JPS62105139A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To maintain always adequate photographic performance for a long period of time without receiving the change in the concn. of bromide ions even if a photosensitive material is processed at a low rate of replenishment by subjecting the material to a developing process for <=150sec at >=30 deg.C by using a color developing soln. contg. an N-hydroxyalkyl substd.-p-phenylenediamine deriv. CONSTITUTION:The resultant dye concn. hardly decreases even if the concn. of the bromide ions increases only when the N-hydroxyalkyl substd.-p- phenylenediamine deriv. is used for the color developing agent in the stage of developing a photographic element for which an emulsion essentially consisting of specific silver halide, i.e., chlorobromide is used. The stability of the dye image is not spoiled if such photographic element is subjected to quick color development in >=30 deg.C and <=150sec range. At least one layer of a green-sensitive silver halide emulsion layer and red-sensitive silver halide emulsion layer are provided between the blue-sensitive silver halide emulsion layer and base in order to solve the problem that the specified photographic performance is not obtainable.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a color development processing method for a silver halide glass photographic light-sensitive material (hereinafter referred to as a photographic element), and in particular, it relates to a method for developing a silver halide glass photographic light-sensitive material (hereinafter referred to as a photographic element). A new processing method that reduces the dependence on bromide ion concentration fluctuations caused by the process and the processing temperature and pH value dependence of color developing solutions, does not impair rapidity, and produces dye images with excellent chromaticity and long shelf life. In particular, it relates to a processing method that requires a small amount of replenishment and has high processing stability.

[Prior Art] Processing of photographic elements basically consists of two steps: color development and desilvering, with desilvering consisting of a bleaching and fixing step or a bleach-fixing step. In addition to this, rinsing treatment, stabilization treatment, etc. are added as additional treatment steps.

In color development, the exposed silver halide is reduced to silver, and at the same time the oxidized aromatic primary amine developing agent reacts with the coupler to form a dye. During this process, halogen ions generated by reduction of silver halide are eluted into the developer and accumulated. Additionally, components contained in the photographic element, such as inhibitors, are also eluted and accumulated in the color developer.

In the desilvering step, the silver produced by development is bleached by an oxidizing agent, and then all silver salts are removed from the photographic element as soluble silver salts by a fixing agent. A one-bath bleach-fixing method is also known in which the bleaching step and the fixing step are carried out simultaneously.

In color developing solutions, development inhibiting substances accumulate as the photographic element is developed as described above, but on the other hand, the color developing agent and benzyl alcohol are consumed or accumulated in the photographic element and taken out, and the concentration of these components decreases. Therefore, in a developing method in which a large amount of photographic elements are continuously processed using an automatic processor, etc., the components of the color developing solution are kept within a certain concentration range in order to avoid changes in the development finish characteristics due to changes in component concentration. A means is needed to maintain it. As such a method, a method of replenishing a replenisher is usually used to supplement the missing components and dilute the unnecessary increased components.

The replenishment of this replenisher inevitably results in large amounts of overflow, which are discarded, making this method a major economic and pollution problem. Therefore, in recent years, in order to reduce the amount of overflow liquid, a so-called concentrated low replenishment method has been widely used, in which these replenishers are concentrated and refilled in small amounts, and another method is to add a regenerant to the overflow liquid and use it again as a replenisher. It has been proposed and put into practical use.

[Problems to be Solved by the Invention] All of these methods substantially reduce the amount of replenishment. If the amount of replenishment is extremely reduced, the concentration of organic inhibitors and halogen ions eluted into the developer will be subject to large changes due to even a slight error in the amount of replenishment.
It also becomes more susceptible to the effects of concentration due to evaporation, and the concentration of the fatigue deposits mentioned above usually increases. For example, when the halogen ion concentration increases, the development reaction is suppressed, and the leg of the characteristic curve is further suppressed. This causes the problem of high contrast. To avoid this, halogen ions are removed from the overflow solution using an ion exchange resin or electrodialysis, and a regenerating agent is added to compensate for the missing components generated during development and lost during regeneration processing, and the solution is regenerated as a replenisher. A method is proposed for use.

These regeneration and concentrated low replenishment methods using ion-exchange resins and electrodialysis are susceptible to fluctuations in bromide ion concentration due to non-emissions and regeneration operations. The difference between the beginning and weekends when the number of orders decreases, and the high season and the off-season is a maximum of 1:5 difference, and the composition of the processing solution is also affected by evaporation and differences in the amount of replenisher. There are disadvantages that make them different.

Therefore, low-replenishment processing and regeneration methods require efforts to quantitatively analyze the components and make the composition constant each time they are regenerated. Therefore, it is difficult to implement these regeneration processing and low-replenishment processing in photo labs, mini-labs, etc. without special skills. There are many things like that.

These problems are primarily due to changes in bromide ions, which are development inhibitors, such as reducing the amount of bromide that accumulates by reducing the amount of silver bromide in the photographic element, or reducing the amount of bromide ions that accumulate due to evaporation or replenishment. It has also been proposed to reduce fluctuations in the concentration of bromide ions due to errors in the amount (see Japanese Patent Application Nos. 59-173189 and 59-205540, etc.).

It is also presumed that these problems can be solved by improving developability, for example by reducing the average grain size of silver halide in the photographic element or by lowering the amount of coated silver. certain 3-methyl-4-
In a color developer using amino-N-ethyl-N-β-methanesulfonamide ethylaniline, even though the developability was improved, the processing stability did not improve as much as expected, and bromide in the developer It is affected by ion concentration.

However, it is an important issue to improve processing stability while shortening processing time.

Conventionally, in color paper processing consisting essentially of silver chlorobromide emulsion, color development was performed at 33°C for 3 minutes and 30 seconds - bleach-fixing 33
°C, 1 minute and 30 seconds - 3 minutes of water washing (or 3 minutes of stabilization) - drying. The total processing time is generally about 8 minutes, but the strong demand of the times is the above-mentioned low replenishment from an economic point of view, but short processing times are also strongly requested from the viewpoint of shortening delivery times. ing.

However, as described above, speeding up the process and stabilizing the process or reducing replenishment are contradictory issues and can be said to be a trade-off relationship.

That is, if the replenishment level is low, the concentration of bromide ions, which are inhibitors, and the concentrations of sulfur compounds and mercapto compounds, which are emulsion stabilizers, increase, impairing rapidity and processing stability.

However, various measures have been taken to speed up color development. In particular, the above-mentioned developing agents, which have traditionally been used as crude drugs most suitable for developing silver chlorobromide emulsions, penetrate slowly into photographic elements, and various penetrants have been investigated to speed up the penetration of color developing agents into photographic elements. For example, a method of adding benzyl alcohol to a color developer to accelerate color development is widely used. However, with this method, 33
A method of increasing the pH of a 0 color developing solution, which had the drawback of not only not developing sufficient color unless it was treated at ℃ for 3 minutes or more, but also being easily affected by the subtle bromide ion concentration. It is also known that when the pH reaches 10.5 or higher,
The problem is that the oxidation of the color developing agent becomes extremely rapid, and because there is no suitable buffer solution, it becomes susceptible to pH changes, making it impossible to obtain stable photographic properties, and increasing the dependence on processing time. There was a point.

It is also known to increase the activity by increasing the color developing agent in the color developing solution, but the color developing agent is very expensive, resulting in a relatively expensive processing solution, and at the same time, the main agent is difficult to dissolve in water and tends to precipitate. It also causes instability and cannot be used practically.

On the other hand, in order to speed up color development, a method is known in which a color developing agent is incorporated into a photographic element in advance6.For example, a method is known in which a color developing agent is incorporated in the form of a metal salt. (U.S. Pat. No. 3,719,492), but it is known that this method has disadvantages in that the photographic element has poor shelf life and is prone to fogging before use and also being prone to fogging during color development.

Furthermore, in order to inactivate the amine part of the color developing agent,
For example, a method of incorporating a color developing agent into ship salt (U.S. Pat. No. 3,342,559, Re5earch
DiscloSure, 1978 No. 151
59) is also known, but it is known that these methods have the disadvantage that color development cannot be started until after the color developing agent has been alkaline hydrolyzed, and the color development is rather delayed.

Furthermore, when a color developing agent is directly incorporated, the color developing agent is unstable, which causes the emulsion to fog during storage, and the emulsion film quality becomes weaker, resulting in various processing problems. It is known.

Furthermore, it is known that 3-pyrazolidones are added to a black and white developer containing a developer such as hydroquinone to accelerate development (for example, F, A).

Written by Mason, Photographic Place
ssingChemistry pages 103-107, Fo
Cal Press, 1888), and the fact of incorporating this compound into photographic elements is described in British Patent No. 767.704; It is incorporated into light-sensitive materials or photographic elements for reversal, and its purpose is to promote only black-and-white development. 3-pyrazolidones are included in photographic elements in order to prevent a decrease in sensitivity in the unexposed state of photographic elements containing two-equivalent magenta couplers, but these techniques have been used to convert one-color development processing into low-replenishment processing. It is not suitable as a rapid method of stabilizing with .

Further, as a conventionally known method of accelerating color development using an accelerator, US Pat. No. 2,950,970;
No. 2,515,147, No. 2.496.803, No. 4,038.075, No. 4.119.4 [No. 12,
British Patent No. 1,430,998, British Patent No. 1,455,413
No. 53-15831, 55-62450, 55-62451, 55-62452, 5
No. 5-62453, Special Publication No. 51-12322, No. 55
Compounds such as those described in No. 49728 have been investigated, but most of them have insufficient accelerating effect, and compounds that show a high accelerating effect not only alleviate the drawback of forming fog. This method was not suitable as a method for improving processing stability.

Furthermore, the provision of a substantially non-photosensitive silver halide emulsion layer in a photographic element to facilitate development was disclosed in Japanese Patent Application Laid-Open No.
No. 23225, No. 56-14236, British Patent 1.3
No. 78.577, OLS 2. It is known as No. f122,922, etc., and its function is to adsorb development inhibiting substances such as unnecessary halogens released during development and unnecessary leaving groups of DIR couplers, and actively promote development. The effect of promoting development was small, and although it was effective against fluctuations in iodide ion concentration, no processing stabilization effect was obtained at all against fluctuations in bromide ion concentration.

On the other hand, the rate of color development varies depending on the type of phenylenediamine derivative used and is said to depend on the redox potential. Among these color developing agents, N
, N-diethyl-p-phenylenediamine sulfur salt and 3-
N-alkyl-substituted color developing agents with low water solubility, such as methyl-4-amino-N,N-diethylaniline hydrochloride, have high development activity and can be speeded up, but the coloring dye tends to fade after processing. is known to be low and undesirable. On the other hand, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline is said to be preferable because of its high developing activity (see U.S. Pat. No. 3,656.950, U.S. Pat. No. 3,658,525, etc.). Although G-P-toluenesulfonate does provide rapid processing speed, it does not provide stable bromide ion concentration and causes significant yellow stain in the unexposed areas of the photographic element after processing, especially when processed for a short time. It has been found that this method cannot be used in rapid processing because it has the disadvantage that the one-color developing agent remains and causes rough staining.

On the other hand, 3-methyl-4-amino-N-ethyl-β-methanesulfonamide ethylaniline sesquisulfate monohydrade and 3- Methyl-4-amino-N-β-hydroxyethylaniline sulfate etc. are published in Photographic Science and Engineering Vol. 1.8. No, 3.5~6
As seen in May, 1884, P. 125-137,
It was said that there was not much difference in the half-wave potential indicating the oxidation-reduction potential, and that both had weak developing activity.

Therefore, it is said that there are almost no color developing agents that have high developing activity for silver chlorobromide emulsions and excellent storage stability of dye images, and generally 3-methyl-4-amino-N-ethyl-N-β- Methanesulfonamidoethylaniline sulfate was used with benzyl alcohol.

However, in this case, as mentioned above, it is easily affected by changes in bromide ion concentration, and another problem with concentrated low replenishment processing in which the amount of replenisher is reduced is that the contamination and accumulation of other processing solution components increases. be.

This is because the rate at which the tank liquid is replaced with replenisher becomes lower due to a decrease in the amount of replenishment, and also because the period of use of the liquid becomes longer. Contamination with other processing solutions is caused by so-called back contamination, in which processing solution components immediately after development are brought into the color developer by splashes from adjacent processing solutions in the processing machine, transport leaders, belts, hangers for hanging the film, etc. It will be done. Among these contaminant components that accumulate, thiosulfate ion, which is a fixing agent, accelerates development. That is, this problem occurs particularly when bleach-fixing is performed directly after color development. In particular, by promoting the shoulder of the photographic characteristic curve, a remarkable increase in contrast is produced. Further, increased contamination of metal salts as bleaching agents, especially ferric salts, accelerates the decomposition of hydroxylamine as a preservative, producing ammonia ions. This decomposition reaction is greatly accelerated at temperatures above 30°C. The generation of ammonia ions, like thiosulfate ions, has the disadvantage of accelerating physical development and increasing contrast.

Therefore, even if the amount of replenishment is reduced in order to improve economy and environmental pollution, rapid processing is possible, photographic performance is maintained constant, and even if the processing solution is used for a long time, the active ingredients will not decompose. At present, there is a strong desire for a color developing solution that can be stably processed without changing photographic processing performance.

The first object of the present invention is to maintain constant appropriate photographic performance over a long period of time without any change in bromide ion concentration even when processed with a color developing solution at a low replenishment amount. To provide a rapid and stable method for processing photographic elements in which colored dyes and uncolored areas do not fade or change color even after long-term storage.

As a result of various studies to achieve the first objective, the present inventors have succeeded in discovering a unique color developing agent that is almost unaffected by the bromide ion concentration when developing a specific silver halide, and has obtained an advantageous result. Although the storage stability of the developed color dyes has been greatly improved, yellow density is easily affected by processing temperature fluctuations and pH fluctuations of the color developer, and the photographic performance of the blue-sensitive emulsion layer is not constant. In the meantime, we have further investigated ways to solve this problem.

[Means for Solving the Problem] As a result, in a method for processing a photographic element having a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support, The silver halide emulsion contained in the light-sensitive silver halide emulsion layer is substantially a silver chlorobromide emulsion, and a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer are provided between the blue-sensitive silver halide emulsion layer and the support. A photographic element provided with at least one sensitive silver halide emulsion layer is processed using a color developer containing an N-hydroxyalkyl-substituted-p-phenylenediamine derivative for 30 minutes.
It has been found that the above object can be achieved by developing at a temperature of not less than 150 seconds.

Hereinafter, the progress that led to the present invention will be explained.

The inventor has discovered that when developing photographic elements using certain silver halide, i.e. silver chlorobromide based emulsions, the color developing agent is N-
It has been surprisingly discovered that only when a hydroxyalkyl-substituted p-phenylenediamine derivative is used, the dye density obtained hardly decreases even if the bromide ion concentration increases. The aforementioned characteristics of this color developing agent cannot be obtained in photographic elements using substantially silver iodobromide emulsions containing more than 0.5 mole % of silver iodide; This is unexpected since silver bromide emulsions have been used exclusively for the development of silver bromide emulsions, and virtually no increase in the bromide ion concentration during the development of photographic elements using silver chlorobromide emulsions results in a significant increase in development speed. The fact that there is no delay in development is unexpected and cannot be understood from the redox potential or half-wave potential of common color developing agents, and there is a possibility that an optimal balance between development speed and coupling speed cannot be maintained. It is extremely unlikely that it will happen,
It was surprising.

However, the inventor encountered the following problem. It is rapid when using N-hydroxyalkyl-substituted-p-phenylenediamine color developing agents, is insensitive to changes in bromide ion concentration, and can be developed especially at high bromide ion concentrations, so it can be refilled in continuous processing. Although it has the great advantage of being able to greatly reduce the amount of chromophoric dye and has extremely high processing stability, it has been found that it has the disadvantage that the storage stability of the resulting color dye, especially the photomagnetochromism, is reduced. The storage stability of zero-dye images is critical and has become a major obstacle, especially in the case of color paper (prints).

The inventor of the tree worked even harder to solve this problem, and as a result,
It was found that this problem is not due to the low storage stability of the dye itself, but because the color developing agent tends to remain in the photographic element, and that this problem can be solved by shortening the color development time. However, shortening the color development time cannot be achieved unless the processability of the photographic element is sufficiently improved - it cannot generally be shortened, but it can be achieved by reducing replenishment and processing stability without compromising the storage stability of the dye image. It has been found that in order to achieve this property, it is necessary to use the color developing solution of the present invention and process at a temperature of 30° C. or higher and within 150 seconds.

In this case, if conventional photographic elements are used as they are, there will be a problem that developing time will be insufficient and sufficient photographic images will not be obtained. Therefore, the inventors of the present invention have conducted further studies and developed a method using the color developing agent of the present invention. Photographic elements in which the silver halide emulsion contained in at least the light-sensitive silver halide emulsion layer is essentially a silver chlorobromide emulsion are treated with N-hydroxy Alkyl substitution -p
- Improving the development speed by processing with a developer containing a phenylenediamine derivative and developing the photographic element rapidly in color at temperatures above 30°C and up to 150 seconds without compromising the stability of the dye image. This has succeeded in achieving the first object of the present invention.

However, according to this technique, although it is not affected by the increase in the bromide ion concentration of the color developer, it is affected by the pI (fluctuations and temperature fluctuations) of the color developer, especially in the blue-sensitive silver halide emulsion layer. It was found that certain photographic performance could not be obtained with regard to yellow density.

In order to solve this problem, at least one layer of a line-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer is provided between the blue-sensitive silver halide emulsion layer and the support. In particular, the inventor's research has revealed that the above-mentioned problem can be solved, and the present invention has been completed. Furthermore, it has been found that the bromide ion concentration dependence can be further improved according to the present invention.

In this specification, "substantially silver chlorobromide emulsion" to "
"Substantially silver chlorobromide emulsion" may contain a trace amount of silver iodide in addition to silver chlorobromide, for example, 0.3 mol % or less, more preferably 0.1 mol % or less iodide. This means that it may contain silver. However, silver chlorobromide emulsions containing no silver iodide are most preferred in the present invention.

In a preferred embodiment of the present invention, the silver halide grains of the blue-sensitive silver halide emulsion layer are provided between the blue-sensitive silver halide emulsion layer and the reflective support, the green-sensitive silver halide emulsion layer, the red The average grain size may be larger than or substantially the same as that of the silver halide grains in at least one layer of the sensitive silver halide emulsion layer.

In addition, in this specification, "lower side" or "lower layer" refers to the side closer to the support or its layer, and "upper side" or "upper layer" conversely refers to the side farther from the support or its layer. .

The present invention will be described in further detail below.

The light-sensitive emulsion layer of a photographic element processed according to the present invention comprises:
It is sufficient as long as at least one layer contains substantially the silver chlorobromide emulsion, but it is preferable that all the blue-sensitive, green-sensitive and red-sensitive light-sensitive emulsion layers contain substantially the silver chlorobromide emulsion, and The silver bromide content of the substantial silver chlorobromide emulsion is preferably 90 mol % or less, particularly 40 to 70 mol %, and the silver bromide content of the green-sensitive and red-sensitive silver halide emulsion layers is preferably 5 to 70 mol %. 6
Particularly preferred is 0 mol%.

The composition of the silver halide contained in the photosensitive emulsion layer not based on the silver chlorobromide emulsion of the present invention is not particularly limited, and any of silver bromide, silver chlorobromide, and silver chloroiodobromide may be used. good.

The average grain size of the silver halide contained in the blue-sensitive silver halide emulsion layer of the present invention is not limited, but
Preferably it is 0.20 to 0.55 Bm, more preferably 0.30 to 0.50 p, m. In terms of processing stability, the average particle size is preferably 0.55 gm or less, while in terms of sensitivity and prevention of magenta color turbidity, the average particle size is 0-201 gm.
Ls or higher is better.

The average grain size of the silver halide contained in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer is also not particularly limited, but is preferably 0.1 to 2 mm, more preferably 0.1 to 2 mm.
2 to Ig,m, particularly preferably 0.25 to 0.8 l.

The average grain size of silver halide can be measured by various methods commonly used in the art for the above purpose, and the average grain size of silver halide is defined as cubic silver halide grains. In the case of , it is the length of its -side, and in the case of a shape other than a cube, it is the length of one side when converted to a cube having the same volume.

In the photographic element of the present invention, it is preferable that the amount of m cloth is small, since there is no delay in development due to an increase in bromide and sufficient dye formation can be achieved even in a short period of time, and is preferably from 0.3 to Ig.
/m2, especially when it is 0.4 to 0.8 g/nf, the maximum effect is obtained.

The silver halide used in the photographic elements of this invention may be a polydisperse emulsion with average grain sizes distributed over a wide range, but substantially monodisperse emulsions are preferred.

The above-mentioned substantially monodisperse silver halide grains are those in which most of the silver halide grains appear to have the same shape and are uniform in grain size when an emulsion is observed using an electron microscope.
And it has a particle size distribution as defined by the following formula, that is, it has a value of 0.20 or less when the standard deviation S of the particle size distribution is divided by the average particle size 7, and is preferably means 0.15 or less.

−≦0.20? The particle size referred to here has the same meaning as the particle size described above regarding the average particle size.

The photographic elements of this invention have three light-sensitive silver halide emulsion layers that differ substantially in color sensitivity: a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer. It has an emulsion layer. The coating position of the three light-sensitive silver halide emulsion layers having different color sensitivities is that one of the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer is placed below the blue-sensitive silver halide emulsion layer. At least one layer of is coated.

A preferred embodiment of the present invention in this respect is that [A] a green-sensitive silver halide emulsion layer is provided below the blue-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer is provided above the blue-sensitive silver halide emulsion layer. It is.

Another preferred embodiment is [A red-sensitive silver halide emulsion layer is provided below the BJ blue-sensitive silver halide emulsion layer, and a green-sensitive silver halide emulsion is provided below the red-sensitive silver halide emulsion layer. layer is provided.

The photographic element of the present invention comprises a green-sensitive silver halide emulsion layer in which the silver halide grains of the blue-sensitive silver halide emulsion layer are provided between the blue-sensitive silver halide emulsion layer and a support;
It is preferable to have a structure in which the average grain size is larger than or substantially the same as that of the silver halide grains in at least one layer of the red-sensitive silver halide emulsion layer. It is as follows. That is, from the support side, the halogen of the blue-sensitive silver halide emulsion layer is arranged as follows: It is preferable that the silver halide grains have an average grain size larger than or substantially the same as that of the silver halide grains in the green-sensitive silver halide emulsion layer. In addition, in the case of a structure having a green-sensitive silver halide emulsion layer, a red-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer arranged from the support side, the silver halide grains of the blue-sensitive silver halide emulsion layer are It is preferable that the average grain size is larger than or substantially the same as that of the silver halide grains in the green-sensitive silver halide emulsion layer and/or the red-sensitive silver halide emulsion layer.

In the present invention, the green-sensitive silver halide emulsion layer, the blue-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer each have two layers.
It is also possible to have more than one layer.

In addition, the two or more layers may have different sensitivities, such as high sensitivity and low sensitivity. However, in the present invention, the description of the average grain size of silver halide grains in the silver halide emulsion layer does not mean a comparison between silver halide emulsion layers having the same color sensitivity, but rather a comparison between silver halide emulsion layers having the same color sensitivity. This refers to a comparison between different silver halide emulsion layers. Also,
To explain a specific example of the structure [8] above, the average grain size is larger than that of the silver halide grains in the blue-sensitive silver halide emulsion layer or the silver halide grains in the red-sensitive silver halide emulsion layer. or if they are substantially the same, the average grain size of the green-sensitive silver halide emulsion layer is larger than that of the silver halide grains of the blue-sensitive silver halide emulsion layer and/or the red-sensitive silver halide emulsion layer. On the other hand, the silver halide grains in the blue-sensitive silver halide emulsion layer may be substantially the same as the halogen grains in the green-sensitive silver halide emulsion layer. When the average grain size of the silver halide grains is larger than or substantially the same as that of the silver halide grains, the red-sensitive silver halide emulsion layer is larger than the silver halide grains of the blue-sensitive silver halide emulsion layer and/or the green-sensitive silver halide emulsion layer. The average grain size of the grains may be larger, substantially the same, or conversely smaller than the grains.In this way, the blue-sensitive silver halide emulsion layer On the other hand, it is preferable that at least one of the lower photosensitive silver halide emulsion layers having different color sensitivities has silver halide grains having a small average grain size or substantially the same grain size.

Regarding the ratio of the average grain size of silver halide grains contained in each layer, referring to the specific examples of the above-mentioned [A] and [old configurations, in both cases, photosensitive silver halide emulsion layers having different color sensitivities are used. It is preferable that the average particle size ratio of the silver halide grains contained in the silver halide grains ranges from the support side to 1:1 to 2:1 to 3, specifically from the support side (1) 1:2:
1, (2) 1:2::l, (3) 1:1:1
The average grain size ratio of silver halide grains is as follows.

However, in another preferred embodiment of the present invention, the average grain size of the silver halide grains in the light-sensitive silver halide emulsion layer gradually increases from the support side, and the silver halide grains in each light-sensitive silver halide emulsion layer The average particle diameter ratio from the support side is 1:1 to 2:1 to 3. That is, to explain a specific example of the above-mentioned [A1 structure], in the green-sensitive silver halide emulsion layer, the di-blue-sensitive silver halide emulsion layer: the red-sensitive silver halide emulsion layer, for example, (1) 1:1
:1.

(2) l:1:2, (3) l:1:3,
(4) 1:2:2, (5) 1:2:3,
(5) An average grain size ratio of silver halide grains such as 1:3::1 is included as a preferred example of the present invention. In addition, in the case of the specific example of the old configuration, (1)
l:1:1, (2) 1:1:2, (3) 1 to
=3, (4) 1:2:2, (5) l:2:3
, (6) average particle size ratios such as 1:3:3 are included as preferred examples of the present invention.

The color development process in the present invention is carried out at 30°C or higher and 150 seconds or less, preferably at 33°C or higher and 120 seconds or less, most preferably at 35°C or higher and 90 seconds or less, and at 30°C or higher. , When processing for more than 150 seconds, the storage stability of the dye deteriorates.

In particular, the processing time takes one more time than the processing temperature.If the processing time exceeds 150 seconds, the ancestral color of the cyan dye will increase significantly, which is undesirable.The processing temperature should be increased to complete the development in a short time rather than to maintain the storage stability of the dye. It is a thing, 30 ° C or higher and 50 ° C or less, the higher the short -time processing is preferable, especially preferably 33 ° C or higher, 48.
The temperature is preferably 35°C or higher and 43°C or lower.

The pH of the color developing solution is usually preferably 7 or more, more preferably in the range of 9 to 13.

The developing agent effective in the present invention is a quaternary ammonium salt of an N-hydroxyalkyl-substituted p-phenylenediamine compound, particularly one represented by the following general formula.

In the formula, R5 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and R2 is a hydrogen atom or having 1 to 4 carbon atoms. an alkyl group, R3 is an alkyl group having 1 to 4 carbon atoms that may have a hydroxyl group, and A is an alkyl group that has at least one hydroxyl group and may have a branch; , more preferably S , R5 and R6 each represent a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms which may have a hydroxyl group, R4 and Rq .

At least one of R6 is a hydroxyl group or an alkyl group having a hydroxyl group, R2, R3 are each Ol
1, 2 or 3, and HX is hydrochloric acid, sulfuric acid, P-)
- Represents luenesulfonic acid, nitric acid or phosphoric acid.

Such p-phenylenediamine color developing agents are unstable in their free amines and are commonly used as salts (most commonly those specified by the formula above); a typical example is as 4-amino-3-methyl-
Examples include N-ethyl-N-(β-hydroxyethyl)-aniline salt and 4-amino-N-ethyl-N-(β-hydroxyethyl)-aniline salt.

Preferably, in the present invention, 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate hydrate [this has been reprinted under the name CD-4 and is In the color photography method of parts (for example, Eastman Kodak C41 method, Konishiroku Photo Industry Co. C
The NK-4 system (used for developing color negative films) has been found to be particularly effective.

Preferred N-hydroxyalkyl-substituted p-phenylenediamine derivatives used in the present invention include the following, but are not limited to these exemplified compounds.

[Exemplary compounds]

H2 H2 NH2 H2 H2 H2 Below margin Hydrochloric acid, sulfuric acid, and pi-mylene sulfone salts of the compounds (1) to (8) above are particularly preferred.

Among these exemplified compounds, No., (1), (2),
(8).

(7) and (8) are preferably used, especially No., (1
), (2) and (8) are preferably used. moreover,
In particular, No. (1) is particularly important because the color developing agent of the present invention, which is preferably used in the present invention, has extremely high solubility in water, and therefore the amount used can range from 1 g to 100 g per processing solution. Preferably, more preferably 3g to 30
It is used in the range of g.

These tohydroxyalkyl-substituted p-phenylenediamine derivatives of the present invention are described in the Journal of the American Chemical Society, Vol. 73, p. 3100 (1951).
It can be easily synthesized by the method described in 2010).

Of course, other color developing agents can be used in combination with the tohydroxyalkyl-substituted p-phenylenediamine derivative developing agent in the color developing solution according to the present invention. A typical color developing agent that may be used in combination is a p-phenylenediamine type, and the following are preferred examples.

4-Amino-N, N-diethylaniline, 3-methyl-
4-Amino-N, N-diethylaniline, 3-methyl-
4-7 minnow N=ethyl-N-β-methoxyethylaniline, 3-methyl-4-amino-N-ethyl-H-β-
Methanesulfonamidoethylaniline, 3-methoxy-
4-Amino-N-ethyl-N-β-methoxyethylaniline, 3-7cetamido 4-amino-N, N-dimethylaniline, N-ethyl-N-β-[β-(β-methoxyethoxy)ethoxy] Ethyl-3-methyl-4-aminoaniline, N-ethyl-N-β-(β-methoxyethoxy)ethyl-3-methyl-4-aminoaniline, and salts thereof such as sulfates, hydrochlorides, sub'Ii; is an acid salt, p
-) luenesulfonate, phosphate, etc.

Further 1, for example, JP-A No. 48-64932, JP-A No. 50-1
No. 31526, No. 51-95849, and Bent et al., Journal of the American Chemical Society, Vol. 73, pp. 1100-3125 (1951).
The ones described above are also listed as representative ones. The amount of the color developing agent that may be used in combination is not particularly limited, but is preferably equal to or less than the same molar amount as the N-hydroxyalkyl-substituted p-phenylenediamine derivative developing agent of the present invention.

The color developing solution of the present invention has a bromide ion concentration of 5 x 10-1
It is preferable that the bromide ion concentration is molar or more, but in the present invention, a high bromide ion concentration is preferable because the amount of replenishment can be reduced.In the conventional development method, a low bromide ion concentration is preferable because it suppresses the development reaction. However, in the combination of the photographic element and the color developer of the present invention, on the contrary, it is preferable that the bromide ion concentration is high, so that the object of the present invention can be better achieved.

In other words, in the invention, the amount of replenishment can be reduced because it is less affected by the bromide ion concentration.

The bromide ion concentration is preferably I x 10-'' molar or more, particularly preferably 1.5 x to-'' molar or more, and if the bromide ion concentration is too high, development will be inhibited and the effect of the bromide ion concentration will begin to be felt6. ×10 −2 mol or more is not preferable, and the chloride ion concentration does not affect it.

A preferred embodiment of the present invention is a low replenishment process, preferably 250 mu/m'', particularly 20 h mu/m2 or less.

In the processing method of the photographic element of the present invention, it is possible to use a color developing bath containing the color developing agent according to the present invention. In addition, various other methods including bath processing, such as a spray method in which the processing liquid is atomized, a web method in which contact is made with a carrier impregnated with the processing liquid, or a developing method using a viscous processing liquid, etc. Processing schemes can be used.

In addition to the above, there are no particular limitations on the processing method for the photographic element of the present invention, and any processing method can be applied.For example,
Typical methods include bleaching and fixing after color development, followed by washing and/or stabilization if necessary; bleaching and fixing are carried out separately after color development, and further washing and/or stabilization as necessary. / or Stable processing method: or prehardening, neutralization, one color development, stop fixing, water washing,
Method of bleaching, fixing, washing with water, post hardening, washing with water, color development, washing with water, supplementary color development, stopping, bleaching, fixing, washing with water,
Any method may be used for processing, such as a method in which the developed silver produced by color development is subjected to halogenation bleaching and then color development is performed again to increase the amount of dye produced.

The color developing solution 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 bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol,
A water softener, a thickening agent, a development accelerator, etc. can also be optionally included.

Examples of additives other than the above that may be added to the color developer include bromides such as potassium bromide and sodium bromide, alkali iodide, 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, preservative single-layer effect promoters, chelating agents, and the like.

Bleaching agents used in bleaching solutions or bleach-fixing solutions in the bleaching process are generally known to be those in which metal ions such as iron, cobalt, and copper are coordinated with aminopolycarboxylic acids or organic acids such as oxalic acid and citric acid. There is. Representative examples of the above aminopolycarboxylic acids include the following.

Ethylenediaminetetraacetic aciddiethylenetriaminepentaacetic acidpropylenediaminetetraacetic acidnitrilotriacetic acidiminodiacetic acid glycol etherdiaminetetraacetic acidethylenediaminetetrapropionic acidethylenediaminetetraacetic acid disodium saltdiethylenetriaminepentaacetic acidpentasodium saltnitrilotriacetic acid sodium saltBleaching solution contains various additives along with the above bleaching agents. When a bleach-fixing solution is used in the bleaching step, a solution containing a silver halide fixing agent in addition to the bleaching agent is used. The bleach-fix solution may further contain a herogen compound such as potassium bromide, and as in the case of the bleach solution described above, various other additives such as pH buffers, optical brighteners, etc. , antifoaming agents, surfactants, preservatives, chelating agents, stabilizers, organic solvents, etc. may be added or contained.

The silver halide fixing agent is, for example, sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, or thiourea, thioether, etc., which react with silver halide and become water-soluble. Compounds that form silver salts can be mentioned.

From the viewpoint of rapid processing, the processing temperature of the photographic element of the present invention in various processing steps other than color development, such as bleach-fixing (or bleaching, fixing), washing with water and stabilization as necessary, is also 30°C. It is preferable to carry out the above.

The photographic element of the present invention is disclosed in JP-A-58-14834, JP-A-58-14834;
-105145, 58-134634 and 58
-18631 and Japanese Patent Application No. 58-2709 and No. 5
A stabilization treatment as an alternative to water washing as shown in No. 9-89288 or the like may be performed.

On the other hand, to explain silver halide grains in more detail, the crystals of silver halide grains may be normal crystals, twin crystals, or other crystals, and the ratio of [1,0-0] planes to [1,1°1] planes is arbitrary. can be used. Furthermore, even if the crystal structure of these silver halide grains is uniform from the inside to the outside, it has a layered structure (core-shell type) in which the inside and outside are different.
Furthermore, these silver halides may be of the type that forms the latent image mainly on the surface or of the type that forms the latent image inside the grain. 1982-113934, patent application 1982
-170070) can also be used.

Silver halide grains particularly preferably used in the present invention are:
It is substantially monodisperse, and may be obtained by any preparation method such as an acidic method, a neutral method, or an ammonia method.

Alternatively, for example, seed particles may be produced using an acidic method, and then grown using an ammonia method, which has a high growth rate, to grow to a predetermined size. When growing silver halide grains, control the I)) I, pAg, etc. in the reaction vessel, and adjust the amount commensurate with the growth rate of silver halide grains as described in JP-A No. 54-48521, for example. It is preferable to implant and mix silver ions and halide ions sequentially and simultaneously.

Preferably, the preparation of silver halide grains according to the present invention is carried out as described above, and the set containing the silver halide grains is referred to herein as a silver halide emulsion.

These silver halide emulsions are composed of active gelatin: sulfur sensitizers such as allylthiocarbamide, thiourea, cystine, etc.; 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 chlorovaladate (these These substances act as sensitizers or fog suppressants depending on the amount. It may also be chemically sensitized (for example, in combination with a 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 hydroxytetrazaindene and mercapto group is produced. It may also contain at least one type of terocyclic compound.

The silver halide used in the present invention is mixed with an appropriate sensitizing dye in an amount of 5 X 10-' to 3 X 1 per mole of silver halide in order to impart photosensitivity to the desired photosensitive solution.
Optical sensitization may be achieved by adding 0 to 3 moles.

Various sensitizing dyes can be used, and each sensitizing dye can be used alone or in combination of two or more types. Examples of the sensitizing dyes that can be advantageously used in the present invention include the following: I can name kimonos.

That is, as sensitizing dyes used in blue-sensitive silver halide emulsions, for example, West German Patent No. 929,080 and US Pat.
, No. 231,658, No. 2,493.7411, No. 2
, No. 503.776, No. 2,5L9.0CII, No. 2
．． 'H2,329, 3.656,959, 3.
[No. i72,897, No. 3,694,217, No. 4
, No. 025,349, No. 4,046,572, British Patent No. 1,242.588, Japanese Patent Publication No. 14030/1973,
Examples include those described in No. 52-24844. # is also used in green-sensitive silver halide emulsions.
As an a-sensitive dye, 1, for example, U.S. Pat. No. 1,939,201
No. 2,072,908, No. 2,739,149, No. 2,945.763, British Patent No. 505,979, etc. This can be cited as a representative example. Further, as a sensitizing dye used in a red-sensitive silver halide emulsion, for example, US Pat.
No. 9,234, No. 2,270,378, No. 2,442
, No. 710, No. 2,454,629, No. 2,776.
Representative examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 280 and the like. Furthermore, U.S. Patent 2,21
: No. 1,995, No. 2,493,748, No. 2,51
Cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in German Patent No. 9,001 and German Patent No. 929.080 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 element 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, Japanese Patent Publication No. 43-493 concerning the combination of benzimidazolocarbocyanine and benzoxazolocarbocyanine.
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 having a benzimidazole nucleus with other cyanine or merocyanine, for example, Japanese Patent Publication Nos. 45-25831 and 47-11
No. 114, No. 47-25379, No. 4B-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.

Furthermore, regarding combinations of benzoxazolocarbocyanine (oxa-carbocyanine) and other carbocyanines, for example, Japanese Patent Publication Nos. 44-32753 and 46
-11627, Japanese Unexamined Patent Publication No. 1483/1983, and Japanese Patent Publication No. 38408/1983 regarding merocyanine.
No. 48-41204, No. 50-40662, #
Kaikai No. 56-25728, Kaikai No. 58-10753, Kaikai No. 5
No. 8-91445, No. 59-116645, No. 50-
No. 33828 etc. are mentioned.

Regarding combinations of thiacarbocyanin and other carbocyanins, for example, Japanese Patent Publications Nos. 43-4932, 43-4933, 45-26470, and 46
-18107, No. 47-8741, JP-A-59-1
No. 14533, etc., and the method described in Japanese Patent Publication No. 49-6207, 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 wood-friendly 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 photosensitive silver halide emulsion layers according to the present invention may contain a coupler, that is, a compound capable of forming a dye by mixing with an oxidized product of a color developing agent.

The yellow couplers used in the present invention include closed ketomethylene compounds, active point -0-aryl substituted couplers called so-called 2-equivalent couplers, and active point -
〇-acyl substituted coupler, active point hydantoin compound substituted coupler, active point urazole compound substituted coupler, active point succinimide compound Th-substituted coupler, active point fluorine stirrup substituted coupler, active point chlorine or bromine substituted 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. 5,057, No. 3,265,506, No. 3.408
, No. 194, No. 3,551,155, No. 3,58
2. : No. 122, No. 3,725,072, No. 3,89
No. 1,445, West German Patent No. 1.547,868, West German Patent Application No. 2,219,917, No. 2, zat, 3at, No. 2,414,006, British Patent No. 1,425.02
No. 0, Special Publication No. 1978-10783, Japanese Patent Publication No. 47-261
No. 33, No. 48-73147, No. 51-102636
No. 50-6341, No. 50-123342, No. 50-130442, No. 51-21827, No. 50
-87650, 52-82424, 52-11
Examples include those described in No. 5219 and No. 58-95346.

Examples of the magenta coupler used in the present invention include pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based, and indacylon-based compounds. These magenta couplers may be not only 4-equivalent couplers like the yellow couplers but also 2-equivalent couplers. Specific examples of magenta couplers include U.S. Pat. Nos. 2,600,788 and 2,983.
, No. 608, No. 3,062,653, No. 1, 127
, No. 269, No. 3,311.476, No. 3,419,
No. 391, No. 3,519,429, No. 3.558,
No. 319, No. 3,582,322, No. 3,615,5
No. 06, No. 3,834,908, No. 1, 891, 4
No. 45, West German Patent No. 1,810.464, West German Patent Application (OL S) 2,408. [I55 No. 2, 4
No. 17,945, No. 2,418.95'9, No. 2,4
No. 24.467, Japanese Patent Publication No. 40-6031, Japanese Patent Publication No. 51
-20826, 52-58922, 49-12
No. 9538, No. 49-74027, No. 5°-1593
No. 36, No. 52-42121, No. 49-74028, No. 50-60233, No. 51-26541, No. 5
Examples include those described in Japanese Patent Application No. 3-55122 and Japanese Patent Application No. 110943/1983.

Furthermore, useful cyan couplers for use in the present invention include, for example, phenolic 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. A specific example of a cyan coupler is U.S. Patent 2. : No. 169,929, No. 2,434,272, No. 2,474,293, No. 2,474,293, No.
No. 2,521,908, No. 2,895,825, No. 3
, No. 034,892, No. 3,311,476, No. 3,
No. 4511.315, No. 3,476.563, No. 4511.315, No. 3,476.563, Ibid.
, 58:1,971, 3, 591,383, 3
, No. 757,411, No. 3,772,002, No. 757,411, No. 3,772,002, Same: l
, No. 933,494, No. 4,004,929, West German Patent Application (OL S) No. 2,414,830, No. 2
, 454.32!1, JP 48-59838, JP 51-26034, JP 48-5055, JP 51-1
No. 46827, No. 52-69624, No. 52-909
No. 32, No. 58-9534.6, Special Publication No. 49-115
Examples include those described in No. 72 and the like.

Couplers such as non-diffusible DIR compounds, colored 7 zenta 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 amount of the above-mentioned coupler that can be used in the present invention is not limited, but is preferably from 1 x 10-' to 5 mol, more preferably from 1 x 10-2 to 5 x 10-1, per mol of silver.

In order to incorporate the above-mentioned couplers into the silver halide emulsion according to the present invention, if the couplers are alkali-soluble, they may be added as an alkaline solution, or if they are oil-soluble, they may be added as described in US Pat. 2,322,027
No. 2,801,170, No. 2,801.171, No. 2,272.191 and No. 2,304. ! 14
According to the method described in each specification of No. 0, the coupler is dissolved in a high-boiling point solvent, if necessary in combination with a low-boiling point solvent, dispersed in the form of fine particles, and added to the silver halide emulsion. preferable. At this time, other hydroquinone derivatives, if necessary,
It is okay to use UV absorbers, anti-fading agents, etc. in combination. It is also possible to use a mixture of two or more couplers.

Further, to explain in detail the preferred method of adding couplers in the present invention, one or more couplers are added, if necessary, with other couplers, hydroquinone derivatives, anti-fading agents, ultraviolet absorbers, etc., organic acid amides, Carbamates, esters, ketones, urea derivatives, ethers, hydrocarbons, etc., especially di-n-butyl phthalate, triresyl phosphate, triphenyl phosphate,
Di-isooctyl azelate, di-n-butyl sepacate, tri-hexyl phosphate, N.

N-ethylucagrylamitoptyl, LN-diethyl laurylamide, n-pentadecyl phenyl ether, di-octyl phthalate, n-nonylphenol, 3
- high boiling point solvents such as pentadecyl phenylethyl ether, 2,5-c-5ec-amylphenylbutyl ether, monophenyl-di-0-chlorophenyl phosphate or fluoroparaffin, and/or methyl acetate, ethyl acetate, propyl acetate, butyl acetate, Dissolved in a low temperature point solvent such as butyl propionate, cyclohexanol, diethylene glycol monoacetate, nitromethane, carbon tetrachloride, chloroform, cyclohexanetetrahydrofuran, methyl alcohol, acetonitrile, dimethylformamide, dioxane, methyl ethyl ketone,
An aqueous solution containing an anionic surfactant such as alkylbenzenesulfonic acid and alkylnaphthalenesulfonic acid and/or a nonionic surfactant such as sorbitan sesquioleate and sorbitan monolaurate and/or a wood-philic binder such as gelatin. and emulsified and dispersed using a high-speed rotary mixer, colloid mill, ultrasonic dispersion device, etc., and added to a silver halide emulsion.

In addition, the above couplers and the like may be dispersed using a latex dispersion method. The latex dispersion method and its effects are described in JP-A Nos. 49-74538, 51-59943, and 5
4-32552 and Research Disclosure, 1975, 8th Sword, No. 14850, pages 77-79.

Suitable latexes include, for example, styrene, acrylate,
Lobetyl acrylate, n-butyl methacrylate,
2-acetoacetoxyethyl methacrylate, 2-(methacryloyloxy)ethyltrimethylammonium methosulfate, 3-(methacryloyloxy)propane-1-sulfonic acid sodium salt, N-isopropylacrylamide, N-(2-(2-methyl-4 -oxopentyl)) acrylamide, 2-acrylamide-2-
Seven-dimensional homopolymers, copolymers and terpolymers such as methylpropanesulfonic acid and the like.

In one or more of the photographic constituent layers of the photographic element of the present invention, a dye (AI dye) that is water-soluble or decolorable with a color developing solution is used.
can be added, and the AI dyes include oxonol dyes, hemioxonol dyes, merocyanine dyes, and azo dyes. Among them, oxonol dyes, hemioxonol dyes, merocyanine dyes, and the like are useful. Examples of AI dyes that can be used include British Patent No. 584.
No. 6G'i, No. 1,277.429, Japanese Unexamined Patent Publication No. 1989-8
No. 5130, No. 49-99620, No. 49-1144
No. 20, No. 49-129537, No. 52-10811
No. 5, No. 59-25845, No. 59-111640, No. 59-111641, U.S. Patent No. 2.274,78
No. 2, No. 2,533,472, No. 2,956,87
No. 9, No. 3,125,448, Ko, 1411.18
No. 7, No. 3,177.078, No. 7, No. 3,177.078, No. 1, 247, 12
No. 7, No. 3,250,601, No. 3,540,887
No. 3,575,704, No. 3,653,90
Examples include those described in No. 5, No. 3,718,472, No. 4.071j12, and No. 4,070,352.

These AI dyes are generally used at a concentration of 2 per mole silver in the emulsion layer.
It is preferable to use X 10-' to 5 X 10-'' moles, more preferably IX10-'' to 2 moles of IXIrow.

The photographic elements of the present invention may contain various photographic additives in addition to those listed above, such as antifoggants, stabilizers, and ultraviolet absorbers as described in Research Disclosure No. 17543.

A color stain inhibitor, a fluorescent whitening agent, a color image fading inhibitor, an antistatic agent, a hardening agent, a surfactant, a plasticizer, a wetting agent, etc. can be used.

In the photographic elements of this invention, the woody colloids used to prepare the emulsions include gelatin, derivative gelatins, graft polymers of gelatin and other polymers, proteins such as albumin and casein, hydroxyethyl cellulose derivatives, carboxylic Any of cellulose derivatives such as methyl cellulose, starch derivatives, mono- or copolymer synthetic wood-philic polymers such as bobbinyl alcohol, polyvinylimidazole, and polyacrylamide are included.

Supports for the photographic elements of the present invention include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with one radiation layer or with a reflector, such as glass plates, cellulose acetate, cellulose nitrate. Or polyester film such as polyethylene terephthalate, polyamide film, polycarbonate film.

Examples include polystyrene films, and other common transparent supports may be used, and these supports are appropriately selected depending on the intended use of the photographic element.

Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used to coat the silver halide emulsion layer and other photographic constituent layers used in the present invention. Also, U.S. Patent No. 2,761
, No. 791 and No. 2,941.8913 can also be used to simultaneously coat two or more layers.

In the photographic element of the present invention, it is optional to provide an intermediate layer having an appropriate thickness depending on the purpose, and a filter layer,
Various layers such as an anti-curl layer, a protective layer, and an antihalation layer can be used in appropriate combinations as a photographic structure r& layer. In these constituent layers, wood-philic colloids that can be used in the emulsion layer as described above can be similarly used as a binder, and can also be contained in the emulsion layer as described above. Various photographic additives can be included.

The photographic element of the present invention is a multilayer color photographic element of at least 3M containing each of a blue-sensitive silver halide emulsion layer, a &apos;-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer. In this specification, it refers not only to the photosensitive emulsion layer, but also to all wood-philic colloid layers on the side coated with the photosensitive emulsion layer, such as intermediate layers, overcoat layers, subbing layers, etc.) The thickness of the gold film is 14u when dry.
Ll or less is preferable, more preferably 13JLm or less,
Particularly preferably, it is 12 pm or less.

[Effects of the Invention] According to the present invention, even when processing is performed using a single color developer with a low replenishment amount, it is not only unaffected by changes in bromide ion concentration, but also unaffected by changes in processing concentration and PTT value of the color developer. It has always maintained a constant and appropriate photographic performance over a long period of time without any damage.
Moreover, it is possible to provide a rapid and stable method for processing photographic elements in which the coloring dyes and uncolored areas obtained do not fade or change color even after long-term storage.

[Examples] Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

Example 1 On a polyethylene-laminated paper support (hereinafter referred to as BS), the following layers were sequentially coated from the support side to prepare silver halide color photographic light-sensitive material sample No. 1.

Layer 1---1.25g/m2 gelatin, 0.22
green-sensitive silver chlorobromide emulsion (silver bromide content and average grain size are shown in Table 1) of 0,62 g/m2 magenta coupler (M -1) (hereinafter referred to as 0-2).

Layer 2 --- 0.70g/go gelatin, 20mg/m
Irradiation dye (A I-1), 10
Intermediate layer (hereinafter referred to as IL) consisting of (AI-2) at mg/m2
).

Layer 3---1.20g/m2 gelatin, 0.3
Blue-sensitive silver chlorobromide emulsion (in terms of silver, the same applies hereinafter)
Silver bromide content and average particle size are shown in Table 1), 0.50
0.80 g/g dissolved in dioctyl phthalate of
rn'' yellow coupler (Y-1) (hereinafter referred to as R-1).

Calendar 4: Interlayer (IL) consisting of 1.20 g/d gelatin.

Calendar 5...1.40g/m2 gelatin, 0.20
g/rn'' red-sensitive silver chlorobromide emulsion (silver bromide content and average grain size are shown in Table 1), rho 45 g/m2 cyan coupler (C -t) <hereinafter referred to as P-2).

Layer 6---1.0 g/m' gelatin and 0.20 g/m'
0.30g/n dissolved in dioctyl phthalate of
calendar containing the following ultraviolet absorber (UV-1) of
(hereinafter referred to as UV).

Layer 7: Calendar containing 0.50 g/rrf of gelatin (hereinafter referred to as Pro).

Table 2 below regarding sample No. 1 created in this way
Samples Nos. 12 to 6 were prepared by changing the layer structure as shown in FIG. In addition, in the green-sensitive silver halide emulsion layers and the red-sensitive silver halide emulsion layers other than 0-2 and P-3,
Emulsions having silver bromide contents and average grain sizes shown in Table 1 were used.

Below is the margin (Y-1) t t (C-1) (AI-1) (AI-2) (UV-1) H O, H engineering (1) In addition, as a hardening agent, 2,4-dichloro - 6-hydroxy S-triazine sodium during Calendar 2, 4 and 7,
Each was added in an amount of 0.017 g per 1 g of gelatin.

Table 1 tlR, blue-sensitive silver halide emulsion, the same applies hereinafter.

120: @sensitive silver halide emulsion, the same applies hereinafter.

Zero 3P, red-sensitive silver halide emulsion, same hereinafter.

Each of the photosensitive material samples Nos. 1 to 6 was exposed through an optical wedge and then processed in the following steps.

Processing steps (38°C) Color development 120 seconds Bleach-fixing 60 seconds Washing 60 seconds Drying 60-80°C 120 seconds The composition of each processing solution is as follows.

[Color developing solution] Pure water 80h Exchangeable benzyl alcohol 15M sulfuric acid hydroxyamine 2.0g Potassium bromide
0.5g sodium chloride
1.0g potassium sulfite
2.0g triethanolamine
2.0g color developing agent (as shown in Table 1) 0.0
23 mol 1-Hydroxyethylidene-1,1-diphosphonic acid (60% aqueous solution) 1.5-mer magnesium chloride 0.3 g Potassium carbonate 2 g Kaycol
l-PK-Conc (fluorescent brightener, manufactured by Shin Nisso Kako Co., Ltd.) 2. Add pure water to make 1 sentence, then add 20% potassium hydroxide or 10% dilute sulfuric acid)
Adjust to I=10.1.

[Bleach-fix solution] Pure water 550 m iron(III) ethylenediaminetetraacetate Ammonium salt 65 g Ammonium thiosulfate (70% aqueous solution) 85 g Sodium hydrogen sulfite 10 g Sodium metabisulfite
Add 2g ethylenediaminetetraacetic acid-disodium 20g pure water to make 11, and adjust to pl=7.0 with aqueous ammonia or dilute sulfuric acid.

Separately, using a color developing solution with the only difference being that the potassium bromide concentration of the above color developing solution was 0.5 g/cross to 1.5 g/view and 3.5 g/stand, samples Nos. 1 to 1 were prepared as above. 6
Each of them was developed.

Sensitometry was performed on each sample obtained by a conventional method. Table 3 shows the changes in color density when the potassium bromide concentration was varied at an exposure dose of 1.0 color density for each sample when the potassium bromide concentration was 0.5 g/JL. Here, ΔD in Table 3 is the difference between the color density when potassium bromide is 0.5 g/H and the color density when potassium bromide is 3.5 g/u, and is the difference between the color density when potassium bromide concentration is changed and the color density when potassium bromide concentration is changed. It represents the magnitude of variation in photographic performance.

Table 3: Comparative color developing agent (CD-33: 3/2H2So4.H2°) It can be seen that in Samples 4 to 4, the change in color development density due to KBr concentration variation is small, and the change in photographic performance is very small.

On the other hand, when a color developing agent (CD-3) other than the present invention was used, sample No. 1 of the present invention compared to comparative sample No. 5.6.
It can be seen that in Samples 4 to 4, the color density change due to KBr concentration fluctuation is small, but the improvement is still small compared to the color developing agent of the present invention.

Examining the results in Table 3 in more detail, the following can be said.

That is, from a comparison of Samples No. 005 and 6 outside the present invention, the average grain size of silver halide grains in the blue-sensitive silver halide emulsion layer is 0.
．． A light-sensitive material (Sample No.
, 5), the processing stability is improved, but from the comparison between the comparative sample N005 and the present invention samples Nos. 3 and 4, the present invention samples Nos. 003 and 4 have further improved processing stability. In the most preferred samples No. 001 and 2, in which the effect was observed and the average grain size of the silver halide grains in the photosensitive silver halide emulsion layer gradually increased from the reflective support side, the effect of improving processing stability was particularly remarkable. Although the above-mentioned improvement effect is seen with both the developing agent of the present invention and the developing agent other than the present invention, it is found that the above-mentioned effect is greater with the developing agent of the present invention.

Note that Table 3 shows that as the bromide ion concentration increased, the amount of replenishment was reduced, indicating that the treatment of the present invention can significantly reduce the amount of replenishment.

Example 2 Samples No. and I of Example 1 were exposed and developed in the same manner as in Example 1 using the same processing solution as in Example 1. A 0 color developer was created by changing the color developing agent as shown in Table 4. The zero color development time used for the processing was varied as shown in Table 4. The treatment temperature was 38°C.

The obtained sample was stored under irradiation with a Canon lamp, and changes in cyan concentration were measured. In other words, when the sample initial concentration of 1.0 when using CD-3 as a color developing agent deteriorates by about 0.3 for each processing time, the same elegance range of the sample treated with other color developing solutions Table 4
It was shown to. At this time, the yellow stain density of the unexposed area of the same sample was measured and similarly shown in Table 4.

Below is a color developing agent for margin comparison (C0D-6). It can be seen that there is no big difference in the fading rate even if the time is 2 seconds, and in particular, the fading is larger in the case of CD-6 than in CD-3.This indicates that the yellow stain density (Dmin) of the unexposed area I can say that too.

On the other hand, when the color developing agent of the present invention is Exemplified Compound (1), when the color development processing time is 180 seconds or more, the color fading is large and the storage stability is extremely low. The same can be said of Dmin).

However, it can be seen that when the color development time is 150 seconds or less, the storage stability is rapidly improved, resulting in more preferable results than when using the above-mentioned CD-3. This is surprising considering that it has traditionally been said that the structure of coloring dyes is closely related to their stability, and it is predicted that the residual amount of color developing agent in the film may also be closely related. Ru.

Example 3 Using the sample of Example 1, the dependence of photographic performance on PTT fluctuation of a single color developer was evaluated.

The potassium bromide concentration of the color developing solution of Example 1 is 3 g/
1, and the pH of the zero color developer using the sulfate of the exemplified compound (1) of N-hydroxyalkyl-substituted p-phenylenediamine promoter as the color developing agent was 9.8, 10.
The treatment was carried out in exactly the same manner as in Example 1, except that the color developing solution had a potassium bromide concentration of 0.5 g/kg, and the sensitometry was evaluated. The obtained results are shown in Table 5.

In the table, the yellow density shows the movement of the color density when the pH is varied at the exposure amount that gives a color density of 1.0 when developed at pH 0.2. ΔD is the range of change in color density, and represents the magnitude of change in photographic performance when pH changes. The color density was measured using a spectral reflection densitometer (PDA-65 manufactured by Konishiroku Photo Industry Co., Ltd.), and only the yellow density is shown in Table 5.

Margin Table 5 Below: As is clear from the results in Table 5, sample No. 1 of the present invention
-4 has a very small fluctuation compared to comparative sample No. 5.6, and it can be seen that even when the pH of the color developer changes, the change in photographic performance is small.Comparing within the present invention samples, Sample No. whose particle size becomes larger sequentially from the support side
, 1.2 is slightly improved over sample No.:l, 4, and is more preferable.

Example 4 Using the sample of Example 1, the dependence of photographic performance on temperature fluctuations of the color developer was evaluated.

The potassium bromide concentration of the color developer of Example 1 was adjusted to 1.3 g/
The temperature of the 0 color developer using the sulfate salt of Exemplified Compound (1) of N-hydroxyalkyl-substituted p-phenylenediamine derivative was 33°C, 36°C, and 40°C. The treatment was carried out in exactly the same manner as in Example 1 (potassium bromide concentration of color developing solution: 0.5 g/d), and sensitometry was evaluated. The results obtained are shown in Table 6.

In the table, the yellow density shows the movement of the color density when the temperature is varied at the exposure amount that gives a color density of 1.0 when developed at a temperature of 36°C. ΔD is the range of variation in color density, and represents the magnitude of variation in photographic performance when pi varies. The color density was measured using a spectral reflection densitometer (PDA-65, manufactured by Konishiroku Photo Industry Co., Ltd.), and only the yellow density is shown in Table 6.

Below is a blank table 6. As is clear from the results of Table 6, sample No. 1 of the present invention
It can be seen that in comparison with Comparative Samples No. 5 and 6, Samples 4 to 4 had very small fluctuations, and the change in photographic performance was small even when temperature fluctuations occurred in the color developing solution.

Claims (10)

[Claims] (1) In a method for developing a silver halide color photographic light-sensitive material having a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support, the photosensitive halogenated The silver halide emulsion contained in the silver emulsion layer is essentially a silver chlorobromide emulsion, and a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion are provided between the blue-sensitive silver halide emulsion layer and the support. At least one of the emulsion layers
The silver halide color photographic light-sensitive material provided with the layer is heated at 30°C or higher for 15 minutes using a color developing solution containing an N-hydroxyalkyl-substituted p-phenylenediamine derivative.
1. A method for processing a silver halide color photographic material, which is characterized in that development is performed in 0 seconds or less. (2) A patent characterized in that the silver halide emulsion of at least one photosensitive silver halide emulsion layer is a substantial silver chlorobromide emulsion with a silver bromide content of 5 to 60 mol % or less A method for processing a silver halide color photographic material according to claim 1. (3) The silver halide color photographic light-sensitive material according to claim 1 or 2, characterized in that the total coating amount of silver in the silver halide color photographic light-sensitive material is 1 g/m^2 or less. Processing method. (4) Claim 1, characterized in that the color developer contains at least 5 x 10^-^3 moles of bromide.
A method for processing a silver halide color photographic material according to any one of items 1 to 3. (5) Claim 4, characterized in that processing is performed with a color developing solution containing 1 x 10^-^2 moles or more of bromide.
A method for processing a silver halide color photographic light-sensitive material as described in . (6) A method for processing a silver halide color photographic light-sensitive material according to claim 4, characterized in that processing is performed with a color developing solution containing 1.5 x 10^-^2 moles or more of bromide. (7) The method for processing a silver halide color photographic light-sensitive material according to claim 3, wherein the total amount of coated silver is 0.8 g/m^2 or less. (8) N-hydroxyalkyl-substituted-p-phenylenediamine derivative is 3-methyl-4-amino-N-ethyl-
8. The method for processing a silver halide color photographic light-sensitive material according to any one of claims 1 to 7, characterized in that the N-β-hydroxyethylaniline salt is used. (9) The silver halide according to any one of claims 1 to 8, characterized in that the color photographic material is processed at a replenishment amount of 250 ml/m^2 or less during continuous processing. A method of processing color photographic materials. (10) A method for processing a silver halide color photographic material according to claim 9, wherein the color photographic material is processed at a replenishment amount of 200 ml/m^2 or less during continuous processing.