JPS6334459B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a method for processing silver halide color photographic light-sensitive materials, and more specifically, it relates to a method for processing silver halide color photographic light-sensitive materials, and more specifically, a method for processing silver halide color photographic materials, which significantly improves rapid processing development and processing stability, and improves the stability of dye images over time. The present invention relates to a method for processing silver halide color photographic materials. [Prior Art] Generally, a silver halide color photographic light-sensitive material has three types of photographic silver halide emulsion layers on a support that are selectively spectrally sensitized to have sensitivity to blue light, green light, and red light. has been painted. For example, in silver halide photographic materials for color negatives, generally a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer are coated in this order from the exposed side. A bleachable yellow filter layer is provided between the blue-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer in order to absorb the blue light that passes through the blue-sensitive silver halide emulsion layer. It is provided. Further, each emulsion layer is provided with other intermediate layers for various special purposes, and a protective layer as the outermost layer. Furthermore, for example, in a silver halide photographic light-sensitive material for color photographic paper, a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer are generally arranged in this order from the exposed side. Similar to silver halide photographic materials for color negatives, intermediate layers such as an ultraviolet absorbing layer and protective layers are provided for special purposes. It is also known that each of these silver halide emulsion layers is provided in a different arrangement from the above, and furthermore, each silver halide emulsion layer is sensitive to substantially the same wavelength range for each color light. It is also known to use a photosensitive silver halide emulsion layer consisting of two layers. In these silver halide color photographic materials, exposed silver halide grains are developed using, for example, an aromatic primary amine color developing agent as a color developing agent, and the resulting color developing agent is oxidized. A dye image is formed by reaction of the product with the dye-forming coupler. In this method, phenolic or naphthol cyan couplers, 5-pyrazolones, pyrazolinobenzimidazoles, pyrazolotriazoles, indazolone or cyano couplers are typically used to form cyan, magenta and yellow dye images, respectively. An acetyl-based magenta coupler and an acylacetamide-based or benzoylmethane-based yellow coupler are used. These dye-forming couplers are contained in the light-sensitive silver halide emulsion layer or in the developer. In recent years, there has been a demand in the industry for silver halide color photographic materials that can be processed quickly, have high image quality, have excellent processing stability, and are inexpensive. There is a need for silver halide color photographic materials that can be processed in various ways. In other words, silver halide color photographic light-sensitive materials are processed on a running basis in automatic processing machines installed in each laboratory, but as part of our efforts to improve our services to users, we are now processing silver halide color photographic materials on the same day that they are received. In recent years, there has been a demand for the product to be returned to the user within a few hours of receipt, and the development of silver halide color photographic materials that can be processed even more quickly is becoming increasingly urgent. ing. Additionally, in running processing, there is a problem in that photographic properties vary greatly between laboratories or even within the same laboratory due to changes in the composition of the processing solution and fluctuations in conditions, making it impossible to obtain stable photographic performance. . Such changes in the composition of the processing solution and fluctuations in conditions are thought to be due to elution and accumulation of photographically active substances from the light-sensitive material during development processing (running), and other causes. Therefore, in order to respond to variations in processing conditions, it is necessary to highly control the development time, the temperature and pH of the developer, and the halogen concentration, especially the bromine ion concentration, in the developer. However, compared to the development time or the temperature and pH of the developer, the bromide ion concentration in the developer is difficult to quantify and difficult to control due to its poor measurability. Therefore, it is particularly necessary to develop a silver halide color photographic light-sensitive material whose photographic performance is less dependent on bromine concentration and has highly excellent processing stability. Processing stability is a problem even with current processing times, but processing stability becomes more of a problem in rapid processing. Furthermore, it is a matter of course that such processing-stabilized silver halide color photographic materials are required to be economically provided at low cost. Therefore, if we look at the conventional techniques for silver halide color photographic materials that can be processed rapidly, for example, there is a technique for making silver halide fine grains as described in JP-A-51-77223, JP-A-58-184142 and A silver halide color photograph of 1-aryl-3-pyrazolidone having a specific structure as described in Japanese Patent Publication No. 56-18939 and a silver halide color photograph as described in Japanese Patent Publication No. 56-18939 Addition technology to photosensitive materials, as well as JP-A-57-144547 and JP-A No. 58-
50534, No. 58-50535, and No. 58-50536, in which 1-arylpyrazolidones are added to silver halide color photographic light-sensitive materials. A technique of using a color development accelerator when developing a silver oxide color photographic light-sensitive material using an aromatic primary amine color developing agent is also known. For example, such color development accelerators include those described in the U.S. Pat.
No. 2950970, No. 2515147, No. 2496903, No.
No. 4038075, No. 4119462, British Patent No. 1430998,
1455413, JP 53-15831, JP 55-62450
No. 55-62451, No. 55-62452, No. 55-
There are compounds described in Japanese Patent Publication No. 62453, Japanese Patent Publication No. 51-12422, Japanese Patent Publication No. 55-62453, Japanese Patent Publication No. 51-12422, Japanese Patent Publication No. 55-49728, etc. However, when these conventional techniques are used, although the processing time is shortened, the processing stability is poor, and there are also problems with fogging and storage stability in same-day performance. When the low silver bromide emulsion described above is used, fewer bromide ions are eluted into the processing solution from the silver halide color photographic light-sensitive material containing the low silver bromide emulsion, and the concentration of bromide ions in the processing solution is set low. However, when a silver halide color photographic material containing a low silver bromide emulsion is processed using a processing solution with a low bromine ion concentration, processing stability is poor. Processing stability here refers to the degree of variation in sensitometry with respect to variations in processing solution composition, pH, temperature, bromide ion concentration, etc., and to contamination of other compounds other than the processing solution composition. Further, even when the above-mentioned fine-grained silver halide was used, there was a drawback that the processing stability was poor, and the sensitivity deteriorated as the grains became finer. These problems occur when the average grain size of silver halide in the blue-sensitive silver halide emulsion layer is 0.20 to 0.55 μm.
The silver bromide content of silver halide in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer was set to 5.
By increasing the content to ~65 mol%, both rapid processability and process stability can be achieved at the same time.
The results of studies conducted by the present inventors have revealed that such light-sensitive materials pose a new problem of processing stains. A well-known method for preventing processing stains is the addition of oxidant scavengers such as hydroquinone derivatives, which undergo a coupling reaction with the oxidized color developing agent and competitively inhibit dye formation. It is preferably used as a method. Therefore, by adding an oxidant scavenger, it is possible to reduce the processing stain of the light-sensitive material as described above. However, according to the study results of the present inventors, when a sufficient amount of oxidant scavenger is added to effectively reduce processing stains, yellow stains are likely to occur in processed images over time. It turned out to be. Furthermore, it has been found that this yellow stain is likely to occur when processing is performed in a processing step consisting of color development, bleach-fixing and water washing, or when the amount of processing per day is extremely small. [Object of the Invention] Therefore, it is an object of the present invention to provide a processing method for processing silver halide color photographic materials that is rapid in processing and has excellent processing stability, and which does not produce any yellow stain even after long-term storage. Accordingly, another object of the present invention is to provide a method for processing photosensitive materials that does not use any washing water and has low energy costs and low pollution loads. [Structure of the Invention] As a result of intensive research, the present inventors have discovered a silver halide emulsion layer having a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer on a support. In color photographic materials,
The average grain size of the silver halide grains in the blue-sensitive silver halide emulsion layer is 0.20 to 0.55 μm, and the silver bromide of the silver halide in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer is 0.20 to 0.55 μm. Content is 5-65 mol%
After a silver halide color photographic light-sensitive material containing an oxidant scavenger is subjected to color development processing, it is processed with a processing solution having fixing ability, and then processed in a stabilization processing step without substantially including a water washing step. It has been found that the object of the present invention can be achieved by doing the following. The present invention will be explained in detail below. The present invention prevents yellow staining over time in processed dye images caused by the use of an oxidant scavenger in an amount sufficient to reduce the processing stain by a stabilizing treatment. . Compounds such as hydroquinone and its derivatives are commonly used to prevent color staining and improve image preservation, but these oxidant scavengers do not react when exposed to strong ultraviolet rays or visible light, or under high temperature and high humidity. It has become clear through studies by the present inventors that yellow staining is likely to occur. Particularly, as in the case of the present invention, when a large amount of the compound is contained in a light-sensitive material in order to prevent processing stains in a silver halide emulsion that is likely to produce processing stains, the above-mentioned problems occur significantly. Further, according to the study results of the present inventors, it has been found that the above-mentioned problem is likely to occur in the processing steps in which a photosensitive material containing the above-mentioned oxidant scavenger is subjected to color development and bleach-fixing processing, and then washed with water. Conventionally, in order to stabilize dye images over time, it was thought that it was necessary to remove excess salt, such as bleach-fix solution, fix solution components, and their decomposed products, by thorough washing with water. However, according to studies conducted by the present inventors, it was discovered that yellow staining is more likely to occur over time if sufficient water washing is performed, which led to the completion of the present invention. The present invention will be explained in more detail below. The silver halide contained in the blue-sensitive silver halide emulsion layer of the present invention has an average grain size (average grain size).
It is 0.20 to 0.55 μm, preferably 0.30 to 0.50 μm.
When the average particle size exceeds 0.55 μm, processing stability is poor;
In particular, the deterioration of processing stability is remarkable when the amount of potassium bromide changes. On the other hand, if the average grain size is less than 0.20 μm, the sensitivity of the blue-sensitive silver halide emulsion layer will be insufficient, resulting in magenta color turbidity. The average grain size of the silver halide contained in the blue-sensitive silver halide emulsion layer of the present invention can be measured by various methods commonly used in the technical field for the above purpose. A typical method is Loveland's "particle size analysis method"
ASTM Symposium on Light Microscopy, 1955, pp. 94-122, or Chapter 2 of ``The Theory of Photographic Processes'' by Mies and James, 3rd edition, Macmillan Publishing Co., Ltd. (1966). There is. The particle size can be measured using the particle's projected area or diameter approximation. If the particles are of substantially uniform shape,
Particle size distribution can be expressed fairly accurately as diameter or projected area. The silver halide used in the light-sensitive material of the present invention may be a polydisperse emulsion in which the average grain size is distributed over a wide range, but a monodisperse emulsion is preferred. The above-mentioned monodisperse emulsion is one in which most of the silver halide grains appear to have the same shape and uniform grain size when the emulsion is observed using an electron microscope, and the coefficient of variation in grain size distribution is 15% or less. It refers to something. The grain size here has the same meaning as the grain size mentioned above regarding the average grain size, and in the case of cubic silver halide grains, the length of one side, or in the case of grains with a shape other than a cube, the same The length of one side when converted to a cube with volume, the individual grain size in this sense is ri, and the number is
When ni, then is defined by the following formula. ＝〓ni ri／〓ni The silver halide contained in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer of the present invention is silver chlorobromide, silver chloroiodobromide, or silver chlorobromide, or silver chloroiobromide. A mixture may be used, with a silver bromide content of 5 to 65 mol%. In the present invention, one or both of the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer may be composed of two or more layers. In the present invention, the silver bromide content refers to the total odor of each layer in the total silver halide contained in each of the all-green light-sensitive silver halide emulsion layer and the all-red light-sensitive silver halide emulsion layer. Refers to the content of silver oxide. When the silver bromide content exceeds 65 mol %, processing stability deteriorates, magenta color becomes cloudy, and image quality deteriorates. On the other hand, when the silver bromide content is less than 5 mol %, processing stability deteriorates significantly. When the silver halide contained in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer of the present invention is silver chloroiodobromide, the silver iodide content does not exceed 2 mol%. It is preferable. The silver bromide content of the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer is preferably 20 to 60 mol%, more preferably 30 to 55 mol%. The silver halide contained in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer of the present invention is also monodisperse like the silver halide contained in the blue-sensitive silver halide emulsion layer. is preferred. The composition of the silver halide contained in the blue-sensitive silver halide emulsion layer is not particularly limited, and may be silver bromide, silver chlorobromide, silver chloroiodobromide, or a mixture thereof. However, silver chlorobromide is preferred, with a silver bromide content of 30 to 95 mol%. Furthermore, the blue-sensitive silver halide emulsion layer in the present invention may consist of two or more layers. The average grain size of the silver halide contained in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer is not particularly limited, but is 0.1 to 2 μm, more preferably 0.2 to 1 μm, particularly preferably 0.25 to 1 μm. It is 0.8 μm. In the silver halide color photographic light-sensitive material of the present invention, the amount of silver (silver coating amount) in the silver halide emulsion layer is preferably 0.3 to 1 g/m ² in the entire photosensitive silver halide emulsion layer. That is, in order to obtain excellent image quality, the silver amount is preferably 1 g/m ² or less, while in order to obtain high maximum density and high sensitivity, the silver amount is 0.3 g/m ² or more. It is preferable that In the present invention, the silver amount is particularly preferably 0.4
~0.8g/ ^m2 . Silver halide compositions preferably used in the blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers of the present invention include silver chlorobromide and silver chloroiodobromide. Furthermore, it may be a combination mixture such as a mixture of silver chloride and silver bromide. That is, when the silver halide emulsion according to the present invention is used in color photographic paper, particularly fast developability is required, so it is preferable that the halogen composition of the silver halide contains chlorine atoms, and at least 1% of the chlorine atoms. Silver chlorobromide or silver chloroiodobromide containing silver chloride is particularly preferred. The monodisperse silver halide grains preferably used in the present invention may be obtained by any conventionally known preparation method such as an acidic method, a neutral method, or an ammonia method. Alternatively, for example, seed particles may be produced using an acidic method, and then grown using an ammonia method, which has a high growth rate, to grow to a predetermined size. PH and pAg in the reaction vessel when growing silver halide grains
It is preferable to simultaneously implant and mix silver ions and halide ions in amounts commensurate with the growth rate of silver halide grains, for example, as described in JP-A No. 54-48521. The silver halide emulsion used in the blue-, green-, or red-sensitive silver halide emulsion layer of the light-sensitive material of the present invention is as follows:
activated gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea, cystine; selenium sensitizers; reduction sensitizers such as stannous salts, thiourea dioxide, polyamines, etc.; noble metal sensitizers such as Gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurothio-3-methylbenzothiazolium chloride, etc., or e.g. ruthenium, palladium, platinum,
Sensitizers of water-soluble salts such as rhodium and iridium, specifically ammonium chloroparadate, potassium chloroplatinate, and sodium chloroparadate (some of these can be used as sensitizers or (acts as a fog suppressant, etc.) alone or in appropriate combinations (for example, a combination of a gold sensitizer and a sulfur sensitizer, a combination of a gold sensitizer and a selenium sensitizer, etc.). It may be felt. The silver halide emulsion is chemically ripened by adding a sulfur-containing compound, and before, during, or after this chemical ripening, a nitrogen-containing heterocyclic compound having at least one hydroxytetrazaindene and mercapto group is added. At least one kind may be contained. To each silver halide emulsion, an appropriate sensitizing dye is added in an amount of 5 x 10 ^-8 to 3 x 10 ^-3 mol per mol of silver halide in order to impart photosensitivity in a desired wavelength range. It may also be optically sensitized. Various sensitizing dyes can be used, and each sensitizing dye can be used alone or in combination of two or more. Examples of sensitizing dyes that can be advantageously used in the present invention include the following. That is, as sensitizing dyes used in the blue-sensitive silver halide emulsion layer, for example, West German Patent No. 929080,
U.S. Patent No. 2231658, U.S. Patent No. 2493748, U.S. Patent No. 2503776,
Same No. 2519001, No. 2912329, No. 3656959, Same No.
No. 3672897, No. 3694217, No. 4025349, No.
No. 4046572, British Patent No. 1242588, Special Publication No. 1977-
Examples include those described in No. 14030 and No. 52-24844. In addition, examples of sensitizing dyes used in green-sensitive silver halide emulsions include U.S. Pat.
Representative examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 2945763, British Patent No. 505979, and the like. Further, as sensitizing dyes used in red-sensitive silver halide emulsions, for example, U.S. Pat.
Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 2454629, No. 2776280, and the like. Furthermore, US Patent No. 2213995, US Patent No. 2493748
Cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in No. 2,519,001, West German Patent No. 929,080, etc. can be advantageously used in green-sensitive silver halide emulsions or red-sensitive silver halide emulsions. These sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used, especially for the purpose of supersensitization.
Typical examples are U.S. Patent No. 2688545, U.S. Patent No. 2977229,
3397060, 3522052, 3527641, 3527641, 3522052, 3527641,
No. 3617293, No. 3628964, No. 3666480, No.
No. 3672898, No. 3679428, No. 3703377, No. 3672898, No. 3679428, No. 3703377, No.
No. 3769301, No. 3814609, No. 3837862, No. 3837862, No. 3814609, No. 3837862, No.
4026707, British Patent No. 1344281, British Patent No. 1507803,
Special Publication No. 43-4936, No. 53-12375, Japanese Patent Publication No. 52-
No. 110618 and No. 52-109925. Next, the "oxidant scavenger" (hereinafter referred to as AS agent) used in the present invention competitively inhibits the formation of a dye due to the reaction between the coupler and the oxidized form of the developing agent. The reaction product with the oxidant has a color that does not practically deteriorate the color balance of color photographs, or it is colorless. These AS agents are broadly classified into the following two types depending on the type of reaction with the oxidized developing agent. That is, the first type is one that returns the oxidized developing agent to the original developing agent and is itself converted into the oxidized form by an oxidation-reduction reaction, and is collectively referred to as a reducing agent. The second type is a so-called colorless coupler that forms a new developer adduct by coupling with an oxidized developer. In order to fully exhibit the effects of the present invention, it is preferable to use a competitive compound that reacts with the oxidized developing agent as quickly as possible. In this sense, the first reducing agent is more preferable among the two types mentioned above. When these reducing agents are added to photographic materials, especially during storage over time, they can cause deterioration of photographic properties due to the decomposition of the compound itself due to air oxidation, or the generation of fog due to the reducing agent acting directly on the silver halide emulsion. Side effects such as these may become a problem. The following general formulas (1) to (10) have been found as having fewer such side effects and having a high scavenging ability for oxidized developing agent. Among these, the general formulas (1) to (4) are preferred, and those represented by (1) and (3) are more preferred, and among them, (3) is the most preferred. General formula (1)

【formula】 General formula (2)

【formula】 General formula (3)

[Exemplary compounds]

(1) 2-Methyl-4-isothiazolin-3-one (2) 5-chloro-2-methyl-4-isothiazolin-3-one (3) 2-methyl-5-phenyl-4-isothiazolin-3-one (4) 4-bromo-5-chloro-2-methyl-4-
Isothiazolin-3-one (5) 2-Hydroxymethyl-4-isothiazolin-3-one (6) 2-(2-ethoxyethyl)-4-isothiazolin-3-one (7) 2-(N-methyl-carbamoyl )-4-isothiazolin-3-one (8) 5-bromomethyl-2-(N-dichlorophenyl-carbamoyl)-4-isothiazoline-
3-one(9) 5-chloro-2-(2-phenylethyl)-4
-isothiazolin-3-one (10) 4-methyl-2-(3,4-dichlorophenyl)-4-isothiazolin-3-one (11) 1,2-benzisothiazolin-3-one (12) 2- (2-bromoethyl)-1,2-benzisothiazolin-3-one (13) 2-methyl-1,2-benzisothiazolin-3-one (14) 2-ethyl-5-nitro-1,2-benzisothiazoline -3-one (15) 2-benzyl-1,2-benzylisothiazolin-3-one (16) 5-chloro-1,2-benzisothiazolin-3-one These exemplary compounds are described in U.S. Pat.
No. 2767172, No. 2767173, No. 2767174, No. 2767172, No. 2767173, No. 2767174, No.
2870015, British Patent No. 848130, French Patent No. 1555416, etc., the synthesis method and examples of application to other fields are described. There are also commercially available products such as Topside 300, Topside 600 (manufactured by Permakem Asia),
It can be obtained under the trade names of Fine Inside J-700 (manufactured by Tokyo Fine Chemical Co., Ltd.) and Proxel GXL (manufactured by ICI Corporation). The amount of the above compound used is 0.01 to 1 per stabilizing solution.
Can be used in the range of 50g, preferably
Adding 0.05-20g gives good results. In addition, examples of the chelating agent include polyphosphates, aminopolycarboxylate salts, oxycarboxylate salts, polyhydroxy compounds, organic phosphates, etc. Among them, aminopolycarboxylate salts and organic phosphates are used in the present invention. Good results can be obtained when used. Furthermore, examples of metal salts include Ba, Ca, Ce, Co,
In, La, Mn, Ni, Pb, Sn, Zn, Ti, Zr, Mg,
Examples include metal salts such as Al and Sr, and these include halides, hydroxides, sulfates, carbonates, phosphates,
It can be supplied as an inorganic salt such as acetate or as a water-soluble chelating agent. The amount used is 1×10 ^-4 per stabilizing liquid.
In the range of 1×10 ⁻¹ mol, preferably 4×10 ⁻⁴
〜2×10 ⁻² mol, more preferably 8×10 ⁻⁴ 〜1×
It is in the range of 10 ^-2 mol. In addition to the above-mentioned compounds, additions to the stabilizing bath of the present invention include fluorescent brighteners, organic sulfur compounds, onium salts, hardeners, quaternary salts, polyethylene oxide derivatives, siloxane derivatives, and other water droplet prevention agents. , boric acid, citric acid, phosphoric acid, acetic acid, or PH adjusters such as sodium hydroxide, sodium acetate, potassium citrate, etc., organic solvents such as methanol, ethanol, ethanol, dimethyl sulfoxide, etc., dispersion of ethylene glycol, polyethylene glycol, etc. and other color tone adjusting agents to improve processing effects,
Addition of various additives for expansion is optional. When the method for supplying the stabilizing liquid in the stabilization treatment step according to the present invention is a multi-tank countercurrent system, it is preferable to supply the stabilizing liquid to the rear bath and overflow from the front bath. The above compounds can be added to the stabilizing tank as a concentrated liquid, or the above compounds and other additives are added to the stabilizing liquid supplied to the stabilizing tank, and then added to the stabilizing liquid. There are various methods such as making it into a liquid, or adding it to the pre-bath of the stabilization treatment process and making it present in the stabilization tank by including it in the photosensitive material to be processed.
It may be added by any method. In the present invention, the pH value of the treatment liquid in the stabilizing bath is preferably in the range of PH4 to 8. this is
If the pH is lower than 4, silver sulfide is likely to be generated, causing problems such as filter clogging, and if the pH is higher than 8, limescale and microorganisms are likely to be generated. used. Further, the pH can be adjusted using the above-mentioned pH adjusting agent. The processing temperature during stabilization treatment is 15°C to 60°C.
℃, preferably in the range of 20℃ to 45℃. In addition, the processing time is preferably as short as possible from the viewpoint of rapid processing, but usually 20 seconds to 10 minutes, most preferably 1 minute to 5 minutes.
It is preferable that the treatment time is shorter in the earlier stage tank and longer in the later stage tank. There is no need for any water washing treatment before or after the stabilization treatment according to the present invention, but the surface cleaning can be done by rinsing with a small amount of water within an extremely short period of time, or by using a sponge, etc. to stabilize the image and adjust the surface properties of the photosensitive material. A treatment tank can be provided for this purpose. Examples of the agent for stabilizing the image and adjusting the surface properties of the photosensitive material include activators such as formalin and its derivatives, siloxane derivatives, polyethylene oxide compounds, and quaternary salts. In the present invention, a processing solution having fixing ability is a processing solution containing a soluble complexing agent that is solubilized as a silver halide complex salt, and includes not only a general fixing solution but also a bleach-fixing solution and a one-bath developing solution. Also included are fixers, one-bath development, bleach-fix solutions. It is preferable that the processing solution having this fixing ability is a bleach-fix solution, and in this case, the effects of the present invention are even greater. Soluble complexing agents include, for example, thiosulfates such as potassium thiosulfate, sodium thiosulfate, ammonium thiosulfate, thiocyanates such as potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate, or thioureas, thioethers, Typical examples include bromide and iodide, but in the present invention, the inclusion of thiosulfate in the processing solution having fixing ability stabilizes dye images over time, improves chemical stability, and improves chemical stability. Desirable for its ability to form soluble complexes with silver halides. The aromatic primary amine color developing agent used in the color developer used in the color development process of the present invention includes known ones that are widely used in various color photographic processes. These developers include aminophenol and p-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. These compounds are also generally used at a concentration of about 0.1 g to about 30 g per color developer, preferably from about 1 g to about 1.5 g per color developer. Examples of aminophenol-based developers include o
-aminophenol, p-aminophenol, 5
-amino-2-oxytoluene, 2-amino-3
-oxytoluene, 2-oxy-3-amino-
Includes 1,4-dimethylbenzene and the like. Particularly useful primary aromatic amino color developers are N,N'-dialkyl-p-phenylenediamine compounds, in which the alkyl group and phenyl group may be substituted with any substituent. Among them, examples of particularly useful compounds include N,N'-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, and N,N'-dimethyl-p-phenylenediamine hydrochloride. , 2-amino-5-(N-ethyl-N-dodecylamino)-
Toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl-N,
N'-diethylaniline, 4-amino-N-(2-
(methoxyethyl)-N-ethyl-3-methylaniline-p-toluenesulfonate and the like. In addition to the above-mentioned primary aromatic amine color developer, the color developer used in the process of the present invention contains various components normally added to color developers, such as sodium hydroxide, sodium carbonate,
Alkali agents such as potassium carbonate, alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners, thickening agents, and the like can also be optionally contained. The pH value of this color developer is usually 7 or more, most commonly about 10 to about 13. In the present invention, after color development processing, processing is performed with a processing liquid having a fixing ability, but if the processing liquid having a fixing ability is a fixing liquid, a bleaching treatment is performed before that. A metal complex salt of an organic acid is used as a bleaching agent in the bleach solution or bleach-fix solution used in the bleaching process, and the metal complex salt oxidizes metallic silver produced during development and converts it into silver halide. At the same time, it has the effect of coloring the uncolored parts of the coloring agent, and its structure is that metal ions such as iron, cobalt, copper, etc. are coordinated with aminopolycarboxylic acid or organic acids such as oxalic acid and citric acid. . The most preferred organic acids used to form such metal complexes of organic acids include polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Specific representative examples of these include the following. [1] Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N-(β-oxyethyl)-N,N',N'-triacetic acid [4] Propylenediaminetetraacetic acid [5] Nitrilotriacetic acid [6] Cyclohexanediaminetetraacetic acid [7] Iminodiacetic acid [8] Dihydroxyethylglycine citric acid (or tartaric acid) [9] Ethyl etherdiaminetetraacetic acid [10] Glycol etherdiaminetetraacetic acid [11] Ethylenediaminetetrapropionic acid [12] Phenylene diamine Tetraacetic acid [13] Ethylenediaminetetraacetic acid disodium salt [14] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [15] Ethylenediaminetetraacetic acid tetrasodium salt [16] Diethylenetriaminepentaacetic acid pentasodium salt [17] Ethylenediamine-N-(β -oxyethyl)-N,N',N'-triacetic acid sodium salt [18] Propylenediaminetetraacetic acid sodium salt [19] Nitrilotriacetic acid sodium salt [20] Cyclohexanediaminetetraacetic acid sodium salt The bleaching agent used is In addition to containing a metal complex salt of an organic acid such as a bleaching agent, various additives may be included. As additives, in particular alkali halides or ammonium halides,
Rehalogenating agents such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide,
It is desirable to include metal salts and chelating agents. In addition, PH buffering agents such as borates, oxalates, acetates, carbonates, and phosphates, alkylamines, polyethylene oxides, and other substances known to be commonly added to bleaching solutions may be added as appropriate. . Furthermore, the fixing solution and bleach-fixing agent include sulfites such as ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, and sodium metabisulfite, boric acid, and borax. , sodium hydroxide, potassium hydroxide,
It can contain one or more PH buffers consisting of various salts such as sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide. When carrying out the process of the present invention while replenishing the bleach-fix solution (bath) with a bleach-fix replenisher, the bleach-fix solution (bath) may contain thiosulfate, thiocyanate, sulfite, etc. These salts may be added to the bleach-fixing replenisher to replenish the processing bath. In the present invention, in order to increase the activity of the bleach-fix solution, air or oxygen may be blown into the bleach-fix bath and the bleach-fix replenisher storage tank, if desired, or an appropriate oxidizing agent,
For example, hydrogen peroxide, bromate, persulfate, etc. may be added as appropriate. In the process of the present invention, silver may be recovered by a known method from processing solutions containing soluble silver complex salts, such as fixing solutions, bleach-fixing solutions, as well as stabilizing solutions. For example, electrolysis method (described in French Patent No. 2299667),
Precipitation method (described in JP-A No. 52-73037, German Patent No. 2331220), ion exchange method (described in JP-A-52-73037, German Patent No. 2331220)
51-17114, German Patent No. 2,548,237) and metal substitution method (as described in British Patent No. 1,353,805), etc. can be effectively used. [Examples] The details of the present invention will be explained below with reference to Examples, but the embodiments of the present invention are not limited thereby. Example 1 On a paper support laminated with polyethylene,
The following layers were sequentially coated from the support side to prepare silver halide color photographic material samples Nos. 1 to 12. Layer 1... 1.2 g/m ² of gelatin, 0.40 g/m ² (in terms of silver, the same applies hereinafter) of blue-sensitive silver chlorobromide emulsion (silver bromide content and average particle size are shown in Table 1), and
Dissolved in 0.50g/ ^m2 dioctyl phthalate
Layer containing 0.80 g/m ² of yellow coupler (Y-1). Layer 2...Intermediate layer consisting of 0.7g/ ^m2 gelatin. Layer 3...1.25 g/m ² gelatin, 0.25 g/m ² green-sensitive silver chlorobromide emulsion (silver bromide content and average grain size are shown in Table 1), and 0.30 g/m ² dioctyl Layer containing 0.62 g/m ² of magenta coupler (M-1) dissolved in phthalate. Layer 4...1.2 g/ ^m2 of gelatin and AS shown in Table 2
an intermediate layer consisting of an agent; Layer 5...1.4 g/m ² gelatin, 0.25 g/m ² red-sensitive silver chlorobromide emulsion (silver bromide content and average grain size are shown in Table 1), and 0.20 g/m ² dioctyl Layer containing 0.45 g/m ² of cyan coupler (C-1) dissolved in phthalate. Layer 6: A layer containing 0.30 g/ ^{m 2 of} Tinuvin 328 (manufactured by Ciba Geigy, UV absorber) dissolved in 1.0 g/m ² of gelatin and 0.20 g/m 2 of dioctyl phthalate. Layer 7: A layer containing 0.5 g/m ² of gelatin. In addition, as a hardening agent, 2,4-dichloro-6-
layer 2 of sodium hydroxy-S-triazine;
0.017 per gram of gelatin in 4 and 7, respectively.
g. This sample was exposed to light using a color printer and processed according to the following steps. Processing steps (1) Color development 38°C 3 minutes 30 seconds (2) Bleach fixing 38°C 1 minute 30 seconds (3) Washing or stabilization 25-30°C 3 minutes (4) Drying 75-80°C approximately 2 minutes Processing solution composition [color developer] Benzyl alcohol 15ml Ethylene glycol 15ml Potassium sulfite 2.0g Potassium bromide 0.7g Sodium chloride 0.2g Potassium carbonate 30.0g Hydroxylamine sulfate 3.0g Polyphosphoric acid (TPPS) 2.5g 3-methyl-4- Amino-N-ethyl-N-(β
-Methanesulfonamidoethyl)-aniline sulfate 5.5g Fluorescent brightener (4,4'-diaminostilbenzsulfonic acid derivative 1.0g Potassium hydroxide 2.0g Water was added to make 1, and potassium hydroxide was added. The pH was adjusted to 10.20. [Bleach-fix solution] Ferric ammonium ethylenediaminetetraacetic acid dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100ml Ammonium sulfite (40% solution) 27.5ml Add water to make 1. , with the addition of potassium carbonate
Adjusted to PH7.10. [Stabilizing liquid] 1-hydroxyethylidene-1,1'-diphosphonic acid 1.0g Magnesium chloride 0.5g Polyvinylpyrrolidone 0.1g Ammonium hydroxide (28% aqueous solution) 3g Add water to make 1, and add sulfuric acid and potassium hydroxide.
Adjusted to PH7.1. The green and yellow density of the unexposed area of the developed sample processed using the above processing method was measured, and then
It was stored for 3 weeks at %RH (relative humidity) and the yellow density was measured in transmission. In addition, the green density of the unexposed area minus the green density of the paper support was taken as the representative property of the treated stain, and the density of the yellow density after storage minus the yellow density before storage was taken as the representative property of the yellow stain. . In addition, as an evaluation of processing stability, potassium bromide in the above color developer was added to 0.5 g, 1.5 g, and 2.5 g.
Development processing was performed as g, and the maximum gamma difference (Δγ) at each potassium bromide concentration was taken as a representative characteristic of processing stability. The measuring device is Sakura optical densitometer.
PDA-65 (manufactured by Konishiroku Photo Industry Co., Ltd.) was used. The results are shown in Table 2.

【table】

[Table] As is clear from Table 2, the photosensitive material of the present invention is
Although it has excellent processing stability as typified by γ fluctuation, processing stains are likely to occur if it is not combined with an AS agent and stabilizing treatment. Furthermore, the photosensitive material of the present invention
When AS agents are combined, processing stability and processing stains are excellent, but if stabilization processing is not combined, yellow stains appear when images are stored after processing. Only the sample of the present invention can obtain good results in processing stability, processing stain and yellow stain. Example 2 In place of the exemplified compound AS-78 of Example 1, AS-
5, AS-98, AS-112, AS-193 and AS-197
was also evaluated in the same manner as in Example (1),
Almost the same results as in Example (1) were obtained. Example 3 In order to examine the influence of the AS agent on photographic performance, evaluation was conducted in the same manner as in Example (1), with the amount of the AS agent varied as shown in Table 3. The results are shown in Table 3.

【table】

〔Effect of the invention〕

According to the present invention, the average grain size of the silver halide grains in the blue-sensitive silver halide emulsion layer is 0.20 to 0.55 μm, which is a silver halide color photographic light-sensitive material having excellent rapid processing and processing stability. , a silver halide color in which the silver bromide content of silver halide in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer is 5 to 65 mol%, and contains an acid scavenger. The yellow stain that occurs when a dye image obtained by processing a photographic light-sensitive material is stored for a long period of time is improved, and there is no need to use any washing water during processing, thereby improving energy costs and pollution loads.

Claims (1)

[Scope of Claims] 1. A silver halide color photographic light-sensitive material having a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support. The average grain size of the silver halide grains in the silver halide emulsion layer is 0.20 to 0.55 μm, and the silver bromide content of the silver halide in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer is is 5 to 65 mol% and contains an oxidant scavenger. After color development processing is performed on the silver halide color photographic light-sensitive material, the material is processed with a processing solution having fixing ability, and subsequently, substantially no water washing step is required. 1. A method for processing a silver halide color photographic light-sensitive material, which comprises processing in a stabilization treatment step. 2 At least 1×10 ^-5 in the stabilization process
2. A method for processing a silver halide color photographic material according to claim 1, wherein the stabilization treatment is carried out in the presence of a soluble iron salt at a molar concentration.