JPS6318727B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method of forming a color photographic image by color development processing of a silver halide color photographic light-sensitive material, and more specifically, the present invention relates to a method of forming a color photographic image by applying a viscous developer to the surface of a silver halide color photographic light-sensitive material and carrying out color development processing. The present invention relates to a novel color photographic image forming method that can stably obtain high quality images with little fog in a short time. A common color development method for silver halide color photographic materials (hereinafter referred to as color photographic materials) is a method using a color developing bath containing an aromatic primary amine color developing agent. Although this method is widely used in color laboratories and the like, the management of pH, halogen ion concentration, developing agent concentration, temperature, etc. in order to maintain constant color development processing performance is complicated, and improvements are desired. Furthermore, as the amount of processing increases, there is a demand for faster processing, and to date considerable speeding up has been achieved by reducing the number of processing steps and shortening the processing time of each step. Among these, in the color development process, the processing time has been shortened by improving the color developer and development accelerator and increasing the processing temperature. However, when the processing temperature is raised, color development (fogging) in unexposed areas becomes noticeable, and the color development processing solution deteriorates significantly. In this regard, advances in hardening agents that provide film properties that can withstand high-temperature processing, antifoggants that prevent the increase in fog caused by high-temperature processing, and preservatives that reduce deterioration of processing solutions have made it possible to raise processing temperatures. is gradually becoming possible. however,
As the processing temperature increases, it becomes difficult to prevent fogging caused by these chemicals and deterioration of the processing solution, and the concentration of chemicals in the color developing solution may change due to the increase in evaporation due to the increase in processing temperature. At the same time, it is becoming difficult to pursue high-temperature, rapid processing using bath processing. Furthermore, as processing speeds up, it becomes difficult to properly terminate the processing upon completion of development, and it tends to be difficult to stably obtain high-quality images. As a developing method that has been considered for rapid processing, there is a viscous developing method in which a viscous developer is applied to the surface of a color photographic light-sensitive material. This viscous development processing method does not require stirring,
It is necessary to avoid uneven development caused by poor or uneven stirring, to obtain images with good resolution due to strong edge effect, to be able to supply the necessary amount of necessary chemicals, and to manage replenishment, etc. However, high-temperature rapid processing increases fog and stains, making it difficult to put into practical use. Currently, it is limited to special uses such as film for movies, soundtracks, recording paper for oscilloscopes, and film for television, and moreover, it is currently almost limited to monochrome photosensitive materials. The following techniques are known regarding this viscous development processing method. That is, U.S. Patent No. 2196226 describes a processing method in which a developer that can be gelatinized by lowering the temperature is applied in a sol state and developed in a gel state.
No. 3347675, No. 3574618, No. 3574618, No. 3347675, No. 3574618, No.
Although it is described in the specifications of No. 3615482, No. 3623868, No. 3944427, and No. 3700451,
High temperature treatment is not possible, and the purpose is different from the treatment of the present invention. Further, the specifications of U.S. Patent No. 3265501, U.S. Patent No. 3561960, East German Patent No. 55547, East German Patent No. 98377, Japanese Patent Publication No. 53-16289, etc. describe the process of developing by applying a viscous developer. However, further improvements in photographic performance such as sensitivity and suppression of fog are desired. Further, these conventional techniques are based on the premise of development processing at a constant temperature. Accordingly, a first object of the present invention is to provide a method for forming a color photographic image using a viscous developer during photographic processing of a color photographic light-sensitive material. A second object of the present invention is to provide a method for forming color photographic images with less stain and fog. A third object of the present invention is to provide a rapid photographic processing method for color photographic materials. A fourth object of the present invention is to provide a method for processing color photographic materials with excellent processing stability. Other objects of the present invention will become apparent from the following description. An object of the present invention is to provide a method for forming a color photographic image in which a viscous developer is applied to the surface of a photosensitive layer side of an imagewise exposed color photosensitive material to develop the image. This can be achieved by performing the development while intermittently lowering the temperature of the applied viscous developer. In this case, the viscosity of the viscous developer is such that it can maintain the amount of processing agent and water necessary for development on the surface of the photosensitive layer of the exposed color photographic light-sensitive material during the development process. can be easily determined by one skilled in the art. If the viscosity is too low, movement of the applied viscous color developing layer occurs, resulting in uneven development. Further, if the viscosity is too high, it is impossible to obtain a desired uniform coating layer of the developer. Generally this viscosity is 1000cps ~
6000cps, preferably 3000cps to 5000cps. Thickeners that can be used in such viscous developers include any high molecular weight compounds that are stable in alkalis and soluble in aqueous alkaline solutions, such as hydroxyethyl cellulose and its derivatives, carboxymethyl cellulose and its derivatives, starch or Rubbers and their derivatives, alginate esters and their derivatives such as salts, synthetic thickeners such as polyvinylpyrrolidone, polyvinyl alcohol, polymethacrylic acid sodium salt, half-amides of copolymers of methyl vinyl ether and ammonium malonate, etc. The thickener is not limited to these, and any thickener may be used as long as it is uniformly dissolved in the color developing solution described below and does not impair photographic properties. The present invention differs from known viscous development processing methods in that substantial development is carried out while lowering the temperature intermittently. In known development processes, not only the viscous development process but also other methods, care has been taken to perform the development process at as constant a temperature as possible. This is because the developability can be easily controlled by controlling the processing time under constant temperature conditions.
This is because it was difficult to change the temperature during processing and it was considered difficult to control the developability. However, it is said that if a viscous developer is applied and substantial development is carried out while the temperature of the viscous developer is continuously lowered, high-quality images with less fog can be stably obtained in a short period of time. The results were surprising. After applying the viscous developer, the actual development is carried out while continuously lowering the temperature of the viscous developer. The completion of development means the time to move on to the next processing step following development, such as washing with water, stopping processing, fixing processing, stop-fixing processing, bleach-fixing processing, etc.). means to consume while decreasing the temperature or while decreasing the temperature and at a constant temperature. however,
The effects of the present invention are achieved by developing while lowering the temperature of the applied viscous developer.
It is preferable to have a large proportion of the time for development while lowering the temperature in the total development time. If this time is short, the effect of the present invention will be reduced, so at least 1 of the time spent for development is /2 or more must be done while lowering the temperature. The method of lowering the temperature described above in the present invention does not need to be constant, and even if the temperature is lowered at a substantially constant temperature,
In addition, the rate of temperature decrease may be increased at the beginning of development, and the rate of temperature decrease may be gradually slowed down over time, regardless of the form of temperature decrease. The higher the temperature of the viscous developer, the better.
When the temperature is above 30°C, the development time is 2/3 that of bath development processing at around 30°C. Also, when development is complete,
If the temperature of the applied developer is below 30℃,
Development does not proceed excessively, and images of stable quality are always obtained. The cooling method for lowering the temperature of the viscous developer in the present invention is not particularly limited. For example, a method of cooling the color photographic material by lowering the surrounding temperature, a method of cooling the color photographic material by bringing the back side of the material into contact with a cooling plate or a cooling roll, etc. can be used. The rate of temperature drop in the present invention can be controlled by changing the amount of energy taken up and the amount of viscous developer applied. Under constant energy absorption conditions, the smaller the coating amount, the faster the temperature decrease rate. However, there is no need to change the amount of chemicals required for color development as the amount of coating changes, and the amount of thickener can be changed according to the amount of coating without damaging the viscosity, and it can be diluted or thickened with water. do it. The components of the viscous developer used in the present invention are not limited as long as they enable the processing method of the present invention. In other words, any viscous aqueous solution that is applied to a color photographic light-sensitive material to form an image can be used in the present invention. An example is a developer solution that does not contain a color developing agent for the material. Examples of the components of the viscous developer of the present invention are shown below, but the present invention is not limited to the following examples. Any aromatic primary amine color developing agent can be used as the aromatic primary amine color developing agent in the viscous (color developing) solution used in the viscous development of the present invention, but in particular p-
Phenylenediamine-based compounds, such as 4-amino-N,N-diethylaniline, 4-amino-N
-ethyl-N-(β-hydroxyethyl)aniline, 4-amino-3-methyl-N-ethyl-N-
(β-methylsulfonamidoethyl)aniline,
4-amino-3-methyl-N,N-diethylaniline, 4-amino-3-methyl-N-ethyl-N
-(β-hydroxyethyl)aniline, 4-amino-3-methyl-N-ethyl-N-(β-methoxyethyl)aniline, etc. sulfates, sulfites, hydrochlorides, p-toluenesulfonates, etc. is used. The viscous (color developing) developer in the present invention can contain various additives described below. Preservatives include various inorganic compounds typified by sodium sulfite and various organic compounds typified by hydroxyamine. As alkali agents, caustic alkali, alkali carbonate, alkali orthophosphate, dibasic phosphate, borax, alkali metaborate, alkali bicarbonate, alkali acetate, etc. are used, but these alkali agents include primary alkali phosphate, boric acid, and hydrochloric acid. It is also effective to use it together with acetic acid, citric acid, etc. as a buffer solution as described in, for example, Kagaku Binran Basic Edition (Maruzen), pages 1312-1320. Furthermore, many known compounds can be used as development inhibitors and antifoggants. Next, typical compounds of development inhibitors and antifoggants that can be effectively used in the present invention are illustrated.
It is not limited to these. [Mercapto compound] (1) 2-mercaptobenzimidazole (2) 2-mercaptobenzthiazole (3) 2-mercapto-5-nitrobenzthiazole (4) 4-methyl-2-mercaptothiazole (5) 4,5- Dimethyl-2-mercaptothiazole (6) 1-phenyl-5-mercaptotetrazole (7) 1,2-dimethyl-5-mercapto-1,
3,4-triazole(8) 2-mercapto-5-phenyl-1,3,4
-Oxadiazole [Azole compound] (9) Benztriazole (10) 5-Nitrobenzimidazole (11) 5-Methylbenztriazole (12) 4-Chlorbenztriazole (13) 5,5-Diphenylthiohydantoin [Oxonium Compounds] (14) N-isopropyl-α-picolinium bromide (15) N-ethyl-2-methylbenzthiazolium chloride [Pigments] (16) Phenosafranine (17) Pinacryptol yellow (18) 1 ,1',3,3,3',3'-hexamethyl-
5,5'-dinitroimidocarbocyanine-p-
Toluenesulfonate (19) 1,3-diaryl-2-[(3,5-dimethyl-1-phenyl-4-pyrazolyl)vinyl]-imida-[4,5-b]quinoxalium iodide [Others] (20) Benzyl adenine (21) 8-oxyquinoline (22) o-phenanthroline (23) Thio, Shugar These are all compounds that adsorb to silver halide or react with silver to form poorly soluble silver salts, and the present invention It can be used advantageously. A wide variety of compounds can be used as development accelerators, such as benzyl alcohol, hydrazine, polyethylene glycol, polyoxyethylene nonionic activators, and phenylprazolidone, p-methylaminophenol, etc. Also included are p-phenylenediamines and monochrome developing agents that exhibit superadditivity. Citrazic acid, H-acid, etc., which are known as competing couplers, can also be used as grain improvers. As the swelling inhibitor, water-soluble salts having a solubility in water of 20 g or more per 100 ml of water at the development temperature can be suitably used. Representative examples include neutral salts such as magnesium sulfate, sodium sulfate, potassium sulfate, and sodium chloride. Salts that are alkaline or acidic in aqueous solution are also effective. In addition, as metal ion sequestering agents, alkali hexametaphosphate, ethylenediaminetetraacetic acid, nitrilotriacetic acid (1-hydroxyethylidene)-
Diphosphonic acid etc. can be used. Further, as antifoaming agents, compounds such as tributyl phosphate, organosiloxane and oxyalkylene block copolymers can be used. In the present invention, before color development is performed, a pre-hardening solution containing a hardening agent such as formalin and succinic aldehyde, an antifogging agent, a swelling inhibitor, a PH buffering agent, etc. is used, and then hydroxyamine and an antifogging agent are used. The color photographic material may be processed with a neutralizing solution containing a pH buffering agent, pH buffering agent, and the like. After viscous color development, conventional photographic processing is carried out, such as a stop solution containing an organic acid, a fixing solution containing an organic acid and sodium or ammonium thiosulfate, red blood salt, potassium dichromate, dichloride, etc. Bleach solutions containing iron or ferric salts of aminopolycarboxylic acids and alkali halides as main components; bleach-fixing solutions containing ferric salts of aminopolycarboxylic acids and fixing components such as sodium thiosulfate and ammonium thiosulfate; Or chloride chloride
Treatments using various treatment solutions such as sodium citrate in combination with an iron bleaching solution, a neutralization bath made of acetic acid, and other stabilizing solutions, washing with water, and drying can be carried out. In addition, after viscous development processing, processing to scrape off the viscous developer using high-pressure water spray or physical means,
A washing treatment may be performed using water containing an ammonium salt, an alkali metal salt, a polyvalent metal ion salt, etc. as the washing water. Further, the processes before and after the viscous development process may be performed by a wet process, a smear process, a spray process, etc. other than bath development. The method of forming a color photographic image according to the present invention can be applied not only to negative color photographic materials, but also to direct positive color photographic materials and positive reversal color photographic materials. In the case of a reversal color photographic material, the viscous development of the present invention may be performed after black and white development. The color photographic materials used in the present invention include ordinary multilayer color photographic materials having a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer for forming cyan, magenta, and yellow dye images. The present invention can be effectively applied to various color photographic materials such as special-purpose color photographic materials having one or two emulsion layers, such as color X-ray photographic materials, false color photographic materials, etc. can. Further, black dye image forming methods such as meta-aminophenol type couplers for forming black dye images described in Japanese Patent Application Laid-open No. 52-42725 and couplers synthesized from hindered aldehyde and pyrarazolone described in Japanese Patent Application No. 12555-1982 are also available. However, the material composition of these color photographic materials is not intended to limit the present invention in any way. The silver halide contained in the color photographic light-sensitive material to which the method of forming a color photographic image according to the present invention can be applied includes silver chloride, silver bromide, silver iodide, and mixed silver halides (for example, silver iodobromide). , iodobromosilver chloride, etc.), and these may be produced by any of a variety of methods, such as direct mixing, simultaneous mixing, and compounding methods, and may vary in grain size, crystal habit, mixing ratio, etc. do not have. The silver halide may also include active gelatin, sulfur sensitizers such as allylthiocarbamide, thiourea, cystine, selenium sensitizers,
Noble metal sensitizers, such as gold sensitizers, specifically potassium chloraurite, potassium aurithiocyanate, potassium chloroaurate, 2-aurothiabenzothiazole methyl chloride, etc., or such as ruthenium, rhodium, palladium,
Sensitizers such as iridium salts, specifically ammonium chloroparadate, potassium chloroplatinate, and sodium chloroparadate,
It is known that these sensitizers act as sensitizers or fog suppressants depending on the amount used, and these sensitizers can be used alone or in combination as appropriate to chemically sensitize. The silver halide is then supported in the form of a so-called silver halide emulsion, which is dispersed in a binder consisting of gelatin or other colloidal substances, such as colloidal albumin, cellulose derivatives, or synthetic resins such as polyvinyl compounds, alone or in combination. It is provided in layers on the body with a subbing layer, an intermediate layer, etc. interposed therebetween as necessary. The silver halide emulsion can be optically sensitized, such as cyanine dyes,
For example, in general color photographic light-sensitive materials that are sensitized by merocyanine dyes, three types of silver halide emulsions each having a different sensitivity wavelength range are used. The emulsion may also be stabilized with triazoles, azaindenes, quaternary benzothiazolium compounds, zinc or cadmium compounds;
Sensitizing compounds of ammonium salt type or polyethylene glycol type may also be included. It may also contain suitable gelatin plasticizers such as glycerin, dihydroxyalkanes such as 1,5-pentadiol, esters of ethylene bisglycols, bis-ethoxydiethylene glycol succinate, amides of acrylic acids, latex, etc. In addition, formaldehyde, halogen-substituted fatty acids such as mucobromic acid, compounds with acid anhydride groups, dicarboxylic acid chlorides, biesters of methanesulfonic acid, and aldehyde groups with 2 to 3
Contains various photographic additives such as gelatin hardeners such as sodium bisulfite derivatives of dialdehydes separated by 5 carbon atoms, or spreading agents such as sabonin, or coating aids such as sulfosuccinates. be able to. This emulsion also contains couplers, such as 5-pyrazone magenta couplers, naphthol and phenolic cyan couplers, yellow couplers having an active methylene group sandwiched between two carbonyls, and the above meta-aminophenol couplers for forming black dyes. and hindered phenol bispyrazolone type couplers, etc., and these may be so-called 2-equivalent or 4-equivalent couplers, or azo-type colored couplers having, for example, an arylazo group at the active site, or a A masking coupler such as a so-called DDR coupler having a releasable dye group may also be contained. At this time, it is preferable to use a colorless coupler, a so-called colorless coupler, in combination with the above-mentioned masking coupler before color development. The dispersant for the coupler used at this time may include, for example, a coupler solvent in the case of a so-called protected coupler. In addition, various couplers such as DIR couplers can be used in combination to improve photographic properties, and for example, a coupler called a so-called competing coupler can also be included. Further, this emulsion may contain an ultraviolet absorber, a fluorescent whitening agent, etc., if necessary. Such a silver halide emulsion is placed on a support via a subbing layer, an intermediate layer, etc., if necessary.
A color photographic material is produced, and at this time, as a support, for example, a film or sheet of paper, laminated paper, glass, cellulose acetate, cellulose nitrate, polyester, polyamide, polystyrene, etc. is used. The selection depends on the intended use of the material. Basically, a color photographic light-sensitive material is composed of a support and a light-sensitive emulsion layer, but as mentioned above, depending on the type of color photographic light-sensitive material, there may be a subbing layer, an intermediate layer, a filter layer, a curl layer, etc. A preventive layer, a protective layer, etc. may be formed in a suitable combination, and the photosensitive emulsion layer itself may be composed of a multilayer of, for example, one with high sensitivity and one with relatively low sensitivity in the same wavelength range or in different wavelength ranges. good. And each of these layers is
It can contain various photographic additives, such as the above-mentioned photographic additives added to the emulsion, and additives that differ depending on the purpose of each layer, such as filter dyes and protective layers in filter layers, etc. etc., may contain a film property improver, an antistatic agent, etc. EXAMPLES The present invention will be explained in more detail below with reference to Examples, but the embodiments of the present invention are not limited thereby. Example 1 2-(1-benzyl-2,4
-dioxoimidazolidin-3-yl)-2-bivalyl-2'-chloro-5'-[4-(2,4-di-t
-Pentylphenoxy)butanamide]acetanilide was dissolved in dibutyl phthalate, protected and dispersed in an aqueous gelatin solution, and then mixed with a silver chlorobromide emulsion and coated. The coupler used at this time and the silver
The coating amount per 100 cm ² was 8.3 mg of coupler and 3.5 mg of silver. On this, a gelatin intermediate layer containing dioctylhydroquinone was provided, and further on this, 3-{2-chloro-5-[1-(ocdadecyl)succinimide]anilino}-1-(2,
4,6-Trichlorophenyl)-5-pyrazolone was dissolved in dibutyl phthalate, protected and dispersed in an aqueous gelatin solution, mixed with a green photosensitive silver chlorobromide emulsion, and then coated and dried. The amount of coupler used at this time was 4.3 mg per 100 cm ² and the amount of silver was 3.9 mg. A gelatin solution of dioctylhydroquinone is applied as a color turbidity prevention layer on top of this layer, and 2-[2-(2,4
-di-t-pentylphenoxy)butanamide]
-4,6-dichloro-5-methylphenol was dissolved in dibutyl phthalate, protected and dispersed in an aqueous gelatin solution, mixed with a red-sensitive silver chlorobromide emulsion, and then coated and dried. The coating amount of the coupler used at this time was 3.0 mg per 100 cm ² and the amount of silver was 2.1 mg. The samples thus obtained were passed through a step wedge and subjected to blue filter exposure, green filter exposure, and red filter exposure, respectively, and were subjected to the following five treatments. [Processing 1] (1) Color development (33℃, 3 minutes 30 seconds) - Bleach fixing -
Washing with water and drying (2) Color developing solution used: Developer solution-1 (3) Bleach-fix solution used: Bleach-fix solution-1 [Processing 2] (1) Viscous development (developing solution preheated to 50℃) (Apply and process for 1 minute 15 seconds while keeping the temperature at 50℃)
Stopping - Bleach-fixing - Washing - Drying (2) Viscous developer used: Developer -2 (3) Stop solution used: Stop solution -1 (4) Bleach-fix solution used: Bleach-fix solution -1 [Processing 3 ~5] (1) Viscous development (applying a heated developer and processing while lowering the temperature over time) - Stopping - Bleach-fixing - Washing with water - Drying (2) Viscous developer used: Developer -2 (3) Stop solution used: Stop solution -1 (4) Bleach-fix solution used: Bleach-fix solution -1 (5) For processing 3, a viscous developer at 70°C was applied and the solution was heated for 1 minute 30 minutes.
The temperature was continuously lowered to 26℃ over 2 seconds. Process 4 brought the temperature down to 24℃ using a 60℃ developer over 1 minute 45 seconds, and Process 5 brought the temperature down to 24℃ using a 50℃ developer over 2 minutes 20 seconds.
The temperature was continuously lowered to ℃. The processing solution used is as follows. [Developer-1] 4-amino-3-methyl-N-ethyl-N-
(β-methylsulfonamidoethyl)aniline 1/2 sulfate monohydrate 5g Sodium sulfite 2g Hydroxylamine 1/2 sulfate 2g Potassium carbonate (anhydrous) 32g Potassium bromide 1.2g Add water to make 1 . PH=10.2 [Developer-2] 4-amino-3-methyl-N-ethyl-N-
(β-methylsulfonamidoethyl)aniline 1/2 sulfate monohydrate 5g Sodium sulfite (anhydrous) 2g Hydroxylamine 1/2 sulfate 2g Potassium carbonate (anhydrous) 32g Potassium bromide 1.2g Carboxymethylcellulose 20g Add water to make 1. PH=10.2 Viscosity 4500cps (25℃) [Stop solution-1] 2g acetic acid aqueous solution [Bleach-fix solution-1] Ethylenediaminetetraacetic acid iron ammonium salt
61g Ethylenediaminetetraacetic acid diammonium salt
5g Ammonium thiosulfate 124.5g Sodium metabisulfite 13.3g Sodium bisulfate 2.7g Add water to make up to 1 and adjust pH to 6.5. Sensitometry was performed on the samples obtained in the above treatments 1 to 5, and yellow (Y),
The sensitivity, fog, and maximum density (Dmm) of magenta (M) and cyan (C) were measured, and the results shown in Table 1 were obtained. In addition, in the table, yellow, magenta,
The cyan sensitivity is a relative sensitivity when the yellow, magenta, and cyan sensitivities of the sample in Processing 1 are each set to 100.

Table 2 also shows the processing stability of development in Process 2 and Process 4. Table 2 shows the sensitometric values at the end of development and after continued development for 15 seconds for each treatment. The development completion times for Process 2 and Process 4 were 1 minute 45 seconds and 1 minute 45 seconds, respectively. Note that the sensitivities in the table indicate relative values to the sensitivity of Treatment 1, as in Table 1.

[Processing 6]

(1) Color development (processed at 27°C for 3 minutes and 30 seconds) - bleach-fixing - washing with water - drying (2) Developer used: Developer - 3 (3) Bleach-fixer used: Bleach-fix as described in Example 1 Solution-1 [Processing 7] (1) Viscous development (Apply a viscous developer preheated to 50℃ and process for 1 minute and 15 seconds while maintaining the temperature at 50℃) - Stop - Bleach-fix - Wash with water - Dry (2) Viscous developer used: Developer solution-4 (3) Stop solution used: Stop solution-1 described in Example 1 (4) Bleach-fix solution used: Bleach-fix solution described in Example 1 [Processing 8] (1) Viscous development (processing by applying a 60°C developer and continuously lowering the temperature of the applied viscous developer to 27°C in 1 minute 45 seconds) - Stop - Bleach fixing
Washing with water and drying (2) Viscous developer used: Developer solution-4 (3) Stop solution used: Stop solution-1 described in Example 1 (4) Bleach-fix solution used: Bleach-fix described in Example 1 Solution-1 The processing solution used is as follows. [Developer-3] 4-Amino-3-methyl-N,N-diethylaniline hydrochloride 2g Sodium sulfite (anhydrous) 2g Hydroxylamine 1/2 sulfate 2g Potassium carbonate (anhydrous) 30g Potassium bromide 2.5g Water In addition, it is set to 1. PH=10.2. [Developer-4] 4-Amino-3-methyl-N,N-diethylaniline hydrochloride 2g Sodium sulfite (anhydrous) 2g Hydroxylamine 1/2 sulfate 2g Potassium carbonate (anhydrous) 30g Potassium bromide 2.5g Carboxymethylcellulose Add 14g water to make 1. PH=10.2. Viscosity 4200cps (25℃). Sensitometry was performed on the samples obtained in the above treatments 6 to 8, and yellow (Y),
The sensitivity, fog and maximum density (Dmax) of magenta (M) and cyan (C) were measured and the results shown in Table 3 were obtained.
In the table, the yellow, magenta, and cyan sensitivities of Processes 7 and 8 are relative sensitivities when the yellow, magenta, and cyan sensitivities of the samples of Process 6 are set as 100, respectively. In order to show the stability of the processing, photographic characteristic values for two levels of development processing time shown in Table 3 are shown.

[Processing 9]

(1) Color development (38°C, 3.5 minutes) - Stop - Bleaching - Fixing - Washing - Stabilization - Drying (2) Color developer used; Developer -5 (3) Stop solution used; Stop solution-1 (4) Bleach solution used; Bleach solution-1 (5) Fixer solution used; Fixer solution-1 (6) Stabilizer solution used; Stabilizer solution-1 [Processing 10] (1) Viscous development (Apply a viscous developer heated to 50℃ in advance and process for 1 minute and 45 seconds while keeping the temperature at 50℃) - Stop - Bleaching - Fixing - Washing - Stabilization - Drying (2) The viscous developer used; Developer solution-6 (3) Stop solution used; Stop solution-1 described in Example 1 (4) Bleach solution used; Bleach solution-1 (5) Fixer solution used; Fixer solution-1 (6) Used Stabilizing solution; Stabilizing solution-1 [Processing 11] (1) Viscous development (applying a 60°C developer and continuously developing the applied viscous developer so that the temperature of the applied viscous developer reaches 25°C in 1 minute and 55 seconds. ) - Stopping - Bleaching - Fixing - Washing - Stabilization - Drying (2) Viscous developer used; Developer solution-6 (3) Stop solution used; Stop solution-1 described in Example 1 ( 4) Bleaching solution used; Bleach solution-1 (5) Fixing solution used; Fixing solution-1 (6) Stabilizing solution used; Stabilizing solution-1 The processing solutions used are as follows. [Developer-5] 4-amino-3-methyl-N-ethyl-N-
(β-Hydroxyethyl)aniline sulfate 4.8g Potassium sulfite (anhydrous) 5.0g Hydroxylamine 1/2 sulfate 2.0g Potassium carbonate (anhydrous) 30g Potassium bicarbonate (anhydrous) 3.5g Sodium bromide 1.0g Add water and set it to 1. PH=10.1. [Developer-6] 4-amino-3-methyl-N-ethyl-N-
(β-Hydroxyethyl)aniline sulfate 4.8g Potassium sulfite (anhydrous) 5.0g Hydroxylamine 1/2 sulfate 2.0g Potassium carbonate (anhydrous) 30g Potassium bicarbonate (anhydrous) 3.5g Sodium bromide 1.0g Carboxymethyl cellulose 20g Add water to make 1. PH=10.1. Viscosity 3800cps (25℃). [Bleach solution-1] Ethylenediaminetetraacetic acid iron ammonium salt
100.0g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0g Add water to make 1, and use ammonia water to adjust the pH.
Adjust to 6.0. [Fixer-1] Ammonium thiosulfate (50% aqueous solution) 162ml Anhydrous sodium sulfite 12.4g Add water to make 1, and adjust to PH6.5 using acetic acid. [Stabilizer-1] Formalin (37% aqueous solution) 5.0ml Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.)
Add 7.5ml water to make 1. Sensitometry was performed on the samples obtained in the above treatments 9 to 11, and yellow (Y),
The sensitivity, fog and maximum density (Dmax) of magenta (M) and cyan (C) were measured and the results shown in Table 4 were obtained.
In the table, the sensitivity of the samples subjected to treatments 10 and 11 is the relative sensitivity when the respective sensitivity values of Y, M, and C of sample No. 9 subjected to treatment 9 are set as 100,
Further, fog was expressed as a value obtained by subtracting the mask density from the minimum density value. In order to show the stability of the processing, the development processing time was set at two levels as shown in Table 4, and the photographic characteristic values for each were shown.

[Table] As is clear from Table 4, the viscous development process of the present invention can be effectively applied to color negative light-sensitive materials using silver iodobromide emulsions, and unlike the known viscous development process, High-quality images can be obtained without increasing fog, development is automatically stopped, and processing stability is excellent.

Claims (1)

[Scope of Claims] 1. A method for forming a color photographic image in which a viscous developer is applied to the surface of a photosensitive layer side of an imagewise exposed silver halide color photographic light-sensitive material and developed, in which the viscous developer is applied. A method for forming a color photographic image, characterized in that substantial development is then carried out while the temperature of the viscous developer is continuously lowered. 2. The method for forming a color photographic image according to claim 1, wherein the temperature of the viscous developer during application is 45° C. or higher. 3 The temperature of the applied viscous developer when development is completed is 30
3. The method for forming a color photographic image according to claim 1 or 2, wherein the temperature is below .degree.