JP2003075962A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide color photographic sensitive material using flat platy silver halide grains of <=0.1 μm grain thickness and having high sensitivity and high image quality and to improve the storage stability of the material. SOLUTION: In the silver halide color photographic sensitive material having at least one blue-sensitive silver halide emulsion layer, at least one green- sensitive silver halide emulsion layer and at least one red-sensitive silver halide emulsion layer on a support, the coating weight of photosensitive silver halide (expressed in terms of silver) is 3.5-8.5 g/m<2> and flat platy grains of >=1.0 μm equivalent circular diameter and <=0.1 μm thickness are contained in all the photosensitive silver halide emulsion layers.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide color photographic material having high sensitivity and improved sharpness.

[0002]

2. Description of the Related Art In recent years, zooming of compact cameras has progressed, and high-power zoom machines such as 3x zoom and 4x zoom have become mainstream. Although these zooms are meaningful for casual enjoyment of pictures, the reality is that they are not always satisfactory in terms of image quality. For example, on the telephoto side, there are models in which the F value of the lens exceeds 10, and there is a tendency for underexposure. In addition, there are many cases of underexposure due to the short reach of the strobe. In order to relieve such a situation, a highly sensitive film film is strongly desired.

In 1996, APS (Advanced Photo S) with a smaller screen size than the conventional 135 format
ystem) has been released. Since the printing magnification is higher than in the past, higher quality film is required.

In order to improve the photographic sensitivity and meet the above requirements, the tabular silver halide grains have been developed in order to make the grains finer. Regarding tabular silver halide grains, U.S. Pat. Nos. (Hereinafter, also referred to as "US") 4,434,226 and 4,439,52 have already been described.
No. 0, 4,414, 310, 4,433, 048
No. 4,414,306, No. 4,459,353, etc., the production method and the use technology are disclosed, and the sensitivity / granularity of Benefits such as relationship improvement are known.

However, if the aspect ratio (equivalent diameter of grain / grain thickness) is increased in order to pursue the advantages of tabular grains, grain thickness becomes thinner. In particular, when particles having a thickness of 0.1 μm or less are used, there is a serious problem that the storage stability as a light-sensitive material is poor and the particles cannot be put to practical use. Therefore, very thin tabular grains having a thickness of 0.1 μm or less could not be used for a film having high image quality and high sensitivity.

[0006]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a high-sensitivity and high-quality silver halide color photographic light-sensitive material using tabular silver halide grains having a grain thickness of 0.1 μm or less and to store the same. It is to improve stability.

[0007]

As a result of intensive studies, it was found that the object of the present invention can be achieved by the following means.
(1) Coating of a photosensitive silver halide in a color photographic light-sensitive material having at least one blue-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer and red-sensitive silver halide emulsion layer on a support. Silver amount is 3.5 g / m ² or more and 8.5 g / m ² or less, and circle equivalent diameter is 1.0 μm
A silver halide color photographic light-sensitive material comprising tabular grains having a thickness of 0.1 μm or less in all light-sensitive silver halide emulsion layers.

(2) The silver halide color photographic light-sensitive material described in (1) above, wherein the film potential on the emulsion layer side of the light-sensitive material is 100 mV to 300 mV less than that of the quinhydrin solution.

(3) The above (1) or (2), which contains at least one selected from the compounds represented by the following general formulas (I), (II) and (III). A silver halide color photographic light-sensitive material described in 1.

General formula (I)

[Chemical 4]

In the general formula (I), R _a1 is an alkyl group, an alkenyl group, an aryl group, an acyl group, an alkyl or aryl sulfonyl group, an alkyl or aryl sulfinyl group, a carbamoyl group, a sulfamoyl group, an alkyl or aryl phosphoryl group, an alkoxy group. It represents a carbonyl group, an aryloxycarbonyl group or a heterocyclic group, and R _a2 represents a hydrogen atom or the group represented by R _a1 . Provided that when R _a1 is an alkyl group, an alkenyl group or an aryl group, R _a2 is an acyl group, an alkyl or aryl sulfonyl group, an alkyl or aryl sulfinyl group, a carbamoyl group, a sulfamoyl group, an alkyl or aryl phosphoryl group, an alkoxycarbonyl group, It is an aryloxycarbonyl group or a heterocyclic group. R _a1 and R _a2 may combine with each other to form a 5- to 7-membered ring.

General formula (II)

[Chemical 5]

In the formula, X ² and Y ² are independently a hydroxyl group, --N
Represents R ²³ R ²⁴ or -NHSO ₂ R ²⁵ . R ²¹ , R ²²
Each independently represents a hydrogen atom or any substituent, and R
²¹ and R ²² may together form a carbocycle or a heterocycle. R ²³ and R ²⁴ each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ²³ and R ²⁴ may together form a heterocycle. R ²⁵ is an alkyl group,
It represents an aryl group, an amino group or a heterocyclic group.

General formula (III)

[Chemical 6]

In the general formula (III), R ₂₁ , R ₂₂ and R ₂₃ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and R ₂₄ is a hydrogen atom, Alkyl group, alkenyl group, alkynyl group, aryl group, or heterocyclic group, or -NR
₂₅ represents R ₂₆ , L ₂₁ represents —CO— or —SO ₂ —, and n represents 0 or 1. R ₂₅ represents a hydrogen atom, a hydroxy group, an amino group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, and R ₂₆ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. Represents R ₂₁ and R ₂₂ , R ₂₁ and R ₂₃ , R ₂₃ and R ₂₄ , or R ₂₄ and R ₂₂ may combine to form a ring.

(4) The halogenated color photographic light-sensitive material as described in any one of (1) to (3) above, wherein the emulsion layer contains metal oxide fine particles having an average particle size of 100 nm or less.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
Coating of the light-sensitive silver halide of the color photographic light-sensitive material of the present invention
Cloth silver amount is 3.5g / m ²8.5 g / m or more²It is the following.
More preferably 3.5 g / m²8.0 g / m or more²Below
is there. Here, the photosensitive silver halide means silver halide.
High sensitivity with chemical and spectral sensitization to increase light sensitivity.
Refers to silver rogenide. Also, the amount of coated silver was applied.
The mass of silver is equimolar to the light-sensitive silver halide. Photosensitive material
There are several known methods to analyze the silver coating amount
And any method may be used, for example, the fluorescent X-ray method is
It's simple.

The equivalent circle diameter of the tabular grains used in the present invention is 1.
0 μm or more, preferably 1.0 μm or more and 10 μm
m or less, and more preferably 1.0 μm or more and 5 μm or less. The thickness is 0.1 μm or less, preferably 0.001 μm or more, and more preferably 0.005 μm or more. In the present invention, tabular grains refer to silver halide grains having two parallel (111) main surfaces facing each other. The tabular grains of the present invention have one twin plane or two or more parallel twin planes. The twin plane is (1) when the ions at all lattice points on both sides of the (111) plane have a mirror image relationship.
11) It means a surface. The tabular grains have a triangular shape, a hexagonal shape, or a truncated triangular shape in the middle when viewed from the direction perpendicular to the main surface, and have outer surfaces parallel to each other.

The equivalent circle diameter and thickness of the tabular grains are the diameter of a circle having an area equal to the projected area of each grain obtained by taking a transmission electron microscope photograph by the replica method (equivalent circle diameter).
And obtain the thickness. In this case, the thickness is calculated from the length of the shadow of the replica. The equivalent circle diameter of all particles and the coefficient of variation thereof, and the thickness of all particles and the coefficient of variation thereof are determined using the values obtained by the above method for 1000 or more particles.

The emulsion of the present invention is preferably monodisperse. Monodisperse means that the coefficient of variation of the equivalent circle diameter of the projected area of all silver halide grains is 30% or less. Particularly preferably, the coefficient of variation of the equivalent circle diameter is 20% or less. Here, the coefficient of variation of the equivalent circle diameter is a value obtained by dividing the standard deviation of the distribution of equivalent circle diameters of individual silver halide grains by the average equivalent circle diameter.

When the silver halide grains are chemically sensitized, if the grains are not uniform, it is difficult to optimally sensitize each grain, resulting in a decrease in photographic sensitivity. From this point,
The thickness of tabular grains is preferably monodisperse. The variation coefficient of thickness is preferably 30% or less, 20%
The following is more preferable.

The twin plane spacing of the tabular grains of the present invention is preferably 0.016 μm or less, more preferably 0.014 μm or less, and more preferably 0.012 μm or less when 50% or more of all grains are in the twin plane spacing. Is most preferred. For tabular grains having three or more twin planes, the distance between the two twin planes that are farthest apart is defined as the twin plane spacing. The twin plane spacing can be obtained by making an ultrathin section of the grain and observing it with a transmission electron microscope. A twin plane spacing of 50% or more of the total number of grains is 0.016 μm or less means that when the twin plane spacing of 1000 or more grains is measured, 500 or more grains are 0.016 μm or less. Good. Similarly, the variation coefficient of the twin plane spacing can be obtained by measuring the twin planes of 1000 or more grains.

The twin plane spacing of tabular grains is also monodisperse from the viewpoint of uniformity between grains, whereby it becomes easier to optimally chemically sensitize each grain. The variation coefficient of the twin plane spacing of tabular grains is preferably 40% or less, and 30
% Or less is more preferable.

The preparation of the tabular grains of the present invention basically comprises a combination of three steps of nucleation, ripening and growth.
U.S. Pat. No. 4,797,354 and JP-A-2-838.
The method described in No. 1 can be referred to for the preparation of tabular grains of the present invention, but the conditions thereof need to be changed. US Pat. Nos. 5,147,771 and 5,147,77
No. 2, No. 5,147,773, No. 5,171,6
No. 59, No. 5,210,013 and No. 5,2.
The method for forming tabular grains using the polyalkylene oxide compound described in No. 52,453 is preferably used for preparing the tabular plate of the present invention.

The preferable 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 silver iodide content of the emulsion grains in the present invention is preferably in the range of 1 to 20 mol%, more preferably 2 to 15 mol%, still more preferably 3 to 10 mol%. If it is less than 1 mol%, effects such as enhancement of dye adsorption and increase of intrinsic sensitivity are difficult to obtain, which is not preferable. If it exceeds 20 mol%, the developing rate is generally delayed, which is not preferable. The range of silver chloride content of the present invention is preferably 0 to 20 mol%, more preferably 0-1.
It is 5 mol%, particularly preferably 0 to 7 mol%, but it may be selected according to the purpose.

The emulsion of the present invention is a halogen having a silver iodide content of 0.7 I to 1.3 I when the specific silver iodide content is I mol% (0.3 <I <20). The silver halide grains preferably account for 100 to 50% of the total number of grains, more preferably 100 to 80%, and even more preferably 100 to 90%. Outside of this range, the effects of the present invention are difficult to obtain, which is not preferable. further,
The emulsion of the present invention has a silver iodide content of 0.8 I to 1.2.
The number of silver halide grains in the range I is 100
It is also preferable to occupy 50 to 50%, more preferably 100 to 80%, still more preferably 100 to 90%.

The value of the specific silver iodide content I is (0.3 <
Any value in the range of I <20) may be set, and an average value when the silver iodide content of each grain is measured may be selected. "Specific silver iodide content (I mol%)" relating to the emulsion of the present invention
Is a specific silver iodide content having a value close to the average silver iodide content calculated from the formulation of the emulsion. I is a specific value within the range of more than 0.3 mol% and less than 20 mol%. The silver iodide content was measured with respect to a specific emulsion grain group isolated from a specific emulsion layer of a silver halide photographic light-sensitive material so that as many grains as possible could fall within the range of 0.7I to 1.3I. Can be specified. Generally, the value is close to the arithmetic average value of the silver iodide content for the above specific emulsion grain group. It is practical to set the I value to the average silver iodide content in the formulation or the measured average silver iodide content. 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, for example, European Patent 147,8.
No. 68.

The tabular grains in the present invention preferably have dislocation lines inside the grains. The introduction of dislocation lines into tabular grains will be described below. A dislocation line is a linear lattice defect on the slip plane of a crystal at the boundary between a region that has already slipped and a region that has not slipped yet. Regarding dislocation lines of silver halide crystals, 1) C.I. R. Berry, J .; A
ppl. Phys. , 27, 636 (1956), 2)
C. R. Berry, D.M. C. Skillman, J .; A
ppl. Phys. , 35, 2165 (1964),
3) J. F. Hamilton, Photo. Sci. E
ng. , 11, 57 (1967), 4) T.I. Shioz
awa, J .; Soc. Photo. Sci. Jap. , 3
4, 16 (1971), 5) T.I. Shiozawa,
J. Soc. Photo. Sci. Jap. , 35, 21
3 (1972) and the like, which can be analyzed by an X-ray diffraction method or a direct observation method using a low-temperature transmission electron microscope. When observing the dislocation lines directly using a transmission electron microscope, be careful not to apply pressure to the grains so that the dislocation lines are generated. The sample is observed by a transmission method in a cooled state so as to prevent damage (for example, printout) due to an electron beam.

On the other hand, as the effect of dislocation lines on the photographic performance, G. C. Farnell, R.M. B. Flint,
J. B. Chapter, J. Photo. Sci. , 1
3, 25 (1965), it has been shown that in a large size high aspect ratio tabular silver halide grain, the place where the latent image nucleus is formed and the defect in the grain have a close relationship. There is. For example, U.S. Pat. No. 4,806,46
No. 1, 5, 498, 516, No. 5, 496, 694
Issue No. 5,476,760 Issue No. 5,567,580
JP-A-4-149541 and JP-A-4-149737 describe techniques for introducing dislocation lines into silver halide grains. It is shown in these patents that tabular grains having dislocation lines introduced therein are superior in photographic characteristics such as sensitivity and pressure property to tabular grains having no dislocation lines. In the present invention, it is preferable to use the emulsions described in these patents.

In the present invention, it is preferable to introduce dislocation lines into the tabular grains as follows. That is, it is the epitaxial growth of a silver halide phase containing silver iodide on a tabular grain (also referred to as a host grain) as a base, and the introduction of dislocation lines by the subsequent formation of a silver halide shell. The silver iodide content of the host grains is preferably 0 to 15 mol%, more preferably 0 to 12 mol%, particularly preferably 0 to 10 mol%, but it may be selected according to the purpose.
If it exceeds 15 mol%, the developing rate is generally delayed, which is not preferable.

The composition of the silver halide phase epitaxially grown on the host grains preferably has a high 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. In the case of silver iodobromide, the silver iodide (iodide ion) content is preferably 1 to 45 mol%, more preferably 5 to 45 mol%, and particularly preferably 10 to 45 mol%. The higher the silver iodide content, the more preferable in terms of forming a misfit required for introducing dislocation lines, but 45 mol% is the solid solution limit of silver iodobromide.

The amount of halogen added to form this 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 amount of silver of the host grains. It is 10 mol%, particularly preferably 2 to 5 mol%. If it is less than 2 mol%, dislocation lines are less likely to be introduced, which is not preferable. When it exceeds 15 mol%, the developing rate is delayed, which is not preferable.

At this time, the high silver iodide content phase is preferably present in the range of 5 to 60 mol% of the total grain silver amount, more preferably 10 to 50 mol%, after the grain formation. , Particularly preferably in the range of 20 to 40 mol%. If it is less than 5 mol% or more than 60 mol%, it is difficult to obtain high sensitivity due to introduction of dislocation lines, which is not preferable. The high silver iodide content phase may be formed on the host grains at any place, and the host grains may be covered or may be formed only on a specific site. It is preferable to control the position of the dislocation lines within.

In the present invention, it is particularly preferable to form the high silver iodide content phase on the side surface and / or the apex portion 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, pAg, solvent concentration, gelatin concentration,
The ionic strength and the like may be freely selected and used. The silver iodide content phase in the grain can be measured by, for example, an analytical electron microscope described in JP-A-7-219102. In forming the high silver iodide content phase on the host grains in the present invention, a method of adding a water-soluble iodide solution such as potassium iodide alone or simultaneously with a water-soluble silver salt solution such as silver nitrate, A method of adding silver halide containing silver halide in the form of fine particles, or, for example, US Pat. Nos. 5,498,516 and 5,527,
The method of releasing iodide ions from an iodide ion-releasing agent by reaction with an alkali or a nucleophile described in No. 664 can be preferably used.

After this high silver iodide content phase is epitaxially grown on host grains, a silver halide shell is formed outside the host tabular grains to introduce dislocation lines. The composition of this silver halide shell may be any of silver bromide, silver iodobromide and silver chloroiodobromide, but silver bromide or silver iodobromide is preferred. In the case of silver iodobromide, the silver iodide content is preferably 0.1 to 12 mol%, more preferably 0.1 to 10 mol%, most preferably 0.1 to 3 mol%.
Is. If it is less than 0.1 mol%, effects such as enhancement of dye adsorption and development acceleration are difficult to obtain, which is not preferable. When it exceeds 12 mol%, the developing rate is delayed, which is not preferable.

The amount of silver used for growing the silver halide shell is preferably 10 to 50 mol% of the total grain silver amount, and more preferably 20 to 40 mol%. The preferred temperature in the above dislocation line introduction process is 30
-80 degreeC, More preferably, it is 35-75 degreeC, Most preferably, it is 35-60 degreeC. In order to control the temperature at a low temperature of less than 30 ° C. or a high temperature of more than 80 ° C., a high-capacity manufacturing apparatus is required, which is not preferable in manufacturing. Further, the preferable pAg in the above dislocation line introduction process is 6.4 to
It is 10.5.

In the case of tabular grains, the position and the number of dislocation lines for each grain when viewed from the direction perpendicular to the main surface can be determined from the photograph of the grain taken using an electron microscope as described above. it can. When introducing dislocation lines 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 as 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 point which is first seen from the side is the grain. The point outside the point where the average silver iodide content of the whole is exceeded or below.

In the present invention, it is preferable to introduce a high density dislocation line into the tabular grain fringe portion, and 1
Tabular grains having zero or more dislocation lines are preferred. More preferably, 30 or more dislocation lines, and even more preferably 50 or more dislocation lines are provided in the grain fringe portion. When dislocation lines are densely present, or when dislocation lines are observed intersecting with each other, the number of dislocation lines per grain may not be clearly counted. However, even in these cases, the number can be counted to about 10, 20, or 30. 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 having 10 or more dislocation lines in each grain fringe portion preferably account for 50% or more, more preferably 80% or more, of the total number of grains. If it is less than 50%, it is difficult to obtain high sensitivity, which is not preferable.

In the present invention, tabular silver halide grains containing 30 or more dislocation lines per grain are 5 in total grain number.
It is preferably 0% or more, more preferably 80%.
Account for more than%. Further, in the tabular grains of the present invention, it is desirable that dislocation line introduction positions in the grains are uniform. In the emulsion of the present invention, silver halide tabular grains in which dislocation lines are substantially localized only in the fringe portion of the grain account for 50% or more, preferably 60% or more, and more preferably 80% of the total number of grains. Occupy the above.

In the present specification, "substantially only the grain fringe portions" means that there are not more than 5 dislocation lines other than the grain fringe portions, that is, the grain central portion. The particle central portion means an inner area surrounded by a fringe area when the particle is viewed from a direction perpendicular to the main surface. In the present invention, when determining the proportion of grains containing dislocation lines and the number of dislocation lines, it is preferable to directly observe the dislocation lines for at least 100 grains, more preferably 200 grains or more, and particularly preferably 300 grains or more. Observe and ask.

In the light-sensitive material of the present invention, the equivalent circle diameter is 1.
Tabular grains having a thickness of 0 μm or more and a thickness of 0.1 μm or less are contained in all light-sensitive silver halide emulsion layers. The photosensitive silver halide emulsion layer means a layer containing a chemically and spectrally sensitized silver halide emulsion. Further, when 10% or more of the number of grains of a certain photosensitive silver halide emulsion layer is occupied by tabular grains having an equivalent circle diameter of 1.0 μm or more and a thickness of 0.1 μm or less, the tabular grains in the silver halide emulsion layer are It is defined as containing particles. The upper limit of the proportion of tabular grains having a circle equivalent diameter of 1.0 μm or more and a thickness of 0.1 μm or less is
It is 100%. The proportion of grains can be easily determined by taking out a silver halide tabular grain from the emulsion layer and determining the equivalent circle diameter and thickness of the grain from the electron micrograph by the replica method described above.

The membrane potential specified in the present invention is as follows. The working electrode is platinum, and the reference electrode is Ag / AgCl /
The one in which a liquid junction was provided on the lower surface by rubbing of glass with 3.3 M KCl (manufactured by Electrochemical Measurement Co., Ltd.). A quinhydrin solution (a powder of quinhydrin, which is a 1: 1 molecular compound of hydroquinone and p-benzoquinone, at pH 4.01 in a phthalate pH standard buffer solution (manufactured by Wako Pure Chemical Industries, Ltd.) under an atmosphere of 25 ° C. and 55% After measuring the potential (Er) of the dissolved solution), 40 μL of a phosphate pH buffer solution (pH 6.
86) is dropped, and after 30 seconds, the membrane surface electrode is brought into contact with
The value after the minute was defined as the film potential (ES) on the emulsion layer film side. The film potential difference ΔE (= of the silver halide color photographic light-sensitive material of the present invention
Es-Er) is preferably 100 mV to 300 mV base, and more preferably 120 mV to 200 mV base.

In the present invention, the following general formulas (I), (II) and (III) are preferably added to improve the storage stability of the silver halide light-sensitive material. In the general formula (I), R _a1 is an alkyl group, an alkenyl group, an aryl group,
It represents an acyl group, an alkyl or aryl sulfonyl group, an alkyl or aryl sulfinyl group, a carbamoyl group, a sulfamoyl group, an alkyl or aryl phosphoryl group, an alkoxycarbonyl group, an aryloxycarbonyl group or a heterocyclic group, and R _a2 represents a hydrogen atom or R _a1. Represents a group represented by. Provided that when R _a1 is an alkyl group, an alkenyl group or an aryl group, R _a2 is an acyl group, an alkyl or aryl sulfonyl group, an alkyl or aryl sulfinyl group, a carbamoyl group, a sulfamoyl group, an alkyl or aryl phosphoryl group, an alkoxycarbonyl group, It is an aryloxycarbonyl group or a heterocyclic group. R _a1 and R _a2 may combine with each other to form a 5- to 7-membered ring.

The compound represented by formula (I) will be further described. R _a1 is an alkyl group (preferably having 1 to 10 carbon atoms).
Alkyl groups such as methyl, ethyl, i-propyl,
Cyclopropyl, butyl, isobutyl, cyclohexyl, t-octyl, benzyl), an alkenyl group (preferably an alkenyl group having 2 to 36 carbon atoms such as allyl,
2-butenyl, isopropenyl, vinyl), aryl group (preferably aryl group having 6 to 12 carbon atoms such as phenyl and naphthyl), acyl group (preferably having 2 to 1 carbon atoms).
2 acyl groups such as acetyl, benzoyl, pivaloyl, butyryl, naphthoyl), alkyl or arylsulfonyl groups (preferably alkyl having 1 to 10 carbons or arylsulfonyl groups having 6 to 10 carbons, such as methanesulfonyl, octanesulfonyl, Benzenesulfonyl, toluenesulfonyl), alkyl or arylsulfinyl group (preferably alkyl having 1 to 12 carbons or arylsulfinyl having 6 to 12 carbons such as methanesulfinyl, benzenesulfinyl), carbamoyl group (also N-substituted carbamoyl group). And preferably a carbamoyl group having 1 to 12 carbon atoms such as N-ethylcarbamoyl, N-phenylcarbamoyl, N, N-dimethylcarbamoyl, N-butyl-N-phenylcarbamoyl), sulfamoyl (Including an N-substituted sulfamoyl group, preferably a sulfamoyl group having 1 to 12 carbon atoms such as N-methylsulfamoyl, N, N-diethylsulfamoyl, N-phenylsulfamoyl), alkyl or arylphosphoryl Group (preferably having 1 to 1 carbon atoms)
12 alkyl or arylphosphoryl group having 6 to 12 carbon atoms, such as methylphosphoryl, phenylphosphoryl, alkoxycarbonyl group (preferably having 2 to 2 carbon atoms).
10 alkoxycarbonyl groups such as methoxycarbonyl, cyclohexyloxycarbonyl, benzyloxycarbonyl, isoamyloxycarbonyl) or aryloxycarbonyl groups (preferably having 7 to 12 carbon atoms).
An aryloxycarbonyl group of, for example, phenoxycarbonyl, naphthoxycarbonyl), a heterocyclic group (a 5- to 7-membered cyclic heterocycle having at least one of a nitrogen atom, a sulfur atom, an oxygen atom or a phosphorus atom as a ring-constituting atom) It is a group to be formed, and the bonding position of the heterocycle (position of monovalent group)
Is a carbon atom, for example 1,3,5-triazine-2
-Yl, 1,2,4-triazin-3-yl, pyridin-2-yl, pyrazinyl, pyrimidinyl, purinyl, quinolyl, imidazolyl, thiazolyl, oxazolyl,
1,2,4-triazol-3-yl, benzimidazol-2-yl, benzthiazolyl, benzoxazolyl, thienyl, furyl, imidazolidinyl, pyrrolinyl, tetrahydrofuryl, morpholinyl, phosphinolin-2-yl). R _a2 represents a hydrogen atom or the group represented by R _a1 .

R _a1 and R _a2 may be further substituted with a substituent. Examples of these substituents include alkyl groups, alkenyl groups, aryl groups, heterocyclic groups, hydroxy groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, amino groups, acylamino groups, sulfonamide groups, alkylamino groups, Arylamino group, carbamoyl group, sulfamoyl group, sulfo group, carboxyl group, halogen atom, cyano group, nitro group, sulfonyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, hydroxyamino group and the like. .

In the general formula (I), R _a2 is a hydrogen atom,
An alkyl group, an alkenyl group, an aryl group, and R
_It is preferable that _a1 is an acyl group, a sulfonyl group, a sulfinyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or a heterocyclic group.

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

[0048]

[Chemical 7]

[0049]

[Chemical 8]

[0050]

[Chemical 9]

These compounds of the present invention are commercially available from J. Org. Che.
m., 27, 4054 ('62), J. Amer. Chem. Soc., 73, 2981
('51), JP-B-49-10692, etc., or a method analogous thereto, which enables easy synthesis. In the present invention, the compound represented by the general formula (I) may be added by dissolving it in water, a water-soluble solvent such as methanol or ethanol, or a mixed solvent thereof, or by emulsifying and dispersing. It may be added in advance as a fine crystal dispersion by a known dispersion method at the time of emulsion preparation.

In the case of dissolving in water, when the solubility is increased by increasing the pH, the pH may be increased or decreased to be dissolved, and then added. In the present invention, two or more kinds of the compounds represented by formula (I) may be used in combination. The coating amount of the compound (I) is 10
Preferably ^{-3 mmol / m 2 ~100mmol / m} 2, 10 -2 mmol / m 2
˜50 mmol / m ² is more preferred.

In the general formula (II), X², Y²Each is German
Vertically hydroxyl group, -NR^{twenty three}R^{twenty four}Or-NHSO₂R^{twenty five}The table
Forget R^{twenty one}, R^{twenty two}Are each independently a hydrogen atom or
Represents a substituent, R^{twenty one}And R^{twenty two}Are jointly carbocycles or heterocycles
It may form a ring. R ^{twenty three}, R^{twenty four}Are each independently hydrogen
Represents an atom, alkyl group, aryl group or heterocyclic group
And R^{twenty three}And R^{twenty four}May jointly form a heterocycle. R
^{twenty five}Is an alkyl group, aryl group, amino group or heterocyclic group
Represents

In the formula (II), X ² is preferably --NR ²³ R
²⁴ or —NHSO ₂ R ²⁵ , and R ²¹ and R ²² each independently preferably represent a hydrogen atom, an alkyl group or an aryl group, or jointly form a carbocycle or a heterocycle.

Specific examples of the compound represented by formula (II) used in the present invention are listed below, but the present invention is not limited thereto.

To incorporate the compound represented by the general formula (II) into the silver halide emulsion layer, they may be dispersed directly in the emulsion or dissolved in a solvent such as water or methanol alone or in a mixed solvent. It may be added to the emulsion.
The emulsion may be added at any stage from emulsion preparation to immediately before coating, but it is preferably added after the grain formation is completed and before the coating solution is prepared. Further, it is also preferable to add it to the coating liquid for the other photographic constituent layers and diffuse it before use. The addition amount of the compound represented by the general formula (II) is preferably 1 × 10 ^-5 to 1 mol, and preferably 1 × 10 ^{-3 to} 5 × 10 ^-1 mol, per 1 mol of silver halide. Particularly preferred.

[0057]

[Chemical 10]

[0058]

[Chemical 11]

[0059]

[Chemical 12]

Next, the compound represented by the general formula (III) will be described. In the general formula (III), R ₂₁ , R ₂₂ and R ₂₃ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and R ₂₄ represents a hydrogen atom, an alkyl group, Alkenyl group, alkynyl group, aryl group, or heterocyclic group, or -NR
₂₅ represents R ₂₆ , L ₂₁ represents —CO— or —SO ₂ —, and n represents 0 or 1. R ₂₅ represents a hydrogen atom, a hydroxy group, an amino group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, and R ₂₆ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or Represents a heterocyclic group. R ₂₁ and R ₂₂ , R ₂₁ and R
₂₃ , R ₂₃ and R ₂₄ , or R ₂₄ and R ₂₂ may be linked to each other to form a ring.

In R ₂₁ , R ₂₂ and R ₂₃ , the alkyl group, alkenyl group and alkynyl group are preferably those having 1 to 30 carbon atoms, particularly straight chain having 1 to 10 carbon atoms,
A branched or cyclic alkyl group, an alkenyl group having 2 to 10 carbon atoms, and an alkynyl group having 2 to 10 carbon atoms. Examples of the alkyl group, alkenyl group, alkynyl group and aralkyl group are methyl, ethyl, propyl, cyclopropyl, allyl, propargyl and benzyl. R ₂₁ , R
_The aryl group in ₂₂ and R ₂₃ is preferably an aryl group having 6 to 30 carbon atoms, particularly a monocyclic or condensed aryl group having 6 to 12 carbon atoms, and examples thereof include phenyl and naphthyl. The heterocyclic group for R ₂₁ , R ₂₂ and R ₂₃ is a saturated or unsaturated 3- to 10-membered heterocyclic group containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. These may be a single ring or may form a condensed ring with another aromatic ring. The heterocycle is preferably a 5- or 6-membered aromatic heterocycle, and examples thereof include pyridyl, imidazolyl, quinolyl, benzimidazolyl, pyrimidyl, pyrazolyl, isoquinolyl, thiazolyl, thienyl, furyl and benzothiazolyl.

In R ₂₄ , an alkyl group, an alkenyl group, an alkynyl group, an aryl group and a heterocyclic group are R ₂₁ , R ₂₂
And synonymous with R ₂₃ . In —NR _{25 and} R ₂₆ of R ₂₄ , the alkyl group, alkenyl group, alkynyl group, aryl group and heterocyclic group of R ₂₅ and R ₂₆ are R ₂₁ , R ₂₂ and R
Synonymous with ₂₃ .

R ₂₁ , R ₂₂ , R ₂₃ , R _{24 of} the general formula (III),
Each group represented by R ₂₅ and R ₂₆ may be substituted, and examples of the substituent include the following. Halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom),
Cyano group, nitro group, ammonio group (for example, trimethylammonio), sulfo group, sulfino group, carboxy group, phosphono group, hydroxy group, mercapto group, hydrazino group, alkyl group (for example, methyl, ethyl, n-propyl, Isopropyl, t-butyl, n-octyl, cyclopentyl, cyclohexyl), alkenyl group (eg, allyl, 2-butenyl, 3-pentenyl), alkynyl group (eg, propargyl, 3-pentynyl), aralkyl group (eg, Benzyl, phenethyl), aryl groups (eg phenyl, naphthyl, 4-methylphenyl), heterocyclic groups (eg pyridyl, furyl, imidazolyl, piperidyl, morpholino), alkoxy groups (eg methoxy, ethoxy, butyloxy), aryl An oxy group (eg, Phenoxy, 2-naphthyloxy),
An alkylthio group (eg, methylthio, ethylthio),
Arylthio group (for example, phenylthio), amino group (for example, unsubstituted amino group, methylamino, dimethylamino, ethylamino, anilino), acyl group (for example, acetyl, benzoyl, formyl, pivaloyl),
Alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl), aryloxycarbonyl group (eg, phenoxycarbonyl), carbamoyl group (eg, unsubstituted carbamoyl, N, N-dimethylcarbamoyl, N-ethylcarbamoyl, N-phenylcarbamoyl) ), An acyloxy group (eg, acetoxy,
Benzoyloxy), acylamino group (eg acetylamino, benzoylamino), alkoxycarbonylamino group (eg methoxycarbonylamino), aryloxycarbonylamino group (eg phenoxycarbonylamino), ureido group (eg unsubstituted ureido) , N-methylureido, N-phenylureido),
Alkylsulfonylamino group (for example, methylsulfonylamino), arylsulfonylamino group (for example, phenylsulfonylamino), alkylsulfonyloxy group (for example, methylsulfonyloxy), arylsulfonyloxy group (for example, phenylsulfonyloxy), alkylsulfonyl Group (for example, mesyl), arylsulfonyl group (for example, tosyl), alkoxysulfonyl group (for example, methoxysulfonyl), aryloxysulfonyl group (for example, phenoxysulfonyl),
Sulfamoyl group (for example, unsubstituted sulfamoyl,
N-methylsulfamoyl, N, N-dimethylsulfamoyl, N-phenylsulfamoyl), alkylsulfinyl group (for example, methylsulfinyl), arylsulfinyl group (for example, phenylsulfinyl), alkoxysulfinyl group (for example, Methoxysulfinyl), aryloxysulfinyl group (eg, phenoxysulfinyl), phosphoramide group (eg, N, N
-Diethylphosphoric acid amide) and the like. These groups may be further substituted. When there are two or more substituents, they may be the same or different.

In the general formula (III), R_{twenty one}And R_{twenty two}, R_{twenty one}
And R_{twenty three}, R_{twenty three}And R_{twenty four}, Or R_{twenty four}And R_{twenty two}Connect to form a ring
You may form. In the general formula (III), when n is 0
Preferably R_{twenty one}, R_{twenty two}And R_{twenty three}Has 1 to 1 carbon atoms
0 alkyl group, alkenyl group having 2 to 10 carbon atoms, charcoal
Alkynyl groups having 2 to 10 primes and C 6 to 10 carbon atoms
Reel group, nitrogen-containing heterocyclic group, R_{twenty four}Is hydrogen atom, charcoal
Alkyl group having 1 to 10 primes, Al having 2 to 10 carbon atoms
Kenyl group, alkynyl group having 2 to 10 carbon atoms, 6 carbon atoms
To 10 aryl groups and nitrogen-containing heterocyclic groups,
R is better_{twenty one}, R_{twenty two}And R_{twenty three}Is a carbon number of 1 to 10
Rukyi group, alkenyl group having 2 to 10 carbon atoms, 2 carbon atoms
To 10 alkynyl groups, aryl having 6 to 10 carbon atoms
Group, a nitrogen-containing heterocyclic group, R_{twenty four}Is a hydrogen atom. n
When is 1, preferably R_{twenty one}, R_{twenty two}And R_{twenty three}Is hydrogen
Child, alkyl group having 1 to 10 carbon atoms, 2 to 10 carbon atoms
Alkenyl group, alkynyl group having 2 to 10 carbon atoms, charcoal
An aryl group having a prime number of 6 to 10 and a nitrogen-containing heterocyclic group,
L_{twenty one}Is -CO- and R_{twenty four}Is a hydrogen atom, having 1 carbon atom
An alkyl group having 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms,
C2-C10 alkynyl groups, C6-C10
Aryl group, nitrogen-containing heterocyclic group, -NR_{twenty five}R₂₆And R
_{twenty five}Is a hydrogen atom, hydroxyl group, amino group, or 1 carbon atom
10 alkyl groups, alkenyl having 2 to 10 carbon atoms
Group, alkynyl group having 2 to 10 carbon atoms, 6 to 1 carbon atom
0 aryl group, nitrogen-containing heterocyclic group, R₂₆Is hydrogen
Child, alkyl group having 1 to 10 carbon atoms, 2 to 10 carbon atoms
Alkenyl group, alkynyl group having 2 to 10 carbon atoms, charcoal
An aryl group having a prime number of 6 to 10 and a nitrogen-containing heterocyclic group,
More preferably R_{twenty one}Is an aryl group having 6 to 10 carbon atoms
Yes, R_{twenty two}, R_{twenty three}Is a hydrogen atom, L_{twenty one}Is -CO-
Yes, R _{twenty four}Is -NR_{twenty five}R₂₆And R_{twenty five}Is a hydrogen atom,
Droxyl group, alkyl group having 1 to 10 carbon atoms, alkene
A nyl group and an alkynyl group.

Specific compounds represented by the general formula (III) are shown below, but the invention is not limited thereto.

[Chemical 13]

[0066]

[Chemical 14]

[0067]

[Chemical 15]

[0068]

[Chemical 16]

[0069]

[Chemical 17]

The compound represented by the general formula (III) is easily available as a commercially available drug or a compound synthesized from a commercially available drug by a known method. As a method for synthesizing the general formula (III), Journal of American Chemical Society (J.Am.Chem.So.
c.), 72, 2762 (1950), Organic Synthesis, Vol. 2, 395
Page, New Experimental Chemistry Course 14-2 and 14-3 (19
(1977) It can be easily synthesized by the method described in Maruzen or the like or a method similar thereto.

Any of the compounds represented by the general formula (III) is preferably added to a layer adjacent to the emulsion layer or to another layer before or during coating with the coating solution and diffused into the emulsion layer. .. It may be added before chemical sensitization, during chemical sensitization, or after chemical sensitization at the time of emulsion preparation.

[0072] While preferred amount depends largely on the type of compound to be added addition method and mentioned above, generally 0.05 mol 5 × 10 ^-6 moles per 1 mole of photosensitive silver halide, and more preferably 1 × 10 ^-5 to 0.005 mol is used. If the amount added is larger than the above amount, adverse effects such as an increase in fog will occur, which is not preferable. General formula (II
The compound represented by I) is preferably added after being dissolved in a water-soluble solvent. The pH may be lowered or raised by an acid or a base, or a surfactant may be coexistent. Further, it can be added as an emulsified dispersion after being dissolved in a high boiling point organic solvent, or may be added as a fine crystal dispersion by a known dispersion method. You may use together the compound of general formula (III) 2 or more types. When two or more kinds are used in combination, they may be added to the same layer or may be added to different layers.

The addition layer, the addition timing, the addition amount, the addition method and the like for the above general formula (III) are common to the general formulas (I) to (III) unless otherwise specified.

The present invention also includes metal oxide fine particles having an average particle size of 100 nm or less, more preferably 80 nm or less. The average particle size can be determined by an electron microscope or a particle size measuring instrument using the laser Doppler effect. As the metal oxide fine particles, oxide fine particles of aluminum, titanium, zirconium, antimony, yttrium, zinc, tin, magnesium or the like can be used. The fine particles are dispersed in water, but a known disperser (for example, Japanese Patent Laid-Open No. 52-927) is used to obtain the dispersion.
16, International Patent 88/074794) can be used.

Although the dispersed fine particles are contained in the emulsion layer, they may be contained in any emulsion layer, but are preferably contained in the highest sensitivity emulsion layer. The metal oxide fine particles are preferably added in an amount of 5% or more and 50% or less by volume, more preferably 10% or more and 40% or less with respect to gelatin (in a dry state) contained in the emulsion layer. preferable.

The emulsions of the present invention and photographic emulsions other than the present invention which can be used in combination with the emulsions of the present invention are described in "Physics and Chemistry of Photography" by Graphide, published by Paul Montel (P. Glafki).
des, Chemie et Phisique Ph
autographique, Paul Montel,
1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photogra.
phic Emulsion Chemistry (F
Ocal Press, 1966)), "Production and Coating of Photographic Emulsions" by Zelikmann et al., published by Focal Press (VL Zelikman et al., Maki).
ng and Coating Photograph
ic Emulsion, Focal Press, 1
964) and the like. 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 halogen salt may be a one-sided mixing method, a simultaneous mixing method or a combination thereof. Good. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one form of the simultaneous mixing method, a method of keeping pAg in the liquid phase where silver halide is formed 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 substantially uniform grain size can be obtained.

A method of adding silver halide grains which have been preliminarily formed into a reaction vessel for preparing an emulsion, US Pat. Nos. 4,334,012, 4,301,241 and 4,150,994. The method described in 1. 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 total addition at one time, divided addition in a plurality of times or continuous addition. It is also effective in some cases to add particles having various halogen compositions in order 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 described in US Pat. Nos. 3,477,852 and 4,1.
42,900, European Patent (hereinafter, also referred to as EU) No. 2
No. 73,429, No. 273,430, and West German Laid-Open Patent No. 3,819,241, which are effective particle forming methods. A solution of soluble halogen or silver halide grains can be added to convert it to a more sparingly soluble silver salt. It is possible to select from a method such as conversion at once, conversion by dividing into plural times, or continuous conversion.

As a grain growth method, in addition to the method of adding a soluble silver salt and a halogen salt at a constant concentration and a constant flow rate, British Patent (hereinafter, also referred to as GB) No. 1,469,480.
U.S. Pat. Nos. 3,650,757 and 4,24.
A particle forming method in which the concentration is changed or the flow rate is changed as described in No. 2,445 is a preferable method. By increasing the concentration or increasing the flow rate, the amount of silver halide 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 if necessary. Furthermore, when adding a plurality of soluble silver salts having different solution compositions, or when adding a plurality of soluble halogen salts having different solution compositions, an addition method in which one is increased and the other is decreased is also an effective method. Is.

A mixer for reacting a solution of a soluble silver salt and a soluble halogen salt is described in US Pat. No. 2,996,287.
No. 3, ibid. 3,342, 605, ibid. 3, 415, 65
No. 0, No. 3,785,777, West German Published Patent No. 2,5
It can be selected and used from the methods described in Nos. 56,885 and 2,555,364.

A silver halide solvent is useful for the purpose of promoting ripening. For example, it is known to have excess halogen ions present in the reactor to accelerate aging. Other ripening agents can also be used. All of these ripening agents can be added to the dispersion medium in the reactor before adding the silver and halide salts,
It is also possible to add halide salts, silver salts or peptizers and to introduce them into the reactor. As another variant, the ripening agent can be introduced independently at the halide salt and silver salt addition stages.

As the ripening agent, for example, ammonia, thiocyanates (eg, rhodan potassium, rhodan ammonium), organic thioether compounds (eg, US Pat. Nos. 3,574,628, 3,021,215, and No. 3,057,724, No. 3,038,805,
No. 4,276,374, No. 4,297,439
No. 3,704,130, No. 4,782,01
3, compounds described in JP-A-57-104926),
Thione compounds (for example, tetra-substituted thioureas described in JP-A-53-82408, JP-A-55-77737, and US Pat. No. 4,221,863, and JP-A-53-1).
No. 44319) and JP-A-57 / 1982.
Examples thereof include mercapto compounds and amine compounds capable of promoting the growth of silver halide grains described in JP-A-202531 (for example, JP-A No. 54-100717).

Gelatin is advantageously used as the protective colloid used in the preparation of the emulsion of the present invention and as the binder of the 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 hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives. ;
Various synthetic hydrophilic polymeric substances such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and other single or copolymers. Can be used.

Examples of gelatin include lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci. Ph
oto. Japan. No. 16. The enzyme-treated gelatin as described in P30 (1966) may be used, and a hydrolyzed product or an enzymatically decomposed product of gelatin may 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 for washing with water can be selected according to the purpose, but it is preferably selected within the range of 5 ° C to 50 ° C. The pH at the time of washing with water can be selected according to the purpose, but it is preferably selected within the range of 2 to 10. More preferably, it is in the range of 3-8. The pAg at the time of washing with water can be selected according to the purpose, but it is preferably selected within the range of 5 to 10. As a method of washing with water, a noodle washing method, a dialysis method using a semipermeable membrane, a centrifugation method, a coagulation sedimentation method, or an ion exchange method can be selected and used. In the case of the coagulation sedimentation method, it can be selected from 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.

The method of adding a chalcogen compound as described in US Pat. No. 3,772,031 during emulsion preparation may be useful. In addition to S, Se and Te, cyanate, thiocyanate, selenocyanic acid, carbonate, phosphate and acetate may be present. The silver halide grain of the present invention has chalcogen sensitization (sulfur sensitization, selenium sensitization, etc.),
At least one of noble metal sensitization (gold sensitization, palladium sensitization, etc.) and reduction sensitization can be carried out at any step of the silver halide emulsion production process. It is preferable to combine two or more sensitizing methods. Various types of emulsions can be prepared depending on which step is chemically sensitized. There are a type in which chemically sensitized nuclei are embedded inside a grain, a type in which a chemical sensitized nucleus is embedded at a shallow position from the grain surface, and a type in which a chemically sensitized nucleus is formed on the surface. In the emulsion of the present invention, the location of the chemically sensitized nuclei can be selected depending on the purpose, but generally preferred is the case where at least one chemically sensitized nucleus is formed near the surface.

One of the chemical sensitizations that can be preferably carried out in the present invention is chalcogen sensitization and noble metal sensitization, either alone or in combination, by TH James, The Photographic Process, No. 4. Edition, published by Macmillan, 1
977, (TH James, The Theor
y of the Photographic Pro
cess, 4th ed, Macmillan, 197
7) Active gelatin as described on pages 67-76, and Research Disclosure, 120, April 1974, 12008; Research Disclosure, 34, June 1975,
13452, U.S. Pat. Nos. 2,642,361, 3,297,446, 3,772,031, 3,857,711, 3,901,714, and 4 , 266,018 and 3,904,41
5 and pAg 5-10, pH 5-8 and temperature 3 as described in British Patent 1,315,755.
Sulfur, selenium, tellurium, gold, platinum at 0-80 ° C,
It can be palladium, iridium or a combination of several of these sensitizers. For precious metal sensitization, gold,
A noble metal salt such as platinum, palladium, or 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. Palladium compound is palladium divalent salt or 4
Means valent salt. A preferred palladium compound is R ₂
It is represented by PdX ₆ or R ₂ PdX ₄ . Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom and represents a chlorine, bromine or iodine atom.

Specifically, K 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 are preferred. The gold compound and the palladium compound are preferably used in combination with thiocyanate or selenocyanate.

As sulfur sensitizers, hypo, thiourea compounds, rhodanine compounds and US Pat. No. 3,857,
711, 4,266,018 and 4,0.
The sulfur-containing compounds described in No. 54,457 can be used. It is also possible to carry out chemical sensitization in the presence of a so-called chemical sensitization aid. Useful chemical sensitization aids include azaindene, azapyridazine, azapyrimidine,
A compound known to suppress fog and increase sensitivity in the process of chemical sensitization is used. Examples of chemical sensitization aid modifiers include U.S. Pat. "Photographic Emulsion Chemistry", pages 138-143.

The emulsion of the present invention is preferably combined with gold sensitization. The amount of the gold sensitizer is preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻⁷ mol, and more preferably 1 × 10 ^{−5 to} 5 × 10 ⁻⁷ mol, per mol of silver halide. The preferable range of the palladium compound is 1 × 10 ⁻³ to 5 × 10 ⁻⁷ . The preferred range of the thiocyan compound or selenocyan compound is 5 × 10 ^-2 to 1 × 10 ^-6 . The preferred amount of sulfur sensitizer used for the silver halide grains of the present invention is from 1 × 10 ⁻⁴ to 1 × 10 ⁴ per mol of silver halide.
^-7 mol, more preferably 1 × 10 ^{-5 to} 5 × 1
It is ^0-7 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, and specifically, colloidal metal selenium, selenoureas (eg, N, N-dimethylselenourea, N, N-diethylselenourea), selenoketones , Selenium compounds such as selenoamides can be used. In some cases, selenium sensitization is preferably used in combination with sulfur sensitization, precious metal sensitization, or both.

During grain formation of the silver halide emulsion of the present invention,
It is preferable to carry out reduction sensitization after grain formation and before or during chemical sensitization or after chemical sensitization. Here, the reduction sensitization is a method of adding a reduction sensitizer to a silver halide emulsion, a low pAg of pAg1 to 7 called silver ripening.
It is possible to select either the method of growing or aging in the above atmosphere or the method of growing or aging in a high pH atmosphere of pH 8 to 11 called high pH aging. 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. Known examples of reduction sensitizers include stannous salts, ascorbic acid and its derivatives, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds and borane compounds. For the reduction sensitization of the present invention, these known reduction sensitizers can be selected and used, or two or more kinds of compounds can be used in combination. As the reduction sensitizer, stannous chloride, thiourea dioxide, dimethylamine borane, ascorbic acid and its derivatives are preferable compounds. The addition amount of the reduction sensitizer depends on the emulsion production conditions, so it is necessary to select the addition amount.
A range of 10 ^-7 to 10 ^-3 mol per mol is suitable.

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 it at an appropriate time during grain growth is preferred. Further, a reduction sensitizer may be added in advance to the water solubility of the water-soluble silver salt or the water-soluble alkali halide, and the silver halide grains may be precipitated using these aqueous solutions. Further, it is also a preferable method to add the solution of the reduction sensitizer in several times as the grains grow, or to continuously add the solution for a long time.

It is preferable to use an oxidizing agent for silver during the process of producing the emulsion of the present invention. What is an oxidizing agent for silver?
It refers to a compound that acts on metallic silver to convert it into silver ions. Particularly effective is a compound that can convert extremely fine silver grains, which are a by-product in the process of forming silver halide grains and the process of chemical sensitization, into silver ions. The silver ions formed here may form a sparingly water-soluble silver salt such as silver halide, silver sulfide or silver selenide, or a silver salt easily soluble in water such as silver nitrate. May be formed.

Even if the oxidizing agent for silver is an inorganic substance,
It may be an organic substance. As an inorganic oxidizer, for example
For example, ozone, hydrogen peroxide and its adducts (eg N 2
aBO ₂・ H₂O₂・ 3H₂O, 2NaCO₃・ 3H₂O₂,
Na_FourP₂O₇・ 2H₂O₂2Na ₂SO_Four・ H₂O₂・ 2H₂
O), peroxyacid salts (eg K₂S₂O₈, K₂C
₂O₆, K₂P₂O₈), A peroxy complex compound (for example,
K₂[Ti (O₂) C₂O_Four] ・ 3H₂O, 4K₂SO_Four・ T
i (O₂) OH / SO_Four・ 2H₂O, Na₃[VO (O₂)
(C₂H_Four)₂] ・ 6H₂O), permanganate (eg,
KMnO_Four), Chromates (eg, K₂Cr₂O₇)
Such as oxyacid salts, halogen elements such as iodine and bromine,
Rogenates (eg potassium periodate), high valence
Metal salts (eg potassium hexacyanoferrate) and
And thiosulfonate.

As the organic oxidant, quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (for example, N-
Bromsuccinimide, chloramine T, chloramine B)
Is given as an example. Preferred oxidants of the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, inorganic oxidizers of thiosulfonates and organic oxidants of quinones. It is a preferable embodiment to use the reduction sensitization and the oxidizing agent for silver in combination. It is possible to select and use the method of applying reduction sensitization after using an oxidizing agent, the reverse method thereof, or the method of coexisting both at the same time. These methods can be selectively used in the grain forming step and the chemical sensitization step.

The photographic emulsion of the present invention may contain various compounds for the purpose of preventing fogging during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. That is, thiazoles, for example, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1
-Phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1 , 3,3a, 7) Tetraazaindenes), pentaazaindenes, and many compounds known as antifoggants or stabilizers can be added.

For example, US Pat. No. 3,954,474
No. 3,982,947, Japanese Patent Publication No. 52-2866
Those described in No. 0 can be used. One of the preferred compounds is the compound described in JP-A-63-212932. Antifoggants and stabilizers can be used at various times before particle formation, during particle formation, after particle formation, in the washing step, during dispersion after washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added depending on the purpose. These compounds are added during emulsion preparation to exert the original antifoggant and stabilizing effects, as well as controlling the crystal wall of grains, reducing grain size, reducing solubility of grains, and chemical enhancement. It can be used for various purposes such as controlling the feeling and controlling the arrangement of dyes.

The photographic emulsion of the present invention is preferably spectrally sensitized with methine dyes or the like in order to exert the effects of the present invention. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes,
Included are styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes.
Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, for example, a pyrroline nucleus, an oxazoline nucleus, a thiozoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei,
And a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, that is, for example, an indolenine nucleus, a benzoindolenine nucleus,
Indole nucleus, benzoxador nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus and quinoline nucleus can be applied. These nuclei may have a substituent on a carbon atom.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, for example,
Pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidine-2,4-dione nucleus, thiazolidine-
A 5,4-membered heterocyclic nucleus such as a 2,4-dione nucleus, a rhodanine nucleus, or 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 especially for the purpose of supersensitization. Typical examples thereof are US Pat. Nos. 2,688,545 and 2,972.
7,229, 3,397,060, 3,5
No. 22,052, No. 3,527,641, No. 3,
617, 293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703,377,
No. 3,769,301, No. 3,814,609
No. 3,837,862, No. 4,026,70
7, British Patent Nos. 1,344,281 and 1,50
No. 7,803, Japanese Patent Publication No. 43-4936, No. 53-12
No. 375, JP-A Nos. 52-110618 and 52-10.
No. 9925. Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance that does not substantially absorb visible light and exhibits supersensitization may be included in the emulsion.

The timing of adding the sensitizing dye to the emulsion may be at any stage in the emulsion preparation which has heretofore been known to be useful. Most commonly, it is carried out after the completion of chemical sensitization and before coating, but it is described in US Pat. No. 3,62.
It is also possible to add spectral sensitization simultaneously with chemical sensitization by adding it at the same time as the chemical sensitizer as described in JP-A-58-113.
It can be carried out prior to the chemical sensitization as described in JP-A 928, or it can be added before the completion of silver halide grain precipitation to start the spectral sensitization. Still further, as taught in U.S. Pat. No. 4,225,666, the compounds are added separately, i.e. some of these compounds are added prior to chemical sensitization and the balance is chemically sensitized. It is also possible to add it after the process described in US Pat.
It may be at any time during the formation of silver halide grains, including the method disclosed in No. 83,756.

The addition amount is 4 × per mol of silver halide.
It can be used in an amount of 10 ⁻⁶ to 8 × 10 ⁻³ mol, but about 5 × 10 ⁻⁵ to 2 × 10 ⁻³ mol is effective for a more preferable silver halide grain size of 0.2 to 1.2 μm. is there. The photosensitive material of the present invention may have at least one photosensitive layer provided on a support. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. Is. The photosensitive layer is a unit photosensitive layer having a color sensitivity to any of blue light, green light, and red light. The red color-sensitive layer, the green color-sensitive layer and the blue color-sensitive layer are arranged in this order from the support side. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers.

A non-photosensitive layer may be provided between the above-mentioned silver halide photosensitive layers and as the uppermost layer and the lowermost layer. These may contain a coupler, a DIR compound, a color mixing inhibitor, etc. described later. A plurality of silver halide emulsion layers constituting each unit photosensitive layer is DE 1,121,470 or G
As described in B923,045, it is preferable to arrange two layers of a high-speed emulsion layer and a low-speed emulsion layer so that the sensitivities of the layers are gradually decreased toward the support. Further, JP-A Nos. 57-112751, 62-200350, and 6
As described in JP-A Nos. 2-206541 and 62-206543, a low-sensitivity emulsion layer may be provided on the side farther from the support and a high-sensitivity 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 (G
L) / high-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH /
RL order or BH / BL / GH / GL / RL / RH
It can be installed in the order of.

Further, as described in JP-B-55-34932, the layers may be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Also, JP-A-56-25738 and 62-6393.
As described in No. 6, it is also possible to arrange 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, a silver halide emulsion layer having the highest photosensitivity in the upper layer, a silver halide emulsion layer having a lower photosensitivity in the middle layer, and a middle layer in the lower layer. An example is an arrangement in which a silver halide emulsion layer having a lower photosensitivity is arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, in the same color-sensitive layer, the medium-sensitivity emulsion layer / You may arrange in order of a high-speed emulsion layer / a low-speed emulsion layer.

In addition, high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer may be arranged in this order. Also, in the case of four or more layers, the arrangement may be changed as described above. In order to improve color reproducibility, US Pat.
744, 4,707,436, JP-A-62-1604.
48, 63-89850, BL, G
It is preferable to dispose a donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layer such as L and RL, adjacent to or close to the main photosensitive layer. The preferred silver halide used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing about 30 mol% or less of silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide.

The silver halide grains in the photographic emulsion have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates.
It may have a crystal defect such as a twin plane or a composite form thereof. The grain size of silver halide is about 0.2μ
Fine particles of m or less or large size particles having a projected area diameter of up to about 10 μm may be used, and a polydisperse emulsion or a monodisperse emulsion may be used.

The silver halide photographic emulsion of the present invention is, for example, Research Disclosure (hereinafter abbreviated as RD) N.
o. 17643 (December 1978), pages 22-23,
"I. Emulsion preparation
ion and types) ”, and ibid. No. 18
716 (November 1979), page 648, ibid. Thirty
7105 (Nov. 1989), pages 863-865, and Graphide, "Physics and Chemistry of Photography," published by Paul Montel, P. Glafkides, Chimieet.
Phisique Photographies,
Paul Montel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GF Duf).
fin, Photographic Emulsion
Chemistry, Focal Press, 19
66), "Production and Coating of Photographic Emulsions" by Zelikmann et al., Published by Focal Press (VL Zelikman, et.
al. , Making and Coating Ph
otographic Emulsion, Focal
Press, 1964) and the like.

The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Silver halides having different compositions may be joined by epitaxial joining, and may be joined with a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used. The above emulsion may be either a surface latent image type which forms a latent image mainly on the surface, an internal latent image type which forms a latent image inside the grain, or a type which has a latent image both on the surface and inside, but a negative type emulsion. It is necessary to be. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used, and the preparation method thereof is described in JP-A-59-133542. The thickness of the shell of this emulsion varies depending on the development process, etc.
-40 nm is preferable, and 5-20 nm is particularly preferable.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. The additive used in such a process is RD No. 1764
3, the same No. 18716 and the same No. No. 307105, and the relevant parts are summarized in the table below.
The light-sensitive material of the present invention includes a light-sensitive silver halide emulsion having a grain size, grain size distribution, halogen composition, grain shape,
Two or more kinds of emulsions having different characteristics of at least one of sensitivity can be mixed and used in the same layer.

The silver halide grains having the surface of the grains described in US Pat. No. 4,082,553, US Pat. No. 4,626,498.
No. 59-214852, wherein the internally fogged silver halide grains and colloidal silver are applied to a photosensitive silver halide emulsion layer and / or a substantially non-photosensitive hydrophilic colloid layer. It is preferable. The fogged silver halide grain inside or on the surface means a silver halide grain which enables uniform (non-imagewise) development regardless of the unexposed area and exposed area of the light-sensitive material. No. 4,626,498, JP-A-59-2148.
No. 52. The silver halide forming the inner core of a core / shell type silver halide grain having a fogged inside may have a different halogen composition. As the silver halide whose inside or surface is fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The average grain size of these fogged silver halide grains is preferably 0.01 to 0.75 [mu] m, more preferably 0.05 to 0.6 [mu] m. Further, the grain shape may be regular grains or polydisperse emulsions, but monodisperse (the weight of silver halide grains or the number of grains is at least 9).
5% has a particle size within ± 40% of the average particle size).

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the development process, and it is preferable that it is not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may optionally contain silver chloride and / or silver iodide. It preferably contains 0.5 to 10 mol% of silver iodide. The fine grain silver halide preferably has an average grain size (average value of circle equivalent diameters of projected areas) of 0.01 to 0.5 μm, and 0.02 to
0.2 μm is more preferable.

The non-photosensitive fine grain silver halide can be prepared in the same manner as in the case of ordinary photosensitive silver halide. The surface of the silver halide grain does not need to be chemically sensitized,
Also, spectral sensitization is not necessary. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, mercapto-based compound or zinc compound in advance. Colloidal silver can be contained in the fine silver halide grain-containing layer. The coated silver amount of the light-sensitive material of the present invention is 3.5 g / m ² or more and 8.5 g / m ²
The following is preferable, and more preferably 4.0 g / m ² or more and 8.0
g / m ² or less.

The photographic additives that can be used in the present invention are also described in RD, and the relevant portions are shown in the table below. Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer Page 23 Page 648 Right column Page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column 866 to 868, supersensitizer, page 649, right column 4. Whitening agent, page 24, page 647, right column, page 868 5. Light absorber, pages 25 to 26, page 649, right column, page 873, filter, page 650, left column, dye, ultraviolet absorber 6. Binder, page 26, page 651, left column 873 to 874, page 7. Plasticizer, page 27, page 650, right Col. 876 Lubricant 8. Coating aid, pp. 26-27 650 Right column 875-876 Surfactant 9. Statistical page 27 650 Right column 876-877 Inhibitor 10. Matting agent 878-879.

Various dye-forming couplers can be used in the light-sensitive material of the present invention, and the following couplers are particularly preferable. Yellow coupler: Formulas (I) and (II) of EP502,424A
A coupler represented by formula (1) of EP513,496A,
A coupler represented by (2) (particularly Y-28 on page 18); EP5
68,037A, a coupler represented by the formula (I) of claim 1; US Pat. No. 5,066,576, column 1, lines 45 to 55, a coupler represented by the general formula (I);
No. 4425, paragraph 0008, coupler represented by general formula (I); EP 498,381 A1, page 40, claim 1
Couplers (especially D-35 on page 18); EP 447,9.
69A1 couplers represented by formula (Y) on page 4 (especially Y
-1 (page 17), Y-54 (page 41)); US 4,476,21.
Couplers represented by formulas (II) to (IV) at lines 36 to 58 of column 7 of 9 (especially II-17,19 (column 17), II-24 (column 19)).

Magenta coupler: JP-A-3-3973
No. 7 (L-57 (bottom right of page 11), L-68 (bottom right of page 12),
L-77 (lower right of page 13); [A-4] -of EP456,257.
63 (page 134), [A-4] -73, -75 (page 139); EP
486, 965 M-4, -6 (page 26), M-7 (page 27);
EP571,959A, M-45 (page 19);
No. 204106, (M-1) (page 6); JP-A-4-3626
No. 31, paragraph 0237, M-22.

Cyan coupler: JP-A-4-204843
No. CX-1,3,4,5,11,12,14,15 (14-1
Page 6); C-7, 10 (35) of JP-A-4-43345.
Page), 34, 35 (page 37), (I-1), (I-17) (42-4
Page 3); the general formula (I) of claim 1 of JP-A-6-67385.
A coupler represented by a) or (Ib). Polymer coupler: P-1, P of JP-A-2-44345
-5 (p. 11).

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237 and GB2,125,5.
70, EP96,873B and DE3,234,533 are preferred. The coupler for correcting the unwanted absorption of the coloring dye is a yellow color cyan dye coupler represented by the formulas (CI), (CII), (CIII) and (CIV) described on page 5 of EP456,257A1 (especially on page 84). YC-86),
Yellow colored magenta coupler Ex described in the EP
M-7 (page 202), EX-1 (page 249), EX-7 (25
1 page), magenta colored cyan coupler CC-9 (column 8), CC-13 (column 10) described in US Pat. No. 4,833,069, (2) (column 8) of US Pat. No. 4,837,136, WO92 / The colorless masking couplers represented by formula (A) in claim 1 of 11575 (in particular, the exemplified compounds on pages 36 to 45) are preferred.

Examples of the compound (including a coupler) which releases a photographically useful compound residue by reacting with an oxidized product of a developing agent include the following. Development inhibitor releasing compound:
Formulas (I) and (II) described on page 11 of EP 378,236A1,
Compounds represented by (III) and (IV) (especially T-101 (30
Page), T-104 (page 31), T-113 (page 36), T-
131 (45 pages), T-144 (51 pages), T-158 (5)
(Page 8)), the formula (I) described on page 7 of EP436,938A2.
Compound represented by (particularly D-49 (page 51)), EP56
Compounds represented by formula (1) of 8,037A (especially (23)
(Page 11)), compounds represented by formulas (I), (II) and (III) described in EP 440,195A2, pages 5 to 6 (particularly I on page 29).
-(1)); Bleach accelerator releasing compound: EP310,125A
Compounds represented by formulas (I) and (I ′) on page 2-5 (especially 61
(60), (61)) and the compound represented by formula (I) of claim 1 of JP-A-6-59411 (particularly (7) (page 7);
Ligand releasing compound: compound represented by LIG-X described in claim 1 of US Pat. No. 4,555,478 (particularly column 12)
21-41 compound).

Leuco dye releasing compounds: US 4,749,6
41 columns 3-8 compounds 1-6; fluorescent dye-releasing compound: COUP-D of claim 1 of US 4,774,181
Compounds represented by YE (particularly compounds 1 to 11 in columns 7 to 10); development accelerator or fogging agent releasing compound: U
Compounds represented by the formulas (1), (2) and (3) in column 3, S4,656,123 (particularly (I-22) in column 25) and EP
ExZK- on page 75, lines 36-38 of 450, 637A2.
2; Compound that releases a group that becomes a dye only upon leaving: U
Compounds of formula (I) as claimed in claim 1 of S4,857,447 (especially Y-1 to Y-19 in columns 25 to 36).

As the additives other than the coupler, the following are preferable. Dispersion medium of oil-soluble organic compound: JP-A-62-215272
P-3,5,16,19,25,30,42,49,54,5
5,66,81,85,86,93 (pages 140-144); Latex for impregnation of oil-soluble organic compounds: US 4,199,3.
Latex described in 63; Oxidized developer scavenger: a compound represented by the formula (I) at column 54 to line 62 of US Pat. No. 4,978,606 (particularly I- (1), (2), (6),
(12) (columns 4 to 5), the formula of column 5, lines 5 to 10 of US Pat. No. 4,923,787 (especially compound 1 (column 3); anti-staining agent: EP 298321A, page 4, lines 30 to 33, formula (I )-(III), especially I-47,72, III-1,27 (24-
Page 48); anti-fading agent: A-6 of EP 298321A,
7,20,21,23,24,25,26,30,37,40,4
2,48,63,90,92,94,164 (69-118)
Pp), US 5,122,444, columns 25-38, II-1.
~ III-23, especially III-10, EP 471347A, 8 ~
12 pages I-1 to III-4, especially II-2, US 5,139,9
No. 31, columns 32-40, A-1 to 48, especially A-3
9,42; Materials that reduce the amount of color-enhancing agent or color-mixing inhibitor used: I-1 on pages 5 to 24 of EP411324A
~ II-15, especially I-46.

Formalin Scavenger: EP4779
32A SCV-1 to 28-Page 24 to 29, especially SCV-
8; Hardener: H- on page 17 of JP-A-1-214845.
1,4,6,8,14, column 1 of US 4,618,573
Compounds (H-1) represented by formulas (VII) to (XII)
~ 54), the formula (6) at the lower right of page 8 of JP-A-2-214852.
Compounds represented by (H-1 to 76), especially H-14, US
Compound described in claim 1 of 3,325,287; Development inhibitor precursor: P of JP-A-62-168139
-24,37,39 (pages 6-7); compounds according to claim 1 of US 5,019,492, in particular column 7, 28,29;
Antiseptic and antifungal agent: US Pat. No. 4,923,790 column 3
~ 15 I-1 to III-43, especially II-1,9,10,18, III
-25; Stabilizers, antifoggants: I-1 to (14) of columns 6 to 16 of US Pat. No. 4,923,793, especially I-1,60, (2), (1
3), US Pat. No. 4,952,483, columns 25-32, compounds 1-65, especially 36: chemical sensitizer: triphenylphosphine selenide, compound 5 of JP-A-5-40324.
0.

Dyes: 15 to 15 of JP-A-3-156450
A-1 to b-20 on page 18, especially a-1, 12, 18, 27,
35, 36, b-5, pages 27-29, V-1 to 23, especially V-
1, EP445627A, pp. 33-55, FI-I-F
-II-43, especially F-I-11, F-II-8, EP 457153
A, pages 17-28, III-1 to 36, especially III-1,3, W
O88 / 04794 8-26 Dye-1 to 124 microcrystalline dispersion, NEP 319999A pages 6-11, compounds 1-22, especially compound 1, EP 519306A formula.
Compounds D-1 to 87 (3 to 2) represented by (1) to (3)
8), compounds 1 to 22 represented by formula (I) of US Pat. No. 4,268,622 (columns 3 to 10), compounds (1) to (31) represented by formula (I) of US Pat. Column 2
9); UV absorber: Compounds (18b) to (18r), 101 to 427 represented by the formula (1) of JP-A-46-3335.
(Pages 6 to 9), compounds (3) to (66) represented by formula (I) of EP 520938A (pages 10 to 44) and compounds HBT-1 to 10 (page 14) represented by formula (III), EP521.
Compounds (1) to (31) represented by formula (1) of 823A (columns 2 to 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, Japanese Patent Publication No.
It is suitable for the film unit with a lens described in Japanese Utility Model Publication No. 3-39784. Suitable supports that can be used in the present invention include, for example, RD.
643, page 28, No. 18716, page 647, right column to page 648, left column, and No. 307105, page 879, can be used. In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, and 23 μm or less.
m or less is more preferable, 18 μm or less is further preferable,
16 μm or less is particularly preferable. The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. T
_1/2 is a saturated film thickness when 90% of the maximum swollen film thickness reached when processed with a color developer at 30 ° C. for 3 minutes and 15 seconds,
It is defined as the time required for the film thickness to reach ½ thereof. The film thickness means the film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and T _1/2 is A Green (A. Gre.
en) et al.'s Photographic Science and
Engineering (Photogr. Sci. En
g.), Section 19, 2, 124 to 129. It can be measured by using a swellometer of the type described. T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating. Also, the swelling rate is 150 to
400% is preferable. The swelling rate is calculated from the maximum swollen film thickness under the conditions described above by the formula: (maximum swollen film thickness-film thickness) /
It can be calculated by the film thickness.

The light-sensitive material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. The back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surface active agent. The swelling ratio of this back layer is 150-
500% is preferable. The light-sensitive material of the present invention has the R
D. No. 17643, pages 28-29, RD No. 18716, 651 left column to right column, and D. No. 307105, 880.
It can be developed by the usual method described on page 881.

Next, the processing liquid for the color negative film used in the present invention will be described. The compounds described in JP-A-4-121739, 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.

It is preferable to use these color developing agents in the range of 0.01 to 0.08 mol, particularly 0.015 to 0.06 mol, and more preferably 0.005 mol per liter of the color developing solution.
It is preferably used in the range of 02 to 0.05 mol.
The replenisher for the color developing solution preferably contains 1.1 to 3 times the concentration of the color developing agent, and particularly preferably 1.3 to 2.5 times.

Hydroxylamine can be widely used as a preservative in the color developing solution. However, when higher preservability is required, substitution of 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). Hydroxylamine is preferred. Among the above, N, N-di (sulfoethyl) hydroxylamine is particularly preferable. These may be used in combination with hydroxylamine, but it is preferable to use one type or two or more types in place of hydroxylamine.

The preservative is 0.02 to 1 L of the color developing solution.
It is preferable to use it in the range of 0.2 mol, and in particular, 0.
It is preferably used in the range of 03 to 0.15 mol, more preferably 0.04 to 0.1 mol. In the replenisher,
As in the case of the color developing agent, it is preferable to contain the preservative in a concentration of 1.1 to 3 times that of the mother liquor (processing tank liquid). The color developer contains an oxide target of the color developing agent.
Sulfite is used as an antioxidant. The sulfite is preferably used in the range of 0.01 to 0.05 mol, and particularly preferably in the range of 0.02 to 0.04 mol, per 1 L of the color developing solution. In the replenisher, these 1.1 ~
It is preferable to use it at a concentration of 3 times.

The pH of the color developing solution is 9.8 to 11.0.
However, the range of 10.0 to 10.5 is particularly preferable, and in the replenisher solution, from these values, 0.1 to 10.5 is preferable.
It is preferable to set a high value in the range of 1.0.
Known buffers such as carbonates, phosphates, sulfosalicylates and borates are used to maintain such a pH stable. The replenishment amount of color developer is 1 m ^{2 of} light-sensitive material.
It is preferably 80 to 1300 milliliters (hereinafter, also referred to as “mL”), but from the viewpoint of reducing the environmental pollution load, it is preferably smaller, specifically 80 to 6
00 mL, more preferably 80 to 400 mL is preferable.

The bromide ion concentration in the color developing solution is usually 0.01 to 0.06 mol per liter, but fog is suppressed while maintaining sensitivity, improving discrimination, and graininess. From the purpose of improving
It is preferable to set 0.015 to 0.03 mol per L. When the bromide ion concentration is set in such a range, the replenisher may contain the bromide ion calculated by the following formula. However, when C becomes negative, it is preferable that the replenisher do 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 of light-sensitive material is colored Amount (mol) of bromide ions eluted from the light-sensitive material to the color-developing solution when developed, V: Replenishment amount (L) of color-developing replenisher for the light-sensitive material of 1 m ² .

Further, when the replenishment amount is reduced or when the bromide ion concentration is set to a high level, 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 treatment liquid having a bleaching ability in the present invention is described in JP-A-4-12555.
The compounds and processing conditions described in No. 8, page 4, lower left column, line 16 to page 7, lower left column, line 6 can be applied. The bleaching agent preferably has an oxidation-reduction potential of 150 mV or higher,
Specific examples thereof include JP-A-5-72694 and 5-1.
Those described in JP-A No. 73312, particularly 1,3-diaminopropanetetraacetic acid, JP-A-5-17312, No. 7
Ferric complex salts of the compounds of Example 1 on page are preferred.

Further, in order to improve the biodegradability of the bleaching agent, JP-A-4-251845 and 4-268552.
It is preferable to use the compound ferric iron complex salts described in JP-A Nos. EP 588,289, 591,934 and JP-A 6-208213 as a bleaching agent. The concentration of these bleaching agents is preferably 0.05 to 0.3 mol per 1 L of a bleaching solution, and is 0.1 to 0.15 for the purpose of securing the bleaching function and reducing the amount discharged to the environment. It is more preferable to design in moles. When the liquid having a bleaching ability is a bleaching liquid, it is preferable to contain 0.2 mol to 1 mol of bromide per 1 L, and particularly preferably 0.3 to 0.8 mol.

The replenisher for the solution having a bleaching ability basically contains the concentration of each component calculated by the following formula. Thereby, the concentration in the mother liquor can be maintained constant. C _R = C _T × (V ₁ + V ₂ ) / V ₁ + C _P C _R : Concentration of component in replenisher C _T : Concentration of component in mother liquor (treatment tank liquid) C _P : Consumed during treatment Replenishment amount of replenishing solution having bleaching ability with respect to a photosensitive material having a component concentration V _{1 of 1} m ² (mL). Bring-in amount (mL) of a photosensitive material having a V _{2 of} 1 m ² from a prebath.

In addition, it is preferable to add a pH buffer to the bleaching solution, and it is particularly preferable to add a dicarboxylic acid having a low odor, such as succinic acid, maleic acid, malonic acid, glutaric acid and adipic acid. In addition, JP-A-53
-95630, RD No. 17129, US3,89
It is also preferable to use a known bleaching accelerator described in 3,858. The bleaching solution contains 50 to 50 m @ ^{2 of} light-sensitive material.
It is preferable to replenish with 1000 mL of bleach replenisher,
Especially 80-500 mL, and further 100-300 mL
Is preferably supplemented. Further, the bleaching solution is preferably aerated.

For the processing solution having fixing ability, compounds and processing conditions described in JP-A-4-125558, page 7, lower left column, line 10 to page 8, lower right column, line 19 can be applied. In particular, in order to improve the fixing speed and the homeostasis, the compounds represented by the general formulas (I) and (II) of JP-A-6-301169 are contained alone or in combination in a processing solution having fixing ability. Preferably. It is also preferable to use the sulfinic acid described in JP-A-1-224762, in addition to p-toluenesulfinate, from the viewpoint of improving the preservability. It is preferable to use ammonium as a cation in a solution having a bleaching ability and a solution having a fixing ability from the viewpoint of improving desilvering ability, but from the viewpoint of reducing environmental pollution, it is preferable to reduce or eliminate ammonium. .

In the bleaching, bleach-fixing and fixing steps, jet stirring described in JP-A-1-309059 is particularly preferable. The replenishing amount of the replenisher in the bleach-fixing or fixing process is 100 to 100 per 1 m ² of the light-sensitive material.
It is 0 mL, preferably 150 to 700 mL, and particularly preferably 200 to 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, it is possible to reduce the silver concentration in the solution and process it, and as a result, the replenishment amount can be reduced. It is also preferable to recover silver off-line and reuse the residual liquid as a replenisher.

The bleach-fixing step and the fixing step can be composed of a plurality of processing tanks, and it is preferable that each tank is of a multistage countercurrent system by cascade piping. In view of the balance with the size of the developing machine, the two-tank cascade configuration is generally efficient, and the ratio of the processing time in the front-stage tank and the rear-stage tank is in the range of 0.5: 1 to 1: 0.5. The range of 0.8: 1 to 1: 0.8 is particularly preferable. In the bleach-fixing solution and the fixing solution, it is preferable to allow a free chelating agent which is not a metal complex to be present from the viewpoint of improving the preservability, but as these chelating agents, the biodegradability described in the bleaching solution is used. It is preferred to use chelating agents. Regarding the washing and stabilizing steps, the contents described in JP-A-4-125558, page 12, lower right column, line 6 to page 13, lower right column, line 16 can be preferably applied. In particular, instead of formaldehyde for the stabilizing solution, EP 504,609 and 519,19
Azolylmethylamines described in No. 0 and JP-A-4-36
From the viewpoint of conservation of the working environment, it is preferable to use the N-methylolazoles described in No. 2943 or to dimerize the magenta coupler into a liquid of a surfactant containing no image stabilizer such as formaldehyde. preferable. Further, in order to reduce the adhesion of dust to the magnetic recording layer coated on the light-sensitive material, the stabilizing solution described in JP-A-6-289559 can be preferably used.

The amount of washing and replenishment of the stabilizing solution depends on the amount of the light-sensitive material 1.
80 to 1000 mL is preferable per m ² , and especially 10
0 to 500 mL, and further 150 to 300 mL is a preferable range from the viewpoint of securing a washing or stabilizing function and reducing waste liquid for environmental protection. In the treatment with such supplemental amount, thiabendazole, 1,2-benzisothiazolin-3-one, 5-chloro-2-methylisothiazoline-3 are contained in order to prevent reproduction of bacteria and mold.
It is preferable to use known antifungal agents such as -one, antibiotics such as gentamicin, and water deionized with an ion exchange resin. It is more effective to use deionized water in combination with antibacterial agents and antibiotics.

Also, the liquid in the tank for washing or stabilizing liquid is
JP-A-3-46652, 3-53246, 3-
55542, 3-121448, 3-1260.
It is also preferable to perform the reverse osmosis membrane treatment described in No. 30 to reduce the replenishment amount, and in this case, the reverse osmosis membrane is preferably a low pressure reverse osmosis membrane. In the processing of the present invention, it is particularly preferable to carry out the evaporation correction of the processing liquid disclosed in JIII Journal of Technical Disclosure, Japanese Patent No. 94-4992. In particular, a method of making a correction using the temperature and humidity information of the environment where the developing machine is installed is preferable based on (Equation-1) on page 2. The water used for evaporation correction is preferably collected from a replenishing tank for washing, and in that case, deionized water is preferably used as the washing replenishing water.

As the treating agent used in the present invention, those described in page 15, right column, line 15 to page 4, left column, line 32 of the above-mentioned Kokai Giho are preferable. As the developing machine used for this purpose, the film processor described in lines 22 to 28 in the right column of page 3 is preferable. Specific examples of preferred processing agents, automatic processors, and evaporation correction methods for carrying out the present invention are as follows.
It is described from page 5, right column, line 11 to page 7, right column, last line of the above-mentioned public technical report.

The supply form of the treating agent used in the present invention is as follows:
It may be in any form such as a concentrated or concentrated liquid preparation, a granule, a powder, a tablet, a paste or an emulsion. As an example of such a treating agent, JP-A-63-63
No. -17453, a liquid agent contained in a container having low oxygen permeability, JP-A-4-19655 and No. 4-230748, vacuum-packed powders or granules, No. 4-221951.
JP-A No. 51-
No. 61837 and JP-A No. 6-102628 disclose a tablet, and JP-A No. 57-500485 discloses a paste-like treatment agent, and any of them can be preferably used. However, from the viewpoint of ease of use, It is preferable to use a liquid prepared at the concentration of the state of use.

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

Next, the processing liquid for the color reversal film used in the present invention will be described. Regarding processing for color reversal film, known technology No. 6 (April 1, 1991), page 1, line 5 to page 10, 5 issued by Aztec Co., Ltd.
Lines, page 15, line 8 to page 24, line 2, all of which can be preferably applied. In processing color reversal films, image stabilizers are included in either the conditioning bath or the final bath. Examples of such an image stabilizer include formaldehyde sodium bisulfite and N-methylolazoles in addition to formalin, and sodium formaldehyde bisulfite or N-methylolazoles are preferable from the viewpoint of working environment, and N-methylol is preferable. As the azole, N-methyloltriazole is particularly preferable. The contents relating to the color developing solution, the bleaching solution, the fixing solution, the washing water, etc. described in the processing of the color negative film can be preferably applied to the processing of the color reversal film.

As a preferred color reversal film processing agent containing the above contents, E-6 manufactured by Eastman Kodak Company is used.
The treating agent and CR-56 treating agent of Fuji Photo Film Co., Ltd. can be mentioned. The color photographic light-sensitive material of the present invention is also suitable as a color negative film for an advanced photo system (hereinafter referred to as APS), and is manufactured by Fuji Photo Film Co., Ltd. (hereinafter referred to as Fuji Film) NE.
Examples include XIA A, NEXIA F, and NEXIA H (ISO 200/100/400 in order) processed into an APS format and stored in a dedicated cartridge. These cartridge films for APS are used by being loaded in APS cameras such as the Epion series represented by Fuji Film Epion 300Z. Further, the color photographic light-sensitive material of the present invention is also suitable for a film with a lens such as Fuji Color Fujirun Super Slim made by Fuji Film.

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

(1) Reception (accepting the exposed cartridge film from the customer) (2) Detaching process (transferring the film from the cartridge to an intermediate cartridge for the developing process) (3) Film developing reattaching process (developed negative film) Return the film to the original cartridge) Print (C, H, P 3 type prints and index prints are continuously and automatically printed on color paper [preferably Fuji Film SUPER FA8]) (6) Verification / shipment (with cartridge) The index print is collated by ID number and shipped together with the print).

These systems include Fujifilm's minilab champion Super FA-298 / FA-278 / FA-258.
/ FA-238 is preferred. FP92 as a film processor
2AL / FP562B / FP562BL / FP362B / FP3622BL can be mentioned, and the recommended treatment chemical is Fujicolor Justit CN-16L. As a printer processor, P1828AR / PP1828A / PP1258
AR / PP1258A / PP728AR / PP728A can be mentioned, and recommended treatment chemical is Fujicolor Justit CP-47L. The detacher used in the detaching process and the rear attacher used in the reattaching process are Fuji Film's DT200 / DT100, respectively.
And AT200 / AT100 are preferred.

The APS system can also be enjoyed by a photo joy system centered on Fuji Film's digital image workstation Aladdin 1000. For example, you can directly load the developed APS cartridge film on Aladdin 1000, negative film, positive film,
35mm film scanner FE-550
You can easily process and edit the digital image data obtained by inputting using the or flat head scanner PE-550. The data can be output as a print by a digital color printer NC-550AL by a photo-fixing type thermal color printing system or a Pictrography 3000 by a laser exposure heat development transfer system, or by an existing lab equipment through a film recorder. Also Alad
The din 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, a photograph can be enjoyed on a TV simply by loading the developed APS cartridge film into the Fuji Film photo player AP-1, and if loaded into the Fuji Film photo scanner AS-1. It is also possible to transfer image information to a PC continuously at high speed.
Fuji Film Photo Vision FV-10 / FV-5 can be used to input films, prints or three-dimensional objects to a personal computer. In addition, a floppy disk,
The image information recorded on a Zip disk, CD-R or hard disk can be processed in various ways on a personal computer using Fujifilm's application software Photo Factory and enjoyed. To output high-quality prints from a personal computer, Fuji Film's digital color printer NC-2 / NC-2D, which is a light-fixing thermal color printing system, is suitable. To store the developed APS cartridge film, Fuji Color Pocket Album AP-5 Pop
L, AP-1 Pop L, AP-1 Pop KG or Cartridge File 16 are preferred.

Next, the magnetic recording layer used in the photosensitive material of the present invention will be described. The light-sensitive material of the present invention may have a magnetic recording layer on the side opposite to the side having the emulsion layer with the support interposed (hereinafter referred to as the back side). The magnetic recording layer used in the present invention is one in which an aqueous or organic solvent-based coating liquid in which magnetic particles are dispersed in a binder is coated on a support.

The magnetic particles used in the present invention are γFe.
₂ O ₃ and other ferromagnetic iron oxides, Co-deposited γFe ₂ O ₃ , Co-deposited magnetite, Co-containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metals, ferromagnetic alloys, hexagonal Ba ferrite, Sr ferrite, Pb ferrite, Ca ferrite or the like can be used. Co-coated ferromagnetic iron oxide such as Co-coated γFe ₂ O ₃ is preferable as the magnetic particles that can be used in the present invention. As the shape, needle shape, rice grain,
It may be spherical, cubic, plate-shaped or 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 3.0 × 10 ^{4 to} 3.0 × 10 ⁵ A / m, particularly preferably 4.0 × 10 ^{4 to} 2.5 × 10 ⁵ A / m. m. The ferromagnetic particles may be surface-treated with silica and / or alumina or an organic material. Further, the magnetic particles may be surface-treated with a silane coupling agent or a titanium coupling agent as described in JP-A-6-161032. In addition, JP-A-4-259911, 5
The magnetic particles described in No. 81652, whose surface is coated with an inorganic or organic substance, can also be used.

As the binder that can be used for the magnetic particles, the thermoplastic resin described in JP-A-4-219569,
A thermosetting resin, a radiation curable resin, a reactive resin, an acid, an alkali or a biodegradable polymer, a natural polymer (a cellulose derivative, a sugar derivative, etc.) and a mixture thereof can be used. The Tg of the above resin is -40 ° C to 30
At 0 ° C, the mass average molecular weight is 20,000 to 1,000,000. For example, vinyl-based copolymer, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose derivatives such as cellulose tripropionate, acrylic resin, polyvinyl acetal resin can be mentioned.
Gelatin is also preferred. Cellulose di (tri) acetate is particularly preferable. The binder can be hardened by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent. As the isocyanate-based crosslinking agent,
Isocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate, and reaction products of these isocyanates and polyalcohols (for example, tolylene diisocyanate 3 mol
And a trimethylolpropane 1 mol reaction product), and a polyisocyanate produced by condensation of these isocyanates, and the like, for example, JP-A-6-593.
No. 57.

As a method of dispersing the above-mentioned magnetic material in the binder, a kneader, a pin type mill, an annular type mill, etc. are preferable and a combination thereof is also preferable, as in the method described in JP-A-6-35092. JP-A-5-08828
The dispersant described in No. 3 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 0.3 μm.
Is about 3 μm. The mass ratio of the magnetic particles to the binder is preferably 0.5: 100 to 60: 100, more preferably 1: 100 to 30: 100. The coating amount of the magnetic particles is 0.005 to 3 g / m ² , preferably 0.0
1-2 g / m ² , more preferably 0.02-0.5 g /
m ² . The transmission yellow density of the magnetic recording layer is 0.0
1 to 0.50 is preferable, 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 the form of a stripe. As a method of applying the magnetic recording layer, an air doctor, blade, air knife, squeeze, impregnation, reverse roll, transfer roll, gravure, kiss, cast, spray,
You can use dips, bars, extrusions, etc.
The coating solutions described in JP-A-5-341436 and the like are preferable.

In the magnetic recording layer, improvement of lubricity, curl adjustment,
It may have functions such as antistatic, adhesion prevention, and head polishing, or may be provided with another functional layer to impart these functions, and at least one kind of particles has a Mohs hardness of 5 or more. The above-mentioned non-spherical inorganic particle abrasive is preferable. 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. The surface of these abrasives may be 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 preferably the same binder as that of the magnetic recording layer is used. Regarding a photosensitive material having a magnetic recording layer, US Pat. No. 5,336,58
No. 9, 5,250,404, 5,229,259
No. 5,215,874 and EP 466,130.

Next, the polyester support which can be used in the light-sensitive material of the present invention will be described. For details, including the light-sensitive material, processing, cartridges and examples described below, see Technical Report, Official Gazette No. 94-6023 (Invention). Association; March 15, 1994). The polyester used for the support is formed of diol and aromatic dicarboxylic acid as essential components, and the aromatic dicarboxylic acid is 2,6-, 1,5-,
1,4- and 2,7-naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, and diols include diethylene glycol, triethylene glycol, cyclohexanedimethanol, bisphenol A and bisphenol. Examples of the polymerized polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. 2, especially preferred
It is a polyester containing 50 to 100 mol% of 6-naphthalenedicarboxylic acid. Among them, polyethylene 2,6-naphthalate is particularly preferable. The weight average molecular weight range is about 5,000 to 200,000. The Tg of the polyester of the present invention is preferably 50 ° C. or higher, more preferably 90 ° C. or higher.

Next, the polyester support is subjected to a heat treatment at a heat treatment temperature of 40 ° C. or higher and lower than Tg, more preferably Tg−20 ° C. or higher and lower than Tg in order to prevent the curling tendency. The heat treatment may be performed at a constant temperature within this temperature range, or the heat treatment may be performed while cooling. The heat treatment time is preferably 0.1 hour or more and 1500 hours or less, more preferably 0.5 hour or more and 200 hours or less. The heat treatment of the support may be carried out in the form of a roll or may be carried out while being conveyed in the form of a web. The surface condition may be improved by imparting unevenness to the surface (for example, applying conductive inorganic fine particles such as SnO ₂ or Sb ₂ O ₅ ). Further, it is desirable to devise a technique such as giving a knurl to the end and slightly raising only the end to prevent the cut end of the winding core from being exposed. These heat treatments may be carried out at any stage after the film formation on the support, after the surface treatment, after the coating of the back layer (antistatic agent, lubricant, etc.), and after the coating of the undercoat. Preferred is after the antistatic agent is applied. An ultraviolet absorber may be kneaded into this polyester. In order to prevent light piping, it is possible to achieve the object by kneading commercially available dyes or pigments for polyester such as Diaresin manufactured by Mitsubishi Kasei and Kayaset manufactured by Nippon Kayaku.

Next, in the present invention, it is preferable to carry out 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 and ozone oxidation treatment can be mentioned. Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment and glow treatment are preferable.

The light-sensitive material of the present invention may also be provided with an undercoat layer on at least one of the emulsion side and the back side. This undercoat layer 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 a copolymer starting from a monomer selected from maleic anhydride, Examples thereof include polyethyleneimine, epoxy resin, grafted gelatin, nitrocellulose and gelatin. Compounds that swell the support include resorcin and p-chlorophenol. For the undercoat layer, chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4) are used as gelatin hardening agents.
-Dichloro-6-hydroxy-S-triazine etc.),
Examples thereof include epichlorohydrin resin and active vinyl sulfone compound. SiO ₂ , TiO ₂ , inorganic fine particles or polymethylmethacrylate copolymer fine particles (0.01 to 10 μm) may be contained as a matting agent.

The light-sensitive material of the present invention may preferably contain an antistatic agent. As those antistatic agents,
Examples thereof include carboxylic acids, carboxylates, polymers containing sulfonates, cationic polymers, and ionic surfactant compounds. The most preferable antistatic agent is ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ ,
A particle size of 0.00 in which at least one selected from SiO ₂ , MgO, BaO, MoO ₃ , and V ₂ O ₅ has a volume resistivity of 10 ⁷ Ωcm or less, more preferably 10 ⁵ Ωcm or less.
1 to 1.0 μm crystalline metal oxide or composite oxide of these (Sb, P, B, In, S, Si, C, etc.)
And fine particles of sol-like metal oxides or composite oxides thereof. As the content in the sensitive material,
5 to 500 mg / m ² is preferable and 10 to ³ is particularly preferable.
It is 50 mg / m ² . Mass ratio of conductive crystalline oxide or its composite oxide and binder (oxide / binder)
Is preferably 1/300 to 100/1, more preferably 1
/ 100 to 100/5.

The light-sensitive material of the present invention preferably has a slip property. The slip agent-containing layer is preferably used on both the emulsion layer side and the back side. A preferable sliding property is a dynamic friction coefficient of 0.25 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 transported at 60 cm / min (25 ° C., 60% RH). In this evaluation, even if the photosensitive material surface is replaced as the mating material, the values are almost the same. Examples of the slip agent that can be used in the present invention include polyorganosiloxane, higher fatty acid amide, higher fatty acid metal salt, ester of higher fatty acid and higher alcohol, and the like.
As the polyorganosiloxane, polydimethylsiloxane, polydiethylsiloxane, polystyrylmethylsiloxane, polymethylphenylsiloxane and the like can be used. The addition layer is preferably the outermost layer of the emulsion layer or the back layer. Particularly, polydimethylsiloxane and ester having a long chain alkyl group are preferable.

The light-sensitive material of the present invention may preferably contain a matting agent. The matting agent may be either on the emulsion side or the back side, but it is particularly preferable to add it to the outermost layer on the emulsion side. The matting agent may be soluble in the treatment liquid or insoluble in the treatment liquid, and preferably both are used in combination. For example, polymethylmethacrylate, poly (methylmethacrylate / methacrylic acid = 9/1 or 5/5 (molar ratio)), polystyrene particles and the like are preferable. 0.8-10 as particle size
μm is preferred, and the particle size distribution is preferably narrow,
It is preferable that 90% or more of the total number of particles be contained within 0.9 to 1.1 times the average particle size. It is also preferable to add fine particles of 0.8 μm or less at the same time in order to enhance the matting property, for example, polymethylmethacrylate (0.2 μm).
m), poly (methyl methacrylate / methacrylic acid = 9
/ 1 (molar ratio), 0.3 μm)), polystyrene particles (0.25 μm), colloidal silica (0.03 μm)
Is mentioned.

The film cartridge that can be used in the light-sensitive material of the present invention will be described below. The main material of the cartridge that can be used in the present invention may be a metal or a synthetic plastic. Preferred plastic materials are polystyrene, polyethylene,
Examples include polypropylene and polyphenyl ether. Further, the cartridge of the present invention may contain various antistatic agents, and carbon black, metal oxide particles, nonions, anions, cations, betaine-based surfactants or polymers can be preferably used. These antistatic patrones are disclosed in JP-A 1-312537,
No. 1-312538. Especially 25 ℃,
A cartridge having a resistance at 25% RH of 1012 Ω or less is preferable. Usually, a plastic patrone is manufactured by using a plastic in which carbon black, a pigment and the like are kneaded in order to impart a light shielding property. The size of the cartridge may be the same as the current 135 size, and the diameter of a 25 mm cartridge of the current 135 size is 22 mm or less in order to miniaturize the camera. The volume of the cartridge case is 30
It is preferably not more than cm ³ , preferably not more than 25 cm ³ . The mass of the plastic used for the cartridge and the cartridge case is preferably 5 to 15 g.

Further, the cartridge that can be used in the present invention may be a cartridge that rotates the spool to feed the film. Further, the film tip may be housed in the cartridge body, and the film tip may be sent to the outside from the port section of the cartridge by rotating the spool shaft in the film feeding direction. These are US 4,83
No. 4,306,5,226,613. The photographic film used in the present invention may be a so-called raw film before development, or may be a developed photographic film. Further, the raw film and the developed photographic film may be housed in the same new cartridge, or may be different cartridges.

[0168]

EXAMPLES Example 1 Silver halide emulsions Em-A to Em- were prepared by the following production method.
O was prepared. (Preparation of Em-A) Aqueous solution 1 containing 1.0 g of low molecular weight gelatin having a mass average molecular weight of 15,000, KBr and 1.0 g.
200 mL was kept at 35 ° C. and vigorously stirred. AgN
30 mL of an aqueous solution containing 1.9 g of O ₃ , 1.5 g of KBr
And low molecular weight gelatin with a weight average molecular weight of 15,000 0.7
Nucleation was performed by adding 30 mL of an aqueous solution containing g by the double jet method for 30 seconds. At this time, the excess concentration of KBr was kept constant. 6 g of KBr was added, and the temperature was raised to 75 ° C. for aging. After completion of the ripening, 35 g of succinated gelatin was added. The pH was adjusted to 5.5. AgNO ₃ , 30g
150 mL of an aqueous solution containing the above and a KBr aqueous solution were added by the double jet method over 16 minutes. At this time, the silver potential was kept at -25 mV against the saturated calomel electrode. Furthermore, A
An aqueous solution containing 110 g of gNO ₃ and an aqueous KBr solution were added by a double jet method over 15 minutes while accelerating the flow rate so that the final flow rate was 1.2 times the initial flow rate. At this time, an AgI fine grain emulsion having a size of 0.03 μm was simultaneously added while accelerating the flow rate so that the silver iodide content would be 3.8%.
And the silver potential was kept at -25 mV. AgNO ₃ , 35g
132 mL of an aqueous solution containing the above and a KBr aqueous solution were added by the double jet method over 7 minutes. The potential at the end of addition is -2
The addition of the KBr aqueous solution was adjusted so as to be 0 mV.

After the temperature was raised to 40 ° C., the following compound 1 was added to K
5.6 g in terms of I was added, and 64 cc of 0.8 M sodium sulfite aqueous solution was further added. Further, an aqueous NaOH solution was added to raise the pH to 9.0 and held for 4 minutes to rapidly generate iodide ions, and then the pH was returned to 5.5. After returning the temperature to 55 ° C., 1 mg of sodium benzenethiosulfonate was added, and further 13 g of lime-processed gelatin having a calcium concentration of 1 ppm was added. After the addition was completed, 250 mL of an aqueous solution containing 70 g of AgNO ₃ and an aqueous KBr solution were added over 20 minutes while maintaining the potential at 60 mV. At this time, 1.0 × 10 ⁻⁵ mol of yellow blood salt was added to 1 mol of silver. After washing with water, add 80 g of lime-processed gelatin with a calcium concentration of 1 ppm, and add 40
The pH was adjusted to 5.8 and pAg 8.7 at ℃.

[0170]

[Chemical 18]

When the contents of calcium, magnesium and strontium in the above emulsion were measured by ICP emission spectroscopy, they were 15 ppm, 2 ppm and 1 ppm, respectively.

The above emulsion was heated to 56 ° C. First, 1 g of a pure AgBr fine grain emulsion having a size of 0.05 μm in terms of Ag was added and shell-attached. Next, sensitizing dyes 1, 2, 3
5. in the form of a solid fine dispersion for each mol of silver.
85 x 10 ^-4 mol, 3.06 x 10 ^-4 mol, 9.00 x
10 ⁻⁶ mol was added. Solid fine dispersions of sensitizing dyes 1, 2, and 3 were prepared as follows. As shown in Table 1, the production conditions are shown in Table 1. After dissolving an inorganic salt in ion-exchanged water, a sensitizing dye is added, and a dissolver blade is used under the condition of 60 ° C.
A solid fine dispersion of sensitizing dyes 1, 2, and 3 was prepared by dispersing at 000 rpm for 20 minutes. When the sensitizing dye is adsorbed and the adsorption of the sensitizing dye reaches 90% of the adsorption amount in the equilibrium state, calcium nitrate is added at a calcium concentration of 250 p.
pm was added. The amount of sensitizing dye adsorbed is determined by separating the solid layer and liquid layer by centrifugal precipitation and measuring the difference between the amount of sensitizing dye added first and the amount of sensitizing dye in the supernatant liquid. The amount of dye was determined. After the addition of calcium nitrate, potassium thiocyanate, chloroauric acid, sodium thiosulfate,
Optimum chemical sensitization was performed by adding N, N-dimethylselenourea and compound 4. 3.40 × 10 ⁻⁶ mol of N, N-dimethylselenourea was added to 1 mol of silver. At the end of the chemical sensitization, Compound 2 and Compound 3 were added, and Em-
A was prepared.

[0173]

[Chemical 19]

[0174]

[Chemical 20]

[0175]

[Chemical 21]

[0176]

[Chemical formula 22]

[0177]

[Chemical formula 23]

[0178]

[Chemical formula 24]

[0179]

[Table 1]

(Preparation of Em-B) In the preparation of Em-A, the amount of KBr added after nucleation was changed to 5 g and the addition amount of Compound 1 was changed to 8.0 g in terms of KI, before chemical sensitization. The amount of the sensitizing dye to be added to each of the sensitizing dyes 1, 2 and 3 was 6.50 × 10 ⁻⁴ mol and 3.40 × 10 ⁻⁴ , respectively.
Mol, 1.00 × 10 ⁻⁵ mol, and the amount of N, N-dimethylselenourea added during chemical sensitization was 4.0.
Em-B was prepared in the same manner as Em-A except that the amount was changed to 0 × 10 ⁻⁶ mol.

(Preparation of Em-C) In the preparation of Em-A, the amount of KBr added after nucleation was changed to 1.5 g,
The amount of the compound 1 added was changed to 7.1 g in terms of KI, and the amount of the sensitizing dye added before chemical sensitization was 7.80 × 10 ⁻⁴ mol for each of the sensitizing dyes 1, 2, and 3, 4.08 x 10
^-4 mol, 1.20 × 10 ^-5 mol, and the amount of N, N-dimethylselenourea added during chemical sensitization is 5.
Em-C was prepared in the same manner as Em-A except that the amount was changed to 00 × 10 ⁻⁶ mol.

(Preparation of Em-E) In the preparation of Em-A, the addition amount of compound 1 was changed to 8.0 g in terms of KI, and the sensitizing dye added before chemical sensitization was sensitizing dye 4,
Change to 5, 6 and add each of 7.73 × 10 ^-4
Em-E was prepared in the same manner as Em-A except that the amounts were 1.65 × 10 ⁻⁴ mol and 6.20 × 10 ⁻⁵ mol, respectively.

[0183]

[Chemical 25]

[0184]

[Chemical formula 26]

[0185]

[Chemical 27]

(Preparation of Em-F) In the preparation of Em-B, the addition amount of Compound 1 was changed to 9.2 g in terms of KI, and the sensitizing dyes added before chemical sensitization were sensitizing dyes 4 and 5. ,
Em-F in the same manner as Em-B except that the addition amount was changed to 6, and the addition amounts were 8.50 × 10 ⁻⁴ mol, 1.82 × 10 ⁻⁴ mol, and 6.82 × 10 ⁻⁵ mol, respectively. Was prepared.

(Preparation of Em-G) In the preparation of Em-C, the sensitizing dyes added before chemical sensitization were sensitizing dyes 4, 5 and
Em-G in the same manner as Em-C except that the addition amount was changed to 6, and the addition amounts were 1.00 × 10 ⁻³ mol, 2.15 × 10 ⁻⁴ mol, and 8.06 × 10 ⁻⁵ mol, respectively. Was prepared.

(Preparation of Em-J) In the preparation of Em-B, the sensitizing dyes to be added before chemical sensitization were changed to sensitizing dyes 7 and 8, and the addition amount of each was 7.65 × 10 ^-4. Mole,
Em-J was prepared in the same manner as Em-B except that the amount was 2.74 × 10 ⁻⁴ mol.

[0189]

[Chemical 28]

[0190]

[Chemical 29]

(Preparation of Em-L) (Preparation of silver bromide seed crystal emulsion) Bromide containing mean sphere-equivalent diameter of 0.6 μm, aspect ratio of 9.0, 1.16 mol of silver per kg of emulsion, and 66 g of gelatin. A silver tabular emulsion was prepared. (Growth Process 1) 0.3 g of modified silicon oil was added to 1250 g of an aqueous solution containing 1.2 g of potassium bromide and succinated gelatin having a succination rate of 98%. After the above silver bromide tabular emulsion containing 0.086 mol of silver was added, the mixture was kept at 78 ° C. and stirred. An aqueous solution containing 18.1 g of silver nitrate, and
The silver iodide fine particles of 03 μm were added so as to be 5.4 mol with respect to silver. Further, at this time, an aqueous potassium bromide solution was added with a double jet while adjusting the pAg to 8.1.

(Growth process 2) After adding 2 mg of sodium benzenethiosulfonate, 0.45 g of 3,5-disulfocatechol disodium salt and thiourea dioxide 2.
5 mg was added. Further, an aqueous solution containing 95.7 g of silver nitrate and an aqueous potassium bromide solution were added over 66 minutes while accelerating with a double jet. At this time, the above-mentioned 0.037 μm silver iodide fine particles were added in an amount of 7.0 mol with respect to silver. At this time, the amount of potassium bromide in the double jet was adjusted so that pAg was 8.1. After the addition was completed, 2 mg of sodium benzenethiosulfonate was added.

(Growth Process 3) An aqueous solution containing 19.5 g of silver nitrate and an aqueous potassium bromide solution were added by a double jet over 16 minutes. At this time, the amount of potassium bromide aqueous solution was adjusted so that pAg was 7.9. (Addition of a sparingly soluble silver halide emulsion 4) After adjusting the above host grains to 9.3 with an aqueous potassium bromide solution,
25 g of 037 μm silver iodide fine grain emulsion was rapidly added within 20 seconds.

(Formation of outermost shell layer 5) Further, 34.9 g of silver nitrate
Was added over 22 minutes. This emulsion was a tabular grain having an average aspect ratio of 9.8 and an average equivalent spherical diameter of 1.4 μm, and the average silver iodide content was 5.5 mol.

(Chemical sensitization) After washing with water, the succination rate was 98.
% Succinated gelatin, calcium nitrate added at 40 ℃
PH was adjusted to 5.8 and pAg 8.7. The temperature was raised to 60 ° C., 5 × 10 ⁻³ mol of 0.07 μm silver bromide fine grain emulsion was added, and 20 minutes later, sensitizing dyes 9, 10 and 11 were added. Then potassium thiocyanate, chloroauric acid, sodium thiosulfate, N, N-dimethylselenourea, compound 4
Was added for optimum chemical sensitization. The compound 3 was added 20 minutes before the end of the chemical sensitization, and the compound 5 was added at the end of the chemical sensitization. Here, optimal chemical sensitization means that the sensitizing dye and each compound are 10 ^-1 to 10 ^-8 per mol of silver halide so that the sensitivity becomes maximum when exposed at 1/100.
It means selected from the addition amount range of mol.

[0196]

[Chemical 30]

[0197]

[Chemical 31]

[0198]

[Chemical 32]

[0199]

[Chemical 33]

[0200]

[Chemical 34]

(Preparation of Em-O) An aqueous gelatin solution (1250 mL of distilled water, 48 g of deionized gelatin, 0.75 g of KBr) was placed in a reaction vessel equipped with a stirrer, and the temperature of the solution was kept at 70 ° C. To this solution, 276 mL of an AgNO ₃ aqueous solution (containing 12.0 g of AgNO ₃ ) and an equimolar KBr aqueous solution were added by the controlled double jet addition method while keeping pAg at 7.26 over 7 minutes. Then, the temperature was lowered to 68 ° C, and thiourea dioxide (0.05
wt%) was added in an amount of 7.6 mL.

Subsequently, 592.9 mL of AgNO ₃ aqueous solution
KB (equal to AgNO ₃ 108.0 g) in equimolar concentration
A mixed aqueous solution of r and KI (2.0 mol% KI) was added by the controlled double jet addition method over 18 minutes and 30 seconds while maintaining pAg at 7.30. Also, 5 minutes before the end of addition, 18.0% of thiosulfonic acid (0.1 wt%) was added.
mL was added.

The obtained particles have a sphere-equivalent diameter of 0.19 μm and a flat particle size.
The cubic grains had a silver iodide content of 1.8 mol%. E
m-O is desalination / washing with normal flocculation method
After re-dispersion, pH was adjusted to 6.2 and pAg at 40 ° C.
 Adjusted to 7.6. Then, regarding Em-O,
Such spectral and chemical sensitization was performed. First, sensitizing dye 1
0, 11, 12 are 3.37 × per mol of silver
10 ^-FourMol / mol, KBr 8.82 × 10^-FourMol / mo
Le, sodium thiosulfate 8.83 × 10^-FiveMol / mol,
Aqueous solution potassium thiocyanate 5.95 × 10^-FourMol / mo
And potassium chloroaurate 3.07 × 10^-FiveMol / mol
Was added and the mixture was aged at 68 ° C. The aging time is
It was adjusted to maximize the sensitivity of 1/100 second exposure.

[0204]

[Chemical 35]

For the preparation of (Em-D, H, I, K, M, N) tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. Further, according to the example of JP-A-3-237450, gold sensitization in the presence of the spectral sensitizing dyes shown in Table 2 and sodium thiocyanate,
Sulfur-sensitized and selenium-sensitized. Emulsions D, H,
I and K contain optimal amounts of Ir and Fe. Emulsion M, N
Is subjected to reduction sensitization at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the example of JP-A-2-191938.

[0206]

[Table 2]

[0207]

[Chemical 36]

[0208]

[Table 3]

In Table 3, dislocation lines as described in JP-A-3-237450 are observed in the tabular grains by using a high voltage electron microscope.

1) Support The support used in this example was prepared by the following method. (I) First layer and subbing layer For a polyethylene naphthalate support having a thickness of 90 μm, the treatment atmosphere pressure is 26.7 Pa on each side of the support.
H ₂ O partial pressure in atmospheric gas 75%, discharge frequency 30 kHz
z, output 2500 W, processing intensity 0.5 kV · A · min / m
Glow discharge treatment was performed in ² . On one side (back side) of this support, a coating solution having the following composition was used as the first layer.
Using the bar coating method of JP-A-8-4589, 5 mL / m
A coating amount of ² was applied.

Conductive fine particle dispersion liquid (SnO ₂ / Sb ₂ O ₅ particle concentration 50 parts by mass 10% aqueous dispersion liquid. Secondary aggregate with primary particle diameter 0.005 μm and average particle diameter 0.05 μm) Gelatin 0.5 parts by mass Water 49 parts by mass Polyglycerol polyglycidyl ether 0.16 parts by mass Poly (degree of polymerization 20) oxyethylene 0.1 parts by mass Sorbitan monolaurate.

Further, after the first layer was applied, it was wrapped around a stainless steel core having a diameter of 20 cm, and heat-treated at 110 ° C. (Tg of PEN support: 119 ° C.) for 48 hours for annealing so that it was heat-treated. After that, the support was sandwiched between the first layer side and the side (emulsion surface side), and a coating solution having the following composition was applied as an undercoat layer for emulsion by a bar coating method at a coating amount of 10 mL / m ² .

[0213]     Gelatin 1.01 parts by mass     Salicylic acid 0.30 parts by mass     Resorcin 0.40 parts by mass     Poly (degree of polymerization 10) oxyethylene nonyl phenyl ether                                                     0.11 parts by mass     3.53 parts by weight of water     Methanol 84.57 parts by mass     n-Propanol 10.08 parts by mass.

Further, second and third layers described later are sequentially coated on the first layer, and then a color negative light-sensitive material having a composition described below is multilayer coated on the opposite side (emulsion side),
A transparent magnetic recording medium with a silver halide emulsion layer was prepared.

(Ii) Second layer (transparent magnetic recording layer) (1) Dispersion of magnetic material Co-deposited γ-Fe ₂ O ₃ magnetic material (average major axis length: 0.25 μm)
m, S _BET : 39 m ² / g, Hc: 831 Oe, σs:
77.1Am ² /kg,σr:37.4Am ² / kg) 1
100 parts by mass, 220 parts by mass of water and 165 parts by mass of a silane coupling agent [3- (poly (degree of polymerization: 10) oxyethynyl) oxypropyl trimethoxysilane] were added, and well kneaded in an open kneader for 3 hours. The coarsely dispersed viscous liquid was dried at 70 ° C. for one day to remove water, and then heat-treated at 110 ° C. for 1 hour to prepare surface-treated magnetic particles.

Further, the following formulation was kneaded again in the open kneader for 4 hours. The surface-treated magnetic particles 855 g Diacetyl cellulose 25.3 g Methyl ethyl ketone 136.3 g Cyclohexanone 136.3 g.

Furthermore, a sand mill (1 /
Finely dispersed at 2000 rpm for 4 hours with a 4G sand mill). As the media, glass beads of 1 mmφ were used. Kneading liquid 45 g Diacetyl cellulose 23.7 g Methyl ethyl ketone 127.7 g Cyclohexanone 127.7 g Further, a magnetic material-containing intermediate liquid was prepared according to the following formulation.

(2) Preparation of magnetic substance-containing intermediate liquid Micromagnetic fine dispersion liquid 674 g Diacetylcellulose solution 24280 g (solid content 4.34%, solvent: methyl ethyl ketone / cyclohexanone = 1/1) cyclohexanone 46 g After that, the mixture was stirred with a disperser to prepare a "magnetic substance-containing intermediate liquid".

An α-alumina abrasive dispersion was prepared according to the following formulation. (A) Sumicorundum AA-1.5 (average primary particle size 1.5 μm, specific surface area 1.3 m ² / g) Preparation of particle dispersion Sumicorundum AA-1.5 152 g Silane coupling agent KBM903 (Shin-Etsu) 0.48 g Diacetyl cellulose solution 227.52 g (solid content 4.5%, solvent: methyl ethyl ketone / cyclohexanone = 1/1) Ceramic-coated sand mill (1 /
It was finely dispersed at 800 rpm for 4 hours using a 4G sand mill). As the media, 1 mmφ zirconia beads were used.

(B) Colloidal silica particle dispersion (fine particles) "MEK-ST" manufactured by Nissan Chemical Co., Ltd. was used. This is a dispersion liquid of colloidal silica having an average primary particle diameter of 0.015 μm with methyl ethyl ketone as a dispersion medium,
The solid content is 30%.

(3) Preparation of Second-Layer Coating Liquid 19053 g of the above-mentioned magnetic substance-containing intermediate liquid 264 g of diacetyl cellulose solution (solid content 4.5%, solvent: methyl ethyl ketone / cyclohexanone = 1/1) Colloidal silica dispersion liquid “MEK -ST "[dispersion b] 128 g (solid content 30%) AA-1.5 dispersion [dispersion a] 12 g Millionate MR-400 (manufactured by Nippon Polyurethane Industry Co., Ltd.) diluent 203 g (solid content 20) %, Diluting solvent: Methyl ethyl ketone / cyclohexanone = 1/1) Methyl ethyl ketone 170 g Cyclohexanone 170 g The coating liquid prepared by mixing and stirring the above was coated with a wire bar so that the coating amount was 29.3 mL / m ² . Dry 1
It was carried out at 10 ° C. The thickness of the magnetic layer after drying is 1.0
It was μm.

(Iii) Third Layer (Layer Containing Higher Fatty Acid Ester Lubricant) (1) Preparation of Dispersion Stock Solution of Lubricant The following solution (a) was dissolved by heating at 100 ° C., added to solution (i), and then dispersed with a high-pressure homogenizer. Then, a dispersion stock solution of the slip agent was prepared. A liquid following compounds 399 parts by weight _{C 6 H 13 CH (OH)} (CH 2) 10 COOC 50 H 101 The following compound 171 parts by weight _{n-C 50 H 101 O (} CH 2 CH 2 O) 16 H Cyclohexanone 830 parts by Lee Liquid cyclohexanone 8600 parts by mass.

(2) Preparation of Spherical Inorganic Particle Dispersion Liquid A spherical inorganic particle dispersion liquid [c1] was prepared according to the following formulation. Isopropyl alcohol 93.54 parts by mass Silane coupling agent KBM903 (Shin-Etsu silicone - made emissions Co.) Compound _{1-1: (CH 3 O) 3} Si- (CH 2) 3 -NH 2) 5.53 parts by weight of compound 2 1 2.93 parts by mass

[Chemical 37] Seahosta KEP50 88.00 parts by mass (amorphous spherical silica, average particle size 0.5 μm, manufactured by Nippon Shokubai Co., Ltd.) After stirring for 10 minutes with the above formulation, the following is further added. 252.93 parts by mass of diacetone alcohol. While cooling and stirring the above liquid with ice, ultrasonic homogenizer "SONIFIER 450 (BRANSON Co., Ltd.)
3) for 3 hours to disperse the spherical inorganic particle dispersion liquid c1.
Was completed.

(3) Preparation of Spherical Organic Polymer Particle Dispersion Liquid A spherical organic polymer particle dispersion liquid [c2] was prepared according to the following formulation. XC99-A8808 (Toshiba Silicone Co., Ltd., spherical crosslinked polysiloxane particles, average particle size 0.9 μm) 60 parts by mass Methyl ethyl ketone 120 parts by mass Cyclohexanone 120 parts by mass (solid content 20%, solvent: methyl ethyl ketone / cyclohexanone = 1/1 ) While cooling with ice and stirring, ultrasonic homogenizer "SONI
FIER450 (manufactured by BRANSON Co., Ltd.) was used to disperse for 2 hours to complete a spherical organic polymer particle dispersion c2.

(4) Preparation of Third Layer Coating Solution The following was added to 542 g of the above-mentioned lubricant dispersion stock solution to prepare a third layer coating solution. Diacetone alcohol 5950 g Cyclohexanone 176 g Ethyl acetate 1700 g The Seahosta KEP50 dispersion [c1] 53.1 g The spherical organic polymer particle dispersion [c2] 300 g FC431 2.65 g (manufactured by 3M Co., Ltd., solid) Min. 50%, solvent: ethyl acetate) BYK310 5.3 g (manufactured by BYK Chemi Japan Ltd., solid content 25%). 10.35 mL / m ^{2 of} the third layer coating solution is applied on the second layer.
Coated at a coating amount of 110 ° C and dried at 97 ° C for 3
After a minute, it was dried.

2) Coating of Photosensitive Layer (Preparation of Sample 001) Next, on the opposite side of the back layer obtained above, each layer having the following composition was multi-layer coated to form a color negative film (Sample 00).
1) was produced. (Composition of photosensitive layer) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin hardening agent (specific compounds are described below, numbers are added after the symbols, and chemical formulas are listed after them). The number corresponding to each component indicates the coating amount expressed in g / m ² , and for silver halide, the coating amount in terms of silver.

[0227]   First layer (first antihalation layer)   Black colloidal silver 0.122   0.07 μm silver iodobromide emulsion silver 0.01   Gelatin 0.919   ExC-1 0.002   ExC-3 0.002   Cpd-2 0.001   HBS-1 0.005   HBS-2 0.002   F-8 0.001.

[0228]   Second layer (second antihalation layer)   Black colloidal silver 0.055   Gelatin 0.425   ExF-1 0.002   Solid Disperse Dye ExF-9 0.120   HBS-1 0.074   F-8 0.001.

[0229]   Third layer (middle layer)   Cpd-1 0.080   HBS-1 0.042   Gelatin 0.300.

[0230]   4th layer (low sensitivity red sensitive emulsion layer)   Em-D Silver 0.577   Em-C Silver 0.347   ExC-1 0.233   ExC-2 0.026   ExC-3 0.129   ExC-4 0.155   ExC-5 0.029   ExC-6 0.013   Cpd-2 0.025   Cpd-4 0.025   ExC-8 0.050   HBS-1 0.114   HBS-5 0.038   Gelatin 1.474.

[0231]   Fifth layer (medium sensitivity red-sensitive emulsion layer)   Em-B silver 0.431   Em-C Silver 0.432   ExC-1 0.154   ExC-2 0.037   ExC-3 0.018   ExC-4 0.103   ExC-5 0.037   ExC-6 0.030   Cpd-2 0.036   Cpd-4 0.028   ExC-7 0.010   HBS-1 0.129   Gelatin 1.086.

[0232]   6th layer (high-sensitivity red-sensitive emulsion layer)   Em-A silver 1.108   ExC-1 0.072   ExC-3 0.035   ExC-6 0.029   Cpd-2 0.064   Cpd-4 0.077   ExC-7 0.040   HBS-1 0.329   HBS-2 0.120   Gelatin 1.245.

[0233]   7th layer (middle layer)   Cpd-1 0.094   Cpd-9 0.369   Solid disperse dye ExF-4 0.030   HBS-1 0.049   Polyethyl acrylate latex 0.088   Gelatin 0.886.

[0234]   Eighth layer (layer that gives a multilayer effect to the red sensitive layer)   Em-J silver 0.293   Em-K Silver 0.293   Cpd-4 0.030   ExM-2 0.057   ExM-3 0.016   ExM-4 0.051   ExY-1 0.008   ExY-6 0.042   ExC-9 0.021   HBS-1 0.090   HBS-3 0.003   HBS-5 0.030   Gelatin 0.610.

[0235]   9th layer (low sensitivity green sensitive emulsion layer)   Em-H silver 0.329   Em-G silver 0.333   Em-I silver 0.088   ExM-2 0.378   ExM-3 0.047   ExY-1 0.009   ExC-9 0.007   HBS-1 0.098   HBS-3 0.010   HBS-4 0.077   HBS-5 0.548   Cpd-5 0.010   Gelatin 1.470.

[0236]   10th layer (medium sensitivity green sensitive emulsion layer)   Em-F silver 0.457   ExM-2 0.049   ExM-3 0.035   ExM-4 0.014   ExY-1 0.003   ExY-5 0.006   ExC-6 0.005   ExC-8 0.010   ExC-9 0.012   HBS-1 0.065   HBS-3 0.002   HBS-5 0.020   Cpd-5 0.004   Gelatin 0.446.

[0237]   11th layer (high sensitivity green sensitive emulsion layer)   Em-E silver 0.794   ExC-6 0.007   ExC-7 0.010   ExM-1 0.022   ExM-2 0.091   ExM-3 0.014   ExM-4 0.017   ExY-5 0.003   Cpd-3 0.004   Cpd-4 0.007   Cpd-5 0.010   HBS-1 0.148   HBS-5 0.037   Polyethyl acrylate latex 0.099   Gelatin 0.939.

[0238]   12th layer (yellow filter layer)   Cpd-1 0.094   Solid disperse dye ExF-2 0.150   Solid disperse dye ExF-5 0.010   Oil-soluble dye ExF-7 0.010   HBS-1 0.049   Gelatin 0.630.

[0239]   13th layer (low sensitivity blue-sensitive emulsion layer)   Em-O silver 0.112   Em-M Silver 0.320   Em-N silver 0.240   ExC-1 0.048   ExY-1 0.012   ExY-2 0.700   ExY-6 0.060   ExC-9 0.012   Cpd-2 0.100   Cpd-3 0.004   HBS-1 0.222   HBS-5 0.074   Gelatin 2.058.

[0240]   14th layer (high-sensitivity blue-sensitive emulsion layer)   Em-L silver 0.714   ExY-2 0.348   ExY-6 0.064   Cpd-2 0.075   Cpd-3 0.001   HBS-1 0.071   Gelatin 0.678.

[0241]   Fifteenth layer (first protective layer)   0.07 μm silver iodobromide emulsion silver 0.301   UV-1 0.211   UV-2 0.132   UV-3 0.198   UV-4 0.026   F-11 0.009   S-1 0.086   HBS-1 0.175   HBS-4 0.050   Gelatin 1.984.

[0242]   16th layer (2nd protective layer)   H-1 0.400   B-1 (diameter 1.7 μm) 0.050   B-2 (diameter 1.7 μm) 0.150   B-3 0.050   S-1 0.200   Gelatin 0.750.

Further, in order to improve the storability, processability, pressure resistance, antifungal / bacteriostatic property, antistatic property and coating property of each layer, W-1 to W-6, B-4 to B are appropriately added. -6, F
-1 to F-17, and lead salt, platinum salt, iridium salt, and rhodium salt.

Preparation of Dispersions of Organic Solid Disperse Dyes ExF-2 of the 12th layer was dispersed by the following method.   2.800 kg of ExF-2 wet cake (containing 17.6% by weight of water)   Octylphenyldiethoxymethanesulfonate sodium                               (31 mass% aqueous solution) 0.376 kg   F-15 (7% aqueous solution) 0.011kg   Water 4.020kg   Total 7.210 kg (PH adjusted to 7.2 with NaOH).

The slurry having the above composition was stirred with a dissolver to roughly disperse the mixture, and then agitator mill LMK-4 was used.
Peripheral speed 10m / s, discharge rate 0.6kg / min, 0.3m
With a filling rate of zirconia beads having a diameter of m of 80%, the dispersion was dispersed until the absorbance ratio of the dispersion became 0.29 to obtain a solid fine particle dispersion. The average particle size of the fine dye particles was 0.29 μm.

[0246] Similarly, ExF-4 and ExF-9
A solid dispersion of was obtained. The average particle size of the dye fine particles was 0.28 μm and 0.49 μm, respectively. ExF-5
Was dispersed by the microprecipitation dispersion method described in Example 1 of EP 549,489A. The average particle size was 0.06 μm.
The compounds used for producing each layer are shown below.

[Chemical 38]

[0247]

[Chemical Formula 39]

[0248]

[Chemical 40]

[0249]

[Chemical 41]

[0250]

[Chemical 42]

[0251]

[Chemical 43]

[0252]

[Chemical 44]

[0253]

[Chemical formula 45]

[0254]

[Chemical formula 46]

[0255]

[Chemical 47]

[0256]

[Chemical 48]

The color negative photosensitive material prepared as described above is designated as Sample 001. The centroid wavelength λ _R of the spectral sensitivity of the red-sensitive layer of Sample 001 was 618 nm. Sample 001, using the light source described in the text, through a continuous wedge to 1/1
It was exposed for 00 seconds. Development was carried out by the following using an automatic processor FP-360B manufactured by Fuji Photo Film Co., Ltd. Incidentally, the overflow solution of the bleaching bath was modified so that the overflow liquid was discharged into the waste liquid tank without flowing into the post-bath. This FP-360B is equipped with the evaporation correction means described in JIII Journal of Technical Disclosure No. 94-4992.

The processing steps and processing liquid compositions are shown below.   (Treatment process)     Process processing time Processing temperature Replenishment amount * Tank capacity   Color development 3 minutes 5 seconds 37.8 ℃ 20 mL 11.5L   Bleach 50 seconds 38.0 ℃ 5 mL 5L   Fixing (1) 50 seconds 38.0 ℃ -5L   Fixing (2) 50 seconds 38.0 ℃ 8 mL 5L   Washing with water 30 seconds 38.0 ℃ 17 mL 3L   Stable (1) 20 seconds 38.0 ℃ −3L   Stable (2) 20 seconds 38.0 ℃ 15 mL 3L   Dry 1 minute 30 seconds 60.0 ℃   * Replenishment amount per 35 mm width of photosensitive material 1.1 m (equivalent to 24 Ex. 1).

The stabilizing solution and the fixing solution were of the countercurrent system from (2) to (1), and the overflow solution of washing water was all introduced into the fixing bath (2). The amount of the developing solution brought into the bleaching process, the amount of the bleaching solution brought into the fixing process, and the amount of the fixing solution brought into the water washing process were 35 mm width of the photosensitive material and 1.1 m.
They were 2.5 mL, 2.0 mL, and 2.0 mL, respectively. The crossover time is 6 seconds in all cases, and this time is included in the processing time of the previous step. Open area 100 cm ² in the color developing solution in the processing machine, 120 cm ² in the bleaching solution, the other processing solutions was about 100 cm ^2.

The composition of the treatment liquid is shown below.   (Color developer) Tank liquid (g) Replenisher (g)   Diethylenetriamine pentaacetic acid 3.0 3.0   Catechol-3,5-disulfonic acid     Disodium 0.3 0.3   Sodium sulfite 3.9 5.3   Potassium carbonate 39.0 39.0   Disodium-N, N-bis (2-sulfur     Honatoethyl) hydroxylamine 1.5 2.0   Potassium bromide 1.3 0.3   Potassium iodide 1.3 mg-   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 4.5 6.5   Add water 1.0L 1.0L   pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.18.

[0261]   (Bleaching solution) Tank solution (g) Replenisher solution (g)   1,3-Diaminopropanetetraacetic acid secondary     Ammonium iron monohydrate 113 170   Ammonium bromide 70 105   Ammonium nitrate 14 21   Succinic acid 34 51   Maleic acid 28 42   Add water 1.0L 1.0L   pH [adjusted with aqueous ammonia] 4.6 4.0.

[0262]   (Fixing (1) Tank liquid)   5:95 (volume ratio) mixture of the above bleaching tank liquid and the following fixing tank liquid   (PH 6.8).

[0263]   (Fixing liquid (2)) Tank liquid (g) Replenishing liquid (g)   Ammonium thiosulfate aqueous solution 240 mL 720 mL   (750g / L)   Imidazole 7 21   Ammonium methanethiosulfonate 5 15   Ammonium methanesulfinate 10 30   Ethylenediaminetetraacetic acid 13 39   Add water 1.0L 1.0L   pH [adjusted with aqueous ammonia and acetic acid] 7.4 7.45.

(Washing water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-produced by Rohm and Haas).
120B) and OH type strongly basic anion exchange resin (the same Amberlite IR-400) are passed through a mixed bed column to adjust the concentration of calcium and magnesium ions to 3 m.
g / L or less, followed by 20 mg / L sodium diisocyanurate dichloride and 150 mg / L sodium sulfate
Was added. The pH of this liquid was in the range of 6.5 to 7.5.

[0265]   (Stabilizing liquid) Common for tank liquid and replenishing liquid (Unit: g)   Sodium p-toluenesulfinate 0.03   Polyoxyethylene-p-monononylphenyl ether 0.2     (Average degree of polymerization 10)   1,2-benzisothiazolin-3-one sodium 0.10   Ethylenediaminetetraacetic acid disodium salt 0.05   1,2,4-triazole 1.3   1,4-bis (1,2,4-triazole-1-     Ilmethyl) piperazine 0.75   1.0L with water added   pH 8.5.

Preparation of (Em-A2) Molecular weight 1500 used in the preparation of Em-A
The low molecular weight gelatin of 0 was replaced with low molecular weight oxidized gelatin. (Low-molecular-weight oxidation-treated gelatin was prepared by adding hydrogen peroxide solution to the oxidation-treated gelatin to cause a chemical reaction and deactivating the residual hydrogen peroxide with catalase.)
At this time, the aging time at 75 ° C. was adjusted so that the particle size was the same. Further, the portion where particles are formed by the double jet method at 75 ° C. during the preparation of Em-A is formed by mixing the silver nitrate solution and the halogen solution using the stirring device described in JP-A-10-43570 instead of the double jet method. The method was changed to a method of forming particles by adding fine particles. At this time, an appropriate amount of low-molecular weight oxidized gelatin was added to the halogen solution. The amount of added dye and the amount of chemical sensitizer were adjusted so that optimum chemical sensitization and spectral sensitization were obtained.

Preparation of (Em-B2) to (Em-N2) Similar to Em-A2, low molecular weight gelatin was replaced with low molecular weight oxidized gelatin, and the grain forming portion at high temperature around 75 ° C was used. Prepared by using the described particle formation method. However, the amount of the sensitizing dye added and the amount of the post-ripening chemical added were adjusted so that the 1/100 sensitivity was maximized. The characteristic values of the prepared emulsion are shown in Table 4.

[0268]

[Table 4]

Sample 0 was a silver halide color photographic light-sensitive material prepared by replacing Em-A of Sample 001 with Em-A2 described above and Em-B of Sample 001 with Em-B2.
02. However, Em-O was replaced with Em-N2. In each of Samples 001 and 002, the coated silver amount of the photosensitive silver halide was 6.9 g / m ² . Sample 002 is also sample 00
The same exposure and development processing as in 1 was performed. The photographic results are shown in Table 5. The sensitivity was indicated by the relative value of the reciprocal of the exposure amount required to reach the density of +0.2 (the sensitivity of Sample 001 was 100).

[0270]

[Table 5]

Since tabular grains having a thickness of 0.1 μm or less have a large reflection of visible light, it has been considered difficult to obtain high sensitivity even when used in a light-sensitive material. It was found that in the system in which the amount of coated silver was large, a clear increase in sensitivity was obtained as described above.

Example 2 Sample 0 in which the coated silver amount was changed by uniformly increasing or decreasing the coated silver amount of the emulsion layer with respect to the sample 001 described above.
11-014 were created. Further, Samples 021 to 024 in which the coating silver amount was changed similarly to Sample 002 were prepared,
Evaluation was performed in the same manner as in Example 1.

[0273]

[Table 6]

Within the range of the coated silver amount of the present invention, the sensitization is remarkable by using tabular grains having a circle equivalent diameter of 1.0 μm or more and a thickness of 0.1 μm or less. However, in the case of a sample having a large amount of coated silver deviating from the present invention and a sample having a small amount thereof, the equivalent circle diameter was 1.
Even when tabular grains having a thickness of 0 μm or more and a thickness of 0.1 μm or less were used, the degree of sensitization was small. It is understood that using a flat plate having an equivalent circle diameter of 1 μm or more and a thickness of 0.1 μm or less in the coated silver amount region of the present invention is important for achieving high sensitivity.

Example 3 Sample 003 was prepared by making the following changes to Sample 002. Remove Cpd-4 of the fourth layer Remove Cpd-4 of the fifth layer Remove Cpd-4 of the sixth layer Remove Cpd-4 of the eighth layer Remove Cpd-4 of the eleventh layer F-10 of each layer , And F-11 are removed Cpd-4, F-10, and F-11 are compounds of the invention. The membrane potential of Sample 003 was +50 mV. Further, the amounts of Cpd-4, F-10, and F-11 were appropriately adjusted to prepare samples 004 to 005 shown in Table 6.
Sample 006 was prepared using Compound (II) -13 in place of Cpd-4, F-10 and F-11 of Sample 002, and Sample 007 was prepared using Compound (III) -11. Samples 002 to 007 were left in an atmosphere of 25 ° C. and 55% for 20 days, and then stored for 2 weeks under the condition of 40 ° C. and 60%, and the change in fog due to storage was examined. The results are shown in the table below.

[0276]

[Table 7]

From the above results, the film potential on the emulsion layer side was -10.
It can be seen that the storage fog deteriorates severely when the voltage is higher than 0 mV. Therefore, it can be seen that keeping the potential of the light-sensitive material within the range of the present invention is very useful for improving the storage stability.

Example 4 Water was added to low molecular weight gelatin, dissolved and stirred at 40 ° C., and commercially available titanium oxide sol (Nikkiso Microtrac U.
A measurement value with PA (68 nm) was added to prepare a titanium oxide fine particle dispersion. Sample 002 of titanium oxide fine particle dispersion
0.3g / m ² for the 10th layer and 0.7g for the 11th layer
/ M ^{2 was} added to prepare Sample 008. Exposure and development were performed in the same manner as in Example 1 to estimate the photographic sensitivity of the red-sensitive layer. The results are shown in the table below.

[0279]

[Table 8]

However, the sensitivity of Sample 002 was set to 100.
It was revealed that the sensitivity of the red-sensitive layer was significantly increased by adding the titanium oxide fine particles to the layer above the red-sensitive layer, and the effect of the present invention was remarkable.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ identification code FI theme code (reference) G03C 1/40 G03C 1/40 1/76 501 1/76 501 501/392 7/392 AZ F term ( Reference) 2H016 BB01 BB02 BC00 BD00 BD01 2H023 BA00 BA03 BA04 CC02 CD00 CD10 DB00

Claims (4)

[Claims] 1. A color photographic light-sensitive material having at least one layer of a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support. Coating silver amount of 3.5g / m
² or more and 8.5 g / m ² or less, and equivalent circle diameter of 1.0
A silver halide color photographic light-sensitive material, characterized in that tabular grains having a thickness of not less than 0.1 μm and not more than 0.1 μm are contained in all light-sensitive silver halide emulsion layers. 2. The silver halide color photographic light-sensitive material according to claim 1, wherein the film potential on the emulsion layer side of the light-sensitive material is 100 mV to 300 mV less than that of the quinhydrin solution. 3. The following general formulas (I), (II), and (II
The silver halide color photographic light-sensitive material according to claim 1 or 2, which contains at least one selected from the compounds represented by I). General formula (I) In formula (I), R _a1 is an alkyl group, an alkenyl group, an aryl group, an acyl group, an alkyl or aryl sulfonyl group, an alkyl or aryl sulfinyl group, a carbamoyl group, a sulfamoyl group, an alkyl or aryl phosphoryl group, an alkoxycarbonyl group, It represents an aryloxycarbonyl group or a heterocyclic group, and R _a2 represents a hydrogen atom or the group represented by R _a1 . Provided that when R _a1 is an alkyl group, an alkenyl group or an aryl group, R _a2 is an acyl group, an alkyl or aryl sulfonyl group, an alkyl or aryl sulfinyl group, a carbamoyl group, a sulfamoyl group, an alkyl or aryl phosphoryl group, an alkoxycarbonyl group, It is an aryloxycarbonyl group or a heterocyclic group. R _a1 and R _a2 are bonded to each other to form 5 to 7
A member ring may be formed. General formula (II) In the formula, X ² and Y ² each independently represent a hydroxyl group, —NR ²³ R ²⁴ or —NHSO ₂ R ²⁵ . R ²¹ and R ²² each independently represent a hydrogen atom or any substituent, and R ²¹ and R ²² may together form a carbocycle or a heterocycle.
R ²³ and R ²⁴ each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ²³ and R ²⁴ may together form a heterocycle. R ²⁵ represents an alkyl group, an aryl group, an amino group or a heterocyclic group. General formula (III): In the general formula (III), R ₂₁ , R ₂₂ and R ₂₃ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and R ₂₄ represents a hydrogen atom, an alkyl group, An alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, or -NR ₂₅ R ₂₆ ,
₂₁ -CO- or -SO ₂ - represents, n represents 0 or 1
Represents R ₂₅ is a hydrogen atom, a hydroxy group, an amino group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group,
Alternatively, it represents a heterocyclic group, and R ₂₆ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. R ₂₁ and R ₂₂ , R ₂₁ and R ₂₃ , R ₂₃ and R ₂₄ , or R ₂₄
And R ₂₂ may combine to form a ring. 4. The halogenated color photographic light-sensitive material according to claim 1, wherein the emulsion layer contains fine metal oxide particles having an average grain size of 100 nm or less.