JP2849662B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and more particularly, to an improved method capable of saving water without causing stains on the processed light-sensitive material. It relates to a processing method.

(Prior Art) In recent years, depletion of water resources has been regarded as a problem, and the importance of water saving has been further increased in the processing of color photosensitive materials.

Against this background, as described in Photographic Processing, November 1979, pages 29 to 32, water conservation by a multi-stage countercurrent water washing method has been practically used, and an image stabilizer has been used instead of the water washing. Similarly, a stabilization process using a multi-stage countercurrent method has begun to be carried out using the stabilized liquid.

However, in these water-saving treatment methods, when the treatment is continued for a long period of time, the stabilizer (thiosulfate) brought into the washing or stabilizing solution gradually decomposes, causing a so-called sulfidation phenomenon. There is a serious problem that the toner adheres to the photosensitive material to be stained.

Once the drying process is completed, it is extremely difficult to remove the stains on the color photosensitive material due to the sulfurization development, and it causes fatal damage to photographing color photosensitive materials such as color negative films and color reversal films. Results.

Another problem is that if the water-saving process is continued, various foreign matters adhere to the photosensitive material transporting roller of the automatic developing machine, which may cause the photosensitive material to be damaged.

However, no method for solving these problems has been found so far, and a heavy burden such as discarding a washing bath and a stabilizing solution at regular intervals and frequently cleaning tanks and racks of automatic developing machines and rollers. The current situation is to respond more to the work.

(Problems to be Solved by the Invention) Accordingly, a first object of the present invention is to provide a processing method capable of saving sufficient water without causing stains or scratches on a photosensitive material. A second object of the present invention is to provide a processing method capable of saving water by drastically reducing heavy maintenance work such as disposal of a liquid and cleaning of each part of an automatic developing machine.

(Means for Solving the Problems) As a result of intensive studies on these problems, the present inventors have processed the exposed silver halide color photographic material in a bath having a fixing ability containing thiosulfate, and then replenished the photographic material. the a method for continuously treated with photosensitive material 1 m ² per 1000ml follows the washing bath or stabilizing bath, crossover time between the bath and the washing bath or stabilizing bath having fixing ability is more than 10 seconds, the Processing of a silver halide color photographic light-sensitive material characterized in that the light-sensitive material is introduced into a washing bath or a stabilizing bath, and the emulsion surface of the light-sensitive material is impinged with a jet of a washing solution or a stabilizing solution within 5 seconds. It has been found that the above objects can be achieved by the method.

In the present invention, the crossover time is the time required for the photosensitive material to move from the liquid surface of the preceding bath to the liquid surface of the subsequent bath. In the present invention, the crossover time is within 10 seconds and the shorter the shorter the better, the better.
Within seconds, particularly preferably within 5 seconds. Although the mechanism of the effect of the present invention is not necessarily clear, by shortening the crossover time to within 10 seconds, the air oxidation of the fixing agent (thiosulfate) contained in the bath having the fixing ability is significantly reduced. It is presumed to prevent sulfurization and generation of foreign matter.

Therefore, the effect of the present invention is that the crossover time between the bath having the fixing ability and the rinsing bath or the stabilizing bath is set to 10 seconds or less. It is preferable that the crossover time between them is also 10 seconds or less in order to further enhance the effect of the present invention.

Of course, the washing bath or the stabilizing bath may be constituted by a single bath. In this case, there is no crossover between the baths constituting the washing bath or the stabilizing bath, and the effect of the present invention has a fixing ability. It only works by keeping the crossover time between the bath and the rinsing or stabilizing bath within 10 seconds.

To reduce the crossover time to 10 seconds or less, there are a method of shortening the crossover distance and a method of increasing the conveying speed of the photosensitive material, but if the conveying speed is increased, a certain processing time is inevitably required for the automatic developing machine. This leads to an increase in size, and the former method is preferable.

Although there are various structures for shortening the crossover distance, preferred examples are shown in FIGS. 1 and 2.

FIG. 1 shows a case where the distance between the entrance and exit of the photosensitive material and the liquid surface is reduced, and FIG. 2 shows a case where the entrance and exit are below the liquid level to further reduce the crossover distance. Each case is characterized in that a liquid seal and squeeze (reference numeral 2 in each drawing) for preventing liquid leakage is provided.

In the present invention, the washing liquid may be simple water, but it is preferable to use deionized water described in JP-A-62-288838 to prevent the growth of microorganisms. In addition, various fungicides and fungicides can be used, and 5-chloro-2-methyl-
Isothiazolone fungicides such as 4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one, as well as Journal of Antibacterial and
Antifungal Agents Vol.11.No.5P.207 ~ 23
3 (1983), and the compounds described in Hiroshi Horiguchi, "Bactericidal and Fungicide Chemistry".

The stabilizing solution is obtained by further adding an image stabilizing function to the washing solution, and includes, for example, a solution to which formalin or an ammonium salt is added. Various chelating agents such as 1-hydroxyethylidene-1,1-diphosphonic acid can be used in the washing solution and the stabilizing solution, in addition to the above compounds.

The washing solution and the stabilizing solution of the present invention include other JP-A-57-8543.
And JP-A-62-288838 can be added.

The effect of the present invention is that the liquid in the washing bath or the stabilizing bath is jetted onto the emulsion surface of the photosensitive material within 3 seconds after the photosensitive material processed in the bath having a fixing ability is introduced into the washing bath or the stabilizing bath. Significantly increased by the collision. When used in combination with such jet collision, the adhesion of foreign matter to the crossover rack roller or the like of the automatic phenomenon machine is reduced, and the effect of preventing contamination and scratches on the photosensitive material itself is enhanced.

The collision of the jet of the washing liquid or the stabilizing liquid within 10 seconds means that after a certain point of the photosensitive material comes into contact with the washing liquid or the stabilizing liquid, the same point is hit by the collision of the center point of the first jet. Means time. Such a jet is generated by sucking a liquid by a pump and discharging the liquid toward the emulsion surface from a nozzle or a slit provided at a position facing the emulsion surface. Specifically, it can be carried out by the method described in JP-A-62-183460. The speed of the jet when colliding with the emulsion surface is preferably as large as possible without interfering with the conveyance of the photosensitive material in the automatic phenomenon machine, and specifically, is preferably in the range of 0.3 m to 3 m per second.

In the present invention, the washing or stabilizing bath is composed of a plurality of tanks, and the flow of the liquid connecting between the tanks is preferably a multi-stage counterflow in the direction opposite to the direction of transport of the photosensitive material, and particularly preferably 2 to 4 tanks A configured one is preferred.

In the present invention, the replenishment rate of the washing bath or stabilizing bath is equal to or less than 1000ml per photosensitive material 1 m ^2, the reduction of extreme replenishment rate fading of dye deposition or the like salt after drying the photosensitive material surface occurs Therefore, it is preferably 200 ml or more and 900 ml or less, particularly preferably 400 ml or more and 800 ml or less.

The specific setting of the replenishing amount differs depending on the tank configuration of the washing bath or the stabilizing bath, and can be set to a lower value as the number of tanks increases.

The pH of the washing bath and the stabilizing bath is preferably in the range of 5 to 9, and particularly preferably in the range of 6 to 8 from the viewpoint of promoting the effect of the present invention. The temperature is in the range of 15 ° C to 45 ° C, but is preferably
The temperature is from 25 ° C to 40 ° C, particularly preferably from 30 ° C to 40 ° C.

In the present invention, it is preferable to provide a squeegee between the bath having a fixing ability and the washing bath or the stabilizing bath and between the respective washing baths and between the stabilizing baths to sufficiently drain the liquid, thereby reducing the replenishing amount and the light exposure. It is possible to more effectively prevent contamination of the material. Further, it is preferable that the surfaces of the washing bath and the stabilizing bath have as little air contact as possible, and it is preferable to cover the liquid surface with a floating pig or the like.

The present invention can be applied when a bath having a fixing ability containing a thiosulfate is used.

Examples of the thiosulfate include ammonium thiosulfate and sodium thiosulfate, with ammonium thiosulfate being particularly preferred.

The bath having fixing ability includes a bleach-fixing bath in addition to the fixing bath. The thiosulfate is a main component of the fixing ability, but may be used in combination with other known fixing agents.

Further, the bath having a fixing ability used in the present invention is 0.08 to
Preferably, it contains 0.24 mol / sulfite. In the combination with the present invention, the sulfite having such a concentration range exhibits an effect of preventing contamination of the roller particularly at the crossover portion, and has an effect of further reducing the adhesion of the contamination to the photosensitive material.

The method of the present invention is preferably carried out in the following processing steps.

1.Color development-bleach-fix-wash 2.Color development-bleach-fix-wash-stable 3.Color development-bleach-bleach-fix-wash-stable 4.Color development-bleach-fix-stable 5.Color development-bleach-stable Fixing-Stable 6. Color developing-Bleaching-Bleaching-Stable 7. Color developing-Fixing-Bleaching-Washing-Stable 8. Color developing-Fixing-Bleaching-Stable 9. Black-white developing-Washing-Color developing-Reversing- Adjustment-Bleaching-Fixing-Washing-Stable The processing solutions used in the above steps are described below.

Developer The color developer used in the development of the photosensitive material of the present invention is
An alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component is preferred. Aminophenol compounds are also useful as the color developing agent.
Phenylenediamine compounds are preferably used, and typical examples thereof are 3-methyl-4-amino-N, N-diethylaniline and 3-methyl-4-amino-N-ethyl-N
-Β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N
-Β-methoxyethylaniline and sulfates, hydrochlorides or p-toluenesulfonates thereof.
These compounds can be used in combination of two or more depending on the purpose.

Color developing solutions are pH buffers such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
It generally contains a development inhibitor or an antifoggant such as a benzimidazole, a benzothiazole or a mercapto compound. If necessary, such as hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazide, triethanolamine, catecholsulfonic acid, and triethylenediamine (1,4-diazabicyclo [2,2,2] octane) Various preservatives, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers,
Fogging agent such as sodium boron hydride, 1
An auxiliary developing agent such as -phenyl-3-pyrazolidone,
Viscosity imparting agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, various chelating agents represented by phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid , Hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, ethylenediamine -Di (o-hydroxyphenylacetic acid) and salts thereof can be mentioned as representative examples.

When the reversal process is performed, color development is usually performed after black and white development. The black-and-white developer includes dihydroxybenzenes such as hydroquinone, 1-phenyl-3-
Known black-and-white developing agents such as 3-pyrazolidones such as pyrazolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination.

The pH of these color developing solutions and black-and-white developing solutions is generally 9 to 12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 or less per square meter of the photographic material, and 500 ml by reducing the bromide ion concentration in the replenishing solution.
It can also be: When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

Bleaching solution, fixing solution, bleach-fixing solution A photographic emulsion layer after color development is usually subjected to bleaching. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further processing in two successive bleach-fix baths,
Fixing processing before bleach-fixing processing or bleaching processing after bleach-fixing processing can be arbitrarily performed according to the purpose.
Examples of the bleaching agent include iron (III), cobalt (III),
Compounds of polyvalent metals such as chromium (IV) and copper (II), peracids, quinones, nitro compounds and the like are used. Representative bleaches include ferricyanide; dichromate; iron (II
Organic complex salts of I) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3
-Use of aminopolycarboxylic acids such as diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, or complex salts such as citric acid, tartaric acid, and malic acid; persulfates; bromates; permanganates; it can. Among these, iron aminopolycarboxylates (II) including iron (III) complex salts of ethylenediaminetetraacetate
I) Complex salts and superacid salts are preferred from the viewpoint of rapid processing and prevention of environmental pollution. In addition, iron (III) aminopolycarboxylate
Complex salts are particularly useful in both bleaching and bleach-fixing solutions. The pH of the bleaching solution or the bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 5.5 to 8, but the processing can be carried out at a lower pH in order to speed up the processing.

A bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their prebaths, if necessary. Specific examples of useful bleach accelerators are described in the following specification: U.S. Pat. No. 3,893,858, West German Patent 1,290,812, JP-A-53-812.
No. 95,630, Research Disclosure No. 17,129 (July 1978), etc .; compounds having a mercapto group or disulfide bond; thiazolidine derivatives described in JP-A-50-140,129; US Pat. No. 3,706,561. Thiourea derivatives; iodide salts described in JP-A-58-16,235; polyoxyethylene compounds described in West German Patent No. 2,748,430; polyamine compounds described in JP-B-45-8836; bromide ions and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large accelerating effect, and particularly preferred are the compounds described in U.S. Pat. No. 3,893,858, West German Patent 1,290,812, and JP-A-53-95,630. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether-based compounds, thioureas, and a large amount of iodide.The use of thiosulfates is common,
In particular, ammonium thiosulfate can be used most widely. As a preservative of the bleach-fixing solution, a sulfite, a bisulfite, a sulfinic acid or a carbonyl bisulfite adduct is preferable.

Black-and-white developers Black-and-white developers include dihydroxybenzenes such as hydroquinone and 3-hydroxybenzenes such as 1-phenyl-3-pyrazolidone.
Known black-and-white developing agents such as pyrazolidones and aminophenols such as N-methyl-P-aminophenol can be used alone or in combination.

Other additives such as a preservative described in the section of the color developing solution can be used.

The silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, or silver iodobromide. The effect is particularly large in an emulsion containing iodine. Among them, a light-sensitive material containing a silver iodobromide emulsion is preferable, and the effect of the present invention is particularly remarkable when a light-sensitive material containing 3 mol% or more of silver iodide is used.

Silver halide grains in photographic emulsions are cubic, octahedral,
It may be one having regular crystals such as tetradecahedron, one having irregular crystal forms such as spherical or plate-like, one having crystal defects such as twin planes, or a complex form thereof.

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

The silver halide photographic emulsion usable in the present invention is described, for example, in Research Disclosure (RD), No. 17643 (1978).
December 23, p. 22-23, "I. Emulsion production (Emulsion prepara
No. 18716 (November 1979)
Mon), p.648, Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (P. Glafkides, Chemic et Phisique P
hotographique Paul Montel., 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Pho
tographic Emulsion Chemistry (Focal Press, 196
6)), "Application for the manufacture of photographic emulsions" by Zerikman et al., Published by Focal Press (VLZelikman et al, Making and
Coating Photographic Emulsion, Focal Press, 1964).

Monodisperse emulsions described in U.S. Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable.

Tabular grains having an aspect ratio of about 5 or more can also be used in the present invention. Tabular grains are provided by Gaft, Photographic Science and Engineerin
g), Vol. 14, pp. 248-257 (1970); U.S. Patent No. 4,434,2
No. 26, 4,414,310, 4,433,048, 4,439,520 and British Patent No. 2,112,157 can be easily prepared.

The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, may have a layered structure, and even if silver halides having different compositions are joined by epitaxial junction. Also, it may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide.

 Also, a mixture of particles of various crystal forms may be used.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. The additive used in such a process is Research Disclosure No. 1
7643 and No. 18716, and the relevant portions are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant portions are shown in the following table.

Inhibitors Various color couplers can be used in the present invention, and specific examples thereof are described in the patents described in the aforementioned Research Disclosure (RD) No. 17643, VII-CG.

As a yellow coupler, for example, U.S. Pat.
No. 501, No. 4,022,620, No. 4,326,024, No. 4,40
No. 1,752, JP-B-58-10739, UK Patent No. 1,425,020
And Nos. 1,476,760 and the like.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable, and US Patent No. 4,310,
No. 619, No. 4,351,897, European Patent No. 73,636, U.S. Pat. No. 3,061,432, No. 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-3355
No. 2, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, U.S. Pat. No. 4,500,630,
No. 4,540,654 are particularly preferable.

Cyan couplers include phenolic and naphthol couplers, U.S. Pat.Nos. 4,052,212, 4,146,396, 4,228,233, 4,296,200,
No. 2,369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826, No. 3,772,002, No. 3,758,308,
No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,
No. 329,729, European Patent No. 121,365A, U.S. Patent No. 3,446,6
No. 22, No. 4,333,999, No. 4,451,559, No. 4,427,
No. 767, EP 161,626A and the like are preferred.

Colored couplers for correcting unwanted absorption of coloring dyes are described in Research Disclosure No. 17643 VII.
Section G, U.S. Pat.No. 4,163,670, JP-B-57-39413,
U.S. Pat.Nos. 4,004,929 and 4,138,258; British Patent No.
Those described in 1,146,368 are preferred.

As a coupler in which the coloring dye has an appropriate diffusivity,
Preferred are those described in U.S. Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent No. 96,570, and West German Patent (Published) No. 3,234,533.

Typical examples of polymerized dye-forming couplers include U.S. Patent Nos. 3,451,820, 4,080,211 and 4,367,282.
And British Patent No. 2,102,173.

Couplers that release a photographically useful residue upon coupling can also be preferably used in the present invention. DIR couplers that release development inhibitors are described in RD17643, VII-F above.
Patents, JP-A-57-151944 and JP-A-57-1542
Nos. 34, 60-184248 and U.S. Pat. No. 4,248,962 are preferred.

Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include UK Patent Nos. 2,097,140 and 2,1
No. 31,188, JP-A Nos. 59-157638 and 59-170840 are preferred.

Others, couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat.No. 4,130,427 and the like, U.S. Pat.Nos. 4,283,472 and 4,338,393,
No. 4,310,618 and the like, multi-equivalent couplers described in
And DIR redox compound-releasing couplers described in -185950, etc., and couplers which release dyes that recolor after release as described in EP 173,302A.

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

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027.

There is also a method using a polymer as a coupler dispersion medium, and various descriptions are given in JP-B-48-30494, U.S. Pat. No. 3,619,195, West German Patent 1,957,467, and JP-B-51-39835.

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

Suitable supports that can be used in the present invention include, for example, those described above.
RD. No. 17643, page 28, and RD. No. 18716, from page 647 right column to page 648 left column.

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

Example 1 On a cellulose triacetate film support provided with an undercoat, layers having the following compositions were applied in a multi-layered manner to prepare a multilayer color photosensitive material 101.

(Composition of photosensitive layer) The number corresponding to each component indicates the coating amount expressed in g / m ² , and for silver halide, the coating amount is expressed in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown per mol of 1 mol of silver halide in the same layer.

First layer (anti-halation layer) Black colloidal silver 0.2 Gelatin 1.0 UV absorber UV-1 0.05 Same UV-2 0.1 Same UV-3 0.1 Dispersed oil OIL-1 0.02 Second layer (Intermediate layer) Fine particle silver bromide (average 0.15 gelatin 1.0 Third layer (first red-sensitive emulsion layer) Monodisperse emulsion (silver iodide 6 mol%, average particle diameter 0.4 μm, coefficient of variation 15%) 1.42 Gelatin 0.9 Sensitizing dye A 2.0 × 10 ^-4 sensitizing dye B 1.0 × 10 ^-4 sensitizing dye C 0.3 × 10 ^-4 Cp-b 0.35 Cp-c 0.052 Cp-d 0.047 D-1 0.023 D-2 0.035 HBS-1 0.10 HBS-2 0.10 4th Layer (intermediate layer) Gelatin 0.8 Cp-b 0.10 HBS-1 0.05 Fifth layer (second red-sensitive emulsion layer) Monodisperse emulsion (silver iodide 6 mol%, average particle size 0.5 μm, variation coefficient 15%) 1.38 Gelatin 1.0 Sensitizing dye A 1.5 × 10 ^-4 Sensitizing dye B 2.0 × 10 ^-4 Sensitizing dye C 0.5 × 10 ^-4 Cp-b 0.150 Cp-d 0.027 D-1 0.005 D-2 0.010 HBS-1 0.050 HBS-2 0.060 6th layer (No. 3 red-sensitive emulsion layer) Monodisperse emulsion (silver iodide 7 mol%, average grain size 1.1 μm, variation coefficient 16%) 2.08 gelatin 1.5 Cp-a 0.060 Cp-c 0.024 Cp-d 0.038 D-1 0.006 HBS-1 0.012 Seventh layer (intermediate layer) Gelatin 1.0 Cpd-A 0.05 HBC-2 0.05 Eighth layer (first green sensitive layer) Monodisperse silver iodobromide emulsion (silver iodide 3 mol%, average grain size 0.4
μm, coefficient of variation 19%) 0.64 Monodispersed silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0.7
1.12 Gelatin 1.0 Sensitizing dye D 1 × 10 ^-4 Sensitizing dye E 4 × 10 ^-4 Sensitizing dye F 1 × 10 ^-4 Cp-h 0.20 Cp-f 0.61 Cp-g 0.084 Cp -K 0.035 Cp-1 0.036 D-3 0.041 D-4 0.018 HBS-1 0.25 HBS-2 0.45 Ninth layer (second green-sensitive emulsion layer) Monodisperse silver iodide emulsion (silver iodide 7 mol%, average grain size) Diameter 1.0
2.07 gelatin 1.5 sensitizing dye D 1.5 × 10 ^-4 sensitizing dye E 2.3 × 10 ^-4 sensitizing dye F 1.5 × 10 ^-4 Cp-f 0.007 Cp-h 0.012 Cp-g 0.009 HBS -2 0.088 10th layer (intermediate layer) Yellow colloidal silver 0.06 gelatin 1.2 Cpd-A 0.3 HBS-1 0.3 11th layer (first blue-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 6 mol%, Average particle size 0.4
μm, coefficient of variation 20%) 0.31 monodispersed silver iodobromide emulsion (5 mol% silver iodide, average grain size 0.9
0.38 Gelatin 2.0 Sensitizing dye G 1 × 10 ^-4 Sensitizing dye H 1 × 10 ^-4 Cp-i 0.63 Cp-j 0.57 D-1 0.020 D-4 0.015 HBS-1 0.05 12th Layer (second blue-sensitive emulsion layer) Monodisperse silver iodide emulsion (silver iodide 8 mol%, average grain size 1.3
μm, coefficient of variation 18%) 0.77 Gelatin 0.5 Sensitizing dye G 5 × 10 ^-5 Sensitizing dye H 5 × 10 ^-5 Cp-i 0.10 Cp-j 0.10 D-4 0.005 HBS-2 0.10 Layer 13 (intermediate layer) Gelatin 0.5 Cp-m 0.1 UV-1 0.1 UV-2 0.1 UV-3 0.1 HBS-1 0.05 HBS-2 0.05 14th layer (protective layer) Monodisperse silver iodobromide emulsion (4 mol% silver iodide, average Particle size 0.05
μm, coefficient of variation 10%) 0.1 gelatin 1.5 polymethyl methacrylate particles (average 1.5 μ) 0.1 S-1 0.2 S-2 0.2 Other surfactant K-1 and gelatin hardener H-1 were added.

The color photographic material prepared as described above was subjected to continuous processing using an automatic developing machine whose structure (fixing bath and stabilizing bath) was partially shown in FIG. The automatic developing machine used had a stabilizing bath consisting of three tanks, a fixing bath and a stabilizing bath (first tank).
-Stabilizing bath (second tank)-The crossover distance between each bath of the stabilizing bath (third tank) was changed to change the crossover time variously, and a jet pipe was attached to and removed from the stabilizing bath. In addition to the cases, the adhesion of dirt to the photosensitive material under various conditions and the adhesion of foreign matter to the roller at the crossover portion were comparatively evaluated.

Continuous processing test No. 1 with the above conditions changed
~ No.8 is the processing amount of the above photosensitive material (35mm width, 5C
45 m / day (provided that the uniform exposure of MS was given), and the processing period was 10 days for each.

When the jet pipe was attached to the stabilizing bath, the discharge rate of the jet was 5 / min, and the time required for the jet to collide with the photosensitive material introduced into the stabilizing bath was 5 seconds. Hereinafter, the processing steps in the continuous processing and the composition of the used processing solution will be described.

(Stable liquid) Common to mother liquor and replenisher (g) Tap water 1.0 Formalin (37%) 1.2 ml 5-Chloro-2-methyl-4-isothiazoline-3-
ON 6.0 mg 2-methyl-4-isothiazolin-3-one 3.0mg surfactant _{[C 10 H 21 -OCH 2 CH 2} O 10 H ] 0.4 Ethylene glycol 1 1.0 The results shown in Table 1.

As shown in Table 1, according to this method (crossover time was set within 10 seconds), the stain on the photosensitive material after processing was greatly reduced, and by using jet impingement and stirring in the stabilizing bath, It can be seen that the adhesion of foreign matter to the crossover roller is also improved. Meaning of evaluation symbols in Table 1 Example 2 On a cellulose triacetate film support having an undercoat, each layer having the following composition was applied in a multi-layered manner to prepare a multilayer color photosensitive material B.

(Composition of photosensitive layer) The number corresponding to each component indicates the coating amount expressed in g / m ² , and for silver halide, it indicates the coating amount in terms of silver. However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer.

(Sample B) First layer; antihalation layer Black colloidal silver silver 0.18 gelatin 0.40 Second layer; intermediate layer 2,5-di-t-pentadecylhydroquinone 0.18 EX-1 0.07 EX-3 0.02 EX-12 0.002 U- 1 0.06 U-2 0.08 U-3 0.10 HBS-1 0.10 HBS-2 0.02 Gelatin 1.04 Third layer (first red-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 6 mol%, average grain size)
0.6μ, variation coefficient 0.15) silver 0.55 sensitizing dye I 6.9 × 10 ^-5 sensitizing dye II 1.8 × 10 ^-5 sensitizing dye III 3.1 × 10 ^-4 sensitizing dye IV 4.0 × 10 ^-5 EX− 2 0.350 HBS-1 0.005 EX-10 0.020 Gelatin 1.20 Fourth layer (second red-sensitive emulsion layer) Tabular silver iodobromide emulsion (10 mol% silver iodide, average grain size)
0.7 μ, average aspect ratio 5.5, average thickness 0.2 μ) silver 1.0 sensitizing dye I 5.1 × 10 ^-5 sensitizing dye II 1.4 × 10 ^-5 sensitizing dye III 2.3 × 10 ^-4 sensitizing dye IV 3.0 × 10 ^{− 5} EX-2 0.400 EX-3 0.050 EX-10 0.015 Gelatin 1.30 Fifth layer (third red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 16 mol%, average grain size 1.1)
μ) silver 1.60 sensitizing dye IX 5.4 × 10 ^-5 sensitizing dye II 1.4 × 10 ^-5 sensitizing dye III 2.4 × 10 ^-4 sensitizing dye IV 3.1 × 10 ^-5 EX-3 0.240 EX-4 0.120 HBS- 1 0.22 HBS-2 0.10 gelatin 1.63 6th layer (intermediate layer) EX-5 0.040 HBS-1 0.020 EX-12 0.004 gelatin 0.80 7th layer (first green-sensitive emulsion layer) Tabular silver iodobromide emulsion (iodide) 6 mol% silver, average particle size
0.6 μ, average aspect ratio 6.0, average thickness 0.15 μ) silver 0.40 sensitizing dye V 3.0 × 10 ^-5 sensitizing dye VI 1.0 × 10 ^-4 sensitizing dye VII 3.8 × 10 ^-4 EX-6 0.260 EX-1 0.021 EX-7 0.030 EX-8 0.025 HBS-1 0.100 HBS-4 0.010 Gelatin 0.75 Eighth layer (second green-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (9 mol% silver iodide, average grain size)
0.7 μ, coefficient of variation 0.18) silver 0.80 sensitizing dye V 2.0 × 10 ^-5 sensitizing dye VI 7.0 × 10 ^-5 sensitizing dye VII 2.6 × 10 ^-4 EX-6 0.180 EX-8 0.010 EX-1 0.008 EX-7 0.012 HBS-1 0.160 HBS-4 0.008 Gelatin 1.10 9th layer (third green-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 12 mol%, average grain size 1.0
μ) silver 1.2 sensitizing dye V 3.5 × 10 ^-5 sensitizing dye VI 8.0 × 10 ^-5 sensitizing dye VII 3.0 × 10 ^-4 EX-6 0.065 EX-11 0.030 EX-1 0.025 HBS-1 0.25 HBS-2 0.10 gelatin 1.74 10th layer (yellow filter layer) yellow colloidal silver silver 0.05 EX-5 0.08 HBS-3 0.03 gelatin 0.95 11th layer (first blue-sensitive emulsion layer) Tabular silver iodobromide emulsion (silver iodide 6 mol) %, Average particle size
0.6μ, average aspect ratio 5.7, average thickness 0.15) silver 0.24 sensitizing dye VIII 3.5 × 10 ^-4 EX-9 0.85 EX-8 0.12 HBS-1 0.28 gelatin 1.28 12th layer (second blue-sensitive emulsion layer) monodispersed Silver iodobromide emulsion (silver iodide 10 mol%, average grain size
0.8μ, variation coefficient 0.16) silver 0.45 sensitizing dye VIII 2.1 × 10 ^-4 EX-9 0.20 EX-10 0.015 HBS-1 0.03 gelatin 0.46 13th layer (3rd blue-sensitive emulsion layer) Silver iodobromide Emulsion (silver iodide 14 mol%, average grain size 1.3μ)
m) silver 0.77 sensitizing dye VIII 2.2 × 10 ^-4 EX-9 0.20 HBS-1 0.07 gelatin 0.69 14th layer (first protective layer) silver iodobromide emulsion (silver iodide 1 mol%, average particle size 0.07)
μ) silver 0.5 U-4 0.11 U-5 0.17 HBS-1 0.90 gelatin 1.00 15th layer (second protective layer) Polymethyl acrylate particles (1.5 μm in diameter) 0.54 S-1 0.15 S-2 0.05 gelatin 0.72 In addition to the above components, a gelatin hardener H-1 and a surfactant were added.

HBS-1; tricresyl phosphate HBS-2; dibutyl phthalate HBS-3; bis (2-ethylexyl) phthalate The color light-sensitive material (35 mm wide) prepared as described above was exposed imagewise, and FIG.
Although not shown in FIG. 2, an automatic developing machine showing a washing bath was used. The washing bath was composed of two tanks having the same structure, and various processing conditions were changed in the same manner as in Example 1 to obtain a washing bath. A similar continuous processing test was performed.

(Bleaching / fixing solution) Common to mother liquor and replenisher (unit: g) Ferric ammonium ammonium diamine tetraacetate dihydrate 50.0 Disodium ethylenediaminetetraacetate 5.0 Sodium sulfite Table 2 Ammonium thiosulfate aqueous solution (70%) 240.0 ml (27%) 6.0ml Add water 1.0L pH 7.2 (Washing water) Common for mother liquor replenisher Tap water is H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type anion Water was passed through a mixed-bed column filled with an exchange resin (Amberlite IR-400) to obtain the following water quality.

(Stabilizing solution) Common to mother liquor and replenisher (unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.3 Disodium ethylenediaminetetraacetate 0.05 Add water (tap) Water) 1.0L pH 5.0−8.0 As shown in Table 2, by setting the crossover time to 10 seconds or less, the contamination of the photosensitive material is remarkably reduced, and the adhesion of foreign substances to the roller is also improved. It can be seen that the effect is further enhanced when the salt concentration is set to 0.12 mol or more.

[Brief description of the drawings]

1 and 2 show a part of a cross section of an automatic developing apparatus used in the present invention. Reference numeral 1 in the figure: treatment liquid level 2: liquid seal / liquid squeeze 3 ... liquid dripping receiving member 4 ... top lid 5 ... transport roller 6 ... transport roller 7 ... counter roller 8 ... photosensitive Material 9 Processing liquid tank 10 Transfer position 11 Floating pig 12 Liquid squeeze and liquid squeeze 13 Liquid dripping receiving member 14 Liquid level 15 Bath with fixing ability 16 … Stabilizing bath (Fig. 1), Rinse bath (Fig. 2) 17… Jet pump 18… Circulation pump 19… Circulation pipe The arrow derived from the jet pipe 17 is discharged from the nozzle provided in the jet pipe. 3 shows a jet of a fixing solution. The fixer 16 is sucked by a pump 18 and passes through a circulation pipe 19 to a jet pipe 17. At position 8, the emulsion surface of the light-sensitive material is on the lower side,
In the fixing solution 16, the emulsion surface is in a shape facing the jet pipe.

──────────────────────────────────────────────────続 き Continuing on the front page Judge, Supreme Referee Susumu Sakai, Judge Mizugaki Osamu, Judge Eichi Rokka (56) References JP-A-63-71846 (JP, A) JP-A-56-146135 (JP, A) JP-A-1-276134 (JP, A) JP-A-62-183460 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) G03C 11/00 G03C 7/00

Claims (1)

(57) [Claims] 1. A water washing bath to not more than exposed silver halide color photographic 1000ml per photosensitive material 1 m ² a replenishment rate then treated with a bath having a fixing ability containing a photosensitive material thiosulfate all the stabilizing bath In the processing method, the crossover time between the bath having a fixing ability and the washing bath or the stabilizing bath is set to 10 seconds or less, and the photosensitive material is introduced within 5 seconds after the photosensitive material is introduced into the washing bath or the stabilizing bath. A method for processing a silver halide color photographic light-sensitive material, wherein the processing is performed by colliding a jet of a washing liquid or a stabilizing liquid with an emulsion surface.