JPH11305369A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide photographic sensitive material having improved storage property and pressure property. SOLUTION: In the red sensitive layer, the gravity center wavelength (λ- R) in the spectral sensitivity distribution of the multilayered effect influenced by other photosensitive silver halide emulsion layers in 500 to 600 nm range satisfies 500 nm<λ- R<560 nm. The difference between λ- R and the gravity center wavelength (λG) in the spectral sensitivity distribution of a green sensitive layer is in the relation of λG-λ- R>=10 nm. Further, at least one green sensitive layer contains a planer silver halide photographic emulsion which is prepared by rapidly adding an emulsion of silver iodide fine particles to host planer particles of silver iodide bromide or silver bromide having (111) principal planes parallel to each other in a dispersion soln. containing water and a dispersion medium so as to introduce dislocation lines to the host particles.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide photographic material. More specifically, the present invention relates to a silver halide color photographic light-sensitive material which is excellent in color reproducibility, improved in pressure and storage stability.

[0002]

2. Description of the Related Art Hitherto, it has been known to utilize an interlayer suppression effect as a means for improving color reproducibility in a color photographic light-sensitive material. In the case of a color negative light-sensitive material, by giving a development suppressing effect from a green-sensitive silver halide emulsion layer (hereinafter also referred to as a green-sensitive layer) to a red-sensitive silver halide emulsion layer (hereinafter also referred to as a red-sensitive layer). The color development of the red-sensitive layer in white exposure can be suppressed as compared with that in the case of red exposure. In the color negative paper system, the gradation is balanced so that, when exposed with white light, grayscale is reproduced on a color print. For this reason, the multilayer effect (interlayer effect; also referred to as an interlayer effect) gives a higher density cyan color development in red exposure than in gray exposure. As a result, it is possible to reproduce red with higher saturation with suppressed cyan color development on the print. Similarly, the effect of suppressing the development from the red-sensitive layer to the green-sensitive layer gives green reproduction with a high degree of saturation.

When the saturation of the primary colors of red, green and blue is increased by using these methods, there is a disadvantage that the hue of yellow to cyanish green is not faithful.
The technology described in US Pat. This technique is based on a blue-sensitive silver halide emulsion layer containing at least one yellow color coupler (hereinafter also referred to as a blue-sensitive layer), a green-sensitive layer containing a magenta color coupler, a silver halide emulsion layer containing a magenta color coupler, In a color light-sensitive material having a red-sensitive silver halide emulsion layer containing a cyan color coupler, the center of gravity wavelength (λ _G ) of the spectral sensitivity distribution of the green-sensitive silver halide emulsion layer is 520 nm <λ _G ≦ 580 nm, and The center-of-gravity wavelength (λ _-R ) of the spectral sensitivity distribution of the magnitude of the multilayer effect that all the red-sensitive silver halide emulsion layers containing the cyan coupler receive from other silver halide emulsion layers in the range of 500 nm to 600 nm is 500 nm. <Λ- _R
≦ 560 nm, and λ _G −λ _−R is 5 nm or more,
It is intended to achieve vivid and faithful color reproduction by using a silver halide color light-sensitive material preferably having a thickness of 10 nm or more.

Here, the red-sensitive silver halide emulsion layer has 50
The center of gravity wavelength λ _-R of the wavelength distribution of the magnitude of the multilayer effect received from other silver halide emulsion layers in the range of 0 nm to 600 nm.
Is obtained as follows.

(1) First, a red filter that transmits a specific wavelength or more or an interference filter that transmits only a specific wavelength so that a red-sensitive layer that emits cyan at a wavelength of 600 nm or more is exposed and other layers are not exposed. Is applied to uniformly expose the red-sensitive layer that develops cyan to an appropriate value.

(2) Next, when a spectral exposure is applied, the blue-sensitive layer and the green-sensitive layer act on the above-mentioned fogged red-sensitive layer emulsion with a layering effect of development suppression to give a reversal image. (See FIG. 1A) (3) From this inverted image, a spectral sensitivity distribution S _-R (λ) as an inverted photosensitive material is obtained. (S for a specific wavelength λ
_-R (λ) is obtained as a relative point from the point a shown in FIG. 1A. (4) The center-of-gravity wavelength (λ- _R ) of the multilayer effect is calculated by the following equation (1). Equation (1)

[0007]

(Equation 1)

S _G (λ) is a spectral sensitivity distribution curve of the green sensitive layer, and a relative value of S _G (λ) at a specific wavelength λ can be obtained from point b shown in FIG. 1B.

Further, Japanese Patent Application Laid-Open No. 1-128847 discloses a method in which the gradation and the size of the layering effect are specified and the skin color is accurately reproduced.

[0010]

However, when a light-sensitive material is produced by such a method, a large amount of silver halide emulsion is used in order to secure an overlay effect of obtaining faithful color reproducibility. Large amounts of DIR coupler must be used. For this reason, in the prior art, since a large amount of silver halide emulsion is used, fog rise and deterioration of pressure fog due to storage of the light-sensitive material have been observed. An object of the present invention is to provide a silver halide color photographic light-sensitive material having improved storage stability and pressure characteristics.

[0011]

The object of the present invention is achieved by a silver halide color photographic light-sensitive material having the following constitution. (1) A blue-sensitive silver halide emulsion layer containing at least one yellow coupler, a green-sensitive silver halide emulsion layer containing a magenta coupler, and a red-sensitive silver halide containing a cyan coupler on a support. The center of the spectral sensitivity distribution of the magnitude of the layering effect that all the red-sensitive silver halide emulsion layers have from 500 nm to 600 nm from other photosensitive silver halide emulsion layers, comprising an emulsion layer and a non-light-sensitive layer; Wavelength (λ- _R ) is 500 nm <λ- _R <560
nm and the center of gravity wavelength (λ _G ) of the spectral sensitivity distribution of at least one of the green-sensitive silver halide emulsion layers and λ _-R
Λ _G -λ _-R ≧ 10 nm, at least one of the green-sensitive silver halide emulsion layers is dispersed in a dispersion medium solution containing water and a dispersion medium. A tabular halide in which dislocation lines are introduced by rapidly adding an emulsion composed of silver iodide fine grains to a host tabular grain composed of silver iodobromide or silver bromide whose main plane is a (111) plane. A silver halide color photographic material comprising a silver photographic emulsion. (2) The tabular silver halide photographic emulsion has an average aspect ratio of 3 or more and has a total projected area of 50.
(1) The silver halide color photographic light-sensitive material as described in (1) above, wherein at least 10% is occupied by a tabular silver halide photographic emulsion having 10 or more dislocation lines per grain in a fringe portion of the grain. (3) The silver halide color photographic light-sensitive material according to (2), wherein the tabular silver halide photographic emulsion has an average aspect ratio of 5 or more. (4) A photographic product provided with an exposure mechanism including a photographic lens and a shutter incorporating the silver halide color photographic light-sensitive material according to any one of (1) to (3).

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

In a color photographic light-sensitive material, it is known to utilize an interlayer suppression effect as a means for improving color reproducibility. In JP-A-61-34541, the center-of-gravity sensitivity wavelength (λ _G ) of the spectral sensitivity distribution of the green-sensitive silver halide emulsion layer is 520 nm <λ _G ≦ 580 nm, and the red-sensitive silver halide emulsion layer is from 500 nm. 600
In the range of nm, the center-of-gravity wavelength (λ- _R ) of the spectral sensitivity distribution of the magnitude of the multilayer effect received from other silver halide emulsion layers is 500.
nm <λ _−R <560 nm, and λ _G −λ _−R is 5
A silver halide color photographic material characterized by a wavelength of at least 10 nm, preferably at least 10 nm, seeks to achieve faithful color reproduction. Here, it is taught that the interlayer effect is applied to the red-sensitive layer only from the short wavelength side of the green-sensitive layer, whereas the interlayer effect is applied from the entire wavelength range of the green-sensitive layer to the red-sensitive layer.

The improvement of the preservability and the pressure resistance of the emulsion used for the green sensitivity is described in JP-A-7-43846 and JP-A-7-43846.
-43847, JP-A-7-128780, JP-A-7-128780
As disclosed in JP-A-140581, it is stated that it is effective to change the sensitizing dye of the emulsion used in the green-sensitive layer, but it is still insufficient for improving pressure resistance. Was. Furthermore, there is no disclosure of the effect of improving fog rise during storage of the light-sensitive material.

In order to improve the pressure property by the method of preparing a silver halide emulsion, the method can be achieved by adding a silver iodide fine grain emulsion at the time of dislocation introduction of a tabular silver halide emulsion in JP-A-8-29904. However, there is no mention of the effect of improving fog increase during storage of the light-sensitive material.

As a result of intensive studies, the present inventor has found that the silver halide emulsion used for the green-sensitive layer can be obtained by dispersing a silver halide emulsion in a dispersion medium solution containing water and a dispersion medium such that the parallel main plane is (111).
The surface is excellent in pressure resistance by using host tabular grains made of silver iodobromide or silver bromide to form grains into which dislocation lines are introduced by rapidly adding an emulsion made of silver iodide fine grains. In addition, it has been found that fog rise during storage can be reduced.

In the tabular silver halide grain emulsion, the aspect ratio means the ratio of the diameter to the thickness of the silver halide grains. That is, it is a value obtained by dividing the diameter of each silver halide grain by the thickness. Here, the diameter indicates the diameter of a circle having an area equal to the projected area of the silver halide grain when observed with a microscope or an electron microscope (referred to as a circle equivalent diameter). Therefore, that the aspect ratio is 5 or more means that the diameter of the circle is 5 times or more with respect to the thickness.

In the present invention, the average aspect ratio means that the equivalent circle diameter in the emulsion is 0.6 μm or more and the grain thickness is 0.3 μm.
It means a value obtained from the average equivalent circle diameter and the average thickness of particles smaller than m.

As an example of the method of measuring the aspect ratio, there is a method of taking a transmission electron microscope photograph by a replica method and obtaining the equivalent circle diameter and thickness of each particle. In this case, the thickness is calculated from the length of the shadow of the replica.

The average aspect ratio of the tabular silver halide grains in the present invention is 3 or more, preferably 5 or more. If the aspect ratio is too large, the variation coefficient of the particle size distribution tends to increase, so that the aspect ratio is usually preferably 20 or less.

Further, in the present invention, the tabular grains have dislocation lines. Dislocation lines of tabular grains are described, for example, in J. Am. F.
Hamilton, Photo. Sci. Eng. , 1
1, 57, (1967); Shiozawa, J .;
Soc. Photo. Sci. Japan, 35, 21
3, (1972), can be observed by a direct method using a transmission electron microscope at a low temperature. That is, the silver halide grains taken out from the emulsion so as not to apply enough pressure to generate dislocation lines on the grains are placed on a mesh for observation with an electron microscope to prevent damage (printout, etc.) by the electron beam. Observation is performed by a transmission method while the sample is cooled. At this time, as the thickness of the particles is larger,
Since the electron beam becomes difficult to transmit, a clearer observation can be obtained by using a high-pressure electron microscope (200 kV or more for particles having a thickness of 0.25 μm). From the particle photograph obtained by such a method, the position and number of dislocation lines can be obtained for each particle when viewed from the direction perpendicular to the main plane.

The number of dislocation lines in the tabular grains of the present invention is 5 or more on average per grain. More preferably, the average is 10 or more per particle. Most preferably, the average is 20 or more per particle. When dislocation lines are densely arranged or when dislocation lines are observed to intersect each other, the number of dislocation lines per grain may not be clearly counted. However, even in these cases, it is possible to count about 10, 20, or 30 pieces, and it can be clearly distinguished from the case where there are only a few pieces. The average number of dislocation lines per particle is determined as the number average by counting the number of dislocation lines for 100 particles or more. Hundreds of dislocation lines may be observed.

The dislocation lines can be introduced, for example, near the outer periphery of the tabular grains. In this case, the dislocation is almost perpendicular to the outer periphery, and a dislocation line is generated from the position of x% of the distance from the center of the tabular grain to the side (outer periphery) to the outer periphery. The value of x is preferably 10 or more and 100 or more.
And more preferably 30 or more and less than 99.
At this time, the shape formed by connecting the starting positions of the dislocation lines is similar to the particle shape, but is not completely similar but may be distorted. This type of dislocation line is not found in the central region of the grain. The direction of the dislocation line is approximately (21
1) Direction but often meandering, sometimes intersecting with each other.

Further, the tabular grains may have dislocation lines almost uniformly over the entire area on the outer periphery, or may have dislocation lines at local positions on the outer periphery. That is, in the case of a hexagonal tabular silver halide grain as an example, dislocation lines may be limited only near six vertices, or dislocation lines may be limited only near one of the vertices. Good. vice versa,
The dislocation lines may be limited to only the sides excluding the vicinity of the six vertices.

Further, dislocation lines may be formed over a region including the center of two parallel main planes of the tabular grains.
When dislocation lines are formed over the entire area of the main plane, the direction of the dislocation lines may be crystallographically approximately (211) when viewed from a direction perpendicular to the main plane. In some cases, the dislocation lines are formed randomly, and the length of each dislocation line is also random. is there. Dislocation lines are often straight or meandering. They also often intersect with each other.

As described above, the position of the dislocation line may be limited to the outer periphery, the main plane, or a local position, or may be formed by combining these. That is, they may exist simultaneously on the main plane on the outer periphery.

The host tabular grain emulsion is opposed (111)
It comprises a main surface and side surfaces connecting the main surface. The host tabular grain emulsion comprises silver iodobromide or silver bromide. Although silver chloride may be contained, the silver chloride content is preferably 8 mol% or less, more preferably 3 mol% or less, or 0 mol%. In the case of silver iodobromide, since the coefficient of variation of the grain size distribution of the tabular grain emulsion is preferably 25% or less, the silver iodide content is preferably 20 mol% or less. By reducing the silver iodide content, the coefficient of variation of the grain size distribution of the tabular grain emulsion can be easily reduced. In particular, the coefficient of variation of the grain size distribution of the host tabular grain emulsion is preferably 20% or less, and the silver iodide content is preferably 10 mol% or less. The coefficient of variation of the silver iodide content distribution between grains is 2
It is preferably 0% or less, particularly preferably 10% or less.

When the host tabular grain emulsion is silver iodobromide, the tabular grain emulsion preferably has a structure within the grains with respect to silver iodide distribution. In this case, the silver iodide distribution may have a double, triple, quadruple, or even more, grain structure. In any case, the outermost layer of the structure is particularly preferably silver bromide containing substantially no silver iodide. Silver bromide containing substantially no silver iodide means that the silver iodide content of the outermost layer is 3 mol% or less, most preferably 1 mol% or less.

In the present invention, the host tabular grain emulsion has an opposing (111) main surface and side surfaces connecting the main surface. At least one twin plane exists between the main surfaces. Two twin planes are usually observed in the host tabular grain emulsion of the present invention. The interval between the two twin planes is US5
As described in US Pat. No. 219,720, it can be smaller than 0.012 μm. Further, Japanese Patent Application Laid-Open No. 5-249585
As described in (1), the value obtained by dividing the distance between the (111) main surfaces by the twin plane spacing may be 15 or more.

In the present invention, the side connecting the opposing (111) main surfaces of the host tabular grain emulsion is 75% of the total side.
It is particularly preferable that the following is composed of the (111) plane. In the present invention, 70% or less of all aspects is (11)
It is more preferable that it is composed of 1) surface.

Whether or not 70% or less of all the side surfaces are composed of the (111) plane can be easily determined from the electron micrograph of the host tabular grains by the shadowed carbon replica method. Usually, 75% or more of the side surface is (11
In the case of a hexagonal tabular grain composed of 1) planes, the six side faces directly connected to the (111) main surface are connected to each other at an acute angle and an obtuse angle with respect to the (111) main surface. On the other hand, when 70% or less of all side surfaces are composed of (111) planes, (1)
11) The six sides directly connected to the main surface are all connected at an obtuse angle to the (111) main surface. By applying shadowing at an angle of 50 ° C. or less, the obtuse angle and the acute angle of the side surface with respect to the main back surface can be determined. Preferably, shadowing at an angle of 30 ° or less and 10 ° or more facilitates determination of an obtuse angle and an acute angle.

Furthermore, a method using adsorption of a sensitizing dye is effective as a method for determining the ratio between the (111) plane and the (100) plane. The Chemical Society of Japan, 1984, Volume 6, Page 94
The ratio between the (111) plane and the (100) plane can be quantitatively determined by using the method described in JP-A No. 2-947.
The ratio of the (111) plane on all side surfaces can be calculated and obtained using the ratio and the above-described circle equivalent diameter and thickness of the tabular grains. In this case, it is assumed that the tabular grain is a cylinder using the equivalent circle diameter and thickness. With this assumption, the ratio of the side surface to the total surface area can be determined. The value obtained by dividing the ratio of the (100) plane obtained by the above-described adsorption of the sensitizing dye by the ratio of the above-mentioned side surfaces and multiplying by 100 is the ratio of the (100) plane in all the side surfaces. By subtracting the value from 100, the ratio of the (111) plane on all side surfaces can be obtained. Preparation of host tabular grain emulsions usually involves nucleation,
It consists basically of three steps of ripening and growth. In the nucleation step, US Pat. No. 4,713,320 and US Pat.
The use of gelatin having a low methionine content described in No. 2120, nucleation at a high pBr described in US Pat. No. 4,914,014, and nucleation in a short time described in JP-A-2-222940 are the host of the present invention. It is extremely effective in the step of forming nuclei for tabular grain emulsions. The ripening step performed in the presence of a low-concentration base as described in US Pat. No. 5,254,453 and at a high pH described in US Pat. No. 5,136,641 may be effective in the ripening step of the host tabular grain emulsion of the present invention. In the growth step, growth is performed at a low temperature described in US Pat. No. 5,248,587, US Pat. No. 4,720,027, and US Pat.
The use of silver iodide fine grains described in No. 3964 is particularly effective in the step of growing the host tabular grain emulsion of the present invention.

In the present invention, dislocation lines are preferably introduced by rapidly adding a silver iodide fine grain emulsion to the silver iodobromide or silver bromide host tabular grain emulsion described above. This step consists essentially of two steps: a step of rapidly adding a silver iodide fine grain emulsion to the host tabular grain emulsion, and a step of growing silver bromide or silver iodobromide to introduce dislocation lines. It is. These two steps may be performed completely separately, or each may be performed at the same time with repetition. It is preferably performed separately. The step of rapidly adding a silver iodide fine grain emulsion to the first host tabular grain emulsion will be described.

When the silver iodide fine grain emulsion is rapidly added,
Preferably, the silver iodide fine grain emulsion is added within 10 minutes. More preferably, it is added within 7 minutes. These conditions can vary depending on the temperature of the system to be added, pBr, pH, the type and concentration of the protective colloid agent such as gelatin, the presence or absence of silver halide solvent, the type and the concentration, etc., but the shorter is preferable as described above. It is preferable that the addition of an aqueous solution of silver salt such as silver nitrate is not substantially performed during the addition.
The temperature of the system at the time of addition is preferably from 40 ° C to 90 ° C,
A temperature of 50 ° C or higher and 80 ° C or lower is particularly preferred. There is no particular limitation on the pBr when adding the silver iodide fine grain emulsion, provided that the above-mentioned conditions for the host tabular grain emulsion are satisfied.

The silver iodide fine grain emulsion only needs to be substantially silver iodide, and may contain silver bromide and / or silver chloride as long as it can form a mixed crystal. Preferably 100%
It is silver iodide. Silver iodide has β-form and γ-form in its crystal structure.
And α-isomer or α-isomer-like structure as described in US Pat. No. 4,672,026. In the present invention, the crystal structure is not particularly limited, but a mixture of β-form and γ-form, more preferably β-form is used. The silver iodide fine grain emulsion may be formed immediately before addition as described in US Pat. Used. The silver iodide fine grain emulsion can be easily formed by the method described in the aforementioned US Pat. No. 4,672,026. A double jet addition method of a silver salt aqueous solution and an iodide salt aqueous solution, in which the grains are formed with a constant pI value during grain formation, is preferred. Where pI is the logarithm of the reciprocal of the I ^- ion concentration of the system. There are no particular restrictions on the temperature, pI, pH, the type and concentration of protective colloid such as gelatin, the presence / absence, type and concentration of a silver halide solvent, but the size of the grains is 0.1 μm or less, more preferably 0.1 μm or less. 07 μm
The following are convenient for the present invention. Although the particle shape cannot be completely specified because of the fine particles, the variation coefficient of the particle size distribution is preferably 25% or less. In particular, when the content is 20% or less, the effect of the present invention is remarkable. Here, the size and size distribution of the silver iodide fine grain emulsion are determined by placing silver iodide fine grains on a mesh for observation with an electron microscope and observing them directly by a transmission method instead of a carbon replica method. This is because the observation error by the carbon replica method becomes large due to the small particle size. Particle size is defined as the diameter of a circle having a projected area equal to the observed particle. The particle size distribution is also determined using the same projected area circle diameter. The most effective silver iodide fine grains in the present invention have a grain size of 0.06 μm or less and 0.02 μm or less.
As described above, the variation coefficient of the particle size distribution is 18% or less.

The silver iodide fine grain emulsion is preferably subjected to ordinary water washing, concentration adjustment of protective colloid agents such as pH, pI, gelatin and the concentration of silver iodide contained therein as described in US Pat. Will be pH 5
It is preferably at least 7 and at most 7. The pI value is preferably set to a pI value at which the solubility of silver iodide is at a minimum or a pI value higher than that value. As the protective colloid, ordinary gelatin having an average molecular weight of about 100,000 is preferably used.
Low molecular weight gelatin having an average molecular weight of 20,000 or less is also preferably used. It is sometimes convenient to use a mixture of gelatins having different molecular weights. The amount of gelatin per kg of emulsion is preferably 10 g or more and 100 g or less. More preferably, it is 20 g or more and 80 g or less. The silver content in terms of silver atoms per kg of the emulsion is preferably 10 g or more and 100 g or more.
g or less. More preferably, it is 20 g or more and 80 g or less. The amount of gelatin and / or silver is preferably selected to a value suitable for rapidly adding a silver iodide fine grain emulsion.

The silver iodide fine grain emulsion is preferably added in an amount of 1 mol% to 1
0 mol% or less. Most preferably, it is 3 mol% or more and 7 mol% or less. By selecting this addition amount, a dislocation line described later is preferably introduced, and the effect of the invention becomes remarkable. The silver iodide fine grain emulsion is usually dissolved and added beforehand, but at the time of addition, it is necessary to sufficiently increase the stirring efficiency of the system. Preferably, the stirring rotation speed is set higher than usual. The addition of an antifoaming agent is effective to prevent the generation of foam during stirring. Specifically, US 5,275,929
The antifoaming agents described in the examples of the above item are used.

After the silver iodide fine grain emulsion is rapidly added to the host tabular grain emulsion, silver bromide or silver iodobromide is grown to preferably introduce dislocation lines. The growth of silver bromide or silver iodobromide may be started before or simultaneously with the addition of the silver iodide fine grain emulsion. Start growing. The time from the addition of the silver iodide fine grain emulsion to the start of the growth of silver bromide or silver iodobromide is preferably within 10 minutes and 1 second or more. More preferably, it is 3 seconds or more within 5 minutes. More preferably, it is within one minute. This time interval is preferably as short as possible, but preferably before the start of the growth of silver bromide or silver iodobromide.

The growth after the addition of the silver iodide fine grain emulsion is preferably silver bromide. In the case of silver iodobromide, the silver iodide content is preferably within 5 mol% with respect to the layer. More preferably, it is within 3 mol%. The silver content of the layer grown after the addition of the silver iodide fine grain emulsion is preferably 20 or more and 70 or less, when the silver content of the host tabular grain emulsion is 100. Most preferably, it is 25 or more and 65 or less. The temperature, pH and pBr for forming this layer are not particularly limited, but the temperature is usually 40 ° C. or more and 90 ° C. or less, and the pH is usually 2 or more and 9 or less. More preferably, a temperature of 50 ° C. or more and 80 ° C. or less, and a pH of 3 or more and 7 or less are used. With respect to pBr, in the present invention, it is preferable that pBr at the end of the formation of the layer be higher than pBr at the beginning of the formation of the layer.
Preferably, the pBr at the beginning of the formation of the layer is 2.9 or less, and the pBr at the end of the formation of the layer is 1.7 or more. More preferably, the pBr at the beginning of the formation of the layer is 2.5 or less, and the pBr at the end of the formation of the layer is 1.9 or more. Most preferably, pBr in the initial stage of the formation of the layer is 2.3 or less and 1 or more. Most preferably, the pBr at the end of the layer is 2.1 or more and 4.5 or less. The dislocation lines in the present invention are preferably introduced by the above method.

Gelatin is advantageously used as a protective colloid used in the preparation of the emulsion of the present invention and as a binder for other hydrophilic colloid layers, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol Use of various kinds of synthetic hydrophilic high-molecular substances such as mono- or copolymers of polyvinyl alcohol, partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be.

As gelatin, besides lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci. Photo. Japan.
16, Enzyme-treated gelatin as described in P30 (1966) may be used.

In the present invention, it is extremely preferable to use gelatin in which a -NH ₂ group is chemically modified as a dispersion medium used for the host tabular grain emulsion. In particular, the hardly soluble silver halide emulsion added after the formation of the host tabular grains is-
When the NH ₂ group contains no chemically modified gelatin as a dispersion medium, it is essential that the host tabular grain emulsion contains a chemically modified gelatin of —NH 2 group as a dispersion medium. In the dispersion medium used in the host tabular grain emulsion is preferably -NH ₂ groups is the ratio of gelatin is chemically modified is 30 wt% or more, more preferably 60 wt% or more, most preferably 90 wt% That is all.

Here, gelatin in which the —NH ₂ group is chemically modified will be described. As the --NH ₂ group in gelatin, the amino group of a gelatin molecule terminal group, a lysine group, a hydroxy lysine group, a histidine group, an amino group of an arginine group, or an amino group of an arginine group if the arginine group has been converted to an oltinine group Can be mentioned. Further, impurity groups such as adenine and guanine groups can also be mentioned. −
Chemical modification of NH ₂ group means adding a reaction reagent to gelatin,
Reacting with the amino group to form a covalent bond or deamination. That is, a primary amino group (—NH ₂ )
To a secondary amino group (—NH—), a tertiary amino group, or a deaminated product.

Specifically, for example, acid anhydrides (maleic anhydride, o-phthalic anhydride, succinic anhydride, isatoic
anhydride, benzoic anhydride, etc.), acid halides (R
_{-COX, R-SO 2 X,} R-O-COX, Phenyl-C
Compounds having an aldehyde group (R-CHO).
Etc.), compounds having an epoxy group, deaminating groups (HN
O ₂ , deaminase, etc.), active ester compounds (sulfonic acid ester, p-nitrophenyl acetate, isopropenyl acetate, methyl-o-chlorobenzoate,
p-nitrophenyl benzoate), isocyanate compounds (such as Aryl isocyanate), active halogen compounds,
For example, [Aryl halide (benzyl bromide, biphenyl-halom
ethanes, benzoyl halomethane, phenyl benzoylhalo-m
ethane, 1-Fluoro-2,4-dinitro-benzene), β-Ketohalid
e, α-haloaliphatic acid, β-halonitrile, (s-triazin
e, pyrimidine, pyridazine, pyrazine, pyridazone, quino
xaline, quinazoline, phthalazine, benzoxazole, benzoth
chloro derivatives of iazole, benzoimidazole)], carbamoylating agents (cyanate, nitrourea, etc.), acrylic type activity 2
Compounds with heavy bond groups (maleimide, acryamine, acryla
mide, acrylonitrile, methylmetha acrylate, vinyl sulp
hone, vinylsulphonate ester, sulphonamide, styrene a
nd vinylpyridine, allylamine, butadiene, isoprene, chl
oroprene, etc.), sultones (butane sultone, propane s
ultone), Guanidine agent (such as o-methylisourea), carb
It can be achieved by adding oxylazide and reacting.

In this case, the —OH group or —COO of gelatin
A reagent that mainly reacts with the —NH ₂ group of gelatin is more preferable than a reagent that also reacts with the H group to form a covalent bond. Mainly 60% or more, preferably 80 to 100
%, More preferably 95 to 100%. Furthermore, an embodiment in which the reaction product does not substantially contain a group in which oxygen of an ether group or a ketone group replaces a chalcogen atom (for example, -S- or thione group) is more preferable. Here, “substantially not contained” refers to preferably 10% or less, more preferably 0 to 3% of the number of the chemically modified groups. Therefore,
Acid anhydrides, sultones, compounds having an active double bond group, carbamoylating agents, active halogen compounds, isocyanate compounds, active ester compounds, compounds having aldehydes, and deamino groups are more preferred. It is more preferable that the chemical modification does not substantially crosslink gelatin molecules. Here, "substantially not possible" means that the content of the chemically modified group is preferably 10% or less, more preferably 0 to 3%.

The details of the chemical modifying agent and the method for modifying the chemical modification of gelatin are described in the following literature,
No. 26449, JP-A-50-3329, U.S. Pat. Nos. 2,525,753, 2,614,928, 2,614,929, 2,763,639 and 2,594. No. 293, No. 3,132,945, edited by Yoshihiro Abiko, glue and gelatin, Chapter II, Japan glue and gelatin industry association (1987), Ward et al., Edited by The Scienc
e and Technology of Gelatin, Chapter 7, Academic Pre
ss (1977) can be referred to. Chemically modified ratio of the number of -NH ₂ groups of the modified gelatin can be obtained as follows. Gelatin without the modification and gelatin with the modification are prepared, and the number of —NH ₂ groups of both is determined as e ₁ and e ₂ . The ratio (%) of the number of chemically modified numbers can be determined from 100 × (e ₁ −e ₂ ) / e ₁ . Determination of the e ₁ and e ₂ are, -NH ₂
Examples include a method utilizing infrared absorption intensity based on a group, an NMR signal intensity of the proton, a color reaction and a fluorescence reaction, and details thereof are described in Analytical Chemistry Handbook, Organic Edition-2, Maruzen (19)
91) can be referred to. Other examples include a change in the titration curve of gelatin and a quantitative method such as a formol titration method.
latin, Chapter 15, Academic Press (1977).

In addition, glutaraldehyde and Britton-Ro
binson A mixture of high pH buffer is added to a gelatin solution of the specified concentration, color is developed, spectral absorption intensity around 450 nm is measured, and colorimetric determination is performed [Photogrnap
hic Gelatin II, p.297-315, Academic Press (1976)
Can be referred to].

[0048] Gelatin -NH ₂ group has been chemically modified for use in the present invention, the proportion of the number of -NH ₂ group has been chemically modified is 30% or more, preferably 50% or more,
More preferably 80% or more, most preferably at least 90% of the -NH ₂ group is chemically modified.

The emulsion of the present invention is preferably washed with water for desalting and dispersed in a newly prepared protective colloid. The temperature of water washing can be selected according to the purpose, but is preferably selected in the range of 5 ° to 50 ° C. The pH at the time of washing can be selected according to the purpose, but is preferably selected from 2 to 10. More preferably, it is in the range of 3 to 8. The pAg at the time of washing can be selected according to the purpose, but is preferably selected from 5 to 10. Noodle washing method, dialysis method using semi-permeable membrane,
It can be selected from centrifugation, coagulation sedimentation, and ion exchange. In the case of the coagulation sedimentation method, a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative, and the like can be selected.

When preparing the emulsion of the present invention, for example, during grain formation,
In the desalting step, at the time of chemical sensitization, the presence of a metal ion salt before coating is preferable depending on the purpose. In the case of doping the grains, it is preferable to add them at the time of grain formation, when modifying the grain surface or when using as a chemical sensitizer, after grain formation and before the end of chemical sensitization. A method of doping the whole grain and a method of doping only the core part, only the shell part, only the epitaxial part, or only the base grain of the grain can be selected. Mg, Ca, Sr, Ba, Al, S
c, Y, LaCr, Mn, Fe, Co, Ni, Cu, Z
n, Ga, Ru, Rh, Pd, Re, Os, Ir, P
t, Au, Cd, Hg, Tl, In, Sn, Pb, Bi
Etc. can be used. These metals can be added as long as they can be dissolved at the time of particle formation, such as ammonium salts, acetates, nitrates, sulfates, phosphates, hydroxides, hexacoordinate complex salts, and tetracoordinate complex salts. For example, CdB
r ₂ , CdCl ₂ , Cd (NO ₃ ) ₂ , Pb (NO ₃ ) ₂ ,
Pb (CH ₃ COO) ₂ , K ₃ [Fe (CN) ₆ ], (NH
₄ ) ₄ [Fe (CN) ₆ ], K ₃ IrCl ₆ , (NH ₄ ) ₃ R
hCl ₆ , K ₄ Ru (CN) _{6 and the} like. The ligand of the coordination compound can be selected from halo, aquo, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo, and carbonyl. These may be used alone or in combination of two or more metal compounds.

The metal compound is preferably added by dissolving a suitable solvent such as water or methanol or acetone in a solvent.
In order to stabilize the solution, an aqueous solution of hydrogen halide (eg, HC
1, HBr, etc.) or alkali halides (eg KC
1, NaCl, KBr, NaBr, etc.). If necessary, an acid or alkali may be added. The metal compound may be added to the reaction vessel before the formation of the particles or may be added during the formation of the particles. It can also be added to a water-soluble silver salt (eg, AgNO ₃ ) or a water-soluble alkali halide (eg, NaCl, KBr, KI) and added continuously during silver halide grain formation. Further, a solution independent of the water-soluble silver salt and alkali halide may be prepared and added continuously at an appropriate time during grain formation. It is also preferable to combine various addition methods.

A method of adding a chalcogenide compound during preparation of an emulsion as described in US Pat. No. 3,772,031 is sometimes useful. In addition to S, Se, Te, cyanide, thiocyanate, selenocyanic acid, carbonate,
Phosphates and acetates may be present.

The silver halide grains of the present invention may be subjected to at least one of sulfur sensitization, selenium sensitization, gold sensitization, palladium sensitization or noble metal sensitization and reduction sensitization in any step of the production process of a silver halide emulsion. Can be applied. It is preferable to combine two or more sensitization methods. Various types of emulsions can be prepared depending on the step of chemical sensitization. There are a type in which a chemical sensitizing nucleus is embedded in the grain, a type in which the chemical sensitizing nucleus is embedded in a position shallow from the grain surface, and a type in which a chemical sensitizing nucleus is formed on the surface. In the emulsion of the present invention, the location of the chemical sensitization nucleus can be selected according to the purpose. Generally, the case where at least one type of chemical sensitization nucleus is formed near the surface is preferred.

One of the chemical sensitizations which can be preferably carried out in the present invention is a chalcogenide sensitization and a noble metal sensitization alone or in combination, and is described by TH James, The Photographic Process, Fourth Edition, Macmillan Company. Published, 1977
Year, (THJames, The Theory of the Photographic Proc
ess, 4th ed, Macmillan, 1977), using active gelatin, as described in pages 67-76, and by Research Disclosure, Vol.
Research Disclosure, 34, June 1975, 13452, U.S. Pat. Nos. 2,642,361, 3,297,446, 3,772,031, and 3; 857,711, 3,901,714, 4,266,018, and 3,904,415, and British Patent 1,31.
PAg 5-10, pH as described in US Pat.
Sulfur, selenium at 5-8 and a temperature of 30-80 ° C.
It can be tellurium, gold, platinum, palladium, iridium or a combination of a plurality of these sensitizers. In the noble metal sensitization, noble metal salts such as gold, platinum, palladium, and iridium can be used, and among them, gold sensitization, palladium sensitization, and a combination of both are preferable. In the case of gold sensitization, known compounds such as chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, and gold selenide can be used. The palladium compound means a divalent palladium salt or a tetravalent salt. Preferred palladium compounds are represented by R ₂ PdX ₆ or R ₂ PdX ₄ . Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom, and represents a chlorine, bromine or iodine atom.

Specifically, K_TwoPdCl_Four, (NH_Four)_Two 
PdCl₆, Na_TwoPdCl_Four, (NH_Four)_TwoPdC
l_Four, Li_TwoPdCl_Four, Na_TwoPdCl₆Or K_Two
PdBr _FourIs preferred. Gold compound and palladium compound
Is used in combination with thiocyanate or selenocyanate.
Preferably. Hypo and thiourine as sulfur sensitizers
Elemental compounds, rhodanine compounds and US Patent No. 3,8
Nos. 57,711, 4,266,018 and 4,
Using sulfur-containing compounds described in U.S. Pat.
Can be. In the presence of so-called chemical sensitization aids
You can also enhance your learning. Useful chemical sensitization aids include
Seinden, azapyridazine, azapyrimidine
Control fog during chemical sensitization and increase sensitivity
Compounds known to be used are used. Chemical sensitization
Examples of auxiliary modifiers are described in U.S. Pat. No. 2,131,038;
3,411,914, 3,554,757,
No. 58-126526 and the above-mentioned "Photograph" by Duffin
Emulsion Chemistry ", pp. 138-143.

The emulsion of the present invention is preferably used in combination with gold sensitization. The preferred amount of the gold sensitizer is 1 × 10 ^-4 to 1 × 10 ^-7 mol, more preferably 1 × 10 ^{-5 to} 5 × 10 ^-7 mol, per mol of silver halide. The preferred range of the palladium compound is from 1 × 10 ⁻³ to 5 × 10 ⁻⁷ . The preferred range of the thiocyan compound or selenocyan compound is from 5 × 10 ⁻² to 1 × 10 ⁻⁶ . The preferred amount of the sulfur sensitizer used for the silver halide grains of the present invention is 1 × 10 ^-4 to 1 × 10 ⁴ per mol of silver halide.
^-7 mol, more preferably 1 × 10 ^{−5 to} 5 × 1.
^0-7 mol.

Selenium sensitization is a preferred sensitization method for the emulsion of the present invention. In selenium sensitization, a known unstable selenium compound is used, and specifically, colloidal metal selenium, selenoureas (eg, N, N-dimethylselenourea, N, N-diethylselenourea, etc.), selenoketone And selenium compounds such as selenoamides can be used. It may be preferable to use selenium sensitization in combination with sulfur sensitization and / or noble metal sensitization.

During the grain formation of the silver halide emulsion of the present invention,
It is preferable to perform reduction sensitization after grain formation and before or during chemical sensitization, or after chemical sensitization. Here, reduction sensitization means a method of adding a reduction sensitizer to a silver halide emulsion, a method of growing in a pAg1 to 7 low pAg atmosphere called silver ripening or a method of ripening, and a method of high pH ripening called pH 8 to 11. Growth or ripening in a high pH atmosphere.
Also, two or more methods can be used in combination. The method of adding a reduction sensitizer is a preferable method because the level of reduction sensitization can be finely adjusted. As reduction sensitizers, stannous salts, ascorbic acid and its derivatives, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds, borane compounds and the like are known. For the reduction sensitization of the present invention, these known reduction sensitizers can be selected and used, and two or more compounds can be used in combination. Stannous chloride, thiourea dioxide, dimethylamine borane, ascorbic acid and derivatives thereof are preferred compounds as reduction sensitizers. Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount, but an appropriate range is from 10 ^-7 to 10 ^-3 mol per mol of silver halide. The reduction sensitizer is dissolved in water or a solvent such as alcohols, glycols, ketones, esters, and amides, and added during grain growth. Although it may be added to the reaction vessel in advance, it is preferable to add it at an appropriate time during grain growth. Further, a reduction sensitizer may be added in advance to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide, and silver halide grains may be precipitated using these aqueous solutions. It is also a preferred method to add the solution of the reduction sensitizer in several portions as the grains grow, or to add the solution continuously for a long time.

During the production process of the emulsion of the present invention, an acid for silver is used.
It is preferable to use an agent. The oxidizing agent for silver is
Has the effect of converting to silver ions by acting on metallic silver
Refers to a compound. Especially the formation process of silver halide grains and
Extremely small silver particles by-produced during chemical sensitization
Is a compound that can be converted into a silver ion. here
The silver ions generated in the above are silver halide, silver sulfide, selenium
It may form a silver salt that is hardly soluble in water such as silver chloride,
And the like, a silver salt easily soluble in water may be formed. Oxidation to silver
The agent may be inorganic or organic. inorganic
Ozone, hydrogen peroxide and its addition
Object (eg, NaBO)_Two・ H_TwoO_Two・ 3H _TwoO, 2Na
CO_Three・ 3H_TwoO_Two, Na_FourP_TwoO₇・ 2H_TwoO_Two, 2
Na_TwoSO _Four・ H_TwoO_Two・ 2H_TwoO), peroxyacid salt
(Eg K_TwoS_TwoO₈, K_TwoC_TwoO ₆, K_TwoP
_TwoO₈), Peroxy complex compounds (eg, K_Two[Ti
(O_Two) C_TwoO _Four] 3H_TwoO, 4K_TwoSO_Four・ Ti
(O_Two) OH ・ SO_Four・ 2H_TwoO, Na_Three[VO (O_Two)
(C_TwoH_Four)_Two・ 6H_TwoO), permanganate (eg,
KMnO_Four ), Chromates (eg, K_TwoCr_TwoO₇)
Which oxyacid salt, halogen element such as iodine or bromine, perhalo
Genoates (eg potassium periodate) of high-valent metals
Salts (eg, potassium hexacyanoferrate) and
Osulfonates and the like. Also, as an organic oxidant
Quinones such as p-quinone, peracetic acid and perbenzoic acid
Compounds that release active halogens, such as organic peroxides
(For example, N-bromosuccinimide, chloramine T,
Lolamin B) is mentioned by way of example.

Preferred oxidizing agents of the present invention are inorganic oxidizing agents such as ozone, hydrogen peroxide and its adducts, halogen elements, thiosulfonates, and organic oxidizing agents such as quinones.
It is a preferred embodiment to use the above-described reduction sensitization and an oxidizing agent for silver in combination. The method can be selected from a method of performing reduction sensitization after using an oxidizing agent, a method reverse thereto, or a method of coexisting the two simultaneously. These methods can be selectively used in both the grain formation step and the chemical sensitization step.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. . That is, thiazoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes such as tria Zaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,
Many compounds known as antifoggants or stabilizers, such as 3,3a, 7) tetraazaindenes, pentaazaindenes and the like can be added. For example, U.S. Patent Nos. 3,954,474 and 3,982,9
No. 47 and JP-B No. 52-28660 can be used. Japanese Patent Application No. Sho 6
There is a compound described in 2-47225. Antifoggants and stabilizers are used at various times before, during and after particle formation, during the water washing step, during dispersion after water washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added according to the purpose. In addition to exhibiting the original antifogging and stabilizing effects by adding during emulsion preparation, it controls the crystal wall of the grains, reduces the grain size, reduces the solubility of the grains, controls the chemical sensitization, It can be used for various purposes such as controlling the arrangement of dyes.

The light-sensitive material of the present invention can be provided with a multilayer effect donor layer containing predetermined spectrally sensitized silver halide grains separately provided in order to provide the above-mentioned multilayer effect on the red-sensitive layer in a specific wavelength range. Is preferably provided. In order to realize the spectral sensitivity of the present invention, the multilayer sensitivity wavelength of the multilayer effect donor layer is set to 510 nm to 540 nm.

When S _-B (λ) is obtained in the same manner as in the above-described procedure for obtaining S _-R (λ), the overlay effect given by the donor layer needs to satisfy the following expression (2). . Equation (2)

[0064]

(Equation 2)

As a material giving the layering effect, a compound which reacts with an oxidation product of a developing agent obtained by development to release a development inhibitor or a precursor thereof is used. For example, D
An IR (development inhibitor releasing type) coupler, a DIR-hydroquinone, a coupler releasing DIR-hydroquinone or a precursor thereof, and the like are used. In the case of a development inhibitor having a large diffusivity, the development suppression effect can be obtained regardless of where the donor layer is located in the multilayer structure, but the development suppression effect in an unintended direction also occurs, so this is corrected. Color the donor layer (e.g., to the same color as the layer affected by the undesired development inhibitor).
Is preferred. In order to obtain the spectral sensitivity of the present invention, magenta color development is preferred.

The silver halide grains used in the layer giving the layering effect to the red-sensitive layer may be a mixture of two or more emulsions having different grain sizes in order to enlarge the exposure latitude.

The donor layer which gives the layer effect to the red-sensitive layer may be provided at any position on the support, but is provided closer to the support than the blue-sensitive layer and farther from the support than the red-sensitive layer. Is preferred. Further, it is more preferable that it is closer to the support than the yellow filter layer.

It is more preferable that the support is closer to the support than the green-sensitive layer and farther from the support than the red-sensitive layer, and it is most preferable that the green-sensitive layer be located adjacent to the support closer to the support. In this case, “adjacent” means that no intermediate layer or the like is interposed.

The layer giving the multilayer effect to the red-sensitive layer may consist of a plurality of layers. In that case, their positions may be adjacent to or separated from each other.

The light-sensitive material of the present invention may have at least one light-sensitive layer provided on a support. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. It is. The light-sensitive layer is a unit light-sensitive layer having color sensitivity to any of blue light, green light, and red light.In a multilayer silver halide color photographic light-sensitive material, the arrangement of the unit light-sensitive layers is generally A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are provided in this order from the support side. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity. A non-light-sensitive layer may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer. These may contain a coupler, a DIR compound, a color mixing inhibitor and the like described below. As described in DE 1,121,470 or GB 923,045, a plurality of silver halide emulsion layers constituting each unit light-sensitive layer are formed by sequentially exposing two layers of a high-speed emulsion layer and a low-speed emulsion layer toward a support. It is preferable to arrange them so that the degree is low. Also, JP-A-57-112751, 62-200350, 62-2
As described in JP-A Nos. 06541 and 62-206543, a low-speed emulsion layer may be provided on the side farther from the support, and a high-speed emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / High sensitivity blue photosensitive layer (BH) / High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (GL) / High sensitivity red photosensitive layer (RH) / In the order of the low-sensitivity red photosensitive layer (RL), or in the order of BH / BL / GL / GH / RH / RL, or BH / BL / GH /
They can be installed in the order of GL / RL / RH.

As described in JP-B-55-34932, the blue-sensitive layer / GH /
They can be arranged in the order of RH / GL / RL. Also, JP-A-56
As described in -25738 and 62-63936, the layers may be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

As described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is a layer having a higher sensitivity than the middle layer. An example is an arrangement in which a silver halide emulsion layer having a low sensitivity is arranged and three layers having different sensitivities are sequentially reduced in sensitivity toward a support. Even when such a three-layer structure having different photosensitivity is used,
As described in JP-A-59-202464, in the same color-sensitive layer, the layers may be arranged in the order of medium-speed emulsion layer / high-speed emulsion layer / low-speed emulsion layer from the side away from the support.

In addition, a high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or a low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer may be arranged in this order.

In the case of four or more layers, the arrangement may be changed as described above.

In order to improve color reproducibility, US Pat. No. 4,663,27
1, 4,705,744, 4,707,436, JP-A-62-160448,
It is preferable to arrange a donor layer (CL) having a multilayer effect having a different spectral sensitivity distribution from that of the main photosensitive layer such as BL, GL, and RL described in the specification of JP-A-63-89850, adjacent to or close to the main photosensitive layer. .

Preferred silver halides for use in the present invention are silver iodobromide, silver iodochloride, or silver iodochlorobromide containing up to about 30 mole percent silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide.

The silver halide grains in the photographic emulsion include those having regular crystals such as cubic, octahedral and tetradecahedral, those having irregular crystal forms such as spherical and plate-like,
It may have a crystal defect such as a twin plane or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 μm or less, or large grains having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion usable in the present invention is, for example, Research Disclosure (hereinafter referred to as RD).
No. 17643 (December 1978), pages 22 to 23, "I. Emulsion preparation and types", and No. 18716 (November 1979), page 648, No. 307105 (1989
Nov., pp. 863-865, and Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (P. Glafkides, Chimie)
et Phisique Photographiques, Paul Montel, 1967),
Duffin, Photographic Emulsion Chemistry, Focal Press (GF Duffin, Photographic Emulsion Chemistry, Foc)
al Press, 1966), "Production and Coating of Photographic Emulsions", by Zelikman et al., Published by Focal Press (VL Zelikman, et a
l., Making and Coating Photographic Emulsion, Foca
l Press, 164).

US Pat. Nos. 3,574,628 and 3,655,394 and GB 1,4
Monodisperse emulsions described in 13,748 are also preferred.

Tabular grains having an aspect ratio of about 3 or more can also be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineering (Gutoff, Photographic Science and E).
ngineering), Vol. 14, pp. 248-257 (1970); US 4,43.
It can be easily prepared by the methods described in 4,226, 4,414,310, 4,433,048, 4,439,520 and GB 2,112,157.

The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, or may have a layered structure. Silver halides having different compositions may be joined by epitaxial joining, or may be joined to a compound other than silver halide, such as, for example, silver rhodanate or lead oxide. Also, a mixture of particles of various crystal forms may be used.

The above emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which the latent image is formed inside the grains, or a type having a latent image on both the surface and the inside. Type emulsion. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used.
-133542. The thickness of the shell of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, and 5 to 40 nm.
-20 nm is particularly preferred.

The silver halide emulsion usually used is one subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such a process are RD No. 17643 and RD No. 187.
16 and No. 307105, and the relevant portions are summarized in the table below.

The light-sensitive material of the present invention comprises a light-sensitive silver halide emulsion having a grain size, a grain size distribution, a halogen composition,
Two or more emulsions differing in at least one characteristic of grain shape and sensitivity can be mixed and used in the same layer.

Silver halide grains having a fogged surface described in US Pat. No. 4,082,553, US Pat. No. 4,626,498, JP-A-59-214852.
It is preferable to apply the silver halide grains and colloidal silver having the inside of the grains described in (1) to the light-sensitive silver halide emulsion layer and / or the substantially light-insensitive hydrophilic colloid layer. The term "silver halide particles having a fogged interior or surface" refers to silver halide grains that can be uniformly (non-imagewise) developed regardless of unexposed portions and exposed portions of the photosensitive material. , Its preparation method is described in US Pat.
It is described in 214852. The silver halide forming the internal nucleus of the core / shell type silver halide grain having the inside of the grain fogged may have a different halogen composition. As the silver halide having the inside or surface of the grain fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The average grain size of these fogged silver halide grains is 0.01 to 0.75 μm, particularly 0.05
~ 0.6 μm is preferred. The grains may be regular grains or polydisperse emulsions, but may be monodisperse (at least 95% of the weight or the number of silver halide grains has a grain size within ± 40% of the average grain size). Is preferable.

In the present invention, it is preferable to use non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the developing process, and are preferably not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide as needed. Preferably, it contains 0.5 to 10 mol% of silver iodide. Fine grain silver halide, average grain size (average value of projected area equivalent circle diameter)
Is preferably 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm.

The fine silver halide grains can be prepared in the same manner as in the case of ordinary light-sensitive silver halide. The surface of the silver halide grains does not need to be optically sensitized, and no spectral sensitization is required. However, before adding this to the coating solution, a triazole-based, azaindene-based,
It is preferable to add a known stabilizer such as a benzothiazolium-based or mercapto-based compound or a zinc compound. Colloidal silver can be contained in the layer containing fine silver halide grains.

The amount of silver applied to the light-sensitive material of the present invention was 6.0 g / m ^2.
Or less, and most preferably 4.5 g / m ² or less.

The photographic additives which can be used in the present invention are also described in RD, and the relevant portions are shown in the following table.

Types of Additives RD17643 RD18716 RD307105 Chemical sensitizer page 23, page 648, right column, page 866 2. 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column, pages 866 to 868 Super sensitizer, page 649, right column Brightener page 24 page 647 page right column page 868 5. 5. Light absorbers, pages 25 to 26, page 649, right column, page 873 Filters, page 650, left column, dyes, ultraviolet absorbers Binder page 26 page 651 left column pages 873 to 874 7. 7. Plasticizer, page 27 page 650, right column, page 876 Lubricant Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876 Surfactant 9. Static 27 pages 650 pages right column 876-877 Inhibitors 10. Matting Agents, pages 878 to 879 Various dye-forming couplers can be used in the light-sensitive material of the present invention, but the following couplers are particularly preferred.

Yellow coupler: Formula (I) of EP 502,424A,
Coupler represented by (II); Formulas (1) and (2) of EP 513,496A
(Especially Y-28 on page 18); EP 568,037A
A coupler of the formula (I) of claim 1 of US Pat.
6,576, column 45, line 45 to 55, couplers represented by the general formula (I); JP-A-4-74425, paragraph 0008, couplers represented by the general formula (I); EP 498,381 A1, page 40, claim 1 Couplers (especially D-35 on page 18); EP 447,969A1-4
Couplers represented by the formula (Y) on the page (especially Y-1 (page 17), Y-
54 (p. 41)); US Pat. No. 4,476,219, column 7, lines 36-58, formula (I
Couplers represented by I) to (IV) (especially II-17, 19 (column
17), II-24 (column 19)).

Magenta coupler; JP-A-3-39737 (L-57 (1
L-68 (lower right of page 12), L-77 (lower right of page 13); EP 456,
257 (A-4) -63 (p. 134), (A-4) -73, -75 (p. 139);
EP486,965 M-4, -6 (page 26), M-7 (page 27); EP 571,959A
M-45 (page 19); JP-A-5-204106 (M-1) (page 6); JP-A-4-204106
M-22 of paragraph 0237 of 362631.

Cyan coupler: CX-1, described in JP-A-4-04843
3,4,5,11,12,14,15 (pages 14 to 16); JP-A 4-43345 C-
7,10 (p. 35), 34, 35 (p. 37), (I-1), (I-17) (pp. 42-43);
A coupler represented by the general formula (Ia) or (Ib) according to claim 1 of JP-A-6-67385. Polymer coupler: P-1, P-5 (p. 11) of JP-A-2-44345.

Examples of couplers in which the coloring dyes have an appropriate diffusibility include US Pat. No. 4,366,237, GB 2,125,570, EP 96,873B,
Those described in DE 3,234,533 are preferred. Couplers for correcting unnecessary absorption of color-forming dyes are yellow colored cyan couplers represented by the formulas (CI), (CII), (CIII) and (CIV) described on page 5 of EP 456,257A1 (especially on page 84). YC-86), the EP
Yellow colored magenta coupler ExM-7 (202
), EX-1 (page 249), EX-7 (page 251), US 4,833,069
Magenta colored cyan coupler CC-9 (column
8), CC-13 (column 10), (2) of US 4,837,136 (column 8),
Colorless masking couplers of formula (A) in claim 1 of WO 92/11575 (especially the exemplified compounds on pages 36 to 45) are preferred.

Examples of the compounds (including couplers) which react with oxidized developing agents to release photographically useful compound residues include the following. Development inhibitor releasing compound:
Compounds of the formulas (I), (II), (III) and (IV) described on page 11 of EP 378,236A1 (especially T-101 (page 30), T-104 (page 31), T-11
3 (page 36), T-131 (page 45), T-144 (page 51), T-158 (page 58)), EP43
Compounds represented by the formula (I) described on page 7 of 6,938A2 (particularly D-49 (page 51)), compounds represented by the formula (1) of EP 568,037A (particularly (23) (page 11)), Compounds of the formulas (I), (II) and (III) described on pages 5 to 6 of EP 440,195 A2 (especially on page 29)
I- (1)); Bleaching accelerator releasing compounds: compounds represented by the formulas (I) and (I ′) on page 5 of EP 310,125A2 (especially (60) and (6) on page 1)
1)) and the compound represented by formula (I) of claim 1 of JP-A-6-59411 (especially (7) (page 7); ligand releasing compound: US 4,5)
A compound represented by LIG-X described in claim 1 of 55,478 (especially, a compound on lines 21 to 41 of column 12); a leuco dye releasing compound: compounds 1 to 6 of columns 3 to 8 of US 4,749,641;
Fluorescent dye releasing compound: Claim 4, COUP of US 4,774,181
-DYE (especially compound 1 in columns 7 to 10)
11); Development accelerator or fogging agent releasing compound: US 4,6
Compounds represented by the formulas (1), (2) and (3) in column 3 of 56,123 (especially (I-22) in column 25) and 75 in EP 450,637A2
ExZK-2 on page 36-38; Compound which releases a group which becomes a dye only after leaving: a compound represented by formula (I) in claim 1 of US Pat. No. 4,857,447 (especially, Y-1 to Y in columns 25 to 36) -19).

As the additives other than the coupler, the following are preferable.

Dispersion medium for oil-soluble organic compound: JP-A-62-215
272 P-3,5,16,19,25,30,42,49,54,55,66,81,85,86,93
Latex for impregnation of oil-soluble organic compound: Latex described in US Pat. No. 4,199,363; Oxidized developing agent scavenger: Compound represented by formula (I) in column 2, lines 54 to 62 of US 4,978,606 Especially I-, (1), (2), (6), (12)
(Columns 4-5), formulas in rows 5-10 of column 2 of US 4,923,787 (especially compound 1 (column 3); stain inhibitor: EP
Formulas (I) to (III) on page 4, lines 30 to 33 of 298321A, especially I-47,7
2, III-1, 27 (pages 24 to 48); Anti-fading agent: A- of EP 298321A
6,7,20,21,23,24,25,26,30,37,40,42,48,63,90,92,94,1
64 (pp. 69-118), II-5 of columns 25-38 of US 5,122,444
III-11, especially III-10, I-1 on pages 8 to 12 of EP 471347A.
III-4, especially II-2, A-1 in columns 32-40 of US 5,139,931
To 48, especially A-39, 42; a material for reducing the amount of the color-enhancing agent or the color-mixing inhibitor to be used: EP 411324A, pages 1 to 24, I-1 to
II-15, especially I-46; Formalin Scavenger: EP 477
SCV-1 to 28 on pages 24 to 29 of 932A, especially SCV-8; hardener: H-1,4,6,8,14 on page 17 of JP-A-1-214845, columns 13 to 23 of US 4,618,573 A compound represented by the formula (VII) to (XII)
Compounds (H-1 to 76) represented by the formula (6) at the lower right of page 8 of JP-A-2-214852, particularly compounds described in claim 1 of H-14, US 3,325,287; Development inhibitor precursor : JP 62
-168139 P-24,37,39 (pages 6-7); compounds described in claim 1 of US 5,019,492, especially 28,29 of column 7; Preservatives, fungicides: columns 3-15 of US 4,923,790 I-1 to III-
43, especially II-1,9,10,18, III-25; Stabilizer, antifoggant: I-1 to (14) of columns 6 to 16 of US 4,923,793, especially I-
1,60, (2), (13), US Pat. No. 4,952,483, Compounds 1 to 65 in columns 25 to 32, especially 36: Chemical sensitizer: triphenylphosphine selenide, compound 50 in JP-A-5-40324; dye: Kaiping
A-1 to b-20 on pages 15 to 18 of 3-156450, especially a-1,12,18,27,3
5, 36, b-5, V-1 to 23 on pages 27 to 29, especially V-1, EP 445627A
FI-1 to F-II-43 on pages 33 to 55, especially FI-11, F-II-8,
EP 457153A III-1 to 36 on pages 17 to 28, especially III-1,3, WO
88/04794 microcrystal dispersion of 8-26 Dye-1 to 124, EP 3
Compounds 1 to 22 on page 6 to 11 of 19999A, especially compound 1, EP 51
Compounds D-1 to 87 represented by Formulas (1) to (3) of 9306A
(Pages 3 to 28), US Pat. No. 4,268,622, compound 1 represented by formula (I)
To 22 (columns 3 to 10), compounds (1) to (31) (columns 2 to 9) represented by the formula (I) in US Pat. No. 4,923,788; UV absorbers: Formula (1) of JP-A-46-3335. Compounds represented by (18b) to (18r),
101 to 427 (pages 6 to 9), compounds (3) to (66) (pages 10 to 44) represented by formula (I) and compounds HBT-1 to 10 (14) represented by formula (III) in EP 520938A. P.), Compounds (1) to (31) represented by the formula (1) in EP 521823A (columns 2 to 9).

In the present invention, calcium may be contained in the following amount in order to improve the storage stability. 7. The content of calcium added to at least one of the silver halide photosensitive layer or the non-photosensitive layer constituting the photosensitive material is 4.0 × 10 ⁻³ g or more based on 1 g of gelatin in the layer to be added.
It suffices if it is 0 × 10 ^-2 g or less. It is preferably 6.0 × 10 ⁻³ g or more and 4.0 × 10 ⁻² g or less, and 12.0 g or less.
It is more preferable that the amount be from × 10 ⁻³ g to 3.0 × 10 ⁻² g.

Further, the total content of calcium contained in the light-sensitive material is 4.0 × 10 ⁻³ g or more and 8.0 × 10 ⁻² g or less per g of gelatin with respect to the total gelatin contained in the light-sensitive material. Is preferred, and 6 × 10 ⁻³ g or more and 4.0 × 1
More preferably, it is 0 ^-2 g or less.

If the calcium content is less than this, the effect on the preservability is small, and if it is more than this, unfavorable effects such as soft gradation are caused, which is not preferable.

Here, the calcium content is expressed in terms of the weight converted to calcium atoms for all compounds containing calcium such as calcium ions and calcium salts.
The calcium can be determined by, for example, ICP emission spectroscopy.

The calcium-added layer may be a photosensitive layer, a non-photosensitive layer, or both layers, but is preferably used for the photosensitive layer. Note that calcium in the support is not included.

As the addition method, any method can be used. For example, it can be added at the time of preparing a coating solution as an aqueous solution of calcium nitrate or the like, and can be added at the time of preparing a silver halide emulsion. When it is added during the preparation of the silver halide emulsion, it can be added at any position from before the formation of the grains to the end of the preparation of the silver halide, but is preferably added after the addition of the dye.

The present invention can be applied to various color photographic materials such as color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. In addition, Tokuhei 2-32615, actual fairness
It is suitable for a film unit with a lens described in 3-39784.

Suitable supports that can be used in the present invention include, for example, the aforementioned RD. No. 17643, page 28, RD. No. 18716, page 647 right column to page 648 left column, and RD. No. 307105, page 879. It is described in.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, further preferably 18 μm or less, and more preferably 16 μm or less. Particularly preferred. Further, the film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. T _1/2 is the time required for the film thickness to reach 1/2 when the saturated film thickness is 90% of the maximum swollen film thickness reached when the color developing solution is processed at 30 ° C. for 3 minutes and 15 seconds. Is defined.
The film thickness means a film thickness measured under humidity control at 25 ° C. and a relative humidity of 55% (2 days), and T _1/2 is a value obtained by A. Green et al. In Photographic Science and Engineering. (Photogr. Sci. Eng.), Vol. 19, pp. 2,124-129, which can be used for measurement. T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. The swelling ratio is preferably from 150 to 400%. The swelling ratio can be calculated from the maximum swelling film thickness under the conditions described above by the following formula: (maximum swelling film thickness-film thickness) / film thickness.

In the light-sensitive material of the present invention, a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm is preferably provided on the side opposite to the side having the emulsion layer.
In this back layer, the above-mentioned light absorber, filter dye,
It is preferable to contain an ultraviolet absorber, an antistatic agent, a hardener, a binder, a plasticizer, a lubricant, a coating aid, and a surfactant. The swelling ratio of this back layer is 150 ~ 500
% Is preferred.

The light-sensitive material of the present invention is prepared according to the above-mentioned RD.
No. 18716, No. 18716, 651 left column to right column, and No. 18716
No. 307105, pages 880 to 881 can be used for development.

Next, the processing solution for a color negative film used in the present invention will be described.

The compounds described in JP-A-4-21739, page 9, upper right column, line 1 to page 11, lower left column, line 4 can be used in the color developer used in the present invention. As a color developing agent for particularly rapid processing, 2-methyl-4-
[N-ethyl-N- (2-hydroxyethyl) amino]
Aniline, 2-methyl-4- [N-ethyl-N- (3-
Hydroxypropyl) amino] aniline, 2-methyl-
4- [N-ethyl-N- (4-hydroxybutyl) amino] aniline is preferred.

These color developing agents are used in an amount of preferably 0.01 to 0.08 mol, more preferably 0.015 to 0.06 mol, and further preferably 0.02 to 0.05 mol, per liter of the color developing solution. The replenisher of the color developing solution preferably contains a color developing agent having a concentration of 1.1 to 3 times, more preferably 1.3 to 2.5 times the concentration.

As a preservative for the color developing solution, hydroxylamine can be used in a wide range. However, when higher preservation is required, substitution with an alkyl group, a hydroxyalkyl group, a sulfoalkyl group, a carboxyalkyl group, or the like is required. A hydroxylamine derivative having a group is preferable, and specifically, N, N-di (sulfoethyl) hydroxylamine, monomethylhydroxylamine, dimethylhydroxylamine, monoethylhydroxylamine, diethylhydroxylamine, N, N-di (carboxyethyl) Hydroxylamines are preferred. Among the above, N, N-di (sulfoethyl) hydroxylamine is particularly preferred. These may be used in combination with hydroxylamine, but it is preferable to use one or more of them instead of hydroxylamine.

The preservative is preferably used in the range of 0.02 to 0.2 mol per liter, particularly preferably 0.03 to 0.15 mol, more preferably 0.04 to 0.1 mol. As in the case of the color developing agent, the replenisher preferably contains a preservative at a concentration of 1.1 to 3 times the concentration of the mother liquor (processing tank solution).

In the color developing solution, a sulfite is used as an anti-tarring agent for the oxide of the color developing agent. The sulfite is preferably used in the range of 0.01 to 0.05 mol per liter, particularly preferably in the range of 0.02 to 0.04 mol.
In the replenisher, it is preferable to use the replenisher at a concentration 1.1 to 3 times the above.

The pH of the color developing solution is preferably in the range of 9.8 to 11.0, particularly preferably 10.0 to 10.5, and the replenisher is set to a higher value in the range of 0.1 to 1.0 from these values. Preferably. In order to stably maintain such a pH, a known buffer such as carbonate, phosphate, sulfosalicylate, and borate is used.

The replenishment amount of the color developing solution is preferably from 80 to 1300 ml per m ² of the light-sensitive material, but is preferably smaller from the viewpoint of reducing environmental pollution load.
80-600 ml, more preferably 80-400 ml.

The bromide ion concentration in the color developing solution is usually 0.01 to 0.06 mol per liter. However, fog is suppressed while maintaining sensitivity, discrimination is improved, and graininess is improved. For this purpose, it is preferably set to 0.015 to 0.03 mol per liter. When the bromide ion concentration is set in such a range, the replenisher may contain bromide ions calculated by the following formula. However, when C becomes negative, it is preferred that the replenisher does not contain bromide ions.

C = A−W / V C: bromide ion concentration in the color developing replenisher (mol / liter) A: target bromide ion concentration in the color developing solution (mol / liter) W: 1 m ² exposure When the material is color-developed, the amount of bromide ion eluted from the light-sensitive material into the color-developing solution (mol) V: The replenishment amount of the color-developing replenisher for 1 m ² of the light-sensitive material (liter) In addition, when a high bromide ion concentration is set, 1-phenyl-3-pyrazolidone or 1-phenyl-2-methyl-2 may be used as a method for increasing sensitivity.
It is also preferable to use a development accelerator such as pyrazolidones represented by -hydroxymethyl-3-pyrazolidone and thioether compounds represented by 3,6-dithia-1,8-octanediol.

The compounds and processing conditions described in JP-A-4-125558, page 4, lower left column, line 16 to page 7, lower left column, line 6 can be applied to the processing solution having bleaching ability in the present invention. .

The bleaching agent preferably has an oxidation-reduction potential of 150 mV or more, and specific examples thereof are described in JP-A-5-72694 and JP-A-5-72694.
Preferred are those described in 5-173312, and in particular, 1,3-diaminopropanetetraacetic acid, and specific example 1 on page 7 of JP-A-5-73312.
Are preferred.

Further, in order to improve the biodegradability of the bleaching agent, JP-A-4-218845, JP-A-4-268552, EP588,289, and 591,
934, a compound ferric complex salt described in JP-A-6-208213 is preferably used as a bleaching agent. The concentration of these bleaching agents is preferably 0.05 to 0.3 mol per liter of a liquid having a bleaching ability.
It is preferable to design from 1 mol to 0.15 mol. If the bleaching solution is bleaching solution,
It is preferable to contain 0.2 mol to 1 mol of bromide, particularly preferably 0.3 to 0.8 mol.

The replenisher of the solution having the bleaching ability basically contains the concentration of each component calculated by the following formula. Thereby, the concentration in the mother liquor can be kept constant.

C _R = C _T × (V ₁ + V ₂ ) / V ₁ + C _P C _R : concentration of component in replenisher C _T : concentration of component in mother liquor (treatment tank solution) C _P : during treatment Concentration of consumed components V ₁ : Replenishment amount of replenisher having bleaching ability for photosensitive material of 1 m ² (milliliter) V ₂ : Amount brought in from prebath by photosensitive material of 1 m ² (milliliter) Preferably contains a pH buffer, particularly preferably a dicarboxylic acid having a low odor, such as succinic acid, maleic acid, malonic acid, glutaric acid, and adipic acid. Also, JP-A-53-95630, RDN
It is also preferable to use known bleaching accelerators described in O. 17129, US 3,893,858.

The bleaching solution contains 50 to 1000 per m ² of the light-sensitive material.
It is preferable to replenish milliliter of bleach replenisher,
Particularly, it is preferable to replenish 80 to 500 ml, more preferably 100 to 300 ml. Further, it is preferable to perform aeration on the bleaching solution.

The processing liquid having a fixing ability is described in
The compounds and processing conditions described on page 7, lower left column, line 10 to page 8, lower right column, line 19 of 4-125558 can be applied.

In particular, in order to improve the fixing speed and the preservability, a processing solution having fixing ability by using the compounds represented by formulas (I) and (II) of JP-A-6-301169, alone or in combination. Is preferably contained. In addition to the use of p-toluenesulfinic acid salts, the use of sulfinic acids described in JP-A-1-224762 is also preferable from the viewpoint of improving the preservation.

It is preferable to use ammonium as a cation in the solution having the bleaching ability or the solution having the fixing ability from the viewpoint of improving the desilvering property. However, from the viewpoint of reducing environmental pollution, ammonium is reduced or reduced to zero. Is more preferred.

In the bleaching, bleach-fixing and fixing steps, it is particularly preferable to perform jet stirring described in JP-A-1-309590.

The replenishment rate of the replenisher in the bleach-fixing or fixing step is from 100 to 1000 ml, preferably from 150 to 700 ml, and particularly preferably from 200 to 600 ml, per m ² of the light-sensitive material.

In the bleach-fixing and fixing steps, it is preferable to install various silver recovery devices in-line or off-line to recover silver. By installing in-line, the processing can be carried out with a reduced silver concentration in the solution, so that the replenishment amount can be reduced. It is also preferable to recover silver off-line and reuse the remaining liquid as a replenisher.

The bleach-fixing step and the fixing step can be constituted by a plurality of processing tanks, and it is preferable that each tank is cascaded to provide a multistage countercurrent system. From the balance with the size of the developing machine, a two-tank cascade configuration is generally effective, and the ratio of the processing time in the former tank and the latter tank is preferably in the range of 0.5: 1 to 1: 0.5. In particular, the range of 0.8: 1 to 1: 0.8 is preferable.

The bleach-fixing solution and the fixing solution preferably contain a free chelating agent which is not in the form of a metal complex from the viewpoint of improving the preservability. These chelating agents are described in connection with the bleaching solution. Preferably, a biodegradable chelating agent is used.

Regarding the washing and stabilizing steps, the contents described in the above-mentioned JP-A-4-125558, page 12, lower right column, line 6 to page 13, right lower column, line 16 can be preferably applied. Especially,
EP 504,609 instead of formaldehyde
Azolylmethylamines described in 519,190 and JP-A-4-36
From the viewpoint of preserving the working environment, it is preferable to use the N-methylolazoles described in 2943, or to dimerize the magenta coupler to obtain a surfactant-free liquid containing no image stabilizer such as formaldehyde. .

In order to reduce the adhesion of dust to the magnetic recording layer applied to the light-sensitive material, a stabilizer described in JP-A-6-289559 can be preferably used.

The amount of washing and replenishment of the stabilizing solution can be adjusted according to the photosensitive material 1
m is preferably from ² per 80 to 1,000 ml, in particular 100
~ 500 ml, and more preferably 150-300 ml, is a preferable range in terms of both securing a washing or stabilizing function and reducing waste liquid for environmental protection. In the treatment carried out with such a replenishing amount, a known method such as thiabendazole, 1,2-benzisothiazolin-3-one and 5-chloro-2-methylisothiazolin-3-one is used to prevent the growth of bacteria and fungi. It is preferable to use water deionized with an antifungal agent, an antibiotic such as gentamicin, or an ion exchange resin. It is more effective to use a combination of deionized water and a bactericide or antibiotic.

Further, the liquid in the washing or stabilizing liquid tank is
JP-A-3-46652, JP-A-3-53246, JP-A-355542, JP-A-3-12144
8, it is also preferable to reduce the replenishment amount by performing the reverse osmosis membrane treatment according to 3-126030, the reverse osmosis membrane in this case,
Preferably, it is a low pressure reverse osmosis membrane.

In the process of the present invention, it is particularly preferable to carry out the correction of the evaporation of the processing solution disclosed in Hatsumei Kyokai Technical Report No. 94-4992. In particular, a method of performing correction using temperature and humidity information of a developing machine installation environment based on (Equation 1) on page 2 is preferable. The water used for evaporation correction is preferably collected from a replenishment tank for washing,
In that case, it is preferable to use deionized water as the washing replenishing water.

As the treating agent used in the present invention, those described in the above-mentioned published technical report from page 3, right column, line 15 to page 4, left column, line 32 are preferable. In addition, as a developing machine used for this,
The film processor described on page 3, right column, lines 22 to 28 is preferred.

Specific examples of preferred processing agents, automatic developing machines, and evaporation correction methods for carrying out the present invention are described in the above-mentioned published technical report, from page 5, right column, line 11 to page 7, right column, last line. Have been.

The supply form of the treating agent used in the present invention is as follows.
It may be in any form, such as a liquid preparation in the form of a liquid used or a concentrated form, or granules, powders, tablets, pastes, and emulsions. As an example of such a treating agent, JP-A-63-1
7453 discloses a liquid agent contained in a container having low oxygen permeability,
19655, 4-230748, vacuum-packed powders or granules, 4-221951, granules containing a water-soluble polymer,
JP-A-51-61837 and JP-A-6-102628 describe tablets and JP-A-57-5
Discloses a paste-like treating agent, which can be preferably used, but from the viewpoint of simplicity at the time of use,
It is preferable to use a liquid that has been prepared in advance in a concentration for use.

The containers for storing these treating agents are made of polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, nylon or the like, alone or as a composite material. These are selected according to the required level of oxygen permeability. For an easily oxidizable liquid such as a color developing solution, a material having low oxygen permeability is preferable, and specifically, a polyethylene terephthalate or a composite material of polyethylene and nylon is preferable. These materials are used in containers having a thickness of 500 to 1500 μm, and preferably have an oxygen permeability of 20 ml / m ² · 24 hrs · atm or less.

Next, a processing solution for a color reversal film that can be used in the present invention will be described. Regarding the processing for the color reversal film, see page 1, line 5 to page 10, line 5, and page 15, line 8 to page 24, 2 of the publicly known technique No. 6 (April 1, 1991) issued by Aztec Co., Ltd. Each row is described in detail, and any of the contents can be preferably applied.

In processing a color reversal film, an image stabilizer is contained in a conditioning bath or a final bath. Such image stabilizers include, in addition to formalin, sodium formaldehyde sodium bisulfite and N-methylolazole, and from the viewpoint of working environment, sodium formaldehyde sodium bisulfite or N-methylolazole is preferable, and N-methylol is preferred. As the azoles, N-methyloltriazole is particularly preferred. Further, the contents relating to the color developing solution, bleaching solution, fixing solution, washing water and the like described in the processing of the color negative film can be preferably applied to the processing of the color reversal film.

A preferred color reversal film treating agent containing the above-mentioned content is E-6 manufactured by Eastman Kodak Company.
Examples of the treating agent include CR-56 treating agent manufactured by Fuji Photo Film Co., Ltd.

Next, the magnetic recording layer that can be used in the present invention will be described.

The magnetic recording layer is obtained by coating an aqueous or organic solvent-based coating solution in which magnetic particles are dispersed in a binder on a support.

The magnetic particles used in the present invention are γFe_TwoO
_Three Such as ferromagnetic iron oxide, Co-coated γFe _TwoO_Three , Co deposited magne
Tight, Co-containing magnetite, ferromagnetic chromium dioxide,
Ferromagnetic metal, ferromagnetic alloy, hexagonal Ba ferrite, Sr
Use ferrite, Pb ferrite, Ca ferrite, etc.
Wear. Co deposited γFe_TwoO_Three Preferred is Co-coated ferromagnetic iron oxide such as
New Needle shape, rice grain shape, spherical shape, cubic shape, plate
The shape may be any. S for specific surface area_BETAt 20m^Two / g or less
Upper is preferred, 30m^Two / g or more is particularly preferred.

The saturation magnetization (σs) of the ferromagnetic material is preferably
3.0 × 10 ⁴ to 3.0 × 10 ⁵ A / m, particularly preferably 4.0
× 10 ^{4 to} 2.5 × 10 ⁵ A / m. The ferromagnetic particles may be subjected to a surface treatment with silica and / or alumina or an organic material. Further, the surface of the magnetic particles may be treated with a silane coupling agent or a titanium coupling agent as described in JP-A-6-161032. Also JP 4-25
Magnetic particles having an inorganic or organic material coated on the surface described in JP-A Nos. 9911 and 5-81652 can also be used.

The binder used for the magnetic particles may be a thermoplastic resin, a thermosetting resin, a radiation-curable resin, a reactive resin, an acid, an alkali or a biodegradable polymer, a natural material described in JP-A-4-219569. Combinations (cellulose derivatives, sugar derivatives, etc.) and mixtures thereof can be used. The above resin has a Tg of -40 ° C to 300 ° C and a weight average molecular weight of 2,000 to 1,000,000. Examples thereof include vinyl copolymers, cellulose derivatives such as cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, and cellulose tripropionate, acrylic resins, and polyvinyl acetal resins, and gelatin is also preferable. Particularly, cellulose di (tri) acetate is preferable. The binder can be cured by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent. Examples of the isocyanate-based crosslinking agent include isocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate, and reaction products of these isocyanates with polyalcohol (for example, 3mol of isocyanate and 1m of trimethylolpropane
ol reaction product), and polyisocyanates formed by condensation of these isocyanates.
For example, it is described in JP-A-6-59357.

As a method for dispersing the above-mentioned magnetic material in the binder, a kneader, a pin type mill, an annular type mill and the like are preferably used, as in the method described in JP-A-6-35092. Dispersants described in JP-A-5-088283 and other known dispersants can be used. The thickness of the magnetic recording layer is 0.1 μm to 10 μm, preferably 0.2 μm to 5 μm.
m, more preferably 0.3 μm to 3 μm. The weight ratio between the magnetic particles and the binder is preferably 0.5: 100 to 60: 100.
And more preferably from 1: 100 to 30: 100. The coating amount of the magnetic particles is 0.005 to 3 g / m2, preferably 0.01 to ² g.
/ m ² , more preferably 0.02 to 0.5 g / m ² . The transmission yellow density of the magnetic recording layer is preferably 0.01 to 0.50,
0.03 to 0.20 is more preferable, and 0.04 to 0.15 is particularly preferable. The magnetic recording layer can be provided on the entire back surface of the photographic support by coating or printing, or in a stripe shape. As a method for applying the magnetic recording layer, an air doctor, blade, air knife, squeeze, impregnation, reverse roll, transfer roll, gravure, kiss, cast, spray, dip, bar, extrusion, etc. can be used. The coating solution described in 341436 is preferred.

In the magnetic recording layer, lubricity improvement, curl control,
It may have functions such as antistatic, anti-adhesion and head polishing, or may provide another functional layer to provide these functions. At least one of the particles has a Mohs hardness of 5 or more. The abrasives of the above non-spherical inorganic particles are preferred. As the composition of the non-spherical inorganic particles, oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide and silicon carbide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable. These abrasives may have their surfaces treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer, etc.) on the magnetic recording layer. As the binder used at this time, the above-mentioned binders can be used, and the same binder as the binder for the magnetic recording layer is preferable. For photosensitive materials having a magnetic recording layer, see US Pat.
5,229,259, 5,215,874 and EP 466,130.

Next, the polyester support preferably used in the present invention will be described. For details including photosensitive materials, treatments, cartridges and examples described later, refer to Published Technical Report, Official Technique No. 94-6023 (Invention Association; 1994.15.). The polyester used in the present invention is formed by using diol and aromatic dicarboxylic acid as essential components. As aromatic dicarboxylic acids, 2,6-, 1,5-, 1,4-, and 2,7-naphthalenedicarboxylic acid, and terephthalic acid are used. Acids, isophthalic acid, phthalic acid, and diols include diethylene glycol, triethylene glycol, cyclohexane dimethanol, bisphenol A, and bisphenol. Examples of the polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred are polyesters containing 50 to 100 mol% of 2,6-naphthalenedicarboxylic acid. Among them, polyethylene-2,
6-naphthalate. Average molecular weight range of about 5,000
Or 200,000. The Tg of the polyester of the present invention is 50
° C or higher, and more preferably 90 ° C or higher.

Next, the polyester support is heat-treated at a heat treatment temperature of 40 ° C. or more and less than Tg, more preferably Tg−20 ° C. or more and less than Tg, in order to make it difficult to form a curl.
The heat treatment may be performed at a constant temperature within this temperature range,
The heat treatment may be performed while cooling. This heat treatment time is
The time is 0.1 to 1500 hours, more preferably 0.5 to 200 hours. The heat treatment of the support may be performed in the form of a roll, or may be performed while being transported in the form of a web. Unevenness is applied to the surface (for example, SnO ₂ or Sb ₂ O ₅
And the like, for example, may be applied to improve the surface state. It is also desirable to take measures such as applying knurls to the ends and making the ends slightly higher so as to prevent the cut end of the core from appearing. These heat treatments are performed after forming the support film.
It may be carried out at any stage after the surface treatment, after the application of the back layer (antistatic agent, slip agent, etc.) and after the application of the undercoat. Preferably after application of the antistatic agent.

An ultraviolet absorber may be incorporated in this polyester. To prevent light piping, the purpose can be achieved by kneading a commercially available dye or pigment for polyester, such as Diaresin manufactured by Mitsubishi Kasei or Kayaset manufactured by Nippon Kayaku.

Next, in the present invention, it is preferable to perform a surface treatment in order to bond the support and the light-sensitive material constituting layer. Chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment,
Surface activation treatments such as laser treatment, mixed acid treatment, ozone oxidation treatment and the like can be mentioned. Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment, and glow treatment are preferable.

Next, the undercoating method will be described. It may be a single layer or two or more layers. As a binder for the undercoat layer,
Starting from copolymers starting from monomers selected from vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride, etc., polyethylene imine, epoxy resin, grafting Gelatin, nitrocellulose and gelatin are included.
Compounds that swell the support include resorcinol and p-chlorophenol. In the undercoat layer, as a gelatin hardener, chromium salt (chromium alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6) are used.
-Hydroxy-S-triazine), epichlorohydrin resin, active vinyl sulfone compound and the like. SiO ₂ , TiO ₂ , inorganic fine particles or polymethyl methacrylate copolymer fine particles (0.01 to 10 μm) may be contained as a matting agent.

In the present invention, an antistatic agent is preferably used. As those antistatic agents, carboxylic acid and carboxylate, polymers including sulfonate,
Examples include cationic polymers and ionic surfactant compounds.

The most preferred antistatic agent is Z
nO, TiO_Two, SnO_Two, Al_TwoO_Three, In_TwoO _Three, SiO_Two, MgO, Ba
O, MoO_Three, V_TwoO_FiveAt least one volume resistor selected from
Resistance rate is 10⁷Ωcm or less, more preferably 10^FiveΩcm or less
Particle size 0.001 ~ 1.0μm crystalline metal oxide
Or these composite oxides (Sb, P, B, In, S, Si, C, etc.)
Fine particles, sol-like metal oxides or these
These are fine particles of a composite oxide.

[0161] The content of the sensitive material, particularly preferably preferably 5 to 500 mg / m ² is 10 to 350 mg / m ^2. The ratio of the amount of the conductive crystalline oxide or its composite oxide to the binder is preferably from 1/300 to 100/1, more preferably from 1/100 to
100/5.

The light-sensitive material of the present invention preferably has a slip property. The slip agent-containing layer is preferably used on both the photosensitive layer surface and the back surface. A preferable slip property is a dynamic friction coefficient of 0.
It is 25 or less and 0.01 or more. The measurement at this time represents the value when transported at 60 cm / min against a stainless steel ball with a diameter of 5 mm (25
° C, 60% RH). In this evaluation, even if the surface of the photosensitive layer is replaced as the partner material, the values are almost the same level.

Examples of the slipping agent usable in the present invention include polyorganosiloxanes, higher fatty acid amides, higher fatty acid metal salts, esters of higher fatty acids and higher alcohols, and polyorganosiloxanes such as polydimethylsiloxane, polydiethyl Siloxane, polystyrylmethylsiloxane, polymethylphenylsiloxane, or the like can be used. The additional layer is preferably the outermost layer of the emulsion layer or the back layer. Particularly, polydimethylsiloxane or an ester having a long-chain alkyl group is preferable.

The light-sensitive material of the present invention preferably contains a matting agent. The matting agent may be on either the emulsion side or the back side, but is particularly preferably added to the outermost layer on the emulsion side.
The matting agent may be soluble in the processing solution or insoluble in the processing solution, and preferably both are used in combination. For example, polymethyl methacrylate, poly (methyl methacrylate / methacrylic acid = 9/1 or 5/5 (molar ratio)), polystyrene particles and the like are preferable. The particle size is preferably 0.8 to 10 μm, and the particle size distribution is preferably narrow, and the average particle size is 0.9 to 10 μm.
It is preferable that 90% or more of the total number of particles is contained during 1.1 times. It is also preferable to simultaneously add fine particles having a size of 0.8 μm or less in order to enhance the matting property. For example, polymethyl methacrylate (0.2 μm), poly (methyl methacrylate / methacrylic acid = 9/1 (molar ratio), 0.3 μm)), Polystyrene particles (0.25 μm), colloidal silica (0.03
μm).

Next, the film cartridge used in the present invention will be described. The main material of the patrone used in the present invention may be metal or synthetic plastic.

Preferred plastic materials are polystyrene, polyethylene, polypropylene, polyphenyl ether and the like. Further, the patrone of the present invention may contain various antistatic agents, and carbon black, metal oxide particles, nonionic, anionic, cationic and betaine surfactants or polymers can be preferably used. These antistatic patrones are disclosed in
37, 1-312538. Particularly, the resistance at 25 ° C. and 25% RH is preferably 10 ¹² Ω or less. Usually, a plastic patrone is manufactured using a plastic into which carbon black, a pigment, or the like is kneaded in order to impart light shielding properties. The size of the patrone may be the same as the current 135 size, and it is effective to reduce the diameter of a 25 mm cartridge of the current 135 size to 22 mm or less in order to reduce the size of the camera.
The volume of a cartridge case, 30cm ³ or less, preferably 25
It is preferably set to not more than cm ³ . The weight of plastic used for patrone and patrone case can range from 5g to 15g
g is preferred.

Further, a patrone used in the present invention to feed a film by rotating a spool may be used. Further, a structure may be employed in which the leading end of the film is stored in the cartridge body, and the leading end of the film is sent out from the port of the cartridge by rotating the spool shaft in the film sending direction. These are disclosed in US Pat. Nos. 4,834,306 and 5,226,613. The photographic film used in the present invention may be a so-called raw film before development or a photographic film that has been subjected to development processing. Also, raw film and developed photographic film may be stored in the same new patrone,
A different patrone may be used.

The photographic product with a built-in photosensitive material of the present invention having an exposure function has a photographic lens such as a monocular lens or an aspherical lens and an exposure mechanism such as a shutter mechanism.
It is a packaging unit having a storage room (film roll chamber) in which a color photographic light-sensitive material is wound and stored directly or in a storage device. It is preferable to store the photosensitive material directly in the storage chamber. The photosensitive material may be placed in a cartridge or a cartridge.

The photographic lens used in the present invention may have a variable diaphragm or a fixed diaphragm. However, in order for a photographic product with a built-in photosensitive material to be easily and easily handled, It is preferable to have a fixed aperture. The aperture value (F value) is preferably 8 or more and 16 or less, and more preferably 10 or more and 14 or less.

The shutter speed may be variable or fixed, but is preferably fixed as with the diaphragm. Preferably 1/50 sec to 1/250 sec, more preferably 1/8
0 second to 1/160 second.

The color photographic light-sensitive material of the present invention is also suitable as a negative film for an advanced photo system (hereinafter referred to as an AP system), and NEXIA A manufactured by Fuji Photo Film Co., Ltd. (hereinafter referred to as Fuji Film). NEXI
Films processed into the AP system format such as AF and NEXIA H (in order, ISO 200/100/400) and stored in a special cartridge can be mentioned. These APs
The system cartridge film is used by loading it onto an AP system camera such as the EPION series (e.g., EPION 300Z) manufactured by Fujifilm. Further, the color photographic light-sensitive material of the present invention is also suitable for a film with a lens such as a super color slim made by Fujifilm.

The film photographed by the above is printed in the minilab system through the following steps. (1) Reception (exposed cartridge film received from customer) (2) Detach process (transfer film from cartridge to intermediate cartridge for development process) (3) Film development (4) Retouch process (developed negative (Return the film to the original cartridge.) (5) Print (continuous automatic printing of C / H / P 3 type prints and index prints on color paper (preferably SUPER FA8 made by FUJIFILM)) (6) Verification and shipment (The cartridge and index print are collated by ID number and shipped together with the print.) These systems include Fujifilm Minilab Champion Super FA-298 / FA-278 / FA-258 / FA-238 and Fujifilm Digital Lab System Frontier. preferable. FP922AL / FP562B / FP562B, AL / FP362B / FP362B, AL are examples of minilab champion film processors, and the recommended treatment chemical is Fujicolor Justit CN-1.
6L and CN-16Q. As a printer processor,
PP3008AR / PP3008A / PP1828AR / PP1828A / PP1258AR / PP1258A
/ PP728AR / PP728A, and the recommended treatment chemicals are Fujicolor Justit CP-47L and CP-40FAII. Frontier System, Scanner & Image Processor
SP-1000 and laser printer & paper processor
LP-1000P or laser printer LP-1000W is used. The detacher used in the detaching step and the reattacher used in the rear attaching step are preferably DT200 / DT100 and AT200 / AT100 of Fujifilm, respectively.

The AP system can be enjoyed by a photo joy system centered on Fujifilm's digital image workstation Aladdin 1000. For example, you can directly load a developed AP system cartridge film into the Aladdin 1000, or transfer image information from negative film, positive film, and print to a 35mm film scanner FE.
The digital image data obtained by inputting using the -550 or PE-550 flat head scanner can be easily processed and edited. The data are stored in a digital color printer NC-550AL using a light fixing type thermal color printing system and a pictograph 3000 using a laser exposure thermal development transfer system.
Or as prints with existing lab equipment through a film recorder. The Aladdin 1000 can also transfer digital information directly to a floppy disk, Zip disk, or via a CD writer.
You can also output to CD-R.

On the other hand, at home, the developed AP system cartridge film is transferred to a Fuji Film Photo Player AP.
You can enjoy photos on TV just by loading it in -1,
By loading it onto a Fujifilm AS-1 photo scanner, image information can be continuously and rapidly captured on a personal computer. To input a film, print or three-dimensional object to a personal computer, use Fujifilm PhotoVision FV-10 / FV
-5 is available. Furthermore, image information recorded on a floppy disk, Zip disk, CD-R, or hard disk can be variously processed and enjoyed on a personal computer using Fujifilm's application software Photo Factory. In order to output high-quality prints from a personal computer, a digital color printer NC-2 / NC-2D manufactured by Fujifilm of a light fixing type thermal color print system is suitable.

In order to store the developed AP system cartridge film, the Fuji Color Pocket Album AP-5 POP L, AP-1 POP L, AP-1 POP KG or the cartridge file 16 is preferable.

[0176]

Example 1 (Preparation of Emulsion E-1) (i) 1200 ml of an aqueous solution containing 5.3 g of KBr and 9.3 g of gelatin having an average molecular weight of 15000 was stirred at 60 ° C. (Ii) Aqueous solution of silver nitrate (containing 12.0 g of AgNO ₃ ) and aqueous solution of halide (containing 8.8 g of KBr)
Was added by a double jet over 1 minute and 20 seconds.
(Iii) —NH _{2 in} gelatin having an average molecular weight of 100,000
Modified gelatin 37 whose groups are phthalated with phthalic anhydride
After the addition of g, the temperature was raised to 75 ° C. (Iv) Thereafter, an aqueous silver nitrate solution (containing 7.0 g of AgNO ₃ ) was added by a single jet over 3 minutes and 50 seconds. (V) Thereafter, 0.1 mol of ammonia was added, and 9 minutes later, the mixture was neutralized with acetic acid to adjust the pH to 5.0. (Vi) Thereafter, an aqueous solution of silver nitrate (containing 130.0 g of AgNO ₃ ) and an aqueous solution of a halide (containing 7.70 mol% of KI based on KBr) are accelerated by a double jet and added over 32 minutes and 10 seconds. did. At this time, the silver potential was -2 with respect to the saturated caramel electrode.
It was kept at 8 mV. (Vii) Then, an aqueous solution of silver nitrate (AgN
O ₃ 48.0 g) and an aqueous KBr solution were added by double jet over 12 minutes and 20 seconds. At this time, the silver potential was kept at +10 mV with respect to the saturated caramel electrode. (Vi
ii) The temperature was lowered to 55 ° C., and an aqueous silver nitrate solution (AgNO ₃
6.5 g) and the KI solution (containing 6.5 g KI) were added over 5 minutes. Then, (ix) an aqueous solution of silver nitrate (containing 80.0 g of AgNO ₃ ) and a KBr solution (KBr
57 g) was added by double jet over 18 minutes and 40 seconds. (X) The resulting emulsion was desalted by flocculation method, gelatin was added, and pH 5.85, pA
g 9.0, and sensitizing dyes ExS-6 and Ex described below.
S-10 was added, followed by optimal chemical sensitization using sodium thiosulfate, potassium thiocyanate, chloroauric acid, and di-methylselenourea. Emulsion E-1 had an average equivalent circle diameter of 1.24 μm, an average thickness of 0.24 μm, an average equivalent spherical diameter of 0.88 μm, a coefficient of variation of equivalent spherical diameter of 24%, an average aspect ratio of 5.1, and an average silver iodide content. 7.2 mol% of tabular grains. Grains of 50% or more of the total projected area had 10 or more dislocation lines in the fringe portion. (Preparation of Emulsions E-2 and E-3) In the production of Emulsion E-1, the average sphere equivalent diameter becomes almost the same by changing the potential with respect to the saturated caramel electrode at the time of double jet addition in step (vi). The average aspect ratio was changed as follows.
Emulsion E-2 had an average aspect ratio of 3.6 and emulsion E-3.
Were tabular grains having an average aspect ratio of 2.2. In both emulsions E-2 and E-3, grains having 50% or more of the total projected area had 10 or more dislocation lines in the fringe portion. (Preparation of Emulsion E-4) In the production of Emulsion E-1, after the step (vii) was completed, the steps from the step (viii) were prepared as follows. (Viii) Aqueous KBr solution was added to adjust the silver potential to −90 mV with respect to the saturated caramel electrode, and then iodide having an average equivalent circle diameter of 0.058 μm and a variation coefficient of equivalent circle diameter of 9.95%. AgNO silver emulsion was prepared within 1 minute.
6.5 g was rapidly added in ₃ equivalents. (Ix) One minute later,
An aqueous silver nitrate solution (containing 80.0 g of AgNO ₃ ) was added over 18 minutes and 40 seconds. (X) The resulting emulsion is desalted by flocculation method, gelatin is added,
5.85, adjusted to pAg 9.0, added the same sensitizing dyes ExS-6 and Ex-10 as the emulsion E-1, and then added sodium thiosulfate, potassium thiocyanate, chloroauric acid, di-methylselenourea Was optimally used for chemical sensitization. Emulsion E-4 had an average circle equivalent diameter of 1.27 μm and an average thickness of 0.
Tabular grains having a particle diameter of 22 μm, an average equivalent sphere diameter of 0.87 μm, a variation coefficient of equivalent sphere diameter of 22%, an average aspect ratio of 5.7, and an average silver iodide content of 7.2 mol% were obtained. 5 of total projected area
0% or more of the grains had 10 or more dislocation lines in the fringe portion. (Preparation of Emulsions E-5 and E-6) In the production of Emulsion E-4, the average sphere equivalent diameter becomes almost the same by changing the potential with respect to the saturated caramel electrode at the time of double jet addition in step (vi). The average aspect ratio was changed as follows.
Emulsion E-5 had an average aspect ratio of 3.8 and emulsion E-6.
Were tabular grains having an average aspect ratio of 2.3. In both emulsions E-5 and E-6, grains having 50% or more of the total projected area had 10 or more dislocation lines in the fringe portion. (Preparation of Emulsion E-7) In the preparation of Emulsion E-4, a silver iodide fine grain emulsion was added without adding the aqueous KBr solution of step (viii). The average spherical equivalent diameter was almost the same, and tabular grains having an average aspect ratio of 5.3 were obtained. Grains of 50% or more of the total projected area had three or more dislocation lines in the fringe portion.

On the undercoated cellulose triacetate film support, each layer having the following composition was applied in multiple layers to prepare Sample 101 as a multilayer color photosensitive material. (Composition of photosensitive layer) The main materials used for each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow coupler H: gelatin Curing agent ExS: Sensitizing dye The number corresponding to each component indicates the coating amount in g / m ² , and for silver halide, it indicates the coating amount in terms of silver. However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer. (Sample 101) First Layer (First Antihalation Layer) Black Colloidal Silver Silver 0.170 Silver Iodobromide Emulsion P Silver 0.011 Gelatin 0.87 ExC-1 0.003 ExC-3 0.003 Cpd-2 0.001 HBS-1 0.004 HBS-2 0.002 Second layer (second antihalation layer) Black colloidal silver Silver 0.073 Gelatin 0.407 ExM-1 0.050 ExF-1 2.0 × 10 ^-3 HBS-1 0.074 Solid disperse dye ExF-2 0.015 Solid disperse dye ExF-3 0.020 Third layer (intermediate layer) Silver iodobromide emulsion O 0.022 ExC-2 0.022 polyethyl acrylate latex 0.085 gelatin 0.294 4th layer (low-speed red-sensitive emulsion layer) silver iodobromide emulsion A silver ^{0.325 ExS-1 5.5 × 10 -4} ExS-2 1.0 × ^{0 -5 ExS-3 2.4 × 10} -4 ExC-1 0.109 ExC-3 0.044 ExC-4 0.072 ExC-5 0.011 ExC-6 0.003 Cpd-2 0.025 Cpd -4 0.025 HBS-1 0.17 Gelatin 0.80 Fifth layer (Medium sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion B Silver 0.26 Silver iodobromide emulsion C Silver 0.56 ExS-15 0.0 × 10 ^-4 ExS-2 1.0 × 10 ^-5 ExS-3 2.0 × 10 ^-4 ExC-1 0.14 ExC-2 0.026 ExC-3 0.020 ExC-4 0.12 ExC-5 0.016 ExC-6 0.007 Cpd-2 0.036 Cpd-4 0.028 HBS-1 0.16 Gelatin 1.18 6th layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion D silver ^{1.50 ExS-1 3.7 × 10 -4} ExS-2 1 × 1 ^{-5 ExS-3 1.8 × 10 -4} ExC-1 0.18 ExC-3 0.07 ExC-6 0.029 ExC-7 0.010 ExY-5 0.008 Cpd-2 0.046 Cpd- 4 0.077 HBS-1 0.25 HBS-2 0.12 Gelatin 2.12 7th layer (intermediate layer) Cpd-1 0.089 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl Acrylate latex 0.83 Gelatin 0.84 Eighth layer (layer giving layering effect to red-sensitive layer) Silver iodobromide emulsion E-1 Silver 0.54 ExS-6 1.7 × 10 ^-4 ExS-10 6 × 10 ^-4 Cpd-4 0.030 ExM-2 0.096 ExM-3 0.028 ExY-1 0.031 HBS-1 0.085 HBS-3 0.003 Gelatin 0.58 Ninth layer (low Green sensitivity emulsion Layer) Silver iodobromide emulsion F silver 0.37 silver iodobromide emulsion G silver 0.30 silver iodobromide emulsion H silver 0.35 ExS-4 2.4 × 10 ^-5 ExS-5 1.0 × 10 ^-4 ExS-6 3.9 × 10 ^-4 ExS-7 7.7 × 10 ^-5 ExS-8 3.3 × 10 ^-4 ExM-2 0.36 ExM-3 0.045 HBS-1 0.28 HBS-3 0.01 HSB-4 0.27 Gelatin 1.39 10th layer (Medium sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion I Silver 0.49 ExS-4 5.3 × 10 ^-5 ExS-7 1.5 × 10 ^-4 ExS-8 6.3 × 10 ^-4 ExC-6 0.009 ExM-2 0.031 ExM-3 0.029 ExY-1 0.006 ExM-4 0.028 HBS-1 0.064 HBS-3 2.1 × 10 ^-3 gelatin 0.44 11th layer (high sensitivity green-sensitive emulsion layer) silver iodobromide emulsion I silver .17 iodobromide emulsion J silver ^{0.82 ExS-4 4.1 × 10 -5} ExS-7 1.1 × 10 -4 ExS-8 4.9 × 10 -4 ExC-6 0.004 ExM- 1 0.016 ExM-3 0.036 ExM-4 0.020 ExM-5 0.004 ExY-5 0.003 ExM-2 0.013 Cpd-3 0.004 Cpd-4 0.007 HBS-10 .18 polyethyl acrylate latex 0.099 gelatin 1.11 12th layer (yellow filter layer) yellow colloidal silver silver 0.010 Cpd-1 0.16 solid dispersion dye ExF-5 0.020 solid dispersion dye ExF-60 0.020 oil-soluble dye ExF-7 0.010 solid disperse dye ExF-8 0.153 HBS-1 0.082 gelatin 1.057 13th layer (low-sensitivity blue-sensitive emulsion layer) iodobromide Silver emulsion K Silver 0.16 Silver iodobromide emulsion L Silver 0.21 Silver iodobromide emulsion M Silver 0.08 ExS-9 4.4 × 10 ^-4 ExS-10 4.0 × 10 ^-4 ExC-1 0.041 ExC-8 0.012 ExY-1 0.035 ExY-2 0.71 ExY-3 0.10 ExY-4 0.005 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS -1 0.24 Gelatin 1.41 14th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion N silver 0.73 ExS-9 3.6 × 10 ^-4 ExC-1 0.013 ExY-20 0.31 ExY-3 0.05 ExY-6 0.062 Cpd-2 0.075 Cpd-3 1.0 × 10 ^-3 HBS-1 0.10 Gelatin 0.91 15th layer (first protective layer) iodine Silver bromide emulsion O silver 0.30 UV-1 0.21 UV-2 0.13 UV-30 20 UV-4 0.025 F-18 0.009 HBS-1 0.12 HBS-4 5.0 × 10 -2 Gelatin 2.3 Layer 16 (second protective layer) H-1 0.40 B- 1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.15 B-3 0.05 S-1 0.20 gelatin 0.75 , Processing, pressure resistance, fungicide
In order to improve antibacterial properties, antistatic properties and coatability, W-
1 to W-5, B-4 to B-6, F-1 to F
-19 and iron, lead, gold, platinum, palladium, iridium, ruthenium, and rhodium salts. Further, 8.5 × 10 ⁻³ mol of calcium per mol of silver halide was added to the coating solution of the eighth layer, and 7.9 × 10 ⁻³ g of calcium was added to the eleventh layer with an aqueous solution of calcium nitrate. A sample was prepared.

Table 1 below shows the AgI content, grain size, surface iodine content and the like of the emulsions represented by the above-mentioned abbreviations. The surface iodine content can be determined by XPS as follows. The sample was transferred to -115 in a 1x10 torr transfer vacuum.
C., and irradiated with MgKα as a probe X-ray at an X-ray source voltage of 8 kV and an X-ray current of 20 mA.
2, measured for Br3d and I3d5 / 2 electrons, the integrated intensity of the measured peak was corrected by a sensitivity factor, and the iodine content of the surface was determined from the intensity ratio.

[0179]

[Table 1]

In Table 1, (1) Emulsions L to O were subjected to reduction sensitization during the preparation of grains using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938.

(2) Emulsions A to D and FO are described in JP-A-3-2
According to the example of No. 37450, gold sensitization, sulfur sensitization and selenium sensitization were performed in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate.

(3) Preparation of tabular grains is disclosed in
According to the example of 58 426, low molecular weight gelatin is used.

(4) Tabular grains are disclosed in JP-A-3-2374.
Dislocation lines as described in No. 50 have been observed using a high voltage electron microscope.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 shown below was dispersed by the following method. That is, water 2
1.7 ml and 3 ml of a 5% aqueous solution of sodium p-octylphenoxyethoxyethoxyethoxyethanesulfonate and 0.5 g of a 5% aqueous solution of 0.5 g of p-octylphenoxypolyoxyethylene ether (polymerization degree 10) were put into a 700 ml pot mill. , Dye ExF-
2 and 5.0 g of zirconium oxide beads (diameter 1 mm)
500 ml was added and the contents were dispersed for 2 hours. For this dispersion, a BO type vibration ball mill manufactured by Chuo Koki was used. After the dispersion, the contents were taken out, added to 8 g of a 12.5% aqueous gelatin solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the dye fine particles is 0.4
It was 4 μm.

Similarly, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle diameter of the fine dye particles is 0.24 μm, 0.45 μm, and 0.52 μm, respectively.
m. ExF-5 was dispersed by the microprecipitation dispersion method described in Example 1 of EP-A-549,489A. The average particle size was 0.06 μm.

The solid dispersion of ExF-8 was dispersed by the following method.

70 g of water and W-2 were added to 1400 g of an ExF-8 wet cake containing 30% of water, and the mixture was stirred.
70 g of xF-8 was added and stirred, and the concentration of ExF-8 was 30%.
Slurry. Next, 1700 ml of zirconia beads having an average particle size of 0.5 mm was filled into Ultra Viscomil (UVM-2) manufactured by Imex Co., Ltd., and the peripheral speed was about 10 m / sec, and the discharge rate was 0.5 liter / min.
For 8 hours.

The compounds used for forming each of the above layers are as shown below.

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(Preparation of Samples 102 to 107) Sample 101
Samples 102 to 107 were prepared by changing the emulsion E-1 in the eighth layer to emulsions E-2 to E-7.

The samples 101 to 107 were evaluated for sensitivity, color reproducibility, change in fog during storage of the photographic material (raw storage), and pressure property by the following methods. (Evaluation of Sensitivity) Continuous wedge exposure was performed using white light, and the magenta density was measured after performing the following development processing. The reciprocal of the exposure amount giving a magenta density of 2.5 (sample 101
Relative value). (Evaluation of fog change during storage of photosensitive material)
After storage for one month under the conditions described above, exposure was performed in the same manner as in the above sensitivity evaluation, development was performed, and the magenta density was measured. The difference from the above sensitivity was examined. (Evaluation of pressure property) After the sample was conditioned at 25 ° C and 55% for 1 day, a load of 5 g was applied to a needle having a diameter of 0.1 mm to scratch the emulsion surface. Thereafter, the film was developed with the following developer, and the magenta density of the scratched portion and the unscratched portion was measured with a densitometer having a 10 μm square parcher size, and the change in density (ΔFog) before and after scratching was examined. (Evaluation of color reproducibility) When evaluating color reproducibility, attention is paid to only one color, and even if the fidelity is improved, the fidelity sometimes deteriorates when looking at another color. It is possible. Therefore, it is necessary to evaluate all hues at the same time and evaluate overall color reproduction. A pointer method is known as an objective and quantitative method for color reproduction of a reflection print image. (MR POINTER; J. Photo
optic Science 34, 81-9
(0, 1986) We evaluated the color reproduction of the sample of the present invention as follows according to the pointer method.

The Macbeth color checker chart was photographed using each sample under artificial daylight illumination in which a photo flood lamp and a Wratten 80B filter were added, and then processed under the following developing conditions. From each of these films,
It was baked on Fujicolor FA paper. At this time, the print density was adjusted so that the red, green, and blue densities (measurement using an X-rite densitometer) according to the fourth middle gray status A (measurement using an X-rite densitometer) coincided with the original chart densities. The reflection print and the original chart thus obtained are measured by a color analyzer (Hitachi, Ltd.), and U ', V', Y 'of each color chart portion are obtained.
Was converted to a value. According to the method of Pointer, the difference between the color chart of the original chart and the color chart of the test sample was quantified to give a hue index. The closer the index is to 100, the closer to the color chart of the original chart.

Next, the method of developing each sample will be described.

(Processing method) Step Processing time Processing temperature Color development 3 minutes 15 seconds 38 ° C. Bleaching 3 minutes 00 seconds 38 ° C. Rinse 30 seconds 24 ° C. Fixing 3 minutes 00 seconds 38 ° C. Rinse (1) 30 seconds 24 ° C. Rinse (2 30 seconds 24 ° C. Stable 30 seconds 38 ° C. Drying 4 minutes 20 seconds 55 ° C. Next, the composition of the processing solution is described. (Color developing solution) (unit: g) diethylenetriaminepentaacetic acid 1.0 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 sodium sulfite 4.0 potassium carbonate 30.0 potassium bromide 1.4 potassium iodide 1.5 mg hydroxylamine sulfate 2.4 4- [N- Ethyl-N- (β-hydroxyethyl) 4.5 amino] -2-methylaniline sulfate 1.0 liter by adding water pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 (bleach-fix solution) (g) Ethylenediaminetetraacetic acid Ferric 100.0 sodium trihydrate disodium ethylenediaminetetraacetate 10.0 3-mercapto-1,2,4-triazole 0.03 ammonium bromide 140.0 ammonium nitrate 30.0 ammonia water (27%) 6.5 ml 1.0 ml with water 6.0 (Fixing solution) Ethylene Amine tetraacetic acid disodium salt 0.5 Ammonium sulfite 20.0 Ammonium thiosulfate aqueous solution (700 g / L) 295.0 mL Acetic acid (90%) 3.3 Add water to 1.0 L pH (adjusted with ammonia water and acetic acid) 6.7 (Stabilized solution) (Unit g) ) P-Nonylphenoxypolyglycidol (glycidol average degree of polymerization 10) 0.2 ethylenediaminetetraacetic acid 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 hydroxyacetic acid 0.02 Hydroxyethyl cellulose 0.1 (Daicel Chemical HEC SP-2000) 1,2-benzisothiazolin-3-one 0.05 Add water and add 1.0 liter pH 8.5

[0211]

[Table 2]

As is clear from the results shown in Table 2 above, the silver halide color photographic light-sensitive material of the present invention has high sensitivity without impairing color reproducibility, and is capable of reducing fog change and pressure during storage of the light-sensitive material. It turns out that it is excellent.

Example 2 In the samples 101 to 107 of Example 1, the cellulose triacetate film of the support was replaced by US Pat.
No. 682, the support used for the sample 104 in Example 1, that is, the undercoat layer and the back layer were provided by the method described in the specification, from column 21, line 54 to column 23, line 29. A heat treated PEN support was used. Further, these samples were loaded into a packaging unit with a photographing function, and the photographic properties of these samples were evaluated in the same manner as in Example 1. As a result, the same results as in Example 1 were obtained.

[Brief description of the drawings]

FIG. 1A is a diagram illustrating a spectral sensitivity distribution curve of a red sensitive layer, and FIG. 1B is a diagram illustrating a spectral sensitivity distribution curve of a green sensitive layer.

Claims (4)

[Claims] 1. A blue-sensitive silver halide emulsion layer containing at least one yellow coupler on a support.
It has a green-sensitive silver halide emulsion layer containing a magenta coupler, a red-sensitive silver halide emulsion layer containing a cyan coupler, and a non-light-sensitive layer, and all the red-sensitive silver halide emulsion layers have a thickness in the range of 500 nm to 600 nm. And the center-of-gravity wavelength (λ _-R ) of the spectral sensitivity distribution of the magnitude of the multilayer effect received from other photosensitive silver halide emulsion layers is 500 nm <λ _-R
<560 nm, and the difference between the center-of-gravity wavelength (λ _G ) and λ _−R of the spectral sensitivity distribution of at least one of the green-sensitive silver halide emulsion layers is λ _G −λ _−R ≧ 10 nm. In a color photographic light-sensitive material, in a dispersion medium solution containing water and a dispersion medium, at least one of the green-sensitive silver halide emulsion layers has a (111) principal parallel plane and a silver iodobromide or odorant. Host tabular grains of silver halide
A silver halide color photographic light-sensitive material comprising a tabular silver halide photographic emulsion into which dislocation lines have been introduced by rapidly adding an emulsion composed of silver iodide fine grains. 2. The tabular silver halide photographic emulsion has an average aspect ratio of 3 or more, and at least 50% of the total projected area has 10 or more dislocation lines per grain in a fringe portion of the grain. 2. The silver halide color photographic light-sensitive material according to claim 1, wherein the photographic material is occupied by a tabular silver halide photographic emulsion. 3. The silver halide color photographic light-sensitive material according to claim 2, wherein said tabular silver halide photographic emulsion has an average aspect ratio of 5 or more. 4. A photographic product provided with an exposure mechanism including a photographic lens and a shutter incorporating the silver halide color photographic light-sensitive material according to claim 1.