JP2001305688A - Photosensitive silver halide photographic emulsion and silver halide photographic sensitive material containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a low fogging and highly sensitive silver halide emulsion and a silver halide photographic sensitive material using the emulsion. SOLUTION: The photosensitive silver halide photographic emulsion contains silver halide grains and is prepared by a method including at least one step for forming grains using gelatin in which the ratio of H2 component to the sum of α-, β- and γ-components is <=0.03 and the ratio of L2 component to the sum of α-, β- and γ-components is <=0.05 and >=50% of the total projected area of the emulsion grains is occupied by flat platy silver halide grains having an aspect ratio of >=4. The silver halide photographic sensitive material has at least one photosensitive silver halide emulsion layer containing the emulsion.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a light-sensitive silver halide photographic emulsion having low fog and high sensitivity, and a silver halide photographic material using the same.

[0002]

2. Description of the Related Art In recent years, demands for silver halide emulsions for photography have become more and more severe.
Improvements in the relationship between fog ratios and higher image quality are required. One of the techniques for increasing the sensitivity and image quality of silver halide emulsions is to use tabular grains, which increase sensitivity, including improvement in color sensitization efficiency by sensitizing dyes, improve the sensitivity / granularity ratio, and improve tabularity. Advantages such as improvement in sharpness and covering power due to specific optical characteristics of particles are known.

[0003] On the other hand, particularly with the increase in sensitivity of silver halide tabular grains, an increase in fog has become a problem, and it has been desired to achieve both of them.

There are several steps in which gelatin is used in the grain formation step of a silver halide emulsion. At least one kind of gelatin is used as a protective colloid for silver halide grains in the nucleation step and the subsequent ripening / growing step.

In recent years, chemically modified gelatin has been actively used as a technique for preparing silver halide tabular grain emulsions having a high aspect ratio. Tokuhei 5-1269
No. 6 discloses a technique for preparing tabular grains having a small thickness by using, as a protective colloid, gelatin in which a thioether group in gelatin has been invalidated with hydrogen peroxide or the like. JP-A-8-82883 discloses a technique for preparing thin tabular grains by invalidating amino groups and thioether groups. JP-A-10-148897 discloses a technique for preparing thin and monodisperse tabular grains by introducing two or more carboxyl groups when chemically modifying an amino group in gelatin. U.S. Pat. Nos. 5,219,720 and 5,334,495 disclose a technique for tabular grains having a small twin plane spacing as one of techniques for improving the sensitivity / granularity ratio of tabular grains.

However, even if the techniques described in these patent applications are used, tabular grains having a high aspect ratio and a narrow twin plane spacing are insufficient to obtain a silver halide emulsion having a low fog and a high sensitivity. Further improvements were desired.

[0007] On the other hand, gelatin currently industrially produced is generally simply derived from collagen contained in animal bones and skins. One of the drawbacks of gelatin derived from animal collagen is that the molecular weight is polydisperse. The fact that the molecular weight is polydisperse is disadvantageous in controlling the physical properties of the dispersion medium having gelatin.

JP-A-56-86193 describes novel gelatins obtained by applying a mechanical shearing force to an aqueous solution of gelatin and a method of using these gelatins as a binder substance in photographic materials. Further, Japanese Society of Photography, Vol. 62, No. 4, pp. 308-312 (1999) discloses a method for controlling the molecular weight distribution, particularly a method for reducing high molecular weight components. In these technical contents, there is neither description nor suggestion about a technique for producing a high-sensitive emulsion with low fog in a method of forming grains having a high aspect ratio and a narrow twin plane spacing as an emulsion.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a light-sensitive silver halide photographic emulsion having low fog and high sensitivity, and a silver halide photographic material using the same.

[0010]

Means for Solving the Problems As a result of intensive studies, the present inventors have obtained tabular grains having a high aspect ratio and a narrow twin plane spacing by using gelatin having a defined molecular weight distribution for gelatin. It has been discovered that the performance of silver halide emulsions is significantly improved (reduction of fog and high sensitivity).

The above object of the present invention has been effectively achieved by the following present invention.

(1) An emulsion containing silver halide grains, wherein the ratio of the H2 component to the sum of the α, β, and γ components of the gelatin is 0.03 or less, and the α, β,
It is produced by a method including at least one step of forming grains using gelatin in which the ratio of the L2 component to the sum of the γ components is 0.05 or less, and at least 50% of the total projected area of the emulsion grains is reduced. A photosensitive silver halide photographic emulsion characterized by being occupied by silver halide tabular grains having an aspect ratio of 4 or more.

(2) 5 of the total projected area of the emulsion grains
0% or more has an aspect ratio of 4 or more and a twin plane spacing of 0.
The photosensitive silver halide photographic emulsion according to the above (1), wherein silver halide grains having a size of not more than 012 μm are occupied.

(3) The above-mentioned emulsion grains are parallel to the (111) plane, have an aspect ratio of 4 or more, contain 10 or more dislocation lines per grain, and are made of silver iodobromide or silver chloroiodobromide. The photosensitive silver halide photographic emulsion according to the above (1) or (2), wherein tabular silver halide grains are contained in 50% or more of the total projected area.

(4) The above-mentioned (1) to (3), wherein the gelatin is obtained by treating the aqueous solution with a high-pressure homogenizer having a pressure difference of 150 MPa or more in a dispersion part. The photosensitive silver halide photographic emulsion according to any one of 1) to 2) above.

(5) In a silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on a support, the silver halide photographic emulsion layer may be any one of the above-mentioned (1) to (4). 5. A silver halide photographic light-sensitive material comprising the photosensitive silver halide photographic emulsion described in 1. above.

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The method for producing gelatin that can be used in the present invention can be produced by a generally used method for producing photographic gelatin, except that the molecular weight distribution is defined within the scope of the present invention. For example, it is described in the first edition, pp. 122-124, edited by The Photographic Society of Japan, "Basic silver halide photography in photographic engineering" (Corona).

The photographic gelatin used in the present invention can be produced from collagen contained in bovine bone, cow skin, pig skin, and the like, and can be extracted by treating them with an acid or an alkali. There is no restriction on the raw material, but it is preferable to use cow bone or cow hide. The gelatin used in the present invention may be an acid-treated gelatin or an alkali-treated gelatin, but an alkali-treated gelatin is preferred. Production of alkali-treated gelatin from bovine bone or cow hide is performed by the steps of demineralization, lime treatment, extraction, filtration, concentration, gelation, and drying. Details of each step are described in, for example, pages 6 to 7 of JP-A-8-179483.

The molecular weight distribution of the gelatin used in the present invention can be defined by separating the components by the method described in The Photographic Society of Japan, Vol. 62, No. 4, pp. 308-312 (1999).
The chromatogram obtained by the gel filtration method was analyzed using a high molecular weight component having a molecular weight of 300,000 or more (H2 component and H1 component, where the H2 component has a higher molecular weight), a γ component having a molecular weight of about 300,000, a β component having a molecular weight of about 200,000, Α component around 10,000, molecular weight 10
It was fractionated into 10,000 or less low molecular weight components (L1 component and L2 component, where L2 component has lower molecular weight).

The ratio of the molecular weight components of the gelatin according to the present invention is defined by the ratio of the peak or shoulder height of each component of the chromatogram obtained by the above method. That is, the ratio of the H2 component to the sum of the α, β, and γ components of the present invention is H2
A value obtained by dividing the peak height of the component by the sum of the peak heights of the α, β, and γ components.
The component ratio indicates a value obtained by dividing the peak height of the L2 component by the sum of the peak heights of the α, β, and γ components.

The ratio of the H2 component to the sum of the α, β, and γ components may be 0.03 or less, but is preferably 0.02 or less.
The following are more preferred. L for the sum of α, β, and γ components
The ratio of the two components may be 0.05 or less, but is preferably 0.04 or less, and more preferably 0.03 or less.

The conditions for measuring the molecular weight distribution of gelatin according to the present invention are shown below. (Measurement conditions) Column: Shodex Asahipak GS-620 7G (8mmI.D. × 500m
m) × 2 Guard column: Shodex Asahipak GS-1G 7B Eluent: 0.1 mol / L phosphate buffer (pH6.8) Flow rate: 0.8 ml / min Column temperature: 50 ° C. Detection: UV230nm Sample injection volume: 110 μL (0.2% Phosphate buffer solution).

Next, a method for improving the molecular weight distribution of the gelatin of the present invention will be described. Ultrasonic irradiation, enzymatic decomposition and the like have been conventionally known for removing high molecular weight components. However, since these methods involve an increase in low molecular weight components, the use of this gelatin in a silver halide photographic material often adversely affects various photographic properties. As described in JP-A-8-179483, the molecular weight can be separated by a coacervation method, but there are problems such as complicated operation and low yield.

In a preferred method for improving the molecular weight distribution of gelatin in the present invention, a high-pressure homogenizer is preferably used. In particular, it is preferable that a high pressure of 150 MPa or more, preferably 210 MPa or more, more preferably 300 MPa or more be applied to the dispersion portion. Further, the maximum linear velocity of the liquid in the dispersion section is preferably 300 m / s or more, more preferably 400 m / s or more, and further preferably 600 m / s.
s is preferred.

Examples of such a dispersing machine include a microfluidizer manufactured by Microfluidics and a nanomizer manufactured by Nanomizer. Examples of the method include a method of causing liquids to collide with each other, and a method of causing liquid to collide with a wall such as Emulsiflex manufactured by Avestin. In particular, as a material to which a high pressure can be applied, DeBee 2000 manufactured by BEE International, which applies a high-pressure jet from an orifice into a coaxial cell to apply a shear force in the cell, is preferably used. As the high-pressure homogenizer used in the present invention, any one can be used as long as a high pressure or a linear velocity required to make the ratio of the H2 component 0.03 or less can be applied.

The gelatin used in the present invention can be used in each of the steps of nucleation, ripening, growth, and dispersion in the particle forming step, and the timing of use is not particularly limited. The preferred amount of gelatin used in the present invention is emulsion 1
0.1-200 g per kg. It may be used in combination with another gelatin.

The shape of the silver halide emulsion of the present invention will be described. In the emulsion of the present invention, the projected area of all grains was 5%.
0% or more is occupied by silver halide tabular grains having an aspect ratio of 4 or more. The aspect ratio of the grains occupying 50% or more of the projected area of all grains is preferably 4 to 60, more preferably 6 to 50, and further preferably 8 to 40.

In the emulsion of the present invention, silver halide tabular grains having an aspect ratio of at least 4 and preferably having a twin plane spacing of at most 0.012 μm comprise 50% of the total projected area of the emulsion grains.
Account for the above. More preferably, silver halide tabular grains having an aspect ratio of 4 or more and a twin plane of 0.010 μm or less occupy 50% or more of the total projected area of the emulsion grains.

In the emulsion of the present invention, silver halide tabular grains having an aspect ratio of at least 8 and a twin plane spacing of at most 0.012 μm preferably account for at least 50% of the total projected area of the emulsion grains. More preferably, silver halide tabular grains having an aspect ratio of 8 or more and a twin plane spacing of 0.010 μm or less occupy 50% or more of the total projected area of the emulsion grains.

The emulsion of the present invention is preferably mainly occupied by silver iodobromide or silver iodochlorobromide tabular grains having a (111) plane as a main plane. Here, the silver halide tabular grains are a general term for silver halide grains having one twin plane or two or more parallel twin planes. The twin plane is (111)
This means the (111) plane when ions at all lattice points on both sides of the plane are in a mirror image relationship. This tabular grain has a triangular shape when the grain is viewed from a direction perpendicular to the main plane,
Square, hexagonal or these are rounded circular shapes, triangular ones are triangular, hexagonal ones are hexagonal, circular ones are circular main parallel planes. Have.

In the emulsion of the present invention, the projected area of tabular grains having an aspect ratio of 4 or more preferably occupies most of the total projected area of the emulsion grains, and more preferably occupies 100 to 95%. More preferably, it accounts for 100 to 98%. Grains other than tabular grains (normal crystals and non-parallel multiple twins)
Is not preferred in terms of homogeneity between particles. The projected area of the particles can be obtained by measuring the area on an electron micrograph and correcting the photographing magnification.

In the emulsion of the present invention, hexagonal tabular grains having an adjacent side ratio (maximum side length / minimum side length) of 1.5 to 1 occupy 100 to 70% of the projected area of all grains in the emulsion. Is preferred. More preferably 100-80%,
More preferably, it accounts for 100 to 90%. Also,
In the emulsion of the present invention, more preferably, hexagonal tabular grains having an adjacent side ratio (maximum side length / minimum side length) of 1.2 to 1 occupy 100 to 50% of the projected area of all grains in the emulsion. . It preferably accounts for 100 to 70%, particularly preferably 100 to 80%. Mixing of tabular grains other than the above hexagons is not preferable in terms of homogeneity between grains.

The equivalent circle equivalent diameter of the tabular grains of the present invention is preferably 0.3 to 6.0 μm, more preferably 0.5 to 5.0 μm, and still more preferably 1.0 to 4.0 μm. is there. The equivalent circle equivalent diameter in the present invention is the diameter of a circle having an area equal to the projected area of the parallel outer surface of the grain, and the average equivalent circle equivalent diameter is the equivalent circle equivalent diameter of all tabular grains in the emulsion. Is the arithmetic mean of

The average grain thickness of the tabular grains of the present invention is preferably from 0.03 to 0.35 μm, more preferably from 0.05 to 0.25 μm, even more preferably from 0.05 to 0.20 μm. . The average grain thickness is the arithmetic average of the grain thicknesses of all tabular grains in the emulsion. Emulsions having an average grain thickness of less than 0.03 μm are difficult to prepare. If it exceeds 0.35 μm, it is difficult to obtain the advantages of tabular grains, which is not preferred.

The thickness of the particles is calculated by evaporating a metal together with a reference latex from an oblique direction of the particles, measuring the shadow length on an electron micrograph, and referring to the shadow length of the latex. From the electron micrograph.

The twin plane spacing is a distance between two twin planes in a particle having two twin planes in the particle,
In a grain having three or more twin planes, it refers to the longest distance among the distances between twin planes. The twin plane can be observed with a transmission electron microscope.

Specifically, a sample in which tabular grains are arranged substantially parallel to the support is prepared, and the sample is cut with a diamond knife to prepare a section having a thickness of about 0.1 μm. By observing the section with a transmission electron microscope, the twin plane of the tabular grain can be detected. When the electron beam passes through the twin plane, a phase shift occurs in the electron wave, and the existence thereof is recognized.

The ratio of the equivalent circle equivalent diameter to the thickness of silver halide grains is called the aspect ratio. That is, it is a value obtained by dividing the equivalent circle diameter of the projected area of each silver halide grain by the grain thickness. As an example of measuring the aspect ratio,
There is a method of obtaining a diameter (equivalent circle equivalent diameter) and a thickness of a circle having an area equal to the projected area of each particle by taking a transmission electron microscope photograph by a replica method. In this case, the thickness is calculated from the length of the shadow of the replica.

The emulsion of the present invention preferably comprises monodisperse grains. The variation coefficient of the grain size (equivalent sphere equivalent diameter) distribution of all silver halide grains of the present invention is preferably 30% to 3%, more preferably 25% to 3%, and even more preferably 20% to 3%. is there. The variation coefficient of the equivalent sphere equivalent diameter distribution is obtained by multiplying the value obtained by dividing the variation (standard deviation) of the equivalent sphere equivalent diameter of each tabular grain by the average equivalent sphere equivalent diameter by 100. If the variation coefficient of the equivalent sphere equivalent diameter distribution of all tabular grains exceeds 30%, it is not preferable in terms of homogeneity between grains. Emulsions of less than 3% are difficult to prepare.

The variation coefficient of the equivalent circle equivalent diameter distribution of all grains of the emulsion of the present invention is preferably as low as possible in terms of homogeneity between grains, and is preferably 20% to 3%. More preferably, it is 15 to 3%. The variation coefficient of the equivalent circle equivalent diameter distribution is obtained by multiplying 100 by a value obtained by dividing the variation (standard deviation) of the equivalent circle equivalent diameter of each particle by the average equivalent circle equivalent diameter.

The variation coefficient of the grain thickness distribution of all tabular grains of the emulsion of the present invention is preferably 25 to 3%, more preferably 20 to 3%, and further preferably 15 to 3%. The variation coefficient of the grain thickness distribution is a value obtained by dividing the variation (standard deviation) of the grain thickness of each tabular grain by the average grain thickness. If the variation coefficient of the grain thickness distribution of all tabular grains exceeds 25%, it is not preferable in terms of homogeneity between grains. Emulsions of less than 3% are difficult to prepare.

The variation coefficient of the twin plane spacing distribution of all grains of the emulsion of the present invention is preferably as low as possible in terms of homogeneity between grains.
Preferably, it is 5% to 3%. More preferably, it is 15 to 3%. The variation coefficient of the twin plane spacing distribution is obtained by multiplying the value obtained by dividing the variation (standard deviation) of the twin plane spacing of individual grains by the average twin plane spacing by 100.

In the present invention, the grain thickness, twin plane spacing, aspect ratio and monodispersity in the above ranges may be selected according to the purpose. It is preferable to use smooth tabular grains.

In the present invention, various methods can be used for forming tabular grains having a high aspect ratio, for example, US Pat. Nos. 5,496,694 and 5,498,51.
The particle forming method described in No. 6 can be used. Further, as a method of forming tabular grains having an ultra-high aspect ratio, the grain forming methods described in U.S. Pat. Nos. 5,494,789 and 5,503,970 can also be used.

In order to form monodisperse tabular grains having a high aspect ratio, it is important to form small-sized twin nuclei in a short time. Therefore, low temperature, high pBr, low p
It is preferable to form nuclei in a short time under a low amount of H and gelatin.

After nucleation, the nuclei of normal crystals, single twins and non-parallel multiple twins are eliminated by physical ripening, and the nuclei of parallel double twins are selectively left. It is preferable to further ripen the remaining parallel double twin nuclei to increase the monodispersity. In addition, physical ripening can be performed, for example, by using P described in US Pat. No. 5,147,771.
Performing in the presence of AO (polyalkylene oxide) is also preferred because it increases monodispersity.

Thereafter, gelatin is added, and then a soluble silver salt and a soluble halogen salt are added to grow grains. It is also preferable to add silver halide fine particles separately prepared in advance or simultaneously prepared in another reaction vessel to supply silver and halide to grow the grains.
It is important to control and optimize the temperature, pH, amount of binder, pBr, supply rates of silver and halogen ions, etc. of the reaction solution even during grain growth. In the emulsion of the present invention, it is preferable to use a low-viscosity dispersion medium in at least one of the grain forming steps (nucleus formation, ripening and growth).
Here, the low-viscosity dispersion medium will be described.

The viscosity of the dispersion medium depends on the protective colloid species and the concentration thereof in the dispersion medium, the temperature of the system, the ionic strength, and the pH.
Greatly affected by Furthermore, depending on the type of protective colloid, the viscosity of the dispersion medium may change over time. The viscosity of the dispersion medium is measured using a rotational viscometer. In the present invention, the viscosity of the dispersion medium was measured after the protective colloid used was allowed to stand for 1 hour after dissolution.

The low viscosity in the present invention is a region where the viscosity of the dispersion medium given by the formula 1 is smaller than η. Equation 1 η = (2.8159−0.0743T) exp {(0.1479−0.0017T) C} where η is the viscosity of the dispersion medium (10 ⁻³ N · s · m ⁻² ), and T is the temperature of the dispersion medium (° C.). ), C is the concentration (% by weight) of the protective colloid in the dispersion medium.

The ionic strength of the dispersion medium is preferably 2 or less.
1.5 or less is more preferable, and 1 or less is further preferable.
The pH of the dispersion medium is preferably 2 to 11, more preferably 3
-10, more preferably 4-9.

Next, the composition of the emulsion of the present invention will be described. To form the silver halide grains used in the present invention,
It is preferable to use silver iodobromide or silver chloroiodobromide. When there is a phase containing iodide or chloride, these phases may be uniformly distributed in the grains or may be localized. Other silver salts such as silver rhodan, silver sulfide, silver selenide, silver carbonate, silver phosphate, and organic acid silver may be contained as separate grains or as part of silver halide grains.

The preferred range of the silver bromide content of the emulsion grains in the present invention is 80 mol% or more, more preferably 90 mol% or more. The preferred silver iodide content of the emulsion grains in the present invention is 1 to 20 mol%, more preferably 2 to 15 mol%, and still more preferably 3 to 10 mol%. If it is less than 1 mol%, it is not preferable because effects such as enhancement of dye adsorption and increase in intrinsic sensitivity are hardly obtained. If it exceeds 20 mol%, the developing speed is generally slow, which is not preferable.

The coefficient of variation of the silver iodide content distribution among the emulsion grains in the present invention is preferably less than 30%, more preferably 25 to 3%, and even more preferably 20 to 3%. Emulsions of less than 3% are difficult to prepare,
If it exceeds 30, it is not preferable in terms of homogeneity between particles.

The silver iodide content of each emulsion grain can be measured by analyzing the composition of each grain using an X-ray microanalyzer. The measuring method is described, for example, in EP 147,868.

The emulsion of the present invention has a surface iodine content of 5 mol%.
It is preferably at most 4 mol%, more preferably at most 3 mol%. If the surface iodine amount exceeds 5 mol%, development inhibition and chemical sensitization inhibition occur, which is not preferable. ESCA measurement of surface iodine content
It can be confirmed by a method (also called XPS) (a method of irradiating X-rays and dispersing photoelectrons coming out of the particle surface).

The emulsion grains of the present invention mainly comprise (111) planes and (100) planes. The proportion of the area of the (111) plane to the total surface area of the emulsion grains of the present invention is at least 70%.

On the other hand, in the emulsion grains of the present invention, (10
The appearance site of the (0) plane is the side surface of the tabular grain, and (111)
The ratio of the area where the (100) plane occupies the emulsion grain surface to the area where the plane occupies the emulsion grain surface is at least 2%, more preferably 3% or more, and further preferably 4% or more. The control of the (100) face ratio is disclosed in
Reference can be made to JP-A-298935 and JP-A-8-334850. The (100) plane ratio is determined by a method utilizing the difference in the adsorption dependency between the (111) plane and the (100) plane in the adsorption of the sensitizing dye, for example, T. Tani, J. Imagin
g Sci., 29, 165 (1985) and the like.

In the emulsion grains of the present invention, 50% or more of the total projected area is preferably occupied by tabular grains having a (100) plane area ratio of 15% or more on the side faces of the grains, and more preferably (100). The area ratio of the surface is 2
Occupied by at least 5% of tabular grains. The area ratio of the (100) plane on the side surface of the tabular grain is described in, for example,
It can be determined from the method described in JP-A-334850.

The tabular grains in the present invention preferably have dislocation lines inside the grains. Hereinafter, introduction of dislocation lines into tabular grains will be described.

A dislocation line is a linear lattice defect on the slip plane of a crystal at the boundary between an already slipped area and a not-yet slipped area. Regarding dislocation lines of silver halide crystals, 1) C.I. R. Berry, J.M. Appl. Phys
s. , 27, 636 (1956), 2) C.I. R. Ber
ry, D.S. C. Skilman, J .; Appl. Phys
s. , 35, 2165 (1964), 3) J. F. Ha
Milton, Photo. Sci. Eng. , 11,5
7 (1967), 4) T.I. Shiozawa, J .; So
c. Photo. Sci. Jap. , 34, 16 (197
1), 5) T.I. Shiozawa, J .; Soc. Pho
t. Sci. Jap. , 35, 213 (1972), which can be analyzed by an X-ray diffraction method or a direct observation method using a low-temperature transmission electron microscope. When directly observing dislocation lines using a transmission electron microscope, place the silver halide grains removed from the emulsion with care not to apply enough pressure to generate dislocation lines on the grains, and place them on a mesh for electron microscope observation. Observation is performed by a transmission method in a state where the sample is cooled so as to prevent damage (for example, printout) by an electron beam.

In this case, the thicker the particle, the more difficult it is for the electron beam to pass through. Therefore, it is better to use a high-pressure electron microscope (200 kV or more for a thickness of 0.25 μm) to observe more clearly. Can be.

On the other hand, the effect of dislocation lines on photographic performance is described in C. Farnell, R .; B. Flint,
J. B. Chanter, J.A. Photo. Sci. , 1
3, 25 (1965) discloses that in a large size high aspect ratio tabular silver halide grain, a place where a latent image nucleus is formed is closely related to a defect in the grain. I have. For example, US Pat. No. 4,806,46
Nos. 1, 5,498,516 and 5,496,694
No. 5,476,760 and 5,567,580
And JP-A-4-149541 and JP-A-4-149737 describe techniques for introducing dislocation lines in silver halide grains while controlling the dislocation lines. In these patents, it is shown that tabular grains into which dislocation lines are introduced are superior in photographic properties such as sensitivity and pressure properties as compared with tabular grains without dislocation lines. In the present invention, it is preferable to use the emulsions described in these patents and the like.

In the present invention, it is preferable to introduce dislocation lines into tabular grains as follows. That is, epitaxial growth of a silver halide phase containing silver iodide on tabular grains (also referred to as host grains) serving as a base, and introduction of dislocation lines by forming a silver halide shell thereafter.

The silver iodide content of the host grains is preferably from 0 to 15 mol%, more preferably from 0 to 12 mol%, and particularly preferably from 0 to 10 mol%. good. If it exceeds 15 mol%, the developing speed is generally slow, which is not preferable.

The composition of the silver halide phase to be epitaxially grown on the host grains preferably has a higher silver iodide content. The silver halide phase to be epitaxially grown may be any of silver iodide, silver iodobromide, silver chloroiodobromide and silver chloroiodide, but is preferably silver iodide or silver iodobromide. Is more preferable. The preferred silver iodide (iodide ion) content in the case of silver iodobromide is 1 to 45 mol%, more preferably 5 to 45 mol%, and particularly preferably 10 to 45 mol%. The silver iodide content is preferably as high as possible in terms of forming a misfit necessary for introducing dislocation lines, but 45 mol% is the solid solubility limit of silver iodobromide.

The amount of halogen added to form the high silver iodide content phase to be epitaxially grown on the host grains is preferably 2 to 15 mol%, more preferably 2 to 15 mol%, of the silver quantity of the host grains. It is 10 mol%, particularly preferably 2 to 5 mol%. If it is less than 2 mol%, dislocation lines are hardly introduced, which is not preferable. If it exceeds 15 mol%, the developing speed is undesirably slow.

At this time, the high silver iodide content phase is preferably present in the range of 5 to 60 mol%, more preferably 10 to 50 mol%, of the total silver content as viewed from the grain formation. And particularly preferably in the range of 20 to 40 mol%. If the amount is less than 5 mol% or more than 60 mol%, it is difficult to obtain high sensitivity by introducing dislocation lines, which is not preferable.

The location where the high silver iodide content phase is formed on the host grains is arbitrary. The phase may be formed so as to cover the host grains or to be formed only in a specific portion. Controlling the location of dislocation lines in the grains by doing so is preferred.

In the present invention, it is particularly preferable to form a high silver iodide content phase at the edge and / or the apex of the host tabular grain. At that time, the composition of the halide to be added, the method of addition, the temperature of the reaction solution, the pAg, the solvent concentration, the gelatin concentration, the ionic strength and the like may be freely selected and used. The silver iodide content phase in the grains is described, for example, in JP-A-7-219102.
And can be measured by the analytical electron microscope described in No.

In forming the high silver iodide content phase on the host grains in the present invention, a water-soluble iodide solution such as potassium iodide is added alone or simultaneously with a water-soluble silver salt solution such as silver nitrate. Or a method in which silver halide containing silver iodide is added in the form of fine grains.
Nos. 516 and 5,527,664, in which an iodide ion is released from an iodide ion releasing agent by reaction with an alkali or a nucleophile, can be preferably used.

After the high silver iodide content phase is epitaxially grown on the host grains and then a silver halide shell is formed outside the host tabular grains, dislocation lines are introduced. The composition of the silver halide shell may be any of silver bromide, silver iodobromide and silver chloroiodobromide, but is preferably silver bromide or silver iodobromide. In the case of silver iodobromide, the preferred silver iodide content is 0.1 to 12 mol%, more preferably 0.1 to 10 mol%, and most preferably 0.1 to 3 mol%.
It is.

If the amount is less than 0.1 mol%, effects such as enhancement of dye adsorption and acceleration of development cannot be obtained, which is not preferable. 12 mol%
If it exceeds, the developing speed is undesirably slow.

The amount of silver used for the growth of the silver halide shell is preferably 10 to 50 mol%, more preferably 20 to 40 mol% of the total silver amount.

The preferred temperature in the above-described dislocation line introduction step is 30 to 80 ° C., more preferably 35 to 75 ° C.
° C, particularly preferably 35 to 60 ° C. Performing temperature control at a low temperature of less than 30 ° C. or at a high temperature of more than 80 ° C. requires a high-performance manufacturing apparatus, which is not preferable in manufacturing. In addition, a preferable pA in the above-described dislocation line introduction process.
g is 6.4 to 10.5.

In the case of tabular grains, the position and the number of dislocation lines for each grain as viewed from the direction perpendicular to the main plane can be determined from the photograph of the grain taken using an electron microscope as described above. it can. When dislocation lines are introduced into the tabular grains of the present invention, it is preferable to limit the dislocation lines to the grain fringe portions as much as possible. The fringe portion referred to in the present invention refers to the outer periphery of the tabular grain. Specifically, in the distribution of silver iodide from the side to the center of the tabular grain, the silver iodide content at a certain point when viewed from the side is the grain. Outside the point where the average silver iodide content exceeds or falls below the average.

In the present invention, it is preferable to introduce high-density dislocation lines into the fringe portions of the tabular grains.
Tabular grains having 10 or more dislocation lines per grain are preferred. More preferably 30 or more, even more preferably 5
Zero or more dislocation lines are present in the particle fringe portion. 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, approximately 10, 20, 30
It can be counted as a book.

The tabular grains of the present invention preferably have a uniform dislocation dose distribution between grains from the viewpoint of homogeneity between grains. In the emulsion of the present invention, silver halide tabular grains containing 10 or more dislocation lines per grain in the fringe portion of the grain preferably occupy 50% or more, more preferably 80% or more of the total projected area. If it is less than 50%, it is difficult to obtain high sensitivity, which is not preferable.

In the present invention, silver halide tabular grains containing 30 or more dislocation lines per grain have a total projected area of 5%.
It preferably accounts for 0% or more, more preferably 80% or more.
Account for more than%.

Further, the tabular grains of the present invention desirably have a uniform dislocation line introduction position in the grains. In the emulsion of the present invention, silver halide tabular grains in which dislocation lines are localized substantially only in the fringe portions of the grains preferably occupy 50% or more of the total projected area, more preferably 60% or more, and further preferably 80%. Account for the above.

The fringe region where the dislocation lines are localized is preferably present over much of the outer periphery when the tabular grains are viewed from a direction perpendicular to the main plane. In this case, it is preferable that the number of grains having dislocation lines localized on all six sides is large.

“Substantially only the particle fringe portion” means that the particle fringe portion does not include five or more dislocation lines in the center of the particle. The particle center refers to an inner region surrounded by a fringe region when the particles are viewed from a direction perpendicular to the main plane.

In the present invention, the region of the fringe portion of the tabular grains is preferably 0.05 to 0.25 μm, more preferably 0.10 to 0.20 μm. Outside this range, an increase in the intrinsic sensitivity is difficult to obtain, which is not preferable.

In the present invention, when calculating the ratio of the particles containing dislocation lines and the number of dislocation lines, it is preferable to directly observe the dislocation lines for at least 100 particles.
More preferably 200 particles or more, particularly preferably 300 particles
Observe for more than particles.

The emulsion of the present invention has a total projected area of 50.
% Or more is preferably occupied by tabular grains having an average silver iodide content of the fringe portion of the grain higher than the average silver iodide content of the grain center portion by 2 mol% or more, more preferably an average of the fringe portion of the grain. The silver iodide content is at least 4 mol% than the average silver iodide content at the center of the grain, and more preferably the average silver iodide content at the fringe portion of the grain is higher than the average silver iodide content at the center of the grain. Is also occupied by tabular grains higher than 5 mol%. The silver iodide content in the tabular grains can be determined, for example, by the method described in JP-A-7-219102 using an analytical electron microscope.

The tabular grains in the present invention preferably contain one or more kinds of photographically useful metal ions or complexes (hereinafter referred to as “metal (complex) ions”) in the grains.

The following describes metal ion doping into silver halide grains. The useful metal (complex) ions are those doped into grains for the purpose of improving the photographic characteristics of the photosensitive silver halide emulsion. These compounds function as transient or permanent traps of electrons or holes in the silver halide crystal, and provide effects such as high sensitivity and high contrast, improvement of reciprocity characteristics, and improvement of pressure property. In the present invention, the metal to be doped in the emulsion grains is iron, ruthenium, rhodium, palladium, cadmium, rhenium, osmium, iridium, platinum, chromium, vanadium and other first to third transition metal elements, gallium, indium, thallium An amphoteric metal element such as lead or lead is preferred. These metal ions are doped in the form of a complex salt or a single salt. In the case of a complex ion, a hexacoordinate halogeno complex or cyano complex using a halogen ion or cyanide (CN) ion as a ligand is preferably used.

Also, nitrosyl (NO) ligand, thionitrosyl (NS) ligand, carbonyl (CO) ligand, thiocarbonyl (NCO) ligand, thiocyanate (NCS) ligand, selenocyanate (NCSe) ligand, tellurocyanate (CNTe) Ligands, dinitrogen (N ₂ ) ligands, azido (N ₃ ) ligands, and also organic ligands such as bipyridyl ligands, cyclopentadienyl ligands, 1,2-dithiorenyl ligands, imidazole ligands, etc. Can also be used. As the ligand, the following polydentate ligand may be used. That is, any of a bidentate ligand such as a bipyridyl ligand, a tridentate ligand such as diethylenetriamine, a tetradentate ligand such as triethylenetetraamine, and a hexadentate ligand such as ethylenediaminetetraacetic acid can be used. May be used. The number of ligands is preferably 6, but
4 may be used. As the organic ligand ligand, those described in U.S. Pat. Nos. 5,457,021, 5,360,712 and 5,462,849 are also preferably used. It is also preferred to incorporate metal ions as oligomers, as described in U.S. Pat. No. 5,024,931.

When incorporating metal (complex) ions into silver halide, it is important that the size of the metal (complex) ions be compatible with the silver halide interstitial distance. In addition, it is essential that a compound of a metal (complex) ion and silver or a halogen ion co-precipitate with silver halide in order to dope the silver halide. Therefore, the metal (complex) ion of the compound with silver or halide ion
Ksp (common logarithm of reciprocal of solubility product) is p
Ksp (silver chloride 9.8, silver bromide 12.3, silver iodide 16.1). Therefore, the pKsp of a compound of a metal (complex) ion with silver or a halogen ion is 8 to 20.
Is preferred.

The doping amount of the above metal complex into silver halide grains is generally in the range of 10 ^-9 to 10 per mol of silver halide.
^-2 mole range. Specifically, the metal complex that provides a transient shallow electron trap in the photosensitive process ranges from 10 ^-6 to 10 ^-2 mole per mole of silver halide, and the metal complex that provides a deep electron trap in the photosensitive process is silver halide. It is preferred to use from 10 ^-9 to 10 ^-5 mole per mole.

The metal (complex) ion content of the emulsion grains can be confirmed by atomic absorption, polarized Zeeman spectroscopy and ICP analysis. The ligand of the metal complex ion is infrared absorption (especially FT-I
R).

The above-mentioned doping of the metal (complex) ions into the silver halide grains may be carried out in the surface phase or internal phase of the grains or in US Pat. Nos. 5,132,203 and 4,997,751.
Any of ultra-shallow surface phases (so-called sub-surfaces) that do not expose metal ions to the surface as described in the above paragraph may be selected according to the purpose. Also, a plurality of metal ions may be doped, and they may be doped in the same phase or different phases. These compounds may be added by mixing the metal salt solution with an aqueous halide solution or a water-soluble silver salt solution during grain formation, or by directly adding the metal salt solution. Further, silver halide emulsion fine particles doped with the metal ion may be added. When the metal salt is dissolved in water or a suitable solvent such as methanol or acetone, an aqueous solution of hydrogen halide (eg, HCl, HBr), thiocyanic acid or a salt thereof, or an alkali halide (eg, KCl ,
It is preferable to use a method of adding NaCl, KBr, NaBr, or the like). It is also preferable to add an acid, an alkali or the like, if necessary, in the same manner.

When metal ions of a cyano complex are doped into emulsion grains, the reaction of gelatin with the cyano complex may generate cyan and inhibit gold sensitization. In such a case, it is preferable to use a compound having a function of inhibiting the reaction between gelatin and a cyano complex, as described in, for example, JP-A-6-308653. Specifically, it is preferable to perform the steps after doping with the metal ion of the cyano complex in the presence of a metal ion such as zinc ion that coordinates with gelatin.

Emulsions of the present invention and photographic emulsions other than the present invention used in combination therewith are described in Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (P. Glafkides,
Chemie et Physique Photog
raphique, Paul Montel, 196
7), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photographi).
c Emulsion Chemistry (Foca
l Press, 1966)), "Production and Coating of Photographic Emulsions", by Zerikman et al., published by Focal Press (VL.
Zelikman et al. , Making an
d Coating Photographic Em
ulsion, Focal Press, 1964). That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halide may be any one of a one-side mixing method, a simultaneous mixing method, and a combination thereof. Good. A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

A method in which silver halide grains previously formed are added to a reaction vessel for preparing an emulsion, US Pat. Nos. 4,334,012, 4,301,241 and 4,150,994. Is optionally preferred. These can be used as seed crystals,
It is also effective when supplied as silver halide for growth. In the latter case, it is preferable to add an emulsion having a small grain size, and the addition method can be selected from the method of adding the whole amount at a time, adding in a plurality of times or adding continuously. It is also effective in some cases to add particles of various halogen compositions to modify the surface.

A method for converting most or only a part of the halogen composition of silver halide grains by a halogen conversion method is disclosed in US Pat. Nos. 3,477,852 and 4,1.
No. 42,900, European Patent 273,429, No. 27
No. 3,430, West German Patent No. 3,819,241, etc., which are effective particle forming methods. A solution of a soluble halogen or silver halide grains can be added to convert the silver salt into a sparingly soluble silver salt. It can be selected from methods such as converting at once, converting into a plurality of times, or converting continuously.

As a method of grain growth, besides a method of adding a soluble silver salt and a halogen salt at a constant concentration and a constant flow rate, British Patent No. 1,469,480 and US Pat.
The particle forming method of changing the concentration or changing the flow rate as described in U.S. Pat. Nos. 0,757 and 4,242,445 is a preferable method. By increasing the concentration or increasing the flow rate, the amount of silver halide to be supplied can be changed by a linear function, a quadratic function, or a more complicated function of the addition time. It is also preferable in some cases to reduce the amount of silver halide supplied as necessary. Further, when adding a plurality of soluble silver salts having different solution compositions or adding a plurality of soluble halide salts having different solution compositions, an addition method of increasing one and decreasing the other is also an effective method. It is.

A mixer for reacting a solution of a soluble silver salt and a soluble halide salt is disclosed in US Pat. No. 2,996,287.
No. 3,342,605 and No. 3,415,65
No. 3,785,777, West German Patent 2,5
No. 56,885 and 2,555,364.

A silver halide solvent is useful for the purpose of accelerating ripening. For example, it is known to have an excess of halogen ions in the reactor to promote ripening. Other ripening agents can also be used. These ripening agents can be incorporated in their entirety in the dispersion medium in the reactor before adding the silver and halide salts,
A halide salt, silver salt or deflocculant can be added and introduced into the reactor. As another variant, the ripening agent can be introduced independently during the halide salt and silver salt addition steps.

The ripening agents include, for example, ammonia, thiocyanate (for example, rhodancali, rhodanammonium), and organic thioether compounds (for example, US Pat. Nos. 3,574,628, 3,021,215, No. 3,057,724, No. 3,038,805,
Nos. 4,276,374 and 4,297,439
No. 3,704,130, No. 4,782,01
No. 3, the compound described in JP-A-57-104926. ), Thione compounds (for example, JP-A-53-8240)
No. 8, No. 55-77737, U.S. Pat.
No. 863, compounds described in JP-A-53-144319) and the growth of silver halide grains described in JP-A-57-202531. Mercapto compounds and amine compounds (for example, JP-A-54-100717).

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, sodium alginate and starch derivatives. Various sugar derivatives such as mono- or copolymers such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole A conductive polymer substance can be used.

Examples of gelatin include lime-treated gelatin, acid-treated gelatin and Bull. Soc. Sci. Ph
oto. Japan. No. 16. Enzyme-treated gelatin as described in P30 (1966) may be used, and a hydrolyzate or enzymatic degradation product of gelatin can also be used.

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 ° C 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. The method for washing can be selected from noodle washing, dialysis using a semipermeable membrane, centrifugal separation, 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.

In some cases, a method of adding a chalcogen compound during preparation of an emulsion as described in US Pat. No. 3,772,031 is also useful. In addition to S, Se, and Te, cyanide, thiocyanate, selenocyanic acid, carbonate, phosphate, and acetate may be present.

The silver halide grains of the present invention can be used in at least one of chalcogen sensitization such as sulfur sensitization and selenium sensitization, noble metal sensitization such as gold sensitization and palladium sensitization, and reduction sensitization. It can be applied in any step of the production process of the silver emulsion. 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 combination of chalcogen sensitization and noble metal sensitization, alone or in combination, and is described by TH (James), The Photographic Process, Vol. Edition, published by Macmillan, 1
977, (TH James, The Theor)
y of the Photographic Pro
cess, 4th ed, Macmillan, 197
7) can be performed using active gelatin as described on pages 67-76, and can also be performed by Research Disclosure, Volume 120, April 1974, 12008; Research Disclosure, Volume 34, June 1975,
13452; U.S. Pat. Nos. 2,642,361; 3,297,446; 3,772,031; 3,857,711; 3,901,714; No. 3,266,018 and No. 3,904,41.
5 and pAg 5-10, pH 5-8 and temperature 30-8 as described in GB 1,315,755.
At 0 ° C., it can be sulfur, selenium, tellurium, gold, platinum, palladium, iridium or a combination of a plurality of these sensitizers. In precious metal sensitization, gold, platinum,
Noble metal salts such as 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 R
It is represented by 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.

More specifically, K ₂ PdCl ₄ , (NH ₄ ) ₂ P
dCl ₆ , Na ₂ PdCl ₄ , (NH ₄ ) ₂ PdCl ₄ , Li
₂ PdCl ₄ , Na ₂ PdCl ₆ or K ₂ PdBr ₄ is preferred. The gold compound and the palladium compound are preferably used in combination with a thiocyanate or a selenocyanate.

As sulfur sensitizers, hypo, thiourea compounds, rhodanine compounds and US Pat. No. 3,857,
Nos. 711, 4,266,018 and 4,0
No. 54,457 can be used. Chemical sensitization can also be performed in the presence of a so-called chemical sensitization aid. Useful chemical sensitization aids include azaindene, azapyridazine, azapyrimidine,
Compounds known to suppress fog and increase sensitivity during the process of chemical sensitization are used. Examples of the chemical sensitization aid modifier are described in U.S. Pat. Nos. 2,131,038, 3,411,914, 3,554,757, JP-A-58-126526 and the above-mentioned duffin. "Photographic 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 1 per mole of silver halide.
It is from × 10 ⁻³ to 5 × 10 ⁻⁷ mol. The preferred range of the thiocyan compound or the selenocyan compound is from 5 × 10 ⁻² to 1 × 10 ⁻⁶ mol per mol of silver halide.
The preferred amount of the sulfur sensitizer used for the silver halide grains of the present invention is 1 × 10 ^-4 to 1 × per mol of silver halide.
10 ^-7 mol, more preferably 1 × 10 ^{-5 to} 5
× 10 ^-7 mol.

Selenium sensitization is a preferred sensitizing method for the emulsion of the present invention. In the selenium sensitization, a known unstable selenium compound is used. Specifically, colloidal metal selenium, selenoureas (for example, N, N-dimethylselenourea, N, N-diethylselenourea), selenoketones And selenium compounds such as selenoamides. 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 is a method in which a reduction sensitizer is added to a silver halide emulsion, or pAg1 called silver ripening.
A method of growing or ripening in a low pAg atmosphere of ~ 7,
Any method of growing or ripening in a high pH atmosphere of pH 8 to 11, which is called high pH ripening, can be selected. 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.

Examples of the reduction sensitizer include stannous salts,
Ascorbic acid and its derivatives, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds and borane compounds 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. As the reduction sensitizer, stannous chloride, thiourea dioxide, dimethylamine borane, ascorbic acid and derivatives thereof are preferred compounds. 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 an organic solvent such as alcohols, glycols, ketones, esters and amides and added during grain growth.
It may be added to the reaction vessel in advance, but a method of adding at an appropriate time during the particle growth is preferable. Alternatively, a reduction sensitizer may be added in advance to the water solubility 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, for example, silver halide, sulfide
May form poorly soluble silver salts such as silver and silver selenide.
And may form a silver salt easily soluble in water such as silver nitrate.
No. The oxidizing agent for silver can be inorganic or organic.
There may be. As the inorganic oxidizing agent, for example, Ozo
Hydrogen peroxide and its adducts (eg, NaBO)_Two
・ H_TwoO_Two・ 3H_TwoO, 2NaCO_Three・ 3H_TwoO_Two, Na_FourP_Two
O7.2H_TwoO_Two, 2Na_TwoSO_Four・ H_TwoO_Two・ 2H_TwoO), pe
Leuoxy acid salt (for example, K_TwoS_TwoO₈, K_TwoC_TwoO₆, K_TwoP_Two
O₈), 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),
Chromate (eg, K_TwoCr_TwoOxygen acids such as O7)
Salts, halogen elements such as iodine and bromine, perhalates
(Eg, potassium periodate), high valent metal salts
(Eg potassium hexacyanoferrate) and thio
There are sulfonates.

Examples of the organic oxidizing agent include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (eg, N-
Bromsuccinimide, chloramine T, chloramine B)
Is given as an 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 fogging during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. . That is, thiazoles, for example, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole);
Mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3
a, 7) known as antifoggants or stabilizers, such as tetraazaindenes and pentaazaindenes;
Many compounds can be added. For example, U.S. Patent Nos. 3,954,474 and 3,982,947,
Those described in JP-B-52-28660 can be used. One of the preferred compounds is disclosed in JP-A-63-21.
2932. 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 photographic emulsion used in the present invention is preferably spectrally sensitized by a methine dye or the like to exhibit the effects of the present invention. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of nuclei usually used as basic heterocyclic nuclei in cyanine dyes can be applied to these dyes. That is, for example, a pyrroline nucleus, an oxazoline nucleus,
Thiozoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus; nuclei in which alicyclic hydrocarbon rings are fused to these nuclei; and aromatic hydrocarbon rings in these nuclei Fused nuclei, for example, indolenine nucleus, benzoindolenine nucleus, indole nucleus, benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus it can. These nuclei may have a substituent on a carbon atom.

The merocyanine dye or the complex merocyanine dye includes, as a nucleus having a ketomethylene structure, for example,
Pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidine-2,4-dione nucleus, thiazolidine-
A 5- or 6-membered heterocyclic nucleus such as a 2,4-dione nucleus, a rhodanine nucleus and a thiobarbituric acid nucleus can be applied.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. Representative examples are U.S. Pat. Nos. 2,688,545 and 2,972.
No. 7,229, No. 3,397,060, No. 3,5
No. 22,052, No. 3,527,641, No. 3,
Nos. 617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703,377,
Nos. 3,769,301 and 3,814,609
No. 3,837,862, No. 4,026,70
7, UK Patent Nos. 1,344,281 and 1,50
7,803, JP-B-43-4936, 53-12
No. 375, JP-A-52-110618, JP-A-52-10
No. 9925.

In addition to the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization.

The sensitizing dye may be added to the emulsion at any stage in the preparation of the emulsion which has hitherto been known to be useful. Most commonly, it is performed after completion of chemical sensitization but before coating, but US Pat.
As described in JP-A-8-969 and JP-A-4225666, spectral sensitization may be carried out simultaneously with chemical sensitization by simultaneous addition with a chemical sensitizer.
It can be carried out prior to chemical sensitization as described in No. 928, or it can be added before the completion of silver halide grain precipitation to start spectral sensitization. Furthermore, these compounds may be added separately as taught in U.S. Pat. No. 4,225,666, i.e., some of these compounds may be added prior to chemical sensitization and the remainder chemically sensitized. It is also possible to add the silver halide grains after the silver halide grains have been formed, and may be added at any time during the formation of silver halide grains, including the method disclosed in U.S. Pat. No. 4,183,756.

The amount of addition was 4 × / mol of silver halide.
Although it can be used in an amount of 10 ^-6 to 8 × 10 ^-3 mol, about 5 × 10 ^-5 to 2 × 10 ^-3 mol is effective when the silver halide grain size is more preferably 0.2 to 1.2 μm. is there.

The light-sensitive material of the present invention may be provided with at least one light-sensitive layer 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, 62-206
As described in 541 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.

Further, as described in JP-B-55-34932, the blue-sensitive layer / GH / RH
They can also be arranged in the order of / GL / RL. JP-A-56-2
As described in 5738 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. The arrangement may be changed as described above even in the case of four or more layers.

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 spectral sensitivity distribution different from that of the main photosensitive layers such as BL, GL, and RL described in the specification of JP-A-63-89850, adjacent to or adjacent to the main photosensitive layer.

The coated silver amount of 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 that can be used in the present invention are 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 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 pages 876-877 Inhibitors 10. Matsuto 878-879.

Although various dye-forming couplers can be used in the light-sensitive material of the present invention, 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 1, lines 45 to 55, couplers represented by general formula (I); JP-A-4-74425, paragraph 0008, couplers represented by 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
(Page 41)); US Pat. No. 4,476,219, column 7, lines 36 to 58, formula (II)
~ (IV) (especially II-17,19 (column 1
7), 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); EP 486,
965 M-4, -6 (p. 26), M-7 (p. 27); EP 571, 959A M-45 (19
(M page) of JP-A-5-204106 (page 6); M-22 of paragraph 0237 of JP-A-4-36631.

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 (page 35), 34, 35 (page 37), (I-1), (I-17) (pages 42 to 43); Japanese Patent Application Laid-Open No. 6-67385, claim 1 wherein the general formula (Ia) or (Ib) ). Polymer coupler: JP-A-2-44345
P-1, P-5 (page 11).

Examples of couplers in which the coloring dye has 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),
Preference is given to colorless masking couplers of formula (A) of claim 1 of WO 92/11575 (especially the exemplary compounds on pages 36 to 45).

Examples of the coupler releasing a photographically useful group 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)), EP 4
Compounds represented by formula (I) described on page 7 of 36,938A2 (especially D-49 (page 51)), compounds represented by formula (1) of EP 568,037A (especially (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 (particularly, (60),
(61)) and the compound represented by the formula (I) of claim 1 of JP-A-6-59411 (particularly (7) (page 7));
A compound represented by LIG-X described in claim 1 of 4,555,478 (especially a compound on line 21 to 41 of column 12); a leuco dye-releasing compound: compound 1 of column 3 to 8 of US 4,749,641
~ 6; fluorescent dye releasing compound: of claim 1 of US 4,774,181
Compound represented by COUP-DYE (especially compounds 1 to 11 in columns 7 to 10); Development accelerator or fogging agent releasing compound: US
4,656,123, compounds of formulas (1), (2), (3) in column 3 (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 of oil-soluble organic compound: P-3, JP-A-62-215272
5, 16, 19, 25, 30, 42, 49, 54, 55, 66, 81, 85, 86,
93 (pp. 140-144); Latex for impregnation of oil-soluble organic compound: latex as described in US Pat. In particular, I- (1), (2), (6), (12)
(Columns 4-5), US Pat. No. 4,923,787, column 5, lines 5-10 (especially compound 1 (column 3); stain inhibitor: EP
Formulas (I) to (III) on page 4, lines 30 to 33 of 298321A, especially I-47, 72,
III-1, 27 (pages 24 to 48); Anti-fading agent: A-6 of EP 298321A,
7, 20, 21, 23, 24, 25, 26, 30, 37, 40, 42, 48, 63,
90, 92, 94, 164 (pages 69 to 118), US 5, 122, 444, column 25
~ 38 II-1 ~ III-23, especially III-10, EP 471347A 8 ~ 12
Pages I-1 to III-4, especially II-2, columns 32 to US 5,139,931
40 A-1 to 48, especially A-39, 42; Material that reduces the amount of color enhancer or color mixture inhibitor used: EP 411324A, pages 5 to 24
I-1 to II-15, especially I-46; Formalin Scavenger: EP
477932A SCV-1 to 28 on pages 24-29, especially SCV-8; hardeners:
Compounds represented by formulas (VII) to (XII) in columns 13 to 23 of H-1,4,6,8,14, US 4,618,573 on page 17 of JP-A-1-148845.
54), the compound (H-1 to 76) represented by the formula (6) on the lower right of page 8 of JP-A-2-214852, especially claim 14 of H-14, US 3,325,287.
Compounds described in the above; Development inhibitor precursor: JP-A-62-1
Compounds described in claim 1 of US Pat. No. 5,019,492, especially 28, 29 of column 7; Preservatives and fungicides: I of columns 3 to 15 of US Pat. No. 4,923,790 -1 to III-4
3, 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 4,952,483, column 25-32, compound 1
~ 65, especially 36: Chemical sensitizer: triphenylphosphine
Selenide, Compound 50 of JP-A-5-40324; Dye: JP-A-3-13-1
A-1 to b-20 on pages 15 to 18 of 56450, especially a-1, 12, 18, 27, 3
5, 36, b-5, V-1 to 23 on pages 27 to 29, especially V-1, EP 445627
FI-1 to F-II-43 on pages 33 to 55 of A, especially FI-11, F-II-8, E
III-36 on pages 17-28 of P 457153A, especially III-1,3, WO 88
/ 04794 8 ~ 26 Dye-1 ~ 124 microcrystal dispersion, EP319999
Compounds 1 to 22, especially Compound 1, EP 519306A on pages 6 to 11 of A
Compounds D-1 to 87 (3 to 2) represented by Formulas (1) to (3)
8), compounds 1 to 22 represented by formula (I) of US 4,268,622.
(Columns 3 to 10), compounds (1) to (31) represented by the formula (I) of US Pat. No. 4,923,788 (columns 2 to 9); UV absorber: JP-A-46-333
Compounds (18b) to (18r) represented by the formula (1) of 5, 101 to 427
(Pages 6 to 9), compound (3) represented by formula (I) in EP 520938A
~ (66) (pages 10 to 44) and the compound HBT-1 represented by the formula (III)
~ 10 (page 14), compound (1) represented by formula (1) of EP 521823A
~ (31) (columns 2-9).

The present invention can be applied to various color light-sensitive 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, 2-26,315 and 3,
Suitable for a film unit with lens described in -39784.

Suitable supports which 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. 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 15 seconds. Is defined.
The film thickness refers to a film thickness measured at 25 ° C. and a relative humidity of 55% under humidity control (2 days), and T _1/2 is a _{value obtained} by A. Green et al. In Photographic Science and Engineering. (Photogr. Sci. Eng.), 19 volumes, 2,124-129
It can be measured by using a serometer (swelling meter) of the type described on page. T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. Also,
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 having a total dry film thickness of 2 to 20 μm (referred to as a back layer) 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 obtained by using the above-mentioned RD.
No. 18716, No. 18716, 651 left column to right column, and N
o. 307105, pages 880 to 881.

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 0.01 to 0.08 per liter of a color developing solution (hereinafter also referred to as “L”).
It is preferable to use it in a molar range, particularly from 0.015 to
Preferably, it is used in an amount of 0.06 mol, more preferably 0.02 to 0.05 mol. Also, the replenisher of the color developing solution has this concentration.
It is preferable to contain 1.1 to 3 times the color developing agent, particularly preferably 1.3 to 2.5 times.

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 an amount of 0.02 to 0.2 mol per liter, particularly 0.03 to 0.15 mol, more preferably 0.03 to 0.15 mol.
It is preferable to use it in the range of 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 agent for preventing tartarization of the oxide of the color developing agent. The sulfite is preferably used in a range of 0.01 to 0.05 mol per liter, particularly preferably in a 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 developer 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 high value within 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 replenishing amount of the color developing solution is preferably from 80 to 1300 ml per m ² of the light-sensitive material (hereinafter also referred to as “mL” as a binder), but is preferably smaller from the viewpoint of reducing the environmental pollution load. Specifically, 80-600 mL,
Further, the volume is preferably 80 to 400 mL.

The bromide ion concentration in the color developing solution is usually from 0.01 to 0.06 mol per liter. However, fog is suppressed while maintaining sensitivity, discrimination is improved, and graininess is improved. From the purpose, per 1L
It is preferably set to 0.015 to 0.03 mol. 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 / L) A: target bromide ion concentration in the color developing solution (mol / L) W: 1 m ² exposure Amount (mol) of bromide ions eluted from the light-sensitive material into the color developer when the material is color-developed. V: Replenishment amount (L) of the color-developing replenisher for 1 m ² of the light-sensitive material.

When the replenishment rate is reduced or when a high bromide ion concentration is set, as a method for increasing the sensitivity, 1-phenyl-3-pyrazolidone or 1-phenyl-
Pyrazolidones represented by 2-methyl-2-hydroxymethyl-3-pyrazolidone and 3,6-dithia-1,8
It is also preferable to use a development accelerator such as a thioether compound represented by 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 include 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.

In order to improve the biodegradability of the bleaching agent, JP-A-4-251845, JP-A-4-268552, EP588,289, EP591,
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 bleaching ability, and particularly preferably 0.1 mol to 0.15 mol for the purpose of reducing the amount discharged to the environment. When the liquid having bleaching ability is a bleaching liquid, it is preferable to contain 0.2 mol to 1 mol of bromide per liter, especially 0.3 to 0.8 mol.
It is preferable to include a mole.

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.

CR = CT × (V1 + V2) / V1 + CP CR: Concentration of component in replenisher CT: Concentration of component in mother liquor (treatment tank solution) CP: Concentration of component consumed during treatment V1: 1 m ² Replenishment amount of replenisher having bleaching ability for photosensitive material (mL) V2: Amount (mL) brought in from the previous bath by 1 m ² of photosensitive material.

In addition, the bleaching solution preferably contains a pH buffer, and 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-53-9
It is also preferred to use the known bleaching accelerators described in US Pat. No. 5,630, RD No. 17129, US Pat.

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

The processing solution having a fixing ability is disclosed 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.

Particularly, in order to improve the fixing speed and the preservability, the processing solution having the fixing ability by using the compounds represented by the general 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 eliminated. Is more preferred. In the bleaching, bleach-fixing and fixing steps, JP-A-1-30
It is particularly preferred to carry out jet stirring as described in 9059. The replenishment amount of the replenisher in the bleach-fixing or fixing process is
100 to 1000 mL per 1 m ^{2 of} photosensitive material, preferably 150 to 1000 mL
700700 mL, particularly preferably 200-600 mL.

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 composed of multiple processing tanks,
Preferably, each tank is cascaded to provide a multi-stage countercurrent system. In general, a two-tank cascade configuration is efficient from the balance with the size of the developing machine, and the ratio of the processing time in the former tank to that in the latter tank is 0.5: 1 to 1: 1.
The ratio is preferably in the range of 1: 0.5, particularly 0.8: 1 to 0.8: 1.
A range of 1: 0.8 is preferred.

It is preferable that a free chelating agent not forming a metal complex is present in the bleach-fixing solution or the fixing solution from the viewpoint of improvement of 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, see JP-A-4-125558, page 12, lower right column, line 6 to page 13, lower right column, page 16.
The contents described in the line can be preferably applied. In particular, EP504,60 instead of formaldehyde is used in the stabilizing solution.
Azolylmethylamines described in 9, 519, 190 and
Use of the N-methylolazoles described in 4-362943 or dimerization of the magenta coupler to form a surfactant-free liquid containing no image stabilizer such as formaldehyde can improve the working environment. Is preferred. Also,
In order to reduce the adhesion of dust to the magnetic recording layer applied to the photosensitive 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
80 to 1000 mL per m ² is preferable, and particularly 100 to 500 mL, and more preferably 150 to 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 performed with such a replenishing amount, thiabendazole, 1, 1
2-benzoisothiazoline-3-one, 5-chloro-2-
It is preferable to use a known fungicide such as methylisothiazolin-3-one, an antibiotic such as gentamicin, or water deionized with an ion exchange resin.
It is more effective to use a combination of deionized water and a bactericide or antibiotic. The liquid in the washing or stabilizing liquid tank is described in 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 the Invention Association's Published Technical Report, Publication 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 treatment agent used in the present invention is:
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 powder 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
JP-A-48585 discloses a paste-like treatment agent, and any of them can be preferably used, but from the viewpoint of simplicity in 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 used in the present invention. Will be described.

For the processing for the color reversal film,
Aztec Co., Ltd. No. 6 (April 1, 1991), page 1, line 5 to page 10, line 5, and page 15, line 8 to line 24
It is described in detail in line 2 of the page, 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. Examples of preferred color reversal film processing agents containing the above contents include Eastman Kodak E-6 processing agent and Fuji Photo Film Co., Ltd.
CR-56 treating agent.

Next, the magnetic recording layer preferably 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 ₂ O
₃ , ferromagnetic iron oxide such as ₃ , Co-coated γFe ₂ O ₃ , Co-coated magnetite, Co-containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy, hexagonal Ba ferrite, Sr ferrite, Pb ferrite , Ca ferrite and the like can be used. Co-coated ferromagnetic iron oxide, such as Co-coated γFe ₂ O _3, is preferred. The shape may be any of needle shape, rice grain shape, spherical shape, cubic shape, plate shape and the like. Preferably at least 20 m ² / g in S _BET is the specific surface area, and particularly preferably equal to or greater than 30 m ² / g. The saturation magnetization (σs) of the ferromagnetic material is preferably from 3.0 × 10 ^{4 to} 3.0 × 10 ⁵ A / m, and particularly preferably from 4.0 × 10 ^{4 to} 2.5 × 10 ⁵ mA / 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. Further, magnetic particles having a surface coated with an inorganic or organic substance described in JP-A-4-259911 and JP-A-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, or 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
It is between 2,000 and 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 preferred. The binder can be cured by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent. As the isocyanate-based crosslinking agent, tolylene diisocyanate,
Isocyanates such as 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and the reaction products of these isocyanates with polyalcohols (for example, the reaction product of 3 mol of tolylene diisocyanate and 1 mol of trimethylolpropane) ), And polyisocyanates formed by condensation of these isocyanates, and the like, which are described in, for example, JP-A-6-59357.

As a method for dispersing the above-mentioned magnetic substance 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,
More preferably, it is 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 1: 100 to 30: 100. The coating amount of the magnetic particles is 0.005 to 3 g / m ² , preferably 0.01 to ² g / m ² , and 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, and 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. Methods for applying the magnetic recording layer include air doctor, blade, air knife, squeeze, impregnation, reverse roll, transfer roll, gravure, kiss, cast, spray,
Dip, bar, extrusion, etc. are available,
The coating liquid described in JP-A-5-341436 is preferred.

The magnetic recording layer has lubricating properties, curl control,
It may have functions such as antistatic, antiadhesion, 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. 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. US 5,336,589, US 5,250,404, US 5,336,589
229,259, 5,215,874 and EP466,130.

Next, the polyester support 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 Technical Publication No. 94-6023 (Invention Association; 1994.3 .15.).
The polyester used in the present invention is formed by using a diol and an aromatic dicarboxylic acid as essential components, and 2,6-, 1,5-, 1,4-, and 2,7 as aromatic dicarboxylic acids.
-Naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, diethylene glycol as diol,
Examples include triethylene glycol, cyclohexanedimethanol, bisphenol A, and bisphenol.
Examples of the polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is a polyester containing 50 to 100 mol% of 2,6-naphthalenedicarboxylic acid. Among them, polyethylene 2,6-naphthalate is particularly preferred. Average molecular weight ranges from about 5,000 to 2
00,000. The Tg of the polyester of the present invention is 50 ° C. or higher, 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, or may be performed while cooling. The heat treatment 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. Irregularities may be imparted to the surface (for example, conductive inorganic fine particles such as SnO ₂ or Sb ₂ O ₅ 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 may be performed at any stage after the formation of the support, 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 absorbent may be mixed in this polyester. In order 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 the binder for the undercoat layer, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, including copolymers starting from monomers selected from maleic anhydride, as a starting material, Examples include polyethyleneimine, epoxy resin, grafted gelatin, nitrocellulose, and gelatin.
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. Examples of such antistatic agents include polymers containing carboxylic acid and carboxylate and sulfonate, cationic polymers, and ionic surfactant compounds.

The most preferred antistatic agent is Zn.
O, TiO_Two, SnO_Two, Al_TwoO_Three, In_TwoO_Three, SiO _Two, MgO, BaO, Mo
O_Three, V_TwoO_FiveAt least one type of volume resistivity selected from
Ten⁷Ωcm or less, more preferably 10^FiveGrains that are Ω · cm or less
0.001 to 1.0 μm crystalline metal oxide or
Of these complex oxides (Sb, P, B, In, S, Si, C, etc.)
Fine particles, sol-like metal oxides or composites of these
Fine particles of composite oxide. The content in the photosensitive material is 5
~ 500mg / m^TwoIs preferably 10 to 350 mg / m^TwoIn
You. Conductive crystalline oxide or its composite oxide and vine
The ratio of the amount of the dough is preferably 1/300 to 100/1, more preferably
Is 1/10 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 a value when the stainless steel ball having a diameter of 5 mm was conveyed at 60 cm / min (25
° C, 60% RH). In this evaluation, even when the surface of the photosensitive layer is replaced as the partner material, the values are almost the same level.

The sliding agents 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 the like, and polyorganosiloxanes include 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 1.1.
It is preferable that 90% or more of the total number of particles be contained during the doubling. 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) and 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 described in JP-A 1-312537 and JP-A 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 135 size at present, and for miniaturization of the camera,
It is also effective to reduce the diameter of the current 135 size 25 mm cartridge to 22 mm or less. The volume of the patrone case is preferably 30 cm ³ or less, more preferably 25 cm ³ or less. The weight of the plastic used for the patrone and the patrone case is preferably 5 g to 15 g.

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 housed 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 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 cartridge film for a system is used by being loaded into a camera for an AP system such as an EPION series (EPION 300Z, etc.) manufactured by FUJIFILM Corporation. Further, the color photographic light-sensitive material of the present invention is also suitable for a film with a lens such as a super slim, which is a Fujicolor photograph run made by FUJIFILM.

The film photographed in these manners is printed through the following steps in the minilab system.

(1) Acceptance (exposed cartridge film received from customer) (2) Detach process (transfer the film from cartridge to intermediate cartridge for development process) (3) Film development (4) Retouch process (development (5) Print (continuous automatic printing of C / H / P3 type print and index print on color paper (preferably SUPER FA8 made by FUJIFILM)) (6) Collation・ Shipping (collating cartridges and index prints with ID numbers, and shipping with prints).

These systems include Fujifilm Minilab Champion Super FA-298 / FA-278 / FA-258 / F
A-238 and Fujifilm Digital Lab System Frontier are preferred. FP922AL / FP562B / FP562B, AL / FP362B / FP as minilab champion film processors
362B, AL, and the recommended treatment chemicals are Fujicolor Justit CN-16L and CN-16Q. As a printer processor, PP3008AR / PP3008A / PP1828AR / PP1828A / PP12
58AR / PP1258A / PP728AR / PP728A, and the recommended treatment chemicals are Fujicolor Justit CP-47L and CP-40FAII. In 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 Fujifilm's DT200 / DT100 and AT200 / AT100, respectively.

The AP system can also be enjoyed by a photo joy system centered on Fujifilm's Aladdin 1000 digital image workstation. 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 output digital information directly to a floppy (registered trademark) disk or Zip disk, or to a CD-R via a CD writer.

On the other hand, at home, the developed AP system cartridge film is transferred to a photo player AP manufactured by FUJIFILM.
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 enter a film, print, or three-dimensional object into a 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.

[0201]

Examples of the present invention will be described below. However, it is not limited to this embodiment. (Example 1) Gelatin-1 to gelatin-4 used as a dispersion medium in the following emulsion preparation are gelatins having the following attributes.

Gelatin-1: Normal alkali-treated ossein gelatin using bovine bone as a raw material. The molecular weight distribution is polydisperse with multiple peaks. The ratio of the H2 component to the sum of the α, β, and γ components of gelatin is 0.07,
The ratio of the L2 component to the sum of the β and γ components was 0.035.

Gelatin-2: Gelatin obtained by reducing the molecular weight of gelatin-1 by the action of an enzyme to make the average molecular weight 15,000, inactivating the enzyme, and drying. The ratio of the H2 component to the sum of the α, β, and γ components of gelatin was 0.007, and the ratio of the L2 component to the sum of the α, β, and γ components of gelatin was 0.098.

Gelatin-3: A 40 ° C. aqueous solution of the above gelatin-1 was introduced into a high-pressure homogenizer, and the flow rate was 460 mL / min.
The gelatin was dried by passing it once at a pressure difference of 100 MPa. The ratio of the H2 component to the sum of the α, β, and γ components of gelatin was 0.011, and the ratio of the L2 component to the sum of the α, β, and γ components of gelatin was 0.035.

Gelatin-4: A 40 ° C. aqueous solution of the above gelatin-1 was introduced into a high-pressure homogenizer, and the flow rate was 460 mL / min.
The gelatin was dried by passing it once at a pressure difference of 150 MPa. The ratio of the H2 component to the sum of the α, β, and γ components of gelatin was 0.005, and the ratio of the L2 component to the sum of the α, β, and γ components of gelatin was 0.033.

(Preparation of emulsion) Emulsion 1-A (Preparation of seed crystal) 5.0 g of the above gelatin-1 and KB
Then, 1600 mL of an aqueous solution containing 4.3 g of r was stirred at 40 ° C., and 41 mL of a 1.2 M AgNO ₃ aqueous solution and K
41 m of a 1.26 M KBr aqueous solution containing 4.3 mol% of I
L was added simultaneously with a double jet for 40 seconds. Then, after adding 22 g of gelatin-1, 58
After raising the temperature to ℃ and adjusting the pAg to 8.44, ammonia was added and the mixture was aged for 15 minutes and then neutralized. Next, 647 mL of a 1.9 M AgNO ₃ aqueous solution and 1.9 M K
The Br aqueous solution and pAg were added at the same time for 55 minutes while accelerating the flow rate while keeping the pAg at 8.10 (the flow rate at the end was 5 times that at the start). Thereafter, the emulsion was cooled to 35 ° C., washed with water by a conventional flocculation method, and dispersed by adding 42 g of gelatin-1 to pH = 6.2 and pAg = 8.9.

(Grain Growth) 48 g of the seed crystal containing silver iodobromide equivalent to 9.3 g of AgNO ₃ was added to 1145 m of water.
L and 31 g of gelatin-1 were added, and the mixture was stirred at 75 ° C. and adjusted to pH = 5.5 and pAg = 8.44. Thereafter, 479 mL of a 1.9 M AgNO ₃ aqueous solution and a 1.7 M KBr aqueous solution containing 2.7 mol% of KI were accelerated while maintaining the pAg at 8.29 (the flow at the end was 2 at the start). .4 times) at the same time for 48 minutes. Furthermore, 50 mL of a 1.9 M AgNO ₃ aqueous solution and 1.9 M KB
r aqueous solution at the same time with a fixed pAg of 8.44.
Minutes. Thereafter, the temperature was lowered to 40 ° C. in 25 minutes, and an aqueous solution containing 10.5 g of sodium p-iodoacetamidobenzenesulfonate (monohydrate) as an iodide ion releasing agent was added, and then 40 mL of a 0.8 M aqueous sodium sulfite solution was added. Was added in a fixed amount for 1 minute to generate iodide ions while controlling the pH at 9.0. After 2 minutes, the temperature was raised to 55 ° C. over 15 minutes, and then the pH was returned to 5.5. Thereafter, sodium benzenethiosulfonate and K ₂ IrC
l ₆ with respect to the total silver content of each grain is 3.8 × 10 ^-6
Mol / mol silver, 1 × 10 ⁻⁸ mol / mol silver was added as a solution, and 1.9 mL of a 1.9 M AgNO ₃ aqueous solution and 1.9 mL were added.
An aqueous KBr solution of M was simultaneously added for 30 minutes in a fixed amount while keeping the pAg at 8.59.

(Washing, dispersion) Thereafter, the emulsion was washed at 35 ° C.
, And washed with water by a conventional flocculation method, the pH was increased, and 70 g of gelatin-1 was added and dispersed.
8, pAg was adjusted to 8.8.

The shape of the grains in the emulsion was determined by taking a transmission electron micrograph by a replica method and measuring 1000 grains (the same applies to the following emulsions 1-B to 1-L).

In the grains in the emulsion thus obtained, tabular grains accounted for 95% (number) or more of all grains, and the ratio of the projected area of tabular grains to the projected area of all grains exceeded 97% (hereinafter, referred to as the following). The same was true for the emulsions 1-B to 1-L). The average equivalent spherical phase diameter of all grains was 1.20 μm (the same applies to the following emulsions 1-B to 1-L).

Table 1 shows the aspect ratio and twin plane spacing of grains occupying 50% or more of the total projected area. Furthermore, a high-pressure type (acceleration voltage 400 k
V) Observation of dislocation lines by electron microscope (introduction position, density,
Distribution). Ratio of tabular grains having 10 or more dislocation lines per grain substantially only in the fringe portion of the obtained emulsion to all grains (projected area%)
Was 80% or more (the same applies to the following emulsions 1-B to 1-L).

(Chemical sensitization) Sensitizing dyes ExS-8, ExS
After addition of -9 and ExS-10, K2IrCl6,
Potassium thiocyanate, chloroauric acid, sodium thiosulfate and N, N-dimethylselenourea were added for optimal chemical sensitization. At the end of chemical sensitization, compound 2 and compound 3 were added.

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[Table 1]

The gelatin used in the grain formation method (preparation of seed crystal, grain growth) of the above method was replaced with the gelatin shown in Table 1, and the temperature at the time of nucleation, pAg, the amount of nucleated silver, the amount of gelatin added and the ripening time And the pAg during grain growth was adjusted to prepare emulsions 1-B to 1-L having the grain shapes shown in Table 1 above.

The following methods were used to prepare silver halide emulsions D to R
Was prepared. (Production method of emulsion D) 31.7 g of phthalated low molecular weight gelatin having a phthalation rate of 97% and a molecular weight of 15,000, KBr3
42.2 L of an aqueous solution containing 1.7 g was maintained at 35 ° C and stirred vigorously. Aqueous solution 15 containing 316.7 g of AgNO ₃
833 mL, 1583 mL of an aqueous solution containing KBr, 221.5 g, and 52.7 g of the above gelatin-4 were added over 1 minute by the double jet method. Immediately after the addition, KBr
After adding 52.8 g, 2485 mL of an aqueous solution containing 398.2 g of AgNO ₃ and 2581 mL of an aqueous solution containing 291.1 g of KBr were added over 2 minutes by a double jet method. Immediately after the addition was completed, 44.8 g of KBr was added.

Thereafter, the temperature was raised to 40 ° C. to ripen. After ripening, 923 g of the above gelatin-4 and KBr, 79.
2 g, an aqueous solution 1 containing 5103 g of AgNO ₃
5947 mL and KBr aqueous solution were accelerated by the double jet method so that the final flow rate was 1.4 times the initial flow rate, and 1
Added over 0 minutes. At this time, the pAg of the bulk emulsion solution in the reaction vessel was kept at 9.90. After washing with water, the above gelatin-4 was added to adjust the pH to 5.7, the pAg, 8.8, the weight in terms of silver per kg of the emulsion to 131.8 g, and the gelatin weight to 64.1 g to obtain a seed emulsion.

46 g of the above gelatin-4, 1.7 of KBr
g of an aqueous solution containing 11 g was maintained at 75 ° C. and stirred vigorously. After adding 9.9 g of the above seed emulsion, 0.3 g of modified silicone oil (L7602 manufactured by Nippon Unicar Co., Ltd.) was added. After adding H ₂ SO ₄ to adjust the pH to 5.5, an aqueous solution containing 7.0 g of AgNO ₃ 67.
6 mL and KBr aqueous solution were added by a double jet method over 6 minutes while accelerating the flow rate so that the final flow rate was 5.1 times the initial flow rate. At this time, the pAg of the bulk emulsion solution in the reaction vessel was kept at 8.15.

2 mg of sodium benzenethiosulfonate
And after addition of thiourea dioxide 2 mg, the AgNO ₃ 1
328 mL of an aqueous solution containing 05.6 g and an aqueous KBr solution were added by a double jet method over a period of 56 minutes while accelerating the flow rate so that the final flow rate was 3.7 times the initial flow rate. At this time, an AgI fine grain emulsion having a grain size of 0.037 μm was simultaneously added at an accelerated flow rate such that the silver iodide content became 27 mol%, and p of the bulk emulsion solution in the reaction vessel was added.
Ag was kept at 8.60. 121.3 mL of an aqueous solution containing 45.6 g of AgNO ₃ and an aqueous KBr solution were added over 22 minutes by a double jet method. At this time, the pAg of the bulk emulsion solution in the reaction vessel was kept at 7.60.

The temperature was raised to 82 ° C., KBr was added to adjust the pAg of the bulk emulsion solution in the reaction vessel to 8.80, and the AgI fine grain emulsion described above was converted to 6.3 in terms of KI weight.
3 g were added. Immediately after the addition is completed, AgNO ₃ is added for 6 hours.
206.2 mL of an aqueous solution containing 6.4 g was added over 16 minutes. During the initial 5 minutes of the addition, the pAg of the bulk emulsion solution in the reaction vessel was kept at 8.80 with an aqueous KBr solution. After washing with water, the above gelatin-4 was added and the mixture was adjusted to pH 5 at 40 ° C.
It adjusted to 8, pAg, and 8.7, and heated up to 60 degreeC. After adding the sensitizing dyes ExS-2 and ExS-3, potassium thiocyanate, chloroauric acid, sodium thiosulfate,
N, N-dimethylselenourea was added for optimal chemical sensitization. At the end of the chemical sensitization, Compound 2 and Compound 1 were added. Here, the optimal chemical sensitization means that the sensitizing dye and each compound are used in an amount of 10 ^-1 to 1 per mol of silver halide.
It means that it was selected from the addition amount range of ^0-8 mol.

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(Preparation of Emulsion E)
1192 mL of an aqueous solution containing 96 g, KBr, and 0.9 g was kept at 40 ° C. and stirred vigorously. AgNO ₃ , 1.49
37.5 mL of an aqueous solution containing 1.0 g of KBr and 37.5 mL of an aqueous solution containing 1.05 g of KBr were added over 30 seconds by a double jet method. After adding 1.2 g of KBr, the temperature was raised to 75 ° C. to ripen. After ripening, 35 g of gelatin-4 above
Was added and the pH was adjusted to 7. 6 mg of thiourea dioxide were added. 116 mL of aqueous solution containing 29 g of AgNO ₃
And KBr aqueous solution were added by a double jet method at an accelerated flow rate such that the final flow rate was three times the initial flow rate. At this time,
The pAg of the bulk emulsion solution in the reaction vessel was kept at 8.15.

Aqueous solution 4 containing 110.2 g of AgNO ₃
40.6 mL and KBr aqueous solution were accelerated by the double jet method so that the final flow rate was 5.1 times the initial flow rate, and 3
Added over 0 minutes. At this time, the AgI fine grain emulsion used in the preparation of Emulsion D was mixed with a silver iodide content of 15.8 mol.
%, And the pAg of the bulk emulsion solution in the reaction vessel was kept at 7.85. A
96.5 mL of an aqueous solution containing 24.1 g of gNO ₃ and KB
The r aqueous solution was added over 3 minutes by the double jet method.
At this time, the pAg of the bulk emulsion solution in the reaction vessel was increased to 7.8.
It was kept at 5.

26 mg of sodium ethylthiosulfonate
Was added, and the temperature was lowered to 55 ° C., an aqueous KBr solution was added, and the pAg of the bulk emulsion solution in the reaction vessel was adjusted to 9.80. 8.5 g of the above-mentioned AgI fine grain emulsion was added in terms of KI weight. Immediately after the addition is completed, 5 AgNO ₃ is added.
228 mL of an aqueous solution containing 7 g was added over 5 minutes.
At this time, p of the bulk emulsion solution in the reaction vessel at the end of the addition
It adjusted with KBr aqueous solution so that Ag might be set to 8.75.
The emulsion was washed with water in almost the same manner as in Emulsion D and chemically sensitized.

(Preparation of Emulsion F)
1 g of an aqueous solution containing 02 g and 0.9 g of KBr
Maintained at 5 ° C. and stirred vigorously. AgNO ₃ , 4.47 g
, 42 mL of an aqueous solution containing 3.16 g of KBr, and 42 mL of an aqueous solution containing 3.16 g of KBr were added over 9 seconds by the double jet method. After adding 2.6 g of KBr, the temperature was raised to 63 ° C. to ripen. After ripening, 41.2 g of the above gelatin-4 was added to N
18.5 g of aCl was added. After adjusting the pH to 7.2, dimethylamine borane, 8 mg, was added. Ag
203 mL of an aqueous solution containing 26 g of NO ₃ and an aqueous KBr solution were added by a double jet method so that the final flow rate was 3.8 times the initial flow rate. At this time, the pAg of the bulk emulsion solution in the reaction vessel was kept at 8.65.

Aqueous solution 4 containing 110.2 g of AgNO ₃
40.6 mL and KBr aqueous solution were accelerated by the double jet method so that the final flow rate was 5.1 times the initial flow rate, and 2
Added over 4 minutes. At this time, the AgI fine grain emulsion used in the preparation of Emulsion D was adjusted to have a silver iodide content of 2.3 mol%.
And the pAg of the bulk emulsion solution in the reaction vessel was kept at 8.50. 1N
After adding 10.7 mL of an aqueous potassium thiocyanate solution, 153.5 m of an aqueous solution containing 24.1 g of AgNO ₃ was added.
L and KBr aqueous solution were added by a double jet method over 2 minutes and 30 seconds. At this time, the pAg of the bulk emulsion solution in the reaction vessel was kept at 8.05.

The pAg of the bulk emulsion solution in the reaction vessel was adjusted to 9.25 by adding an aqueous KBr solution. A mentioned above
6.4 g of the gI fine grain emulsion was added in terms of KI weight. Immediately after the addition, an aqueous solution 40 containing 57 g of AgNO ₃
4 mL was added over 45 minutes. At this time, an aqueous KBr solution was used so that the pAg of the bulk emulsion solution in the reaction vessel at the end of the addition was 8.65. The emulsion was washed with water in almost the same manner as in Emulsion D and chemically sensitized.

(Preparation of Emulsion G) In the preparation of Emulsion F, the amount of AgNO ₃ added during nucleation was changed to 2.3 times. Then, 404 mL of an aqueous solution containing 57 g of the final AgNO ₃
Was adjusted so that the pAg of the bulk emulsion solution in the reaction vessel at the end of the addition was 6.85 with an aqueous KBr solution. Other than that, it was prepared almost in the same manner as Emulsion F.

(Preparation of Emulsion H) 1300 mL of an aqueous solution containing 1.0 g of KBr and 1.1 g of the above gelatin-4 was added to 35
C. and stirred (preparation of 1st liquid). Ag-1 aqueous solution (containing 4.9 g of AgNO ₃ in 100 mL) 38
mL and an X-1 aqueous solution (5.2 mL of KBr in 100 mL).
g-1) and G-1 aqueous solution (100 m
L contains 8.0 g of the above gelatin-4) 8.5 m
L was added by a triple jet method at a constant flow rate over 30 seconds (addition 1). Thereafter, 6.5 g of KBr was added, and the temperature was raised to 75 ° C. After a ripening step for 12 minutes after the temperature was raised, 300 mL of an aqueous G-2 solution (containing 12.7 g of the above gelatin-4 in 100 mL) was added,
Further, 2.1 g of disodium 4,5-dihydroxy-1,3-disulfonate monohydrate and 0.1 g of thiourea dioxide were added.
002 g was added sequentially at one minute intervals.

Next, an Ag-2 aqueous solution (A in 100 mL)
Gno ₃ which contained 22.1 g) and 157 mL, X-2
Aqueous solution (containing 15.5 g of KBr in 100 mL)
Was added by the double jet method over 14 minutes. At this time, the final flow rate of addition of the Ag-2 aqueous solution is 3.
The flow rate was accelerated so as to be four times, and the addition of the X-2 aqueous solution was performed so that the pAg of the bulk emulsion solution in the reaction vessel was maintained at 8.30 (addition 2). Next, an aqueous solution of Ag-3 (containing 32.0 g of AgNO ₃ in 100 mL) 3
29 mL and X-3 aqueous solution (2 mL of KBr in 100 mL)
1.5 g, containing 1.2 g of KI) by the double jet method over 27 minutes. At this time, the addition of the Ag-3 aqueous solution accelerates the flow rate so that the final flow rate becomes 1.6 times the initial flow rate, and the addition of the X-3 aqueous solution reduces the pAg of the bulk emulsion solution in the reaction vessel to 8.30. This was done to keep (addition 3). Further, 156 mL of an Ag-4 aqueous solution (containing 32.0 g of AgNO ₃ in 100 mL) and X-
Four aqueous solutions (containing 22.4 g of KBr in 100 mL) were added by the double jet method over 17 minutes.
At this time, the Ag-4 aqueous solution was added at a constant flow rate, and X
-4 aqueous solution was added to the pA of the bulk emulsion solution in the reaction vessel.
g was maintained at 7.52 (addition 4).

Thereafter, 0.0025 g of sodium benzenethiosulfonate and 125 mL of a G-3 aqueous solution (containing 12.0 g of the above gelatin-4 in 100 mL) were added.
They were added sequentially at one minute intervals. Then KBr4
3.7 g of pAg of the bulk emulsion solution in the reaction vessel
Was adjusted to 9.00, and then an AgI fine particle emulsion (13.0 g of AgI fine particles having an average particle size of 0.047 μm in 100 g) was used.
73.9 g), and 2 minutes later, Ag was added.
249 mL of -4 aqueous solution and X-4 aqueous solution were added by a double jet method. At this time, the Ag-4 aqueous solution was added at a constant flow rate over 9 minutes, and the X-4 aqueous solution was added to the first 3.3.
The pAg of the bulk emulsion solution in the reaction
The addition was carried out so as to maintain the pAg of the bulk emulsion solution in the reaction vessel to be finally 8.4 (addition 5).

Thereafter, desalting was carried out by a usual flocculation method, and then water, NaOH and the above gelatin-4 were added with stirring, and the mixture was adjusted to pH 6.4 and pAg at 56 ° C.
It was adjusted to 8.6.

The obtained emulsion had an average equivalent sphere equivalent diameter of 0.
99 μm, the average value of the aspect ratio is 13.5, the average value of the AgI content is 3.94 mol%, and the parallel main plane is (11
1) XPS composed of tabular silver halide grains
The AgI content on the surface of the silver halide grains measured by was 2.6 mol%.

Subsequently, the following sensitizing dyes ExS-4 and ExS
S-5 and ExS-6, potassium thiocyanate, chloroauric acid, sodium thiosulfate, and N, N-dimethylselenourea were sequentially added, and after optimal chemical sensitization, the following water-soluble mercapto compound MER-1 was added. And MER-2 in a ratio of 4: 1 for a total of 3.6 per mole of silver halide.
Chemical sensitization was terminated by adding ^10-4 mol. The amount of each sensitizing dye used was 5.50 × 10 ⁻⁴ mol for ExS- ⁴ , 1.30 × 10 ⁻⁴ mol for ExS-5, and 4.65 × for ExS-6 per mol of silver halide. 10 ^-5
Optimal chemical sensitization in moles.

[0238]

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(Preparation method of emulsion I)
1200 mL of an aqueous solution containing 75 g, KBr and 0.9 g was maintained at 39 ° C., the pH was adjusted to 1.8, and the mixture was vigorously stirred.
An aqueous solution containing 1.85 g of AgNO ₃ and 1.5 mol%
Of KBr containing KI was added over 16 seconds by the double jet method. At this time, the excess concentration of KBr was kept constant. The temperature was raised to 54 ° C. and ripened. After aging, 20 g of the above gelatin-4 was added. After adjusting the pH to 5.9, 2.9 g of KBr was added. AgNO ₃ , 27.
288 mL of an aqueous solution containing 4 g and an aqueous KBr solution were added over 53 minutes by the double jet method. At this time, an AgI fine grain emulsion having a grain size of 0.03 μm was simultaneously added so that the silver iodide content became 4.1 mol%, and the pAg of the bulk emulsion solution in the reaction vessel was kept at 9.40.

After adding 2.5 g of KBr, AgNO
_{3. An} aqueous solution containing 87.7 g and an aqueous KBr solution were added over 63 minutes by a double jet method while accelerating the flow rate so that the final flow rate was 1.2 times the initial flow rate. At this time, the AgI fine grain emulsion was adjusted to have a silver iodide content of 10.5 mol%.
And the pAg of the bulk emulsion solution in the reaction vessel was maintained at 9.50. Ag
132 mL of an aqueous solution containing 41.8 g of NO ₃ and an aqueous KBr solution were added over 25 minutes by the double jet method. 7. The pAg of the bulk emulsion solution in the reaction vessel at the end of the addition is 8.
The addition of the aqueous KBr solution was adjusted to be 15. pH
Was adjusted to 7.3, and 1 mg of thiourea dioxide was added.

After adjusting the pAg of the bulk emulsion solution in the reaction vessel to 9.50 by adding KBr, 5.73 g of the above-mentioned AgI fine grain emulsion was added in terms of KI weight. Immediately after the addition is completed, an aqueous solution 60 containing 66.4 g of AgNO _{3 is} added.
9 mL was added over 10 minutes. During the initial 6 minutes of the addition, the pAg of the bulk emulsion solution in the reaction vessel was maintained at 9.50 with an aqueous KBr solution. After washing with water, the above gelatin-4 was added and the pH was adjusted to 6.5, pAg, and 8.2 at 40 ° C.
It was chemically sensitized in the same manner as in Emulsion H. The amount of the sensitizing dye used was 1.08 for ExS-4 per mole of silver halide.
× 10 ^-3 mol, ExS-5 2.56 × 10 ^-4 mol, E
xS-6 is 9.16 × 10 ^-5 mol.

(Preparation of Emulsion J)
An aqueous solution (1200 mL) containing 70 g, KBr, 0.9 g, KI, 0.175 g, and the modified silicone oil 0.2 g used in the preparation of Emulsion D was kept at 33 ° C., adjusted to pH 1.8, and stirred vigorously. An aqueous solution containing 1.8 g of AgNO ₃ and an aqueous KBr solution containing 3.2 mol% of KI were added over 9 seconds by a double jet method. At this time, the excess concentration of KBr was kept constant. The temperature was raised to 62 ° C. and ripened. After aging, 27.8 g of the above gelatin-4 was added.

After adjusting the pH to 6.3, KBr;
9 g were added. 270 mL of an aqueous solution containing 27.58 g of AgNO ₃ and an aqueous KBr solution were subjected to 37 by a double jet method.
Added over minutes. At this time, the particle size prepared by mixing the aqueous solution of gelatin-4, the aqueous solution of AgNO _{3, and the} aqueous solution of KI in a separate chamber having a magnetic coupling induction type stirrer described in JP-A-10-43570 and immediately before addition was added. A 0.008 μm AgI fine grain emulsion was simultaneously added so that the silver iodide content was 4.1 mol%, and the pAg of the bulk emulsion solution in the reaction vessel was kept at 9.15.

After adding 2.6 g of KBr, AgNO was added.
_An aqueous solution containing 87.7 g of ₃ and an aqueous KBr solution were added by a double jet method over a period of 49 minutes while accelerating the flow rate so that the final flow rate was 3.1 times the initial flow rate. At this time, the AgI fine grain emulsion prepared by mixing immediately before the addition was accelerated simultaneously so that the silver iodide content became 7.9 mol%, and the pAg of the bulk emulsion solution in the reaction vessel was increased to 9.3.
It was kept at zero. After adding 1 mg of thiourea dioxide, A
Gno _3, an aqueous solution containing 41.8 g 132 mL of KBr
The aqueous solution was added by the double jet method over 20 minutes.
The addition of the aqueous KBr solution was adjusted so that the pAg of the bulk emulsion solution in the reaction vessel at the end of the addition was 7.90.

After the temperature was raised to 78 ° C. and the pH was adjusted to 9.1, KBr was added to add pBr of the bulk emulsion solution in the reaction vessel.
Ag was set to 8.70. AgI used in the preparation of Emulsion D
5.73 g of the fine grain emulsion was added in terms of KI weight. Immediately after the addition, AgNO _3, an aqueous solution containing 66.4 g 3
21 mL was added over 4 minutes. During the first two minutes of the addition, the pAg of the bulk emulsion solution in the reaction vessel was kept at 8.70 with an aqueous KBr solution. It was washed with water in almost the same manner as in Emulsion H and chemically sensitized. The amount of the sensitizing dye used was 1.25 × 10 ⁻³ mol of ExS-4 per mol of silver halide, and
-5 is 2.85 × 10 ^-4 mol, ExS-6 is 3.29 ×
10 ^-5 mol.

(Production Method of Emulsion K)
An aqueous solution containing 7.8 g, 6.2 g of KBr, and 0.46 g of KI was maintained at 45 ° C. and stirred vigorously. AgNO ₃ , 1
An aqueous solution containing 1.85 g and an aqueous solution containing 3.8 g of KBr were added by a double jet method over 45 seconds. 63 ° C
After the temperature was raised, 24.1 g of the above gelatin-4 was added and the mixture was aged. After aging, an aqueous solution containing 133.4 g of AgNO ₃ and an aqueous KBr solution were added over 20 minutes by a double jet method so that the final flow rate was 2.6 times the initial flow rate. At this time, the pAg of the bulk emulsion solution in the reaction vessel was kept at 7.60. 10 minutes after the start of the addition, K ₂ IrC
0.1 mg of ₁₆ was added. After adding 7 g of NaCl, an aqueous solution containing 45.6 g of AgNO ₃ and an aqueous KBr solution were added over 12 minutes by a double jet method. At this time, the pAg of the bulk emulsion solution in the reaction vessel was kept at 6.90.

In addition, 100 mL of an aqueous solution containing 29 mg of yellow blood salt was added over 6 minutes from the start of the addition. 1 for KBr
After adding 4.4 g, 6.3 g of the AgI fine grain emulsion used in the preparation of Emulsion D was added in terms of KI weight. Immediately after the addition, an aqueous solution containing 42.7 g of AgNO ₃ and KB
The r aqueous solution was added by a double jet method over 11 minutes. At this time, the pAg of the bulk emulsion solution in the reaction vessel was kept at 6.90. It was washed with water in almost the same manner as in Emulsion H and chemically sensitized. The amount of the sensitizing dye used was 5.79 × 10 ⁻⁴ mol of ExS-4 per mol of silver halide, and
-5 is 1.32 × 10 ⁻⁴ mol, ExS-6 is 1.52 ×
10 ^-5 mol.

(Preparation of Emulsion L) Emulsion K was prepared in substantially the same manner except that the temperature during nucleation was changed to 35 ° C. The amount of the sensitizing dye used was 1 silver halide.
9.66 × 10 ⁻⁴ mol of ExS-4 per mol, Ex
2.20 × 10 ^-4 mol of S-5, 2.54 of ExS-6
× 10 ^-5 mol.

(Production Method of Emulsion M)
1200 mL of an aqueous solution containing 75 g, KBr and 0.9 g was maintained at 39 ° C., the pH was adjusted to 1.8, and the mixture was vigorously stirred.
Aqueous solution containing 0.34 g of AgNO ₃ and 1.5 mol%
Of KBr containing KI was added over 16 seconds by the double jet method. At this time, the excess concentration of KBr was kept constant. The temperature was raised to 54 ° C. and ripened. After the ripening, 20 g of the above gelatin-4 was added. After adjusting the pH to 5.9, 2.9 g of KBr was added. Thiourea dioxide,
After addition of 3 mg, 288 mL of an aqueous solution containing 28.8 g of AgNO ₃ and an aqueous KBr solution were added by a double jet method for 5 minutes.
Added over 8 minutes. At this time, the particle size is 0.03μ.
AgI fine grain emulsion having a silver iodide content of 4.1 mol
%, And the pAg of the bulk emulsion solution in the reaction vessel was kept at 9.40.

After adding 2.5 g of KBr, AgNO was added.
_{3. An} aqueous solution containing 87.7 g and an aqueous KBr solution were added over 69 minutes by a double jet method while accelerating the flow rate so that the final flow rate was 1.2 times the initial flow rate. At this time, the AgI fine grain emulsion was adjusted to have a silver iodide content of 10.5 mol%
And the pAg of the bulk emulsion solution in the reaction vessel was maintained at 9.50. Ag
132 mL of an aqueous solution containing 41.8 g of NO ₃ and an aqueous KBr solution were added over 27 minutes by the double jet method. 7. The pAg of the bulk emulsion solution in the reaction vessel at the end of the addition is
The addition of the aqueous KBr solution was adjusted to be 15.

Sodium benzenethiosulfonate 2 mg
Was added, and KBr was added to adjust the pAg of the bulk emulsion solution in the reaction vessel to 9.50.
5.73 g of the fine grain emulsion was added in terms of KI weight. Immediately after the addition, an aqueous solution 6 containing 66.4 g of AgNO ₃
09 mL was added over 11 minutes. For the first 6 minutes of the addition, pAg of the bulk emulsion solution in the reaction vessel with KBr aqueous solution
Was maintained at 9.50. After washing with water, the above gelatin-4 was added and adjusted to pH 6.5, pAg, 8.2 at 40 ° C.,
The temperature was raised to 56 ° C. Sensitizing dyes ExS-4 and ExS-
7 was added, and then potassium thiocyanate, chloroauric acid, sodium thiosulfate, and N, N-dimethylselenourea were added and ripened for optimal chemical sensitization. At the end of chemical sensitization, compound 4 and compound 5 were added. The amount of the sensitizing dye used was 3.69 × 10 ^-4 mol for ExS- ^{4 and} 8.19 × 10 ^{-4 for} ExS-7 per mol of silver halide.
Is a mole.

[0252]

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(Preparation of Emulsion O) In the preparation of Emulsion 1-A, 78 mL of a 1.2 M AgNO ₃ aqueous solution added at the time of preparing seed crystals and 78 mL of a 1.26 M KBr aqueous solution containing 4.3 mol% of KI were added. changed. Otherwise, 1-A
It was prepared in the same manner as described above.

(Preparation method of emulsion P)
9 g, KBr, and 1.3 g of an aqueous solution containing 5.3 g
The mixture was kept at 0 ° C. and stirred vigorously. 27 mL of an aqueous solution containing 8.75 g of AgNO ₃ and 36 mL of an aqueous solution containing 6.45 g of KBr were added over 1 minute by the double jet method.
After the temperature was raised to 75 ° C., 21 mL of an aqueous solution containing 6.9 g of AgNO ₃ was added over 2 minutes. NH4NO _3, 2
After sequentially adding 6 g, 1N, NaOH, and 56 mL,
Matured. After aging, the pH was adjusted to 4.8. AgN
438 mL of an aqueous solution containing 141 g of O ₃ and 10 mL of KBr.
458 mL of an aqueous solution containing 2.6 g was added by a double jet method so that the final flow rate was four times the initial flow rate.

After the temperature was lowered to 55 ° C., the amount of AgNO ₃ was changed to 7.1.
g and an aqueous solution containing 6.46 g of KI were added over 5 minutes by the double jet method. KBr
Was added, and 4 mg of sodium benzenethiosulfonate and 0.05 mg of K ₂ IrCl ₆ were added.
177 mL of an aqueous solution containing 57.2 g of AgNO ₃ and KB
223 mL of an aqueous solution containing 40.2 g of r was added by the double jet method over 8 minutes. The emulsion was washed with water in almost the same manner as in Emulsion N and chemically sensitized.

(Preparation of Emulsions Q and R) Emulsions K and L were prepared almost in the same manner. However, the chemical sensitization was carried out in substantially the same manner as for emulsion O.

Table 2 shows the characteristic values of the silver halide emulsion.
The results are summarized in Table 3. The surface iodine content can be determined by XPS as follows. 6.7 x 10 samples
Cool to -115 ° C in a vacuum of ^-4 Pa or less, and probe X
MgKα as X-ray source voltage 8 kV, X-ray current 20 m
Irradiation with A, Ag3d5 / 2, Br3d, I3d5 / 2
Electrons were measured, the integrated intensity of the measured peak was corrected with a sensitivity factor, and the iodine content of the surface was determined from the intensity ratio. In the silver halide grains of the emulsions D to R, dislocation lines as described in JP-A-3-237450 were observed using a high-pressure electron microscope. Emulsions S and T are non-photosensitive silver iodobromide emulsions.

[0258]

[Table 2]

[0259]

[Table 3]

1) Support The support used in this example was prepared by the following method.

100 parts by weight of polyethylene-2,6-naphthalate polymer and Tinuvin as an ultraviolet absorber
P. 326 (manufactured by Ciba-Geigy) and 2 parts by weight, and then melted at 300 ° C.
It was extruded from the die, stretched 3.3 times at 140 ° C., stretched 3.3 times at 130 ° C., and heat-set at 250 ° C. for 6 seconds to form a 90 μm-thick PEN (polyethylene). A naphthalate) film was obtained. Note that this P
The EN film has a blue dye, a magenta dye and a yellow dye (disclosed in Japanese Patent Publication No. 94-6023).
-1, I-4, I-6, I-24, I-26, I-2
7, II-5) was added in an appropriate amount. Furthermore, diameter 20cm
And a heat history of 110 ° C. for 48 hours was given to obtain a support that is less likely to have a curl.

2) Coating of Undercoat Layer The support was subjected to a corona discharge treatment, a UV discharge treatment, and a glow discharge treatment on both surfaces, and then gelatin 0.1 g / m ² and sodium α- Sulfodi-2-
Ethylhexyl succinate 0.01 g / m ² , salicylic acid 0.04 g / m ² , p-chlorophenol 0.2 g
/ M ² , (CH ₂ ＣＨCHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH
₂ 0.012 g / m ² , and an undercoat solution of polyamide-epichlorohydrin polycondensate 0.02 g / m ² (10 mL /
m ² , using a bar coater) and an undercoat layer was provided on the high temperature side during stretching. Drying was performed at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were at 115 ° C.).

3) Coating of Back Layer An antistatic layer having the following composition, a magnetic recording layer, and a sliding layer were formed as a back layer on one surface of the support after the undercoating.

3-1) Coating of antistatic layer A tin oxide-antimony oxide composite having an average particle diameter of 0.005 μm has a specific resistance of 5 Ω · cm, a dispersion of fine particle powder (secondary aggregated particle diameter of about 0.08 μm). ) and 0.2 g / m ^2, gelatin _{^{0.05g / m 2, (CH 2}} = CHSO 2 CH 2 CH 2 N
HCO) ₂ CH ₂ 0.02 g / m ² , poly (degree of polymerization 10)
Oxyethylene-p-nonylphenol 0.005 g /
It was coated with m ² and resorcin.

3-2) Coating of Magnetic Recording Layer Cobalt-γ-iron oxide coated with 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) (specific surface area 43 m ²⁾ / G, major axis 0.14 μm, single axis 0.03 μm, saturation magnetization 89 Am ²
/ Kg, Fe ^{+ 2} / Fe ⁺³ = 6/94, the surface of which is treated with silicon oxide aluminum oxide at 2% by weight of iron oxide) 0.0
6 g / m ² was added to diacetyl cellulose 1.2 g / m ² (dispersion of iron oxide was performed by an open kneader and a sand mill), and C ₂ H ₅ C (CH ₂ OCONH-C ₆ H) was used as a curing agent.
0.3 g / m ² of ₃ (CH ₃ ) NCO) ₃ was applied by a bar coater using acetone, methyl ethyl ketone, and cyclohexanone as a solvent to obtain a magnetic recording layer having a thickness of 1.2 μm. Silica particles (0.3 μm) and 3-
Abrasive aluminum oxide (0.15 μm) coated with poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) was coated at 10 mg / each.
m ² . Drying was performed at 115 ° C. for 6 minutes (all rollers and conveying devices in the drying zone were 115 ° C.).
° C). X- light increase of the color density of about 0.1 D ^B of the magnetic recording layer in the (blue filter), and saturation magnetization moment of the magnetic recording layer is 4.2Am ² / kg, a coercive force 7.3
× 10 ⁴ A / m, and the squareness ratio was 65%.

3-3) Preparation of Sliding Layer Diacetylcellulose (25 mg / m ² ), C ₆ H ₁₃ CH
(OH) C ₁₀ H ₂₀ COOC ₄₀ H ₈₁ (Compound a, 6 mg /
m ² ) / C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H (compound b,
9 mg / m ² ) mixture was applied. In addition, this mixture is xylene / propylene monomethyl ether (1/1 /
In 1), the mixture was melted at 105 ° C., and poured into and dispersed in propylene monomethyl ether (10-fold amount) at room temperature, and then dispersed in acetone (average particle size: 0.01 μm). As a matting agent, silica particles (0.3 μm) and aluminum oxide (0.15 μm) coated with 3-poly (degree of polymerization 15) oxyethylenepropyloxytrimethoxysilane (15% by weight) as an abrasive are each 15 mg / m 2.
² was added. Drying was performed at 115 ° C. for 6 minutes (all rollers and conveying devices in the drying zone were 115 ° C.)
° C). The sliding layer has a dynamic friction coefficient of 0.06 (stainless steel hard ball of 5 mmφ, load of 100 g, speed of 6 cm / min), a static friction coefficient of 0.07 (clip method), and a kinetic friction coefficient of 0.12 between the emulsion surface and the sliding layer described later. Excellent characteristics.

4) Coating of Photosensitive Layer Next, on the side opposite to the back layer obtained above, layers having the following compositions were applied in a multi-layered manner to prepare a sample as a color negative 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 hardener (Specific compounds are described below, numbers are added after symbols, and chemical formulas are listed after the numbers.) The number corresponding to each component is expressed in g / m ^2. In the case of silver halide, the amount is shown in terms of silver.

First Layer (First Antihalation Layer) Black Colloidal Silver Silver 0.155 Silver Iodobromide Emulsion T Silver 0.01 Gelatin 0.87 ExC-1 0.002 ExC-3 0.002 Cpd-20 0.001 HBS-1 0.004 HBS-2 0.002.

Second Layer (Second Antihalation Layer) Black Colloidal Silver Silver 0.011 Gelatin 0.407 ExM-1 0.050 ExF-1 2.0 × 10 ^-3 HBS-1 0.074 Solid Disperse Dye ExF -2 0.014 solid disperse dye ExF-3 0.020.

Third layer (intermediate layer) Silver iodobromide emulsion S 0.020 ExC-2 0.022 polyethyl acrylate latex 0.085 gelatin 0.294.

Fourth layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion R silver 0.065 Silver iodobromide emulsion Q silver 0.258 ExC-1 0.109 ExC-3 0.044 ExC-40 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 Speed Red Sensitive Emulsion Layer) Silver iodobromide emulsion P silver 0.21 silver iodobromide emulsion O silver 0.62 ExC-1 0.14 ExC-2 0.026 ExC-30 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.

Sixth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion 1-A silver 1.47 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.

Seventh 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 that Gives Layering Effect to Red Sensitive Layer) Silver iodobromide emulsion M 0.560 Cpd-3 0.020 Cpd-4 0.030 ExM-2 0.096 ExM-30 028 ExY-1 0.031 ExG-1 0.006 HBS-1 0.085 HBS-3 0.003 Gelatin 0.58.

Ninth layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion L silver 0.39 silver iodobromide emulsion K silver 0.28 silver iodobromide emulsion J silver 0.35 ExM-2 0.36 ExM-3 0.045 ExG-1 0.005 Cpd-3 0.010 HBS-1 0.28 HBS-3 0.01 HBS-4 0.27 Gelatin 1.39.

Tenth Layer (Medium Speed Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion I Silver 0.45 ExC-6 0.009 ExM-2 0.031 ExM-3 0.029 ExY-1 0.006 ExM- 4 0.028 ExG-1 0.005 Cpd-3 0.006 HBS-1 0.064 HBS-3 2.1 × 10 ^-3 gelatin 0.44.

Eleventh Layer (High Sensitive Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion H 0.99 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 ExG-1 0.005 Cpd-3 0.004 Cpd-4 0.007 HBS-1 0.18 Polyethyl acrylate latex 0.099 Gelatin 1. 11.

Twelfth Layer (Yellow Filter Layer) Yellow Colloidal Silver Silver 0.010 Cpd-1 0.16 Oil-soluble Dye ExF-5 0.010 Solid Dispersion Dye ExF-6 0.020 HBS-1 0.082 Gelatin 1 .057.

Thirteenth layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion G silver 0.18 silver iodobromide emulsion E silver 0.20 silver iodobromide emulsion F silver 0.07 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-10 .24 gelatin 1.41.

Fourteenth layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion D Silver 0.75 ExC-1 0.013 ExY-2 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.

Fifteenth Layer (First Protective Layer) Silver Iodobromide Emulsion S Silver 0.30 UV-1 0.21 UV-2 0.13 UV-3 0.20 UV-4 0.025 F-180 0.0009 HBS-1 0.12 HBS-4 5.0 × 10 ^-2 gelatin 2.3.

Sixteenth layer (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-30 .05 S-1 0.20 gelatin 0.75.

Further, in order to improve the storability, processability, pressure resistance, fungicidal and bacteriostatic properties, antistatic properties and coatability of each layer, W-1 to W-5, B-4 to B -6, F
-1 to F-18, and iron salts, lead salts, gold salts, platinum salts,
It contains palladium, iridium, ruthenium and rhodium salts. Further, 8.5 × 10 ^-3 g per mol of silver halide to the coating solution of the eighth layer, a 7.9 × 10 ^-3 grams of calcium in the 11th layer was added with an aqueous solution of calcium nitrate to form Sample .

Preparation of Dispersion of Organic Solid Disperse Dye ExF-3 shown below was dispersed by the following method. That is, water 2
1.7 mL and 5 mL of 5% aqueous solution of sodium p-octylphenoxyethoxyethoxyethanesulfonic acid 3 mL and 5 mL
A 0.5% aqueous solution of p-octylphenoxypolyoxyethylene ether (degree of polymerization 10) was placed in a 700 mL pot mill, and 5.0 g of the dye ExF-3 and 500 mL of zirconium oxide beads (1 mm in diameter) were added. Was dispersed for 2 hours. For this dispersion, a BO type vibration ball mill manufactured by Chuo Koki was used. After dispersing, take out the contents,
It was 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 fine dye particles was 0.44 μm.

In the same manner, a solid dispersion of ExF-4 was obtained. The average particle size of the dye fine particles was 0.52 μm. E
xF-2 is disclosed in European Patent Application Publication (EP) 549,489.
Microprecipitation described in Example 1 of the specification of A (Microp
(recipitation) dispersion method.
The average particle size was 0.06 μm.

The solid dispersion of ExF-6 was dispersed by the following method. ExF-6 wet cake 2 containing 18% water
In 800 g, 4.0 kg of water and a 3% solution of W-2 were added to 37 g.
6 g was added and stirred to obtain a slurry having a concentration of ExF-6 of 32%. 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.
Milling was performed for 8 hours at a discharge rate of 0.5 l / min at m / sec.

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

[0290]

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[0291]

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[0292]

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[0293]

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[0294]

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[0295]

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[0296]

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[0297]

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[0298]

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[0299]

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[0300]

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[0301]

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[0302]

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[0303]

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(Preparation of Each Sample) As described above, the sample 101
It was created. Samples 102 to 11 of Sample 101 in which high-sensitivity red-sensitive emulsion 1-A of the sixth layer was changed to 1-B to 1-L.
2 was created. The details of the changes are shown in Table 1 below.

These samples were subjected to a hardening treatment at 40 ° C. and a relative humidity of 70% for 14 hours. Thereafter, exposure was performed for 1/100 second through a continuous wedge and a gelatin filter SC-39 (a long-wavelength light transmission filter having a cutoff wavelength of 390 nm) manufactured by FUJIFILM Corporation. The development was performed as follows using an automatic developing machine FP-360B manufactured by Fuji Photo Film Co., Ltd. The remodeling was performed so that the overflow solution of the bleaching bath was not discharged to the post-bath but was entirely discharged to the waste liquid tank. This FP-360B is an invention association disclosed technique 94-49.
No. 92 is mounted.

The processing steps and the composition of the processing solution are shown below. (Processing process) Process Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 37.8 ° C 20 mL 11.5L Bleaching 50 seconds 38.0 ° C 5 mL 5L Fixing (1) 50 seconds 38.0 ° C-5L Fixing 38.0 ℃ 8mL 5L Rinse with water 30sec 38.0 ℃ 17mL 3L stable (1) 20sec 38.0 ℃-3L stable (2) 20sec 38.0 ℃ 15mL 3L Dry 1 min 30sec 60.0 ℃ 35 mm per 1.1 m width (equivalent to 24 Ex. 1 line).

The stabilizing solution and the fixing solution were of a countercurrent type from (2) to (1), and the overflow of the washing water was all introduced into the fixing bath (2). The amount of the developer brought into the bleaching step, the amount of the bleaching liquid brought into the fixing step, and the amount of the fixing liquid brought into the washing step were 35 mm in width of the photosensitive material and 1.1 m in width.
2.5 mL, 2.0 mL, and 2.0 mL, respectively. The crossover time is 6 seconds in each case, and this time is included in the processing time of the previous step.

The opening area of the above processor is 10 parts with the color developing solution.
0cm ² , 120cm ^{2 for} bleaching solution, about 1 other processing solution
00 cm ² .

The composition of the processing solution is shown below. (Color developing solution) Tank solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 3.0 3.0 Catechol-3,5-disulfonate disodium 0.3 0.3 Sodium sulfite 3.9 5.3 Potassium carbonate 39.0 39.0 Disodium-N, N-bis (2-sulfonatoethyl) hydroxylamine 1.5 2.0 Potassium bromide 1.3 0.3 Potassium iodide 1.3mg-4-Hydroxy-6 Methyl-1,3,3a, 7-tetrazaindene 0.05-hydroxylamine sulfate 2.4 3.3 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate Salt 4.5 6.5 Add water 1.0 L 1.0 L pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.18.

(Bleaching solution) Tank solution (g) Replenisher solution (g) Ferric ammonium 1,3-diaminopropanetetraacetate monohydrate 113 170 Ammonium bromide 70 105 Ammonium nitrate 14 21 Succinic acid 34 51 Maleic acid 28 42 Water was added and 1.0 L 1.0 L pH [adjusted with ammonia water] 4.6 4.0.

(Fixing (1) tank liquid) A 5/95 (volume ratio) mixed solution (pH:
6.8).

(Fixing (2)) Tank solution (g) Replenisher (g) Ammonium thiosulfate aqueous solution 240 mL 720 mL (750 g / L) Imidazole 7 21 Ammonium methanethiosulfonate 515 Ammonium methanesulfinate 10 30 Ethylenediaminetetraacetic acid 13 39 Add water 1.0 L 1.0 L pH [adjusted with aqueous ammonia and acetic acid] 7.4 7.45.

(Washing water) Tap water was replaced with H-type strongly acidic cation exchange resin (Amberlite IR- manufactured by Rohm and Haas Co.)
120B) and a mixed bed column packed with an OH type strongly basic anion exchange resin (Amberlite IR-400) to reduce the calcium and magnesium ion concentration to 3 m.
g / L or less, followed by sodium diisocyanurate 20 mg / L and sodium sulfate 150 mg / L
Was added. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizing solution) Common to tank solution and replenisher (unit g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether 0.2 (Average degree of polymerization: 10) 1,2-benzo Isothiazolin-3-one sodium 0.10 Ethylenediaminetetraacetic acid disodium salt 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0. 75 Add water to 1.0 L pH 8.5.

(Development and Evaluation) Samples 101 to 112
Was processed as described above, and the density of the processed sample was measured with a red filter, and the photographic performance was evaluated. The sensitivity was evaluated by the relative value of the reciprocal of the exposure required for the cyan density to reach the fog density + 0.15 density. The values of the sample 101 are shown as relative values with each being 100. Similarly, the fog was also shown as a relative value with the value of Sample 101 being 100 (the smaller the value, the lower the fog).

The results are shown in Table 1. Samples 101 to 104
As is evident from the above, the use of gelatin satisfying the H2 component and the L2 component defined in the present invention in an emulsion having an aspect ratio of 4 or more results in good fog and good sensitivity (significant fog reduction and high sensitivity). I understand. Sample 105
~ 108, the twin plane spacing is 0.012
It turns out that it is more preferable if the thickness is less than μm. On the other hand, sample 10
As is clear from 9 to 112, in emulsions having an aspect ratio of 3 or less, the influence of gelatin on photographic properties is small. The effect of the emulsion having an aspect ratio of 4 or more was remarkable in the study of the present invention.

Claims (5)

[Claims] An emulsion containing silver halide grains,
The emulsion was prepared by using gelatin having a ratio of the H2 component to the sum of the α, β, and γ components of the gelatin of 0.03 or less and a ratio of the L2 component to the sum of the α, β, and γ components of the gelatin of 0.05 or less. A photosensitive material produced by a method including at least one forming step, wherein silver halide tabular grains having an aspect ratio of 4 or more occupy 50% or more of the total projected area of the emulsion grains. Silver halide photographic emulsion. 2. An emulsion grain having an aspect ratio of 4 or more and a twin plane spacing of 0.012 or more of 50% or more of the total projected area of the emulsion grains.
2. A photosensitive silver halide photographic emulsion according to claim 1, wherein silver halide grains having a size of not more than .mu.m are occupied. 3. The main plane parallel to the emulsion grains is (11)
1) The surface has an aspect ratio of 4 or more, contains 10 or more dislocation lines per grain, and contains tabular silver halide grains composed of silver iodobromide or silver chloroiodobromide in 50% or more of the total projected area. The photosensitive silver halide photographic emulsion according to claim 1 or 2, wherein 4. The gelatin according to claim 1, wherein the gelatin is obtained by treating the aqueous solution with a high-pressure homogenizer having a pressure difference of 150 MPa or more in a dispersion part. 2. The photosensitive silver halide photographic emulsion according to item 1. 5. A silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support, wherein the silver halide photographic emulsion layer is as described in any one of claims 1 to 4. A silver halide photographic light-sensitive material containing a light-sensitive silver halide photographic emulsion.