JP2887881B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a method for processing a silver halide color photographic light-sensitive material (hereinafter also referred to as a light-sensitive material). The present invention relates to an automatic developing machine and a processing method which enable processing.

BACKGROUND OF THE INVENTION Generally, in order to obtain a color image by processing an imagewise exposed light-sensitive material, after the color development step, the generated metallic silver is desilvered and then washed with water, stable or replaced with water. A processing step is provided.

However, the photosensitive material is subjected to running processing by an automatic developing machine provided in a development facility. As a part of service improvement for users, development processing is performed within the day of development acceptance and returned to the user. In recent years, it has been even required to return the product within hours of reception, and the development of rapid processing technology is urgently required.

As a result, the processing time, process and temperature of the main color paper photosensitive materials at present have reached the following levels. That is, for example, the development time of color printing paper is 8.5
The processing time is 32.8 ° C to 33 ° C, and the processing time consists of three steps of color development 3.5 minutes, bleach-fix 1.5 minutes, and water washing 3.5 minutes. The system technology included in this step is disclosed in US Pat. No. 3,582,32.
No. 2 and West German Open Patent (OLS) 2,160,872.

More recently, rapid processing with color paper using an emulsion mainly composed of silver chloride, called Process RA-4 (development time is 3 minutes, processing temperature is 35 ° C, breakdown of color development 45 seconds, bleaching Eastman Kodak Company) has also been proposed.

Looking at the conventional techniques for rapid processing of these photosensitive materials, (1) techniques based on improvements in photosensitive materials, (2) techniques based on physical means during development processing, and (3) techniques based on improving the composition of processing solutions used in development processing Regarding the above (1), improvement of the silver halide composition (for example, a technique for forming fine particles of silver halide as described in JP-A-51-77223, JP-A-58-18142, and Kuniaki 56-189
No. 39, silver bromide technology for lowering silver bromide), use of additives (for example, halogenation of 1-aryl-3-pyrazolidone having a specific structure as described in JP-A-56-64339). Techniques to be added to silver color photographic light-sensitive materials and JP-A-57-144457, JP-A-58-50534, JP-A-58-50535 and 58
A technique of adding 1-arylpyrazolidones to a light-sensitive material as described in JP-A-50536), a technique using a high-speed reactive coupler (for example, JP-B-51-10783, JP-A-50-123)
Nos. 342 and 51-102636), techniques for thinning photographic constituent layers (for example, techniques for thinning photographic constituent layers described in JP-A-62-65040), and the like. Regarding the above (2), a stirring technique for the treatment liquid (for example,
Japanese Patent Application Laid-Open No. Sho 62-180369), and the above-mentioned (3) relates to a technique using a development accelerator, a technique for thickening a color developing agent, a halogen ion, In particular, a technique for lowering the concentration of bromide ions is known.

In the above-mentioned various rapid processing techniques, techniques using a photosensitive material using high-concentration silver chloride according to the technique (1) (for example, JP-A-58-95345, JP-A-60-19140, and JP-A-60-19140)
-95736) provides particularly excellent speed-up performance, and recently, for example, Eastman Kodak Co., Ltd. has published Konica Corporation as Ektacolor 2001 paper.
Has been put to practical use as Konica Color QA paper.

However, all of these rapid techniques tend to cause fogging in the unexposed areas of the light-sensitive material due to the formation of a physically or chemically highly active state, particularly in high concentrations of silver chloride (especially 80 mol% or more). Having a silver chloride constituent layer)
A photosensitive material using the compound has a shortcoming that fog tends to occur as well as good quick characteristics. In particular, when the photosensitive material is a color paper, the fog occurring in the unexposed portion becomes a serious problem as the commercial value is lost.

The present inventors have been searching for a process that is even faster than the above-mentioned process RA-4. It has been found that the ratio of time existing in the gas in the time required for entering the processing liquid in a certain step) has a great effect on fog during rapid processing, and the present invention has been achieved.

The effect is not always clear, but if the air time ratio is increased, the oxide or organic inhibitor of the color developing agent in the developing solution or the photosensitive material tends to be selectively adsorbed to the photosensitive nucleus of the unexposed portion of the silver halide. The bleaching solution or bleach-fixing solution has an increased airtime ratio, so that the ethylenediaminetetraacetic acid ferrous salt used as a bleaching agent attached to the photosensitive material becomes ferric. It is presumed that the salt easily forms a salt, thereby facilitating the bleaching reaction.

Further, by increasing the air time ratio during the color development step, it was also confirmed that dyeing to the lower turn roller of the automatic developing machine, which tends to occur during high activity processing, was suppressed. This is because in the ultra-rapid processing, the emulsion layer rapidly swells and forms a dye in a color developing solution.
When a pressure is physically applied to the emulsion surface by a roller or the like, the formed dye is eluted and dyed on the turn roller. This dyed dye is transferred to another photosensitive material, and there is no problem of causing a problem. It turns out. It is presumed that swelling can be controlled and dyeing can be improved by increasing the airtime ratio.

Further, by increasing the air time ratio in the bleaching step or the bleach-fixing step, the regeneration of ferrous ethylenediaminetetraacetic acid, a ferrous salt, which is a bleaching agent, to the ferric salt is promoted, and the residual silver is reduced. It turns out.

The present invention has been made based on these findings.Each of the above-mentioned effects has overturned the common sense in the photographic industry that the shorter the air time of the automatic developing machine, the better, and the surprising effect. I can say.

[Object of the Invention] Accordingly, an object of the present invention is, firstly, to provide a method for processing a light-sensitive material which enables ultra-rapid processing. A second object is to provide a stable method with less fogging even during ultra-rapid processing. It is an object of the present invention to provide a method for processing a photosensitive material which enables the above processing. A third object of the present invention is to provide a method for processing a photographic material in which dyeing of the photographic material on a lower turn roller of an automatic developing machine is improved. A fourth object is to provide a method for processing a light-sensitive material having improved desilvering performance. Other objects will become apparent in the following specification.

[Structure of the Invention] The present inventors have conducted intensive studies to achieve the above object, and as a result, have accomplished the present invention.

The processing method for a silver halide color photographic light-sensitive material according to the present invention is a method for processing an imagewise exposed silver halide color photographic light-sensitive material in a color development processing step and a processing step having a bleaching ability. Wherein the silver halide color photographic light-sensitive material to be processed is provided with at least one emulsion layer containing at least 80 mol% of silver chloride, and the processing solution used in the color development step is: It contains a compound of the following general formula [I], and the air time ratio of at least one of the treatment steps is 25 to 65%.

In the formula, R ₁ and R ₂ each represent an alkyl group or a hydrogen atom. However, both R ₁ and R ₂ are not hydrogen atoms at the same time. R ₁ and R ₂ may form a ring.

In the present invention, the air time (Air-tim)
e) The ratio refers to the ratio of the time that the photosensitive material is present in the air in the time from the time when the photosensitive material comes into contact with the processing solution in the processing step to the time when the photosensitive material comes into contact with the processing solution in the next step. The air time ratio is the time A from the contact of the leading end of the photosensitive material with the color developing solution to the contact of the leading end with the bleaching or bleach-fixing solution, which is the next step, that is, the processing time of the color developing process. A ratio (B / A × 100) of the time (B / A × 100) of the time (air time) from the end of the color developing solution to the time of entering the next step of bleaching or bleach-fixing solution.
(%)). When the color developing tank is composed of, for example, two tanks and there is a time for contacting with air between them, the total of the time existing in the air is defined as B.

The airtime ratio of other processing solutions such as a bleaching solution or a fixing solution or a bleach-fixing solution or a stabilizing solution is similarly defined.

In the present invention, the air time ratio is in the range of 25 to 65%.

In the color developing solution used in the present invention, a compound represented by the general formula [I] (hereinafter sometimes referred to as the preservative of the present invention) is rapidly used instead of hydroxylamine conventionally used as a preservative. It is preferably used from the viewpoint of properties and fog suppression.

In the formula, R ₁ and R ₂ each represent an alkyl group or a hydrogen atom. However, both R ₁ and R ₂ are not hydrogen atoms at the same time. R ₁ and R ₂ may form a ring.

In the general formula [I], represents R ₁ and R ₂ are each an alkyl group or a hydrogen atom are not hydrogen atoms at the same time, R ₁
And the alkyl groups represented by R ₂ may be the same or different, and are each preferably an alkyl group having 1 to 3 carbon atoms. R ₁
And the alkyl group of R ₂ includes those having a substituent, and R ₁ and R ₂ may combine to form a ring, for example, to form a heterocyclic ring such as piperidine or morpholine.

Specific examples of the hydroxylamine compound represented by the general formula [I] are described in U.S. Pat. Nos. 3,287,125 and 3,293,034.
No. 3,287,124, etc., and particularly preferred specific exemplary compounds are shown below.

These compounds of the present invention usually contain free amine, hydrochloride, sulfate, p-toluenesulfonate, oxalate,
It is used in the form of phosphate, acetate and the like.

The concentration of the compound represented by the general formula [I] of the present invention in the color developing solution is usually 0.2 g / to 50 g /, preferably 0.5 g /
3030 g /, more preferably 1 g / 〜15 g /.

The compound represented by the general formula [I] of the present invention is used in a conventional color developing solution for a light-sensitive material in place of hydroxylamine sulfate which has been widely used as a preservative. Among the compounds, for example, N, N-diethylhydroxylamine is known to be used as a preservative of the black-and-white developing agent in a color developing solution to which a black-and-white developing agent is added, and for example, a color developing solution containing a coupler. Develop color photographic light-sensitive material by reversal method using
In the so-called external coloring method, there is a technique used with phenidone (see Japanese Patent Publication No. 45-22198).

The color developer used in the present invention has a sulfite concentration of 4 × per color developer in view of development processability and dye dyeing.
It is preferably at most 10 ^-3 mol, more preferably 2
× 10 ^{-4 to} 0 mol. This is because when the concentration of sulfurous acid in the color developing solution is high, the high silver chloride emulsion is much more susceptible to the effects than the conventionally used silver bromide-containing emulsion, and causes a significant decrease in the density.

Examples of the sulfite used in the present invention include sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, and the like.

In the present invention, p-phenyldiamine having a water-soluble group is preferable as the developing agent. The water-soluble group of the p-phenylenediamine compound having the water-soluble group is
those having at least one the p- phenylenediamine compound amino group or on a benzene nucleus of a specific water-soluble _{group, - (CH 2) n -CH} 2 OH, - (CH 2) m -NHSO 2 _{- (CH 2) n -CH 3} , - (CH 2) m -O- (CH 2) n -CH 3, - (CH 2 CH 2 O) n C m H 2m + 1 (m and n each is 0 .) representing the more integer, - COOH group, and as -SO ₃ H group and the like.

In the present invention, the following color developing agents are preferably used from the viewpoint of suppressing fog during rapid processing.

Among the color developing agents exemplified above, those preferably used in the present invention are exemplified by No. (A'-1), (A'-2),
(A'-3), (A'-4), (A'-6), (A'-
7) and (A'-15), and particularly preferably No. (A'-1).

The above color developing agents are usually used in the form of salts such as hydrochloride, sulfate, p-toluenesulfonate and the like.

The p-phenylenediamine compound having a water-soluble group used in the present invention is preferably at least 1.5 × 10 ^-2 mol, more preferably at least 2.0 × 10 ^-2 per mol of color developer from the viewpoint of rapidity. The range is from 1.0 to 10 ^-1 mol, and particularly preferably from 2.5 x 10 ^{-2 to} 7.0 to 10 ^-2 mol.

The color developing solution of the present invention may contain the following developing solution components in addition to the above components.

As the alkaline agent, for example, sodium hydroxide, potassium hydroxide, silicate, sodium metaborate, potassium metaborate, trisodium phosphate, potassium triphosphate,
Borax and the like can be used alone or in combination in such a range that the above-mentioned effect, that is, no precipitation occurs, and the pH stabilizing effect is maintained. Furthermore, various salts such as disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate, and borate are used for the purpose of preparation or for the purpose of increasing ionic strength. can do.

If necessary, inorganic and organic antifoggants can be added.

Furthermore, it is preferable to use the following development accelerators in the color developing solution of the present invention. As development accelerators, U.S. Pat.Nos. 2,648,604, 3,671,247, and various pyridinium compounds represented by Japanese Patent Publication No. 44-9503, other cationic compounds, cationic dyes such as phenosafranine, and thallium nitrate Neutral salts such as US Patent 2,533,99
No. 2, 531,832, 2,950,970, 2,577,127 and JP-B-44-9504, polyethylene glycol and its derivatives, nonionic compounds such as polythioethers, and organic solvents described in JP-B-44-9509. And organic amines, ethanolamine, ethylenediamine, diethanolamine, triethanolamine and the like. Further, phenethyl alcohol described in U.S. Pat. No. 2,304,925 and others, acetylene glycol, methyl ethyl ketone, cyclohexanone, thioethers, pyridine, ammonia, hydrazine, amines and the like can be mentioned.

Benzyl alcohol is not preferably used in the present invention, and it is preferable to eliminate the use of poorly soluble organic solvents represented by the above-mentioned phenethyl alcohol in order to achieve the object of the present invention efficiently. The use of the color developing solution for a long period of time, particularly in the running process in a low replenishment system, tends to generate tar, and the generation of such tar significantly impairs the commercial value due to adhesion to the processed paper photosensitive material. Even a serious failure.

In addition, poorly soluble organic solvents have poor solubility in water, so that not only is it necessary to use a stirrer to adjust the color developing solution itself, but also the use of such a stirrer causes a poor dissolution rate. Therefore, the effect of accelerating the development is limited.

Furthermore, poorly soluble organic solvents have large pollution load values such as biochemical oxygen demand (BOD) and cannot be disposed of in sewers or rivers. Since it has problems such as requiring labor and cost, it is preferable to reduce or eliminate not only benzyl alcohol but also other poorly soluble organic solvents as much as possible.

Further, the color developing solution of the present invention may contain, as necessary, ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, and other JP-B-47-33378, JP-B-44-9509. Can be used as an organic solvent for increasing the solubility of the developing agent.

Further, an auxiliary developer can be used together with the developing agent. These auxiliary developers include, for example, N-methyl-p-aminophenol sulfate (methol),
Phenidone, N, N'-diethyl-p-aminophenol hydrochloride, N, N, N ', N'-tetramethyl-p-phenylenediamine hydrochloride and the like are known, and the amount of addition is usually 0.01 g. ~ 1.0 g / is preferred.

Furthermore, various additives such as a stain inhibitor, an anti-sludge agent, and a layering effect promoter can be used.

Further, it is preferable to add the following chelating agent to the color developing solution of the present invention from the viewpoint of the effects of the present invention. That is, examples include diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, ethylenediaminetetramethylenephosphonic acid, and 1-hydroxyethylidene-1,1-diphosphonic acid.

Each component of the color developing solution is added to a certain amount of water sequentially,
It can be adjusted by stirring. In this case, the component having low solubility in water can be added by mixing with the above-mentioned organic solvent such as triethanolamine. More generally, a concentrated aqueous solution containing a plurality of components each of which can coexist stably, or a solid solution prepared in a small container in advance added to water, adjusted by stirring, and adjusted as the color developing solution of the present invention. Obtainable.

In the present invention, the above-mentioned color developing solution can be used in an arbitrary pH range, but is preferably from pH 9.5 to 13.0, more preferably from pH 9.8 to 12.0, from the viewpoint of rapid processing.

The processing time of the color developing step of the present invention is preferably 35 seconds or less from the viewpoint of the effect of dyeing the lower roller and suppressing fogging of the unexposed portion, more preferably 3 seconds to 30 seconds,
It is particularly preferably in the range from 5 seconds to 25 seconds, particularly preferably in the range from 7 seconds to 20 seconds.

In the present invention, various processing methods such as a spray method for spraying a processing liquid, a web method by contact with a carrier impregnated with the processing liquid, and a developing method using a viscous processing liquid are used. However, the processing step comprises at least steps such as color development, bleaching or bleach-fixing.

In the present invention, a bleaching step or a bleach-fixing step is provided immediately after the color development processing step.

The bleaching agent that can be used in the bleaching solution and the bleach-fixing solution used in the present invention is not limited, but is preferably a metal complex salt of an organic acid. The complex salt is obtained by coordinating metal ions such as iron, cobalt and copper with an organic acid such as polycarboxylic acid, aminopolycarboxylic acid or oxalic acid or citric acid. The most preferred organic acids used to form such metal complexes of organic acids include aminopolycarboxylic acids. These aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

Specific representative examples of these organic acids include the following.

[B-1] Ethylenediaminetetraacetic acid [B-2] Diethylenetriaminepentaacetic acid [B-3] Ethylenediamine-N- (β-oxyethyl) -N, N ′, N′-triacetic acid [B-4] 1,3- Propylenediaminetetraacetic acid [B-5] Nitrilotriacetic acid [B-6] Cyclohexanediaminetetraacetic acid [B-7] Iminodiacetic acid [B-8] 1,2-Propylenediaminetetraacetic acid [B-9] Ethyl ether diaminetetra Acetic acid [B-10] Glycol etherdiaminetetraacetic acid [B-11] Ethylenediaminetetrapropionic acid [B-12] Ammonium ethylenediaminetetraacetate [B-13] Ethylenediaminetetraacetic acid disodium salt [B-14] Ethylenediaminetetraacetic acid tetra ( Trimethylammonium) salt [B-15] ethylenediaminetetra Acid tetrasodium salt [B-16] diethylenetriaminepentaacetic acid pentaammonium salt [B-17] ethylenediamine-N- (β-oxyethyl) -N, N ', N'-triacetate sodium salt [B-18] propylenediaminetetraacetate Sodium acetate salt [B-19] Nitriloacetic acid sodium salt [B-20] Cyclohexanediaminetetraacetic acid sodium salt Among these bleaching agents, [B-2] and [B
-4], [B-6], [B-10], and [B-16] are preferable from the viewpoint of quick processing and suppression of fogging. Particularly preferred are [B-2] and [B-16].

These bleaching agents are 5-450 g /, more preferably 20-2 g
Use at 50g /. To the bleach-fixing solution, a solution having a composition containing a silver halide fixing agent in addition to the bleaching agent as described above and, if necessary, a sulfite as a preservative is applied. Further, a special bleach-fixing solution having a composition comprising a combination of an iron (III) ethylenediaminetetraacetate bleach and a large amount of a halide such as ammonium bromide can be used.
As the halide, besides ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide and the like may also be used. it can.

As the silver halide fixing agent contained in the bleach-fix solution, a compound capable of forming a water-soluble complex salt by reacting with silver halide as used in ordinary fixing processing, such as potassium thiosulfate, sodium thiosulfate, and ammonium thiosulfate And thiocyanates such as potassium thiocyanate, sodium thiocyanate and ammonium thiocyanate, thiourea, thioether and the like. These fixing agents are used in an amount of at least 5 g / dissolveable range, but generally used in an amount of 50 g to 350 g /.

In addition, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
Various pH buffers such as sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide can be used alone or in combination of two or more. Furthermore, various fluorescent whitening agents, antifoaming agents or surfactants can be added. Also, preservatives such as bisulfite adducts of aldehyde compounds such as hydroxylamine, hydrazine and formaldehyde bisulfite adducts, organic chelating agents such as aminopolycarboxylic acids or stabilizers such as nitro alcohols and nitrates, methanol, dimethyl sulfo An organic solvent such as amide and dimethyl sulfoxide can be appropriately contained.

The bleaching solution and the bleach-fixing solution used in the present invention are described in
No.-280, Japanese Patent Publication No. 45-8506, Copper No. 46-556, Belgian Patent No. 770,910, Japanese Patent Publication No. 45-8836, Japanese Patent Publication No. 53-9854, JP-A Nos. 54-71634 and 49-42349. The various bleaching accelerators described can be added.

The pH of the bleach-fixing solution is generally used at pH 4.0 or higher and pH 9.5 or higher from the viewpoint of storage stability and bleaching ability.
It is used at a pH of 4.5 or more and a pH of 8.5 or more, and more preferably, at a pH of 5.0 or more and 8.0 or less. The pH of the bleaching solution is generally in the range of 1.0 to 7.0, and preferably in the range of 2.5 to 5.5 from the viewpoint of rapid processing. Processing temperature is 80
C., preferably 55.degree. C. or less, while suppressing evaporation and the like. The processing step using these processing solutions having a bleaching ability (bleaching solution and bleach-fixing solution) is preferably within 40 seconds, more preferably 3 seconds to 35 seconds, particularly preferably 5 seconds to 30 seconds from the viewpoint of the effects of the present invention. Seconds, most preferably from 7 seconds to 25 seconds.

Hereinafter, a preferred embodiment of the stabilization process will be described.

Compounds preferably used in the stabilizing solution include chelating agents having a chelate stability constant for iron ions of 8 or more, and these are preferably used in order to suppress the stain in unexposed areas and achieve the object of the present invention.

Here, the chelate stability constant is LGSillen ・ AEMa
rtell, “Stability Constants of Metal-ion Compl
exes ", The Chemical Society, London (1964). S. Chabe
“Organic Sequestering Agent” by rek AEMartell
s ", a constant generally known by Wiley (1959) and the like.

Examples of the chelating agent having a chelating stability constant for iron ions of 8 or more preferably used in the stabilizer include an organic carboxylic acid chelating agent, an organic phosphoric acid chelating agent, an inorganic phosphoric acid chelating agent, and a polyhydroxy compound. Note that the iron ion means ferric ion (Fe ³⁺ ).

Specific examples of the chelating agent having a chelate stability constant with ferric ion of 8 or more include the following compounds, but are not limited thereto. That is,
Ethylenediamine diorthohydroxyphenylacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, dihydroxyethylglycine,
Ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, diaminopropanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, nitrilotrimethylenephosphonic acid , 1-hydroxyethylidene-1,1-diphosphonic acid, 1,1-diphosphonoethane-2-carboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,2 , 3-tricarboxylic acid,
Catechol-3,5-diphosphonic acid, sodium pyrophosphate, sodium terapolyphosphate, sodium hexametaphosphate, particularly preferably diethylenetriaminepentaacetic acid, nitrilotriacetic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonate Acid, etc., among which 1-hydroxyethylidene-1,1
Diphosphonic acid is most preferably used.

The amount of the chelating agent used is 0.01 to 50 g per stabilizing solution.
And more preferably in the range of 0.05 to 20 g.

Further, as a compound to be added to the stabilizer, an ammonium compound is mentioned as a particularly preferred compound.

These are supplied by ammonium salts of various inorganic compounds, and specific examples include ammonium hydroxide, ammonium bromide, ammonium carbonate, ammonium chloride, and ammonium acetate.

Further, in the present invention, an ion exchange resin treatment is performed, and calcium ions and magnesium ions are reduced to 10 ppm.
The following stabilizer may be used.

The pH of the stabilizer applicable to the present invention is in the range of 5.5 to 10.0. As the pH adjuster that can be contained in the stabilizer that can be applied to the present invention, any commonly used alkali agent or acid agent can be used.

The treatment temperature of the stabilization treatment is preferably from 15C to 60C, and more preferably from 20C to 45C. The shorter the processing time, the more preferable from the viewpoint of effectively achieving the object of the present invention. It is preferably from 3 seconds to 50 seconds, and most preferably from 5 seconds to 40 seconds. In the case of a multi-vessel stabilization treatment, it is preferred that the treatment be performed in a shorter time in the front tank and longer in the rear tank. In particular, it is desirable to sequentially perform the treatment with a treatment time that is 20% to 50% longer than that of the preceding tank.

When a stable replenishing solution is supplied in the stabilization treatment step applicable to the present invention, in the case of a multi-tank countercurrent method, it is preferable that the replenishing solution is supplied to a post-bath and overflowed to a pre-bath. Of course, it can also be processed in a single tank. As a method for adding the above compound, various methods such as adding the above compound and other additives to the stabilizer supplied to the stabilizer tank as a concentrated solution or adding the above compound and other additives to the stabilizer and supplying the same to the stabilizer replenisher can be used. However, any of these addition methods may be used.

The replenishing amount of the stabilizing solution in the stabilizing step applicable to the present invention is preferably 0.1 to 50 times the carry-in amount of the prebath (bleach-fixing solution) per unit area of the light-sensitive material, from the viewpoint of rapid processing and preservation of the dye image. 0.5 to 30 times is preferred. However, in the present invention, a batch disposable system is preferable from the viewpoint of miniaturization of the automatic developing machine.

The stabilization tank in the stabilization treatment applicable to the present invention is 1 to 5
It is preferably a tank, particularly preferably 1 to 3 tanks, most preferably 1 tank.

Further, the processing time of all processing steps (excluding the drying step) such as the color development step, the bleach-fixing step and the stabilization step in the present invention is preferably 90 seconds or less, from the viewpoint of suppressing fogging of the unexposed area, and particularly preferably. From 6 seconds to 75 seconds, more preferably from 9 seconds to 60 seconds, most preferably
The range is 15 seconds to 50 seconds.

The silver halide grains preferably used in the light-sensitive material applied to the present invention are silver halide grains containing at least 80 mol% or more of silver chloride from the viewpoint of rapid processing, preferably 90 mol% or more, more preferably Those containing at least 95 mol%, most preferably at least 99 mol%.

The preferred silver halide grains can contain silver bromide and / or silver iodide as a silver halide composition in addition to silver chloride. In this case, the silver bromide content is 20 mol% or less, preferably
It is at most 10 mol%, more preferably at most 5 mol%, most preferably at most 1 mol%, and when silver iodide is present, at most 1 mol%, preferably at most 0.5 mol%. Such a silver halide grain comprising at least 80 mol% of silver chloride may be applied to at least one silver halide emulsion layer, but is preferably applied to all silver halide emulsion layers. .

The crystal of the silver halide grains may be a normal crystal, a twin crystal or any other crystal, and any ratio of [1.0.0] plane to [1.1.1] plane can be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a layered structure (core-shell type) in which the inside and the outside are different. These silver halides may be of a type in which a latent image is mainly formed on the surface or of a type in which a latent image is formed inside a grain. Further, tabular silver halide grains (see JP-A-58-113934 and JP-A-61-4795) can also be used.

Further, the silver halide grains may be obtained by any preparation method such as an acid method, a neutral method or an ammonia method.

Further, for example, a method may be used in which seed particles are formed by an acidic method and further grown by an ammonia method having a high growth rate to grow to a predetermined size. When growing silver halide grains, controlling the pH, pAg, etc. in the reaction vessel, for example, an amount of silver ion corresponding to the growth rate of the silver halide grains as described in JP-A-54-48521. And halide ions are sequentially and simultaneously injected and mixed.

The preparation of the silver halide grains is preferably performed as described above. The composition containing the silver halide grains is referred to herein as a silver halide emulsion.

The silver halide emulsion layer used in the present invention has a color coupler. These color couplers react with the color developer oxidation products to form non-diffusible dyes. The color coupler is advantageously incorporated in or in close proximity to the photosensitive layer in non-diffusible form.

Thus, the red-sensitive layer can contain, for example, a non-diffusible color coupler which produces a cyan partial color image, generally a phenol or α-naphthol coupler. The green light-sensitive layer comprises, for example, at least one non-diffusible color coupler which produces a magenta partial color image.
A pyrazolone-based color coupler and a pyrazolotriazole; The blue-sensitive layer can include, for example, at least one non-diffusing color coupler that produces a yellow partial color image, generally a color coupler having an open chain ketomethylene group. The color coupler is for example 6
It can be a-, 4- or 2-equivalent coupler.

In the present invention, a 2-equivalent coupler is particularly preferred.

Suitable couplers are disclosed, for example, in the following publications: Agfa's research report (Mitteilunglnausden Forschu
ngslaboratorien der Agfa), Leverkusen / Munchen, Vol.III.p.111 (196
1) “Color coupler” (Farbkuppler) by W.Pelz; K. Venkataraman, “The Chemirsry of Synthetic D”
yes), Vol. 4, 341-387, Academic Press (Acad
emic Press), "The Theory of the Photograph Process"
ic Process), 4th edition, pages 353-362; and Research Disclosure No. 17643, section VII.

In the present invention, in particular, magenta couplers represented by the general formula [M-1] as described on page 26 of JP-A-63-106655 (specific examples of these magenta couplers are described in JP-A-63-106655). No. 1 to No. 77 described in JP-A-106655, pages 29 to 34.) A cyan coupler represented by the general formula [CI] or [C-II] also described on page 34 (Specific examples of cyan couplers include (C′-1) to (C′-82) described in the same specification, pages 37 to 42,
(C "-1) to (C" -36)), and 20
The high-speed yellow coupler described on page 21 (specific examples of cyan couplers include (Y'-1) to (Y'-39) described on pages 21 to 26 of the same specification) can be used as the light-sensitive material of the present invention. It is preferable to use them in combination from the viewpoint of the effects of the object of the present invention.

In the present invention, when a high-silver chloride light-sensitive material of the present invention is used in combination with a nitrogen-containing red-ring mercapto compound, not only the effects of the present invention can be achieved well, but also bleach-fix in a color developing solution. Since another effect is obtained in that the effect on the photographic performance caused when the liquid is mixed is extremely small, this is a more preferable embodiment in the present invention.

Specific examples of these nitrogen-containing nitrogen-containing mercapto compounds include (I ') described in JP-A-63-106655, pages 42 to 45.
-1) to (I'-87).

The silver halide emulsion in the present invention can be chemically sensitized. Sulfur-containing compounds such as allyl isothiocyanate, allyl thiourea or thiosulfate are particularly preferred. Reducing agents can also be used as chemical sensitizers, for example silver compounds as described in Belgian Patents 493,464 and 568,687, and polyamines or aminomethylsulfinic acid derivatives such as, for example, diethylenetriamine according to Belgian Patent 547,323. is there. Noble metals and noble metal compounds such as gold, platinum, palladium, iridium, ruthenium or rhodium are also suitable sensitizers. This chemical sensitization method is described in a paper by R. Kosiovsky in Zeilschrift Vissenshaftriche Photography (Z. Wiss. Photo.) 46 , 65-72 (1951). Being done;
See also Research Disclosure No. 17643, Section III above.

The silver halide emulsion in the present invention is sensitized by an optically known method, for example, a common polymethine dye such as neuthocyanine, basic or acidic carbocyanine, rhodocyanine, hemicyanine, styryl dye, oxonol and the like. You can: FM
Hamer 「Cyanine soybean and
"Related Compounds" (The Cyanine Dyes and
related Compounds) (1964) Ullman's Hemi (Ul)
lmanns Enzyklpadie dertechnischen Chemie) 4th edition, 18
Vol., P. 431 and following, and Research Tis Closure No. 17643, Section IV above.

Commonly used antifoggants and stabilizers can be used in the silver halide emulsion of the present invention. Azaindene is a particularly suitable stabilizer, with tetra- and pentazaindene being preferred, especially those substituted with hydroxyl or amino groups. Compounds of this kind are described, for example, in Birr's article, Zeitschrift Vissenshaftrich Photography (Z.Wiss.Phot) 4
7, 1952, pp. 2-58, and Research Disclosure No. 17643, supra, Section IV.

The components of the light-sensitive material can be contained by a usual known method; for example, US Pat. Nos. 2,322,027 and 2,533,5
No. 14, 3,689,271, 3,764,336 and 3,765,897
No. The components of the light-sensitive material, such as couplers and UV absorbers, can also be included in the form of a charged latex; DE-A 2,541,274 and EP-A 1
See No. 4,921. The components can also be fixed in the light-sensitive material as polymers; see, for example, DE 2,044,
No. 992, U.S. Pat. Nos. 3,370,952 and 4,080,211.

Usual supports can be used as supports for the light-sensitive material, for example, supports of cellulose esters such as cellulose acetate and supports of polyester. Paper supports are also suitable, and they can be coated, for example, with polyolefins, especially polyethylene or polypropylene; in this regard, see Research Disclosure No. 17643, supra, section VVI.

In the present invention, as a photosensitive material, if it is a photosensitive material processed by a so-called internal developing method containing a coupler in the photosensitive material, color paper, color negative film, color positive film, color reversal film for slide, color for video The present invention can be applied to any photosensitive material such as a reversal film, a color reversal film for TV, and a reversal color paper.

[Effects of the Invention] According to the present invention, it is possible to provide an automatic developing machine for a photosensitive material enabling ultra-rapid processing and a processing method for a photosensitive material using the automatic developing machine. An automatic developing machine for a photosensitive material with less occurrence of fog and a method for processing a photosensitive material using the automatic developing machine, and an automatic developing machine for a photosensitive material having improved desilvering performance and the automatic developing machine And a method for processing a photosensitive material using the same. Further, it is possible to provide a method and an apparatus for processing a photosensitive material in which the dyeing of the photosensitive material onto the lower turn roller of the automatic developing machine is improved.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 The following layers were sequentially coated on a polyethylene-coated paper support from the support side to prepare a photosensitive material.

The average molecular weight of polyethylene coated paper is 10
200 parts by weight of polyethylene with a density of 0,000 and a density of 0.95
2,000, anatase type titanium oxide in a mixture of polyethylene 20 parts by weight of density 0.80 was added 6.7 wt%, to form a coating layer having a thickness of 0.035mm on the fine paper surface of the weight 165 g / m ² by an extrusion coating method, The back surface was provided with a coating layer having a thickness of 0.040 mm using only polyethylene. After pretreatment by corona discharge was performed on the polyethylene-coated surface of the support, the following layers were sequentially applied.

First layer: a blue-sensitive silver halide emulsion layer comprising a silver chlorobromide emulsion containing 0.5 mol% of silver bromide, wherein the emulsion contains 340 g of gelatin per mol of silver halide and has the following structure per mol of silver halide. 2,5-di-t-butylhydroquinone 200 mg / m ² sensitized with 2.4 × 10 ^-4 mol of sensitizing dye [III] (using isopropyl alcohol as a solvent), and dissolved and dispersed in dibutyl phthalate. And a yellow coupler containing 2.1 × 10 ^-1 mol of [Y] having the following structure per mol of silver halide and coated so as to have a silver amount of 300 mg / m ² .

Second layer: 310 mg / m ^{2 of} di-t-octylhydroquinone dissolved and dispersed in dibutyl phthalate, ^{2 as} an ultraviolet absorber
-(2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-
5'-t-butylphenyl) benzotriazole, 2-
(2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chloro-benzotriazole and 2-
Mixture of (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chloro-benzotriazole (1: 1:
1: 1) Gelatin gelatin layer containing 200mg / m ² 2000mg /
is applied so that the m ^2.

Third layer: A green-sensitive silver halide emulsion layer comprising a silver chlorobromide emulsion containing 0.3 mol% of silver bromide. The emulsion contains 460 g of gelatin per mol of silver halide and has the following structure per mol of silver halide. 2,5-Di-t-butylhydroquinone and magenta coupler sensitized with 2.5 × 10 ^-4 mol of sensitizing dye [I] and dissolved in a solvent consisting of dibutyl phthalate and tricresyl phosphate 2: 1 [M] having a structure of 1.5 × 10 ^-1 mol per mol of silver halide, and a silver amount of 200 mg / m 2
It is applied to be ² . As an antioxidant, 2,2,4-trimethyl-6-lauryloxy-7-t-
0.30 mol of octylchroman was added per 1 mol of coupler.

Fourth layer: 25 mg / m ^{2 of} di-t-octylhydroquinone dissolved and dispersed in dioctyl phthalate and 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole as an ultraviolet absorber , 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2
-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5'-chloro-benzotriazole and 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) 5-chloro - mixture of benzotriazole (2: 1.5: 1.5: 2) a gelatin layer containing 500 mg / m ^2, is coated so as to gelatin 2000 mg / m ^2.

Fifth layer: A red-sensitive silver halide emulsion layer composed of a silver chlorobromide emulsion containing 0.3 mol% of silver bromide. The emulsion contains 500 g of gelatin per mol of silver halide and has the following structure per mol of silver halide. Sensitized with 2.5 × 10 ^-4 mol of sensitizing dye [II],
2,5-di-t- dissolved and dispersed in dibutyl phthalate
Butyl hydroquinone 160 mg / m ² and [C] having the following structure as a cyan coupler were used in an amount of 3.8 × 10 4 per mol of silver halide.
It is coated so as to contain ^-1 mol and to have a silver amount of 250 mg / m ² .

Sixth layer: This is a gelatin layer, which is coated with gelatin at a concentration of 900 mg / m ² .

The silver halide emulsions used for the respective photosensitive emulsion layers (first, third, and fifth layers) were prepared by the method described in JP-B-46-7772, and each was prepared by using sodium thiosulfate pentahydrate. Chemically sensitized, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (2.5 g per mol of silver halide) as a stabilizer and bis (vinylsulfonylmethyl) ether ( (12 mg per 1 g of gelatin) and saponin as a coating aid.

After exposing the color paper produced by the above method, the treatment was performed using the following treatment steps and treatment liquid.

[Color developing tank liquid] Benzyl alcohol 0.5 g Diethylene glycol 10 g Potassium bromide 0.01 g Potassium chloride 2.3 g Potassium sulfite (50% solution) 0.5 mL Color developing agent (3-methyl-4-amino-N-ethyl-N- (β -Methanesulfonamidoethyl) -aniline sulfate 5.0 g diethylhydroxylamine (85%) 5.0 g triethanolamine 10.0 g potassium carbonate 30 g ethylenediaminetetraacetate sodium salt 2.0 g fluorescent brightener (Nippon Soda Co., Ltd. Keiko PK-Conc) 2.0g Add water and finish to 1 and add potassium hydroxide or sulfuric acid
The pH was adjusted to 10.15.

[Color development auxiliary liquid] Benzyl alcohol 0.5 g Diethylene glycol 10 g Potassium chloride 3.0 g Potassium sulfite (50% solution) 0.5 ml Color developing agent (3-methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) ) -Aniline sulfate 8.0 g Diethylhydroxylamine (85%) 7.0 g Triethanolamine 10.0 g Potassium carbonate 30 g Sodium ethylenediaminetetraacetate 2.0 g Fluorescent whitening agent (Nippon Soda Co., Ltd. Keiko PK-Conc) 2.5 g Add water And finish with potassium hydroxide or sulfuric acid
The pH was adjusted to 10.40.

[Bleaching and fixing tank solution and replenisher] Ferric ammonium salt of diethylenetriaminepentaacetic acid 65.0 g Diethylenetriminepentaacetic acid 3.0 g Ammonium thiosulfate (70% solution) 100.0 ml 5-amino-1,3,4-thiadiazole-2-thiol
0.5g Ammonium sulfite (40% solution) 27.5ml Adjust the pH to 6.50 with aqueous ammonia or glacial acetic acid, and add water to make the total amount to be 1.

[Stable tank solution and replenisher] Orthophenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazoline-3-
On 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g ethylene glycol 1.0 g Tinopearl SFP (manufactured by Ciba Geigy) 2 g 1-hydroxyethylidene-1,1-diphosphonic acid (60
% Aqueous solution) 3.0 g BiCl ₃ (45% aqueous _{solution) 0.65g MgSO 4 · 7H 2 O} 0.2g PVP ( polyvinylpyrrolidone) 1.0 g of aqueous ammonia (25% aqueous ammonium hydroxide) 2.5 g nitrilotriacetic acid, trisodium salt 1.5g Water To 1 and to pH 7.5 with aqueous ammonia and sulfuric acid.

A running process was performed using the color paper and the processing solution prepared as described above.

In the running process, the automatic developing machine is filled with the above-described color developing tank solution, filled with the bleach-fixing tank solution and the stabilizing tank solution, and while the color paper sample is being processed, the above-mentioned color developing replenisher is added every three minutes. The bleach-fix replenisher and the stable replenisher were replenished through a metering pump.

The amount of replenishment to the color developing tank is 1m of color paper
² per 180 ml, 1 m ² per blix replenisher 200ml as replenishing amount to the bleach-fixing tank, the replenishing amount of the stabilizing tank 1 m ²
250 ml of the stable replenisher was replenished.

The running process was a continuous process until the capacity of the color developing tank became 5 times.

An experiment was conducted by changing the air time ratio as shown in Table 1 for the processing time of the color developing process of the automatic developing machine.

Further, the processing temperature of the color development step is set to a processing time of 3 to
60 ° C for 5 seconds, 50 ° C for 7-15 seconds, 40 ° C for 20-35 seconds, 40 ° C
The development was carried out at 35 ° C. for 6060 seconds so that the development activity became almost constant.

The magenta fog density of the unexposed portion of the processed color paper sample after the running process was measured with a photoelectric densitometer, and the dyeing state of the cyan dye was observed.

 The results are summarized in Table 1.

In the table, ○ means that cyan dyeing is not recognized on a white background, △ means that it is slightly recognized, and X means that it is clearly occurring enough to lose commercial value. When different signs are connected by “「 ”, it means an intermediate degree. Further, the greater the number of crosses, the greater this degree.

From Table 1 above, the air time ratio in the color development process is 25 to
At 60%, the magenta fog density is low and the cyan dyeing is relatively good.

These effects are particularly good when the color development time is within 35 seconds, particularly in the range of 3 to 30 seconds, particularly in the range of 5 to 25 seconds, and most preferably in the range of 7 to 20 seconds. It can be seen that it is in the range of seconds.

Example 2 Each of the emulsion layers of the color paper sample used in the experiment of Example 1 was coated with an exemplified compound (I'-24) or (I'-41) of a heterocyclic mercapto compound described in JP-A-63-106655. ,
(I'-60), (I'-66), (I'-79), (I'-
An experiment was conducted in the same manner as in Example 1 except that 0.12 mg / m ² of each of No. 84) was added. As a result, the magenta stain concentration in the unexposed portions was further improved by 20 to 30%.

Example 3 The magenta coupler [M] in the color paper sample used in the experiment of Example 1 was replaced with the magenta coupler [M] of JP-A-63-106655, No. 29.
To page 34, pyrazolotriazole type magenta couplers (M'-1), (M'-2), (M'-4), (M '
-21), (M'-37), (M'-61), and (M'-63), and the same experiment was carried out. The cyan dye dyeing was almost the same as in Example 1. However, the magenta fog density of the unexposed area was 0.01, which was extremely good.

Example 4 Diethylhydroxylamine in the color developing solution used in the experiment of Example 1 was replaced with an exemplified compound A of the same mole number of a hydroxylamine derivative (a compound represented by the general formula [I]).
-13, A-18, A-21, and A-7, except that they were changed to respectively, the same experiment was performed. As a result, almost the same results as in Example 1 were obtained. Was changed to the same number of moles of hydroxylamine sulfate, the maximum density of yellow was reduced by 0.65, and the dyeing of cyan became worse.

Example 5 The cyan coupler [C] in the color paper sample used in the experiment of Example 1 was replaced with the cyan coupler [C] in JP-A-63-106655, Nos. 34 to
Cyan couplers (C'-2) and (C'-2) described on page 42.
7), (C'-32), (C'-33), (C'-34),
(C'-36), (C'-37), (C'-38), (C'-
39), (C'-53), (C "-2), (C" -8) and (C "-9), and the same experiment was carried out. 20-40% improvement.

Example 6 The following layers were sequentially coated on a polyethylene-coated paper support from the support side to prepare a light-sensitive material.

The average molecular weight of polyethylene coated paper is 10
200 parts by weight of polyethylene with a density of 0,000 and a density of 0.95
6.7% by weight of anatase type titanium oxide was added to a mixture of 20 parts by weight of polyethylene having a density of 2,000 and a density of 0.80, and a coating layer having a thickness of 0.035 mm was formed on the surface of high-quality paper having a weight of 165 g / m ² by extrusion coating. Used a coating layer having a thickness of 0.040 mm made of only polyethylene. After pretreatment by corona discharge was performed on the polyethylene-coated surface of the support, the following layers were sequentially applied.

First layer: a blue-sensitive silver halide emulsion layer comprising a silver chlorobromide emulsion containing 0.4 mol% of silver bromide, wherein the emulsion contains 340 g of gelatin per mol of silver halide and has the above structure per mol of silver halide. 2,5-di-t-butylhydroquinone 200 mg / m ² sensitized with 2.4 × 10 ^-4 mol of sensitizing dye [III] (using isopropyl alcohol as a solvent), and dissolved and dispersed in dibutyl phthalate. And a yellow coupler containing 2.1 × 10 ^-1 mol of [Y] having the above structure per mol of silver halide, and coated so as to have a silver amount of 310 mg / m ² .

Second layer: 310 mg / m ^{2 of} di-t-octylhydroquinone dissolved and dispersed in dibutyl phthalate, ^{2 as} an ultraviolet absorber
-(2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-
5'-t-butylphenyl) benzotriazole, 2-
(2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chloro-benzotriazole and 2-
Mixture of (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chloro-benzotriazole (1: 1:
1: 1) Gelatin gelatin layer containing 200mg / m ² 1900mg /
is applied so that the m ^2.

Third layer: a green-sensitive silver halide emulsion layer comprising a silver chlorobromide emulsion containing 0.4 mol% of silver bromide, wherein the emulsion contains 460 g of gelatin per mol of silver halide and has the above-mentioned structure per mol of silver halide. 2,5-Di-t-butylhydroquinone and magenta coupler sensitized with 2.5 × 10 ^-4 mol of sensitizing dye [I] and dissolved in a solvent consisting of dibutyl phthalate and tricresyl phosphate 2: 1 [M] having a structure of 1.5 × 10 ^-1 mol per mol of silver halide, and a silver amount of 200 mg / m 2
It is applied to be ² . As an antioxidant, 2,2,4-trimethyl-6-lauryloxy-7-t-
Octyl chroman was added in an amount of 0.29 mol per 1 mol of the coupler.

Fourth layer: 25 mg / m ^{2 of} di-t-octylhydroquinone dissolved and dispersed in dioctyl phthalate and 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole as an ultraviolet absorber , 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2
-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5'-chloro-benzotriazole and 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) 5-chloro - mixture of benzotriazole (2: 1.5: 1.5: 2) a gelatin layer containing 500 mg / m ^2, is coated so as to gelatin 2000 mg / m ^2.

Fifth layer: A red-sensitive silver halide emulsion layer comprising a silver chlorobromide emulsion containing 0.4 mol% of silver bromide, wherein the emulsion contains 500 g of gelatin per mol of silver halide and has the above structure per mol of silver halide. Sensitized with 2.5 × 10 ^-4 mol of sensitizing dye [II],
2,5-di-t- dissolved and dispersed in dibutyl phthalate
Butyl hydroquinone 160 mg / m ² and [C] having the above structure as a cyan coupler were converted to 3.8 × 10 4 per mol of silver halide.
It is coated so as to contain ^-1 mol and to have a silver amount of 240 mg / m ² .

Sixth layer: This is a gelatin layer, which is coated with gelatin at a concentration of 900 mg / m ² .

The silver halide emulsions used for the respective photosensitive emulsion layers (first, third, and fifth layers) were prepared by the method described in JP-B-46-7772, and each was prepared by using sodium thiosulfate pentahydrate. Chemically sensitized, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (2.5 g per mol of silver halide) as a stabilizer, and bis (vinylsulfonylmethyl) ether (as a hardening agent) (11 mg per g of gelatin) and saponin as a coating aid.

The sensitizing dyes and couplers used were the same as those described in Example 1.

After exposing the color paper produced by the above method, the treatment was performed using the following treatment steps and treatment liquid.

[Color developing tank solution] diethylene glycol 10 g potassium bromide 0.01 g potassium chloride 2.3 g potassium sulfite (50% solution) 0.5 ml color developing agent (3-methyl-4-amino-N-ethyl-N- (β-methanesulfonamide) Ethyl) -aniline sulfate 6.8 g Diethylhydroxylamine (85%) 5.0 g Triethanolamine 10.0 g Potassium carbonate 30 g Sodium ethylenediaminetetraacetate 2.0 g Fluorescent whitening agent (Nippon Soda Co., Ltd. Keiko PK-Conc) 2.0 g Water Add 1 and add potassium hydroxide or sulfuric acid
The pH was adjusted to 10.15.

[Color developing aid] Diethylene glycol 10 g Potassium chloride 3.0 g Potassium sulfite (50% solution) 0.5 ml Color developing agent (3-methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) -aniline sulfate Salt 8.4 g Diethylhydroxylamine (85%) 7.0 g Triethanolamine 10.0 g Potassium carbonate 30 g Sodium ethylenediaminetetraacetate 2.0 g Optical brightener (Nippon Soda Co., Ltd. Keikoru PK-Conc) 2.5 g Finished with water by adding water With potassium hydroxide or sulfuric acid
The pH was adjusted to 10.40.

[Bleaching and fixing tank solution and replenisher] Ferric ammonium salt of diethylenetriaminepentaacetic acid 65.0 g Diethylenetriaminepentaacetic acid 3.0 g Ammonium thiosulfate (70% solution) 100.0 ml 5-amino-1,3,4-thiadiazole-2-thiol
0.5g Ammonium sulfite (40% solution) 27.5ml Adjust the pH to 6.50 with aqueous ammonia or glacial acetic acid, and add water to make the total amount to be 1.

[Stable tank solution and replenisher] Orthophenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazoline-3-
On 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g ethylene glycol 1.0 g Tinopearl SFP (manufactured by Ciba Geigy) 2 g 1-hydroxyethylidene-1,1-diphosphonic acid (60
% Aqueous solution) 3.0 g BiCl ₃ (45% aqueous _{solution) 0.65g MgSO 4 · 7H 2 O} 0.2g PVP ( polyvinylpyrrolidone) 1.0 g of aqueous ammonia (25% aqueous ammonium hydroxide) 2.5 g nitrilotriacetic acid, trisodium salt 1.5g Water To 1 and to pH 7.5 with aqueous ammonia and sulfuric acid.

A running process was performed using the color paper and the processing solution prepared as described above.

In the running process, the automatic developing machine is filled with the above-described color developing tank solution, filled with the bleach-fixing tank solution and the stabilizing tank solution, and while the color paper sample is being processed, the above-mentioned color developing replenisher is added every three minutes. The bleach-fix replenisher and the stable replenisher were replenished through a metering pump.

The amount of replenishment to the color developing tank is 1m of color paper
² per 180ml, 1 m ² per blix replenisher 180ml as replenishing amount to the bleach-fixing tank, the replenishing amount of the stabilizing tank 1 m ²
250 ml of the stable replenisher was replenished.

In the running processing, continuous processing was performed until the capacity of the bleach-fixing tank became 5 times.

Experiments were conducted by changing the processing time and the air time ratio in the bleach-fixing process of the automatic developing machine as shown in Table 2.

Further, the processing temperature in the bleach-fixing step is such that the processing time is 3 to
60 ° C for 5 seconds, 50 ° C for 7-15 seconds, 40 ° C for 20-35 seconds, 40 ° C
The development was carried out at 35 ° C. for 6060 seconds so that the development activity became almost constant.

The magenta fog density of the unexposed portion of the processed color paper sample after the running process was measured by a photoelectric densitometer, and the residual silver amount of the highest density portion was measured by a fluorescent X-ray method.

 Table 2 summarizes the results.

From the above Table 2, the air time ratio in the bleach-fixing step is 25 to
When it is within the range of 60%, it is understood that the magenta fog density is low and the residual silver amount is fine, which is good. Further, when the processing time of the bleach-fixing step is within 40 seconds, these effects are further improved, and the range of 3 to 35 seconds is particularly good, and the range of 5 to 30 seconds is particularly good. It can be seen that the range of 7 seconds to 25 seconds is the best.

Example 7 The magenta coupler [M] in the color paper sample used in the experiment of Example 6 was replaced with the magenta coupler [M] of JP-A-63-106655, No. 29.
To page 34, pyrazolotriazole type magenta couplers (M'-1), (M'-2), (M'-4), (M '
-21), (M'-37), (M'-61), and (M'-63), and the same experiment was carried out. The residual silver amount was almost the same as in Example 1. However, the magenta fog density in the unexposed area was further reduced by 20 to 30%, which was extremely good.

Example 8 Diethylhydroxylamine in the color developing solution used in the experiment (No. 2-7) of Example 6 was replaced with an exemplified compound of the same mole number of a hydroxylamine derivative (a compound represented by the general formula [I]). The same experiment as in Example 6 was carried out, except that A-13, A-18, A-21 and A-7 were changed, respectively. As a result, almost the same results as in Example 6 were obtained. When the amine was changed to the same molar number of hydroxylamine sulfate, the maximum concentration of yellow was 2.98 to 2.27.
, Ie, 0.71 lower, and the residual silver amount also worsened.

Example 9 The cyan coupler [C] in the color paper sample used in the experiment of Example 6 was replaced with the cyan coupler [C] No. 34 to JP-A-63-106655.
Cyan couplers (C'-2) and (C'-2) described on page 42.
7), (C'-32), (C'-33), (C'-34),
(C'-36), (C'-37), (C'-38), (C'-
39), (C'-53), (C "-2), (C" -8) and (C "-9), and the same experiment was carried out. ~ 30% improvement.

Example 10 The silver chloride content of the silver chlorobromide emulsion in each emulsion layer used in Example 1 was changed as shown in Table 3 below.
The experiment was performed in the same manner as in Nos. 1-13 and No. 1-18.

The magenta fog density of the unexposed portion and the yellow density of the highest density portion of the processed color paper sample were measured with a photoelectric densitometer, and the dyeing status of the cyan dye was observed.
The results are shown in Table 3.

In the table, the meanings of ○, Δ, ×, etc. are the same as those in Table 1.

Table 3 shows that when the air time is within the range of the present invention, the fog density and cyan dyeing are good. In particular, when the silver chloride content is 80 mol% or more, it can be seen that a sufficient dye concentration is provided and rapid processing characteristics are obtained. It can be seen that a more satisfactory dye concentration can be obtained particularly at 90 mol% or more, especially at 95 mol% or more, most preferably at 99 mol% or more.

Example 11 Using the color paper prepared in Example 1, after exposure, a running experiment was performed using the following processing steps and processing liquid.

The same color developing solution and stabilizing solution as in Example 1 were used.

[Bleaching tank solution and replenisher] 1.3-ammonium ferric ammonium propylenediaminetetraacetate 45 g ammonium ferric ammonium salt of ethylenediaminetetraacetic acid 40 g ammonium bromide 160 g ammonium acetate 35 g imidazole 2 g ammonia water (25% solution) 8 ml And adjusted to pH 4.0 using aqueous ammonia and acetic acid.

[Fixing tank solution and replenisher] Diethylenetriaminepentaacetic acid 3.0 g Ammonium thiosulfate (70% solution) 100.0 ml Ammonium sulfite (40% solution) 27.5 ml Adjust the pH to 6.50 with aqueous ammonia or glacial acetic acid, and add water to adjust the total volume. Let it be 1.

The air time ratio of the color developing step and the bleaching step in the above processing steps was changed as shown in Table 4 below, and the magenta fog density of the unexposed area was measured.

 The results are summarized in Table 4.

According to Table 4 above, when the air time ratio is within the range of the present invention, the fog density is good. Therefore, it is better to perform the bleach-fixing process than to perform the bleaching process subsequent to the color development. It turns out that the suppression effect is good.

Example 12 Using the photosensitive material and the processing solution described in Example 1, a running processing experiment was carried out by changing the air time ratio and the processing time in the color developing step, the bleach-fixing step and the stabilizing step as shown in Table 5 below.

 Table 5 summarizes the results.

The processing temperature is 50 ° C for 15 seconds of color development and 40 seconds for color development.
The experiment was conducted at 35 ° C. for 15 seconds, 50 ° C. for 15 seconds, and 35 ° C. for 50 seconds.

From the above Table 5, it can be seen that the effect of the present invention becomes remarkable when the air time ratio is in the range of 15 to 65% in all the steps. Further, it can also be seen that the processing time is good when the color development is within 35 seconds and the bleach-fix is within 40 seconds, and the fogging suppressing effect is good.

Hereinafter, an apparatus for processing a photosensitive material according to the present invention will be described with reference to the accompanying drawings. As an example, an embodiment of an automatic photographic paper developing apparatus will be described.

In the figure, reference numeral 1 denotes a mounting unit for mounting a magazine 3 containing a printing paper 2 on which a printed latent image is formed by a printing machine (not shown), and is provided on a side wall of the automatic developing machine main body 4.

The leading end of the photographic paper 2 attached to the mounting portion 1 is inserted into a nip roll 5 at the entrance of the main body, and is automatically processed through a color developing tank 6, a bleach-fixing tank 7, and a stabilizing tank 8, and then dried.
It is dried at 10 and emerges from an outlet 11 provided at the top of the body 4. In addition, each processing does not necessarily need to be a bathtub type, and may be a spray type or the like.

The photographic paper 2 coming out of the drying unit 10 is processed using the rough surface roller mechanism 12 when image quality processing from glossy to matte is required.

Reference numeral 13 denotes a fixed roller in contact with the back side of the photographic paper 2, and reference numeral 14 denotes a movable roller in contact with the front side of the photographic paper 2. Both ends of the fixed roller 13 are rotatably supported by a shaft fixing member. As the movable roller 14, a rough roller is used. If a matte surface is to be formed as required, the motor is turned on by a changeover switch input, the cam is moved to the position shown in the figure, and the motor is stopped by operating the cam position detection microswitch. The movable roller 14 is attached to the fixed roller 13 by the accumulation of the tension spring with the rotation of the cam.
Contact (or approach).

The photographic paper subjected to image quality processing as necessary passes through an accumulation unit 22 for buffering a change in processing speed, temporarily stops at a cutter unit 23, and after the mark is detected by a cutter mark detection unit 24, It is cut by the cutter 25.
As the cutter 25, for example, a direct-acting cutting blade is used, but it is not limited to this, and another cutter may be used.

The photographic paper cut into a predetermined size is accumulated on the tray 26. The collecting position may be above the main body 4 as shown, or may be at another location.

When all the processing steps after the drying unit 10 are provided on the main body 4, one end edge of the top plate provided with all the above-described processing steps is hinged or the like so that the above-mentioned maintenance step can be performed. It is preferable to be able to open and close by pivoting.

In the figure, reference numeral 27 denotes a water supply tank (preferably a non-pipe, replaceable type), 28 denotes a waste liquid tank, and 29 denotes a control system box.

In the figure, the time from the point when the photosensitive material passes point a to the point where the same point reaches point c is the processing time of the color development processing step. Similarly, from the point when the photosensitive material passes point b, the same point is reached. Is the air time in the color development processing step. The time from the point when the photosensitive material passes the point c to the point where the same location reaches the point e is the processing time of the bleach-fixing process. The time until the point is the air time in the bleach-fixing process.

The processing tank (for example, the color developing tank 6) may be turned twice or more by the lower turn roller 30 as shown in FIG. 2, and a step of contacting with air may be interposed once or more. The time from the passage of time until the same point reaches the point 1 is the processing time of the color development processing step, and the time until the photosensitive material goes from the point g to the point h.
The total time of the time from point i to point j and the time from point k to point l is the air time in the color development process.

Regardless of the configuration of FIG. 2, for example, continuous processing is performed by two or more independent color developing tanks, or continuous processing is performed by two or more color developing tanks in which a liquid is introduced by a forward flow method or a reverse flow method. In the case of color development,
The processing time and the air time are calculated as in the embodiment shown in the figure.

Processing with a processing solution having bleaching ability is performed twice or more, such as processing with a bleach-fixing solution → processing with a bleach-fixing solution, processing with a bleaching solution → processing with a bleach-fixing solution, processing with a bleach-fixing solution → processing with a fixing solution. Also in the case where the processing is performed separately, the processing time and the air time having the bleaching ability are calculated as in the embodiment shown in FIG. The replenisher may be of a forward flow type or a reverse flow type.

The method of taking the air time is not limited to the embodiment shown in FIGS. 1 and 2 and may be any method.

For example, as shown in FIG. 3, a pair of blades 32A, 32B capable of maintaining liquid tightness is provided above and below each of a pair of conveying rollers 31A, 31B arranged side by side to form an inert gas such as air or nitrogen. An automatic developing machine having a configuration in which a color developing tank 6 and a tank 7 having bleaching ability are arranged side by side with a certain gas chamber 33 (see JP-A-62-9350) may be used. -1147
No.).

Further, for example, as shown in FIG. 4 to FIG. 6, an automatic developing machine having a configuration in which a transport roller 31 and a squeeze roller or a combined squeeze transport roller 34 are disposed at an appropriate position in a passage may be used. Good (JP-A-61-
77851, 63-167362, U.S. Pat. No. 3,769,897).

Further, for example, as shown in FIG. 7, an automatic developing machine having a configuration in which a liquid-tight dish-shaped color developing tank 6, a bleach-fix tank 7 and a stabilizing tank 8 each having a liquid circulating system 35 are arranged in multiple stages. Good (see Japanese Patent Application No. 63-283045).

Further, as described in U.S. Pat.No. 3,336,853, an automatic developing machine in which a conveying roller is disposed so as to cover the processing tank to form a slit-shaped processing tank, U.S. Pat.
As described in No. 456, an automatic developing machine for applying a liquid to a squeeze roller to remove attached solid matter, U.S. Pat.
As described in No. 791, the present invention can also be applied to an automatic developing machine or the like in which a transport roller having a tapered shape is provided at the entrance and exit of the processing tank so that the transport of the paper photosensitive material is straightened. Of course you can.

[Brief description of the drawings]

FIG. 1 is a schematic side view showing one embodiment of a processing apparatus optimal for use in the method for processing a photosensitive material according to the present invention, and FIGS.
FIG. 7 is a schematic side view of a main part showing another embodiment of the automatic developing machine according to the present invention. 1: Mounting section 2: Printing paper 3: Magazine 4: Main body 5: Nip roll 6: Color developing tank 7: Bleaching and fixing tank 8: Stabilizing tank 10: Drying section 11: Exit 12: Rough roller 13: Fixed roller 14: Movable Roller 22: Accumulation unit 23: Cutter unit 24: Cutter mark detection unit 25: Cutter 26: Receiving tray 27: Water tank 28: Waste liquid tank 29: Control system box 30: Lower turn roller 31, 31A, 31B: Transport roller 32A, 32B : Blade 33: Gas chamber 34: Squeeze roller, squeeze and transfer roller 35: Liquid circulation system

──────────────────────────────────────────────────続 き Continuation of the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) G03D 3/00-17/00 G03C 7/00-7/46

Claims (1)

(57) [Claims] 1. A method for processing a silver halide color photographic light-sensitive material, wherein the imagewise exposed silver halide color photographic light-sensitive material is processed in a color development processing step and a processing step having a bleaching ability. The silver color photographic light-sensitive material is provided with at least one emulsion layer containing at least 80 mol% of silver chloride, and the processing solution used in the color development processing step contains a compound of the following general formula [I]. A method of processing a silver halide color photographic light-sensitive material, characterized in that at least one airtime ratio in the processing step is 25 to 65%. In the formula, R ₁ and R ₂ each represent an alkyl group or a hydrogen atom. However, both R ₁ and R ₂ are not hydrogen atoms at the same time. R ₁ and R ₂ may form a ring.