JPH0668620B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

The present invention relates to a color development processing method of a silver halide color photographic light-sensitive material (hereinafter referred to as a photographic element), and more specifically, it relates to a change of a replenishment amount and an influence of evaporation. Dyes with little dependency on fluctuations in bromide ion concentration and treatment time, which can be processed rapidly, and which have high sharpness, can prevent color contamination after treatment, and have excellent photofading properties and high storage stability. The present invention relates to a novel processing method for obtaining an image, and particularly to a processing method with a small replenishment amount and high processing stability.

PRIOR ART The processing of photographic elements basically consists of two steps, color development and desilvering, which consists of a bleaching and fixing step or a bleach-fixing step. In addition to this, rinse treatment, stabilization treatment, and the like are added as additional treatment steps.

In color development exposed silver halide is reduced to silver while the oxidized aromatic primary amine developing agent reacts with the coupler to form a dye. During this process, halogen ions generated by the reduction of silver halide are eluted and accumulated in the developer. In addition, components such as inhibitors contained in the photographic element are also eluted and accumulated in the color developing solution. In the desilvering process, the silver produced by development is bleached with an oxidizing agent and then all silver salts are removed from the photographic element as soluble silver salts with a fixing agent. There is also known a one-bath bleach-fix processing method in which the bleaching step and the fixing step are collectively processed at the same time.

In the color developing solution, the development-inhibiting substance accumulates by developing the photographic element as described above, while the color developing agent and benzyl alcohol are consumed or accumulated in the photographic element and taken out, and the concentration of these components is It will decrease. Therefore, in the development processing method in which a large amount of photographic elements are continuously processed by an automatic developing machine or the like, a means for keeping the components of the color developing solution within a constant concentration range is provided in order to avoid the change of the development finish characteristics due to the change of the component concentrations. is necessary. As such means, a method of replenishing a replenisher for diluting unnecessary increasing components and supplementing deficient components is usually adopted.
Since the replenishment of the replenisher inevitably causes a large amount of overflow and is discarded, this method poses a serious economic and pollution problem. Therefore, in recent years, in order to reduce the overflow solution, a so-called concentrated low replenishment method in which these replenishers are concentrated and replenished in small amounts is widely used. Alternatively, a method in which a regenerant is added to the overflow solution to use it again as a replenisher is also used. Proposed and put to practical use.

[Problems to be Solved by the Invention] These are methods in which the replenishment amount is substantially reduced. If the replenishment amount is extremely reduced, the organic inhibitor and halogen ion concentration eluted in the developer will undergo a large concentration change even with a slight replenishment amount error.
In addition, it is also susceptible to the effect of concentration due to evaporation, and normally the concentration of the above-mentioned fatigue accumulation increases. For example, when the halogen ion concentration rises, the development reaction is suppressed, or the leg portions of the characteristic curve are further suppressed, which causes a problem of high contrast. To avoid this, halogen ions are removed from the overflow solution by ion exchange resin or electrodialysis, and a regenerant is added to replenish the deficient components generated during development and the deficient components lost during the regeneration process, and regenerated as a replenisher. The method to use is proposed.

Regeneration by these ion exchange resins and electrodialysis and concentrated low replenishment methods are easily affected by fluctuations in bromide ion concentration due to the effects of evaporation and regeneration operations. Separately, there is a difference in processing amount, especially at the beginning of the week when orders are high and orders are received. The difference between the high-season and the off-season is the maximum difference of 1: 5, and the composition of the processing solution is drastically different because it is affected by evaporation and the difference in the amount of replenisher. There is a drawback that ends up.

Therefore, in the low replenishment processing and the regenerating method, it is necessary to quantitatively analyze the components for each regeneration and make an effort to make the composition constant, so that it is difficult to carry out the regenerating processing or the low replenishment processing in a laboratory or a minilab without special skills. There are many things.

Such problems are mainly due to changes in the bromide ion, which is a development inhibitor. For example, by reducing the amount of silver bromide in the photographic element, the amount of accumulated bromide ion is reduced or evaporation or replenishment is replenished. It has also been proposed to reduce fluctuations in the concentration of bromide ions due to error in the amount (Japanese Patent Application No.
See 59-173189 and 59-205540. ).

It is presumed that these problems can be solved by, for example, reducing the average grain size of silver halide in the photographic element or improving the developability by reducing the amount of coated silver. In a color developing solution using a certain 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamide ethylaniline, improving the developing property causes a change in the bromide ion concentration in the developing solution. The result is the opposite of the expectation that it will be easily received and the processing stability will be impaired.

However, it is an important issue to shorten the processing time and increase the processing stability.

Conventionally, in color paper processing consisting essentially of silver chlorobromide emulsion, color development is 33 ° C, 3 minutes 30 seconds-bleach-fixing 33 ° C, 1
Minutes 30 seconds-Washing 3 minutes (or stabilizing treatment 3 minutes) -Drying. The total processing time is generally about 8 minutes, but the strong demand of the times is the above-mentioned low replenishment in the economic sense, but short-time processing is also strongly demanded from the viewpoint of shortening the delivery time. ing.

However, as described above, speeding up and stabilization of processing or low replenishment are contradictory problems, and can be said to be a trade-off relationship.

That is, if the replenishment rate is lowered, the concentration of bromide ion as an inhibitor and the concentration of a sulfur compound or a mercapto compound as an emulsion stabilizer are increased, impairing the rapidity and impairing the processing stability.

However, various measures have conventionally been taken to speed up color development for speeding up. Particularly, the above-mentioned developing agents that have been conventionally used as the most suitable developing agents for silver chlorobromide emulsions have a slow permeation of the color developing agent into the photographic element, and various penetrating agents for accelerating it have been studied. For example, a method of adding benzyl alcohol to a color developing solution to accelerate color developing is widely used. However, with this method,
If the treatment was not performed for 3 minutes or more, the color was not sufficiently developed, and besides, there was a drawback that it was easily affected by the subtle bromide ion concentration. A method of increasing the pH of the color developing solution is also known, but when the pH is 10.5 or more, the oxidation of the color developing agent becomes remarkably fast, and there is no suitable buffer solution, so it is susceptible to pH changes and stable. However, there is a problem in that the photographic characteristics described above cannot be obtained and the dependence of processing time increases.

A method of increasing the activity by increasing the color developing agent in the color developing solution is also known, but it is said that the color developing agent becomes an expensive processing solution because it is very expensive, and at the same time, the main agent is difficult to dissolve in water and easily precipitates. Instability also occurs and it is not practically usable.

On the other hand, there is known a method of incorporating a color developing agent into a photographic element in advance in order to achieve rapid color development. For example, a method of incorporating a color developing agent in the form of a metal salt is known (US Pat. No. 3,719,492), but with this method, the photographic element has poor raw storability and is fogged before use or fog during color development. It is known to have the drawback of being easy.

Furthermore, in order to inactivate the amine part of the color developing agent,
For example, a method of forming a Schiff salt and incorporating a color developing agent (US Pat. No. 3,342,559, Research Disclosure, 1976).
No. 15159) is also known, but it is known that these methods have the drawback that color development cannot be started until the color developing agent is hydrolyzed with alkali, and rather the color development is delayed. .

Furthermore, when the color developing agent is directly incorporated, in addition to the drawback that the emulsion during storage is fogged because of the unstable color developing agent, the emulsion film quality becomes weak and various processing problems occur. Known to be.

Furthermore, it is known that 3-pyrazolidones are added to a black-and-white developer containing a developer such as hydroquinone to accelerate development (eg, LFA Mason, Photographi
c Processing Chemistry 103-107 pages, published by Focal Press, 1
966). The fact of incorporating this compound into photographic elements is
Although described in British Patent No. 767,704, in the technique described in the above-mentioned patent specification, it is incorporated in a silver halide photographic light-sensitive material for black and white or a photographic element for reversal, and its purpose is to promote only black and white development. In addition, in addition,
No. -52422 discloses that 3-pyrazolidones are incorporated in a photographic element for the purpose of preventing a reduction in sensitivity of a photographic element containing a 2-equivalent magenta coupler having an oxy type organic split-off group at an active site in an unexposed state. However, these techniques are not suitable as a rapid method for stabilizing the color development process with a low replenishment process.

Further, as a method of accelerating color development by a conventionally known accelerator, US Pat. Nos. 2,950,970 and 2,515,1
No. 47, No. 2,496,903, No. 4,038,075, No. 4,119,462
No., British Patents 1,430,998, 1,455,413, JP-A-53-
No. 15831, No. 55-62450, No. 55-62451, No. 55-62452
No. 55-62453, Japanese Patent Publication No. 51-12322, 55-49728
Although the compounds described in No. 1 and the like were examined, most of the compounds have insufficient promoting effect, and compounds showing a high promoting effect have not only the drawback that fog is formed but also the processing stability. Was not suitable as a method for improving

Further, provision of a substantially light-insensitive silver halide emulsion layer in a photographic element to accelerate development is described in JP-A-50-23.
225, 56-14236, British Patent 1,378,577, OLS2,62
It is known as No. 2,922, etc., but its function is to adsorb development inhibiting substances such as unnecessary halogens released during development and unnecessary leaving groups of DIR couplers, and it does not actively promote development. In addition, the effect of promoting development was small, and although it was effective for the fluctuation of the iodide ion concentration, no processing stabilizing effect was obtained for the fluctuation of the bromide ion concentration.

On the other hand, the speed of color development differs depending on the type of para-phenylenediamine derivative used and is said to depend on the redox potential. Among these color developing agents, N,
N-diethyl-P-phenylenediamine sulfate and 3-methyl-4-
N-Alkyl-substituted, low water-soluble color developing agents such as amino-N, N-diethylaniline hydrochloride have high developing activity and can be accelerated, but the color fading dyes after processing have low dark fading properties and are not preferred. It is known. On the other hand, it is said that it has a high developing activity and is preferable (US Pat. Nos. 3,656,950 and 3,6,950).
58,525, etc.) 3-Methyl-4-amino-N-ethyl-N-β-
Methoxyethylaniline-di-P-toluenesulfonate is certainly quick, but it is not stable in bromide ion concentration, and yellow stain is remarkably generated in the unexposed area of the photographic element after processing. When processed for time,
It has been found that the color developing agent remains unacceptable for rapid processing because it has a drawback that it causes stain generation.

On the other hand, 3-methyl-4 in which a water-soluble alkylsulfonamide group or hydroxyalkyl group was introduced into the N-alkyl group
-Amino-N-ethyl-β-methanesulfonamide ethylaniline sesquisulfate monohydrate and 3-methyl-4
-Amino-N-β-hydroxyethylaniline sulphate has a redox potential as seen in Photographic Science and Engineering Vol.8, No. 3.5-June, 1964, P.125-137. It was said that there was not much difference in the half-wave potentials shown and that both had weak developing activities.

Therefore, it is considered that there is almost no color developing agent having a high development activity for a silver chlorobromide emulsion and an excellent storage stability of a dye image, and generally 3-methyl-4-amino-N-ethyl-N-
β-Methanesulfonamidoethylaniline sulfate was used with benzyl alcohol.

However, in this case, as described above, it is easily affected by the change in the bromide ion concentration. Further, in the concentrated and low replenishment process in which the replenisher is reduced, another problem is an increase in mixing and accumulation of other treatment liquid components. This is because the tank liquid is renewed with the replenishing liquid at a low rate due to the decrease in the replenishing amount, and the service life of the liquid is prolonged.
Contamination of other processing solutions is caused by so-called back contamination in which the processing solution components immediately after development are brought into the color developing solution by splashing of the adjacent processing solution in the processor, a transport leader, a belt or a hanger for hanging the film. Be done. Among these accumulated mixed components, the thiosulfate ion as the fixing agent accelerates the development. That is, this problem particularly strongly occurs when the bleach-fixing process is performed directly after color development. Particularly by promoting the shoulder of the photographic characteristic curve, a significant increase in contrast occurs. Further, an increase in the content of a metal salt as a bleaching agent, especially a ferric salt, promotes the decomposition of hydroxylamine as a preservative to generate ammonia ions. This decomposition reaction is greatly accelerated above 30 ° C. The generation of this ammonia ion promotes physical development similarly to thiosulfate ion, and has a drawback that high contrast is obtained.

Therefore, even if the amount of replenishment is reduced to improve economic and environmental pollution, rapid processing is possible, the photographic performance is maintained constant, and the active ingredient is decomposed even when the processing solution is used for a long time. At present, there is a strong demand for the emergence of a color developing solution that can be stably processed without changing the photographic processing performance.

That is, even when processed with a low replenishing amount using a color developing solution, the bromide ion concentration does not change and constant and appropriate photographic performance can always be maintained for a long period of time, and the obtained coloring dye or uncolored portion is There is a strong demand for the development of a rapid and stable photographic element processing method that does not fade or discolor even after long-term storage.

Therefore, the applicant of the present invention has proposed a technique of Japanese Patent Application No.
The invention shown in No. 60-104698 was previously proposed. The previously proposed technique is a process for developing a photographic element having a photographic constituent layer comprising 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, and at least 1 The photographic element in which the silver halide emulsion of the photosensitive emulsion layer of the layer is substantially a silver chlorobromide emulsion, and the film swelling speed T1 / 2 of the binder of the photographic constituent layer is 30 seconds or less is N-
It is characterized in that processing is carried out at 30 ° C. or higher and 150 seconds or shorter using a color developer containing a hydroxyalkyl-substituted-p-phenylenediamine derivative.

On the other hand, in the industry, high-quality silver halide color photographic light-sensitive materials are desired, and in particular, silver halide photographic light-sensitive materials for color negatives are used for photography and printed on silver halide photographic light-sensitive materials for color photographic paper. In the so-called color negative / positive system for obtaining a final image, there is a problem that the silver halide photographic light-sensitive material for color photographic paper is low in image quality, particularly low in image sharpness, as compared with the silver halide photographic light-sensitive material for color negative. As the prevention technology,
British Patents 584,609 and 1,277,429, JP-A-48-85130
No. 49-99620, 49-114420, 49-129537
No. 52-108115, No. 59-25845, U.S. Pat.
82, 2,533,472, 2,956,879, 3,125,448
No. 3,148,187, No. 3,177,078, No. 3,247,127,
3,540,887, 3,575,704, 3,653,905, 3,7
It is known to incorporate water-soluble dyes into photographic elements as described in 18,472, 4,071,312, 4,070,352 and the like.

Therefore, the present inventor has attempted to increase the sharpness of the image by applying such a water-soluble dye to the previously proposed technique, and has found the following problems.

That is, the sharpness is improved by increasing the reflection density, and the processing with the N-hydroxyalkyl-substituted-p-phenylenediamine derivative developing agent enables rapid processing and reduces the dependency on the fluctuation of the bromide ion. It was found that the sex deteriorates. 30 ℃ to prevent this
From the above, it is preferable to carry out the treatment for 150 seconds or less, in which case the water-soluble dye is found to remain in the photographic element and easily cause color stain.

The above-mentioned drawbacks are especially caused by color paper (print).
In the case of, it is fatal and becomes a big obstacle.

Therefore, an object of the present invention is to obtain a constant and proper photographic performance for a long period of time without being affected by a change in bromide ion concentration even when rapidly processed with a low replenishing amount using a color developer. Provide a rapid and stable method for processing a photographic element that not only does not cause fading or discoloration even when the colored dye or uncolored part is stored for a long period of time, but also has high sharpness and can prevent color contamination after processing. Especially.

[Means for Solving the Problem] The processing method of the present invention which achieves the above object comprises a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a reflective support. A method of developing a photographic element having a photographic constituent layer comprising a silver halide emulsion of at least one light sensitive emulsion layer being a substantial silver chlorobromide emulsion, and in at least one of said photographic constituent layers To a photographic element containing at least one compound represented by the following general formula (I) or (II), and having an optical reflection density of 0.5 or more at 470 nm, 550 nm or 680 nm is N-hydroxyalkyl-substituted-p- It is characterized in that a color developer containing a phenylenediamine derivative is used for development processing at 30 ° C. or higher and 150 seconds or shorter.

General formula (I) In the formula, R, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are hydrogen atom, halogen atom, hydroxy group, alkyl group, alkoxy group, -SO ₃ M
Alternatively, it represents -NHCH ₂ SO ₃ M. M represents a cation.

General formula (II) In the formula, R ₆ and R ₆ ′ each represent an alkyl group, an aryl group or a heterocyclic group. R ₇ and R ₇ ′ are each a hydroxy group, an alkoxy group, a substituted alkoxy group, a cyano group, a trifluoromethyl group, —COOR ₈ , —CONHR ₈ , —NHCOR ₈ , an amino group, and an alkyl group having 1 to 4 carbon atoms. A substituted amino group or (Wherein p and q represent 1 or 2 and X represents an oxygen atom, a sulfur atom or a —CH ₂ — group). R ₈ represents a hydrogen atom, an alkyl group or an aryl group. L represents a methine group. n represents 0, 1 or 2.
M represents a cation.

According to the present invention, the object of the present invention can be achieved, and in particular,
Previously proposed technology and water-soluble or N-hydroxyalkyl substitution
-By using a specific dye that decolorizes with a color developer containing a p-phenylenediamine derivative developing agent, all of high sharpness, rapid processing, low replenishment, image storability, processing variability and post-processing color contamination can be reduced. It was surprising by the inventor that satisfactory results were obtained in terms of points.

In the present specification, "substantially silver chlorobromide emulsion" to "substantially silver chlorobromide emulsion" means that a trace amount of silver iodide may be contained in addition to silver chlorobromide, and for example, 0.3 This means that silver iodide may be contained in an amount of not more than mol%, more preferably not more than 0.1 mol%. However, silver chlorobromide emulsions containing no silver iodide are most preferred in the present invention.

Further, in the present specification, the photographic constituent layer means all hydrophilic colloid layers involved in image formation, for example, a silver halide emulsion layer, an undercoat layer, an intermediate layer (simple intermediate layer, filter layer, ultraviolet absorbing layer, Antihalation layer etc.), protective layer etc. As described above, the photographic constitutional layer of the present invention means all hydrophilic colloid layers on the side of the reflective support on which the photosensitive silver halide emulsion layer is coated.

Hereinafter, the present invention will be described in more detail.

First, the compounds represented by the general formulas (I) and (II) used in the present invention will be described.

General formula (I) In the formula, R, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are hydrogen atoms; halogen atoms (for example, chlorine atoms, bromine atoms, fluorine atoms); hydroxy groups; alkyl groups, preferably 1 to 1 carbon atoms. 4 alkyl groups (eg, methyl, ethyl, propyl);
It represents an alkoxy group (for example, a methoxy group, an ethoxy group, a propoxy group); -SO ₃ M; or a -NHCH ₂ SO ₃ M group. M
Is a cation and represents an alkali metal (eg, sodium atom, potassium atom); ammonium, an organic ammonium salt (eg, pyridinium, piperidinium, triethylammonium, triethanolamine, etc.).

Typical specific examples of the compound represented by the general formula (I) are shown below, but the invention is not limited thereto.

[Exemplified compound]

General formula (II) In the formula, R ₆ and R ₆ ′ each represent an optionally substituted alkyl group, an aryl group or a heterocyclic group, and as the aryl group, 4-sulfophenyl group, 4- (δ-sulfobutyl) phenyl group, 3-sulfophenyl group, 2,5-disulfophenyl group, 3,5-disulfophenyl group, 6,8-disulfo-2-
Naphthyl group, 4,8-disulfo-2-naphthyl group, 3,5-dicarboxyphenyl group, 4-carboxyphenyl group and the like, and this aryl group is a sulfo group, a sulfoalkyl group, a carboxy group, and a carbon number of 1 to 5 An alkyl group (for example, a methyl group,
It may have an ethyl group, etc.), a halogen atom (eg, chlorine atom, bromine atom, etc.), an alkoxy group having 1 to 4 carbon atoms (eg, methoxy group, ethoxy group, etc.), or a phenoxy group.

Further, the sulfo group may be bonded to the aryl group via a divalent organic group, for example, 4- (4-sulfophenoxy)
Examples thereof include a phenyl group, a 4- (2-sulfoethyl) phenyl group, a 3- (sulfomethylamino) phenyl group and a 4- (2-sulfoethoxy) phenyl group.

The alkyl group represented by R ₆ and R ₆ ′ may be linear, branched or cyclic and preferably has 1 to 4 carbon atoms, and examples thereof include an ethyl group and a β-sulfoethyl group.

Examples of the heterocyclic group include a 2- (6-sulfo) benzthiazolyl group and a 2- (6-sulfo) benzoxazolyl group, and a halogen atom (for example, a fluorine atom,
Chlorine atom, bromine atom etc.), alkyl group (eg methyl group, ethyl group etc.), aryl group (eg phenyl group etc.), carboxyl group, sulfo group, hydroxy group, alkoxy group (eg methoxy group etc.), aryloxy It may have a substituent such as a group (eg, a phenoxy group).

R ₇ and R ₇ ′ are each a hydroxy group; an alkoxy group having 1 to 4 carbon atoms (eg, methoxy group, ethoxy group, isopropoxy group, n-butyl group); a substituted alkoxy group, for example, a halogen atom or a carbon atom having up to 2 carbon atoms. alkoxy group having 1 to 4 carbon atoms which is substituted with an alkoxy group (e.g. beta-chloroethoxy group, beta-methoxyethoxy group), cyano groups, trifluoromethyl _{group; -COOR 8, -CONHR 8, -NHCOR} 8 (R ₈ represents a hydrogen atom; an alkyl group, preferably an alkyl group having 1 to 4 carbon atoms; or an aryl group, for example, a phenyl group or a naphthyl group, wherein the alkyl group and the aryl group have a sulfo group or a carboxy group as a substituent. An amino group; a substituted amino group substituted with an alkyl group having 1 to 4 carbon atoms (eg, ethylamino group, dimethylamino group, diethylamino group) Di -n- butylamino group); or (Wherein p and q represent an integer of 1 or 2 and X represents an oxygen atom, a sulfur atom or a -CH ₂ -group) (for example, a morpholino group, a piperidino group,
Piperazino group).

The methine group represented by L is substituted with an alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group, isopropyl group, tertiary butyl group, etc.) or aryl group (eg, phenyl group, tolyl group, etc.). May be.

Further, at least one of the sulfo group, sulfoalkyl group and carboxy group of the compound is an alkali metal (eg sodium, potassium), alkaline earth metal (eg calcium, magnesium) ammonia or an organic base (eg diethylamine, triethylamine, morpholine, Pyridine, piperidine, etc.) may form a salt. n represents 0, 1 or 2. M represents the above cation.

Next, typical examples of the compound represented by the general formula (II) are shown below, but the invention is not limited thereto.

[Exemplified compound]

The compound represented by the general formula (I) or (II) (hereinafter,
It is called the AI dye of the present invention. ) Can be added to the light-sensitive silver halide emulsion layer and / or the non-light-sensitive photographic constituent layer.

Two or more kinds of the AI dye of the present invention may be contained in the same layer. Also, the same AI dye may be included in two or more different layers.

Generally, these AI dyes of the present invention are preferably used in an amount of 2 × 10 ^{−4 to} 5 × 10 ⁻² mol, and more preferably 1 × 10 ⁻³ to 1 × 10 ⁻² mol per mol of silver in all emulsion layers. .

Photographic elements containing the AI dyes of this invention are 470 nm, 550 nm or 680 nm.
The optical reflection density of nm is 0.5 or more, the AI dye of the present invention is a dye that is water-soluble or decolorized by a developing solution, and if the optical reflection density is less than 0.5, the effect of improving the image sharpness is not seen. In addition, the color reproducibility is poor. Although the upper limit of the optical reflection density is not limited, it is 2.0 in terms of sensitivity and decolorization property.
The following is preferable.

The light sensitive emulsion layers of the photographic element processed according to this invention are:
At least one layer may be substantially composed of a silver chlorobromide emulsion (hereinafter referred to as the silver chlorobromide emulsion of the present invention), but all of the light-sensitive emulsion layers are composed of the silver chlorobromide emulsion of the present invention. Preferably.

It is preferable that the coated silver amount in the photographic element of the present invention is small in that there is no delay in development with respect to increase in bromide and sufficient dye formation can be performed even in a short time, and 0.3 to 1 g / m ² , particularly 0.4.
The maximum effect is obtained at ~ 0.8g / m ² .

The crystal of the silver halide grain used in the present invention may be a normal crystal, a twin crystal or another crystal, and has a [1.0.0] plane and a [1.1.1] plane.
Any surface ratio can be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may be a layered or phase structure (core shell type) having different inside and outside. . Further, these silver halides may be of a type that forms a latent image mainly on the surface or may be of a type that is formed inside the grain. Further, tabular silver halide grains (JP-A-58-113934)
Japanese Patent Application No. 59-170070).

The silver halide used in the photographic element of the present invention may be a polydisperse emulsion having a wide distribution of average grain sizes, but a substantially monodisperse emulsion is preferred.

The above-mentioned substantially monodisperse silver halide grains, most of the silver halide grains appear to have the same shape when the emulsion is observed by an electron micrograph, and the grain sizes are uniform,
Further, it has a particle size distribution as defined by the following formula. That is, when the standard deviation s of the particle size distribution is divided by the average particle size, the value is 0.20 or less, preferably 0.
15 or less.

The average grain size of silver halide can be measured by various methods generally used in the art for the above purpose, and the average grain size of the silver halide can be cubic silver halide grains. In the case of, it is the length of one 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.

The color development treatment in the present invention is performed at 30 ° C or higher for 150 seconds or less, preferably 33 ° C or higher and 120 seconds or less, and most preferably 35 ° C or higher and 90 seconds or less.
When the treatment is performed at 30 ° C. or higher for 150 seconds or longer, the storage stability of the dye deteriorates. In particular, the treatment time is more important than the treatment temperature, and if it exceeds 150 seconds, the photobleaching property of the cyan dye remarkably increases, which is not preferable. The processing temperature is higher than the storage stability of the dye in order to finish development in a short time, and is preferably 30 ° C. or higher and 50 ° C. or lower, higher is rather preferable because short-time processing is possible, and particularly preferable. Is 33 ° C
Or more, 48 ℃ or less, most preferably 35 ℃ or more, 43 ℃
It is to process below.

The pH of the color developer is usually preferably 7 or more, more preferably 9 to 13.

The developing agents effective in the present invention are quaternary ammonium salts of N-hydroxyalkyl-substituted-p-phenylenediamine compounds, especially those represented by the following general formula.

In the formula, R ₁ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and R ₂ is a hydrogen atom or 1 to 4 carbon atoms. Is an alkyl group having R 1 and R ₃ may have a hydroxyl group 1
Is an alkyl group having 4 to 4 carbon atoms, A is an alkyl group having at least one hydroxyl group and optionally having a branch, and more preferably Is. R ₄ , R ₅ and R ₆ each represent a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms which may have a hydroxyl group, and at least one of R ₄ , R ₅ and R ₆ is a hydroxyl group. Alternatively, it is an alkyl group having a hydroxyl group. n ₁ , n ₂ and n ₃ are 0,
1, 2 or 3 and HX represents hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, nitric acid or phosphoric acid.

Such p-phenylenediamine color developing agents are unstable with their free amines and are commonly used as salts (most commonly identified by the above formula). Typical example is 4-amino-3-methyl-N-ethyl
-N- (β-hydroxyethyl) -aniline salt and 4-amino-
N-ethyl-N- (β-hydroxyethyl) -aniline salt may be mentioned.

Preferably, in the present invention, 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) -aniline sulfate-
Hydrate [This is commercially available under the name CD-4, and is used in most color photographic systems (eg Eastman Kodak C41 system or Konishi Roku Photo Co., Ltd. CNK-4 system for developing color negative film). Has been used) to be particularly effective.

Preferred N-hydroxyalkyl-substituted-p for use in the present invention
-Phenylenediamine derivatives include the followings, but are not limited to these exemplified compounds.

[Exemplified compound]

Hydrochloric acid, sulfuric acid, and p-toluenesulfonic acid salt of the compounds (1) to (8) are particularly preferable.

Among these exemplified compounds NO. (1), (2), (6), (7) and (8)
Are preferably used, and particularly, NO. (1), (2) and (6) are preferably used. Further, particularly NO. (1) is particularly preferably used in the present invention, and the solubility of the color developing agent of the present invention in water is extremely high, so that the use amount thereof is preferably in the range of 1 g to 100 g per processing solution. It is preferably used in a range of 3 to 30 g, more preferably.

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

It is needless to say that the color developing agent according to the present invention can be used in combination with other color developing agents in addition to the N-hydroxyalkyl-substituted-p-phenylenediamine derivative developing agent. Typical color developing agents that may be used in combination are p-phenylenediamine type compounds, and the following are preferred examples.

4-amino-N, N-diethylaniline, 3-methyl-4-amino-
N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N
-β-methoxyethylaniline, 3-methyl-4-amino-N-
Ethyl-N-β-metasulfonamidoethylaniline, 3-
Methoxy-4-amino-N-ethyl-N-β-methoxyethylaniline, 3-acetamido-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, sulfites, p-toluenesulfonates and phosphates.

Further, for example, JP-A-48-64932, 50-131526,
No. 51-95849 and Bent's Journal of the American Chemical Society, Volume 73, 3100-
The one described on page 3125 (1951) is also mentioned as a typical example. The amount of the color developing agent that may be used in combination is not particularly limited, but is preferably the same molar amount or less with respect to the color developing agent of the present invention.

The color developer of the present invention preferably has a bromide ion concentration of 5 × 10 ⁻³ mol or more. In the present invention, a higher bromide ion concentration is preferable because the replenishment amount can be reduced. In the conventional developing method, it has been said that the bromide ion concentration is preferably low because it suppresses the development reaction, but in the combination of the photographic element and the color developing solution of the present invention, it is quite opposite that the bromide ion concentration is preferably high, and The object of the invention is achieved. In other words, in the present invention, the replenishment amount can be reduced because it is less affected by the bromide ion concentration.

The bromide ion concentration is preferably 1 × 10 ^-2 mol or more, particularly preferably 1.5 × 10 ^-2 mol or more. If the bromide ion concentration is too high, development is suppressed and the influence of the bromide ion concentration begins to occur. ^-2 mol or more is not preferable. The chloride ion concentration has no effect.

The processing system for the photographic element of the present invention can use a color developing bath containing the color developing agent according to the present invention. In addition, various treatments such as bath treatment, for example, a spray method in which the treatment liquid is atomized, a wetting method by contact with a carrier impregnated with the treatment liquid, or a development method using a viscous treatment liquid Any scheme can be used.

In addition to the above, the method of processing the photographic element of the present invention is not particularly limited, and any processing method can be applied. For example,
Typical examples thereof include a method of performing bleach-fixing treatment after color development and further washing and / or stabilizing treatment if necessary, and a method of performing bleaching and fixing separately after color development, and further washing with water and / or as necessary. Or a method of stabilizing treatment;
Alternatively, pre-hardening, neutralization, color development, stop-fixing, washing, bleaching, fixing, washing, post-hardening, washing in this order, color developing, washing, supplementary color developing, stopping, bleaching, fixing, washing, Any method may be used, such as a method in which the development is performed in the order of stability, a development method in which developed silver produced by color development is subjected to halogenation bleaching, and then color development is performed again to increase the amount of dye formed.

In the color developer used in the present invention, various components that are usually added, for example, sodium hydroxide, an alkali agent such as sodium carbonate, an alkali metal sulfite,
Alkali metal bisulfite, alkali metal thiocyanate, alkali metal halide, benzyl alcohol,
A water softening agent, a thickening agent, a development accelerator and the like may be optionally contained.

Examples of additives other than the above added to the color developing solution include potassium bromide, bromide such as sodium bromide,
Alkali iodide, nitrobenzimidazole, mercaptobenzimidazole, 5-methyl-benzotriazole,
In addition to compounds for rapid processing liquids such as 1-phenyl-5-mercaptotetrazole, there are stain inhibitors, anti-sludge agents, preservatives, layering effect accelerators, chelating agents and the like.

As the bleaching agent used in the bleaching solution or the bleach-fixing solution in the bleaching step, those in which metal ions such as iron, cobalt and copper are coordinated with an organic acid such as aminopolycarboxylic acid or oxalic acid, citric acid are generally known. There is. And the following can be mentioned as a typical example of said amino polycarboxylic acid.

Ethylenediaminetetraacetic acid Diethylenetriaminepentaacetic acid Propylenediaminetetraacetic acid Nitrilotriacetic acid Iminodiacetic acid Glycol etherdiaminetetraacetic acid Ethylenediaminetetrapropionic acid Ethylenediaminetetraacetic acid disodium salt Diethylenetriaminepentaacetic acid pentasodium salt Nitrilotriacetic acid sodium salt You may contain an agent. When a bleach-fixing solution is used in the bleaching step, a solution having a composition containing a silver halide fixing agent in addition to the bleaching agent is applied. Further, the bleach-fixing solution may further contain a halogen compound such as potassium bromide. And, as in the case of the bleaching solution, various other additives such as pH buffer, fluorescent whitening agent, defoaming agent, surfactant, preservative, chelating agent, stabilizer, organic solvent, etc. Addition,
It may be contained.

The silver halide fixing agent is, for example, sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, or thiourea, thioether, etc. Compounds forming a silver salt of

Processing other than color development of the photographic element of the present invention, for example, bleach-fixing (or bleaching, fixing), and further, various processing steps such as washing and stabilization, if necessary, is carried out at a temperature of 30 ° C. from the viewpoint of rapid processing. It is preferable to carry out the above.

The photographic elements of the present invention are disclosed in JP-A Nos. 58-14834 and 58-105145.
No. 58-134634, No. 58-18631 and Japanese Patent Application No. 58
-2709 and 59-89288 may be subjected to water washing alternative stabilization treatment.

In one or more of the photographic constituent layers of the photographic element of the present invention, a dye (AI dye) other than the AI dye of the present invention, which is decolorizable with a water-soluble or color developing solution, is used within a range not impairing the effects of the present invention. Can be used together.

The 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 ammonium method.

Further, for example, a method may be used in which seed particles are formed by an acidic method and further grown by an ammonia method having a high growth rate to grow to a predetermined size. When the silver halide grains are grown, the pH, pAg, etc. in the reaction vessel are controlled, and the amount of silver ions corresponding to the growth rate of the silver halide grains as described in JP-A-54-48521 is used. It is preferable to sequentially and simultaneously inject and mix halide ions with halide ions.

The silver halide grains according to the present invention are preferably prepared as described above. The composition containing the silver halide grains is referred to herein as a silver halide emulsion.

These silver halide emulsions include active gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea, and cystine; sulfur sensitizers; selenium sensitizers; reduction sensitizers such as stannous salt and thiourea dioxide. Noble metal sensitizers such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurothio-3-methylbenzothiazolium chloride, or ruthenium, palladium, platinum, rhodium, iridium Water-soluble salt sensitizers such as ammonium chloroparadate, potassium chloroplatinate and sodium chloroparadate (some of these are used as sensitizers or antifoggants depending on the amount). Etc.) or in combination as appropriate (for example, a gold sensitizer and a sulfur sensitizer are used in combination, Combination etc. with a sensitizer and a selenium sensitizer) to be chemically sensitized.

The silver halide emulsion according to the present invention is chemically ripened by adding a sulfur-containing compound, and before, during, or after the chemical ripening, at least one kind of nitrogen-containing heteroaryl having a hydroxytetrazaindene and a mercapto group. You may make it contain at least 1 sort (s) of a ring compound.

The silver halide used in the present invention contains a suitable sensitizing dye in an amount of 5 × 10 ^{−8 to} 3 × 10 ^{−3 with} respect to 1 mol of silver halide in order to impart photosensitivity to a desired wavelength region. It may be optically sensitized by adding a mole. Various kinds of sensitizing dyes can be used, and one kind or a combination of two or more kinds of sensitizing dyes can be used. Examples of the sensitizing dye that can be advantageously used in the present invention include the following.

That is, as a sensitizing dye used in a blue-sensitive silver halide emulsion, for example, West German Patent 929,080 and U.S. Pat.
No. 2,493,748, 2,503,776, 2,519,001,
2,912,329, 3,656,959, 3,672,897, 3,6
94,217, 4,025,349, 4,046,572, British patent 1,
242,588, Japanese Examined Patent Publication Nos. 44-14030, 52-24844 and the like can be mentioned. Examples of sensitizing dyes used in green-sensitive silver halide emulsions include U.S. Patents 1,939,201, 2,072,908, 2,739,149, and
Typical examples thereof include cyanine dyes, merocyanine dyes and complex cyanine dyes such as those described in 2,945,763 and British Patent 505,979. Further, as the sensitizing dye used in the red-sensitive silver halide emulsion, for example, U.S. Pat.Nos. 2,269,234 and 2,270,378,
Representative examples thereof include cyanine dyes, merocyanine dyes, or complex cyanine dyes such as those described in Nos. 2,442,710, 2,454,629, and 2,776,280. Furthermore, U.S. Patents 2,213,995 and 2,493,7
Cyanine dyes, merocyanine dyes or complex cyanine dyes such as those described in Nos. 48, 2,519,001 and West German Patent 929,080 can be advantageously used in a green-sensitive silver halide emulsion or a red-sensitive silver halide emulsion.

These sensitizing dyes may be used alone or in combination.

The photographic element of the present invention may be optionally optically sensitized to a desired wavelength region by a spectral sensitization method using a cyanine or merocyanine dye alone or in combination.

A particularly preferable example of the spectral sensitization method is, for example, Japanese Patent Publication No. 43936/43936, which relates to a combination of benzimidazolocarbocyanine and benzoxazolocarbocyanine.
No. 43, No. 22884, No. 45-18433, No. 47-37443,
48-28293, 49-6209, 53-12375, JP
52-23931, 52-51932, 54-80118, 58-1
53926, 59-116646, 59-116647 and the like.

Further, as a combination of a carbocyanine having a benzimidazole nucleus and another cyanine or merocyanine, for example, Japanese Patent Publication Nos. 45-25831, 47-11114 and 47
-25379, 48-38406, 48-38407, 54-345
No. 35, No. 55-1569, JP-A No. 50-33220, No. 50-38526
No. 51, No. 51-107127, No. 51-115820, No. 51-135528
No. 52-104916 and No. 52-104917.

Furthermore, examples of combinations of benzoxazolocarbocyanine (oxacarbocyanine) with other carbocyanines include, for example, JP-B-44-32753 and 46-11627.
JP-A-57-1483, and those relating to merocyanine include, for example, JP-B-48-38408, 48-41204, and 50-
40662, JP-A-56-25728, 58-10753, 58-9
1445, 59-116645, 50-33828 and the like.

Further, examples of combinations of thiacarbocyanine with other carbocyanines include, for example, Japanese Patent Publication Nos. 43-4932 and 43-43.
-4933, 45-26470, 46-18107, 47-8741
JP-A-59-114533, etc., and the method described in JP-B-49-6207 using zeromethine or dimethine merocyanine, monomethine or trimethine cyanine and styryl dyes can be advantageously used.

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 a fluorinated alcohol described in JP-B-50-40659 can be prepared in advance. It is used by dissolving it in the hydrophilic organic solvent.

The silver halide emulsion may be added at any time from the start of chemical ripening, during ripening, and at the end of ripening, and in some cases, it may be added immediately before the emulsion coating.

Each silver halide emulsion layer according to the present invention may contain a coupler, that is, a compound capable of reacting with an oxidized product of an N-hydroxyalkyl-substituted-p-phenylenediamine derivative developing agent to form a dye.

In the present invention, various yellow couplers, magenta couplers and cyan couplers can be used as the above-mentioned coupler. These couplers may be 2-equivalent type, 4-equivalent type coupler, or may be a combination of the two. Further, in combination with these couplers, a diffusible dye-releasing coupler and the like may be used. It is also possible to use.

Examples of the yellow coupler include a closed ketomethylene compound and an active site called a so-called 2-equivalent coupler.
o-aryl substituted coupler, active point-o-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, active point -o
-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. Patents 2,875,057 and 3,265,506.
No. 3,408,194, 3,551,155, 3,582,322,
3,725,072, 3,891,445, West German patent 1,547,868
No. 2, West German Application Publication No. 2,219,917, No. 2,261,361, No. 2,41
4,006, British Patent 1,425,020, Japanese Patent Publication No. 51-10783,
JP-A-47-26133, JP-A-48-73147, JP-A-51-102636,
50-6341, 50-123342, 50-130442, 51
-21827, 50-87650, 52-82424, 52-115
Examples thereof include those described in No. 219 and No. 58-95346.

Examples of the magenta coupler used in the present invention include pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based and indazolone-based compounds.

These magenta couplers are the same as the yellow couplers 4
Not only the equivalent type coupler but also a two equivalent type coupler may be used. As a specific example of the magenta coupler, US Pat.
600,788, 2,983,608, 3,062,653, 3,127,2
No. 69, No. 3,311,476, No. 3,419,391, No. 3,519,429
No., No. 3,558,319, No. 3,582,322, No. 3,615,506,
No. 3,834,908, No. 3,891,445, West German patent 1,810,464
Issue, West German patent application (OLS) 2,408,665, 2,417,945
No. 2, 2,418,959, 2,424,467, Japanese Patent Publication No. 40-6031
No. 51-20826, No. 52-58922, No. 49-129538.
No. 49-74027, No. 50-159336, No. 52-42121,
49-74028, 50-60233, 51-26541, 53
-55122, Japanese Patent Application No. 55-110943 and the like can be mentioned.

Further, useful cyan couplers used in the present invention include, for example, phenol type and naphthol type couplers. And 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. Patents 2,369,929 and 2,434,272.
No. 2, 2,474,293, 2,521,908, 2,895,826,
3,034,892, 3,311,476, 3,458,315, 3,4
76,563, 3,583,971, 3,591,383, 3,767,41
No. 1, 4,004,929, West German patent application (OLS) 2,414,830
No. 2,454,329, JP-A-48-59838, 51-26034.
No. 48-5055, 51-146827, 52-69624,
Examples thereof include those described in Nos. 52-90932 and 58-95346.

The amount of the above-mentioned coupler usable in the present invention is not limited, but is preferably 1 × 10 ^{−3 to} 5 mol, and more preferably 1 × 10 ^{−2 to} 5 × 10 ⁻¹ , per mol of silver.

The photographic element of the present invention may contain a compound (DIR compound) which releases or forms a development inhibitor by reacting with an oxidized product of an N-hydroxyalkyl-substituted-p-phenylenediamine derivative developing agent.

To incorporate these couplers in the silver halide emulsion according to the present invention, when the couplers and the like are alkali-soluble, they may be added as an alkaline solution,
When it is oil-soluble, it can be prepared according to, for example, U.S. Pat.
No. 2, No. 2,801,170, No. 2,801,171, No. 2,272,19
No. 1 and No. 2,304,940 According to the method described in each specification, couplers and the like are dissolved in a high-boiling point solvent, if necessary in combination with a low-boiling point solvent, dispersed in fine particles and added to a silver halide emulsion. Is preferred. At this time, other hydroquinone derivatives, ultraviolet absorbers, anti-fading agents and the like may be used in combination if necessary. It is also possible to use a mixture of two or more couplers. Further, to describe in detail the addition method of couplers and the like in the present invention,
Organic acid amides, carbamates, esters, ketones, urea derivatives, ethers, together with one or more couplers, if necessary, other couplers, hydroquinone derivatives, anti-fading agents, ultraviolet absorbers and the like. , Hydrocarbons, etc., especially di-n-butyl phthalate, tri-cresyl phosphate, triphenyl phosphate, di-isooctyl azelate, di-n-butyl sebacate, tri-n-hexyl phosphate, -N, N-di -Ethyl-caprylamidobutyl, -N, N-diethyllaurylamide, n-pentadecyl phenyl ether, di-octyl phthalate, n-nonylphenol, 3-pentadecyl phenyl ethyl ether, 2,5-di-sec-amylphenyl High boiling solvents such as butyl ether, monophenyl-di-o-chlorophenyl phosphate or fluoroparaffin, And / or methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, cyclohexanol, diethylene glycol monoacetate, nitromethane, carbon tetrachloride, chloroform, cyclohexanetetrahydrofuran, methyl alcohol, acetonitrile, dimethylformamide, dioxane, methyl ethyl ketone, etc. Dissolves in a low boiling point solvent and is anionic surfactants such as alkylbenzene sulfonic acid and alkylnaphthalene sulfonic acid and / or nonionic surfactants such as sorbitan sesquioleate and sorbitan monolauric acid ester and / or hydrophilicity such as gelatin. Mixed with an aqueous solution containing a hydrophilic binder, emulsified and dispersed with a high-speed rotating mixer, colloid mill or ultrasonic dispersion device, etc., and silver halide emulsion It is added.

In addition, the above-mentioned couplers and the like may be dispersed by using a latex dispersion method. The latex dispersion method and its effect are described in JP-A-49-74538, JP-A-51-59943, JP-A-54-32552 and Research Disclosure, August 1976, NO.148.
50, p. 77-79.

Suitable latices include, for example, styrene, acrylates,
n-butyl acrylate, n-butyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2- (methacryloyloxy) ethyltrimethylammonium methosulfate, 3- (methacryloyloxy) propane-1-sulfonic acid sodium salt, N-isopropylacrylamide,
Homopolymers, copolymers and terpolymers of monomers such as N- [2- (2-methyl-4-oxopentyl)] acrylamide, 2-acrylamido-2-methylpropanesulfonic acid and the like.

The photographic elements of this invention can contain various other photographic additives. For example, antifoggants, stabilizers, ultraviolet absorbers, color stain inhibitors, fluorescent whitening agents, color image fading inhibitors, antistatic agents, hardeners, surface active agents described in Research Disclosure Magazine No. 17643. Agents, plasticizers, wetting agents and the like can be used, and particularly when an ultraviolet absorber is used, it is preferably polymerized or liquefied as described above.

In the photographic element of the present invention, hydrophilic colloids used for preparing emulsions include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, albumin, protein such as casein, hydroxyethyl cellulose derivative, carboxymethyl cellulose. And the like, such as cellulose derivatives, starch derivatives, polyvinyl alcohol, polyvinyl imidazole, polyacrylamide, and other single or copolymer synthetic hydrophilic polymers.

Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used for coating the emulsion layers and other photographic constituent layers used in the present invention. Also, U.S. Patents 2,761,791 and 2,94
It is also possible to use a simultaneous coating method of two or more layers according to the method described in 1,898.

In the photographic element of the present invention, it is optional to provide an intermediate layer according to the purpose, and various layers such as a filter layer, an anti-curl layer, a protective layer and an antihalation layer may be appropriately combined and used as a photographic constituent layer. You can In these photographic constituent layers, a hydrophilic colloid which can be used in the emulsion layer as described above can be similarly used as a binder, and in the layer, the hydrophilic colloid can be contained in the emulsion layer as described above. Various photographic additives can be included.

The support of the photographic element of the present invention includes, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, a transparent support provided with a reflective layer, or in combination with a reflector, such as a glass plate, cellulose acetate, cellulose nitrate or Examples thereof include polyester films such as polyethylene terephthalate, polyamide films, polycarbonate films, polystyrene films, and the like, and these supports are appropriately selected according to the intended use of the photographic element.

[Effect of the Invention] According to the present invention, constant and appropriate photographic performance can always be maintained for a long period of time without being affected by changes in bromide ion concentration even when rapidly processed with a low replenishing amount using a color developer. Furthermore, a method for processing a photographic element that is highly sharp and yet capable of preventing color contamination after processing, and that does not cause fading or discoloration of the obtained coloring dye or uncolored portion even after long-term storage, is provided. Can be provided.

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

Example 1 On a paper support laminated on both sides with polyethylene, the following layers were sequentially coated from the support side to prepare photographic element sample No. 1.

Layer 1 ... 1.2 g / m ² gelatin, 0.32 g / m ² (silver equivalent, the same applies below) blue-sensitive silver chlorobromide emulsion (silver bromide content 80 mol%), 0.50 g / m ² 0.80 dissolved in dioctyl phthalate
A layer containing g / m ² of a yellow coupler (Y-1).

Layer 2 An intermediate layer comprising 0.70 g / m ² of gelatin, 12 mg / m ² of the AI dye exemplified compound (A-1), and 6 mg / m ² of (B-22).

Layer 3: 1.25 g / m ² gelatin, 0.25 g / m ² green-sensitive silver chlorobromide emulsion (silver bromide content 70 mol%), 0.62 g dissolved in 0.30 g / m ² dioctyl phthalate / m ² layer containing magenta coupler (M-1).

Layer 4: an intermediate layer consisting of 1.20 g / m ² of gelatin.

Layer 5 ··· 1.20g / m ² of gelatin, 0.30 g / m ² of red-sensitive silver chlorobromide emulsion (silver bromide content 70 mol%), 0.45 g dissolved in dioctyl phthalate 0.20 g / m ² A layer containing a cyan coupler (C-1) of / m ² .

Layer 6 ... 0.30 g / m ² UV absorber dissolved in 1.00 g / m ² gelatin and 0.20 g / m ² dioctyl phthalate (UV-
A layer containing 1).

Layer 7 ... A layer containing 0.50 g / m ² of gelatin.

As a hardener, 2,4-dichloro-6-hydroxy-S-triazine sodium was added to layers 2, 4 and 7 so that the amount was 0.017 g per 1 g of gelatin.

In addition, Sample N was prepared in the same manner as Sample No. 1 except that the amount of the AI dye (B-22) in Layer 2 in Sample No. 1 was changed to 18 mg / m ^2.
Compared with O.2, instead of layer 2 AI dye (B-22)
Samples No. 3 and No. 4 were prepared using (1).

Each of the above sample Nos. 1 to 4 was exposed through a wedge for measuring MTF value and then processed in the next step.

Processing step (38 ° C.) Color development 1 minute 30 seconds Bleach fixing 1 minute 30 seconds Washing with water 1 minute Drying 60-80 ° C. 2 minutes The composition of each processing solution is as follows.

[Color developer] Pure water 800 ml Benzyl alcohol 15 ml Hydroxyamine sulfate 2.0 g Potassium bromide 0.6 g Sodium chloride 1.0 g Potassium sulfite 2.0 g Triethanolamine 2.0 g Color developing agent (sulfate of Exemplified Compound (1)) 6.0 g 1 -Hydroxyethylidene-1,1-diphosphonic acid (60% aqueous solution) 1.5 ml Potassium carbonate 32 g Whitex BB (50% aqueous solution) (optical brightener, Sumitomo Chemical Co., Ltd.) 2 ml Add pure water to 20% Adjust the pH to 10.2 with potassium hydroxide or 10% dilute sulfuric acid.

[Bleach-fixing solution] Pure water 550 ml Ethylenediaminetetraacetic acid iron (III) ammonium 65 g Ammonium thiosulfate 85 g Sodium hydrogen sulfite 10 g Sodium metabisulfite 2 g Ethylenediaminetetraacetic acid-2 sodium 20 g Sodium bromide 10 g Add 1 to add aqueous ammonia. Or pH with dilute sulfuric acid
Adjust to 7.0.

Contamination (optical density at λ = 550 nm) and MTF (Modulatio Transfer Function) of each sample after the above treatment was determined by a microdensitometer, and the spatial frequency was 5 lines / mm.
The MTF values at The determination of the sharpness of an image by MTF is well known to those skilled in the art.
of the photographic process 3rd edition ”. The results are shown in Table 1.

Further, the sample No. 2 was exposed through an optical wedge, and then processed in the same manner as described above, except that the concentrations of the color developing agent and potassium bromide in the color developing solution were changed as shown in Table 2.

Sensitometry was performed on each of the obtained samples by a conventional method. Concentration of each sample at a potassium bromide concentration of 0.6 g /
Table 2 shows the movement of the concentration when the concentration of potassium bromide was varied, with the concentration in the exposed area near 1.0 being 100. The color density ratio is the spectral reflection densitometer PDA-65 (made by Konishi Rokusha Kogyo Co., Ltd.)
Table 2 shows only the cyan density measured by the above method.

Color developing agent for comparison [CD-3] [CD-6] As is clear from Tables 1 and 2, it can be seen that the present invention has high sharpness and no color contamination in the rapid processing of 1 minute and 30 seconds, and has a small dependency on the bromide ion concentration and can be stably processed.

Claims (10)

[Claims] 1. A silver halide color photographic light-sensitive material having a photographic constituent layer comprising a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a reflective support. The silver halide emulsion of at least one light-sensitive emulsion layer is substantially a silver chlorobromide emulsion, and at least one of the photographic constituent layers has the following general formula (I) or (II) A silver halide color photographic light-sensitive material having an optical reflection density of 0.5 or more at 470 nm, 550 nm or 680 nm, and an N-hydroxyalkyl-substituted-P-phenylenediamine derivative. 30 ° C using color developer
A method of processing a silver halide color photographic light-sensitive material, characterized by performing development processing for 150 seconds or less. General formula (I) In the formula, R, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are hydrogen atom, halogen atom, hydroxy group, alkyl group, alkoxy group, -SO ₃ M
Alternatively, it represents -NHCH ₂ SO ₃ M. M represents a cation. General formula (II) In the formula, R ₆ and R ₆ ′ each represent an alkyl group, an aryl group or a heterocyclic group. R ₇ and R ₇ ′ are each a hydroxy group, an alkoxy group, a substituted alkoxy group, a cyano group, a trifluoromethyl group, —COOR ₈ , —CONHR ₈ , —NHCOR ₈ , an amino group, and an alkyl group having 1 to 4 carbon atoms. A substituted amino group or (Wherein p and q represent 1 or 2 and X represents an oxygen atom, a sulfur atom or a —CH ₂ — group). R ₈ represents a hydrogen atom, an alkyl group or an aryl group. L represents a methine group. n represents 0, 1 or 2.
M represents a cation. 2. A silver halide emulsion in at least one light-sensitive emulsion layer is a substantial silver chlorobromide emulsion having a silver bromide content of 90 mol% or less. First
5. A method for processing a silver halide color photographic light-sensitive material as described in the above item. 3. The silver halide color photographic light-sensitive material according to claim 1 or 2, wherein the total silver coating amount of the silver halide color photographic light-sensitive material is 1 g / m ² or less. Processing method. 4. A silver halide color photographic light-sensitive material according to any one of claims 1 to 3, wherein the color developing solution contains at least 5 × 10 ^-3 mol of bromide. Processing method. 5. The method for processing a silver halide color photographic light-sensitive material according to claim 4, which comprises processing with a color developer containing 1 × 10 ^-2 mol or more of bromide. 6. A process according to claim 4, wherein the color developer is treated with a color developer containing 1.5 × 10 ^-2 mol or more of bromide.
5. A method for processing a silver halide color photographic light-sensitive material as described in the above item. 7. The method of processing a silver halide color photographic light-sensitive material according to claim 3, wherein the total coated silver amount is 0.8 g / m ² or less. 8. An N-hydroxyalkyl-substituted-P-phenylenediamine derivative is 3-methyl-4-amino-N-ethyl-N-β-
A method for processing a silver halide color photographic light-sensitive material according to any one of claims 1 to 7, which is a hydroxyethylaniline salt. 9. The halogenation according to any one of claims 1 to 8, wherein the replenishing amount is 250 ml / m ² or less when continuously processing the color photographic light-sensitive material. Processing method of silver color photographic light-sensitive material. 10. The method for processing a silver halide color photographic light-sensitive material according to claim 9, wherein the replenishing amount in the continuous processing of the color photographic light-sensitive material is 200 ml / m ² or less. .