JPH0214690B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for forming a color photographic image by color development processing of a silver halide color photographic light-sensitive material. More specifically, it is a novel technology that allows images with high sensitivity and less fog to be obtained in a short time by applying a viscous developer to the surface of a silver halide color photographic light-sensitive material and continuously increasing the temperature of the developer. The present invention relates to a method for forming color photographic images. 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, speeding up of processing is required, and considerable speeding up has been achieved to date 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, it is now possible to raise the processing temperature due to advances in high-film 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 the deterioration of processing solutions. is gradually becoming possible. However, as the processing temperature increases, it becomes difficult to prevent fogging and deterioration of the processing solution caused by these chemicals, and the concentration of the chemicals in the color developer changes due to the increase in evaporation amount as the processing temperature increases. In conjunction with this, it has become difficult to pursue high-temperature, rapid processing using bath processing. 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, does not cause uneven development caused by poor or uneven stirring, and has a strong edge effect, so images with good resolution can be obtained. It is possible to supply the necessary amount of drugs, and there is no need for management such as replenishment.
It has advantages such as being able to process small amounts of color photographic materials without using special equipment and being able to always use fresh solution, but it has not been put into practical use because high-temperature, rapid processing increases fog and stains. Currently, they are limited to special uses such as movie films, soundtracks, recording paper for oscilloscopes, and television films, and moreover, they are almost exclusively limited to monochrome photosensitive materials. The following techniques are known regarding this viscous development processing method. That is, U.S. Pat. No. 2,196,226 discloses 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. 3615482, No. 3615482, No.
Although it is described in the specifications of 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. Also, US Patent No. 3265501, US Patent No. 3561960, East German Patent
Specifications of No. 55547 and No. 98377, Special Publication No. 1973-
No. 16289 and other documents describe a process of developing by applying a viscous developer, but further improvements are desired in terms of improving photographic performance such as sensitivity and suppression of fog. 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 method for forming color photographic images that allows rapid photographic processing of color photographic materials. 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 a color photographic material which has been imagewise exposed, and development is completed after the application of the viscous developer. This is a method of continuously increasing the temperature of the viscous developer until the temperature rises, and is achieved by ensuring that the difference between the temperature at 2/3 of the heating time and the temperature at the completion of development is 5°C or more. be done. The viscosity of the viscous developer is sufficient as long as it maintains 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 readily 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 maleate, etc. The thickener is not limited to these, and any thickener may be used as long as it is uniformly dissolved in a common color developing solution and does not impair photographic properties. The present invention differs from known viscous development processing methods in that development is carried out while the temperature is continuously raised. In known development processes, not only the viscous development process but also other methods, care has been taken to perform the development process at a constant temperature as much as possible. This is because the developability can be easily controlled by controlling the processing time under constant temperature conditions, and it is difficult to change the temperature during processing, and it was thought that it would be difficult to control the developability. . However, when the viscous developer was applied and the temperature of the viscous developer was continuously raised until the development was completed, a surprising result was obtained in which fog was reduced without impairing the color density. Here, development completion indicates a state in which image density does not increase and fog increases even if development is continued further. Continuously increasing the temperature of the viscous developer until the development is completed means that during the color development process, the temperature of the applied viscous developer is increased over time and the process is terminated before reaching a constant temperature state. mean something The method of raising the temperature in the present invention does not need to be constant, and even if the temperature is raised at a substantially constant rate,
In addition, the temperature increase rate may be increased at the beginning of development and gradually slowed down over time, regardless of the temperature increase method, but in order to minimize fog after development is completed, processing In order to reduce changes in developability due to time errors, it is preferable that the temperature increase rate at the end of development near the completion of development be as slow as possible. The method of raising the temperature in the present invention is such that when the heating time is 1, the temperature difference between the temperature after 2/3 of the heating time and the temperature at the completion of development (preferably 55°C or less) is 5°C. This is because if this temperature difference is less than 5° C., fogging may occur. The heating method for raising the viscous developer in the present invention is not particularly limited. Examples of heating methods include heating the color photographic material by increasing the temperature of the air surrounding it during viscous development processing, heating the back side of the color photographic material by bringing it into contact with a hot plate or hot roll, and using ultrasonic waves. There are methods of heating by activating molecular motion, and any heating method such as thermal convection, thermal conduction, thermal radiation, and molecular motion heating may be employed. In the present invention, the rate of temperature rise due to heating and the development processing time are inversely proportional, and the higher the temperature rise rate, the shorter the processing time, but as is known in the art, the development time at high temperatures is longer. The more time passes, the more severe fogging becomes, and even in the developing method of the present invention, when the temperature of the viscous developer exceeds 55°C, fogging becomes relatively easy. Therefore, in the present invention, the temperature at the time of completion of development is preferably 55° C. or lower. The rate of temperature increase in the present invention can be controlled by changing the amount of energy supplied and the amount of viscous developer applied. Under constant energy supply conditions, the rate of temperature rise decreases as the coating amount increases. However, it is not necessary to change the amount of chemicals required for color development as the amount of coating changes, and it is sufficient to dilute or thicken with water according to the amount of coating without damaging the viscosity. When the developing method of the present invention is followed, images with less fog and high sensitivity can be obtained. Although there are many unknown reasons for this, the inventors believe that in the exposed area, development progresses while the suppressing effect of halogen ions released as development progresses and the development promoting effect associated with temperature rise are appropriately balanced. It is presumed that at the processing stage where fog is a problem, halogen ions generated by the development of exposed areas reach unexposed areas, and this is to strongly suppress fog development. The viscous developer used in the present invention is not limited to its components as long as it enables 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. Any aromatic primary amine color developing agent may be used in the viscous (color developing) developer used in the viscous development of the present invention, but in particular p-
Phenylenediamine 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 forming) 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 hydroxylamine. 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-phenyl-1,3,4-oxadiazole [azole compound] (9) Benztriazole (10) 5-nitrobenzimidazole (11) 5-methylbenztriazole (12) ) 4-Chlorbenztriazole (13) 5,5-diphenylthiohydantoin [oxonium compound] (14) N-isopropyl-α-picolinium bromide (15) N-ethyl-2-methylbenzthiazolium chloride [pigment (16) Phenosafranin (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]imidazo[4,5-b] Quinoxalium iodide [Others] (20) Benzyl adenine (21) 8-oxyquinoline (22) o-phenanthroline (23) Thiosyuga The compounds prepared can be advantageously used in the present invention. A wide variety of compounds can be used as development accelerators, such as benzyl alcohol, hydrazine, polyethylene glycol, polyoxyethylene nonionic activators, and phenylpyrazolidone, p-methylaminophenol, etc. Also mentioned are p-phenylene diamines 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 buffer, etc. is used, and then hydroxylamine 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; Alternatively, treatment with various treatment liquids such as sodium citrate in combination with a bleaching solution of ferric chloride, a neutralization bath made of acetic acid, other stabilizing liquids, washing with water, drying, etc. 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 ammonium salts, alkali metal salts, salts of polyvalent metal ions, etc. as the washing water. Further, the processes before and after the viscous development process may be performed by web process, smear process, 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. Furthermore, black dye image forming methods such as the meta-aminophenol type coupler for black dye development formation described in JP-A No. 52-42725 and the type coupler synthesized from hindered aldehyde and pyrarazolone described in Japanese Patent Application No. 54-12555 However, the material composition of these color photographic materials is not intended to limit the present invention in any way. Silver halides contained in color photographic light-sensitive materials to which the method for forming color photographic images according to the present invention can be applied include silver chloride, silver bromide, silver iodide, and mixed silver halides (for example, silver iodobromide). , iodobromosilver chloride, etc.)
These may be produced by any of a variety of methods, such as direct mixing, simultaneous mixing, and convergence methods, regardless of particle size, crystal habit, mixing ratio, etc. The silver halide may also include active gelatin, sulfur sensitizers such as allylthiocarbamide, thiourea, cystine, selenium sensitizers, noble metal sensitizers such as gold sensitizers, and specifically potassium chloroolite. , potassium aurithiocyanate, potassium chloroaurate, 2-aurothiabenzothiazole methyl chloride, etc., or sensitizers such as ruthenium, rhodium, palladium, iridium salts, in particular ammonium chloroparadate, potassium chloroplatinate and sodium. Chloroparadite, etc., are known to act as sensitizers or fog suppressants depending on the amount of these sensitizers, either alone or in combination as appropriate. Can be sensitized. 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. and also 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 compounds with 2 to 3 aldehyde groups
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 saponins, 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, the above-mentioned meta-aminophenol couplers for forming black dyes, and It can contain hindered phenol bispyrazolone type couplers, etc., and these have so-called 2 equivalents or 4 equivalents.
It may be an equivalent coupler, or an azo colored coupler having, for example, an arylazo group at the active site, or a so-called colored coupler having a detachable dye group at the active site.
It may also contain masking couplers such as DDR couplers. 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 for improving photographic properties can be used in combination, and for example, so-called competing couplers 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 layered 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 prevention layer, a protective layer, etc. are laminated or provided in an appropriate combination, and the photosensitive emulsion layer itself is composed of, for example, a layer with high sensitivity and a layer with relatively low sensitivity in the same wavelength range or in different wavelength ranges. It's okay. Each of these layers can contain various photographic additives, such as the photographic additives added to the emulsion mentioned above, and additives that differ depending on the purpose of each layer, such as filter layers, etc. dye for filters,
The protective layer 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
-Dioxyimidazolidin-3-yl)-2-pivalyl-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 top of this, a gelatin intermediate layer containing dioctylhydroquinone is provided, and on top of this, 3-{2-chloro-5-[1-(octadecyl)succinimide]anilino}-1- is added as a coupler.
(2,4,6-Trichlorophenyl)-5-pyrazolone was dissolved in dibutyl phthalate, protected and dispersed in an aqueous gelatin solution, mixed with a green-sensitive silver chlorobromide emulsion, and then coated and dried. The amount of coupler used at this time was 4.3 mg per 100 ^cm2 , and the amount of silver was 3.9
It was 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, and red-sensitive silver chlorobromide was added. After mixing with the emulsion, it was 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 and drying (2) Color developing solution used; Developer solution - 1 (3) Bleach-fixing solution used; Bleach-fix solution - 1 [Processing 2] (1) Viscous development (Developing solution heated to 50℃ in advance) Apply and process for 1 minute and 30 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 developer at 25°C and processing while increasing the temperature over time) - Stop - Bleach-fix - Washing - Drying (2) Viscous developer used; Developer -2 (3) Stop solution used; Stop solution -1 (4) Bleach-fix solution used; Bleach-fix solution -1 (5) Process 3 is a viscous developer that was applied to 54℃ over 2 minutes and 30 seconds. Process 4 by continuously increasing the temperature of
temperature to 52℃ in 2 minutes, and process 5 in 1 minute 30 seconds.
The temperature was raised continuously to 53°C. 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 (anhydrous) 2g Hydroxylamine 1/2 sulfate 2g Potassium carbonate (anhydrous) 32g Potassium bromide 1.2g Add water Set to 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 Carboxymethyl cellulose 20g Add water to make 1. PH=10.2. viscosity
4500cps (25℃) [Stop solution-1] 2% 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 the 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 (Dmax) 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] Also, the development progress status of Process 2 and Process 5 is shown in the second table.
Shown in the table. 1 minute, 1 minute 15 seconds, 1 minute in process 5
The temperatures of the applied viscous developer after processing for 30 seconds are 44°C, 49°C, and 53°C, 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-fixing 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 1-1 [Processing 8] (1) Viscous development (processing by applying a 25°C developer and continuously increasing the temperature of the applied viscous developer to 54°C in 1 minute and 30 seconds) - Stop - Bleach fixing
Washing with water and drying (2) Viscous developer used; Developer solution-4 (3) Stop solution used; Stop solution described in Example 1-1 (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 Add to make 1. PH=10.2. [Developer-4] 4-Amino-3-methyl-NN-diethylaniline hydrochloride 2g Sodium sulfite (anhydrous) 2g Hydroxylamine 1/2 sulfate 2g Potassium carbonate (anhydrous) 30g Potassium bromide 2.5g Carboxymethyl cell Roll 14g Add 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. Also, to show the progress of development,
The photographic characteristic values during processing are also shown. 1 in process 8
The temperatures of the developer during processing for 1 minute, 15 seconds, and 1 minute 30 seconds were 47°C, 51°C, and 54°C, respectively.

[Processing 9]

(1) Color development (38℃, 3.5 minutes) - Stop - Bleaching -
Fixing - Washing - Stabilization - Drying (2) Color developing solution used; Developer solution -5 (3) Stop solution used; Stop solution described in Example 1 -1 (4) Bleaching solution used; Bleach solution -1 ( 5) Fixer used; Fixer - 1 (6) Stabilizer used; Stabilizer - 1 [Processing 10] (1) Viscous development (Apply a viscous developer heated to 50℃ in advance, and lower the temperature. Processing for 1 minute and 45 seconds while maintaining at 50°C) - Stop - Bleaching - Fixing - Washing - Stabilization - Drying (2) Viscous developer used; Developer - 6 (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 11] (1) Viscous development (Apply a developer at 25℃ and process by continuously raising the temperature of the applied viscous developer to 52℃ in 2 minutes) - Stop - Bleaching - Fixing - Washing - Stabilization - Drying ( 2) Viscous developer used; Developer solution-6 (3) Stop solution used; Stop solution described in Example 1-1 (4) Bleach solution used; Bleach solution-1 (5) Fixer solution used; Fixer-1 (6) Stabilizing solution used; Stabilizing solution-1 The processing solution used is 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 Carboxymethyl cellulose 2.0 g Add water to make 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 2.0 g 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 the pH to 6.5 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 addition, photographic characteristic values during processing are also shown to show the progress of development. 1 in process 11
The temperatures of the developer during processing for minutes 30 seconds, 1 minute 45 seconds, and 2 minutes were 45°C, 49°C, and 52°C, respectively.

[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, It can be seen that sensitivity and maximum density can be improved without increasing fog, and development time can also be shortened. In addition, for Processes 3 to 5, Processes 8 and 11, the difference between the temperature at 2/3 of the temperature increase time and the temperature at the completion of development was 5°C or more.

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; It is a method of continuously increasing the temperature of the viscous developer until the post-development is completed, and the difference between the temperature at the time of 2/3 of the temperature increase time and the temperature at the completion of development is 5°C or more. A method for forming a color photographic image, characterized in that: 2. The method of forming a color photographic image according to claim 1, characterized in that the temperature rise rate of the applied viscous developer is slowed down over time. 3 The temperature of the applied viscous developer at the time of completion of development is 55
3. The method for forming a color photographic image according to claim 1 or 2, wherein the temperature is below .degree.