JPS62275255A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the color photograph capable of giving rapidly a stable coloring matter image and having excellent shelf-life by processing the titled material in a presence of an one kind of a specific compd. using a specific color developer and a solvent. CONSTITUTION:In the processing method comprising 3 steps of color-developing, bleach-fixing and stabilizing treatments of the titled material composed substantially silver chlorobromide emulsion, the color developer contains 1.5X10<-2>mol of at least one kind of p-phenylene diamine type developing agent having an alkylsulfoneamidealkyl group binded to an aromatic ring or to an amino type nitrogen atom and has >=10.3 pH. The color developer comprises water and the solvent other than water which has <=0.003vol ratio of the solvent having >=logP 0.4 per the solvent having < logP 0.4. The titled material is processed at >30 deg.C, and <=120sec in the presence of at least one kind of the compd. shown by formulas I-IV wherein X2 and X3 are each sulfur atom or oxygen atom, X1 and X4 are each SH group or OH group.

Description

[Detailed description of the invention]

3. Detailed Description of the Invention [Field of Application of Dou Tojo] The present invention relates to a color development processing method for a silver halide color photographic light-sensitive material (hereinafter referred to as a light-sensitive material). A quick, water-free wash that allows you to obtain images with a stable dye level A and excellent storage stability even in the dark, and can process with a small amount of stabilizing solution without rinsing with water. This invention relates to a stabilization treatment method. [Prior art] Processing of color photosensitive materials basically involves color development, desilvering,
Desilvering involves either a bleaching and fixing process or a bleach-fixing process in which bleaching and fixing are performed in the same bath. Recently, a waterless washing process called a stabilization process has been proposed as an alternative to the water washing process, 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, the photographic emulsion layer generally contains a non-diffusible turnip or color and is developed in a color developing solution. Methods are also known in which M-containing coupling reactions occur in photographic materials. Further, couplers to be incorporated into light-sensitive materials are generally made non-diffusible by being dispersed in a non-water bathing high boiling point organic solvent and then added thereto. This method involves introducing polymeric alkyl side chains into the coupler and the pallast group to make the coupler non-diffusible, which is advantageous in terms of color reproducibility, color purity, image storage stability, etc., and is very commonly carried out. ing. [Problems to be solved by the invention] The color developing solution for processing such light-sensitive materials contains an aromatic whistle primary amine color developing herbal medicine and a poorly soluble monomer solvent (a solvent with a log P of 0.4 or higher). It is also well known that it is contained. The most well-known organic solvents of this type are poorly soluble alcohols, which are used to accelerate the reaction between color developing chemicals and image-forming couplers, i.e., to promote the coupling reaction.
Used to enhance efficacy. This type of alcohol is often referred to as a "development accelerator 1" or "development booster." U.S. Pat. No. 2.304.925 or 3,814.
Benzyl alcohol is particularly useful for this purpose, as seen in US Pat. In order to supply a large amount of the color developing chemical in a short time into the oil spheres in which the coupler is dispersed, and to distribute a relatively large amount of the color developing chemical into the swollen gelatin film than in the bulk of the developer, the color developing agent is The use of poorly soluble alcohols, such as benzyl alcohol, which is thought to promote color development, is due to the high concentration of color developing chemicals in the oil and gelatin in the photosensitive material during processing, resulting in a high residual concentration after processing. This has the drawback of increasing the color density, which is the biggest cause of deterioration in the storage stability of single-dye image preparations. Furthermore, what has made this problem more obvious and emphasized 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 for photosensitive materials to be thoroughly washed. The water-washing process that had previously been used 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 JP-A-58-14834, No. 58.
-105145, 58-134634, 58-
No. 18631, and patent application No. 58-2709, same number 59
Details are described in specifications such as No.-89288. In all of these methods, it is not possible to sufficiently wash the color developing chemical adsorbed to the gelatin film in the light-sensitive material or the color developing chemical distributed in the coupler dispersion oil to reduce the residual concentration, which leads to problems with the storage stability of dye images. is markedly deteriorated. As a completely different problem, poorly soluble solvents such as benzyl alcohol with a logP of 0.4 or more have long caused separate problems 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 chemical will be distributed and dissolved at a high concentration in this portion, resulting in oxidation and the formation of tar after a few days, leading to a serious malfunction. One solution for incorporating benzyl alcohol into the color developer is to use a solvent outside the water body with a togp of less than 0.4, such as ethylene glycol, diethylene glycol, or -
A method of solubilizing benzyl alcohol by adding diethyleneimine, triethanolamine, etc. is known. This method is described in US Pat. No. 3,574,619. Furthermore, the disadvantage of a solvent such as benzyl alcohol is that it deteriorates the solubility of the color developing herbal medicine during the night, so the concentration of the color developing herbal medicine in the color developer cannot be sufficiently increased.
My guess is that development is not being promoted and speeding up is only half-hearted. A particularly serious problem is that when using a developer containing benzyl alcohol, there is a limit to the amount of color developing herbal medicine that can be dissolved in the replenisher, which is advantageous in terms of labor-saving and requires less replenishment. The problem is that it cannot be enriched 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. 58-50532). However, even with this, the speeding up is not sufficient; the processing time is longer than a certain amount of time, and compared to the coupling reaction, only the silver conversion reaction is sped up, so as a result, the color is not enough! ! I can't get the degree. In order to solve these problems, the present inventors
A silver chlorobromide emulsion containing substantially no poorly soluble solvent with P of 0.5 or more and a high alkaline developer of -10.3 or more that contains a specific color developing crude drug at a certain concentration or more. proposed to process color photographic materials consisting of. 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 drug has already reached a sufficient level, so the development speed of silver halide becomes rate-limiting. Unable to obtain sufficient dye density. On the other hand, due to economic and pollution problems, efforts have been made recently to reduce the overflow of the color developing solution. 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, if the amount of replenishment is reduced, the concentration of development inhibiting substances such as ions eluted from the photosensitive material will increase, and the development speed of silver oxide will be suppressed, so it is necessary to avoid the presence of poorly soluble organic solvents. It was found that the decrease in dye density due to short-term treatment was magnified in systems with a high temperature. Furthermore, low replenishment lengthens the stagnation time of the processing solution and increases the concentration of the oxidized product of the color developing herbal medicine, which tends to cause fogging. [Object of the Invention] The object of the present invention is, first, to provide a method for processing color photographic materials that can quickly obtain stable dye images, and second, to eliminate the water washing process and reduce the water quality protect, and
It is an object of the present invention to provide a processing method that does not leave harmful processing chemicals in the processed photographic materials and produces color photographs that are safe and have excellent preservation. E3 includes K, which provides a color photographic processing method in which dissolution is easy and processing solutions can be easily adjusted. Other objects of the invention will become apparent from the description below. [Means for Solving the Problem] The present inventors have conducted extensive studies to achieve the above-mentioned object of the present invention, and have developed a silver halide color photographic light-sensitive material consisting essentially of a silver chlorobromide emulsion. Color development, bleach fixing,
In the processing method in which the stabilization treatment is performed in three steps, the color developing solution contains at least a p-phenylenediamine-based color developing crude drug having an alkylsulfonamide alkyl group bonded to an aromatic nucleus or an amino nitrogen with a P) of 110.3 or more. containing at least 1.5 x 10-2 moles of one type, the solvent is water and the logPo outside the water plate, tOg for the volume of the solvent less than 4
Po, composed of 4 or more solvents, developed at 30 ° C. or higher and within 120 seconds.The following general formula CI], CII
They have found that this can be achieved by treatment in the presence of at least one of I, (I [[] or [■]). (C
H2 Gaff Xa2m1 In the above formula, X2 and X3 each represent a sulfur atom or an oxygen atom, and Xl and X4 each represent a SH group or an OH group. In addition, nl and R2+ R3*m each represent a positive integer from O to 500, and nl + R2+
At least one of n3 is an integer greater than O. General formula [■] In the above formula, R1* R2 is a hydrogen atom, methyl/
+4, an alkyl group such as an ethyl group or a globyl group, or R1
and R2 represent a heterocyclic group which may contain oxygen or nitrogen to form a ring. A2. A3. A4 is an alkyl group such as a hydrogen atom, methyl group, or ethyl group, R3, R4
each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. General formula CID Rs In the above formula, Rs, R6, R, and R8 each represent a hydrogen atom, an alkyl group, an aralkyl group, or a substituted or unsubstituted allyl group. A2 represents a nitrogen atom or a phosphorus atom. R8 is a substituted or unsubstituted alkylene group, and R5 and R
8 may be a substituted or unsubstituted pyridinium group with an open ring. X5 represents an anion group such as a halogen atom, OH1 sulfate group, or nitric acid group. General formula [■] R. In the above formula, Y represents a hydrogen atom, a hydroxyl group, or -N R:z. Also, R9,R,. , R11, R12, and R43 each represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, a carbamoyl group, an acetyl group, or an amine group, and X represents an oxygen atom, a sulfur atom, or /N-R14. , where R14 represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms. Furthermore, t, rn2, and R4 represent Oll, 2, or 3. The present invention uses a specific color developing crude drug and a specific color developing solution...
By combining a specific silver halide emulsion and a specific silver halide emulsion, the coupling rate between the coupler and the color developing chemical can be increased without impairing the image stability of the color image, and by using a specific development accelerator, the coupling rate can be increased. This will be achieved, but will be discussed in detail later. The present inventors used a high-density color developing solution in which the development accelerator specified by the general formula of the present invention is substantially free of poorly soluble organic solvents and contains the color developing crude drug of the present invention at a certain concentration or more. It has been found that in some cases, short-term rapid treatment of 90 seconds or less is particularly effective. The coupling speed between the coupler and the color developing herbal agent is accelerated by processing with a high color developing solution which is substantially free of poorly soluble organic solvents and which contains the color developing herbal agent of the present invention at a certain concentration or more. Furthermore, by using the development accelerator of the present invention, the speed of development of silver halide is likely to be accelerated, and the speed of dye formation is increased when both the coupling speed and the development speed of silver halide are equal. This method was carried out with maximum efficiency, achieved extremely high speed, and achieved 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 decrease in the amount of replenishment, and the greater the amount of accumulation, the more effective it is, so extremely low replenishment is possible. found. Furthermore, as a result of continued studies, the present inventors found that the silver halide emulsion is silver chlorobromide, in particular, the silver bromide content is 90 moles or less, and the film swelling rate T112 of the binder of the emulsion is 20 seconds or less. If this is the case and the color development process is performed for 30 seconds or less, the effects of the present invention can be significantly obtained. That is, we have also discovered the surprising fact that extremely high speed and extremely low replenishment can be obtained without impairing the stability of dye images. Furthermore, the present inventors have found that when the color developing solution does not substantially contain hydroxylamine, it is possible to highly optimize the coupling rate and the development rate of silver halide, resulting in even shorter processing times. It has been discovered that it is possible to do this, and the object of the present invention has been successfully achieved. Specific examples of the general formulas m, cm], [m], IJ) are shown below, but the invention is not limited thereto. Exemplary compounds represented by the general formula [IJ include I-IHO
(CH2)2S(CH2)2S(SH2)20H[2H
O(CH2), 08(CH2)2S(CH2)+oOH
! -3H8O5-0-(CH2CH20)35-8o3
H[4HO(CH2), 5(CH2),. 5 (CH2)
30H1-5HO(CH2), 5(CH2)3S(CH
2) 30H1-6HO(CH2)28(CH,2)20
(CH2)20(CH2)2S(CH2)20H1-7
Ho(aH2cH20)15CH2CH20H[8HO
(CH2)48(CH2)3S(CH2)40H1-1
0HO(CH,2)3S(CH2)28(CH2)30
H■-S I HO(CH2)2S(CH2)20H Exemplary compounds represented by the general formula (Ir) include NH2 H2 H2 H2 Exemplary compounds represented by the general formula [■] lff-1
(]-carboxyethyl)methicyto9decylsulfonium hydroxide m-2(4-sulfobutyl)tumethyldodecylammonium hydroxide ■-3(cal is xymethyl)dimethyloctadecyl ammonium hydroxide 111-4(1-carbyxyethyl)methyl Exemplary compounds of hexadecylsulfonium hydroxide represented by the general formula ["lY] are: H N'H2 CH3 CH3 CH3 CH3 These compounds shown in the present invention are
No. 4, No. 083201242, No. 032950970,
US3706562, 083893862, RD1
It can be easily synthesized according to the method described in No. 5176 and the like. Compounds (I), [11], (III) of the present invention
(ID may be contained in the photosensitive material or in the color developing solution. When added to the photosensitive material, the amount of compound COD added is 1 mole of silver halide. The amount is 0.001 mol to 1 mol, preferably 0.001 mol to 1 mol.
．． 005 mol to 0.5 mol. The compound [■] may be added to each emulsion layer (''# sensitive layer, green sensitive layer, red sensitive layer), or may be added to all emulsion layers.Furthermore, it may be added to the layer adjacent to the emulsion. It may be added to the undercoat layer, the lowest layer in contact with the undercoat layer, or
It is preferable to add it to the bottom layer of the emulsion layer. As for the method of addition, it is preferable to directly disperse it in an emulsion, or to dissolve it in water or alcohol and then disperse it in gelatin or an emulsion. Compounds shown in the present invention [:I) CITE [:I[
r] The amount of CIVI added to the color developing solution is preferably 0.01 g to 50 g/l, more preferably 0105 I to 60 g/l, particularly preferably 0. 1. It is used in the range of F to 309/l. In the present invention, among the above compounds, compounds represented by the general formula CD are more preferably used from the viewpoint of the desired effects of the present invention. Among the compounds represented by the general formula [ID, the compounds represented by (1-1) and (1-11) are particularly preferred from the viewpoint of the desired effects of the present invention. In this specification, the term "substantially silver chlorobromide emulsion" means that it may contain a trace amount of silver iodide in addition to silver chlorobromide, for example, 0.3 molar or less, more preferably 0.3 molar or less. It is contemplated that it may contain up to 1 mole of silver iodide. However, in the present invention, silver chlorobromide emulsions containing silver iodide are most preferred. The present invention will be explained in more detail below. The hydrophilic binder used to coat silver rhodanide in color photographic light-sensitive materials is usually gelatin, but when using high molecular weight polymers, the film swelling rate T is smaller than 20 seconds. The film swelling rate T'A of the binder can be measured according to any method known in the art, for example A, Gree
n and G, 1. P. Levenson, J. photo, set −
It can be measured by using a swellometer (swelling film) of the type described in 20, p. 205-210, and TI7 is the maximum swollen film thickness reached when processed in color development at 30°C for 3 minutes and 30 seconds. The 90th ratio is defined as the saturated film thickness, and is defined as the time required to reach most of the film thickness. The binder of the photographic structured layer used in the silver halide color photographic light-sensitive material of the present invention has a swelling rate T1/2 of 20
The lower limit is 2 seconds or less, and the smaller the better, but the lower limit is preferably 2 seconds or more because if it is too small, the film will not be hardened and failures such as scratches will easily occur. Particularly preferably, the time is 15 seconds or less, most preferably 10 seconds or less. If the time is longer than 20 seconds, the storage stability of the dye 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. The membrane swelling rate TI4 can be adjusted by the amount of hardener used. It is sufficient that at least one of the light-sensitive emulsion layers of the silver halide color photographic light-sensitive material processed according to the present invention consists essentially of a silver chlorobromide emulsion; Preferably, it consists of a silver emulsion. The silver chlorobromide has a silver bromide content of preferably 90 molar or less, less than 70 molar, and 40 molar or more because the smaller the silver bromide mole, the more sufficient dye formation can be obtained even in a short color development time. gives the most favorable result. Furthermore, the smaller the amount of silver coated, the more preferable it is from the standpoint of sufficient dye formation even in a short time; less than 19 i/m", particularly preferably less than 0.8 i/m", and more preferably less than 0.7 i/m".
The maximum effect is obtained when the thickness of the layer is 1 m'' or less.The color development process is performed at 30°C or higher and 120 seconds or less, preferably 33°C or higher and 120 seconds or less, particularly preferably 33°C or higher and 90 seconds or less, most preferably. The processing time is 33°C or higher and 60 seconds or less. If the processing is performed at 30°C or higher and 150 seconds or more, the storage stability of the dye deteriorates.Temperature and processing time are particularly important, and if the processing time exceeds 150 seconds. This is undesirable because the dark brown color of the red dye is markedly reduced.The processing temperature is raised to ensure the storage stability of the dye and to complete the development in a short time, and if it is 30°C or higher and 50°C or lower, It is preferable that the higher the value, the shorter the processing time.
From the viewpoint of storage stability, it is better not to be too high, 33℃
As mentioned above, it is desirable to process at 45° C. or lower. logPo, 4, which is not preferable to be added to the developer in the present invention
The above solvents are aliphatic alcohols, aliphatic glycol ethers, alicyclic alcohols, or aromatic alcohols, and among these, those having 5 to 20 carbon atoms. A specific example is benzyl alcohol Log P 1.1
00-Hydroxynebenzyl alcohol Log
P 0.73 cyclohexanol lo
gP 1.232-benzyloxyethanol
tog P O,41 anisyl alcohol
1. og O,701-Interno#
tog PO, 4 or more phenylethyl alcohol Log P 1.36p-tolylcarbinol Log P 1.36n-butanol togo, 4 or more phenol Ip-hydroxybenzyl alcohol! benzylamine
Examples include 1,) glycol monobutyl ether tog P 0.41. In addition, solvents with a logP of less than 0.4 are mainly those with a carbon number of 0 to 4, such as aliphatic alcohols and organic acids.
o may be less than 4 and is not particularly limited, but specific examples include acetic acid ethanol acetone propionate gulonozenol ethylene glycol diethylene glycol triethylene glycol triethanolamine jetanolamine. The tog P according to the present invention is a value determined from the partition coefficient P of n-octatool/water. The P value is determined by the formula below. The logarithm of the P value thus obtained is the Log P value, and this value has been widely used in the field of concentrated medicine as a measure of fat solubility. L
og p value is ``Chemical Levi, (Chernic
alReview) J Magazine 1971 Vol. 71 No. 5
tOgPoct- in the table described on pages 55 to 613
You can also know by Although it can also be determined by the calculation method described in, for example, Ecochemistry, Vol. 6, pages 3 to 11, it is preferable to use actual measurements, and particularly preferably values measured using an n-octatool. It is preferable to use Particularly preferred p-7 enylenediamine color developing crude drugs in the present invention have at least one alkylsulfonamide alkyl substituent bonded to an aromatic nucleus or amine nitrogen, specifically (2) C2H4SO2NHC
2H48, /C2H5H2 (3) CH3SO2NT (C2H4\, C3H. (4) CH3SO2NHC2HC2H5ゝ[5)
Examples include C2H48 and C'2H5. These color developing agents are hydrochloride, sulfur salt, and phosphate. p-) Used in the form of toluene sulfate and other salts. - of the color developing solution of the present invention is used at 103 or more, preferably 10.50 or more, particularly preferably 10.75 or more, and the upper limit is related to the capricity of the photographic emulsion, but in general, the higher the value, the more preferable it is. Used in the range of .8 to 13. In the present invention, since the solubility of the color developing crude drug in water is extremely low, the amount used is preferably in the range of 1.5 x 10 mol or more, more preferably 1.5 x 10 to 30 x 10 mol. used in range. These alkyl sulfonamide alkyl kfjl of the present invention
Substituted p-p-7-nylenenoamine derivatives are published in Journal of American Chemical Society, Vol. 73, 31.
It can be easily synthesized by the method described in Section 00 (1951). The color developing solution of the present invention has a bromide ion concentration of 5 x 10-5.
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 contains back-sensitive emulsion, back-sensitive emulsion,
In a multilayer color photographic material having three or more layers including each of a green-sensitive emulsion layer and a red-sensitive emulsion layer, when the time A until the film swelling time reaches its maximum, that is, the film swelling rate Tμ, is 20 seconds or less, the maximum value 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, Ty
2 is preferably 20 seconds or less. In the present invention, it is preferable that hydroxylamine is not substantially contained, but hydroxylamine includes free amines, sulfates, oxalates, hydrochlorides, phosphates, carbonates, vinegar If salts, etc. Water-soluble acid addition salts are also included. Further, "substantially not containing" means that the concentration of hydroxylamine in the color developing solution is 0.007 mol or less per 11, but 0 is most preferable. 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 solution according to the present invention. In addition, various other methods including bath treatment,
For example, various treatment methods can be used, such as a spray set in which the treatment liquid is atomized, a web method in which contact is made with a carrier impregnated with the treatment liquid, or a cash-in method using a viscous treatment liquid. It consists of 63 steps including color development, bleach-fixing, and stabilization. Alkali agents such as sodium carbonate, alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali metal rhodanides, polystyrene sulfonic acid, water softeners, ethylene glycol, diethylene glycol, triethanolamine, thickening It is also possible to optionally contain agents, growth promoters, and the like. 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 I-7enyl-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 developing solution is determined by the amount contained in the light-sensitive material and the amount of replenishment of the color developing solution, but the effects of the present invention will be considered. For effective performance, 0.2g
/1 or more is preferable, more preferably 0.5g/
It is 1 or more. Aminopolycaldates and organic phosphonates are mainly used as chelating agents in the developer. 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 10.0, more preferably in the range of 6.3 to 9.5. and particularly preferably p) is in the range of 17.0 to 9.0. As the P)I regulator 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 amount of replenishment of the stabilizing solution of the present invention is 3000ml or less (per m2 of photosensitive material), preferably 500d or less, particularly preferably 5Qml to 5Qml.
It is in the range of 0Qml. The present invention is most effective when the amount of water-washing substitute stabilizing solution refilled into the stabilizing bath is small, and the replenishing amount is 1 to 50 times the amount brought in from the previous bath per unit load of photosensitive material to be processed. The effect of the present invention is particularly significant in a range of 2 to 20 times. The treatment temperature for the stabilization treatment is preferably in the range of 15°C to 60°C, preferably 20°C to 45°C. In addition, from the viewpoint of rapid processing, it is preferable that the processing time be as short as possible, but it is usually 20 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 perform the processing sequentially with a processing time of 50 steps and 7 steps. After the stabilization treatment according to the present invention, no water rinsing treatment is required at all, but rinsing with a small amount of water within a very short time, surface cleaning, etc. can be optionally performed if necessary. When the method for supplying the water-washing substitute stabilizing solution in the stabilization treatment step according to the present invention is a multi-bath countercurrent system, it is preferable to supply it to the rear bath and allow the oats to flow 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 1.002 or more as a result of continuous processing, contamination of the unexposed area will occur. Although there is a tendency for the pollution to become severe, according to the present invention, the occurrence of contamination under such conditions is also significantly reduced. 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 1 to 3, and preferably 9 or less at most. The bleaching agent that can be used in the constant N bleaching solution used in the present invention is a metal complex salt of a monoacid. The complex salt is one in which metal ions such as iron, cobalt, copper, etc. are coordinated with aminoborigonic acid or organic acids such as oxalic acid and citric acid. The most preferred organic acid used to form such a monoacid metal complex is 1,41J Cal? Examples include phosphoric acid. These polycarboxylic acids or amino-licals? The acid may be a prucari metal salt, an ammonium salt or a water-soluble amine salt. Specific examples of these include the following. [1] Ethylenediaminetetraacetic acid [2] Noethylenetriaminebentaacetic acid C3] -I-ethylenediamine-N-(β-oxyethyl) -N,N',N'-triacetic acid [4] Propylenediaminetetraacetic acid [5]
Nitrilotriacetic acid [6] Cyclohexanediaminetetraacetic acid [7]
Iminonoacetic acid [8] Dihydroxyethylglycine citric acid (or tartaric acid)

[9] Ethyl ether diamine tetraacetic acid []0]
Glycol ether diamine tetraacetic acid [111 ethylenediaminetetrapropionic acid 1:12] Phenylenediaminetetraacetic acid [13] Ethylenediaminetetraacetic acid nonodium salt [14] Ethylenediamine/tetraacetic acid tetra(trimethylammonium) salt [5] Ethylenediaminetetraacetic acid tetrasodium salt Salt [16] Diethylenetriaminepentaacetic acid (Ween) sodium salt C17] 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 bleaches are 5-45o,! 9 g/l, preferably 20 to 250 g/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, iron ethylenediaminetetraacetate (I[[)
A bleaching constant M solution containing a complex salt bleach and a small amount of a halide such as ammonium bromide other than the silver halide fixing agent mentioned above, or conversely a composition containing a large amount of a halide such as ammonium bromide. It is also possible to use a special bleach-fix solution consisting of a combination of a bleach-fixing agent No. 1 consisting of an ethylenediaminetetraacetic acid iron(III) complex salt bleaching agent and a large amount of a halide such as ammonium bromide. 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 agent contained in the bleach constant M solution is a compound that reacts with tin halide to form a water-soluble complex salt, such as potassium thiosulfate, sodium thiosulfate, etc., which is used in ordinary fixing processing. Typical examples include thiosulfates such as ammonium thiosulfate, thiocyanates such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, thioureas, and thioethers. These fixatives are used in a range that can dissolve 5g/1 or more, but generally 709 to 250.9/1.
! Use with. The bleach-fix solution contains boric acid, borax, sodium hydroxide,
Various 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 fluorescent whitening agents, antifoaming agents, or surfactants can be contained. Also, preservatives such as hydroxylamine, hydranone, bisulfite adducts of aldehyde compounds, and aminopolycal? An organic chelating agent such as phosphoric acid, a stabilizer such as nitroalcohol or nitrate, an M-organic solvent such as methanol, trimethylsulfamide, trimethylsulfoxide, etc. can be contained as appropriate. The bleach-fix solution used in the present invention includes JP-A-46-280, JP-B No. 45-8505, JP-B No. 46-556, Belgian Patent No. 770,910, JP-B No. 45-8836,
Various whitening accelerators described in JP-A-53-9854, JP-A-54-71634 and JP-A-49-42349 can be added. - of the bleach-fix solution is used at 4.0 or more, but generally Pl'' is used at 15.0 or more p) (9.5 or less, preferably p) (6.0 or more - 8.5 or less More specifically, the most preferable - is processing at a temperature of 6.5 or more and 8.5 or less.The processing temperature is 80°C or less, which is 3°C or more, preferably 5°C or more lower than the temperature of the processing solution in the color developing tank. The photographic constituent layer of the silver halide color photographic light-sensitive material of the present invention preferably contains a dye that is water-soluble or decolorable with a color developing solution ( AI dyes include oxonol dyes, hemioxonol dyes, merocyanine dyes, and azo dyes. Among them, oxonol dyes, hemioxonol dyes, merocyanine dyes, etc. are useful. Examples of AI dyes that can be used include British Patent 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,
2.533,472, 2,956,879, 3,125,448, 3.148,187, 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 are generally used per mole of silver in the emulsion layer.
1) It is preferable to use 2×10 to 5×10 mol, more preferably 1×10 to 1×10 mol. The crystals of the silver halide grains may be normal crystals, twin crystals, or other crystals, and any ratio of [:], O, O] planes to [:1.1.1] planes 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-shell type) in which the inside and outside are different. In addition, these I.
Silver rhodanide 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. In the present invention, core-shell emulsions (substantially monodisperse) are preferred as silver halide grains, which are particularly preferably used in terms of rapid processing and improved stability of image dyes. It may be obtained by any preparation method such as the oxidation method or the ammonia method. Alternatively, for example, seed particles may be grown by an acidic method, and then grown by an ammonia method, which has a high growth rate, to grow to a predetermined size. When growing silver halide grains, the voice inside the reaction vessel, pAg, etc. 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-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 Sugi 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, nonoradium, platinum, rhodium, iridium, etc., specifically ammonium chlorono, radate, potassium chlorooleate and sodium chloroparadate (These kinds of substances act as sensitizers or capri suppressants depending on the amount.) They can be used alone or in appropriate combinations (for example, gold sensitizers and sulfur sensitizers in combination, gold sensitizers, etc.). Chemical sensitization may be carried out by using a combination of a sensitizer and a selenium sensitizer, etc.). The silver halide emulsion according to the present invention is subjected to chemical ripening by adding a sulfur-containing compound, and the silver halide emulsion containing at least one human 90-xytetrazaindene and a mercapto group is prepared before, during, or after the chemical ripening. It may also contain at least one nitrogen heterocyclic compound. The silver halide used in the present invention is treated with an appropriate sensitizing dye in order to impart photosensitivity to the desired wavelength range.
5 X 10-8 to 3 X per mole of silver rhodanide
Optical sensitization may be carried out by adding 10 −3 mol. Various sensitizing dyes can be used, and each sensitizing dye can be used alone or in combination of two or more. Examples of the sensitizing dyes that can be advantageously used in the present invention include the following. That is, as sensitizing dyes used in blue-sensitive silver halide emulsions, for example, Japanese Patent No. 929,080 and U.S. Pat.
, 231.658, 2,493,748, 2,
No. 503.776, No. 2,519,001, No. 2,9
No. 12,329, No. 3,656,959, No. 3,67
No. 2,897, No. 3,694,217, No. 4,025
, No. 349, No. 4,046,572, British Patent 1, 2
No. 42,588, Special Publication No. 44-14030, No. 52-
Examples include those described in No. 24844 and the like. In addition, as sensitizing dyes used in green-sensitive silver halide emulsions, for example, U.S. Pat.
No. 072,908, No. 2,739,149, No. 2,9
Representative examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 45.763, British Patent No. 505.979, and the like. Further, as a sensitizing dye used in a red-sensitive silver halide emulsion, for example, U.S. Pat.
No. 2,270,378, No. 2,442,710, No. 2,454,629, No. 2,776,280, etc. This can be cited as a representative example. Furthermore, U.S. Patent Nos. 2,213,995 and 2,493
, No. 748, No. 2,519,001, West German Patent No. 929
Cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in , No. 080, etc. can be advantageously used in green-sensitive silver halide emulsions or red-sensitive silver rhodanide 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 example of a particularly preferred spectral sensitization method is Japanese Patent Publication No. 43-493 concerning the combination of benzimidazolocal cyanine and benzoxazolocardocyanine.
No. 6, No. 43-22884, No. 45-18433,
No. 47-37443, No. 48-28293, No. 49
No.-6209, No. 53-12375, JP-A-52-2
No. 3931, No. 52-51932, No. 54-8011
No. 8, No. 58-153926, No. 59-116646
No. 59-116647 and the like. Further, regarding the combination of carbocyanine with M benzimidazole nucleus and other cyanine or melonanine, for example, Japanese Patent Publication Nos. 45-25831 and 47-11 disclose
No. 114, No. 47-25379, No. 48-38406
No. 48-38407, No. 54-34535, No. 55-1569, JP-A-50-33220, No. 50
-38526, 51-107127, 51-1
No. 15820, No. 51-135528, No. 52-10
No. 4916, No. 52-104917, and the like. Further, regarding combinations of penzoxazolocalgecyanin (oxa-carbocyanine) and other carbocyanins, for example, Japanese Patent Publication No. 44-32753, No. 46
-11627, Japanese Unexamined Patent Publication No. 1483/1983, and Japanese Patent Publication No. 38408/1983 regarding merocyanine.
No. 48-41204, No. 50-40662, JP-A No. 56-25728, No. 58-10753, No. 5
No. 8-91445, No. 59-116645, No. 50-
No. 33828 etc. are mentioned. Regarding the combination with thiacargecyanine and other carbocyanins, for example, Japanese Patent Publications Nos. 43-4932, 43-4933, 45-26470, 46
-18107, No. 47-8741, JP-A-59-1
The method described in Japanese Patent Publication No. 14533, etc., and further using 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 may be made at any time such as at the start of chemical ripening of the silver halide emulsion, during ripening, or at the end of ripening, and in some cases, it may be added at a step immediately before coating the emulsion. Each of the silver halide emulsion layers according to the present invention can contain a coupler, that is, a compound capable of reacting with an oxidized product of a one-color developing drug to form a dye. 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 may be a closed ketomethylene compound or a so-called 2-equivalent type coupler.
〇-aryl substituted Kaglar, 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. 107]-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. 51-21827, No. 50-87650, No. 52-
No. 82424, No. 52-115219, No. 58-95
Examples include those described in No. 346 and the like. Examples of the magenta coupler used in the present invention include pyrazolone-based, pyrazolotriazole-based, birazolinobenzimimezole-based, and indasilone-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. Pat. 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. 3,891,445, West German Patent No. 1,810,464, West German Patent Application (On
, S) No. 2,408,665, No. 2,417,94
No. 5, No. 2,418.959, No. 2,424,467
No., Special Publication No. 40-6031, Japanese Patent Publication No. 51-20826
No. 52-58922, No. 49-129538,
No. 49-74027, No. 50-159336, No. 5
No. 2-42121, No. 49-74028, No. 50-6
No. 0233, No. 51-26541, No. 53-5512
No. 2, Japanese Patent Application No. 110943/1987, 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 yellow couplers. Specific examples of cyan couplers include U.S. Pat. Nos. 2,369,929 and 2.
, No. 434.272, No. 2,474,293, No. 2,
No. 521,908, No. 2,895,826, No. 3,0
No. 34,892, No. 3,311,476, No. 3,45
No. 8,315, No. 3,476,563, No. 3,583
, No. 971, No. 3,591,383, No. 3,767,
No. 411, No. 3,772,002, No. 3,933,4
No. 94, No. 4,004,929, West German patent application (OL
S) 2,414.830, 2,454,329, JP 48-59838, JP 51-26034,
PI No. 48-5055, No. 51-146827, No. 52-69624, No. 52-90932, No. 58-
Examples include those described in Japanese Patent Publication No. 95346, Japanese Patent Publication No. 11572/1983, and the like. 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 % Application No. 193611 of the present applicant, and polymer couplers are described in Japanese Patent Application No. 59-1 of the present applicant.
72151 can be referred to. The method of adding the above coupler that can be used in the present invention to the photographic constituent layer of the present invention is the conventional method 9, and the amount of the above coupler added is not limited, but per mole of silver, 91X]O
-5 to 5 mol, more preferably 1 x 10-2
˜5×10−′. The silver halide color photographic material of the present invention may contain various other photographic additives. For example, antifogging agents, stabilizers, ultraviolet absorbers, color stain inhibitors, fluorescent whitening agents, color image fading inhibitors, antistatic agents, hardeners, and interfaces are described in Research Disclosure No. 7643. Activators, plasticizers, wetting agents, etc. can be used. In the silver halide color photographic light-sensitive material of the present invention, the hydrophilic colloids used for preparing the emulsion include 6,
Gelatin, derivative gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein,
Examples include any of cellulose-conducting conductors such as hydroxyethyl cellulose derivatives and carboxymethyl cellulose, starch-conducting conductors, single or copolymer synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinylimidazole, and polyacrylamide. Supports for the silver halide color photographic light-sensitive material of the present invention include, for example, baryta paper, polyethylene-coated paper, paper propylene synthetic paper, transparent supports provided with a reflective layer or in combination with a reflector, such as glass plates, cellulose Examples include polyester films such as acetate, cellulose nitrate, or 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 I-rodanide emulsion layer and other photographic constituent layers used in the present invention, various coating methods can be used, such as decoating coating, air doctor coating, curtain coating, and hopper coating. US Patent 2,76
1,791 and 2,941,898 can also be used to simultaneously coat two or more layers. 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, a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a red-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer are arranged sequentially from the support side. is preferred. Each of these light-sensitive silver halide emulsion layers may consist of two or more layers, and the effects of the present invention are achieved when all of these light-sensitive emulsion layers are substantially free from silver chlorobromide emulsion. It's large. In the photosensitive material of the present invention, it is optional to provide an intermediate layer with an appropriate thickness depending on the purpose, and a filter layer,
They can be used in appropriate combinations as all constituent layers of various layers such as an anti-curl layer, a protective layer, and an anti-rage layer. Hydrophilic colloids that can be used in the emulsion layers as described above can be used as binders in these constituent layers. Further, the layer can contain various photographic additives that can be contained in the emulsion layer as described above. Examples are shown below, but it goes without saying that the present invention is not limited to these Examples. The present invention will be specifically described below with reference to Examples, but the embodiments of the present invention are not limited thereto. Example 1 1 below 8 on a polyethylene laminated paper support
A silver halide color photographic light-sensitive material was prepared by applying two layers to the neck plate (hereinafter referred to as sample A of the present invention). In addition,
Unless otherwise specified, the amounts added below indicate the amounts per 1 m"A. Layer 1: A layer containing 1.0.!ir of gelatin. Layer 2: A layer containing 1.2 g of gelatin. Gelatin, 0.4 F, blue-sensitive silver chlorobromide emulsion (silver bromide content 80 molar, average grain size 0.5 μm) (in terms of silver, the same applies below) and 0.5 g of dioctyl phthalate) K !Understood., a layer containing yellow coupler (Y-1) shown below of sog. Layer 3... A layer containing 0.7 g of gelatin. (Intermediate layer) Layer 4... A layer containing 1.2 g of gelatin. Gelatin, 0.41 green-sensitive silver chlorobromide emulsion (silver bromide content 70 molar, average grain size 0.5
μm) and the 1-zenta coupler shown below (M-
A layer containing 1). Layer 5: A layer containing the gelatin of 1.2.9. (Intermediate layer) Layer 6: 1.4 g of gelatin, 0.31.9 g of red-sensitive silver chlorobromide emulsion (silver bromide content of 70 mol or more, average grain size of 0.4 μm) and 0.21 g of gelatin 0.45.9 cyan coupler shown below dissolved in dioctyl phthalate (
A layer containing C-1). Layer 7: 0.30 g Tinupin 328 dissolved in 1.0 g gelatin and 0.2 g dioctyl phthalate.
(Ciba Geigy). Layer 8: A layer containing 0.51 gelatin. Yellow coupler (Y-1) t Magenta coupler (M-1) t L Cyan coupler (C-1) t Bis(vinylsulfonyl)thyl) as a hard AI agent
Ether was added to layers 1.3.5 and 8 at a rate of 0.015.9 per gram of gelatin, respectively. Color E.2- exploded in the above method was subjected to decomposition exposure or neutral exposure, and then developed using the following processing steps and processing solution. Base ring treatment step [1] Color development 38°C 40 seconds [2] Bleach-fixing 38°C 50 seconds [3] Treatment with water washing substitute stabilizer 25°C to 35°C 50 seconds [4] Drying 60 to 80°C approximately 2 minutes Processing solution composition (color developing solution) The color developing solution prepared as described above was continued as B, and the exemplified compound (1-1) was removed from the color developing solution, and the other conditions were the same as the comparative color developing solution A. was created and used. <Bleach-fix solution> Washing substitute stabilizer> Measure the true color reflection density of the highest density part of each sample, where only yellow was developed by decomposition exposure after processing, using a Sakura photodensitometer PDA-6.
5 (manufactured by Konishiroku Photo Industry ■). Further, this sample was subjected to a color development process and then a stop and fixing process, after which the amount of developed silver was measured using a fluorescent X-ray method. Additionally, neutral exposed and processed samples were heated to 85°C. The sample was stored for 6 weeks under 70% RH, and the concentration reduction rate of the highest concentration portion of the sample after storage was determined. The results are summarized in Table 1 below. As is clear from Table 1, when the concentration of pennol alcohol in the color developer is high, the development speed is relatively fast even at low pH, but the fading rate of the cyan dye after storage is high. On the other hand, color development yI! When the concentration of benzyl alcohol in the solution is lowered or not added, the concentration of the color developing crude drug is relatively high concentration range as in the present invention, and the development speed can be increased by increasing P)'I. When the compound of the present invention is added, the development speed is dramatically increased, 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 effect of accelerating development in the high range, which is the vocal range of the present invention, and showed good results. In addition, when we measured the amount of developed silver in the area where the blue coloring density was 1.5 for a sample with pH 11.0 without the addition of pennol alcohol, it was found that when the compound of the present invention was added, it was 90.25 g per 1 m2 of color paper. However, when the compound of the present invention was not added, the developed silver was as low as 0.22.9%, and when the compound of the present invention was added, the developed silver It is thought that the overall development speed was increased because the development of the silver oxide was accelerated and occurred prior to the coupling reaction between the coupler and the color developing herbal medicine. Example 2 The sample used in Example 1 was treated according to the same treatment steps as in Example 1. However, the concentration of benzyl alcohol in the color developing solution was set to 0, - was set to 11, and the compounds of the present invention shown in Table 2 below were added as shown in Table 2 per color developing solution. The results are shown in Table 2. Table 2 As shown in Table 2 above, even when the compound of the present invention was added to the color developer, a sufficient accelerating effect was similarly obtained. Moreover, the compound 1-2.1-8゜If-1,I[-3,
Similar effects were obtained with I[-2, ff-1, and IV-5. Example 3 The same experiment as in Example 1 was conducted except that the benzyl alcohol in the color developing solution used in Experimental Example 1 was changed to the following, and the amount of color herbal medicine added in the developer was changed as appropriate. . 0-Hydroxybenzyl alcohol Log P
0173 cyclohexano-/I/lo
g P 1.23 Phenyl ether alcohol Lo
g P 1.36 Diethylene glycol monobutyl ether Log P 0.41 As a result, even if the concentration of the color herbal medicine was low, sufficient color density could be obtained, but the storage stability of the dye was extremely poor. . Another effect is that the use of these solvents with a Log P of 0.4 or more has the disadvantage that the solubility of the processing solution is significantly poor, but the processing solution of the present invention is easily dissolved and is extremely easy to prepare. This effect was confirmed. This is p log
It can be seen that better results can be obtained in the present invention if a solvent with P of 0.4 or more is not used. Example 4 In addition to color developing solutions A and H used in Example 1, l-11 and I
-5, I[-3, I[[-3,
It was set as G. After exposing the sample solution used in Example 1, development processing was performed according to the same processing steps as in Example 1. The composition of each treatment solution was the same as that used in Example-1, but the concentration of potassium bromide in the coloring ring gI solution was changed as shown in Table 3 below. However, the concentration of benzyl alcohol in the color developing solution was set to 0, - was set to 11, and the maximum blue reflection density after processing was measured. The results are shown in Table 2. Table 3 As shown in Table 3 above, as the concentration of potassium bromide in the color developer increases, in the sample not containing the compound of the present invention,
Although a decrease in color density occurred, in the sample containing the compound of the present invention, there was almost no decrease and a sufficient color density was obtained. Therefore, it is suggested that by using the compound of the present invention in the color developing solution of the present invention, high halogen concentration tolerance can be obtained and low replenishment can be achieved. Example 5 A sample similar to that used in Example 4 was used and processed according to the same processing steps as in the color developer of Example 4. However, the concentration of color developer crude drug CD-3 in the color developer was varied as shown in Table 4 below, and the maximum density of the paper after treatment was measured. Table 4 As shown in Table 4 above, rapid development speed can be obtained by using 1.5X]O mol or more of the color developing crude drug of the present invention per liter and processing at high temperature in the presence of the compound of the present invention. Obtained. Example 6 The solubility in the color developer solution of Example 1 was measured using the following five types of color developer crude drugs. Color developing crude drug H5C2C2H5 H2 (B) H2 C2H4NHsO2CH3 H5C2\/ ■) H5C2'', N, c・H・OH (乃 H5C2\/C2H40CH3 As a result, pJ
The solubility at 411.0 is ■CD-3>CD-6) CD
-4> CD-1) CD-2@. Especially C
It was found that D-3 has a unique effect in that the solubility significantly increases at pH of 10.3 or higher. In addition to these, it was found that CD-3 and CD-6 can be highly concentrated by increasing the concentration, and CD-3 is particularly preferred. On the other hand, it was found that the solubility of color developing crude drugs other than CD-3 did not improve even if the - concentration was increased. Example 7 Using the color paper used in Example 1, processing was performed according to the same processing steps as in Example 1. However, color developer B was used, the concentration of benzyl alcohol was O, and the concentration of human 90xylamine sulfate was changed as shown in Table 5 below. Further, the color development time was set to 30 seconds. Table 5 1 10.0 3 3.7 0.672 #1
1.2 0.66 3 N 0.5 0.6 0.684 # 0
0.0 0.67 5 10.2 3 3.7 0.826 tr
l 1.2 0.827 If O,50,6
0,83 8tt OO,00,81 910,533,71,60 10N 1 1.2 1.63 11 /IO,50,61,86 12# OO,02,13 1311,033,71,88 14111,21 ,90 15# 0.5 0.6 2.26 16 1 0 0.0 2.38 17 12.0 3 3.7 2.3118 N
1 1.2 2.3219 p O,50,6
2,58 20If 0 0.0 2.60 As shown in Table 5 above, if the treatment is performed for a shorter time, the
In the pH range, the color density does not change even if the concentration of hydroxylamine sulfate is changed, but at pH 10.5 or higher, the color density improves by reducing the concentration of hydroxylamine sulfate to 0.5 g/l or less. Furthermore, more favorable results were obtained by setting the concentration to 0. Patent applicant Roku Konishi Photo Industry Co., Ltd. Procedural amendment (method) % formula % 2. Name of the invention Processing method for silver halide color photographic light-sensitive materials 3. Relationship with the case where the amendment is made Patent applicant address Shinjuku, Tokyo Konishiroku Photo Industry Co., Ltd., 1-26-2, Nishi-Shinjuku, 1-chome, Nishi-Shinjuku, 1-26-2, Sakura-cho, Hino-shi, Tokyo 191 Japan (0425-83-1521)
Patent Department 5, Specification to be amended 6: Engraving of the specification of the contents of the amendment

Claims (6)

[Claims] (1) A silver halide color photographic light-sensitive material consisting essentially of a silver chlorobromide emulsion is subjected to color development, bleach-fixing, and stabilization processing.
In the processing method in which the color developing solution is
At least one p-phenylenediamine-based color developing crude drug having an alkyl sulfonamido alkyl group bonded to the aromatic nucleus or to the amino nitrogen with an alkyl sulfonamido alkyl group of at least 10.3 and at least 1.5
×10^-^2 mole content, solvent is water and log of other than water
It is composed of a solvent with a log P0.4 or higher solubility ratio of 0.003 or less to the volume of the P0.4 or lower solvent, and development is performed at 30°C or higher and within 120 seconds using the following general formula [
1. A method for processing a silver halide color photographic light-sensitive material, characterized in that it is processed in the presence of at least one of [I], [II], [III], or [IV]. General Formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the above formula, X_2 and X_3 each represent a sulfur atom or an oxygen atom, and X_1 and X_4 each represent an SH group or an OH group. Also n_1, n_2, n_3, m_
1 represents a positive integer from 0 to 500, n_1,
At least one of n_2 and n_3 is an integer greater than 0. General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the above formula, R_1 and R_2 are each a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, or R_
1 and R_2 represent a heterocyclic group which may contain oxygen or nitrogen to form a ring. A_2, A_3 and A_4 each represent a hydrogen atom, an alkyl group such as a methyl group or an ethyl group, or a halogen atom such as chlorine, fluorine or bromine. A_1
represents a hydroxyl group or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. However, R_3 and R_4 each represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. General formula [III] ▲ Numerical formulas, chemical formulas, tables, etc. are included▼ In the above formula, R_5, R_6, R_7, and R_8 each represent a hydrogen atom, an alkyl group, an aralkyl group, or a substituted or unsubstituted allyl group. A_2 represents a nitrogen atom or a phosphorus atom. Further, R_8 is a substituted or unsubstituted alkylene group, R_5 and R_8 form a ring, and may be a substituted or unsubstituted pyridinium group. X_5 is a halogen atom, OH
, represents an anionic group such as a sulfate group or a nitrate group. General formula [IV] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the above formula, Y is a hydrogen atom, a hydroxyl group, or ▲ Numerical formula, chemical formula,
There are tables etc. Represents ▼. Also, R_9, R_1_0
, R_1_1, R_1_2, and R_1_3 each represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, a carbamoyl group, an acetyl group, or an amino group, and X represents an oxygen atom, a sulfur atom, or >N-R_1_4. , where R_1_4 represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms. Furthermore, l, m_2, and n_4 represent 0, 1, 2, or 3. (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 film swelling rate T1/2 of the emulsion film (binder) of the silver halide color photographic material is 20 seconds or less, and the color development treatment is performed at 30°C or higher for 20 seconds or more and 90 seconds or less. A method for processing a silver halide color photographic light-sensitive material according to any one of claims 1 and 2. (4) A method for processing a silver halide color photographic material according to any one of claims 1 to 3, characterized in that the color developer has a pH of 10.5 or more. (5) The method for processing a silver halide color photographic material according to any one of claims 1 to 4, wherein the color developer has a pH of 10.75 or more. (6) A method for processing a silver halide color photographic material according to any one of claims 1 to 5, characterized in that the color developing solution does not substantially contain hydroxylamine.