JPS62180363A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a dye image rapidly and stably by combining a specified color developing agent with a specified pH of a color developing soln. and a specified halide emulsion and using a specified development accelerator. CONSTITUTION:Processing is carried out with a color developing soln. of >=10.3pH at >=30 deg.C for <=120sec in the presence of at least one kind of compound represented by formula II (where X is H or acetyl, R1' is aryl and each of R2'-R5' is H, halogen, alkyl or aryl). The developing soln. contains >=1.5mu10<-2>mol at least one kind of p- phenylenediamine type color developing agent represented by formula I (where n=2, 3 or 4, R1 is 1-6C alkyl or hydroxyalkyl, R2 is H, 1-6C alkyl, hydroxyalkyl or 1-6C alkoxyalkyl an R3 is H, 1-6C alkyl or alkoxy). The solvent in the developing soln. is composed of water, a solvent (a) having <0.4logP and a solvent (b) having >=0.4logP. The volume ratio of the solvent (b) to the solvent (a) is <=0.003. The amount of the compound represented by the formula II in the developing soln. depends on the kind of the compound but the preferred amount is 5X10<-2>-5X10<-7>mol/l. The compound may be directly added to the developing soln. or may be added to the preceding bath and brought into the developing soln. by a silve halide color photographic sensitive material. The preferred pH of the developing soln. is >=10.50.

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a method for color development processing of silver halide color photographic materials (hereinafter referred to as "photosensitive materials"), and more specifically, a method for obtaining stable dye density even when color development processing is performed for an extremely short time. The present invention relates to a rapid water-free stabilization processing method that can obtain images with excellent storage stability in a dark place and that can be processed without washing with water and with a small amount of stabilizing solution replenished. [Prior art] Processing of color photosensitive materials basically involves color development, desilvering,
It consists of three steps: washing with water, and desilvering is either a bleaching and fixing step or a bleach-fixing step in which bleaching and fixing are performed in the same bath. Recently, instead of the water-washing process, a waterless washing process called stabilization process has been proposed, and it is well known that the process consisting of the three steps of color development, bleach-fixing, and stabilization process is widely used. In these color photographic systems, a non-diffusible coupler is generally contained in the photographic emulsion layer, and development is carried out using a color developing agent in a color developing solution. It is also known how to induce Campling reactions in photographic materials. The coupler contained in the light-sensitive material is generally made non-diffusible by being dispersed in a water-insoluble high-boiling organic solvent. This method is considered to be advantageous in terms of a-color reproducibility, color purity, image storage stability, etc., and is extremely commonly carried out. It is being said. [Problems to be Solved by the Invention] Color developing solutions for processing such light-sensitive materials contain an aromatic primary amine color developing agent and a poorly soluble organic solvent (1).
It is also well known that a solvent with a P of 0.4 or more is contained. The best known organic solvents of this type are:
A poorly soluble alcohol is used to accelerate the reaction between the color developing agent and the image-forming coupler, ie, to increase the efficiency of the coupling reaction. This type of alcohol is often referred to as a "development accelerator 1 or 1 development booster." Benzyl alcohol is particularly effective for this purpose, as seen in US Pat. No. 2,304,925 or 3,814°606. In order to supply a large amount of color developing agent in a short time to a uniform width of oil in which a coupler is dispersed, and furthermore, to distribute a relatively large amount of color developing agent into the swollen gelatin film as well as in the bulk of the developer, color development is performed. The use of poorly soluble alcohols, such as benzyl alcohol, which is thought to promote the development of color, increases the residual concentration after development due to the high concentration of the color developing agent in the oil and gelatin in the photosensitive material during processing. This has the disadvantage that the dye image quality becomes high, which is the biggest cause of deterioration in the storage stability of dye images. Furthermore, what has brought this problem to light and emphasized it is the recent rapid processing that has shortened the total processing time.Another major cause is the supply of large amounts of washing water, which makes it difficult to clean photosensitive materials. The water-washing process, which used to be a cleaning process, was removed from photographic processing, and a stabilization process that supplied a small amount of replenishment began to replace the water-washing process. These waterless washing stabilization treatments are described in Japanese Patent Application Laid-Open No. 58-14834.
No. 58-105145, No. 58-134634, No. 58-18631, and patent application No. 58-2709.
The details are given in the specifications such as No. 59-89288. In all of these methods, it is not possible to sufficiently wash the color developing agent adsorbed to the gelatin film in the light-sensitive material or the color developing agent distributed in the coupler dispersion oil and reduce the residual concentration, resulting in poor storage stability of the dye image. is markedly deteriorated. As a completely different topic, poorly soluble solvents such as benzyl alcohol with lP of 0.4 or more have long been of concern due to the poor solubility of these compounds in water. For example, when preparing a developer solution, benzyl alcohol tends to dissolve very slowly, requiring extensive forced stirring and/or heating of the solution water. If even a portion of the benzyl alcohol remains undissolved, the color developing agent will be distributed at a high concentration in this portion, and as it dissolves, it will be oxidized several days later, resulting in the formation of 1 tar, resulting in a serious malfunction. One solution to incorporating benzyl alcohol into a color developer is to add a solvent other than water with a disability P of less than 0.4, such as ethylene glycol, diethylene glycol, polyethyleneimine, triethanolamine, etc. Methods of solubilization are known. This method is described in US Pat. No. 3,574,619. Furthermore, the disadvantage of using a solvent such as benzyl alcohol is that it deteriorates the solubility of the color developing agent in the solution, so the concentration of the color developing agent in the color developing solution cannot be sufficiently increased, and development is not promoted as quickly as expected. The problem is that the transformation is only half-hearted. A particularly serious problem is that when the concentrated low-replenishment process, which is advantageous in terms of labor-saving work and requires a small amount of replenishment, uses a developer containing benzyl alcohol, there is a limit to the amount of color developing agent that can be dissolved in the replenisher. The problem is that it cannot be thickened beyond a certain amount. Therefore, a method is known in which a pyrazolidone derivative is contained in a light-sensitive material to suppress the concentration of benzyl alcohol in a color developing solution to a low level (Japanese Patent Laid-Open No. 58-505
No. 32). However, even this method does not speed up the process sufficiently; it requires a certain amount of processing time or more, and compared to the coupling reaction, only the silver development reaction is accelerated, resulting in sufficient dye density. I can't. In order to resolve these interlayers, we
A color photograph consisting essentially of a silver chlorobromide emulsion in a highly alkaline developer with a pH of 103 or higher that does not substantially contain a poorly soluble solvent with a pH of 0.4 or higher and that contains a specific color developing agent at a certain concentration or higher. Suggested processing of materials. This has made it possible to increase the storage stability of the dye image and to increase the speed of the coupling reaction without using a poorly soluble solvent. However, when trying to achieve even faster processing in a shorter period of time, the coupling speed between the coupler and the oxide of the color developing agent has already reached a sufficient level, so the development speed of silver halide becomes rate-limiting. , it is not possible to obtain sufficient dye density. On the other hand, due to economic and pollution problems, efforts have recently been made to reduce the overflow of color developing solutions. In particular, with the rise of small-volume processing laboratories, a so-called concentrated low-replenishment method in which the replenisher is concentrated and replenished in small amounts is being used, and the need for even lower replenishment is increasing. However, when the amount of replenishment is reduced, the concentration of development inhibiting substances such as halogen ions eluted from the photosensitive material increases.
It has been found that in systems where a poorly soluble organic solvent does not exist, the decrease in dye density due to short-time processing is magnified because the development speed of silver halide is suppressed. In addition, low replenishment results in a prolonged retention time of the processing solution and an increase in the concentration of oxidized color developing agent, etc., which tends to cause fogging. [Object of the Invention] The object of the present invention is, firstly, to provide a method for processing color photographic materials that can quickly and stably obtain dye images, and secondly, to eliminate the washing process and to conserve water resources. The purpose of the present invention is to provide a processing method that can obtain color photographs that are safe and have excellent storage properties, without leaving any harmful processing chemicals on the processed photographic materials. To provide an adjustable color photo processing method. Other objects of the invention will become apparent from the description below. [Means for Solving the Problem] As a result of various studies to achieve the above-mentioned object of the present invention, the present inventors developed a silver halide color photographic light-sensitive material consisting essentially of silver chlorobromide, which was developed by color development. , bleach-fixing, and stabilization processing, in which the color developing solution has a pH of 10.3 or higher and has a p
- Log P0 for the volume of a solvent containing at least 1,5XIO-'' moles of at least one color developing agent based on phenylenediamine, and the solvent has a pupil of water and an extra-water pupil p of less than 0.4.
．． It is composed of solvents with a volume ratio of 4 or more solvents of O, OO3 or less, is developed at 30°C or higher, and is developed in the presence of at least one compound represented by the following general formula (II) within 120 seconds. We have discovered that this can be achieved by processing. General formula CI) NM. [In the formula, n is an integer of 2 to 4, and R1 is a carbon number of 1 to 6
is an alkyl group or hydroxyalkyl group, R2 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group, or an alkoxyalkyl group having 1 to 6 carbon atoms, and R5 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms. 6 is an alkyl group or an alkoxy group. General formula [II] Rζ [wherein, ] The present invention relates to a specific color developing agent and a specific color developer.
By combining H, and a specific silver halide emulsion, the coupling rate between the coupler and the color developing agent is increased without impairing the image stability of the color image, and a specific development accelerator is further used. In particular, this can be achieved, but the details will be described later. The present inventors have discovered that the development accelerator represented by the general formula [II] of the present invention is substantially free of poorly soluble organic solvents and contains the color developing agent of the present invention at a certain concentration or more for color development. It has been found that when processed with a liquid, it is particularly effective in short-term rapid processing of less than 100 seconds.It is substantially free of poorly soluble organic solvents and contains the color developing agent of the present invention at a certain concentration or more. Processing with a high pH color developer will speed up the compression of the coupler and color developing agent, and the use of the development accelerators of the present invention will likely speed up the development of silver halide. When the coupling speed and the silver halide development speed are both equal, the dye formation speed is maximized, and an extremely high speed is obtained, thereby achieving the object of the present invention. In addition, it is effective in increasing the accumulation of halogen ions such as bromide ions and organic inhibitors due to a reduction in the amount of replenishment, and the higher the amount of accumulation, the more effective it is. Furthermore, as a result of continued investigation, the present inventors found that the binder for an emulsion in which the silver halide emulsion is silver chlorobromide, and in particular, the silver bromide content is less than 100% by mole. The effects of the present invention can be significantly obtained when the film swelling rate T3A of the dye image is less than 1 second and the color development process is less than 1 second. First, we have discovered the surprising fact that extremely high speed and extremely low replenishment can be obtained, and we have succeeded in achieving the object of the present invention.General formula [II] of the present invention In the compound represented by
X is preferably a hydrogen atom. Examples of the aryl group represented by RC in the general formula [II] include phenyl group and naphthyl group, with phenyl group being preferred. This aryl group may have a substituent. Examples of substituents include alkyl groups (e.g., methyl group, ethyl group, propyl group, etc.), halogen atoms (e.g., chlorine atom, bromine atom, etc.), alkoxy groups (e.g., methoxy group, ethoxy group, butoxy group, etc.),
Examples include an alkylsulfonyl group, an arylsulfonyl group, an amide group (eg, a methylamide group, an ethylamide group, a sulfo group, etc.). Among these substituents, a methyl group is preferred. One or more of these substituents can be present and can be present at any position; however, when the aryl group is a phenyl group, the substituent is preferably at the 4-position. The alkyl group represented by R≦, present, fluoride, and R≦ in general formula [II] is preferably a hydrogen atom, a halogen atom, and an alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a butyl group). etc.). This alkyl group can have substituents. As the substituent, a human myxyl group, an amino group, and an acyloxy group are preferable. Further, examples of the aryl group represented by 马, R, R (and R≦) include phenyl group, naphthyl group, etc., and phenyl group is preferable. It may have the above substituents, and examples of the substituents include alkyl groups (e.g., methyl, ethyl, propyl, etc.), halogen atoms (e.g., chlorine, bromine, etc.), alkoxy groups (e.g., methoxy group, ethoxy group, etc.) and human myxyl group, etc. Representative specific examples of the compound represented by the general formula [II] used in the present invention are shown below, but the compound of the present invention is not limited thereto. Exemplary compounds] ll-5n-8 [-6ll-9 11-7ll-10 n-11n-14 II-13[-16 [-17II-m [-+8 ll-2
11I-19ll-22 ■-O ■-26II
-24n-27 II-25I [-Roll-29n-32 II-3On-Oll-31ll-34 II-35ll-38 ■-A ■-39II
-37II -1lO [-,11n -44 II-42II -45 II -113n -46 III -,17II -50 II-48ll-51 ■-49 Among the above representative compounds, those that are more preferable for the present invention are n-1, ll-2, ll-4, ■-13, ■
-14, ■-15, ■-16, n-17, ll-18,
I[-23, I[-24, ll-25, ■-26, ■-
34, ■-35, ■-36, ■-A, ■-49. The compound represented by the general formula [II] is commercially available, but US Pat.
704゜762, JP-A-56-64339 and JP-A No. 56-64339
It can be synthesized according to No. B-50535. The compound CII) of the present invention may be contained in a three-color developer which may be contained in a light-sensitive material. When added to a light-sensitive material, the amount of the compound (III) to be added is from 10.001 mol to 1 mol, preferably from 0.00 s mol to 0.5 mol, per 1 mol of silver halide.Compound [II] may be added to each emulsion layer (blue-sensitive layer, green-sensitive layer, red-sensitive layer), or may be added to a non-emulsion intermediate layer or protective layer. It may be added to the emulsion layer.Furthermore, it may be added to the layer adjacent to the emulsion.Generally, it is added to the undercoat layer, the lowest layer above the undercoat layer, or the lowest layer in the emulsion layer. It is preferable to add the compound by directly dispersing it in an emulsion, or by dissolving it in water or alcohol and then dispersing it in gelatin or an emulsion. The content in the liquid varies depending on the compound, but is preferably 5X10-2 mol/l-5X10-fumol/l, more preferably 5X10-3 mol/l-5X10-' mol/l.General of the present invention The compound represented by the formula [1] may be added directly to the developer, or may be added to the developer and carried by the silver halide color photographic light-sensitive material. "Silver chlorobromide emulsion" means that it may contain a trace amount of silver iodide in addition to silver chlorobromide,
For example, this means that silver iodide may be contained in an amount of 0.3 mol % or less, more preferably 0.1 mol or less. However, silver chlorobromide emulsions containing no silver iodide are most preferred in the present invention. The present invention will be explained in more detail below. The hydrophilic binder used to coat silver halide (for color photographic photosensitive materials) is usually gelatin, but high-molecular polymers may also be used, and the film swelling rate T% is smaller than that of additives. The membrane swelling rate T% of the binder can be measured according to any method known in the art, for example, A. Green and G. I. P. Levenson. J, photo0. sci, 20, p20
It can be measured by using a swellometer (swelling film) of the type described in 5-2) 0, and T3/4 is the maximum swelling film reached when color development is performed at 30°C for 3 minutes and 30 seconds. 90% of the thickness is defined as the saturated film thickness, and is defined as the time required to reach this % film thickness (see Figure 2). The binder of the photographic constituent layer used in the silver halide color photographic light-sensitive material of the present invention has a swelling rate T% of m seconds or less, and the smaller the better, but if the lower limit is too small, the film will not be hardened and problems such as scratches will occur. 2 seconds or more is preferable since this tends to occur. Particularly preferably, the time is 15 seconds or less, most preferably 10 seconds or less. When the addition time is greater than 100 seconds, the storage stability of the dye image tends to be low, and a sufficiently rapid development time cannot be obtained, making it impossible to obtain sufficient dye formation in a short period of time. Membrane II wetting rate T3A can be adjusted by the amount of hardener used. The light-sensitive emulsion layer of the silver halide color photographic light-sensitive material processed according to the present invention only needs to have at least one layer consisting essentially of a silver chloride bromide emulsion; Preferably, it consists of a silver bromide emulsion. The silver chlorobromide content (a) is preferably 70 mol% or less, because the smaller the mol% of silver bromide, the more sufficient dye formation can be obtained even in a short color development time. The most preferable result is obtained when the content is 40 mol% or more. Furthermore, the smaller the amount of silver coated, the more preferable it is since sufficient pigment formation can be achieved in a short time;
r? Especially preferably ri0.8f/rr? The maximum effect is obtained when the temperature is further below 0.7F/-. The color development process is carried out at a temperature of 30°C or higher and 120 seconds or less, preferably 3
3°C or higher, 120 seconds or less, particularly preferably 33°C or higher,
The processing time is 90 seconds or less, most preferably 33 or more ω seconds or less, and if the processing is performed for 30 seconds or more, the storage stability of the dye deteriorates.In particular, the temperature and treatment time are This is important, and if the time exceeds 150 seconds, the fading resistance of the red dye will be markedly reduced, which is undesirable.The processing temperature is raised to complete the development in a short time rather than to preserve the storage stability of the dye, and is 30°C. that's all,
If the temperature is 50°C or higher, the higher the temperature, the shorter the processing time, which is preferable, but from the viewpoint of image storage stability, it is better not to be too high, and it is desirable to process at a temperature of 33°C or higher and 45°C or lower. In the present invention, logs that are not desirable to be added to the developer, etc.
The solvent with P0.4 or higher is an aliphatic alcohol, an aliphatic glycol ether, an alicyclic alcohol, or an aromatic alcohol, and among these, those having 5 to 20 carbon atoms are used. A specific example is benzyl alcohol
logPl, 100-hydroxybenzyl alcohol IOgp0. '7:3-n clohexanol
l■P1232-be/zyloxyethanol 1. P0.41 Anisyl alcohol
1. gp0.7゜1-pentanol phenylethyl alcohol logPl, 36
p-Tolylcarbinol 10gP1.3
6n-butanol Pupil P0.4
Examples of the above include phenol p-hydroxybenzyl alcohol, benzylamine diethylene glycol monobutyl ether, IogP0.41, and the like. In addition, solvents with an IogP of less than 0.4 are mainly those with a carbon number of 0 to 4, such as aliphatic alcohols and organic acids.
Although it may be less than 0.4 and is not particularly limited, specific examples include acetic acid, ethanol, acetone, propio/acid, propatool, ethylene glycol, diethylene glycol, triethylene glycol, triethanolamine, jetanolamine, etc. can be given. In the present invention, a preferred p-phenylenediamine color developing agent is represented by the general formula CII], but more preferably R1 is an alkyl group having 1 to 4 carbon atoms, and R2 is hydrogen or a C1 to 4 alkyl group. R3 is particularly preferably an alkyl group having 1 to 4 carbon atoms, most preferably R2 is an alkyl group having 1 to 4 carbon atoms. Specifically, (I-1) (I-4) (I-2)
(I-5) (I-3)
(I-6) (1-7)
(I-10) (I-s)
(1-u)(I-9) <t
-12) (I-13) (I-14) etc., but in order to more effectively enhance the effects of the present invention, compounds (I-1) (I-2) (I-3)
(I-4) (I-5) (I-11) (I-12)
(I-13) (I-14) are preferred, and (I-1) CI-2) (I-3) is particularly preferred. These color developers are hydrochloride, sulfate, phosphate, p-)
It is used in the form of luene sulfate. The color developing solution of the present invention is used at a pH of 10.3 or higher, preferably 10.50 or higher, and particularly preferably Filo. It is 75 or more, and the upper limit is related to the capricity of the photographic emulsion, but in general, the higher it is, the more preferable it is, and it is used in the range of 108 to 13. In the present invention, since the solubility of the color developing agent in water is extremely high, the amount used is preferably within the range of 1.5XIO-2 mol per 11 of the processing solution. J liketLl;
t1. The color developing agent of the present invention may be used in combination of two or more types.
Further, it may be used in combination with other color developing agents shown below. <A) H5C2\N/C,H. D-1 These alkyl sulfonamide alkyl-substituted -
p~Phenylenediamine derivatives are described in Journal of American Chemical Society, Vol. 73, 3. '
It can be easily synthesized by the method described on page 100 (1951). The bromide ion concentration of the color developing solution of the present invention is 5 x 10-j
Although it is preferable that the bromide is molar or more, in the present invention, the higher the bromide, the lower the replenishment amount, so it is preferable. In conventional development methods, bromide suppresses the development reaction, and it has been said that the lower the bromide content, the better; however, in the combination of the color photographic light-sensitive material and developer of the present invention, the color photographic material of the present invention has a blue-sensitive emulsion layer, a green-sensitive emulsion layer, and a green-sensitive emulsion layer. In a multilayer color photographic light-sensitive material having three or more layers including each of an emulsion layer and a red-sensitive emulsion layer, when the % of time until the film swelling time reaches the maximum, that is, the film swelling rate T% is 9 seconds or less, the maximum swelling time is reached. However, the thickness of the gold film when dried is 13 μm or less, preferably 12 μm or less, particularly preferably 10 μm or less, but in any case, T
3A is preferably 20 seconds or less. In the processing method of the photographic light-sensitive material of the present invention, it is possible to use a color developing solution containing the color developing main portion according to the present invention. In addition, various other methods including bath processing, such as a spray set in which the processing liquid is atomized, a web method using contact with a carrier impregnated with the processing liquid, and a developing method using a viscous processing liquid, are also available. However, the processing steps essentially include color development, bleach-fixing,
It consists of three steps: and stabilization treatment. The color developer used in the present invention further contains various commonly added components, such as alkaline agents such as sodium hydroxide and sodium carbonate, alkali metal sulfites,
Alkali metal bisulfite, alkali metal thiocyanate, alkali metal halide, polystyrene sulfonic acid, water-concentrating agent, ethylene glycol, diethylene glycol, triethanolamine, thickening agent, development accelerator, etc. may optionally be included. can. Examples of additives other than those mentioned above that are added to the color developer include bromides such as potassium bromide and ammonium bromide, alkali iodides, nitrobenzimidazole, mercaptobenzimidazole, 5-methyl-benzotriazole,
In addition to compounds for rapid processing solutions such as 1-phenyl-5-mercaptotetrazole, there are anti-stain agents, anti-sludge agents, preservatives, interlayer effect promoters, chelating agents, and the like. Furthermore, the concentration of bromide ions such as potassium bromide and ammonium bromide added to the color developer is determined by the amount contained in the light-sensitive material and the amount of replenishment of the color developer. In order to exhibit the effect effectively, it is preferably 0.22 or more, more preferably 0.52 or more per color developer. As the chelating agent in the developer, aminopolycarboxylic acid salts and organic phosphonates are mainly used. In order to achieve the present invention more effectively, the pH of the water washing alternative stabilizer in the present invention is preferably in the range of 5.5 to 100, more preferably in the range of 6.3 to 95, and particularly preferably is in the range of pH 7.0 to 90. As the pH adjusting agent that can be contained in the water washing alternative stabilizer of the present invention, any commonly known alkaline agents or acid agents can be used. The present invention is most effective when the amount of water-washing substitute stabilizing solution refilled into the stabilizing bath is small; The range is preferable, and the effect of the present invention is particularly significant in the range of 2 to 20 times. The stabilization treatment temperature is 15°C to ω°C, preferably 1-1
The temperature range is preferably from 20'C to 45C. In addition, from the viewpoint of rapid processing, it is preferable that the processing time be as short as possible, but it is usually 4 seconds or more.
The treatment time is 10 minutes, most preferably 1 to 3 minutes, and in the case of multiple tank stabilization treatment, it is preferable that the first stage tank be treated for a short time and the second stage tank be treated for a long time. Especially 20% of the anterior tank
It is desirable to process sequentially with 50% more processing time. After the stabilization treatment according to the present invention, no water rinsing treatment is required, but rinsing with a small amount of water within a short period of time, surface cleaning, etc. can be optionally performed as necessary. When the method for supplying the washing substitute stabilizing solution in the stabilization treatment step according to the present invention is a multi-tank countercurrent method, it is preferable to supply it to the rear bath and overflow from the front bath. Of course, it can also be treated in a single tank. The above compounds can be added as a concentrated solution to the stabilization tank, or the above compounds and other additives may be added to the washing alternative stabilizing solution supplied to the stabilizing tank, and then added to the washing alternative stabilizing replenishment solution. Although there are various methods such as using it as a supply liquid, it may be added by any method. Conventionally, photosensitive materials were processed with a bleach-fix solution after color development.
Next, in the treatment method of processing with a washing substitute stabilizing solution, if the specific gravity of the washing substitute stabilizing solution at 24°C in the final tank of the washing substitute stabilization treatment becomes 1002 or more as a result of continuous processing, contamination of the unexposed area will be severe. However, according to the present invention, the occurrence of contamination under such conditions is also significantly improved. In the present invention, processing with a bleach-fix solution and subsequent treatment with a water wash substitute stabilizing solution without substantial washing with water,
In other words, this indicates that a bleach-fix bath is followed by direct washing with a stabilizing solution, which is an alternative to washing with water. are completely different. In this way, in the present invention, treatment with a stabilizing solution refers to a treatment for stabilization treatment that is performed immediately after treatment with a bleach-fixing solution and does not substantially involve washing with water.
The processing liquid used for this stabilization treatment is called a water washing alternative stabilizing liquid,
The treatment tank is called a stabilization bath or stabilization tank. In the present invention, the effect of the present invention is great when the number of stabilizing tanks is 1 to 5. Particularly preferably, the number of stabilizing tanks is 1 to 3, and the number of stabilizing tanks is preferably 9 or less. Bleaching agents that can be used in the bleach-fix solution used in the present invention are metal complex salts of organic acids. The complex salt is one in which a metal ion such as iron, cobalt or copper is coordinated with an aminopolycarboxylic acid or an organic acid such as oxalic acid or citric acid. The most preferred organic acid used to form such a metal complex salt of an organic acid is a polycarboxylic acid. These polycarboxylic acids or aminopolycarboxylic acids Ir1
7. It may be a metal salt, an ammonium salt, or a water-soluble amine salt. Specific examples of these include the following. [1] Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N-(β-oxyethyl) -N, N', N
' -) Solacetic acid [・1] Propylenediaminetetraacetic acid [5] Nitrilotriacetic acid [6] Nclohexanediaminetetraacetic acid [7] Iminodiacetic acid [8] Dihydroxyethylglycide/citric acid (or tartaric acid)

[9] Ethyl ether diamine tetraacetic acid [10] Glycol ether diamine tetraacetic acid [11] Ethylene diamine tetraprobionic acid [12] Phenyl diamine tetra acetic acid [13] Ethylene diamine tetra acetic acid disodium salt [14] Ethylene diamine tetra acetate tetra(trimethyl ammonium) salt [15] Ethylenediaminetetraacetic acid tetrasodium salt [16] Diethylenetriaminepentaacetic acid pentasodium salt (:17] Ethylenediamine-N-(β-oxyethyl') -N, N', N'-) diacetic acid sodium salt [ 18] Propylene diamine tetraacetic acid sodium salt; [19] Nitriloacetic acid sodium salt; [20] Cyclohexane diamine tetraacetic acid sodium salt. These bleaching agents are used at a concentration of 5 to 450 f/13, more preferably 20 to 250 f/l. The bleach-fixing solution contains a silver halide fixing agent in addition to the above bleaching agent, and if necessary, a sulfite salt as a preservative. In addition, a bleach-fix solution consisting of an ethylenediaminetetraacetate iron ([) complex salt bleach and a small amount of a halogenide such as ammonium bromide other than the above-mentioned silver halide fixer, or conversely, a bleach-fix solution containing a small amount of a halogenide such as ammonium bromide, or conversely, an ammonium bromide Like no.
A bleach-fixing solution consisting of a composition containing a large amount of chloride,
Furthermore, a special bleach-fixing solution having a composition consisting of a combination of an ethylenediaminetetraacetic acid iron (III) complex salt bleaching agent and a large amount of a halide such as ammonium bromide may also be used. As the halides, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can also be used. can. The silver halide fixing agents contained in the bleach-fixing solution include compounds that react with silver halide to form water-soluble complex salts, such as potassium thiosulfate and sodium thiosulfate, which are used in ordinary fixing processes. Typical examples include thiosulfates such as ammonium thiosulfate, thiocyanates such as potassium thiocyanate, sodium thiocyanate, ammonium thio/anate, thioureas, thioethers, and the like. These fixing agents are used in an amount of 5 g/l or more within the range that can be dissolved, but generally 702 to 2509 g/l.
Use with 1. The bleach-fix solution contains boric acid, borax, sodium hydroxide,
Various pH buffering agents such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide may be contained alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents, or surfactants can be contained. In addition, preservatives such as hydroxylamine, hydrazine, bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitroalcohols and nitrates, and organic A solvent and the like can be contained as appropriate. The bleach-fix solution used in the present invention includes JP-A No. 46-280, JP-B No. 45-8506, JP-B No. 46-556, Belgian Patent No. 770,910, JP-B No. 45-8836,
Various bleach accelerators described in JP-A-53-9854, JP-A-54-71634 and JP-A-49-42349 can be added. The pH of the bleach-fix solution used is 40 or higher, but generally r
It is used at a pH of 5.0 to 9.5, preferably at a pH of 6.0 to 8.5, and more preferably at a pi of 6.5 to 8.5.The temperature of the treatment is It is used at a temperature lower than or equal to 80°C by 3°C or more, preferably at least 5°C lower than the processing solution temperature in the color developing tank, but preferably at 55°C or lower to suppress evaporation.Halogenation of the present invention A water-soluble or color-decolorizing dye (AI dye) can be added to the photographic constituent layer of the silver color photographic light-sensitive material. Examples of the AI dye include oxonol dyes, hemioquinonol dyes, melonanine dyes, and azo dyes. Among them, oxonol dyes, hemioquinol dyes, and solo 7-anine dyes are useful. Examples of AI dyes that can be used include British Patent No. 584.60.
No. 9, No. 1,277.429, Japanese Unexamined Patent Publication No. 48-8513
No. 0, No. 49-99620, No. 49-114420, No. 49-129537, No. 52-108115,
No. 59-25845, No. 59-111640, No. 5
No. 9-111641, U.S. Patent No. 2,274,782,
No. 2,533,472, No. 2,956,879, No. 3,125,448, No. 3,148.187, No. 3
, No. 177.078, No. 3.247, 127, No. 3,
No. 260,601, No. 3,540.887, No. 3.5
No. 75,704, No. 3,653,905, No. 3,71
No. 8,472, No. 4.071,312, No. 4,070
, No. 352 can be mentioned. These AI dyes generally contain 52
It is preferable to use X10-3 to 5X10-' moles,
More preferably, 1X10-2 to 1X10-' moles are used. The crystals of the silver halide grains may be normal crystals, twin crystals, or other crystals, and any ratio of the [1,O,01 plane to the [:1.1.1] plane can be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a layered structure (core-nel type) in which the inside and outside are different. Further, these silver halides may be of a type that forms a latent image mainly on the surface or of a type that forms a latent image inside the grain. Furthermore, tabular silver halide grains (see JP-A-58-113934 and Japanese Patent Application No. 59-170070) can also be used. Silver halide grains that are particularly preferably used in the present invention are those that are substantially monodisperse, and core/L emulsions are preferred because they can improve rapid processing and the stability of image dyes. It may be obtained by any preparation method such as the neutral method or the ammonia method. Alternatively, for example, seed particles may be grown by an acidic method or by an ammonia method, which has a faster growth rate, to grow to a predetermined thickness. When growing silver halide grains, the pH%, pAg, etc. in the reaction vessel are controlled, and the amount of silver ions commensurate with the growth rate of silver halide grains is controlled, for example, as described in JP-A No. 54-48521. It is preferable to implant and mix the and halide ions sequentially and simultaneously. Preferably, the silver halide grains according to the present invention are prepared as described above. A composition containing the silver halide grains is referred to herein as a silver halide emulsion. These silver halide emulsions contain 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-aurothiol-3-
Sensitizers such as methylbenzothiazolium chloride or water-soluble salts such as ruthenium, palladium, platinum, rhodium, iridium, etc., specifically ammonium chlorovaladate, potassium chloroaurate and sodium chloroparadate (these Depending on the amount, they act as sensitizers or fog suppressants. It may also be chemically sensitized (eg, in combination with a selenium sensitizer). The silver halide emulsion according to the present invention is chemically ripened by adding a sulfur-containing compound, and before, during, or after this chemical ripening, a nitrogen-containing emulsion having at least one hydroquinotetrazaindene and a mercapto group is produced. It may contain at least one type of heterocyclic compound. The silver halide used in the present invention is mixed with an appropriate sensitizing dye of 5XIO''8 to 3X10-3 per mole of silver halide in order to impart photosensitivity to the desired wavelength range.
Optical sensitization may be achieved by adding molar amounts. 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 a sensitizing dye used in a blue-sensitive silver halide emulsion, for example, West German Patent No. 929.080, US Patent No. 2,231,658, No. 2,493.748, No. 2
, No. 503.776, No. 2,519,001, No. 2,
No. 912,329, No. 3,656,959, No. 3.6
No. 72.897, No. 3,694,217, No. 4,02
No. 5,349, No. 4.046,572, British Patent No. 1,
No. 242.588, Special Publication No. 44-14030, No. 52
-24844 etc. can be mentioned. In addition, examples of sensitizing dyes used in green-sensitive silver halide emulsions include, for example, U.S. Pat.
, No. 072,908, No. 2,739,149, No. 2,
Cyanine dyes, merocyanine dyes, and the like described in British Patent No. 945,763 and British Patent No. 505,979 are representative examples of complex cyanine dyes. Further, as sensitizing dyes used in red-sensitive silver halide emulsions, for example, U.S. Patent No. 2,269,23
No. 4, No. 2,270.378, No. 2,442.710
Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in Japanese Patent No. 2,454,629, No. 2,776.280, and the like. Furthermore, U.S. Patent 2,213.99
No. 5, No. 2.493,748, No. 2,519,001
Cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in German Patent No. 929,080 and the like 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. The photographic material of the present invention may be optically sensitized in a desired wavelength range by a spectral sensitization method using cyanine or merocyanine dyes alone or in combination, if necessary. A typical particularly preferred spectral sensitization method is, for example, the Japanese Patent Publication No. 43-49 on the combination of benzimidazolocarbocyanine and benzoxazolocarbocyanine.
No. 36, No. 43-22884, No. 45-18433, No. 47-37443, No. 48-28293, No. 4
No. 9-6209, No. 53-12375, Japanese Unexamined Patent Publication No. 1983-
No. 23931, No. 52-51932, No. 54-801
No. 18, No. 58-153926, No. 59-11664
6, No. 59-116647, and the like. Further, regarding combinations of carbocyanine having a benzimidazole nucleus with other cyanines or merocyanines, for example, Japanese Patent Publications Nos. 45-25831 and 47-1
No. 1114, No. 47-25379, No. 48-3840
No. 6, No. 48-38407, No. 54-34535,
No. 55-1569, JP-A No. 50-33220, No. 5
No. 0-38526, No. 51-107127, No. 51-
No. 115820, No. 51-135528, No. 52-1
No. 04916, No. 52-104917, and the like. Furthermore, regarding combinations of benzoxazolocarbonanine (oxa-carbocyanine) and other carbocyanines, for example, Japanese Patent Publication No. 44-32753, No. 4
No. 6-11627, JP-A-57-1483, and regarding merocyanine, for example, JP-B No. 48-384.
No. 08, No. 48-41204, No. 50-40662, JP-A No. 56-25728, No. 58-10753,
No. 58-91445, No. 59-116645, No. 5
No. 0-33828 and the like. Regarding combinations of thiacarbocyanine and other carbocyanins, for example, Japanese Patent Publication No. 43-4932
No. 43-4933, No. 45-26470, No. 4
No. 6-18107, No. 47-8741, JP-A-59-
No. 114533, etc., and the method described in Japanese Patent Publication No. 114533, which uses zeromethine or dimethine merocyanine, monomethine or trimethine cyanine, and styryl dye, can be advantageously used. In order to add these sensitizing dyes to the silver halide emulsion according to the present invention, a dye solution such as methyl alcohol, ethyl alcohol, acetone, dimethylformamide, or fluorinated alcohol described in Japanese Patent Publication No. 40659/1984 is used in advance. It is used by dissolving it in a hydrophilic organic solvent. The addition can be made at any time such as at the start of chemical ripening, during ripening, or at the end of chemical ripening of the silver halide emulsion. It can contain compounds that can react with the body to form a pigment. As the above-mentioned couplers that can be used in the present invention, various yellow couplers, magenta couplers and cyan couplers can be used without particular limitation. These couplers may be so-called 2-equivalent type couplers or 4-equivalent type couplers, and in combination with these couplers, it is also possible to use diffusible dye-releasing type couplers. The yellow coupler includes an open-chain ketomethylene compound and a so-called two-equivalent type coupler.
〇-aryl substituted coupler, active point -〇-acyl substituted coupler, active point hydantoin compound substituted coupler, active point urazole compound substituted coupler and active point succinimide compound substituted coupler, active point fluorine substituted coupler, active point chlorine or bromine substituted coupler Coupler, active point -〇-
Sulfonyl-substituted couplers and the like can be used as effective yellow couplers. Specific examples of yellow couplers that can be used include U.S. Pat.
, No. 265,506, No. 3,408.194, No. 3,
No. 551,155, No. 3.582,322, No. 3.7
No. 25,072, No. 3.891.445, West German Patent 1
．． No. 547,868, West German Application Publication No. 2.219,917
No. 2.261,361, No. 2,414,006, British Patent No. 1.425.020, Special Publication No. 1983-107
No. 83, JP-A-47-26133, JP-A No. 48-7314
No. 7, No. 51-102636, No. 50-6341,
No. 50-123342, No. 50-130442, No. 51-. No. 21827, No. 50-87650, No. 52
-82424, 52-115219, 58-9
Examples include those described in No. 5346 and the like. Examples of the magenta coupler used in the present invention include pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based, and indazolo/based compounds. These magenta couplers may be not only 4-equivalent type couplers but also 2-equivalent type couplers like the yellow couplers. Specific examples of magenta couplers include U.S. Patent Nos. 2,600.788 and 2,983.
．． No. 608, No. 3.062゜653, No. 3.127,
No. 269, No. 3,311,476, No. 3,419゜3
No. 91, No. 3,519,429, No. 3,558,31
No. 9, No. 3.582゜322, No. 3,615,506
No. 3.834,908, No. 3.891°・145
No., West German Patent No. 1,810.464, West German Patent Application (o
t, S) 2.408,665, 2,417,9
No. 45, No. 2,418.959, No. 2,424,46
No. 7, Special Publication No. 40-6031, Japanese Patent Publication No. 51-2082
No. 6, No. 52-58922, No. 49-129538, No. 49-74027, No. 50-159336, No. 52-42121, No. 49-74028, No. 50-
No. 60233, No. 51-26541, No. 53-551
22, Japanese Patent Application No. 55-110943, and the like. Further, useful cyan couplers used in the present invention include, for example, phenol couplers, naphthol couplers, and the like. These cyan couplers may be not only 4-equivalent type couplers but also 2-equivalent type couplers like the Yea couplers. Specific examples of cyan couplers include U.S. Pat.
, 434.272, 2.474゜293, 2.
No. 521.908, No. 2.895,826, No. 3.0
34゜892, 3,311,476, 3,45
8.315, 3,476゜563, 3,583
．． No. 971, No. 3.591,383, No. 3.767°411, No. 3.772,002, No. 3.933.4
No. 94, No. 4.004°929, West German patent application (OL
S) No. 2,414,830, No. 2,454,329
No. 48-59838, 51-26034, 48-5055, 51-146827, 5
No. 2-69624, No. 52-90932, No. 58-9
Examples include those described in Japanese Patent Publication No. 5346 and Japanese Patent Publication No. 11572/1983. Couplers such as non-diffusible DIR compounds, colored magenta or cyan couplers, polymer couplers, and diffusible DIR compounds may be used in combination in the silver halide emulsion layer of the present invention and other photographic constituent layers. Non-diffusible DIR compounds, colored magenta or cyan couplers are described in Japanese Patent Application No. 59-193611 filed by the present applicant, and polymer couplers are described in Japanese Patent Application No. 1987-1 filed by the present applicant.
72151 can be referred to. The above coupler that can be used in the present invention is shown in the photograph of the present invention (1'
4. The method of adding the coupler during layer formation is the same as before, and the amount of the coupler added is not limited, but it is 1X per mole of silver.
l0-3 to 5 mol is preferred, more preferably lXl0
-2 to 5X10-'. The silver halide color photographic material of the present invention may contain various other photographic additives. For example, antifoggants, stabilizers, ultraviolet absorbers, color stain inhibitors, optical brighteners, color image fading inhibitors, antistatic agents, as described in Research Disclosure Magazine 17643';
Hardeners, surfactants, plasticizers, wetting agents, etc. can be used. In the silver halide color photographic light-sensitive material of the present invention, the hydrophilic colloids used to prepare the emulsion include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein, and hydroxyl colloids. Examples include cellulose derivatives such as ethyl cellulose derivatives and carboxymethyl cellulose, starch derivatives, single or copolymer synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinylimidazole, and polyacrylamide. Examples of the support for the silver halide photosensitive material of the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with a reflective layer or a reflector, such as glass plates, Examples include polyester films such as cellulose acetate, cellulose nitrate, and polyethylene terephthalate, polyamide films, polycarbonate films, and polystyrene films, and other common transparent supports may also be used. These supports are appropriately selected depending on the intended use of the photosensitive material. For coating the silver halide emulsion layer and other photographic constituent layers used in the present invention, a number of coating methods can be used, such as dipping coating, air doctor coating, curtain coating, and hopper coating. Also, U.S. Patent No. 2,76
It is also possible to use the simultaneous coating method of two or more layers by the method described in No. 1,791 and No. 2,941,898. In the present invention, the coating position of each emulsion layer can be determined arbitrarily. For example, in the case of a full-color photosensitive material for photographic paper, it is preferable to sequentially arrange a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer from the support side. . Each of these photosensitive silver halide emulsion layers may consist of two or more layers. The effects of the present invention are most effective when all of these photosensitive emulsion layers are substantially composed of silver chlorobromide emulsion. In the photosensitive material of the present invention, it is optional to provide an intermediate layer with an appropriate thickness depending on the purpose.
Various layers such as an anti-curl layer, a protective layer, an anti-rayon layer, etc. (14 layers) can be used in combination as appropriate.These constituent layers can be used as an IT binder in the emulsion layer as described above. Hydrophilic colloids that can be used can similarly be used, and various photographic additives that can be included in the emulsion layer as described above can be contained in the layer. The invention will be specifically described, but the embodiments of the invention are not limited thereto.Example 1 The following 8 was prepared on a paper support laminated with polyethylene.
A silver halide color photographic light-sensitive material was prepared by sequentially applying the two layers (hereinafter referred to as sample A of the present invention). Note that the amounts added below are 1rr? unless otherwise specified. Indicates the amount of winnings. Layer 1...30 Exemplary Compounds (II-1) and 1
．． 02 gelatin-containing layer. Layer 2: 1.22 gelatin, 0.35 f (in terms of silver, the same applies hereinafter) blue-sensitive silver chlorobromide emulsion (silver bromide content (mole %), average grain size 0.5 μm) and 0.52 dioctyl phthalate. A layer containing the yellow coupler (Y-1) shown below. Layer 3: Layer containing 0.72 gelatin. (Intermediate layer) Layer 4: 1.22 gelatin, 0.359 green-sensitive silver chlorobromide emulsion (silver bromide content 70 mol%, average grain size 0.5 μm) and 0.32 dioctyl phthalate The magenta coupler shown below at 0,62 f dissolved in
A layer containing M-1). Layer 5: Layer containing 1.22 gelatin. (Intermediate layer) Layer 6... 1.42 gelatin, 0.359 red-sensitive silver chlorobromide emulsion (silver bromide content 70 mol%, average grain size 0.4 μm) and 0.22 dioctyl phthalate The following cyan coupler (C
-1) A layer containing. Layer 7...0.309 tinupin 328 dissolved in 1.02 gelatin and 022 dioctyl phthalate
(manufactured by Ciba Geigy). Layer 8: Layer containing 0.52 gelatin. Yellow coupler (Y-1) C7! Magenta coupler (M-1) CI! -7, hereinafter remainder uncoupler (C-1) Note that bis(vinylsulfonylmethyl) ether is added as a hardening agent to the layers 1.3.5 and 8 in an amount of 0.015f per 12 gelatin, respectively. did. The color vapor prepared in the above manner was designated as Sample B, and then Exemplified Compound (II-1) was removed from Layer 1, and Comparative Sample A was prepared and used in the same manner as above. The color paper produced by the above method was subjected to decomposition exposure or neutral exposure, and then developed using the following processing steps and processing solution. Standard processing steps [1] Color development: 40 seconds at ℃ [2] Bleach-fixing: 10 seconds at 25°C to 35°C in a water-washing alternative stabilizing solution [4] Drying: 60°C to 80°C Approximately 2 minutes Processing solution composition <Color developing solution> (Adjust to the pH shown in Table 1. <Bleach-fixing solution> Washing substitute stabilizing solution) Sakura photodensitometer PDA with blue reflection a degree
-65 (manufactured by Konishiroku Photo Industry) was used for measurement. Furthermore, this sample was subjected to a color development process and then a stop and fixing process, and then the amount of developed silver was measured using a fluorescent X-ray method. Furthermore, the neutrally exposed and treated samples were heated at 85°C and 70%
The sample was stored for 6 weeks in an RH cell, and the rate of decrease in concentration of the highest concentration portion of the sample after storage was determined. The results are summarized as 1 and shown in Table 1 below. -As is clear from Table 1 below, when the concentration of benzyl alcohol in the color developer is high, the development speed is relatively fast even at low pH, but the fading rate of cyan dye after storage at high temperature and high humidity. is large. On the other hand, if the concentration of benzyl alcohol in the color developing solution is low or not added, in the relatively high concentration range of the color developing agent as in the present invention, p
The development speed can be increased by increasing H, and when the compound of the present invention is added, the development speed increases dramatically, and the rate of fading of the cyan dye due to storage is also small. Furthermore, it was found that the compound of the present invention has a high development promoting effect in the high pH region, which is the pH region of the present invention, and showed good results. In addition, when we measured the amount of developed silver in the area with a blue reflection color density of 1.5 for a sample with a pH of 11.0 without the addition of be/zyl alcohol, we found that when the compound of the present invention was added, the amount of developed silver was 0 per color paper. However, in the case where the compound of the present invention was not added, the amount of developed silver was as low as 0.192 per m'' of color paper, and when the compound of the present invention was added, the amount of developed silver was as low as 0.192. It seems that the total development speed was increased because the development of the silver halide was accelerated and occurred prior to the coupling reaction between the coupler and the color developing agent.Example 2 In Example 1 The sample A used was processed according to the same processing steps as in Example 1.However, the concentration of benzyl alcohol in the color developer was O, the pH was 11, and the following Table 2
10 per color development i11 of each of the compounds of the present invention shown in
0m9 was added. The results are shown in Table 2. Table 2 As shown in Table 2 above, even when compound (1) of the present invention was added to the color developing solution, a sufficient accelerating effect was similarly obtained. Compounds of the present invention [-13, [-14, II-16,
[-17,[-,18,■-O,■-24,■Partial,■
Similar effects were obtained for -26, ■-35, ■-36, ■-Seki, and ■-51. Example 3 The same experiment as in Example 1 was carried out except that the benzyl alcohol in the color developer used in Example 1 was changed to the following, and the amount of coloring agent added in the developer was changed as appropriate. I did it. 0-Hydroxybenzyl alcohol logP0.73
7 Clohexanol logP 1.
23 phenyl ether alcohol +ogP1.
36 diethylene glycol monobutyl ether log P0.41 As a result, although sufficient coloring density could be obtained even if the concentration of the coloring agent was low, the storage stability of the dye was extremely poor. Another effect is that the use of these solvents with a logP of 0.4 or more has the disadvantage that the solubility of the processing solution is significantly reduced, but the processing solution of the present invention is easily dissolved and is extremely easy to prepare. Some effects have been confirmed. Therefore, it can be seen that better results can be obtained in the present invention by not using a solvent having a log P of O,=1 or more. Example 4 In addition to samples A and B used in Example 1, instead of the compound i-1 of the present invention used in Example 1, ■-2, 11-4,
Samples to which ■-15, ■-49, and ■-20 were added were prepared and designated as samples C, D, E, F, and G, respectively. After exposing the above sample to light, it was developed according to the same processing steps as in Example 1. The composition of each processing solution was the same as that used in Example 1, but the degree of potassium bromide in the color developing solution was changed as shown in Table 3 below. However, the concentration of benzyl alcohol in the color developing solution was O, the pH was 11, and the results of measuring the maximum density of blue reflection after processing are shown in Table 2.・, Below is Table 3. As shown in Table 3 above, when the concentration of potassium bromide in the color developer increases, the color density decreases in the sample that does not contain the compound of the present invention, but in the case of the sample that does not contain the compound of the present invention. In the sample containing compound qB, there was almost no decrease and sufficient color density was obtained. Therefore, it is suggested that by using the compound (1) of the present invention in the color developing solution of the present invention, high halogen concentration tolerance can be obtained and low replenishment becomes possible. Example 5 Using the same treatment solution as used in Example 11, sample B was treated according to the same treatment steps as in Example 4. however,
The concentration of the color developer iCD-6 (exemplified compound 1-1) in the color developer was varied as shown in Table 1 below, and the maximum blue reflection density of the paper after treatment was measured. As shown in Table 4 above, rapid development speed can be obtained by using the color developing agent of the present invention in an amount of 1.5 Xl0-2 mol or more per 12 and processing at high pH in the presence of the compound of the present invention. Ta. Example 6 An experiment similar to Example 5 was carried out by changing a part of the color developing agent added to the color developing agent used in Example 5 to the compound of the present invention as described in f, and the results were as follows: ' was determined to have a high concentration of 1lll+. Table 5 As shown in Table 5 above, even when the developing agent of the present invention and other developing agents were used in combination, the same effects as when used alone were obtained. Example 7 Using the following three types of color developing agents, the solubility in the color developing solution was measured when the concentration of nobenzyl alcohol (logP=1.1) in the color developing solution was changed.Color developing agent Color developing agent Liquid composition be/zyl alcohol (logP=1.1) 0-15
It changed to m/. Hydroxyamine sulfate 2.01 Potassium bromide 0.62 Sodium chloride 1.02 Potassium sulfite 2. Ottriethanolamine 2,021-hydroquinethylidene-1,1-diphosphonic acid (60% aqueous solution) 1.5ml
! Magnesium chloride 0.32 Potassium carbonate 322 Fluorescent brightener (Keikor-PK-Conc) Add 2 ml of pure water to make 11, and adjust to p)l==IQ,l with 20% potassium hydroxide or 10% dilute sulfuric acid. . As can be seen from the relative solubility curve in Figure 1, the solubility of CD-3 in a color developer is hardly affected by the concentration of benzyl alcohol, but CD-6 has a significantly higher solubility in a system without benzyl alcohol. shows. Therefore, CD-6 has a trace amount of benzyl alcohol or
Alternatively, it can be seen that high Q can be achieved by not adding any additives.

[Brief explanation of drawings]

Figure 1 illustrates the difference in solubility of various color developing agents when the concentration of benzyl alcohol in the color developing solution is changed. Applicant Konishi Roku Photo Industry Co., Ltd. Hand 6' and Total 11↑ Positive 1L1; Processing method: Lhli
Relationship with the case of a person who takes corrective action Patent applicant address: 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Contact address: Konishiroku Photo Industry Co., Ltd., 1-Sakura-cho, Hino-shi, Tokyo, 191 Japan (0425-83-1521)
Patent Department 5, Specifications subject to amendment: 4 G, hlt correct content

Claims (4)

[Claims] (1) In a processing method in which a silver halide color photographic light-sensitive material consisting essentially of silver chlorobromide is processed in three steps of color development, bleach-fixing, and stabilization treatment, the color developer has a pH of 10
．． 3 or more, contains at least 1.5 x 10^-^2 moles of at least one p-phenylenediamine color developing agent represented by the following general formula [I], and has a log P0 of water or a solvent other than water. log PO for volumes of solvent less than .4.
The presence of at least one compound represented by the following general formula [II] within 120 seconds, consisting of a solvent with a volume ratio of 4 or more solvents and 0.003 or less, and development at 30° C. or higher, and within 120 seconds. 1. A method for processing a silver halide color photographic light-sensitive material, characterized in that the material is processed under the following conditions. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, n is an integer from 2 to 4, and R_1 is a carbon number of 1 to
6 alkyl group or hydroxyalkyl group, R_
2 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group, or an alkoxyalkyl group having 1 to 6 carbon atoms, and R_3 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,
Or it is an alkoxy group. General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, X represents a hydrogen atom or an acetyl group, and R_1
' represents an aryl group, R_2', R_3', R_4
' and R_5' each represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group. ] (2) If the color developer is water or a solvent other than water, the log P0
．． Claim 1, characterized in that it consists of less than 4 solvents and does not substantially contain any solvent with a log P of 0.4 or more.
Treatment method described in section. (3) The method for processing a silver halide color photographic material according to claim 1 or 2, wherein the color developer has a pH of 10.5 or more. (4) The method for processing a silver halide color photographic light-sensitive material according to any one of claims 1 to 3, wherein the color developer has a pH of 10.75 or more.