JPH06175250A - Silver halide emulsion and silver halide color photosensitive material - Google Patents

Abstract

PURPOSE:To provide a silver halide emulsion extremely improved in sharpness and improved in pressure property and a silver halide photographic sensitive material using the emulsion and to provide the silver halide emulsion excellent in sharpness, color reproducible aptitude and pressure property without deteriorating gradation and the silver halide photographic sensitive material using the emulsion. CONSTITUTION:At least 70% of total projected area of a silver halide particle contained in the emulsion is a platelike silver halide particle having >=2.0 aspect ratio expressed in diameter/thickness ratio and <=0.5mum thickness, the coefficient of thickness variation of the platelike silver halide particle is <=20% and all parallel main plane of the platelike silver halide particle facing to each other and <=90% of the plane of the edge part has (111) crystal plane.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide emulsion useful in the field of photography and a silver halide color photographic light-sensitive material using the emulsion. More specifically, a silver halide emulsion having remarkably improved sharpness and improved pressure characteristics, and a silver halide color photographic light-sensitive material using the emulsion and having excellent sharpness, pressure characteristics, color reproduction characteristics and gradation. It is about materials.

[0002]

[Prior Art and its Problems] In recent years, in the field of silver halide color photographic light-sensitive materials, ISO 1600 to 320
Higher image sensitivities are being demanded due to advances in ultra-high sensitivity represented by 0 and small formats represented by disk films. In response to such demands, much research has been done centering on the improvement of silver halide emulsions.

For example, US Pat. No. 4,439,520
No. 62-99751 and 62-115435.
And each publication, a tabular silver halide emulsion having a grain thickness of less than 0.3 μm and an aspect ratio of 8: 1 or more was used for a high-sensitivity layer, and high sensitivity and excellent sharpness of a dye image were obtained. A multilayer color photographic light-sensitive material is disclosed. Further, JP-A-57-93344, JP-A-54-145135 and JP-A-57-93135.
No. 151,944 discloses a technique for improving sharpness by using a diffusive DIR.

Here, tabular grains are mainly a technique for improving sharpness by an optical effect, and a DIR compound is classified as a technique for improving sharpness by a developing effect. In particular, light scattering by silver halide grains has a large effect on sharpness, and the shape is flat and the thickness is 0.3 μm.
When it is less than m, the sharpness is remarkably improved as shown in the above-mentioned respective publications. With respect to such tabular silver halide grains, many techniques have been disclosed in addition to the above publications. For example, JP-A-58-113926
Nos. 58-113927 and 58-113926 disclose emulsion grains having an aspect ratio of 8 or more.

The aspect ratio as used herein is indicated by the ratio of the diameter to the thickness of tabular silver halide grains. Further, the grain diameter means the diameter of a circle having an area equal to the projected area of the grain when the emulsion is observed with a microscope or an electron microscope. The thickness is indicated by the distance between two parallel planes constituting a tabular silver halide grain.

Further, tabular silver halide grains are characterized in that they are more difficult to monodisperse than non-tabular silver halide grains (normal crystal grains), and various attempts have been made so far to monodisperse tabular silver halide grains. Have been made and several patents have been disclosed.

Japanese Patent Laid-Open Nos. 52-153428 and 55-1
42329, 61-112142, 51-39.
No. 027 and French Patent No. 253,406 disclose monodisperse technology for tabular silver halide grains, but all have a low aspect ratio of less than 3, or a mixture of hexagonal tabular and triangular tabular plates. However, they are insufficient as monodisperse tabular grains. As tabular grains having uniform shapes and grain sizes, there are disclosed in JP-A-63-151618 and JP-A-1-2.
No. 13637 and JP-A-2-838 disclose monodisperse tabular grains mainly having a hexagonal shape.

However, such tabular silver halide grains have very poor pressure characteristics, and it has been difficult to improve the sharpness without deteriorating the pressure characteristics in the prior art. The pressure characteristics mean two things: so-called pressure fog in which an unexposed portion is developed when a pressure is applied to a silver halide photographic light-sensitive material, and pressure desensitization in which sensitivity decreases during exposure. If these characteristics are poor, they will cause serious defects as a silver halide photographic light-sensitive material.

As for the pressure characteristic, as the thickness of the flat plate is naturally mechanically weaker, the deterioration of the pressure characteristic is large. However, even if the thickness is the same, the higher the aspect ratio, the more deteriorated. This is because even if the materials have the same mechanical strength, a larger moment is more likely to be applied to the flat plate than to the spherical shape. The pressure characteristics differ depending on the silver halide shape, the halogen composition distribution in the silver halide grains, and the chemical sensitization conditions.

Generally, when chemical sensitization is insufficient (chemical ripening is insufficient), pressure desensitization is poor, and when chemical sensitization is excessive, pressure desensitization is reduced but pressure fog is deteriorated.

The presence of a high iodine portion inside the silver halide grains improves the pressure fog but tends to deteriorate the pressure fog.

The silver halide composition may be silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, depending on the purpose and use of the light-sensitive material.
Although silver iodobromide or the like is used, silver iodobromide is often used in a color film for general photography. The composition distribution inside the silver halide grains is optimized and used for gradation adjustment, color reproduction characteristics and sensitivity adjustment in addition to pressure characteristics. Therefore, when the color reproducibility and the gradation are improved, the contradictory problem that the pressure characteristic is deteriorated often occurs.

For example, when the silver iodide is made to have a high iodine, the sensitivity is increased, but the light absorption wavelength region peculiar to the silver halide has a long wavelength and adversely affects the color reproducibility. Color reproducibility can be improved by using silver iodobromide. However, if the silver iodide is made to have a low iodide content, the developability (developing speed) of the silver halide grains is improved and the gradation becomes hard. Further, even with the same halogen composition, tabular silver halide grains have a faster developing speed, and therefore, the problem of hard contrast becomes remarkable.

In general, higher monodispersity of silver halide grains is preferable in terms of sensitivity and pressure characteristics. However, when monodisperse silver halide grains are used, gradation becomes harder and color reproducibility is improved. When tabular silver halide grains having a low iodide are used for the purpose of improving the image quality and improving the sharpness, only a light-sensitive material having extremely high contrast can be obtained. Especially in a color negative film that requires a wide exposure latitude and a soft gradation, this gradation problem is important and excellent in color reproduction characteristics, that is, low iodine, and excellent sharpness and pressure characteristics. There is a demand for an emulsion that does not impair the gradation.

[0015]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide emulsion having significantly improved sharpness and improved pressure characteristics, and a silver halide photographic light-sensitive material using the emulsion. Another object of the present invention is to provide a silver halide emulsion excellent in sharpness, color reproducibility and pressure characteristics without impairing gradation, and a silver halide photographic light-sensitive material using the emulsion.

[0016]

DETAILED DESCRIPTION OF THE INVENTION The inventors of the present invention have made earnest studies and found that the objects of the present invention can be achieved by the inventions of the present application described below.

That is, at least 70% of the total projected area of silver halide grains contained in the emulsion has an aspect ratio represented by a diameter / thickness ratio of 2.0 or more and a thickness of 0.5 μm.
The tabular silver halide grains are as follows, and the variation coefficient of the thickness of the tabular silver halide grains is 20% or less,
And a silver halide emulsion characterized in that all of the parallel main planes of the tabular silver halide grains facing each other and 90% or less of the faces of the edge portions are (111) crystal faces, or contained in the emulsion At least 70% of the total projected area of the silver halide grain is a tabular silver halide grain having an aspect ratio represented by a diameter / thickness ratio of 2.0 or more and a thickness of 0.5 μm or less. The main plane shape of the tabular silver halide grains is hexagonal with a maximum adjacent side ratio of 1.0 to 2.0, and all the parallel main planes of the tabular silver halide grains facing each other and the edge portion 90% or less of the surface is (1
11) At least 70% of the total projected area of a silver halide emulsion characterized by being a crystal plane or a silver halide grain contained in the emulsion has an aspect ratio represented by a diameter / thickness ratio of 2.0. And tabular silver halide grains having a thickness of 0.5 μm or less, the relative standard deviation of the silver iodide content of the tabular silver halide grains is 20% or less, and the tabular halide All of the parallel major planes of the silver particles facing each other, and 75% or less of the surface of the edge portion are (11
1) At least one of the silver halide emulsions having a crystal plane is provided on one side on a transparent support, and at least one red-sensitive layer, green-sensitive layer, blue-sensitive layer and non-photosensitive layer are provided on each side. A silver halide color light-sensitive material characterized in that it is contained in at least one of the light-sensitive layers of the silver halide color light-sensitive material having a photographic constituent layer consisting of a light-sensitive layer.

The present invention will be described in detail below. The aspect ratio of tabular silver halide grains contained in the silver halide emulsion of the present invention (hereinafter sometimes abbreviated as tabular grains of the present invention) refers to the diameter / thickness ratio of the grains,
The diameter of a silver halide grain refers to the diameter of a circle having an area equal to the projected area of the grain, and the thickness refers to the distance between two parallel planes forming a tabular silver halide grain.

In the present invention, the hexagonal tabular grains mean that the (111) plane has a hexagonal shape and the maximum adjacency ratio thereof is 1.0 to 2.0. Here, the maximum adjacent side ratio is the ratio of the length of the side having the maximum length to the length of the side having the minimum length forming a hexagon. The hexagonal tabular grain of the present invention has a maximum adjacent side ratio of 1.0.
If it is ˜2.0, the corners may be somewhat rounded. The length of a side when the corner is slightly rounded is represented by the distance between the straight line portion of the side and the intersection with the line obtained by extending the straight line portion of the adjacent side.

It is preferable that 1/2 or more of each side forming the hexagon of the hexagonal tabular grain of the present invention is substantially linear, and particularly 4/5 or more is substantially linear. In the present invention, the ratio of adjacent sides is 1.0 to 1.
It is more preferably 5.

The silver halide emulsion of the present invention generally comprises a dispersion medium and silver halide grains, and has a projected area of 70% or more, more preferably 80% or more, of the projected area of the silver halide grains.
More preferably, 90% or more has a ratio of adjacent sides of 1.0 to 2.
It is a hexagon of 0 and is occupied by tabular silver halide grains having two parallel twin planes.

The hexagonal tabular grains referred to in the present invention are characterized by having a plurality of parallel twin planes (for example, two sheets), which is a thin section of an emulsion-coated film at a low temperature (liquid nitrogen). The temperature can be confirmed by observing with a transmission electron microscope.

The coefficient of variation of the grain size referred to in the present invention represents the degree of variation in grain size, and preferably the maximum adjacent side ratio is 1.
It is a percentage display value of a value obtained by dividing the standard deviation of the circle-converted diameter of the projected area of hexagonal tabular grains of 0 to 2.0 by the average grain size.

The variation coefficient of thickness referred to in the present invention represents the degree of variation in the thickness of the tabular grains of the present invention, and preferably the hexagonal tabular grains having the maximum adjacent side ratio of 1.0 to 2.0. It is a percentage display value of the value obtained by dividing the standard deviation of the thickness by the average thickness.

In the silver halide grains of the present invention, at least 70% of the total projected area is a tabular grain having an aspect ratio of 2.0 or more, but at least 80% of the total projected area has an aspect ratio of 3.0 to 7.0. Preferably there is.

It is also preferable that at least 80% of the total projected area has an aspect ratio of 3.0 to 4.9, and at least 80% of the total projected area has an aspect ratio of 3.
More preferably, it is 0 to 4.9.

If the aspect ratio is too large, the maximum moment applied to the silver halide grains when the pressure is applied to the light-sensitive material becomes large, so that the pressure characteristics (pressure desensitization, pressure fog) deteriorate. On the contrary, if the aspect ratio is too small, the grain thickness increases, the projected diameter decreases, and the length approaches the length for scattering visible light.

Thus, the value of the aspect ratio is the pressure characteristic,
Although it has an optimum value from the viewpoint of sharpness, it is naturally preferable that the proportion of grains outside the preferable aspect ratio range is small due to the distribution of silver halide grains.

In the silver halide grain of the present invention, at least 70% of the total projected area has an even number of twin planes parallel to the principal plane, and the principal plane has a maximum adjacent side ratio of 2.0 to 1. Although it is a hexagon of 0, it is preferred that at least 90% of the total projected area be such a hexagonal plate.

It is preferable that at least 70% of the total projected area is a hexagonal flat plate having a maximum adjacent side ratio of 1.0 to 1.5, and at least 90% of the total projected area is a maximum adjacent side ratio of 1. It is preferably a hexagonal flat plate of 0 to 1.5. When the hexagonal plate ratio is low, the mixing ratio of silver halide grains having other shapes, that is, normal crystals, triangular twin crystals, and various multiple twin crystals is high.

Since chemical sensitization is strongly influenced by the shape of silver halide grains, surface index of the surface, composition, defects, etc., when grains having different shapes are mixed, the degree of chemical sensitization depends on the shape of each grain. However, not only the optimum chemical sensitization conditions cannot be obtained in terms of sensitivity and fog, but also particles with poor chemical ripening with poor pressure desensitization characteristics and particles with excessive chemical ripening with poor pressure fog are produced. Since they are mixed, the total pressure characteristics are insufficient. Also, under the condition that a large number of hexagonal tabular grains (square triangular triangles) having a high maximum adjacent side ratio are generated, the variation in the maximum adjacent side ratio is likely to be large, that is, a particle group with a large difference in shape is obtained, which is the optimum for chemical ripening. It is not preferable because it becomes difficult to emulsify and similarly the emulsion becomes inferior in pressure characteristics.

Pure silver bromide and silver iodobromide can be preferably used in the silver halide emulsion of the present invention. The average silver iodide content in silver iodobromide is preferably 10 mol% or less, more preferably 9 mol% or less, and further preferably 8 mol% or less from the viewpoint of color reproduction suitability. Pure silver bromide having a silver iodide content of less than 0.5 mol% is also preferable from the viewpoint of color reproducibility, but it is preferable that a small amount of silver iodide is contained from the viewpoint of emulsion stability. From the overall viewpoint, the optimum range of the silver iodide content is 0.1 to 9 mol%, preferably 0.5 to 9 mol%, and more preferably, since the gradation becomes harder due to iodination. Is 1 to 8 mol%.

The average silver iodide content is preferably in the above range from the viewpoints of color reproducibility and gradation, but the silver iodide content of each silver halide grain in the emulsion is chemically similar to that of the above-mentioned grain shape. Since it affects the sensitization, it is preferable that the grains are uniform from the viewpoint of pressure characteristics. The silver iodide content of each grain can be measured using XMA (X-ray microanalyzer). When the percentage of the standard deviation of the silver iodide content of each grain measured by XMA with respect to the average silver iodide content is defined as a relative standard deviation value (JP-A-60-254032), the relative standard deviation is 20%
From the viewpoint of pressure characteristics, it is preferably 15% or less, more preferably 15% or less.

The hexagonal tabular grain of the present invention has a diameter of 0.4 μm.
It is preferably not less than 0.5, more preferably 0.5 to
The thickness is 3.0 μm, more preferably 0.5 to 1.7 μm.

The average thickness of the tabular grains of the present invention is 0.05 to
It is preferably 0.5 μm, more preferably 0.
05-0.35 μm, more preferably 0.05-0.2
It is 0 μm. Particle size and thickness can be optimized for best sensitivity, sharpness, and pressure characteristics. sensitivity,
Other factors that influence the sharpness and pressure characteristics of the photosensitive material (thickness of hydrophilic colloid layer, hardness, chemical aging conditions,
The optimum particle size and thickness differ depending on the type and amount of DIR compound, ISO sensitivity of photosensitive material, amount of silver, etc.). The sharpness deteriorates as the average particle diameter and the average thickness are closer to the scattering length (0.3 μm to 0.5 μm). The thicker the thickness, the better the pressure characteristics. Even with the same thickness, the higher the aspect ratio, the worse the pressure characteristics. The sensitivity increases as the grain size increases, but the granularity deteriorates. Therefore, it is no different from conventional emulsions that it is preferable to select the minimum grain size for obtaining the required sensitivity.

From the viewpoint of pressure characteristics, the variation in particle size is
As described above, it is preferable that the grain size is as small as possible, that is, the monodispersity is high. However, since the emulsion of the present invention uses tabular grains and low-iodine grains having a high development rate, gradation becomes a problem, and graininess becomes a problem. By making the diameter monodisperse, it becomes unusable because the contrast becomes further hardened. For this reason, an optimum value is selected for the distribution of particle diameters in a range where both pressure characteristics and gradation are compatible. The optimum variation coefficient of the grain size is 1 to 30%, and the hexagonal tabular grain of the present invention has the variation coefficient in this range. More preferably 1
26%. If the value of the coefficient of variation is too large, the suitability for chemical aging becomes insufficient and the pressure characteristics deteriorate due to the above-mentioned presumed reasons. If the value of the coefficient of variation is less than 1%, the gradation becomes harder, which is not preferable, but since the pressure characteristics are improved, there are contradictory requirements for the coefficient of variation. According to the studies by the present inventors, at least 70% of the silver halide grains of the present invention, that is, the total projected area is in the range of the aspect ratio of 2.0 or more, and at least 70% of the total projected area is the maximum adjacent side ratio of 1.0 The tabular silver halide grains having a hexagonal shape of .about.2.0 have the improved pressure characteristics as described above, and have good pressure characteristics up to a region where the variation coefficient of the grain size is relatively large. Was found. That is, in the hexagonal tabular grains having the above aspect ratio, even if the variation coefficient of the grain size is in the range of 1 to 30%, the pressure characteristics are not deteriorated as compared with an emulsion having a monodispersity of less than 1%. Therefore, it is possible to obtain excellent gradation without impairing the pressure characteristics in the range of the variation coefficient of 1 to 30%. This is because the variation in shape is a greater obstacle to the optimization of chemical sensitization than the variation in particle size.By making the shape uniform, chemical sensitization is possible even if there is some variation in particle size. The feeling indicates that the particles are sufficiently uniformly applied. In the case of a polydisperse emulsion having a coefficient of variation of 30% or more, even if it is a hexagonal tabular grain having an aspect ratio of 3.0 to 7.0, the pressure characteristics are significantly deteriorated due to nonuniform chemical sensitization.

The optimum thickness of the silver halide grains used in the present invention is selected in consideration of the pressure characteristics and the sharpness as described above. However, even if the average thickness is the same, the variation in the thickness is small. Is preferred. That is, even if the particles have an average thickness that is preferable in terms of pressure characteristics and sharpness, some too thick particles cause light scattering and cause deterioration of sharpness, and some too thin particles cause pressure. It is considered that this is because fog and pressure desensitization are caused to cause deterioration of pressure characteristics and cause defects of the emulsion. The grain thickness distribution, or coefficient of variation of thickness, is expressed as the percentage of the standard deviation of the thickness of individual grains to the average thickness. The variation coefficient of thickness of the hexagonal tabular grain of the present invention is 20% or less, preferably 15% or less.

The emulsion of the present invention is useful for various light-sensitive materials, but in particular, the light-sensitive material of the present invention, that is, at least one light-sensitive silver halide emulsion layer and at least one light-sensitive emulsion layer on a support. A non-light-sensitive hydrophilic colloid layer, at least one light-sensitive silver halide emulsion layer containing the silver halide emulsion of the present invention, and a light-sensitive silver halide emulsion layer farthest from the support. The effect is remarkable in the silver halide photographic light-sensitive material in which the total dry film thickness of the non-photosensitive all-hydrophilic colloid layer separated from the support is 2.0 μm or less. This is because the hydrophilic colloid layer (hereinafter referred to as a protective layer) existing in the outermost layer of the light-sensitive material has a role of protecting the silver halide emulsion layer from pressure desensitization and pressure fog,
It is considered that the light-sensitive material having a thinner protective layer has a poorer pressure characteristic and the property of the pressure characteristic of the emulsion is strongly reflected in the performance of the light-sensitive material.

When the thickness of the protective layer of the light-sensitive material is increased, the pressure characteristics are improved, but the sharpness of the silver halide emulsion layer coated below the protection layer (on the side closer to the support) is deteriorated. A thin protective layer is preferable for achieving high image quality, and the silver halide emulsion of the present invention having excellent pressure characteristics is particularly effective and useful in a light-sensitive material having such a thin protective layer and excellent in sharpness. . Further, since the sharpness of the light-sensitive material having a thin protective layer is less deteriorated by the protective layer, the light scattering by the silver halide grains becomes dominant, and the sharpness of the light-sensitive material having such a thin protective layer is particularly high. The effect of tabular silver halide grains is remarkable.

The thickness of the protective layer means the total dry film thickness of the non-photosensitive all hydrophilic colloid layer which is farther from the support than the photosensitive silver halide emulsion layer farthest from the support. The material can be sectioned with a microtome and measured using a light or electron microscope. The effect of the pressure characteristic and the sharpness of the emulsion of the present invention is that the thickness is 2.0 μm.
Remarkably in the light-sensitive material having the following thin film protective layer,
If the thickness is 1.5 μm or less, the effect becomes more remarkable.

Since the effects of the present invention can be obtained in a light-sensitive material having a thin protective layer as described above, it is useful in various light-sensitive materials such as monochrome light-sensitive materials, color reversal films, color negative films, etc. It is very effective and useful in light-sensitive materials. That is, at least one red-sensitive silver halide emulsion layer containing a cyan color-forming coupler, at least one green-sensitive silver halide emulsion layer containing a magenta color-forming coupler and at least one blue-sensitive silver halide emulsion layer containing a yellow color-forming coupler are provided on a support. In the silver halide color photographic light-sensitive material, it is preferable to use the tabular silver halide emulsion of the present invention in the green-sensitive silver halide emulsion layer and / or the blue-sensitive silver halide emulsion layer because of excellent sharpness and pressure characteristics. It is useful. This is because the blue-sensitive layer and the green-sensitive layer are located relatively far from the support, that is, near the protective layer and are easily affected by pressure, and the sharpening of the silver halide emulsion layer located closer to the support. It is considered that this is because light scattering easily influences the degree.

When the silver halide emulsion of the present invention is used in the blue-sensitive layer and / or the green-sensitive layer, each color-sensitive layer may be composed of a single silver halide emulsion layer or a plurality of layers having different sensitivities. It may be formed more. When the layer containing the silver halide emulsion of the present invention comprises a plurality of layers, the effect can be obtained by containing the silver halide emulsion of the present invention in at least one of the layers, but the present invention can be used in two or more layers. It is preferable to contain the silver halide emulsion of.

In the present invention, the hexagonal tabular grain composition may be any of silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodobromide, etc. It is preferably silver halide. The content of silver iodide is preferably in the above range, but it may have a uniform crystal structure, a halogen composition having different internal and external halogen compositions, or a layered structure. It is also preferable that the grains contain reduction sensitized silver nuclei. Whether or not it has the reduction sensitized silver nuclei is easily observed because an inversion image of the existing internal fog is observed when exposed and internally developed by a conventional method and an HD curve is written. You can judge.

In the present invention, the emulsion can be a core / shell type emulsion. The core / shell type emulsion here means at least the inner structure and outer layers thereof, such as the double structure type grains shown in JP-A 61-148442 and the multiple structure grains shown in JP-A 61-245151. A particle consisting of at least one layer of For example, a high iodide content phase, that is, a silver iodide content of 10 mol% or more, preferably 20
A core consisting of grains having a silver iodobromide or silver chloroiodobromide phase content of not less than mol%, more preferably not less than 25 mol% /
It can be a shell emulsion.

When the silver halide emulsion of the present invention is produced, the usual single jet method, double jet method and controlled double jet method can be used within the range satisfying the conditions of the present invention. The controlled double jet method is particularly preferable in that strict control of pH and pAg is easy.

In the controlled double jet method, iodine ions can be supplied usually by an aqueous solution of an alkali iodide salt or a mixed aqueous solution with another alkali halide salt. A more preferable mode of supplying iodide ions is a method of supplying solid silver iodide as described in JP-A-1-323215.

According to this method, crystal growth is carried out by triple jetting of an ammoniacal silver salt aqueous solution or a water-soluble silver salt aqueous solution, an alkali bromide salt aqueous solution, and a suspension containing silver iodide grains by triple jet. The pH and pAg can be controlled by the same method as the ordinary controlled double jet method. According to this method, it is possible to efficiently and uniformly form a high iodide content phase, and by combining it with the silver halide emulsion of the present invention, it has excellent sharpness and pressure characteristics which are the object of the present invention. A silver halide emulsion can be obtained more effectively. Similarly, in order to obtain a uniform silver halide emulsion, a method of growing fine silver iodobromide grains on seed grains by Ostwald ripening as described in JP-A-1-183417 is useful.

In carrying out the present invention to obtain a silver halide emulsion, various means applicable in this field can be used. For example, various heavy metal salts, complex salt doping technology, desalination (dissolved matter removal) technology to silver halide grains,
Chemical sensitization, physical ripening and spectral sensitization techniques can be used.

In the present invention, it is particularly important that 90% or less of all the parallel main planes of the tabular silver halide grains which face each other and the planes of the edge portions are (111) crystal planes. Usually, the main plane of tabular silver halide grains is (11
1) surface. It is well known that the crystal plane of the edge portion other than the main plane is usually only the (111) plane. That 90% or less of the face of the edge portion is the (111) crystal face means that the edge portion has more than 10% of crystal faces other than the (111) face. In the present invention, the (100) plane is preferable as a crystal plane other than the (111) plane. In the present invention, the (111) crystal plane of the edge portion surface is preferably 75% or less. That is, it is particularly preferable that more than 25% of crystal planes other than the (111) plane exist. And it is (10
It is preferably 0) plane. In the present invention, the method for measuring the crystal plane of the edge portion of the tabular silver halide grain is described in Journal of Imaging Science, vol.29, No 5, Sept.
The method reported by Tani et al. In 1985, SPRINGFIELD US P.165-171 can be used. In the present invention, the surface of the edge portion of the tabular silver halide grains (1
11) Various known methods can be used in combination to bring the crystal plane to 90% or less, preferably 75% or less, and particularly when the tabular silver halide grains are formed, the pH is near neutral, preferably Can be achieved by setting the pH to 4 or more and 9 or less, or by forming tabular silver halide grains in the presence of a crystal plane selective adsorption type compound. As the compound, a sensitizing dye for photography or a nitrogen-containing heterocyclic compound is useful. A silver halide emulsion used in the silver halide color photographic light-sensitive material of the present invention, which is a silver halide grain composed of two or more phases having different silver iodide contents, wherein the average silver iodide content is contained. A silver halide grain containing a silver halide grain having a higher ratio than the silver iodide content of the outer phase of the grain is preferable.

The fact that the average silver iodide content of the grains is higher than the silver iodide content of the outer phase of the grains can be measured by the following method.

When the silver halide emulsion is an emulsion containing silver halide grains having an average grain size / grain thickness of less than 2, the average silver iodide content determined by the fluorescent X-ray diffraction method ( When J ₁ ) is compared with the silver iodide content (J ₂ ) on the grain surface determined by X-ray photoelectron spectroscopy, the relationship of J ₁ > J ₂ is satisfied.

The particle size mentioned here is the diameter of the circumscribed circle of the surface where the projected area of the particle is maximum.

X-ray photoelectron spectroscopy will be described.

Prior to measurement by X-ray photoelectron spectroscopy,
The emulsion is pretreated as follows. First, a pronase solution is added to the emulsion and gelatin is decomposed by stirring at 40 ° C. for 1 hour. Next, the emulsion particles are settled by centrifugation and the supernatant liquid is removed. Then, an aqueous solution of pronase is added, and gelatin is decomposed again under the above conditions. After centrifuging this sample again and removing the supernatant, distilled water is added to redisperse the emulsion seeds in distilled water, and the mixture is centrifuged to remove the supernatant. After repeating this washing operation three times, the emulsion grains are re-distributed in ethanol. This is thinly applied on a mirror-polished silicon wafer to obtain a measurement sample.

For measurement by X-ray photoelectron spectroscopy, an ESCA / SAM560 type manufactured by PHI was used as an apparatus, and an X-ray for excitation was used.
To Mg-Kα line, X-ray source voltage 15KV, X-ray source current 40m
A, the pass energy is 50 eV.

Ag3 was used to determine the surface halide composition.
d, Br З d, I3d 3/2 electrons are detected.

Calculation of the composition ratio is as follows. The relative sensitivity coefficient method is used using the integrated intensity of each peak. Ag3d, 8r3
d, I3d З / 2 5.10, 0 as relative sensitivity coefficient, respectively.
By using 18,4.592 the composition ratio is given in atomic percent.

When the silver halide emulsion used in the present invention contains grains having an average grain size / grain thickness of less than 2, the grain size distribution is preferably monodisperse. The monodisperse silver halide emulsion means that the weight of silver halide contained in the grain size range of ± 20% around the average grain size is 60% or more of the total weight of silver halide grains, preferably It is 70% or more, more preferably 80% or more.

[0059] Here, the average particle size, the product ni × ri ³ of the frequency ni and ri ³ particles having a particle size ri is defined as the particle size ri when the maximum (three significant figures, the least significant Numbers are rounded to 4).

The term "particle size" used herein means the diameter of spherical silver halide grains, and the diameter of grains having a non-spherical shape when the projected image is converted into a circular image of the same area. Is.

The particle size can be obtained, for example, by enlarging the particles from 10,000 to 50,000 times by an electron microscope and measuring the particle diameter on the print or the area at the time of projection (measurement particle). The number is indiscriminately 1000 or more.) The particularly preferred highly monodisperse emulsion of the present invention is (standard deviation / average grain size) × 100 = broadness of distribution defined by breadth (%) of distribution. Is less than 20%,
It is more preferably 15% or less.

Here, the average grain size and the standard deviation of the grain size are obtained from ri defined above.

The silver iodide content (J ₂ ) on the surface of the grain in the silver halide emulsion of the present invention having an average grain size / thickness of grain of less than ₂ is 6 to 0 mol by X-ray photoelectron spectroscopy. It is preferably in the range of 5 to 0 mol%, particularly preferably 4 to 0.01 mol%.

The above-described silver halide emulsion having an average value of grain size / grain thickness of less than 2 is preferably monodisperse, and is preferably a core / shell type.

The core / shell type silver halide emulsion having an average value of grain size / grain thickness of less than 2 has a grain structure composed of two or more phases having different silver iodide contents. The phase having the highest silver iodide content (called the core) is composed of silver halide grains other than the outermost surface layer (called the shell).

The internal phase (core) silver iodide content having the highest silver iodide content is preferably 6 to 40 mol%, more preferably 8 to 38 mol%, and particularly preferably.
It is 10 to 25 mol%. The silver iodide content of the outermost surface phase is preferably less than 6 mol%, more preferably 0 to 4.0 mol%.

The proportion of the shell portion of the core / shell type silver halide grain is preferably 10 to 80% by volume, more preferably 15 to 70%, and particularly preferably 20 to 60%.

The volume ratio of the core portion is preferably 10 to 80% of the total volume of the particles, and more preferably 20 to 50%.

The difference in content between the core part having a high silver iodide content and the shell part having a low content of the halogenated recording grains may have a sharp boundary, or the boundary may change continuously without being obvious. Those having an intermediate phase having a silver iodide content intermediate between the core and the shell are preferably used between the core and the shell.

When the core / shell type silver halide grain having the above-mentioned intermediate layer is used, the volume of the intermediate layer is 5% of the whole grain.
.About.60%, more preferably 20 to 55%. The difference in silver iodide content between the shell and the intermediate layer and between the intermediate layer and the core is preferably 3 mol% or more. It is preferably 6 mol% or more.

The core / shell type silver halide emulsion is preferably silver iodobromide, and its average silver iodide content is 4 to.
20 mol% is preferable, and 5 to 15 mol% is more preferable. Further, silver chloride may be contained within a range that does not impair the effects of the present invention.

Core / shell type silver halide emulsions are disclosed in
59-177535, 60-138538, 59-52238, 60-143331,
It can be produced by a known method disclosed in, for example, 60-35726 and 60-258536.

When a core / shell type silver halide emulsion is grown starting from seed grains as in the method described in JP-A-60-138538, it has a halogen composition region different from the core in the grain central portion. It is possible.

In such a case, the halogen composition of the seed grains may be any composition such as silver bromide, silver iodobromide, silver chloroiodobromide, silver chlorobromide and silver chloride. 15 mol% content
The following silver iodobromide or silver bromide is preferred.

The proportion of the seed grains in the total silver halide is preferably 50% or less by volume, particularly preferably 10% or less.

The distribution state of silver iodide in the above core / shell type silver halide grains can be detected by various physical measurement methods. For example, it is described in Abstracts of Annual Meeting of the Photographic Society of Japan, 1981. As described above, it can be investigated by measuring luminescence at a low temperature or by an X-ray diffraction method.

The core / shell type silver halide grain may be a normal crystal such as a cube, an tetrahedron or an octahedron, may be composed of twins, or may be a mixture thereof, but may be a normal crystal. Preferably there is.

When the silver halide emulsion is a tabular silver halide emulsion having an average grain size / grain thickness of 5 or more, the average silver iodide content (J ₁ ) and the X-ray microanalysis method, the average of the measured values of the silver iodide content measured on the silver halide crystal at a distance of 80% or more from the central part in the grain size direction of the silver halide grain (J When comparing ₃ ), the relationship of J ₁ > J ₃ is satisfied.

The X-ray microanalysis method will be described.

Silver halide grains are dispersed in a grid for electron microscope observation in which an energy dispersive X-ray analyzer is set in an electron microscope, and the magnification is set so that one grain is in the CRT field of view by cooling with liquid nitrogen, and the magnification is constant. Time AgLα and ILα ray intensities are integrated. The silver iodide content can be calculated using an ILα / AgLα intensity ratio and a calibration curve prepared in advance.

In the tabular silver halide emulsion having an average grain size / grain thickness of 2 or more, the average grain size / grain thickness is more preferably 3 or more and 7 or less, and particularly preferably 3 or more and 5 or less. .

In the tabular silver halide emulsion having an average grain size / grain thickness of 2 or more, the average grain size / grain thickness is more preferably 3 or more and 7 or less, and particularly 3 or more and 5 or less. preferable.

In the tabular silver halide emulsion of the present invention in which the average value of grain size / grain thickness is 2 or more, 80% from the central part in the grain size direction of silver halide grains by X-ray microanalysis method. The average value (J ₃ ) of the measured values of the silver iodide content measured on the silver halide crystals separated from each other as described above is preferably 6 to 0 mol%, and more preferably 5 to 0 mol%.
Mol%, particularly preferably 4-0.01 mol%.
The average thickness of the tabular silver halide grains is preferably 0.5 to 0.01 μm, particularly preferably 0.3 to 0.05 μm. The average grain size of silver halide grains contained in the tabular silver halide emulsion is preferably 0.5 to 30 μm, more preferably 1.0 to 20.
μm.

In the tabular silver halide emulsion having an average value of grain size / grain thickness of 2 or more, silver iodide is preferably localized in the center of the grain.

In the tabular silver halide emulsion in which the average value of grain size / grain thickness is 2 or more and silver iodide is localized in the central portion of the grain, the high iodine containing phase in the central portion is the grain. Is preferably 80% or less, particularly 60 to 10%. The silver iodide content in the central portion is preferably 5 to 40 mol%, particularly 10 to
35 mol% is preferred. The low iodine content phase (peripheral portion) surrounding the high iodine content phase in the central portion is composed of silver iodobromide having a silver iodide content of 0 to 10 mol%, more preferably 0.1 to 6.0 mol%. Is preferred.

The tabular silver halide emulsion in which silver iodide is localized at the center can be obtained by the known method disclosed in JP-A-59-99433.

In the silver halide color photographic light-sensitive material of the present invention, the average silver iodide content of all silver halide emulsions in the negative silver halide photographic light-sensitive material is preferably 0.1 to 15 mol%, It is more preferably 0.5 to 12 mol% and particularly preferably 4 to 10 mol%.

The average grain size of all silver halide emulsions in the silver halide color light-sensitive material is preferably 2.0 μm or less, more preferably 0.1 to 1.0 μm or less.

In the present invention, when the silver halide emulsion is twinned, an emulsion containing grains having two twin planes parallel to the principal plane is preferable, and the average aspect ratio thereof is less than 5. Certain emulsions are preferred. In the case of such an emulsion, the shape of the main plane has a maximum adjacent side ratio of 1.0 to 2.0.
Are preferably used, and octahedral emulsions are also preferably used.

The difference in content between the core portion having a high silver iodide content and the shell portion having a low silver iodide content in the silver halide grains is described in JP-A-60 / 1985.
-143331 may have a clear boundary, or may be prepared by continuously changing the silver iodide content like the emulsion disclosed in JP-A Nos. 2-943 and 3-202848. Although it may be a prepared emulsion, X of silver halide emulsion is particularly preferred.
An emulsion in which the line diffraction signal pattern is controlled so as to show substantially one peak is preferred. Examples of such an emulsion include the emulsion described in the claims of JP-A-3-l68734.

A general photographic gelatin is preferably used as the hydrophilic colloid in the production of the silver halide emulsion used in the present invention, and the gelatin having a tyrosine content of 30 μmol or less per 1 g of dried gelatin is More preferable. The silver halide emulsion used in the present invention is preferably one prepared by a known method. For example, the grain growth condition may be any environment of so-called acidic method, ammonia method, and neutral method, and the silver potential and temperature during growth can take any values as required. As a method for producing an emulsion mainly composed of twin crystals, it is preferable to form grains through a nucleation step and an Ostwald ripening step. In this case, the nucleation temperature is preferably 40 ° C or lower, and pBr1.0 to 2.5
Is preferred.

In the silver halide emulsion used in the present invention, each apex of the grain may be rounded.

It is preferable to control the development so that the development is started at or near the apexes of all or part of grains of the silver halide emulsion used in the present invention, or at the ridges or in the vicinity of the ridges. In particular, in the case of twin grain preparation, it is preferable that the development is controlled to start from the intersection of the twin plane and the ridge.

In the method for producing a silver halide emulsion used in the present invention, the average mixing time of the additive solution in the reaction vessel is preferably 10 seconds or less.

The silver halide emulsion used in the present invention is desalted by a conventional method, but it is not preferable to use a so-called aggregating agent because the aggregating agent remains on the grain surface and in the vicinity thereof. These cause, for example, a problem that they become an obstacle when adsorbing a sensitizing dye or a chemical sensitizer on the particles after forming the particles as is usually done.

The silver halide emulsion used in the present invention has a relative standard deviation of the silver iodide content of individual grains of 20 as in the claims of JP-A-60-254032 and 60-143332. % Or less, and more preferably an emulsion having a core made of silver iodobromide containing 20 mol% or more of silver iodide as in the claims of JP-A-3-182738.

When the silver halide emulsion used in the present invention is tabular, the longest distance between two or more parallel twin planes of the tabular grains is the same as in the claims of JP-A-63-163451. Grains having a ratio of the distance (a) to the grain thickness (b) of 5 or more are preferably 50% or more of all tabular grains, and the twin plane distance is 10Å as in the claims of Japanese Patent Application 3-353043.
It is even more desirable that it is ~ 100Å.

When the silver halide emulsion used in the present invention contains grains having two or more kinds of halogens, it is disclosed in JP-A-2-
An emulsion containing silver halide grains grown in the presence of silver halide grains having a solubility product smaller than that of the growing silver halide grains for at least one period of the grain growth process as in claim 167537. Is desirable,
It is particularly preferable to use silver iodide as the silver halide grain having a small solubility product.

The silver halide emulsion used in the present invention is obtained by grain growth using silver halide fine grains in the same manner as the grains disclosed in JP-A 1-183417, 1-183644 and 1-183645. Is also preferable. In particular, as in the claims of Japanese Patent Application No. 3-218608, the number of silver halide fine grains used for grain growth is two or more, and at least one of them is preferably composed of only one type of halogen element.

In the silver halide emulsion used in the present invention, it is preferable to add an oxidizing agent for silver during grain growth in the same manner as the grains disclosed in JP-A-3-196135 and 3-196138. In particular, when it is produced by using seed particles as in the method described in the patent application of Japanese Patent Application No. 4-15845, it is preferable to add the seed particles before the seed particles grow. Further, as the oxidizing agent, an inorganic acid such as a halogen element or nitric acid is preferable.

These silver halide emulsions include active gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea and cystine; sulfur sensitizers; selenium sensitizers; reduction sensitizers such as stannous salts. Thiourea dioxide, polyamine ascorbic acid, etc .; noble metal sensitizers, such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurothio-3-methylbenzothiazolium chloride, etc. or ruthenium, palladium,
Sensitizers of water-soluble groups such as platinum, rhodium and iridium, specifically ammonium chloroparadate, potassium chloroplatinate and sodium chloroparadate (some of these may be sensitizers or Acts as an antifoggant, etc.) or in combination as appropriate (for example, a gold sensitizer and a sulfur sensitizer are combined, a gold sensitizer and a selenium sensitizer are combined, etc.) and chemically sensitized. May be felt.

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

The silver halide is added with a suitable sensitizing dye in an amount of 5 × 10 ^{−5 to} 3 × 10 ⁻³ mol per mol of the silver halide in order to impart photosensitivity to a desired photosensitive wavelength region. You may make the optical nuisance. Various sensitizing dyes can be used, and 1 type or a combination of 2 or more types of sensitizing dyes can be used.

Examples of the sensitizing dye that can be advantageously used in the present invention include the followings.

That is, as sensitizing dyes used in blue-sensitive silver halide emulsions, for example, West German Patent 929,080, US Patents 2,231,658, 2,493,748, 2,503,776, and
2,519,001, 2,912,329, 3,656,959, 3,67
2,897, 3,694,217, 4,025,349, 4,046,572
No., British Patent No. 1,242,588, Japanese Patent Publication No. 44-14030, 52-2
Those listed in No. 4844 and the like can be mentioned. In particular, the dye disclosed in Japanese Patent Application No. 3-343348 is preferably used.

Examples of the sensitizing dye used in the green-sensitive silver halide emulsion include, for example, US Pat.
72,908, 2,7 З9,149, 2,945,763, British special poem 5
Representative examples thereof include cyanine dyes, merocyanine dyes, and complex cyanine dyes described in No. 05,979.

Further, as the sensitizing dye used in the red-sensitive silver halide emulsion, there are, for example, US Patent Nos. 2,269,234 and 2,2.
70,378, 2,442,710, 2,454,629, 2,776,28
Representative examples thereof include cyanine dyes, merocyanine dyes, and complex cyanine dyes described in No. 0 and the like. Furthermore, U.S. Patent 2,2l3,995
, 2,493,748, 2,519,001, West German Patent 929,080
Cyanine dyes, merocyanine dyes or complex cyanine dyes such as those described in JP-A No. 1994-242242 can be advantageously used for green-sensitive silver halide emulsions or red-sensitive silver halide emulsions.

These sensitizing dyes may be used alone,
Also, these may be used in combination.

If desired, optical sensitization may be carried out in a desired wavelength range by a spectral sensitization method using a single or combination of cyanine or merocyanine dyes.

A typical example of a particularly preferable spectral sensitization method is, for example, JP-B-43-43, which relates to a combination of benzimidazolocarbocyanine and benzoxazolocarbocyanine.
-4936, 43-22884, 45-18433, 47-37443
No. 48-28293, No. 49-6209, No. 53-12375, JP-A No. 52-23931, No. 52-51932, No. 54-80118, and No. 58-153.
Methods described in No. 926, No. 59-116646, No. 59-116647 and the like can be mentioned.

The combination of carbocyanine having a benzimidazole nucleus with another cyanine or merocyanine is described in, for example, Japanese Patent Publication Nos. 45-25831 and 47-1.
No. 1114, No. 47-25379, No. 48-38406, No. 48-38407,
54-34535, 55-l569, JP-A-50-33220, 50-
38526, 51-l07127, 51-1l5820, 51-135528
No. 52-104916, No. 52-1049l7, etc.

Further, as a combination of benzoxazolocarbocyanine (oxacarbocyanine) and another carbocyanine, for example, JP-B-44-32753,
46-11627, JP-A-57-1483, and those relating to merocyanine include, for example, JP-B-48-38408, JP-A-48-41204,
50-40662, JP-A-56-25728, 58-10753, 58
-91445, 59-116645, 50-33828, etc.

The combination of thiacarbocyanine with other carbocyanine is described in, for example, Japanese Patent Publication No.
43-4932, 43-4933, 45-26470, 46-l8107
No. 47-8741 and JP-A-59-114533, and the method described in JP-B-49-6207 using zeromethine or dimethine merocyanine, monomethine or trimethine cyanine and styryl dye is advantageously used. be able to.

In order to add these sensitizing dyes, a dye solution such as methyl alcohol, ethyl alcohol, acetone, dimethylformamide, or Japanese Patent Publication No.
It is used by dissolving it in a hydrophilic organic solvent such as fluorinated alcohol described in 50-40659.

The silver halide emulsion may be added at any time at 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.

The combination of sensitizing dyes particularly preferable in the present invention is the combination disclosed in Japanese Patent Application No. 3-109171. That is, a combination of at least one of the asymmetric cyanine dyes and a symmetric cyanine dye having each of the heterocyclic nuclei constituting the dye is preferable.

Various silver halide emulsions can be used in the color light-sensitive material of the present invention. The method for producing a silver halide emulsion and the additives used in the production are Research Disclosure No. 17643, No. 18716 and N.
o.308119 (hereinafter RD17643, RD18716 and RD3081 respectively
(Abbreviated as 19)). The following describes the content and location of RD308119.

[Item] [Page of RD308119] Iodine composition 993 I-A Manufacturing method 993 I-A and 994 E Crystal habit Normal crystal 993 I-A Twin twin 993 I-A Epitaxial 993 I -A term Halogen composition Uniform 993 IB term Non-uniform 993 IB term Halogen conversion 994 I-C term Halogen substitution 994 I-C Metal-containing 994 I-D term Monodisperse 995 I-F term Solvent addition 995 I-F item Latent image forming position Surface 995 I-G item Internal 995 I-G item Applicable negatives 995 I-H item Positive (including internal fog particles) 995 I-H item Emulsion mixture 995 I -J Item Desalination 995 II-A The silver halide emulsion used in the present invention is physically ripened,
Chemical ripening and spectral sensitization can be performed. Additives used in such processes are RD17643, RD18716 and RD30.
8119. The location of the description is shown below.

[Item] [Page of RD308119] [RD17643] [RD18716] Chemical sensitizer 996 III-A Item 23 648 Spectral sensitizer 996 IV-A-A, B, C, D, H, I, Item J 23-24 648-9 Supersensitizer 996 IV-AE, Item J 23-24 648-9 Antifoggant 998 VI 24-25 649 Stabilizer 998 VI 24-25 649 Can be used in the present invention Known photographic additives are also described in Research Disclosure above. The relevant description is shown below.

As the yellow dye-forming coupler, known acylacetanilide type couplers can be preferably used. Among these, benzoylacetanilide compounds and pivaloylacetanilide compounds are advantageous.

Specific examples of yellow couplers that can be used include British Patent 1,077,874, JP-B-45-40757, JP-A-47-1031,
47-26133, 48-94432, 50-87650, 51
-3631, 52-115219, 54-99433, 54-133
329, 56-30127, U.S. Patents 2,875,057, 3,25
3,924, 3,265,506, 3,408,194, 3,551,155
No. 3,551,156, 3,664,841, 3,725,072,
3,730,722, 3,891,445, 3,900,483, 3,9
29,484, 3,933,500, 3,973,968, 3,990,89
No. 6, No. 4,012,259, No. 4,022,620, No. 4,029,508,
4,057,432, 4,106,942, 4,133,958, 4,2
69,936, 4,286,053, 4,304,845, 4,314,023
No. 4,336,327, 4,356,258, 4,386,155,
No. 4,401,752, etc.

As the magenta dye-forming coupler, a 5-pyrazolone type coupler, a pyrazolobenzimidazole type coupler, a pyrazoloazole type coupler, and an open chain acylacetonitrile type coupler can be preferably used.

Specific examples of magenta couplers that can be advantageously used include Japanese Patent Application Nos. 58-164882, 58-167326 and 58-206321.
No. 58, No. 58-214863, No. 58-217339, No. 59-24653, Japanese Patent Publication No. 40-6031, No. 40-6035, No. 45-40757, No. 47-27.
No. 411, No. 49-37854, JP-A No. 50-13041, No. 51-265
No. 41, No. 51-37646, No. 51-105820, No. 52-42121
No. 53-123129, No. 53-125835, No. 53-129035
No. 54-48540, No. 56-29236, No. 56-75648, No. 5
7-17950, 57-35858, 57-146251, 59-99
437, British Patent 1,252,418, US Patent 2,600,788,
3,005,712, 3,062,653, 3,127,269, 3,2
14,437, 3,253,924, 3,311,476, 3,419,39
No. 1, 3,519,429, 3,558,319, 3,582,322,
No. 3,615,506, No. 3,658,544, No. 3,705,896, No. 3,7
25,067, 3,758,309, 3,823,156, 3,834,90
No. 8, No. 3,891,445, No. 3,907,571, No. 3,926,631,
3,928,044, 3,935,015, 3,960,571, 4,0
76,533, 4,133,686, 4,237,217, 4,241,16
No. 8, No. 4,264,723, No. 4,301,235, No. 4,310,623, etc.

Particularly preferred magenta couplers are:
It is represented by the following general formula [MI].

[0125]

[Chemical 1]

[In the formula, R ₁ and R ₂ represent a hydrogen atom or a substituent.

X ₁ represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent] The magenta coupler represented by the above general formula [MI] according to the present invention will be described in detail.

In the general formula [MI], R ₁ and R ₂ represent a hydrogen atom or a substituent.

The substituent represented by R ₁ and R ₂ is not particularly limited, but typical examples thereof include alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl and cycloalkyl groups. In addition to these, a halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl,
Phosphonyl, acyl, carbamoyl, sulfamoyl,
Cyano, alkoxy, aryloxy, heterocyclic oxy,
Siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio groups, and spiro compound residues, Examples include bridged hydrocarbon compound residues.

The alkyl group represented by R ₁ and R ₂ preferably has 1 to 32 carbon atoms and may be linear or branched. The aryl group represented by R ₁ and R ₂ is preferably a phenyl group.

Examples of the acylamino group represented by R ₁ and R ₂ include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group represented by R ₁ and R ₂ include an alkylsulfonylamino group and an arylsulfonylamino group.

Examples of the alkyl component and aryl component in the alkylthio group and arylthio group represented by R ₁ and R ₂ include the alkyl group and aryl group represented by R above. The alkenyl group represented by R ₁ and R ₂ has 2 carbon atoms.
~ 32, cycloalkyl groups having 3 to 12 carbon atoms,
Particularly preferred is 5 to 7, and the alkenyl group may be linear or branched.

The cycloalkenyl group represented by R ₁ and R ₂ is preferably one having 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms.

The sulfonyl group represented by R ₁ and R ₂ is an alkylsulfonyl group, an arylsulfonyl group, etc .; The sulfinyl group is an alkylsulfinyl group, an arylsulfinyl group, etc .; The phosphonyl group is an alkylphosphonyl group, an alkoxyphosphonyl group. Groups, aryloxyphosphonyl groups, arylphosphonyl groups and the like; acyl groups such as alkylcarbonyl groups and arylcarbonyl groups;
The carbamoyl group is an alkylcarbamoyl group, an arylcarbamoyl group or the like; the sulfamoyl group is an alkylsulfamoyl group, an arylsulfamoyl group or the like;
An alkylcarbonyloxy group as the acyloxy group,
Arylcarbonyloxy group etc .; carbamoyloxy group as alkylcarbamoyloxy group, arylcarbamoyloxy group etc .; ureido group as alkylureido group, arylureido group etc .; sulfamoylamino group as alkylsulfamoylamino group, aryl Sulfamoylamino group etc .; 5- to 7-membered heterocyclic groups are preferable, and specifically, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc .; heterocyclic oxy group Is preferably a 5- to 7-membered heterocycle, for example, 3,4,5,6-tetrahydropyranyl-2-oxy group, 1-phenyltetrazole-5-oxy group and the like; A 5- to 7-membered heterocyclic thio group is preferred,
For example, 2-pyridylthio group, 2-benzothiazolylthio group,
2,4-diphenoxy-1,3,5-triazole-6-thio group and the like;
As the siloxy group, trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc .; as the imide group, succinimide group, 3-heptadecylsuccinimide group, phthalimide group, glutarimide group, etc .; as the spiro compound residue Spiro [3.3] heptan-1-yl, etc .; bridged hydrocarbon compound residues include bicyclo [2.2.1] heptan-1-yl, tricyclo [3.3.1.1 ³⁷ ] decan-1-yl, 7,7-dimethyl -Bicyclo [2.2.1] heptan-1-yl and the like can be mentioned.

Examples of the group capable of splitting off upon reaction with the oxidation product of the color developing agent represented by X ₁ include, for example, a halogen atom (chlorine atom, bromine atom, fluorine atom, etc.) and alkoxy, aryloxy, heterocyclic oxy, acyloxy, Sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyl oxalyloxy, alkoxy oxalyloxy, alkylthio, arylthio, heterocycle thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocycle bonded by N atom,
Examples thereof include alkyloxycarbonylamino, aryloxycarbonylamino, and carboxyl groups.

Typical examples of magenta couplers represented by the general formula [MI] are shown below.

[0138]

[Chemical 2]

[0139]

[Chemical 3]

The magenta coupler represented by the general formula [MI] (hereinafter referred to as magenta coupler [MI]) is a journal of the chemical society (Journa).
l of the Chemical Society), Perkin I
(1977), 2047-2052, US Pat. No. 3,725,067, JP-A-5
9-99437, 58-42045, 59-162548, 59-17195
No. 6, No. 60-33552, No. 60-43659, No. 60-172982, No.
It can be synthesized with reference to 60-190779, 62-209457 and 63-307453.

The magenta coupler [MI] is usually used in an amount of 1 × 10 ⁻³ to 1 mol, preferably 1 × 10 ⁻² to 8 × 10 ⁻¹ mol per mol of silver halide. it can. In the present invention, the magenta coupler [MI] is contained in at least one of the green-sensitive silver halide emulsion layers.

In order to incorporate the magenta coupler [MI] into the silver halide emulsion layer, a conventionally known method can be used,
For example, a mixture of a high boiling point solvent such as known dibutyl phthalate and tricresyl phosphate and a low boiling point solvent such as butyl acetate and ethyl acetate may be added to a magenta coupler [M
-I] alone or in combination of two or more, and then dissolved, and then mixed with an aqueous gelatin solution containing a surfactant, and then emulsified and dispersed using a high-speed rotating mixer, colloid mill or ultrasonic disperser. Alternatively, a method of directly adding to the emulsion can be adopted. Further, after setting the above emulsified dispersion liquid, it may be shredded, washed with water, and then added to the emulsion.

As the cyan dye forming coupler, a naphthol type coupler and a phenol type coupler can be preferably used.

Specific examples of cyan couplers that can be advantageously used include British Patents 1,038,331 and 1,543,040, Japanese Patent Publication No. 48-
36894, JP-A-48-59838, 50-137137, 51-
146828, 53-105226, 54-115230, 56-29235
No. 56, No. 56-104333, No. 56-126833, No. 57-133650
Issue 57-155538, Issue 57-204545, Issue 58-118643
, 59-31953, 59-31954, 59-59656, 59
59-124341, 59-166956, US Patent 2,369,929,
2,423,730, 2,434,272, 2,474,293, 2,6
98,794, 2,772,162, 2,801,171, 2,895,82
No. 6, No. 3,253,924, No. 3,311,476, No. 3,458,315,
3,476,563, 3,591,383, 3,737,316, 3,7
58,308, 3,767,411, 3,790,384, 3,880,66
No. 1, 3,926,634, 4,004,929, 4,009,035,
4,012,258, 4,052,212, 4,124,396, 4,1
34,766, 4,138,258, 4,146,396, 4,149,88
No. 6, No. 4,178,183, No. 4,205,990, No. 4,254,212,
4,264,722, 4,288,532, 4,296,199, 4,2
96,200, 4,299,914, 4,333,999, 4,334,01
1, No. 4,386.155, No. 4,401,752, No. 4,427,767, etc.

Particularly preferred cyan couplers are ureidophenol cyan couplers.

The ureidophenol cyan coupler is a phenol cyan coupler having an ureido group at the 2-position, and is preferably one represented by the following general formula [CU].

[0147]

[Chemical 4]

General Formula [CU] In the formula, X ¹ represents a hydrogen atom or a group capable of splitting off upon coupling with an aromatic primary amine color developing agent. R ¹
Represents an aryl group or a heterocyclic group, R ² represents an aliphatic group or an aryl group, each group represented by R ¹ or R ² includes those having a substituent, the R ¹ or R ² 2 amount R ¹ and R ² alone or in combination to impart a diffusion resistance to a coupler represented by the general formula [CU] and a dye formed from the coupler. It has the necessary shape or size.

Examples of the aryl group represented by R ¹ or R ² include a phenyl group and a naphthyl group.

Examples of the substituent of the group represented by R ¹ or R ² include a halogen atom and nitro, cyano, alkyl, aryl, amino, hydroxy, acyl, alkoxycarbonyl, aryloxycarbonyl, alkylsulfonyl, arylsulfonyl, Examples thereof include alkoxysulfonyl, aryloxysulfonyl, carbamoyl, sulfamoyl, acyloxy, carbonamide, and sulfonamide groups. The number of the substituents is preferably 1 to 5, and when 2 or more, each substituent is the same or different. Good.

Preferred as the substituent for R ¹ are a halogen atom, an alkylsulfonyl group and a cyano group.

Preferred as R ² is the following general formula [C
U-II].

[0153]

[Chemical 5]

In the formula, J represents an oxygen atom or a sulfur atom.
k represents an integer of 0 to 4, l represents 0 or 1, and when k is 2 or more, a plurality of R ⁴ may be the same or different. R ³
Represents an alkylene group, and R ⁴ represents a substituent.

The substituent represented by R ⁴ is, for example,
Alkyl, aryl, alkoxy, aryloxy, hydroxy, acyloxy, alkylcarbonyloxy,
Arylcarbonyloxy, carboxy, alkoxycarbonyl, aryloxycarbonyl, alkylthio,
Examples include groups such as acyl, acylamino, sulfonamide, carbamoyl, and sulfamoyl.

The leaving group represented by X ¹ is, for example, an aryloxy group, an alkoxy group, an acyloxy group, an arylthio group, an alkylthio group or a sulfonamide in which a halogen atom, an oxygen atom or a nitrogen atom is directly bonded to the coupling position. Group, a succinimide group, and the like, and further specific examples include U.S. Patents 3,476,563 and 3,749,735.
No. 4, JP-A-47-42525, JP-B-48-36894, JP-A-Sho 50
-10135, 50-117422, 50-130441, 51-1
08841, 50-120334, 52-18315, 53-10522
Examples include those described in No. 6. The phenolic cyan coupler having a ureido group at the 2-position may be used in combination with another cyan coupler, and the usage ratio in that case is preferably 10 mol% or more.

Specific examples of the phenolic coupler having a 2-position ureido group are shown below, but the invention is not limited thereto.

[0158]

[Chemical 6]

[0159]

[Chemical 7]

Other specific examples of the phenolic coupler having a ureido group other than those exemplified above include, for example, JP-A-56-65134, JP-A-57-204543, and JP-A-57-204544.
57-204545, 58-33249, 58-33253, 5
8-98731, 58-118643, 58-179838, 58-
No. 187928, No. 59-65844, No. 59-71051, No. 59-8604
No. 8, No. 59-105644, No. 59-111643, No. 59-111644
No. 59-131939, 59-165058, 59-177558,
59-180559, 59-198455, 60-35731,
60-37557, 60-49335, 60-49336, 60-5
0533, 60-91355, 60-107649, 60-10765
0, 61-2757, 61-18948, 61-20039, 6
1-42658, 61-56348, 61-65241, 61-72244
Issue 61-72245, Issue 61-75350, Issue 61-75351, Issue 62
-173467, 63-33745, 63-159848, 63-16145
No. 0, No. 63-161451, JP-A No. 1-172751, No. 1-172952
Issue 1-172953, 1-172954, 1-219747, 1-
253738, 1-253739, 1-253740, 1-253741
Issue 1-253742, Issue 1-253743, Issue 1-254756 RD-30,
Those described in each publication such as 164 are listed. The addition amount of the phenolic coupler having an ureido group is usually preferably 1.0 × 10 ⁻³ mol to 1.0 mol, and more preferably 5.0 × 10 ⁻³ mol to 8.0 × 10 ⁻¹ mol per mol of silver halide. is there. In the present invention, a colored coupler can be added to the photographic constituent layer to mainly adjust the masking property. As the colored coupler, all known ones can be used, but as the colored magenta coupler, Japanese Patent Publication No.
-30615, U.S. Pat. No. 5,001,262, and Japanese Patent Application Laid-Open No. 4-16939, those having a phenyl group substituted with 5 chlorine atoms at the 1-position of a pyrazolone ring are preferable, and particularly those represented by the following general formula [CM] Those shown are preferred.

[0161]

[Chemical 8]

[Wherein, R ¹ represents a substituent, R ³ represents a halogen atom or an alkoxy group, R ² represents a carboxamido group, a sulfonamide group, an imide group, a carbamoyl group,
It represents a sulfamoyl group, an alkoxycarbonyl group or an alkoxycarboxamide group. m is 0-5, n is 0
Represents an integer of 4;

The present invention will be described in more detail below.

Examples of the substituent represented by R ¹ include an alkyl group, an alkoxy group, an aryl group, an acylamino group, a sulfonamide group, a hydroxyl group, a halogen atom, a sulfamoyl group and a carboxyl group.
These groups may further have a substituent.

R ¹ is preferably an alkyl group, an alkoxy group, a hydroxyl group or an acylamino group, and most preferably an alkoxy group.

The halogen atom represented by R ³ is, for example, a chlorine atom, a bromine atom or a fluorine atom, and the alkoxy group is, for example, a methoxy group or a dodecyl group. R ³ is preferably a chlorine atom.

The carboxamide group represented by R ² is, for example, a 2,4-di-t-pentylphenoxyacetamide group, and the sulfonamide group is, for example, a 4-dodecyloxyphenylsulfonamide group, for example There is an ocdadecenylsuccinimide group, and the carbamoyl group includes, for example, a 4- (2,4-di-t-pentylphenoxy) butylaminocarbonyl group, and the sulfamoyl group includes, for example, a tetradecanesulfamoyl group. Examples of the alkoxycarbonyl group include a tetradecaneoxycarbonyl group, and examples of the alkoxycarboxamide group include a dodecyloxycarboxamide group.

R ² is preferably a carboxamide group, which is substituted at the p-position with respect to R ³ . Further, m is preferably 1 or 2, and n is 1.

Specific examples of the compound represented by the above general formula [CM] according to the present invention will be given below, but the present invention is not limited thereto.

[0170]

[Chemical 9]

[0171]

[Chemical 10]

[0172]

[Chemical 11]

In the present invention, it is preferable to add a fluorine-containing surfactant in the photographic constitution, and particularly, it is preferable to add a combination of an anion type fluorine-containing surfactant and a cationic type fluorine-containing surfactant to the surface protective layer. Is preferred.

Examples of the fluorine-containing anionic surfactant preferably used in the present invention include those represented by the following general formula [FA].

[0175]

[Chemical 12]

In the formula, Cf represents an n-valent group containing at least 3 fluorine atoms and at least 2 carbon atoms, and Y
Is -COOM -, - SO ₃ M, represents an -OSO ₃ M or -P (= O) (OM) 2, where M represents a hydrogen atom, or an alkali metal atom or an ammonium group,, l is 1 or It is 2.

Further preferably used fluorine-containing anionic surfactants are those represented by the following general formula [FA '].

[0178]

[Chemical 13]

In the formula, Rf represents a fluorine-substituted alkyl group having 3 to 30 carbon atoms or an aryl group, and D represents -O-, -COO-, -C.
ON (R ¹ )-or —SO ₂ N (R ¹ ) — represents a divalent group having 1 to 12 carbon atoms and containing at least one bond, wherein R ¹ is alkyl having 1 to 5 carbon atoms. represents a group, t is 1 or 2, and Y is _{-COOM -, - SO 3 M,} -OSO 3 M or -P (= O) (OM)
Represents ₂ , where M represents a hydrogen atom, an alkali metal atom or an ammonium group.

The specific examples of the compounds will be given below, but the invention is not limited thereto.

[0181]

[Chemical 14]

The fluorine-containing cationic surfactant used in the present invention is a compound represented by the following general formula [FK].

[0183] Formula [FK] Rh-T-X ⁺ Z ^- However, Rh is 1-20C hydrocarbon group having a carbon, at least one hydrogen atom is substituted with a fluorine atom. T represents a chemical bond or a divalent group. X ⁺ represents a cationic group and Z ⁻ represents a counter anion.

Examples of Rh are -CnF _{2n + 1} , (n = 1 to 10, especially 3 to 12), HCmF ₂ m-, -CmF ₂ m _-1 , and -C ₃ mF ₆ m _-1 (m = 1-4) can be mentioned.

As an example of T,

[0186]

[Chemical 15]

Mention may be made of these.

Also, as an example of X ⁺ ,

[0189]

[Chemical 16]

Mention may be made of these.

R'represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may be substituted with a hydroxyl group.

A'represents an alkylene group or an arylene group, p represents 0 to 6 and q represents 1 to 20.

[0193] Z ^- as an example of,

[0194]

[Chemical 17]

Mention may be made of these.

Specific examples of the fluorine-containing cationic surfactant preferably used in the present invention will be given below.

[0197]

[Chemical 18]

In the present invention, it is more preferable to use a particularly insoluble sulfonamide type fluorine-containing surfactant in the same layer as the anionic surfactant. What is refractory here?
2 g of the surfactant was added to 100 cc of pure water at 23 ° C., and the mixture was stirred for 1 hour and left at 23 ° C. for 24 hours to form a precipitate, or when a floating material was observed, it was made insoluble. For example, F
K-1, FK-8, FK-15, FK-16, etc. correspond, but are not limited to these and can be distinguished by the above test.

The fluorine-containing anionic surfactant according to the present invention or the fluorine-containing anionic surfactant according to the present invention is, for example, US Pat. Nos. 2,559,751, 2,567,011 and 2,
732,398, 2,764,602, 2,806,866, 2,809,9
No. 98, No. 2,915,376, No. 2,915,528, No. 2,934,450,
2,937,098, 2,957,031, 3,472,894, 3,
555,089, 2,918,501, British Patent 1,143,927,
1,130,822, JP-B-45-37304, JP-A-47-9613,
50-121243, 50-117705, 49-134614, 50-117
Nos. 727, 52-41182, 51-12392, British Chemical Society (J. Chem. Soc.) 1950, page 2789, 1957, second
574 and 2640, Journal of the American Chemical Society (J. Amer. Chem. Soc.)
Volume 79, page 2549 (1957), Oil Chemistry (J. Japan. Oil Chemists)
Soc.) 12: 653, Journal of the Society of Organic Chemistry (J.Org.Chem.) 3rd
Volume 0, page 3524 (1965) and the like.

Among these fluorine-containing surfactants according to the present invention, a certain kind is a trade name of Megafac F from Dainippon Ink and Chemicals Incorporated, and Fluorad (from Minnesota Mining and Manufacturing Company). Fluorad) FC, trade name Monflor from Imperial Chemical Industries, EIDupont from Nemeras & Company Zonyls, or Ricovet from Farbeberke Hoechst. (Licowet) VPF is commercially available under the trade name.

The total amount of the fluorine-containing cationic surfactant and the fluorine-containing anionic surfactant used in the present invention is preferably 0.1 to 1000 mg per 1 m ² , and preferably 0.1.
5-300 mg, more preferably 1.0-150 mg is good. When used in combination, two or more kinds of fluorine-containing cationic surfactant and fluorine-containing anionic surfactant may be used together. In addition, a fluorine-containing nonionic surfactant, a fluorine-containing betaine surfactant and a hydrocarbon-based surfactant may be used in combination.

The addition ratio of the fluorine-containing anionic surfactant and the fluorine-containing cationic surfactant of the present invention is preferably 1:10 to 10: 1 in molar ratio, and further 3: 7 to 7: 3.
Is preferred.

The addition location of the fluorine-containing anionic surfactant and fluorine-containing cationic surfactant of the present invention is not particularly limited, but it is preferably a surface protective layer, or may be a surface layer of an intermediate product, When a back layer is provided, it may be the surface layer on the back layer side. The lower limit of the total dry film thickness of the photographic constituent layers (all hydrophilic colloid layers) of the photographic light-sensitive material of the silver halide color photographic light-sensitive material (hereinafter referred to as the film thickness on the emulsion side) is the silver halide emulsion, the coupler included There is a limit depending on the amount of oil, oil, additives, etc., and the preferred emulsion surface thickness is 5
μm to 25 μm, and more preferably 10 μm to 20 μm. In addition, the distance from the outermost surface of the emulsion surface to the lower end of the emulsion layer closest to the support is preferably 14 μm or less, and the emulsion layer having the color sensitivity different from that of the emulsion layer is 10 μm to the lower end of the emulsion layer next to the support. The following are preferred.

As a method for thinning the color photosensitive material,
There is a method of reducing the amount of hydrophilic colloid which is a binder. The purpose is to hold silver halide and coupler micro oil droplets dissolved in high boiling point solvents, to prevent fog rise due to mechanical stress, and to prevent color turbidity due to diffusion of oxidized developing agent between layers. Since the hydrophilic colloid is added, the amount can be reduced within a range that does not impair their purpose.

As another method of thinning, there is a method of using a coupler having a high color forming property or a coupler having a high molecular extinction coefficient.

As another method of thinning the layer, a method of reducing the amount of the high boiling point solvent, or a method of thinning the intermediate layer by adding a scavenger of an oxidized product of a developing agent to the intermediate layer between layers having different color sensitivities Etc.

The total amount of silver halide contained in the light-sensitive silver halide emulsion contained in all emulsion layers of the silver halide color photographic light-sensitive material is preferably 10.0 g / m ² or less, more preferably 2.5 to 9.0. g / m ² , more preferably 3.0 to 8.
0 g / m ^2, particularly preferably 3.5~6.5g / m ^2.

The total hydrophilic protective colloid layer coated on the emulsion layer side of the support of the silver halide color photographic light-sensitive material has a swollen film thickness of 180% to 350% of the dry film thickness when developed. Is preferable, and particularly preferably 200% to 300%.

The technique for adjusting the swollen film thickness is well known to those skilled in the art, and can be carried out, for example, by appropriately selecting the amount and type of the hardener.

[0210] Examples of the hardening agent include aldehyde-based agents and aziridine-based agents (for example, PB Report 19,921, US Patent 2,950,197).
Nos. 2,964,404, 2,983,311, 3,271,175, each of which is described in JP-B-46-40898 and JP-A-50-91315), isoxazole-based (e.g., U.S. Pat.No.331,609). Those described in the specification), epoxy-based (for example, U.S. Patent 3,047,394, West German Patent 1,085,663, British Patent 1,033,518 each specification, those described in JP-B-48-35495), vinyl sulfone-based (for example, PB report
19,920, West German Patents 1,100,942, 2,337,412, 2,
545,722, 2,635,518, 2,635,518, 2,742,3
08, 2,749,260, British Patent 1,251,091, Japanese Patent Application No. 45
-54236, 48-ll0996, U.S. Patents 3,539,644, 3,
Those described in each specification of 490,911), acryloyl-based (for example, Japanese Patent Application No. 48-27949, those described in each specification of US Pat. No. 3,640,720), carbodiimide-based (for example, US Pat. Nos. 4,061,499, Japanese Patent Publication No. 46-38715 and Japanese Patent Application No. 49-15095), triazines (for example, West German patent)
2,4l0,973, 2,553,915, each specification of U.S. Pat.No. 3,325,287, those described in JP-A-52-l2722), polymer type (for example, British Patent 822,061, U.S. Patent 3,623,878)
Nos. 3,396,029 and 3,226,234
47-18578, 18579, and 47-48896), other maleimide grandchildren, acetylene-based, methanesulfonic acid ester-based (N-methylol-based) hardeners alone or Can be used in combination. As a useful combination technology, for example, West German Patents 2,447,587, 2,505,746,
2,514,245, U.S. Patent 4,047,957, 3,832,181
Nos. 3,840,370, JP-A Nos. 48-43319 and 5
The combinations described in JP-A Nos. 0-63062, 52-l27329, and JP-B-48-32364 can be mentioned.

In the present invention, it is preferable that the carboxy-active hardener is used for hardening. For carboxy-activated hardeners, Japanese Examined Patent Publication Nos. 56-12853 and 58-32699
No. 4, JP-A-49-51945, JP-A-51-59625, JP-A-61-9641 and carbamoylammonium salt-based hardeners shown in Belgian Patent 825,726. Amidinium-based hardeners shown in JP-A-60-225148, carbodiimide-based hardeners shown in JP-A-51-126125 and JP-A-52-48311, JP-B-58-50699,
Pyridinium salt type hardeners disclosed in JP-A-57-44140, 57-46538 and 52-54427, and JP-A-50-38540
No. 52-93470, No. 56-43353, No. 58-113929, and the compounds described in US Pat. No. 3,321,313 are also preferable.

Specific examples of particularly preferable carboxy-active type hardeners are shown below. As another preferred specific example, JP-A-2-214852, p. H-1 to H-8 shown in 489 to 495
There are two.

[0213]

[Chemical 19]

In the present invention, the amount of the hardener used can be arbitrarily selected according to the purpose. Usually, it can be used in a ratio of 0.01 to 20% by weight based on dry gelatin. Particularly preferably, it is used in a proportion in the range of 0.05 to 15% by weight.

In the present invention, the photographic layer using a hardener is not particularly limited as long as it is a gelatin-containing layer, and not only a silver halide emulsion layer but also a non-photosensitive layer such as an undercoat layer, a back layer, a filter layer and an intermediate layer. , A gelatin-containing photographic layer such as an overcoat layer.

The above-mentioned hardener may be used alone, or 2
You may mix and use 1 or more types. It may be used in combination with other hardeners known so far.

A silver halide photographic light-sensitive material obtained by coating a photographic layer containing a gelatin-containing layer containing a hardener is
The hardening rate varies depending on the storage conditions, and it is preferable that the temperature range is 15 ° C to 45 ° C. Further, the water content of the light-sensitive material is preferably adjusted so that the equilibrium water content is 50 to 80% relative humidity.

If the storage temperature and the water content of the light-sensitive material are too low, the film-hardening speed becomes slow, which is not preferable. On the contrary, if the temperature and the water content are too high, the photographic characteristics may be affected. In the present invention, the swollen film thickness at the time of development is defined as the thickness after being dipped in the following solution kept at 38 ° C. for 3 minutes.

Solution for measuring swelling degree (color developing solution) 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline / sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine1 / 2 Sulfate 2.0 g Anhydrous potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make 1 liter.

The swollen film thickness is measured, for example, by A. Green and I.B. Levenson Journal of Photographic Science (J. Photogr. Sci.), 20 , 205 (1
972) It can be measured by the method described.

The dry film thickness means the film thickness measured at 23 ° C. and 55% humidity. Regarding each film thickness, the cross section of the dried sample is enlarged and photographed with an operating electron microscope, and the film thickness of each layer is measured.

As the above-mentioned all-hydrophilic protective colloid layer,
In addition to the above-mentioned blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers each having at least one layer, a protective layer, an antihalation layer, a yellow filter layer, an intermediate layer, etc. which are coated as necessary are included. .

The layer structure of the silver halide color photographic light-sensitive material capable of exhibiting the effect of the present invention is, in order from the support, colloidal silver antihalation layer (intermediate layer) red-sensitive layer (intermediate layer) green-sensitive layer (intermediate layer). Colloidal silver yellow filter layer Blue-sensitive layer (must-required layer) A protective layer is applied, and then from the support colloidal silver antihalation layer (intermediate layer) Red-sensitive layer (intermediate layer) Red-sensitive layer (intermediate layer) Green-sensitive Layer (colloidal silver yellow filter layer) Blue-sensitive layer (intermediate layer) protective layer is applied.

The layers in parentheses may be omitted.

Each of the red-sensitive layer, the green-sensitive layer and the blue-sensitive layer is preferably divided into a low sensitivity layer and a high sensitivity layer.

Also, at least one of a red-sensitive layer, a green-sensitive layer and a blue-sensitive layer as described in JP-B-49-15495.
The layer structure is divided into three partial layers, the layer structure is divided into a high-sensitivity emulsion layer unit and a low-sensitivity emulsion layer unit as described in JP-A-51-49027 and West German Laid-Open Publication No. 2,622,922.
No. 2,622,923, No. 2,622,924, No. 2,704,826 and No. 2,704,797, and the like.

Further, in the present invention, JP-A-57-177551
It is also possible to apply the layer structure described in each publication of No. 59-177552 and No. 59-180555.

A photographic constituent layer of a silver halide color photographic light-sensitive material contains a dye (A
I dye) can be added, and as the AI dye,
Oxonol dyes, hemioxonol dyes, merocyanine dyes and azo dyes are included. Of these, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful. Examples of AI dyes that can be used include British patents.
584,609, 1,277,429, JP-A-48-85130, 49-9
9620, 49-114420, 49-129537, 52-108115
No. 59, No. 25845, No. 59-111640, No. 59-111641, No. 2,274,782, No. 2,533,472, No. 2,956,079,
3,125,448, 3,148,187, 3,177,078, 3,2
47,127, 3,260,601, 3,540,887, 3,575,70
No. 4, No. 3,653,905, No. 3,718,472, No. 4,070,352 can be mentioned.

Generally, these AI dyes are preferably used in an amount of 2 × 10 ^{-3 to} 5 × 10 ^-1 mol per mol of silver in the emulsion layer.

The DIR compound used in the present invention is a compound capable of releasing a development inhibitor by reacting with an oxidized product of a color developing agent.

A typical example of such a DIR compound is a DIR coupler in which a group capable of forming a compound having a development inhibiting action when released from the active site is introduced into the active site of the coupler. Patent 935,454,
U.S. Pat. Nos. 3,227,545, 4,095,984, and 4,149,886 are described. The above-mentioned DIR coupler has a property that upon coupling reaction with an oxidant of a color developing agent, the mother nucleus of the coupler forms a dye, while releasing a development inhibitor. In the present invention, U.S. Pat.
8,041, 3,958,993, 3,961,959, 4,052,213
Release agent is released when it undergoes a coupling reaction with an oxidant of a color developing agent as described in JP-A Nos. 53-110529, 54-13333 and 55-161237. Also included are compounds that do not form pigments. Furthermore, JP-A-54-
No. 145135, No. 56-114946 and No. 57-154234, when reacted with an oxidant of a color developing agent as described in, the mother nucleus forms a dye or a colorless compound, while the released timing group The present invention also includes so-called timing DIR compounds, which are compounds that release a development inhibitor by an intramolecular nucleophilic substitution reaction or a elimination reaction.

[0232] Further, as described above in the coupler mother nucleus which forms a completely diffusible dye when reacted with the oxidant of the color developing agent described in JP-A-58-160954 and JP-A-58-162949. Timing DIR compounds to which a timing group is attached can be used.

Further, in addition to the DIR compound, a compound which releases a development inhibitor upon development can be used in the present invention. For example, US Pat. Nos. 3,297,445 and 3,379,529, West German patent application (OLS) 2,417,914, JP Sho 52-15271, same
53-9116, 59-123838, 59-127038 and the like.

The amount of the DIR compound contained in the light-sensitive material is preferably in the range of 1 × 10 ^-4 mol to 10 × 10 ^-1 mol per mol of silver.

In the present invention, better effects can be obtained by using colloidal silver. As the colloidal silver, any of those known for photography can be used, and examples thereof include yellow colloidal silver, red colloidal silver and black colloidal silver.

The colloidal silver may be added at either the light-sensitive layer or the light-insensitive layer in the light-sensitive material, but the low light-insensitive layer is preferable. The coating amount of colloidal silver in the photosensitive material is 0.001g
To 1.0 g / m ^2, preferably ^{0.005g / m 2 ~0.5g / m 2} , particularly preferably ^{0.01g / m 2 ~0.3g / m 2} .

As the ultraviolet absorber, those represented by the following general formula [U] are preferable.

[0238]

[Chemical 20]

(In the general formula [U], R ₁ , R ₂ and R ₃ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkenyl group, a nitro group or a hydroxyl group. .) Each group represented by R _{1 to} R ₃ includes a group having a substituent.

Of the groups represented by R ₁ and R ₂ , a hydrogen atom, an alkyl group, an alkoxy group and an aryl group are preferable, and a hydrogen atom, an alkyl group and an alkoxy group are particularly preferable. Among the groups represented by R ₃ , a hydrogen atom, a halogen atom and an alkoxy group are particularly preferable.

At least one of R _{1 to} R ₃ is preferably an alkyl group. Further, at least one of R _{1 to} R ₃ is preferably a branched alkyl group.

Representative specific examples will be shown.

[0243]

[Chemical 21]

In the present invention, it is effective to use an ultraviolet absorber which is liquid at room temperature. About this
2- (2 ′) represented by the general formula [a] of 3-175443 Publication P, 323
-Hydroxyphenyl) benzotriazole compounds are preferred. As specific compounds, 27 kinds of exemplified compounds a-1L to a-27L in P.323 of the publication are particularly preferable.
Further, as shown in the publication, it is effective to use at least one liquid ultraviolet absorber in combination with at least one of the ultraviolet absorbers represented by the general formulas [I] and [II]. The present invention is also effective in that it can enhance the ultraviolet absorption effect without deteriorating the physical properties of the material.

The addition amount of the compound represented by the general formula [U] is 0.1 to 3 with respect to the binder of the layer to which the compound is added.
It is preferably 00% by weight, more preferably 1 to 200% by weight.

As the binder (or protective colloid) of the silver halide emulsion of the present invention, it is advantageous to use gelatin. However, gelatin derivatives, graft polymers of gelatin and other polymers, other proteins and sugar derivatives. Also, hydrophilic colloids such as cellulose derivatives and synthetic hydrophilic polymer substances such as homopolymers or copolymers can be used.

As the gelatin, the above-mentioned various gelatins can be used.

Examples of the gelatin derivative include gelatin such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleimide compounds, polyalkyleonoxides and epoxy compounds. Those obtained by reacting various compounds are used. A specific example is U.S. Pat.
3,132,945, 3,186,846, 3,312,553, British Patents 861,414, 1,033,189, 1,005,784, Japanese Patent Publication No. 4
It is described in No. 2-26845. In the present invention, it is preferable to use low calcium gelatin having a low calcium content among gelatin as described above.

Examples of proteins include albumin, casein,
As the cellulose derivative, hydroxyethyl cellulose, carboxymethyl cellulose, sulfuric acid ester of cellulose, and as the sugar derivative, sodium alginate,
Starch derivatives are preferred.

As the graft polymer of the above-mentioned gelatin and other polymers, gelatin is a homopolymer of acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, and vinyl monomers such as acrylonitrile and styrene.
Alternatively, a grafted copolymer can be used. In particular, polymers that are somewhat compatible with gelatin,
For example, a graft polymer with a polymer such as acrylic acid, acrylamide, methacrylamide, or hydroxyalkyl methacrylate is preferable. Examples of these are US patents
2,763,625, 2,831,767, 2,956,884. Typical synthetic hydrophilic polymer substances are homopolymers or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole and the like. , For example West German patent application (OLS) 2,312,708,
U.S. Patents 3,620,751 and 3,879,205, Japanese Patent Publication No. 43-7561
No. The photographic emulsion layer of the light-sensitive material using the silver halide emulsion of the present invention, and the other hydrophilic colloid layer, cross-link the binder (or protective colloid) molecule,
Hardening can be carried out by using one or two or more hardening agents for increasing the film strength. The hardener can be added in an amount such that the photosensitive material can be hardened to the extent that it is not necessary to add the hardener to the processing liquid, but it is also possible to add the hardener to the processing liquid.

As a hardening agent, aldehyde type and aziridine type (for example, PB Report 19921, US Pat. No. 2,950,197) can be used.
No. 2, No. 2,964,404, No. 2,983,311, No. 3,271,175,
JP-B-46-40898, JP-A-50-91315), isoxazole-based compounds (e.g., those described in U.S. Pat.No. 331,609), epoxy-based compounds (e.g., U.S. Pat.No. 3,047,394).
No. 1, West German Patent No. 1,085,663, British Patent No. 1,033,518, Japanese Patent Publication No. 48-35495), vinyl sulfone type (for example, PB Report 19920, West German Patent Nos. 1,100,942, 2,33).
7,412, 2,545,722, 2,635,518, 2,742,308
No. 2,749,260, British Patent 1,251,091, Japanese Patent Application No. 45-
54236, 48-110996, U.S. Patents 3,539,644, 3,
490,911), acryloyl series (eg,
Japanese Patent Application No. 48-27949, those described in U.S. Pat.No. 3,640,720), carbodiimide type (for example, U.S. Pat.
Issue 4,043,818, Issue 4,061,499, Japanese Patent Publication No. 46-38715
No., those described in Japanese Patent Application No. 49-15095), triazines (for example, those described in West German Patents 2,410,973, 2,553,915, U.S. Patent 3,325,287, and Japanese Patent Laid-Open No. 52-12722),
Polymer type (eg British patent 822,061, US patent 3,62
No. 3,878, No. 3,396,029, No. 3,226,234, Japanese Patent Publication No. 47-1
8578, 18579 and 47-48896)),
Other maleimide-based, acetylene-based, methanesulfonic acid ester-based, and N-methylol-based hardening agents can be used alone or in combination.

As a useful combination technique, for example, West German Patent
2,447,587, 2,505,746, 2,514,245, U.S. Pat.Nos. 4,047,957, 3,832,181, 3,840,370, JP-A-48-43319, 50-63062, 52-127329, and JP-B-48-32364. And combinations described in.

In the present invention, the effect is enhanced by using a vinyl sulfone type hardener.

The vinyl sulfone type hardener is a compound having a vinyl group bonded to a sulfonyl group or a group capable of forming a vinyl group, preferably a vinyl group bonded to a sulfonyl group or a group capable of forming a vinyl group. Have at least two. For example, the compound represented by the following general formula [VS-I] is preferably used in the present invention.

General formula [VS-I] L- (SO ₂ -X) m In the above general formula [VS-I], L represents an m-valent linking group, and X represents —CH═CH ₂ or —CH ₂ CH ₂ Y, Y represents a group capable of being eliminated in the form of HY by a base, such as a halogen atom, a sulfonyloxy group, a sulfooxy group (including a salt), a residue of a tertiary amine and the like. m represents an integer of 2 to 10, but m
Is 2 or more, -SO ₂ -X may be the same or different from each other.

The m-valent linking group L is, for example, an aliphatic hydrocarbon group (eg, alkylene, alkylidene, alkylidyne, etc., or a group formed by combining these), an aromatic hydrocarbon group (eg, arylene, etc.) Alternatively, a group formed by combining these) —O—, —NR′— (R ′ represents a hydrogen atom or an alkyl group having preferably 1 to 15 carbon atoms), —S—, —N <, ―CO, ―SO―, ―SO ₂ ― or ―SO
It is an m-valent group formed by combining one or a plurality of the bonds represented by _3- , and when two or more -NR'- are included, R's thereof are bonded to each other to form a ring. Good. The linking group L further includes those having a substituent such as a hydroxyl group, an alkoxy group, a carbamoyl group, a sulfamoyl group, an alkyl group or an aryl group.

As a specific example of X, --CH ₂ ═CH ₂ or --CH
₂ CH ₂ Cl and the like are preferable.

Typical examples of vinyl sulfone type hardeners are shown below.

[0259]

[Chemical formula 22]

The vinyl sulfone type hardener used in the present invention is, for example, German Patent 1,100,942 and US Patent 3,490,9.
Aromatic compounds such as those described in No. 11 etc., Japanese Patent Publication No. 44
-29622, 47-25373, 47-24259 and the like, an alkyl compound bonded with a hetero atom,
Sulfonamides, ester compounds as described in JP-B-47-8736 and 1,3,5-tris [β- (vinylsulfonyl) as described in JP-A-49-24435.
Propionyl] -hexahydro-s-triazine or alkyl compounds such as those described in JP-B-50-35807 and JP-A-51-44164, and compounds described in JP-A-59-18944, etc. Include.

These vinyl sulfone type hardeners are dissolved in water or an organic solvent and used in an amount of 0.005 to 20% by weight, preferably 0.02 to 10% by weight, based on the binder (eg gelatin).

For addition to the photographic layer, a batch method, an in-line addition method, or the like is adopted.

The layer in which these hardeners are added to the photographic layer is not particularly limited, and may be added to, for example, one uppermost layer, one lowermost layer or all layers.

The photographic emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material using the silver halide emulsion of the present invention include
Various surfactants can be used for the purpose of improving coatability, antistatic properties, improving slipperiness, emulsifying and dispersing, preventing adhesion, improving photographic properties (development acceleration, film hardening, sensitization, etc.).

Examples of the anionic surfactant include alkylcarboxylic acid salts, alkylsulfonic acid salts, alkylbenzenesulfonic acid salts, alkylnaphthalenesulfonic acid salts, alkyl sulfuric acid esters, alkyl phosphoric acid esters, N-acyl-N-alkyl salts. Acidic groups such as carboxyl group, sulfo group, phospho group, sulfuric acid ester group, phosphoric acid ester group such as taurines, sulfosuccinic acid esters, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphoric acid esters, etc. Those containing are preferred.

As the amphoteric surfactant, for example, amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfuric acid or phosphoric acid esters, alkyl betaines, amine oxides and the like are preferable.

Examples of the cationic surfactant include alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and phosphonium compounds containing an aliphatic or heterocyclic ring. Sulfonium salts and the like are preferable.

Examples of the nonionic surfactants include saponins (steroids), alkylene oxide derivatives (eg polyethylene glycol, polyethylene glycol / polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters). , Polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, polyethylene oxide adducts of silicon), glycidol derivatives (eg alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, sugars And the like are preferable.

In the present invention, anionic surfactants are more preferable, and those shown in the above S-1 to S-12 are particularly preferable.

In coating a photographic light-sensitive material using the silver halide emulsion of the present invention, a thickener may be used to improve coatability.

The light-sensitive material using the silver halide emulsion of the present invention can be provided with auxiliary layers such as a filter layer, an antihalation layer, and / or an irradiation prevention layer. In these layers and / or in the emulsion layers, dyes which are bleached or bleached from the light-sensitive material during the development process may be contained.

The filter dyes or dyes used for various purposes such as prevention of irradiation include oxanol dyes, hemioxanol dyes, merocyanine dyes, cyanine dyes, styryl dyes and azo dyes. Of these, oxanol dyes, hemioxanol dyes and merocyanine dyes are useful.

Specific examples of dyes that can be used are West German Patent 616,007.
No., British Patents 584,609, 1,177,429, Japanese Patent Publication No. 26-77
77, 39-22069, 54-38129, JP-A-48-8513
No. 0, 49-99620, 49-114420, 49-129537
No. 50-28827, No. 52-108115, No. 57-185038
U.S. Pat.Nos. 1,878,961, 1,884,035, 1,912,79
No. 7, No. 2,098,891, No. 2,150,695, No. 2,274,782,
2,298,731, 2,409,612, 2,461,484, 2,5
27,583, 2,533,472, 2,865,752, 2,956,87
No. 9, No. 3,094,418, No. 3,125,448, No. 3,148,187,
3,177,078, 3,247,127, 3,260,601, 3,2
82,699, 3,409,433, 3,540,887, 3,575,70
No. 4, No. 3,653,905, No. 3,718,472, No. 3,865,817,
4,070,352, 4,071,312, PB Report 74175, P
HOTO.ABS. Are those described in 1 28 ('21), and the like. In the present invention, various polymer latexes are used for the purpose of improving the film physical properties of the binder of the light-sensitive material, improving the adhesiveness of the coating film, improving the dimensional stability, and further improving the developing characteristics. Is preferably added. In particular, an aqueous dispersion type one synthesized by emulsion polymerization is preferable.

As the polymer latex, a single kind of monomer compound may be a homopolymer, but different 2
So-called copolymers composed of more than one type are preferable in that the properties of the polymer latex can be easily controlled by the combination thereof.

The monomer compound constituting the polymer latex used in the present invention is preferably an ethylenic monomer compound.

More specific examples of these monomer compounds include acrylic acid esters such as methyl acrylate, ethyl acrylate, i-propyl acrylate, n-butyl acrylate, t-butyl acrylate, hexyl acrylate and 2-ethylhexyl acrylate. , Cyanoethyl acrylate, 2-acetoxyethyl acrylate, dimethylaminoethyl acrylate, benzyl acrylate, phenyl acrylate, 2
-Hydroxyethyl acrylate, etc .; Examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, 2- Ethoxyethyl methacrylate, etc .; Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl salicylate and the like.

Examples of olefins include dicyclopentadiene, ethylene, propylene, 1-butene, 1-butene.
Pentene, vinyl chloride, vinylidene chloride, isoprene,
Examples thereof include chloroprene, butadiene, 2,3-dimethylbutadiene and the like. Examples of styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, chloromethylstyrene, and methoxystyrene.

Examples of crotonic acid esters include butyl crotonic acid and hexyl crotonic acid.

Examples of the itaconic acid diesters include dimethyl itaconate, diethyl itaconate, dibutyl itaconate and the like.

Examples of maleic acid diesters include diethyl maleate, dimethyl maleate, dibutyl maleate and the like.

Examples of fumaric acid diesters include:
Examples include diethyl fumarate, dimethyl fumarate, dibutyl fumarate, and the like.

As acrylamides, acrylamide, methyl acrylamide, ethyl acrylamide, propyl acrylamide, butyl acrylamide, dimethyl acrylamide and the like; as methacrylamides,
For example, methacrylamide, methylmethacrylamide,
Ethyl methacrylamide, propyl methacrylamide,
Butylmethacrylamide, etc .; as the allyl compound,
For example, allyl acetate, allyl caproate, allyl laurate, allyl benzoate and the like; as vinyl ethers, for example, methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether and the like;
Examples of vinyl ketones include methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone and the like; examples of vinyl heterocyclic compounds include vinyl pyridine, N-vinyl imidazole, N-vinyl oxazolidone, N-vinyl triazole, N -Vinylpyrrolidone, etc .; glycidyl esters, for example, glycidyl acrylate, glycidyl methacrylate, etc .; unsaturated nitriles, for example, acrylonitrile,
Examples thereof include methacrylonitrile. Further, polyfunctional monomers such as divinylbenzene, methylenebisacrylamide, ethylene glycol dimethacrylate and the like can also be used. Further, acrylic acid, methacrylic acid, itaconic acid, maleic acid and the like can be mentioned. These acids may be salts of alkali metals (eg sodium, potassium etc.) or ammonium ions. Still other monomer compounds include U.S. Pat.
3,438,708, 3,554,987, 4,215,195, 4,24
The crosslinkable monomers described in JP-A-7,673 and JP-A-57-205735 can be used. Specific examples of such crosslinkable monomers include N- (2-acetoacetoxyethyl) acrylamide, N- {2- (2-acetoacetoxyethoxy) ethyl} acrylamide and the like. Among these monomer compounds, acrylic acid esters, methacrylic acid esters, vinyl esters, styrenes and olefins are preferably used.

Regarding the method for synthesizing the latex of the present invention,
U.S. Patents 2,852,386, 2,853,457, 3,411,911
No. 3,411,912, 4,197,127, Belgian Patent 688,
No. 882, No. 691,360, No. 712,823, Japanese Patent Publication No.45-5331
No. 60-18540, No. 51-130217, No. 58-13783
It is described in detail in No. 1 and No. 55-50240.

The average particle size of the latex of the present invention is 0.01 to 0.
8 μm is particularly preferable, and any one having a thickness of 0.005 to 2.0 μm can be used.

The molecular weight is not specified, but 1,000
-1,000,000, preferably 2,000-500,000. or,
Glass transition temperature is -40 ~ 150 ℃, preferably -40
~ 20 ° C.

The latex of the present invention can be contained in the photographic constituent layer as it is or after being dispersed in water. The content of the latex is 5 to 60 relative to the binder of the photographic constituent layer.
It is preferably added by weight%. The place of addition may be a photosensitive layer or a non-photosensitive layer, but a photosensitive layer is more preferable.

In the present invention, it is preferable to add a high boiling solvent dispersion.

The high boiling point solvent used in the present invention means a boiling point
It is not less than 150 ° C, preferably 200 ° C to 400 ° C.
Examples of the high boiling point solvent used in the present invention include inorganic acid esters, organic acid esters, polyhydric alcohol esters, epoxidized oils and the like as described in detail below.

Examples of the inorganic acid esters include phosphoric acid esters, specifically, triethyl phosphate, tributyl phosphate, tri-n-octyl phosphate, diphenyl-n-octyl phosphate, butyl-2-xylenyl phosphate. , Triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate and the like. Examples of the organic acid ester include first lower fatty acid ester, for example, citric acid ester, specifically, tributyl citrate, acetyl tributyl citrate,
Examples include triethyl citrate, acetyl triethyl citrate, tricyclohexyl citrate, acetyl trioctyl citrate, acetyl octyl decyl citrate, and the like.

Examples of the higher fatty acid ester of the organic acid ester include butyl stearate, methoxyethyl oleate, methyl acetylricinoleate, ethyl acetylricinoleate, methoxyethyl acetylricinoleate and the like. Furthermore, in the present invention, the organic acid ester includes aliphatic and aromatic divalent organic acid esters.

As the aliphatic divalent organic acid ester,
Examples include dibutyl adipate, di-2-ethylhexyl adipate, di-n-octyl adipate, di-n-octyl sebacate, dibutyl sebacate, di-2-ethylhexyl azelate, di-i-decyl adipate, and the like. Examples of aromatic divalent organic acid esters include phthalic acid esters, such as dimethyl phthalate,
Di-i-isopropyl phthalate, diethyl phthalate,
Dibutylphthalate, dibutylterephthalate, butylbenzylphthalate, dibutoxyethylphthalate, dihexylphthalate, dicyclohexylphthalate, di-n-heptylphthalate, di-n-octylphthalate, di-2-ethylhexylphthalate, di-2-ethylhexylterephthalate, di 2-ethylhexyl isophthalate, di-n-nonyl phthalate, di-n-nonyl isophthalate, butyl cyclohexyl phthalate, dibutyl tetrachlorophthalate, dibutyl isophthalate, dicapryl phthalate, di-2-methoxyethyl phthalate, diisobutyl phthalate, etc. Can be mentioned.

Further, as the polyhydric alcohol ester,
For example, glycol esters are the main ones, specifically, ethylphthalylethyl glycolate, butylphthalylbutyl glycolate, methylphthalylethyl glycolate, etc., diethylene glycol dibenzoate, dipropylene glycol dibenzoate, and sucrose. Examples thereof include benzoate.

Examples of the epoxidized oils include epoxidized soybean fat, glycidyl oleate, aryl 9,10-epoxystearate phosphate, 2-ethylhexyl 9,10-epoxystearate, epoxidized tall oil fatty acid- 2
-Ethylhexyl, epoxidized tall oil alkyl and the like can be mentioned.

In the present invention, as the high boiling point solvent added to the non-photosensitive layer, one kind of solvent may be used alone,
Two or more different types may be mixed and dispersed and added, or two or more different types may be separately dispersed and mixed and added.

When added to at least one of the non-photosensitive layers, the high boiling point solvent used in the present invention is added as an oil-in-water type dispersion as in general silver halide color photographic light-sensitive materials. Is preferred. That is, a hydrophilic colloid solution such as an aqueous gelatin solution and a high boiling point solvent are mixed in the presence of a surfactant, and dispersed by an ultrasonic homogenizer, a homomixer, a pressure jet machine or the like to obtain a dispersion. .

In the present invention, the coating amount of the high boiling point solvent in the light-sensitive material is preferably in the range of 0.05 to 5.0 g / m ² ,
Particularly, the range of 0.2 to 2.0 g / m ² is preferable. In the present invention, a UV absorber, an antistatic agent, an antistain agent, an anti-irradiation dye, a hardener, etc. may be added to the non-photosensitive layer containing the high boiling point solvent, if necessary. I do not care.

The hydrophilic colloid layers such as the protective layer and the intermediate layer of the light-sensitive material of the present invention are protected by ultraviolet rays in order to prevent fogging due to discharge caused by charging of the light-sensitive material due to friction and the like and to prevent deterioration of the image by UV light. It may contain an absorbent.

As the ultraviolet absorber, a benzophenone compound (for example, JP-A-46-2784, US Pat. No. 3,215,530) is used.
No. 3,698,907), butadiene compounds
(For example, those described in US Pat.No. 4,045,229), 4-thiazolidone compounds (for example, US Pat.
3,352,681), benzotriazole compounds substituted with an aryl group (for example, Japanese Patent Publication No. 36-10466).
No. 41-1687, 42-26187, 44-29620, and
48-41572, JP-A-54-95233, 57-142975, U.S. Patents 3,253,921, 3,533,794, 3,754,919
No., 3,794,493, 4,009,038, 4,220,711,
Nos. 4,323,633 and RD22519), benzodioxazole compounds (for example, those described in U.S. Patent 3,700,455), cinnamic acid ester compounds (for example, U.S. Patents 3,705,805, 3,707,375, and JP-A-52- Those described in No. 49029) can be used.

Furthermore, US Pat. No. 3,499,762 and JP-A-54-4
Those described in No. 8535 can also be used. UV absorbing couplers (for example, α-naphthol cyan dye forming couplers) and UV absorbing polymers (for example,
JP-A-58-111942, JP-A-58-178351, JP-A-58-181041,
Nos. 59-19945 and 59-23344) and the like can be used.

These ultraviolet absorbers may be mordanted in a specific layer. Particularly preferred is a structure in which a benzotriazole compound is used in combination.

Colored couplers include, for example, British Patent Nos. 937,621, 1,035,959, 1,255,111, and JP-A-4.
8-22028, 52-42121, JP-B-38-22335, 44
-2016, 44-15754, U.S. Patents 2,449,966, 2,
521,908, 2,543,691, 2,801,171, 2,983,6
08, 3,005,712, 3,034,892, 3,061,432
Issue 3,419,391, Issue 3,476,560, Issue 3,476,563,
3,481,741, 3,519,429, 3,853,971, 3,6
22,328, 3,684,514, 4,004,929, 4,070,19
No. 1, 4,138,258, 4,138,264, 4,163,670,
Those described in Nos. 4,292,400 and 4,369,248 can be used.

In particular, it is preferable to use a suitable combination of a yellow color magenta coupler, a magenta color cyan coupler and a yellow color cyan coupler.

An image stabilizer which prevents deterioration of a dye image can be used in a light-sensitive material using the silver halide emulsion of the present invention.

Examples of image stabilizers include hydroquinone derivatives, gallic acid derivatives, phenol derivatives and their bis forms, hydroxycoumarans and their spiro forms, hydroxychromans and their spiro forms, piperidine derivatives, aromatic amine compounds, and benzodioxane derivatives. , Benzdioxole derivatives, silicon atom-containing compounds, thioether compounds and the like are preferable. As a specific example, US Patent 1,
410,846, JP-A-49-134326, 52-35633, 52
-147434, 52-150630, 54-145530, 55-
No. 6321, No. 55-21004, No. 55-124141, No. 59-3342
No. 59-5246, 59-10539, Japanese Patent Publication No. 48-31625
No. 49-20973, 49-20974, 50-23813,
52-27534, U.S. Patents 2,360,290, 2,418,613
No., No. 2,675,314, No. 2,701,197, No. 2,704,713,
2,710,801, 2,728,659, 2,732,300, 2,7
35,765, 2,816,028, 3,069,262, 3,336,13
No. 5, No. 3,432,300, No. 3,457,079, No. 3,573,050,
3,574,627, 3,698,909, 3,700,455, 3,7
64,337, 3,935,016, 3,982,944, 4,013,70
No. 1, 4,133,495, 4,120,723, 4,155,765,
4,159,910, 4,254,216, 4,268,593, 4,2
79,990, 4,332,886, 4,360,589, 4,430,42
No. 5, No. 4,452,884 and the like.

Particularly, the hydroquinone derivative type is preferred.

In the present invention, the colloid layer formed on the surface side of the silver halide emulsion layer formed on the side farthest from the support contains substantially non-photosensitive fine grain silver halide grains. The colloid layer is generally formed as a protective layer for the photographic constituent layers. The term "substantially non-photosensitive silver halide grains" as used herein refers to particles that are not substantially developed in a developing solution, and any such particles can be used. It is preferable that it is not substantially developed and dissolved. Further, the fine particles mean a particle diameter capable of minimizing light scattering, preferably having an average particle size of 0.3 μm or less, and an average particle diameter of 0.01
˜0.2 μm is preferable, and 0.02 to 0.15 μm is more preferable. The distribution of particles may be wide or narrow, but a narrow distribution is preferable.

The silver halide grains used as the substantially non-photosensitive fine silver halide grains are silver chloride, silver bromide,
Any of silver iodide, silver iodobromide, silver chlorobromide, silver chloroiodobromide and the like can be used, and these silver halides may be used alone or in combination of two or more kinds. The silver halide grains are preferably silver halide containing silver bromide, more preferably silver iodobromide containing 15 mol% or less of silver iodide from the viewpoint of solubility.
Silver iodobromide containing -10 mol% of silver iodide is more preferable, and silver iodobromide containing 2-8 mol% of silver iodide is particularly preferable. The silver halide grains may be physically aged with a rhodanate ion, a cyano ion, a thiocyanate ion or the like, or may be etched with a silver halide solvent.

These silver halide grains are manufactured by various manufacturing methods such as a neutral method, a half ammonia method, an ammonia method and the like, and are manufactured by various manufacturing types such as a simultaneous mixing method and a conversion method. Silver halide in the non-photosensitive layer is 0.1 to 3.0
g / m ² is preferably applied, more preferably 0.3 to 2.0
g / m ^2, particularly preferably used by applying 0.5 to 1.0 g / m ^2. However, the coated silver amount is converted to silver. The non-photosensitive layer contains a matting agent such as colloidal silica and polymethylmethacrylate, a high boiling point solvent (such as tricresyl phosphate and dioctyl phthalate), an ultraviolet absorber, an antioxidant, a lipophilic component such as a hydroquinone derivative, and an interface. A coating aid such as an activator and a gelatin hardened emulsion may be used at the same time.

Gelatin is generally used as a binder for the non-photosensitive layer, but a protein such as colloidal albumin, agar, gum arabic, alginic acid, and a cellulose derivative may be used in place of part or all of gelatin. , Sugar derivatives and starch derivatives can also be used.

A formalin scavenger can be used in the light-sensitive material of the present invention in order to prevent deterioration of the magenta dye-forming coupler and the like due to formalin during storage of the light-sensitive material.

Examples of formalin scavengers include JP-A-50-87028, 57-133450, and 58-150950.
U.S. Patents 2,895,827, 3,652,278 and 3,811,891
Issue 4,003,748, 4,411,987, 4,414,309,
4,418,142, 4,464,463, U.S. Defense Patent 900,028
West German patents 3,223,699, 3,227,961, 3,227,96
Nos. 2, RD10133 and the like can be preferably used. Aiming to reduce the gloss of the light-sensitive material, improve writing properties, prevent sticking of the light-sensitive materials to each other in the silver halide emulsion layer and / or other hydrophilic colloid layers of the light-sensitive material using the silver halide emulsion of the present invention. A matting agent can be added.

Matting agents include British Patent 1,055,713
U.S. Patents 1,939,213, 2,221,873, 2,268,66
No. 2, No. 2,322,037, No. 2,376,005, No. 2,391,181,
2,701,245, 2,992,101, 3,079,257, 3,2
62,782, 3,443,946, 3,516,832, 3,539,34
Organic matting agents described in No. 4, No. 3,591,379, No. 3,754,924, No. 3,767,448, West German Patent 2,529,321
No., British Patent Nos. 760,775 and 1,260,772, U.S. Patent No. 1,20
1,905, 2,192,241, 3,053,662, 3,062,649
No. 3,257,206, 3,322,555, 3,353,958,
3,370,951, 3,411,907, 3,437,484, 3,5
23,022, 3,615,554, 3,635,714, 3,769,02
Inorganic matting agents described in No. 0, No. 4,021,245, No. 4,029,504 and the like can be preferably used. The matting agent preferably has a particle size of 0.05 to 10 μm. The amount to be added is preferably 1 to 300 mg / m ² .

In the present invention, the dry film thickness of the photographic constituent layer is
It is preferably 16 μm or less. Here, the photographic constituent layers include a red light-sensitive silver halide emulsion layer, a green light-sensitive silver halide emulsion layer and a blue light-sensitive silver halide emulsion layer, as well as an intermediate layer, a filter layer and a protective layer which are provided as necessary. It means a constituent layer excluding a support including layers. The dry film thickness is 23
The film thickness measured at a temperature of 55 ° C. and 55% humidity, and the film thickness can be measured by enlarging the cross section of the dried sample with a scanning electron microscope. The thickness can be determined individually.

The thickness from the upper end surface of the emulsion layer farthest from the support to the lower end surface of the emulsion layer closest to the support is 14 μm.
The following are preferred.

The light-sensitive material of the present invention preferably has a water absorption rate represented by the following formula (1) of 170 to 230%.

Formula (1) Water absorption rate = [(B−A) / (A−
C)] × 100 (%) In the formula (1), A: the weight of the photosensitive material under the temperature and humidity conditions of 23 ° C. and 55% RH. The weight of the photosensitive material after being immersed in a developer having the following composition for 3 minutes and 15 seconds C: The weight of the photosensitive material after peeling off the coating layer under the same temperature and humidity conditions as A. Developer composition Water 800 ml Potassium carbonate 30 g Sodium hydrogencarbonate 2.5g Potassium sulfite 3.0g Sodium bromide 1.3g Potassium iodide 1.2mg Hydroxylamine sulfate 2.5g Sodium chloride 0.6g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline Sulfate 4.5g Diethylenetriaminepentaacetic acid 3.0g Potassium hydroxide 1.2g Add water to make 1 liter and adjust to pH 10.06 with potassium hydroxide or 20% sulfuric acid.

The silver halide material of the present invention is, if necessary, subjected to corona discharge, ultraviolet ray irradiation, flame treatment or the like on the surface of the support, and then directly or on the surface of the support for adhesion, antistatic property and dimensional stability. It may be applied via one or more subbing layers to improve the properties, abrasion resistance, hardness, antihalation, frictional properties, and / or other properties.

Examples of the undercoat layer of a polyethylene terephthalate film include those disclosed in JP-A-59-19941 and 59-77439.
It is preferable to use the undercoat layer described in JP-B No. 59-224841 and JP-B No. 58-53029. Further, as the undercoat layer of the cellulose triacetate film support, US Pat.
Those disclosed in Japanese Patent Publication No. 852,378 and Japanese Patent Publication No. 43-13826 are preferable.

In the present invention, as a method of storing in a state where the relative humidity is 55% or less, sealed packaging is preferable.
The hermetically sealed packaging referred to in the present invention means carrying out moisture-proof packaging which is well known in the field of ordinary packaging.

As a packaging material, an aluminum plate, a tin plate,
Metals such as aluminum foil, metal foil, glass, or polymers such as polyethylene, polyvinyl chloride, polystyrene, polyvinylidene chloride, polypropylene, polycarbonate, polyamide, etc., various polymers and cellophane, paper, aluminum foil, etc. (Laminate material in packaging terms) or the like is used.

As a sealing method for sealing, an adhesive method using various adhesives, a heat fusion method such as heat sealing, or a method using a cartridge case which is common in the photographic industry can be used. Details of these sealing methods are described in "Food Packaging Technology Handbook", Japan Packaging Technology Association (eds.), Pages 573-609.

The silver halide light-sensitive material stored at a relative humidity of 55% or less in the present invention means the weight W ₁ ⁵⁵ measured within 30 seconds after opening the silver halide light-sensitive material at 25 ° C. and 55% relative humidity. The difference ΔW ⁵⁵ = W ₂ ⁵⁵ −W ₁ ⁵⁵ from the measured weight W ₂ ⁵⁵ after storage for 3 days or more under the same conditions is defined to be zero or more.

The preferred conditions of the present invention are 25 ° C. and relative humidity of 30.
The weight change ΔW ^{30 in} % becomes negative, and a more preferable condition is that the weight change ΔW ³⁵ becomes negative at 25 ° C. and relative humidity 35%.

In the present invention, the roll type photographic light-sensitive material is preferably a cartridge case made of a polymer such as polyethylene or polypropylene, and the sheet-type photographic light-sensitive material is preferably heat-sealed polyethylene or the like. These hermetic packages may be doubled.

As a method for packaging by reducing the relative humidity as in the present invention, the silver halide photographic light-sensitive material may be packaged in a room having a low humidity, or a method in which the light-sensitive material is dried more than usual at the time of drying. Alternatively, the humidity may be lowered by putting a desiccant such as silica gel in the sealed product.

In practicing the present invention, static failure is often caused due to low humidity. For preventing this static failure, it is well known as an antistatic agent.

Known photographic additives that can be used in the present invention are also described in the above-mentioned Research Disclosure. The relevant description is shown below.

[Item] [Page of RD308119] [RD17643] [RD18716] Color turbidity inhibitor 1002 VII-I item 25 650 Dye image stabilizer 1001 VII-J item 25 Whitening agent 998 V 24 UV absorber 1003 VIIIC , XIII-C 25-26 Light absorber 1003 VIII 25-26 Light scattering agent 1003 VIII Filter dye 1003 VIII 25-26 Binder 1003 IX 26 651 Antistatic agent 1006 XIII 27 650 Hardener 1004 X 26 651 Plasticizer 1006 XII 27 650 Lubricants 1006 XII 27 650 Activators / Coating aids 1005 XI 26 to 27 650 Matte agents 1007 XVI Developers (contained in sensitive materials) 1011 XXB Various couplers can be used in the present invention. The specific examples are described in the following RD. The relevant description is shown below.

[Item] [Page of RD308119] [RD17643] Yellow coupler 1001 VII-D item VII C-G item Magenta coupler 1001 VII-D item VII C-G item Cyan coupler 1001 VII-D item VII C-G Item Colored coupler 1002 VII-G item VII G item DIR coupler 1001 VII-F item VII F item BAR coupler 1002 VII-F item Other useful residues 1001 VII-F item Emission coupler Alkali-soluble coupler 1001 VII-E item The additives used in the invention can be added by the dispersion method described in RD308119 page 1007, item XIV.

In the present invention, the above-mentioned RD17643 page 28,
The supports described in RD18716 pages 647-8 and RD308119 page 1009, section XIX can be used.

The color light-sensitive material of the present invention has the above-mentioned RD30.
8119 Auxiliary layers such as a filter layer and an intermediate layer described in Item VII-K can be provided.

The color light-sensitive material of the present invention is RD308119 VII
Various layer configurations such as the forward layer, the reverse layer, and the unit configuration described in the section -K can be adopted.

The color light-sensitive material of the present invention is applied to various color light-sensitive materials represented by color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. can do.

Preferred specific processing steps of the processing method according to the present invention are shown below.

(1) Color development-bleach-fix-wash (2) Color development-bleach-fix-wash-stable (3) Color development-bleach-fix-stable (4) Color development-bleach-fix-first Stable-Second stability (5) Color development-bleach-bleach-fix-wash (6) Color development-bleach-bleach-fix-wash-stable (7) Color development-bleach-bleach-stable (8) Color development-bleach -Bleaching and fixing-First stability-Second stability Among these steps, (3), (4), (7),
(8) is preferable, and (3) and (4) are particularly preferable.

The bleaching solution and the bleach-fixing solution according to the present invention include
Imidazole and its derivatives or the following general formulas [I] to [I
The effect of the object of the present invention can be better achieved by containing at least one compound represented by X]. Further, since it has another effect of improving the precipitation caused by silver in the bleaching solution, it is more preferably used in the present invention.

[0337]

[Chemical formula 23]

In the formula, Q represents an atomic group necessary for forming a nitrogen-containing heterocycle (including a condensed 5- or 6-membered unsaturated ring), and R ₁ represents a hydrogen atom or the number of carbon atoms. It represents 1 to 6 alkyl groups, cycloalkyl groups, aryl groups, heterocyclic groups (including those in which 5- to 6-membered unsaturated rings are condensed) or amino groups.

[0339]

[Chemical formula 24]

In the formula, R ₂ and R ₃ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, an amino group, an acyl group having 1 to 3 carbon atoms, an aryl group or an alkenyl group. Represents

A is

[0342]

[Chemical 25]

Or represents an n ₁ -valent heterocyclic residue (including a condensed 5- or 6-membered unsaturated ring), X is = S, =
Represents O or = NR ", where R and R'are each R ₂
And R ₃ have the same meaning, X ′ has the same meaning as X, Z has a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic residue, an alkyl group, or —S—B—Y <(R ₄ ). (R ₅ ), M represents a divalent metal atom, R ″ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic residue (5- to 6-membered). (Including those in which unsaturated rings are condensed) or an amino group, and n _{1 to} n ₆ and m ₁ to
m ₅ represents an integer of 1 to 6, respectively. B has 1 carbon atom
Represents an alkylene group of ~ 6,

[0344]

[Chemical formula 26]

And R ₄ and R ₅ are R ₂ and R _3, respectively.
Is synonymous with. However, R ₄ and R ₅ are respectively —B—SZ
Or R ₂ and R ₃ , R and R ′, and R ₄ and R ₅ may be bonded to each other to form a ring. The compound represented by the formula includes enol compounds and salts thereof.

[0346]

[Chemical 27]

In the formula, R ₆ and R ₇ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, an amino group, an acyl group having 1 to 3 carbon atoms, an aryl group or an alkenyl group. Alternatively, it represents -B ₁ -S-Z ₁ . However,
R ₆ and R ₇ may combine with each other to form a ring. Y ₁ represents> N— or> CH—, B ₁ represents an alkylene group having 1 to 6 carbon atoms, Z ₁ represents a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic residue. Or −S−B ₁ −Y
₁ <(R ₆ ) (R ₇ ) is represented. n ₇ represents an integer of 1 to 6.

[0348]

[Chemical 28]

In the formula, R ₈ and R ₉ are respectively

[0350]

[Chemical 29]

R ₁₀ is an alkyl group or — (CH ₂ ) n ₈ S
O ₃ ^- represents a. (However, when R ₁₀ is — (CH ₂ ) n ₈ SO ₃ ^— , 1 represents 0 and when it is an alkyl group, 1 represents.) G ⁻ represents an anion. n ₈ is an integer of 1-6.

[0352]

[Chemical 30]

[0353]

[Chemical 31]

In the formula, D ₁ , D ₂ , D ₃ and D ₄ each represent a mere bond, an alkylene group having 1 to 8 carbon atoms or a vinylene group, and q ₁ , q ₂ , q ₃ and q ₄ Are 0,
Represents 1 or 2. The ring formed with the sulfur atom may be further condensed with a 5- or 6-membered saturated or unsaturated ring.

[0355]

[Chemical 32]

In the formula, X ₂ is -COOM ', -OH, -SO ₃ M', -CON.
H ₂ , -SO ₂ NH ₂ , -NH ₂ , -SH, -CN, -CO ₂ R ₁₆ , -SO ₂ R ₁₆ , -OR
₁₆ , -NR ₁₆ R ₁₇ , -SR ₁₆ , -SO ₃ R ₁₆ , -NHCOR ₁₆ , -NHSO
₂ R ₁₆ , -OCOR ₁₆ or -SO ₂ R ₁₆ and Y ₂ is

[0357]

[Chemical 33]

Or, it represents a hydrogen atom, and m ₉ and n ₉ each represent an integer of 1-10. R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ ,
R ₁₇ and R ₁₈ are each a hydrogen atom, a lower alkyl group,
Acyl group or

[0359]

[Chemical 34]

R ₁₆ represents a lower alkyl group, and R ₁₉ represents -N
R ₂₀ R _21, represent -OR ₂₂ or -SR _22, R ₂₀ and R ₂₁ each represent a hydrogen atom or a lower alkyl group, R ₂₂ is R ₁₈
Represents a group of atoms necessary to combine with to form a ring. R ₂₀
Alternatively, R ₁₁ may combine with R ₁₈ to form a ring. M'represents a hydrogen atom or a cation.

[0361]

[Chemical 35]

In the formula, Ar represents a divalent aryl group or a divalent organic group in which an aryl group and an oxygen atom and / or an alkylene group are combined, and B ₂ and B ₃ each represent a lower alkylene group. , R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ each represent a hydroxy-substituted lower alkyl group, and x and y
Each represent 0 or 1. G'represents an anion,
z represents 0, 1 or 2.

[0363]

[Chemical 36]

In the formula, R ₂₉ and R ₃₀ each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group,
₃₁ represents a hydrogen atom or an alkyl group, and R ₃₂ represents a hydrogen atom or a carboxy group.

General formula [I] preferably used in the present invention
The compounds represented by [IX] to [IX] are generally used as a bleaching accelerator, and are hereinafter referred to as the bleaching accelerator of the present invention.

Typical examples of the bleaching accelerator of the present invention represented by the above general formulas [I] to [IX] include, for example, the following, but are not limited thereto. Absent.

[0367]

[Chemical 37]

[0368]

[Chemical 38]

[0369]

[Chemical Formula 39]

[0370]

[Chemical 40]

[0371]

[Chemical 41]

[0372]

[Chemical 42]

[0373]

[Chemical 43]

[0374]

[Chemical 44]

In addition to the bleaching accelerator of the present invention exemplified above,
Exemplified compound Nos. Described on pages 51 to 115 of Japanese Patent Application No. 60-263568 can be similarly used.

These bleaching accelerators may be used alone or in combination of two or more kinds, and the addition amount is generally about 0.01 to 100 g per liter of the bleaching solution or the bleach-fixing solution with good results. can get. However, generally, when the addition amount is too small, the bleaching promoting effect is small, and when the addition amount is more than necessary, precipitation may occur to contaminate the silver halide color photographic light-sensitive material to be processed.
It is preferably 0.05 to 50 g, and more preferably 0.05 to 15 g, per liter of the bleaching solution or the bleach-fixing solution.

When a bleaching accelerator is added, it may be added and dissolved as it is, but it is generally dissolved in water, an alkali, an organic acid or the like in advance and then added. If necessary, methanol or ethanol is added. It can also be added by dissolving it using an organic solvent such as acetone.

The bleaching solution of the present invention can be used at a pH of 0.2 to 8.0, preferably 1.0 or more and 7.0 or less, more preferably 2.0 or more and 6.5 or less. The treatment temperature used is 20 to 45 ° C, preferably 25 to 42 ° C. A halide such as ammonium bromide is usually added to the bleaching solution of the present invention.

The bleaching solution of the present invention contains various kinds of boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide and the like. A pH buffer consisting of a salt may be contained alone or in combination of two or more kinds. Further, various fluorescent whitening agents, antifoaming agents, surfactants and antifungal agents may be contained.

The bleaching agent used in the bleaching solution and the bleach-fixing solution according to the present invention is preferably a ferric complex salt of aminocarboxylic acid or aminophosphonic acid. The aminocarboxylic acid and aminophosphonic acid are amino compounds having at least two carboxylic acid groups and at least 2
It represents an amino compound having one or more phosphonic acid groups, and is preferably a compound represented by the following general formulas [XII] and [XIII].

[0380]

[Chemical formula 45]

In the formula, E is a substituted or unsubstituted alkylene group, cycloalkylene group, phenylene group, --R ₈₃ OR ₈₃ OR
₈₃ ―, ―R ₈₃ ZR ₈₃ ―, where Z is> NR ₈₃ −A ₆ and> N−A ₆
R ₇₉ and R ₈₃ represent a substituted or unsubstituted alkylene group, A _{2 to} A ₆ represent a hydrogen atom, —OH, —COOM, —PO ₃ M ₂ , and M is a hydrogen atom or an alkali metal atom. Represents

Next, these general formulas [XII] and [XIII]
Preferred specific examples of the compound represented by are listed below.

[Exemplified Compound] [XII-1] Ethylenediaminetetraacetic acid [XII-2] Diethylenetriaminepentaacetic acid [XII-3] Ethylenediamine-N- (β-hydroxyethyl) -N, N ′, N′-triacetic acid [XII-3] XII-4] 1,3-Propylenediaminetetraacetic acid [XII-5] Triethylenetetraminehexaacetic acid [XII-6] Cyclohexanediaminetetraacetic acid [XII-7] 1,2-Diaminopropanetetraacetic acid [XII-8] 1 , 3-Diaminopropan-2-ol tetraacetic acid [XII-9] Ethyl ether diamine tetraacetic acid [XII-10] Glycol ether diamine tetraacetic acid [XII-11] Ethylenediaminetetrapropionic acid [XII-12] Phenylenediamine tetraacetic acid [XII-9] XII-13] Ethylenediaminetetraacetic acid disodium salt [XII-14] Ethylenediaminetetraacetic acid tetra (trimethylammonium) salt [XII-15] Ethylenediaminetetraacetic acid tetranaphtholium Salt [XII-16] Diethylenetriamine pentaacetic acid pentasodium salt [XII-17] Ethylenediamine-N- (β-hydroxyethyl) -N, N ', N'-triacetic acid sodium salt [XII-18] Propylenediaminetetraacetic acid sodium salt Salt [XII-19] Ethylenediaminetetramethylenephosphonic acid [XII-20] Cyclohexanediaminetetraacetic acid sodium salt [XII-21] Diethylenetriamine pentamethylenephosphonic acid [XII-22] Cyclohexanediaminetetramethylenephosphonic acid [XIII-1] Nitrilot-3 Acetate [XIII-2] Methyliminodiacetic acid [XIII-3] Hydroxyethyliminodiacetic acid [XIII-4] Nitrilotripropionic acid [XIII-5] Nitrilotrimethylenephosphonic acid [XIII-6] Iminodimethylenephosphonic acid [XIII-7 ] Hydroxyethyliminodimethylenephosphonic acid [XIII-8] Nitrilotriacetate Trinatriu Salt as a particularly preferred compound for use in terms of the effect of an object of the present invention in these amino acids and aminophosphonic acids (XII-1), (XII-2), (XII-4), (XII-
6), (XII-7), (XII-10), (XII-19), (XIII-1), (XIII
-5) is mentioned. Among these, the particularly desirable one in terms of the effects of the present invention is (XII-4).
Is.

The ferric iron complex salt of the organic acid according to the present invention is
Used as free acid (hydrogen salt), alkali metal salt such as sodium salt, potassium salt, lithium salt, or ammonium salt, or water-soluble amine salt such as triethanolamine salt, preferably potassium salt, sodium salt And ammonium salts are used. At least one of these ferric complex salts may be used, but two or more thereof may be used in combination. The amount used can be arbitrarily selected and needs to be selected depending on the amount of silver of the light-sensitive material to be processed and the silver halide composition. For example, it can be used in an amount of 0.01 mol or more per liter of a bleaching solution or a bleach-fixing solution, It is preferably used in an amount of 0.05 to 1.0 mol. It should be noted that it is desirable that the replenisher is used after being concentrated to the maximum solubility so as to be concentrated and low in replenishment.

The replenishing amount of the bleaching solution according to the present invention is preferably 20 to 500 ml, more preferably 30 to 350 ml, and most preferably 40 to 300 ml per 1 m ^{2 of the} silver halide color photographic light-sensitive material. It is preferably 50 to 250 ml. A so-called fixing agent is essential for the fixing solution and the bleach-fixing solution according to the present invention.

As the fixing agent, a compound which reacts with silver halide to form a complex salt of an aqueous solution, for example, thiosulfates such as potassium thiosulfate, sodium thiosulfate and ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, thiocyanic acid. Examples thereof include thiocyanates such as ammonium, thiourea and thioether.

In addition to these fixing agents, fixing solutions and bleach-fixing solutions further include ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite and metabisulfite. A pH buffering agent comprising sulfite such as sodium and various salts such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide. Can be used alone or in combination of two or more.

Further, it is desirable to add a large amount of an alkali halide or ammonium halide, for example, a rehalogenating agent such as potassium bromide, sodium bromide, sodium chloride or ammonium bromide. In addition, pH buffers such as borate, oxalate, acetate, carbonate, phosphate, etc., alkylamines,
What is known to be added to a normal fixing solution and a bleach-fixing solution, such as polyethylene oxides, can be appropriately added.

The fixing agent is used in an amount of 0.1 mol or more per liter of the processing liquid, and is preferably used from the viewpoint of the effect of the object of the present invention.
It is used in the range from 0.6 to 4 mol, particularly preferably in the range from 0.9 to 3.0 mol, particularly preferably in the range from 1.1 to 2.0 mol.

In the present invention, in order to increase the activity of the bleaching solution or the bleach-fixing solution, air or oxygen may be blown in the processing bath and the tank for storing the processing replenisher, if desired, or suitable oxidation is carried out. Agents such as hydrogen peroxide, bromate, persulfate and the like may be appropriately added.

The fixing solution and the bleach-fixing solution according to the present invention exhibit the effects of the present invention more favorably when the replenishing amount is 800 ml or less per 1 m ^{2 of the} light-sensitive material. Especially photosensitive material 1
Good results are obtained with 20 to 650 ml per m ² , especially 30 to 400 ml.

When the fixer and the bleach-fixer according to the present invention contain 0.1 l to 10 g / l of iodide (ammonium iodide, potassium iodide, sodium iodide, lithium iodide, etc.) The effect of the present invention is further promoted. Especially 0.3-5g / l,
Especially preferably 0.5-3 g / l, most preferably 0.8-2 g / l
With good results.

The processing solution having fixing ability (fixing solution or bleach-fixing solution) according to the present invention is used by adding a compound represented by the following general formula [FA ″] or a compound of the following compound group [FB]. In this case, not only the effect of the object of the present invention is better exhibited, but also another effect that sludge generated when processing a small amount of a sensitive material for a long period of time using a fixing solution or a bleach-fixing solution is extremely small. Since it is added, it is more preferably used in the present invention.

[0395]

[Chemical formula 46]

[In the formula, R'and R "each represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group or a nitrogen-containing heterocycle. N'represents 2 or 3.] General formula [FA" ] Specific exemplified compounds represented by the following are shown below.

[0397]

[Chemical 47]

These compounds represented by the general formula [FA ″] can be synthesized by a general method as described in US Pat. Nos. 3,335,161 and 3,260,718.

Compounds [FB] FB-1 thiourea FB-2 ammonium iodide FB-3 potassium iodide FB-4 ammonium thiocyanate FB-5 potassium thiocyanate FB-6 sodium thiocyanate FB-7 thiocyanocatechol The compound represented by the general formula [FA ″] and the compound of the compound group [FB] may be used alone or in combination of two or more kinds. For example, thiourea and ammonium thiocyanate and ammonium iodide, thiourea and ammonium thiocyanate, (FA-12)
And (FA-12) and ammonium thiocyanate, (FA-12) and ammonium iodide, (FA-12) and (FA-32), (FA-12) and (FA-38), and the like are preferable. Take as an example.

Further, the addition amount of the compound represented by the general formula [FA ″] and the compound of the compound group [FB] is preferably in the range of 0.1 g to 200 g per liter of the treatment liquid.
A sulfurous acid adduct is preferably used in the fixing solution and the bleach-fixing solution according to the present invention from the viewpoint of the effect of the object of the present invention.

Examples of the compound capable of forming a stable sulfite adduct with the sulfite ion include a compound having an aldehyde group, a compound having a cyclic hemiacetal, a compound having an α-dicarbonyl group and a nitrile group. The compounds having the above can be listed, but the general formula is preferable.
The compounds represented by (AI) to (A-II) are particularly preferably used.

Preferred specific examples other than the compounds represented by formulas (AI) to (A-II) are shown below.

[0403]

[Chemical 48]

A ₂ , A ₃ , A ₄ and A ₅ are hydrogen atoms and have 1 to 10 carbon atoms.
6 represents an alkyl group, a formyl group, an acyl group or an alkenyl group. The alkyl group having 1 to 6 carbon atoms includes linear or branched ones, for example, methyl group, ethyl group,
n-propyl group, iso-propyl group, n-butyl group, n-
A barrel group, an iso-barrel group, a hexane group, an isohexane group, etc. may be mentioned and may be substituted. Specifically, formyl group (for example, each group of formylmethyl, 2-formylethyl etc.), amino group (For example, groups such as aminomethyl and aminoethyl), hydroxyl group (for example, groups such as hydroxymethyl, 2-hydroxyethyl, and 2-hydroxypropyl), alkoxy group (for example, groups such as methoxy and ethoxy), halogen atom (Eg, each group such as chloromethyl, trichloromethyl, dibromomethyl, etc.) and the like.

The alkenyl group includes substituted and unsubstituted groups, the unsubstituted group includes groups such as vinyl and 2-propenyl, and the substituted groups include, for example, 1,2-dichloro-2- Examples include groups such as carboxyvinyl and 2-phenylvinyl.

Specific examples of the compounds represented by the above general formula are shown below, but the invention is not limited thereto.

[0407]

[Chemical 49]

AO-8 sodium formaldehyde bisulfite AO-9 sodium acetaldehyde sodium bisulfite AO-10 sodium propionaldehyde bisulfite These compounds and sulfite addition compounds are preferably used in the range of 0.1 to 80 g per liter of the treatment liquid, more preferably, It is in the range of 0.5 to 40 g.

In the processing method of the present invention, it is preferable that the bleaching solution, the fixing solution and the bleach-fixing solution are subjected to forced liquid agitation. The reason is that not only the effects of the object of the present invention are better exhibited, but also rapid processing suitability is obtained.

Here, the forced liquid agitation means that the liquid is not normally diffused and moved, but that the liquid is agitated by adding a stirring means.

The following methods can be given as the forced stirring means. High-pressure spray treatment method or spray stirring method 1. Air bubbling method 3. Ultrasonic wave oscillation method 4. Vibration processing method.

[0412] The high-pressure spray processing method means a discharge pressure of 0.1 kg /
It refers to a method in which a processing solution is directly sprayed from a spray nozzle onto a photosensitive material by applying a pressure of cm ² or more, and a stirring method of spraying is a discharge pressure of 0.1 kg / cm from the nozzle.
^This refers to a method in which a processing liquid is directly applied in the processing liquid by applying a pressure of ² or more, and the photosensitive material is sprayed, and a pressure pump or a liquid feed pump is generally used as a pressure source. Pressure pumps include plant jar pumps, gear pumps, magnet pumps, and cascade pumps.For example, Maruyama Seisakusho's 15-LPM type, 10-BFM type, 20-BFM type, 25-BFM type, etc. are known as examples. ing.

As the liquid feed pump, for example, there are MD-30 type, MO-56 type, MDH-25 type and MDK-32 type manufactured by Iwaki.

On the other hand, the nozzles and spray nozzles include straight type, fan type, circular type, full-face type, ring type, etc., which have a strong impact force and are effective enough to give a slight vibration to the photosensitive material to be processed. . The impact force of the spray is mainly determined by the flow rate (l / min) s spray pressure (Kg / cm ² ). Therefore, there is a need for a pressurizing device capable of adjusting the pressure in proportion to the number of spray nozzles so that the effect can be sufficiently exerted. The most preferable pressure is 0.3 to 10 kg / cm ² , and if it is less than this, the effect is not obtained, and if it is too large, the photosensitive material may be scratched or damaged.

[0415] Next, the air bubbling treatment method means that a sparger is installed at the bottom of the lower conveying roller of the treatment liquid tank,
This is a method in which air or an inert gas is sent to a sparger, the photosensitive material is vibrated by the bubbles discharged from its mouth, and the processing liquid is effectively contacted with the front surface, back surface, and side surface of the photosensitive material.

The material of the sparger is hard vinyl chloride,
Corrosion-resistant materials such as polyethylene-coated stainless steel, sintered metal, etc. are suitable, and the perforation diameter is such that the discharged bubbles are perforated from 2 mm to 30 mm, which is 5 mm to 15 mm. By doing so, a better effect can be obtained. Examples of the method for sending air include an air compressor, such as Hitachi's Bevicon (0.4KW, BU7TL), and an air pump, such as Iwaki's air pump (Ap220 type). The amount of air required is 2l / min to 30l / min for each rack of the automatic processor, and 5l / min to 20l / min.
Gives even more favorable results. The amount of air or inert gas must be adjusted according to the size of the processing liquid tank and the amount of photosensitive material, but the amount of air or inert gas must be adjusted so that the vibration width of the photosensitive material due to air bubbles is 0.2 to 20 mm. Is preferably sent. Next, the ultrasonic wave oscillating treatment method is a method in which an ultrasonic wave oscillating machine is installed in the space of the bottom or the side wall in the processing liquid tank of the automatic developing machine and the photosensitive material is irradiated with ultrasonic waves to enhance the development promoting efficiency. . As the ultrasonic oscillator, for example, a magnetostrictive nickel vibrator (horn type) and a magnetostrictive barium titanate vibrator (holder type) manufactured by Ultrasonic Industry Co., Ltd. are used.

The oscillator frequency of the ultrasonic oscillator is 5
Although the thing of -1000 KHz is used, especially the thing of 10-50 KHz is preferable also from the viewpoint of the effect of the objective of this invention, and the damage of the equipment of an automatic processor. As a method of irradiating the photosensitive material with ultrasonic waves, the photosensitive material may be directly irradiated or indirectly provided with a reflector, but since the ultrasonic waves are attenuated in proportion to the irradiation distance, direct irradiation is performed. It is preferable to allow it. The irradiation time is preferably at least 1 second or longer. In the case of partial irradiation, any of the initial stage, the intermediate stage and the late stage of the treatment process may be performed.

Further, the vibration treatment method means an intermediate position between the upper roller and the lower roller in the automatic developing machine processing liquid tank.
This is a method in which the photosensitive material is vibrated to effectively perform the immersion treatment. As the vibrator of the vibration source, for example, V-2B and V-4B types manufactured by Shinko Electric Co., Ltd. are generally used. The vibrator is installed by fixing the vibrator on the upper part of the immersion processing tank of the automatic developing machine and applying the vibrator from the back side of the photosensitive material. The frequency of the vibrator is preferably 100 to 10,000 times / min. The most preferred range is 500-6000 times / mi
n. The amplitude of the light-sensitive material to be processed is 0.2-30 mm, preferably 1-20 mm. If it is lower than this, there is no effect,
If it is too large, the photosensitive material may be scratched. The number of vibrators to be installed varies depending on the size of the automatic processor. However, in the case where the processing tanks are multi-processing tanks, a preferable effect can be obtained if one or more processing tanks are installed in each processing tank.

As another preferred embodiment of the processing method of the present invention, there is a method of flowing a part or all of the overflow solution of the color developing solution according to the present invention into the bleaching solution which is the subsequent step. This is because generation of sludge in the bleaching solution is improved when a certain amount of the color developing solution according to the present invention is flowed into the bleaching solution.

Further, in addition to the above system, when a part or all of the overflow solution of the stabilizing solution in the subsequent step is poured into the bleach-fixing solution or the fixing solution, the effect of improving the silver recovery efficiency is excellently exhibited.

In the present invention, the time for processing the silver halide color photographic light-sensitive material with the color developing solution is preferably 240 seconds or less, more preferably 220 seconds or less, and further preferably 20 to 150 seconds.

In the present invention, by processing the above silver halide color photographic light-sensitive material in a short time, surprisingly, not only the effect of the present invention can be exhibited but also the graininess of the dye image obtained can be improved. .

Further, in the method for processing a silver halide color photographic light-sensitive material of the present invention, the color developing solution is preferably an aromatic primary amine type color developing agent, preferably 5.0 × 10 ⁻³ mol per liter of the processing solution. It is a color developing solution containing the above. More preferably 1.0 × 10 ^-2 mol or more, more preferably
A color developing solution containing 1.5 × 10 ^{-2 to} 2 × 10 ^-1 mol of the developing agent as a main component is preferable.

When the photographic light-sensitive material is activated by increasing the concentration of such a color developing agent, an image having excellent sharpness and improved graininess can be obtained by the short-time processing as described above. This is especially noticeable in magenta dye images.

The color developing agent of the color developing solution which can be preferably used in the present invention will be described below.

The aromatic primary amine type color developing agents used in the above preferable color developing solution include known ones widely used in various color photographic processes. Aminophenol-based and p-
A phenylenediamine derivative is included. Since these compounds are more stable than the free state, they are generally used in the form of salts, for example, hydrochlorides or sulfates.

Examples of aminophenol-based developers include o-aminephenol, p-aminophenol, 5-amino-2-oxytoluene, 2-amino-3-oxytoluene, 2-
Oxy-3-amino-1,4-dimethylbenzene and the like are included.
In the present invention, the aromatic primary amine color developing agent which is particularly useful in the present invention is preferable because the desired effect is more effectively exhibited and the crystal deposition property on the inner wall of the color developing layer of the automatic processor is improved. It is an aromatic primary amine color developing agent having an amino group having at least one water-soluble group, and particularly preferably a compound represented by the following general formula [E].

[0428]

[Chemical 50]

In the formula, R ¹ represents a hydrogen atom, a halogen atom or an alkyl group, and the alkyl group represents a linear or branched alkyl group having 1 to 5 carbon atoms, which may have a substituent. R ² and R ³ represent a hydrogen atom or an alkyl group or an aryl group, and these groups may have a substituent.
And at least one of R ² and R ³ is an alkyl group substituted by a water-soluble group such as a hydroxyl group, a carboxylic acid group, a sulfonic acid group, an amino group, a sulfonamide group or-[(CH ₂ ) qO] pR ⁴ . .

This alkyl group may further have a substituent.

R ⁴ represents a hydrogen atom or an alkyl group, the alkyl group represents a linear or branched alkyl group having 1 to 5 carbon atoms, and p and q represent integers of 1 to 5.

Next, the compounds represented by the above general formula [E] are listed, but the invention is not limited thereto.

[0433]

[Chemical 51]

The p-phenylenediamine derivative represented by the general formula [E] can be used as a salt of an organic acid or an inorganic acid, for example, hydrochloride, sulfate, phosphate, p-toluenesulfonate, sulfite. , Oxalate, benzenedisulfonate and the like can be used.

Preferred compounds for use in the color developing solution used in the present invention are sulfite, hydroxylamine and development inhibitor.

As the above-mentioned sulfite, sodium sulfite,
There are sodium bisulfite, potassium sulfite, potassium bisulfite and the like, and it is preferably used in the range of 0.1 to 40 g / l, more preferably 0.5 to 10 g / l.

The above hydroxylamine is used as a counter salt for hydrochlorides, sulfates and the like, and is preferably used in the range of 0.1 to 40 g / l, more preferably 0.5 to 10 g / l.

Further, the development inhibitors preferably used in the color developing solution include halides such as sodium chloride, potassium chloride, sodium bromide, potassium bromide, sodium iodide and potassium iodide, and organic inhibitors. The addition amount thereof is preferably 0.005 to 30 g / l, more preferably 0.01 to 20 g / l. Examples of the organic inhibitor preferably used in the practice of the present invention include nitrogen-containing heterocyclic compounds, mercapto group-containing compounds, aromatic compounds, onium compounds and compounds having an iodine atom as a substituent. The compounds exemplified below are those exemplified below.

However, the compounds that can be used are not limited to the following compounds.

[0440]

[Chemical 52]

Further, in carrying out the present invention, Japanese Patent Application No. 61-
No. 12781 Nos. 96 to 100 General formulas [RI] to [R
The organic inhibitor represented by —XIII] can be used, and the effect of the present invention can be more effectively achieved by using the organic inhibitor in combination with the organic inhibitor of the present invention.

Further, the organic inhibitor in the present invention is as described above, and more concretely, the above-mentioned Japanese Patent Application No.
-12781, pages 101 to 113, (Z-1) to (Z-
3), (Z-6), (Z-8) to (Z-13), (Z-15) to (Z-17),
(Z-19), (Z-22) ~ (Z-25), (Z-29), (Z-31) ~ (Z
-38), (Z-40), (Z-41), (Z-43) to (Z-64) and (Z
-66) to (Z-73).

In the color developer used in the present invention, various components usually added, for example, alkali agents such as sodium hydroxide and sodium carbonate, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, A water softener, a thickening agent, a development accelerator and the like may be optionally contained.

Examples of the additives other than those mentioned above which are added to the color developing solution include stain inhibitors, anti-sludge agents, preservatives, multi-layer effect accelerators and chelating agents.

The color developing solution of the present invention has a pH of 9 or more, especially a pH of
It is preferably used in H9-13.

Further, the processing temperature of the color developing solution is set to 38 in order to achieve better effects for the purpose of the present invention.
C. or higher is preferable, a range of 40 to 70.degree. C. is particularly preferable, and a range of 43 to 60.degree. C. is most preferable.

In addition to the above, the processing method of the photographic light-sensitive material of the present invention is not particularly limited and any processing method can be applied.

In the present invention, when the chelating agent represented by the following general formulas [I ″] to [V ″] is used in the color developing solution, the effect of the object of the present invention can be better exhibited.

[0449]

[Chemical 53]

In the general formulas [II ″] and [III ″], L is an alkylene group, a cycloalkylene group, a phenylene group, —L ₈
─O─L ₈ ─O─L ₈ or ─L ₉ ─Z─L ₉ ─. Where Z is

[0451]

[Chemical 54]

L _{1 to} L ₁₃ each represent an alkylene group. R _{3 to} R ₁₃ are each a hydrogen atom, a hydroxyl group, or a carboxylic acid group.
(Including its salt) or phosphonic acid group (including its salt).

However, at least two of R _{3 to} R ₆ are carboxylic acid groups (including salts thereof) or phosphonic acid groups (including salts thereof), and at least two of R _{7 to} R ₉ are present. One is a carboxylic acid group (including a salt thereof) or a phosphonic acid group (including a salt thereof).

[0454]

[Chemical 55]

In the general formulas [IV ″] and [V ″], R ₁ , R ₂ ,
R ₃ and R ₄ are each a hydrogen atom, a halogen atom, a sulfonic acid group, an alkyl group having 1 to 7 carbon atoms, —OR ₅ , —COOR ₆ ,
-CON <(R ₇ ) (R ₈ ) or phenyl group.

R ₅ , R ₆ , R ₇ and R ₈ each represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. However,
When R ₂ represents --OH or a hydrogen atom, R ₁ represents a halogen atom, a sulfonic acid group, an alkyl group having 1 to 7 carbon atoms,
RO ₅ -COOR _6, represents a _{-CON <(R 7) (R} 8) or phenyl group. However, n is an integer of 1 to 3.

As the compound represented by the above general formula [I ″], 1-hydroxyethylidene-1,1-diphosphonic acid, 1-hydroxypropylidene-1,1-diphosphonic acid,
1-hydroxy-1,1-diphosphonomethane and the like are mentioned, and particularly preferably 1-hydroxyethylidene-1,1-
Diphosphonic acid, the compound is an alkali metal salt,
It can also be used as an ammonium salt.

The amount of the above compound added is preferably in the range of 1 × 10 ^-4 mol to 0.5 mol per liter of color developer,
Particularly preferably, it is in the range of 4 × 10 ⁻⁴ mol to 0.1 mol.

In the general formulas [II ″] and [III ″],
The alkylene group represented by L, the cycloalkylene group and the phenylene group, and the alkylene group represented by L _{1 to} L ₁₃ include those having a substituent.

Next, these general formulas [II ″] and [II
Preferred specific examples of the compound represented by I ″] are shown below.

[Exemplified Compound] [II ″ -1] Ethylenediaminetetraacetic acid [II ″ -2] Diethylenetriaminepentaacetic acid [II ″ -3] Ethylenediamine-N- (β-hydroxyethyl) -N, N ′, N′- Triacetic acid [II "-4] Propylenediaminetetraacetic acid [II" -5] Triethylenetetramine hexaacetic acid [II "-6] Cyclohexanediaminetetraacetic acid [II" -7] 1,2-Diaminopropanetetraacetic acid [II " -8] 1,3-Diaminopropan-2-ol tetraacetic acid [II "-9] Ethyletherdiaminetetraacetic acid [II" -10] Glycoletherdiaminetetraacetic acid [II "-11] Ethylenediaminetetrapropionic acid [II" -12] Phenylenediaminetetraacetic acid [II ″ -13] Ethylenediaminetetraacetic acid disodium salt [III-1] Nitrilotriacetic acid [III-2] Iminodiacetic acid [III-3] Nitrilotripropionic acid [III-4] Nitrilotrimethylene Phosphonic acid [I II-5] Iminodimethylenephosphonic acid [III-6] Nitrilotriacetic acid trisodium salt Among these chelating agents of the present invention, as the compound particularly preferably used from the viewpoint of the effect of the object of the present invention, [II ″
-1], [II "-2], [II" -5], [II "-8], [II"-
19], [III ″ -1], and [III ″ -4]. In particular, [II-2] is preferably used because it causes less precipitation with time.

The amount of these chelating agents of the present invention added is
It is preferably used in the range of 0.1 to 20 g per liter of color developing solution, and particularly preferably in the range of 0.3 to 5 g in view of the object of the present invention.

In the above general formulas [IV ″] and [V ″], R ₁ , R
₂ , R ₃ and R ₄ are each a hydrogen atom, a halogen atom, a sulfonic acid group, an alkyl group having 1 to 7 carbon atoms, -RO ₅ -COO
_{R 6, -CON <(R 7} ) (R 8) or is a phenyl group. Also, R ₅ , R ₆ ,
R ₇ and R ₈ each represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. However, when R ₂ represents --OH or a hydrogen atom, R ₁ represents a halogen atom, a sulfonic acid group, an alkyl group having 1 to 7 carbon atoms, --RO ₅ --COOR ₆ , --CON <(R ₇ ) (R
₈ ) or a phenyl group.

Examples of the alkyl group represented by R ₁ , R ₂ , R ₃ and R ₄ include a methyl group, an ethyl group, an i-propyl group, a propyl group, a t-butyl group, a butyl group, a hydroxymethyl group and a hydroxy group. Ethyl group, methylcarboxylic acid group,
Examples thereof include a benzyl group and the like, and the alkyl group represented by R ₅ , R ₆ , R ₇ and R ₈ has the same meaning as described above, and further includes an octyl group.

Examples of the phenyl group represented by R ₁ , R ₂ , R ₃ and R ₄ include a phenyl group, a 2-hydroxyphenyl group and a 4-aminophenyl group.

Typical specific examples of the compound represented by the above general formula [IV ″] or [V ″] are shown below, but the invention is not limited thereto.

(IV "-1) 4-i-propyl-1,2-dihydroxybenzene (IV" -2) 1,2-dihydroxybenzene-3,5-disulfonic acid (IV "-3) 1,2, 3-Trihydroxybenzene-5-carboxylic acid (IV ″ -4) 1,2,3-trihydroxybenzene-5-carboxymethyl ester (IV ″ -5) 1,2,3-trihydroxybenzene-5-carboxy -N-Butyl ester (IV ″ -6) 5-t-butyl-1,2,3-trihydroxybenzene (IV ″ -7) 1,2-dihydroxybenzene-3,5,6-trisulfonic acid (IV ″ -8) 1,2-Dihydroxybenzene-3,4,6-trisulfonic acid (V ″ −1) 2,3-dihydroxynaphthalene-6-sulfonic acid (V ″ −2) 2,3,8-tri Hydroxynaphthalene-6-sulfonic acid (V ″ -3) 2,3-dihydroxynaphthalene-6-carboxylic acid (V ″ -4) 2,3-dihydroxy-8-isopropyl-naphthalene (V ″ -5) 2,3 -Dihydro Sheet chloro --6
Sulfonic Acid Among the above compounds, as a compound which is particularly preferably used in the present invention, 1,2-dihydroxybenzene-3,5-disulfonic acid can be mentioned, and it can also be used as an alkali metal salt such as sodium salt and potassium salt.

In the present invention, the compound may be used in the range of 5 mg to 20 g per liter of the developing solution,
Good results are obtained by adding preferably 10 mg to 10 g, more preferably 20 mg to 3 g.

The compounds of the present invention may be used alone or in combination. For example, a combination of aminopolycarboxylic acid and organic phosphonic acid is preferable.

When the color developer of the present invention contains the compound represented by the following general formula [2 '], the effect of the object of the present invention can be exhibited more favorably, and therefore the color developer of the present invention can be obtained. It is preferable to use

[0471]

[Chemical 56]

In the formula, R ₁ and R ₂ each represent an alkyl group, an alkenyl group, an aryl group or a hydrogen atom. However,
Neither R ₁ nor R ₂ is a hydrogen atom at the same time.
R ₁ and R ₂ may form a ring.

In the general formula [2 ′], R ₁ and R ₂ are not a hydrogen atom at the same time and represent a substituted or unsubstituted alkyl group, an aryl group or a hydrogen atom, which are represented by R ₁ and R _2. The alkyl group and the alkenyl group may be the same or different. The alkyl group, alkenyl group and aryl group of R ₁ and R ₂ include those having a substituent, and R ₁
Examples of the ring formed by combining R ₂ and R ₂ include a heterocycle such as piperidinefolyl.

As a substituent of R ₁ and R _2, a hydroxy group,
An alkoxy group, an alkyl group or an aryl sulfone group, an amide group, a carboxyl group, a cyano group, a sulfo group, a nitro group and an amino group.

Specific examples of the hydroxylamine compound represented by the general formula [2 ′] are described in US Pat. No. 3,287,125.
No. 3,293,034, No. 3,287,124, etc., but particularly preferred specific exemplified compounds are shown below.

[0476]

[Chemical 57]

[0477]

[Chemical 58]

These hydroxyamine compounds are usually used in the form of hydrochloride, sulfate, p-toluenesulfonate, oxalate, phosphate, acetate and those without salt. The concentration of the compound represented by the general formula [2 ′] of the present invention in the color developer is usually 0.2 to 50 g / l. Further, even if these compounds represented by the general formula [2 ′] are used alone,
Also, two or more kinds may be used in combination.

An aldehyde derivative is preferably used in the stabilizing solution (hereinafter, also referred to as stabilizing solution) used in the present invention.

The aldehyde derivative has the following general formula [I
It is a compound represented by V ']-[VI'].

[0481]

[Chemical 59]

In the formula, R ₁₆ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a formyl group, an acetyl group, an acetonyl group and a hydroxyl group or an alkoxy group, a formyl group, an amino group, a hydroxyimino group, a halogen atom and the like. It represents an optionally substituted alkyl group having 1 to 5 carbon atoms. R ₁₇ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ₁₈ is an optionally substituted alkyl group having 1 to 5 carbon atoms, M is an alkali metal, and R ₁₉ and R ₂₀ are hydrogen atoms or substituted Also, an alkyl group having 1 to 5 carbon atoms, n represents an integer of 0 to 4.

Specific examples of the compounds represented by the above general formula are shown below, but the invention is not limited thereto.

[Exemplified Compounds] IV-1 Formaldehyde IV-2 Acetaldehyde IV-3 Propionaldehyde IV-4 Isobutyraldehyde IV-5 n-Butylaldehyde IV-6 n-Barrelaldehyde IV-7 Isovaleraldehyde IV-8 Methylethyl Acetaldehyde IV-9 Trimethylacetaldehyde IV-10 n-Hexaldehyde IV-11 Methyl-n-propylacetaldehyde IV-12 Isohexaaldehyde IV-13 Glyoxal IV-14 Malonaldehyde IV-15 Succinaldehyde IV-16 Glutaraldehyde IV- 17 Adipaldehyde IV-18 Methylglyoxal IV-19 Acetoacetaldehyde IV-20 Glycolaldehyde IV-21 Ethoxyacetaldehyde IV-22 Aminoacetaldehyde IV-23 Betainealdehyde IV-24 Chloral IV-25 Chloro Cetaldehyde IV-26 Dichloroacetaldehyde IV-27 Bromar IV-28 Dibromoacetaldehyde IV-29 Iodoacetaldehyde IV-30 α-Chloropropionacetaldehyde IV-31 α-Bromopropionacetaldehyde IV-32 Mucochloric acid V-1 Formaldehyde sodium bisulfite V -2 Sodium acetaldehyde bisulfite V-3 Propionaldehyde sodium bisulfite V-4 Butyraldehyde sodium bisulfite VI-1 Succinic acid aldehyde sodium bisulfite VI-2 Glutaraldehyde bis sodium bisulfite VI-3 β-Methylglutaraldehyde bis bis heavy salt Sodium sulfite VI-4 Maleic acid dialdehyde bis sodium bisulfite The above aldehyde derivative is represented by the general formula (I
The compound represented by V ′) is preferably used in the range of 2.0 × 10 ^{−5 to} 2.0 × 10 ⁻² mol, and the compound represented by the general formula (V) or (VI) is 2.0 × 10 ^{−5 to} 8.0. × 10 ^-2 mol.

In addition, among the above aldehyde derivatives, the general formula
The compound represented by [V ′] is advantageously used in terms of reducing pollution and preventing sulfidation. Also in the present invention, hexamethylenetetramine-based compounds and N-methylol-based compounds are preferably used in the stabilizing solution for the stability of dye images, especially for preventing yellow stain. Hexamethylenetetramine compounds are hexamethylenetetramine and its derivatives.

As the hexamethylenetetramine derivative, for example, a hexamethylenetetramine halogen addition product, an inorganic acid addition product, a metal salt addition product, a phenol derivative addition product, an alkylsulfonic acid addition product, an arylsulfonic acid addition product, an alkylsulfate addition product. Compounds, alkylcarboxylic acid adducts, arylcarboxylic acid adducts, alkyl halide adducts, and the like. Hexamethylenetetramine and its derivatives are specifically described by Beilsteins Handbuch der Organischen Chemie (Be
ilsteins Handbuch der Organischen Chemie), Vol. 26, Vol. 26, pp. 200-212.

Of these, those soluble in water are preferred in the present invention.

Typical examples of the hexamethylenetetramine compounds are shown below, but the invention is not limited thereto.

[0489]

[Chemical 60]

The above compound is easily available as a commercial product, or can be easily synthesized by the method described in the above literature.

The hexamethylenetetramine compounds may be used alone or in combination of two or more. The amount added is preferably 0.05 g or more, and more preferably 0.3 to 20 g, per liter of stabilizing solution. The N-methylol compound is shown in US Pat. No. 4,859,574, and includes dimethylolguanidine, trimethylolurea, dimethylolurea, trimethylolmelamine, hexamethylolmelamine and the like. Addition amount per liter of stabilizing solution
The amount is 0.05 to 20 g, preferably 0.1 to 10 g / l. Within this range, the effect of the present invention is effectively exhibited.

The stabilizing solution has a surface tension of 8 to 60 dyne / cm (20 ° C)
The stabilization of the dye image is improved by giving Particularly, at least one compound selected from the following general formula [I '], general formula [II'] and water-soluble organic siloxane compounds is particularly preferably used from the viewpoint of effect.

The surface tension of the stabilizing solution used in the processing of the light-sensitive material of the present invention is described in "Analysis and Test Methods of Surfactants" (Fumio Kitahara, Shigeo Hayano, Ichiro Hara, published March 1, 1982,
It is measured by a general measuring method described in Kodansha Co., Ltd., etc., and in the present invention, it is a value of the surface tension measured by an ordinary general measuring method at 20 ° C.

Next, the general formula [I '], the general formula [II'] and the water-soluble organosiloxane compound used in the present invention will be explained.

[0495]

[Chemical formula 61]

In the formula, R ₁ is a monovalent organic group, for example, an alkyl group having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms,
It represents hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl and the like. Or has 3 to 20 carbon atoms
Is an aryl group substituted with an alkyl group, and the substituent is preferably an alkyl group having 3 to 12 carbon atoms, such as propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl. Represents The aryl group is phenyl, tolyl, xynyl, biphenyl, naphthyl or the like, preferably phenyl or tolyl. The position at which the alkyl group is bonded to the aryl group may be any of the ortho, meta and para positions. R ₂ represents an ethylene group or a propylene group, m
Represents an integer of 4 to 50.

X ₁ represents a hydrogen atom, —SO ₃ M or —PO ₃ M ₂ , and M represents a hydrogen atom, an alkali metal (sodium, potassium or lithium etc.) or —NH ₄ .

[0498]

[Chemical formula 62]

In the formula, R ₃ , R ₄ , R ₅ and R ₆ each represent a hydrogen atom, an alkyl group or a phenyl group, and the total number of carbon atoms of R ₃ , R ₄ , R ₅ and R ₆ is 3 to 50. X ₂ represents a halogen atom, a hydroxyl group, a sulfuric acid group, a carbonic acid group, a nitric acid group, an acetic acid group or a p-toluenesulfonic acid group anion.

Next, specific representative examples of the compounds represented by the general formulas [I '] and [II'] and the water-soluble organic siloxane compound of the present invention will be shown, but the present invention is not limited thereto.

[0501]

[Chemical formula 63]

[0502]

[Chemical 64]

The compounds represented by the above general formulas [I '] and [II'] and the water-soluble organic siloxane compound may be used alone or in combination. Furthermore, the amount added is 0.01 per liter of stabilizing solution.
Good effect when used in the range of up to 20 g. 0.01
If the amount is less than g, stains on the surface of the sensitive material are conspicuous, and if the amount is more than 20 g, a large amount of the organosiloxane compound adheres to the surface of the sensitive material to cause stains.

Of the compounds represented by the above general formulas [I ′] and [II ′] and the water-soluble organic siloxane compounds, the compounds preferably used in the present invention are represented by the above general formula [I ′]. It is a compound that has a large effect on the prevention of silver sulfide generation.

The water-soluble organic siloxane compound of the present invention is, for example, disclosed in JP-A-47-18333, JP-B-55-51172,
JP-B-51-37538, JP-A-49-62128 and U.S. Pat.
It means a general water-soluble organic siloxane compound as described in No. 545,970.

Among the above water-soluble organic siloxane compounds, the compound represented by the following general formula [III ′] is preferably used.

[0507]

[Chemical 65]

R ₉ , R ₁₀ and R ₁₁ each represent a lower alkyl group (preferably an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl and propyl), and R ₉ , R ₁₀ and R 11
₁₁ may be the same or different. l is 1
4 represents an integer of 4, and p and q represent an integer of 1 to 15.

Specific examples of the compound represented by the general formula [III '] are shown below.

[0510]

[Chemical formula 66]

The replenishing amount of the stabilizing solution used in the present invention is from 1 to 80 times, and from 2 to 60 times, the amount carried in from the prebath per unit area of the color light-sensitive material for photographing to be processed. In the present invention, the concentration of the pre-bath component (bleach-fixing solution or fixing solution) in the stabilizing solution is 1/500 in the final tank of the stabilizing solution.
The following is preferably 1/1000 or less, but is 1/500 to 1/100000, preferably 1 in view of low pollution and liquid storability.
It is necessary to configure the processing tank of the stabilizing tank so that it becomes / 2000 to 1 / 50,000.

The stabilization treatment tank is composed of a plurality of tanks, and the plurality of tanks are preferably 2 to 6 tanks.

[0513] In the case where the number of stabilizing treatment tanks is 2 to 6, and the counter current method (method of supplying to the rear bath and causing overflow from the front bath), the effect of the present invention, particularly low pollution and image preservation It is also preferable from the standpoint of improving. Particularly preferably, it is 2 to 3 tanks, and further preferably 2 tanks.

[0514] The carry-in amount varies depending on the type of the light-sensitive material, the running speed of the automatic developing machine, the running method, the squeeze method of the surface of the light-sensitive material, etc. Usually, the carry-on amount is 50 ~
The replenishing amount is 150 ml / m ² , and the effect of the present invention on the carry-in amount is more remarkable in the range of 50 to 4.0 l / m ² , and the particularly effective replenishing amount is 200 to 1500 ml / m ² . In range.

[0515] The treatment temperature of the treatment with the stabilizing solution is 15 to 60 ° C.
It is preferably in the range of 20 to 45 ° C.

In the stabilizing solution, the following general formula [VII ']
It is preferable to add a chelating agent represented by [IX ′] for improving the white background of the unexposed area and preventing yellow stain of the dye image after storage.

[0517]

[Chemical formula 67]

R _{1 to} R ₆ represent an alkylene group.

A _{1 to} A ₃ each represent --COOM or --PO ₃ M ₂ , and A ₄ and A ₅ each represent a hydrogen atom, a hydroxyl group, --COOM or --PO ₃ M ₂ . M represents a hydrogen atom or an alkali metal atom.

[0520]

[Chemical 68]

In the formula, R ₇ represents an alkyl group, an aryl group or a nitrogen-containing 6-membered ring group. M represents a hydrogen atom or an alkali metal atom.

[0522]

[Chemical 69]

In the formula, R ₈ , R ₉ and R ₁₀ each represent a hydrogen atom, a hydroxyl group, --COOM, --PO ₃ M ₂ or an alkyl group,
B ₁ , B ₂ and B ₃ are each a hydrogen atom, a hydroxyl group, --COOM, --PO
₃ M ₂ or -N <(J) (J) is represented. J represents a hydrogen atom, an alkyl group, —C ₂ H ₄ OH or —PO ₃ M ₂ . M represents a hydrogen atom or an alkali metal atom, and n and m each represent 0 or 1.

The following are the general formulas [VII '], [VIII'], [IX ']
Some specific examples of the chelating agent represented by are shown below, but the invention is not limited thereto.

[0525]

[Chemical 70]

The chelating agent preferably used in the stabilizer is preferably 0.01 to 100 g, more preferably 0.05 to 50 g, and particularly preferably 0.1 to 20 g, per liter of the stabilizer.

In addition, the stabilizing solution preferably used in the present invention
As the pH value, in addition to the effects of the present invention, the range of pH 4.0 to 9.0 is preferable for the purpose of improving image storability, more preferably 4.5 to 9.0, and particularly preferably 5.0 to 8.5. is there.

As the pH adjusting agent which can be contained in the stabilizing solution preferably used in the present invention, any of generally known alkali agents or acid agents can be used. Stabilizers preferably used in the present invention include organic acid salts (citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid, etc.), pH adjusting agents.
(Phosphates, borates, hydrochloric acids, sulfates, etc.), surfactants, preservatives, metal salts of Bi, Mg, Zn, Ni, Al, Sn, Ti, Zr and the like can be added. These compounds may be added in any combination within the range necessary for maintaining the pH of the stabilizing bath according to the present invention and not adversely affecting the stability during storage of color photographic images and the occurrence of precipitation. It doesn't matter.

Antifungal agents preferably used in the respective stabilizers of the present invention include hydroxybenzoic acid ester compounds, phenol compounds, thiazole compounds, pyridine compounds,
Guanidine compounds, carbamate compounds, morpholine compounds, quaternary phosphonium compounds, ammonium compounds, urea compounds, isoxazole compounds, propanolamine compounds, sulfamide compounds,
Amino acid compounds, active halogen-releasing compounds and benzotriazole compounds.

Examples of the hydroxybenzoic acid ester compound include hydroxybenzoic acid methyl ester, ethyl ester, propyl ester and butyl ester.
Preferred are butyl ester, i-butyl ester and propyl ester of hydroxybenzoic acid, and more preferred is a mixture of the three hydroxybenzoic acid esters.

The phenolic compound preferably used as the antifungal agent in the present invention is a compound which may have an alkyl group, a halogen group, a nitro group, a hydroxyl group, a carboxylic acid group, an amino group, a phenyl group or the like as a substituent. , Preferably o-
Phenylphenol, o-cyclohexylphenol, phenol, nitrophenol, chlorophenol, cresol, guaiacol, aminophenol and the like.

Particularly preferably, orthophenylphenol exhibits remarkable antifungal properties in combination with bisulfite adducts of aldehyde derivatives.

The thiazole-based compound is a compound having a nitrogen atom and a sulfur atom in the 5-membered ring, preferably 1,2-benzisothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 2-octyl- 4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-chloro-4-thiazolyl-benzimidazole.

Specific examples of the pyridine compound include 2,6-dimethylpyridine, 2,4,6-trimethylpyridine, sodium-2-pyridinethiol-1-oxide and the like, but preferably sodium-2-pyridinethiol It is -1-oxide.

Specific examples of the guanidine-based compound include cyclohexidine, polyhexamethylene, biguanidine hydrochloride,
There is dodecylguanidine hydrochloride, preferably dodecylguanidine and its salts.

Specific examples of the carbamate compound include methyl-1- (butylcarbamoyl) -2-benzimidazole carbamate and methylimidazole carbamate.

The morpholine compound is specifically 4- (2-
Examples include nitrobutyl) morpholine and 4- (3-nitrobutyl) morpholine.

The quaternary phosphonium compound includes tetraalkylphosphonium salt, tetraalkoxyphosphonium salt and the like, preferably tetraalkylphosphonium salt, and more specific preferred compounds are tributyl-tetradecylphosphonium chloride and triphenyl nitro. There is phenylphosphonium chloride.

Specific examples of the quaternary ammonium compound include a benzalkonium salt, a benzethonium salt, a tetraalkylammonium salt and an alkylpyridinium salt, and specifically, dodecyldimethylbenzylammonium chloride, didecyldimethylammonium chloride and laurylpyridinium chloride. Etc.

The urea compound is specifically N- (3,4-dichlorophenyl) -N '-(4-chlorophenyl) urea, N- (3
-Trifluoromethyl-4-chlorophenyl) -N '-(4
-Chlorophenyl) urea, etc.

The isoxazole-based compound is specifically 3
-Hydroxy-5-methylisoxazole and the like.

The propanolamine compounds include n-propanols and i-propanols. Specifically, DL-
2-benzylamino-1-propanol, 3-diethylamino-1-propanol, 2-dimethylamino-2-methyl-1-propanol, 3-amino-1-propanol, i
-Propanolamine, Di-i-propanolamine, N, N
-Dimethyl-i-propanolamine and the like.

Examples of the sulfamide compounds include o-nitrobenzenesulfamide, p-aminobenzenesulfamide, 4-chloro-3,5-dinitrobenzenesulfamide,
Examples include α-amino-p-toluenesulfamide.

Specific examples of the amino acid compound include N-lauryl-β-alanine.

As the active halogen-releasing compound, sodium hypochlorite, sodium dichloroisocyanurate,
Examples thereof include trichloroisocyanuric acid, chloramine T, chloramine B, dichlorodimethylhydantoin and chlorobromodimethylhydantoin, with sodium hypochlorite, sodium dichloroisocyanurate and trichloroisocyanuric acid being preferred.

Specific examples of the benzotriazole-based compound include the following.

[0547]

[Chemical 71]

Among the antifungal agents, the compounds preferably used in the present invention are phenol compounds, thiazole compounds, pyridine compounds, guanidine compounds, quaternary ammonium compounds, active halogen-releasing compounds, benzotriazole compounds. It is a compound. Further, particularly preferable are a phenolic compound, a thiazole compound, an active halogen-releasing compound and a benzotriazole compound in view of liquid storage stability. The amount of antifungal agent added to the stabilizer is
If the amount is less than 0.001 g per liter of the washing-stabilizing substitute solution, the effect of the object of the present invention is small, and if it exceeds 50 g, it is not preferable in terms of cost and the storage stability of the dye image is adversely deteriorated. Used in, preferably 0.005
Used in the range of ~ 10g.

In the processing of the light-sensitive material of the present invention, silver may be recovered by various methods from a stabilizing solution as well as a processing solution containing a soluble silver salt such as a fixing solution and a bleach-fixing solution. For example, electrolysis method (French patent 2,299,667), precipitation method (JP-A 52-73037, West German patent 2,331,220), ion exchange method (JP-A 51-17114, German patent) 2,548,2
37) and metal replacement method (described in British Patent 1,353,805) can be effectively used. Further, when recovering silver, the soluble silver salt is recovered as an overflow solution of the processing solution and silver is recovered by the above method, and the residual solution may be disposed of as a waste solution. May be used.
It is particularly preferred to mix the stabilizer with the fixer or the bleach-fixer before recovering the silver.

Further, a treatment of bringing the stabilizing solution into contact with an ion exchange resin, an electrodialysis treatment (see Japanese Patent Application No. 59-96352), a reverse osmosis treatment (see Japanese Patent Application No. 59-96352) and the like can be used.

If the water used for the stabilizing solution is deionized in advance, it is preferably used because the anti-vibrating property of the stabilizing solution, the stability of the stabilizing solution and the image storability can be improved. As the means for deionizing treatment, any one may be used as long as it makes the conductivity of the washing water after treatment 50 μs / cm or less or Ca, Mg ions 5 ppm or less, for example, by an ion exchange resin or a reverse osmosis membrane. The treatments are preferably used alone or in combination. The ion exchange resin and the reverse osmosis membrane are described in detail in Kokai Giho No. 87-1984, but it is preferable to use a strongly acidic H type cation exchange resin and a strongly basic OH type anion exchange resin.

In the present invention, the salt concentration in the stabilizing solution is 1000 pp.
When it is m or less, preferably 800 ppm or less, the washing effect is enhanced, and the white background is improved and the anti-vibration property is good.

The treatment time of the stabilizing solution in the present invention is 2 minutes or less, preferably 1 minute 30 seconds or less, and particularly preferably 1 minute or less, in order to exert the effect of the present invention, particularly the effect on the processing stabilizing solution.

In the present invention, it is preferred that the silver halide emulsion is structured by adding fine grain silver iodide in the process from chemical ripening to coating. Here, during the process from the chemical ripening to the coating includes during the chemical ripening, and thereafter, when it is provided for coating to form a light-sensitive material, fine grain silver iodide is added until then. Means that.

The fine grain silver iodide used in the present invention will be described.

With respect to silver iodide, generally cubic γ-
Although AgI and hexagonal β-AgI are known, the fine grain silver iodide used in the present invention may have any crystal structure or a mixture thereof.

The fine grain silver halide used in the present invention preferably has good monodispersibility, and is preferably adjusted by the double jet method while controlling the temperature, pH and pAg.

The grain size of fine grain silver iodide is 0.2
It is preferably not more than μm, more preferably 0.02 to 0.1 μm.

Next, the addition amount of fine silver iodide grains will be described.

The addition amount of fine silver iodide grains is preferably 1/100 dmol or less per 1 mol of the emulsion of the present invention, when the average grain size of the emulsion of the present invention is d (μm). The range of 1 / 20,000 d to 1/300 d mol per mol is preferred, and the most preferred range is 1/5000 d to 1/500 d mol per mol of the emulsion of the present invention. The fine grain silver iodide in the present invention may be added in any step from the chemical ripening step to immediately before coating, but it is preferably added in the chemical ripening step. The term "chemical ripening step" as used herein refers to a period from the time when the physical ripening and desalting operations of the emulsion of the present invention are completed to the time when an operation for adding a chemical sensitizer and then stopping the chemical ripening is performed. Refers to.

As a method of ending the chemical ripening,
Although a method of lowering the temperature, a method of lowering the pH, and a method of using a chemical ripening stopper are known, the method of using the chemical ripening stopper is preferable in consideration of the stability of the emulsion. Examples of the chemical aging inhibitor include halides (eg, potassium bromide, sodium chloride, etc.), organic compounds known as antifoggants or stabilizers (eg, 4-hydroxy-6).
-Methyl-1,3,3a-7-tetrazaindene etc.) is known. These are used alone or in combination of a plurality of compounds.

The fine grain silver iodide may be added in several times with a time interval, or another chemically ripened emulsion may be added after the fine grain silver iodide is added. The temperature of the emulsion of the present invention when adding fine grain silver iodide is 30 to
The range of 80 ° C is preferable, and the range of 40 to 65 ° C is particularly preferable.

Further, the present invention is preferably carried out under the condition that after the addition of the fine grain silver iodide to be added, until just before coating, a part or the whole of the fine grain silver iodide is lost. More preferable conditions are the fine grain silver halide added. 20% or more of the above has disappeared just before coating. The amount of disappearance is quantified by centrifuging the emulsion or coating solution after addition of fine grain silver iodide under appropriate conditions and then measuring the absorption spectrum of the supernatant.
This can be carried out by comparing with the absorption spectrum of a fine grain silver iodide solution of known concentration.

[0564]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples.

Example-1 (Preparation of seed emulsion) A hexagonal tabular seed emulsion was prepared by the following method.
6215 moles were made.

<Solution A> Osine gelatin 4.26 g Distilled water 1700 ml Polyisopropylene-polyethyleneoxy-disuccinic acid ester sodium salt 10% aqueous ethanol solution 0.4 ml KBr 1.9 g 10% H ₂ SO ₄ 10.2 ml <solution B> 1.255 N AgNO ₃ aqueous solution 497 ml <Solution C> KBr 84.6 g KI 7.5 g Made to 604 ml with distilled water <Solution D> 1.75 N KBr aqueous solution At the following silver potential control amount 35 ° C, Japanese Patent Publication 58-58288. Issue 58-
Using the mixing stirrer described in the specification of No. 58289, 9.08 ml of each of solution B and solution C was added to solution A by the simultaneous mixing method over a period of 2 minutes to perform nucleation.

After stopping the addition of Solution B and Solution C, 3
Take 0 minutes to raise the temperature of solution A to 60 ° C.,
The solutions B and C were again mixed by the simultaneous mixing method at 19.5 m each.
It was added at a flow rate of 1 / min for 25 minutes. During this period, the silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) was controlled to be +6 mV using the solution D. After the addition was completed, the pH was adjusted to 6 with 3% KOH, an aqueous solution containing 21.3 g of ossein gelatin was added, and seed emulsion E was added.
It was set to M-0. Seed emulsion EM-0 thus prepared
90% or more of the total projected area of the silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0. The hexagonal tabular plate has an average thickness of 0.07 μm and an average diameter (converted to a circle diameter). ) Was 0.5 μm by electron microscope observation. Seed emulsion EM-0 contains 0.6215 moles of silver halide in 4612 ml of emulsion.

Example-2 (Preparation of tabular emulsion of the present invention) A tabular silver iodobromide emulsion EM-1 of the present invention containing 2.46 mol% AgI was prepared using the following four kinds of solutions. .

<Solution A> Seed emulsion EM-0 0.6215 mol (4612 ml) <Solution B> 3.50 N AgNO ₃ aqueous solution 1467 ml <Solution C> KBr 599 g KI 17.0 g Distilled water to 1467 ml <Solution D> 1.75N KBr aqueous solution At the following silver potential control amount of 60 ° C., Japanese Patent Publication Nos. 58-58288 and 58-58-58
Using a mixing stirrer described in Japanese Patent No. 58289, the total amount of Solution B and Solution C was adjusted to 1 by Solution 1:
Addition growth was performed at a flow rate of 5.45 ml / min for 95.14 minutes.

The silver potential during this period was +28.
It was controlled to be 0 mV.

After completion of the addition, water was washed by a precipitation method (using phenylcarbamoylated gelatin) according to a conventional method to remove excess salts, and then 47.57 g of ossein gelatin.
A gelatin aqueous solution containing was added, and the mixture was stirred and redispersed.

This emulsion EM-1 contained 5.756 mol of silver halide in 2445 ml of emulsion, and the pH of the emulsion solution at 40 ° C. was adjusted to 5.8 and pAg was adjusted to 8.06.

About 3000 particles of EM-1 were observed and measured with an electron microscope to analyze the shape. The results are shown in Table 1. EM-1 had (111) parallel principal planes, and the ratio of the (111) planes to the edges was 80%.

Example 3 (Preparation of Emulsion EM-2 of the Present Invention) A tabular silver iodobromide emulsion EM-2 of the present invention containing 1.0 mol% AgI was prepared using the following 7 kinds of solutions. .

<Solution A> Alkali-processed gelatin 1.0 g 4N nitric acid aqueous solution 1.0 ml NaBr 2.44 g PLARONIC TM-L63 5.21% by weight Distilled water is added to make 1.0 liter <Solution B> AgNO ₃ 1.91 g Distilled water is added, Make it 14.2 ml <Solution C> NaBr 1.31g Add distilled water to make 14.0 ml <Solution D> Ammonium sulfate 1.86 g 2.5N sodium hydroxide 11.8 ml Make distilled water to make 28.5 ml <Solution E> Alkaline Processed gelatin 16.7g 4N nitric acid aqueous solution 5.3ml Add distilled water to make 88.7ml <Solution F> AgNO ₃ 197.9g Add distilled water to make 728ml <Solution G> NaBr 124g KI 2.0g Add distilled water , 724.7 ml, and at 45 ° C., using the same stirring mixer as in Example-1, 6.7 ml of solution B was added to 6.7 ml of solution B, and 6.7 ml of solution C was added for 1 minute. During this period, pAg was 9.71, and the addition rate was constant. Mixing was continued for 1 minute, and the temperature was raised to 60 ° C in 9 minutes. Thereafter, the entire amount of Solution D was added, and mixing was continued for 9 minutes.

To the solution E, the whole amount of the solution E was added, and after mixing for 2 minutes, 31.6 μg of ammonium hexachlororhodate was added and 2.5
Mix for minutes. Further, the remaining amounts of solution B and solution C were added at a constant rate for 7.5 minutes.

After that, 474.7 ml of solution F and 473.6 ml of solution G
Was added for 64 minutes. Further subsequently, 253.3 ml of solution F and 251.1 ml of solution G were added for 19 minutes.

Washing with water was carried out in the same manner as in Example 1, and the mixture was stirred and redispersed. The analysis results are shown in Table 1.

EM-2 had (111) parallel main planes, and the ratio of the (111) planes to the edges was 70%.

Example 4 (Preparation of Comparative Tabular Grains) Using the following four kinds of solutions
Comparative tabular silver iodobromide emulsion EM containing 2.0 mol% AgI
-4 was created.

<Solution A> Osein gelatin 7.7 g Seed emulsion (EM-0) 0.02875 mol Polyisopropylene-polyethyleneoxy-disuccinic acid ester sodium salt 10% ethanol solution 2.0 ml Distilled water is added to make 800 ml <solution B> 1.5 N by addition of aqueous AgNO ₃ solution 183Cc <solution c> NBr 91g KI 2.60g ossein gelatin 10.98g distilled water, to 548.4Ml <solution D> 3.5 N KBr aqueous silver potential control amount <solution E> 1.0 N Aqueous solution of HNO ₃ pH controlled amount at 65 ℃, using a mixing stirrer shown in JP-B-58-58288, 58-58289, the total amount of solution B and solution C in solution A by the following simultaneous mixing method The additive growth was carried out in a pattern like this.

During this period, the silver potential was controlled to be -1 mV and pH was 2.0.

[Minutes] Solution B Solution C Addition time Flow rate [ml / min] 10 2.23 6.69 20 4.39 13.17 40 6.54 19.62 41.15 6.67 20.01 Addition was 41.15 minutes.

The addition flow rate was increased linearly from the start to the end of the addition. The above shows 0, 20, 40, and the flow rate at the end.

After completion of the addition, water was washed by a precipitation method (using phenylcarbamoylated gelatin) according to a conventional method to remove excess salts, and then 47.57 g of ossein gelatin.
A gelatin aqueous solution containing was added, and the mixture was stirred and redispersed.

This emulsion EM-3 contained 5.756 mol of silver halide in 2445 ml of emulsion, and the pH of the emulsion solution at 40 ° C. was adjusted to 5.8 and pAg was adjusted to 8.06.

About 3000 particles of EM-3 were observed and measured with an electron microscope to analyze the shape. The results are shown in Table 1.

[0588]

[Table 1]

Example 5 The following photographic constitutional layer was provided on the undercoated cellulose acetate ester film having a thickness of 115 μm.

(Composition of photographic constituent layers) The coating amount of silver halide and colloidal silver is g / m ² in terms of metallic silver.
The amounts are expressed in units, the amounts added in g / m ² for couplers, additives and gelatin, and the sensitizing dyes are expressed in moles per mole of silver halide in the same layer. The sample 101 is shown below.

Sample 101 First layer: Antihalation layer Black colloidal silver 0.16 Ultraviolet absorber (UV-1) 0.20 High boiling point solvent (Oil-1) 0.16 Gelatin 1.23 Second layer: Intermediate layer Compound (SC-1) 0.15 High Boiling point solvent (Oil-2) 0.17 Gelatin 1.27 Third layer: low-sensitivity red-sensitive layer Silver iodobromide emulsion (average grain size 0.38 µm, silver iodide content rate 8.0 mol%) 0.50 Silver iodobromide emulsion (average grain size) 0.27 μm, silver iodide content 2.0 mol%) 0.21 Sensitizing dye (SD-1) 2.8 × 10 ^-4 Sensitizing dye (SD-2) 1.9 × 10 ^-4 Sensitizing dye (SD-3) 1.9 × 10 ^-5 Sensitizing dye (SD- ⁴ ) 1.0 × 10 ^-4 Cyan coupler (C-1) 0.48 Cyan coupler (C-2) 0.14 Colored cyan coupler (CC-1) 0.021 DIR compound (D-1) 0.020 High boiling point Solvent (Oil-1) 0.53 Gelatin 1.30 Fourth layer: Medium-sensitive red-sensitive layer Silver iodobromide emulsion (average grain size 0.52 μm, silver iodide content 8.0 mol% 0.62 Silver iodobromide emulsion (average grain size 0.38 .mu.m, a silver iodide content of 8.0 mol%) 0.27 Sensitizing dye (SD─1) 2.3 × 10 ^-4 Sensitizing dye (SD─2) 1.2 × 10 ^-4 increase Sensitizing dye (SD-3) 1.6 × 10 ^-5 Sensitizing dye (SD- ⁴ ) 1.2 × 10 ^-4 Cyan coupler (C-1) 0.15 Cyan coupler (C-2) 0.18 Colored cyan coupler (CC-1) 0.030 DIR compound (D-1) 0.013 High boiling point solvent (Oil-1) 0.30 Gelatin 0.93 Fifth layer: high-sensitivity red-sensitive layer Silver iodobromide emulsion (EM-1) 1.27 Sensitizing dye (SD-1) 1.3 × 10 ^-4 Sensitizing dye (SD-2) 1.3 × 10 ^-4 Sensitizing dye (SD-3) 1.6 × 10 ^-5 Cyan coupler (C-2) 0.12 Colored cyan coupler (CC-1) 0.013 High boiling point solvent (Oil) ─ 1) 0.14 Gelatin 0.91 Sixth layer: Intermediate layer Compound (SC-1) 0.09 High boiling point solvent (Oil-2) 0.11 Gelatin 0.80 Seventh layer: Low sensitivity green sensitive layer Silver iodobromide emulsion (average grain size 0.38 μm , Silver content of 8.0 mol%) 0.61 Silver iodobromide emulsion (average particle diameter 0.27 [mu] m, silver iodide content 2.0 mol%) 0.20 Sensitizing dye (SD─4) 7.4 × 10 ^-5 Sensitizing dye (SD─5 ) 6.6 × 10 ^-4 Magenta coupler (M-1) 0.18 Magenta coupler (M-2) 0.44 Colored magenta coupler (CM-1) 0.12 High boiling point solvent (Oil-2) 0.75 Gelatin 1.95 8th layer: Medium sensitivity green sensitivity Layer Silver iodobromide emulsion (average grain size 0.59 μm, silver iodide content 8.0 mol%) 0.87 Sensitizing dye (SD-6) 2.4 × 10 ^-4 Sensitizing dye (SD-7) 2.4 × 10 ^-4 Magenta Coupler (M-1) 0.058 Magenta coupler (M-2) 0.13 Colored magenta coupler (CM-1) 0.070 DIR compound (D-2) 0.025 DIR compound (D-3) 0.002 High boiling point solvent (Oil-2) 0.50 Gelatin 1.00 9th layer: High-sensitivity green-sensitive layer Silver iodobromide emulsion (EM-1) 1.27 Sensitizing dye (SD-6) 1.4 × 10 ^-4 Sensitizing dye (SD-7) 1.4 × 1 0 ^-4 Magenta coupler (M-2) 0.084 Magenta coupler (M-3) 0.064 Colored magenta coupler (CM-1) 0.012 High boiling point solvent (Oil-1) 0.27 High boiling point solvent (Oil-2) 0.012 Gelatin 1.00 10th Layer: Yellow filter layer Yellow colloidal silver 0.08 Color stain inhibitor (SC-2) 0.15 Formalin scavenger (HS-1) 0.20 High boiling point solvent (Oil-2) 0.19 Gelatin 1.10 11th layer: Intermediate layer Formalin scavenger (HS-1) ) 0.20 Gelatin 0.60 12th layer: Low-sensitivity blue-sensitive layer Silver iodobromide emulsion (average grain size 0.38 μm, silver iodide content 8.0 mol%) 0.22 Silver iodobromide emulsion (average grain size 0.27 μm, silver iodide) Content 2.0 mol%) 0.03 Sensitizing dye (SD-8) 4.9 × 10 ^-4 Yellow coupler (Y-1) 0.75 DIR compound (D-1) 0.010 High boiling point solvent (Oil-2) 0.30 Gelatin 1.20 13th layer : Medium sensitivity blue sensitive layer Silver iodobromide emulsion (average grain size 0 .59 μm, silver iodide content 8.0 mol%) 0.30 Sensitizing dye (SD-8) 1.6 × 10 ^-4 Sensitizing dye (SD-9) 7.2 × 10 ^-5 Yellow coupler (Y-1) 0.10 DIR compound ( D-1) 0.010 High boiling point solvent (Oil-2) 0.046 Gelatin 0.47 14th layer: High sensitivity blue-sensitive layer Silver iodobromide emulsion (EM-1) 0.85 Sensitizing dye (SD-8) 7.3 × 10 ^-5 increase Dye-sensitizing agent (SD-9) 2.8 × 10 ^-5 Yellow coupler (Y-1) 0.11 High boiling point solvent (Oil-2) 0.046 Gelatin 0.80 15th layer: 1st protective layer Silver iodobromide emulsion (average grain size 0.08 μm , Silver iodide content 1.0 mol%) 0.40 UV absorber (UV-1) 0.065 UV absorber (UV-2) 0.10 High boiling solvent (Oil-1) 0.07 High boiling solvent (Oil-3) 0.07 Formalin scavenger ( HS-1) 0.40 Gelatin 1.31 16th layer: 2nd protective layer Alkali-soluble matting agent (average particle size 2 μm) 0.15 Polymethylmethacrylate (average particle size 3 μm) 0.1. 04 Sliding agent (WAX-1) 0.04 Gelatin 0.55 In addition to the above composition, a coating aid Su-1, a dispersion aid Su-2, a viscosity modifier, a hardener H-1, H-2, Stabilizer ST-1, Antifoggant AF-1, Weight average molecular weight: 1
Two types of AF-2 with 000 and weight average molecular weight of 1,100,000
And the preservative DI-1 was added. The amount of DI-1 added is 9.
It was 4 mg / m ² .

[0592]

[Chemical 72]

[0593]

[Chemical formula 73]

[0594]

[Chemical 74]

[0595]

[Chemical 75]

[0596]

[Chemical 76]

[0597]

[Chemical 77]

[0598]

[Chemical 78]

[0599]

[Chemical 79]

Next, the fifth layer and the ninth layer in the above sample 101
Samples 101 to 103 were prepared in the same manner except that the silver iodobromide emulsions used in the 14th and 14th layers were used as shown in Table 2.

The samples 101 to 103 prepared as described above were evaluated.

However, each sample was divided into two parts, one part was subjected to sensitometric evaluation, and the other part was evaluated for pressure resistance described later.

[Treatment Process] Treatment process Treatment time Treatment temperature Replenishment amount * Color development 3 minutes 15 seconds 38 ± 0.3 ℃ 780cc. Bleach 45 seconds 38 ± 2.0 ℃ 150cc. Fixation 1 minute 30 seconds 38 ± 2.0 ℃ 830cc. Stability 60 seconds 38 ± 5.0 ℃ 830cc. Drying 1 minute 55 ± 5.0 ℃ − * Replenishment amount is the value per 1 m ² of light-sensitive material.

The following color developing solution, bleaching solution, fixing solution, stabilizing solution and its replenishing solution were used.

Color developer water 800 cc. Potassium carbonate 30 g Sodium hydrogen carbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4-Amino-3-methyl-N -Ethyl-N- (β-hydroxylethyl) aniline sulfate 4.5g Diethylenetriaminepentaacetic acid 3.0g Potassium hydroxide 1.2g Add water to make 1 liter and add potassium hydroxide or 20%
Adjust to pH 10.06 with sulfuric acid.

Color development replenisher replenisher Water 800 cc. Potassium carbonate 35 g Sodium hydrogen carbonate 3 g Potassium sulfite 5 g Sodium bromide 0.4 g Hydroxylamine sulfate 3.1 g 4-Amino-methyl-N-ethyl-N-aniline sulfate (β-hydroxyl Ethyl) 6.3g Potassium hydroxide 2g Diethylenetriaminepentaacetic acid 3.0g Add water to make 1 liter and add potassium hydroxide or 20%
Adjust to pH 10.18 with.

Bleaching solution Water 700 cc. 1,3 Diaminopropanetetraacetic acid iron (III) ammonium 125 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 40 g Ammonium bromide 150 g Glacial acetic acid 40 g Water was added to make 1 liter, and aqueous ammonia or glacial acetic acid was used. Adjust to pH 4.4.

Bleaching Replenisher Water 700 cc. 1,3 Diaminopropanetetraacetic acid iron (III) ammonium 175 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 50 g Ammonium bromide 200 g Glacial acetic acid 56 g After adjusting to pH 4.4 with ammonia water or glacial acetic acid Add water to make 1 liter.

Fixing solution Water 800 cc. Ammonium thiocyanate 120 g Ammonium thiosulfate 150 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.2 using aqueous ammonia or glacial acetic acid, add water to make 1 liter.

Fixing replenisher water 800 cc. Ammonium thiocyanate 150 g Ammonium thiosulfate 180 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.5 with aqueous ammonia or glacial acetic acid, add water to make 1 liter.

Stabilizer and Stable Replenisher Water 900 cc. Paraoctylphenyl polyoxyethylene ether (n = 10) 2.0 g Dimethylolurea 0.5 g Hexamethylenetetramine 0.2 g 1,2-Benzisothiazolin-3-one 0.1 g Siloxane (UCC) L-77) 0.1g ammonia water 0.5cc. Add water to make 1 liter, then use ammonia water or 50%
Adjust to pH 8.5 with sulfuric acid.

(Evaluation of pressure resistance) After applying a load of 5 g from the photographic constituent layer side with a scratch hardness meter of a needle having a needle head radius of 0.3 mm, development processing was carried out, and the pressure was measured at a transmission density of about 0.7 with a microdensitometer. The change in concentration was measured. The change in concentration due to pressure can be indicated by ΔD, or the samples can be visually observed to perform relative ranking.

The results are shown in Table 2.

[0614]

[Table 2]

As shown in Table 2, the present invention is superior to the comparative examples.

[0616]

According to the present invention, a silver halide emulsion having significantly improved sharpness and improved pressure characteristics and a silver halide photographic light-sensitive material using the emulsion are provided. It is possible to provide a silver halide emulsion excellent in sharpness, color reproducibility, and pressure characteristics without impairing tonality and a silver halide photographic light-sensitive material using the emulsion.

Claims (4)

[Claims] 1. A flat plate in which at least 70% of the total projected area of silver halide grains contained in the emulsion has an aspect ratio represented by a diameter / thickness ratio of 2.0 or more and a thickness of 0.5 μm or less. -Like silver halide grains, the variation coefficient of thickness of the tabular silver halide grains is 20% or less, and all of the parallel main planes of the tabular silver halide grains facing each other and the surface of the edge portion 90% or less of (111) crystal faces are silver halide emulsions. 2. A flat plate in which at least 70% of the total projected area of silver halide grains contained in the emulsion has an aspect ratio represented by a diameter / thickness ratio of 2.0 or more and a thickness of 0.5 μm or less. -Shaped silver halide grains, and the shape of the main plane of the tabular silver halide grains has a maximum adjacent side ratio of 1.0 to
A hexagon of 2.0, and 90% or less of all the parallel main planes of the tabular silver halide grains that face each other and the edge portion are (111) crystal faces. Silver halide emulsion. 3. A flat plate in which at least 70% of the total projected area of silver halide grains contained in the emulsion has an aspect ratio represented by a diameter / thickness ratio of 2.0 or more and a thickness of 0.5 μm or less. -Like silver halide grains, the relative standard deviation of the silver iodide content of the tabular silver halide grains is 20% or less, and all of the parallel main planes of the tabular silver halide grains facing each other. A silver halide emulsion characterized in that 75% or less of the face of the edge portion is a (111) crystal face. 4. A silver halide color light-sensitive material having, on one side on a transparent support, a photographic constituent layer comprising at least one red-sensitive layer, green-sensitive layer, blue-sensitive layer and non-photosensitive layer, respectively. A silver halide color light-sensitive material characterized in that at least one of said light-sensitive layers contains at least one silver halide emulsion according to claim 1, 2, or 3.