesive tape, insertion part, color developer tank, bleach tank, bleach-fix tank, fixer tank, washing tank, stabilizing (1) tank, stabilizing (2) tank・Drying room・Nozzle

Claims (2)

[Claims] (1) In a method in which a silver halide color photographic light-sensitive material is subjected to color development without being refilled with a color developer replenisher, and then processed with a processing solution having fixing ability, the replenishment amount of the color developer replenisher is A method for processing a silver halide color photographic light-sensitive material, characterized in that the amount is 650 ml or less per 1 m^2 of the material, and the processing liquid having fixing ability contains an imidazole compound at 0.1 mol/l or more. (2) The processing method according to claim (1), wherein the silver halide color photographic light-sensitive material is processed with a processing solution containing glycolic acid and/or lactic acid and having bleaching ability after color development.