JP2000321702A - Photosensitive silver halide emulsion, its preparation and silver halide photographic sensitive material containing same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide photographic emulsion excellent in sensitivity to fogging ratio and sensitivity to graininess ratio and having remarkably improved preservability. SOLUTION: In the photosensitive silver halide emulsion, >=50% of the total projected area of silver halide grains is occupied by tabular silver halide grains having an aspect ratio of >=8, the average iodine content of all the grains is >=2 mol% and the tabular grains contain >=10 dislocation lines. The emulsion has been subjected to chemical sensitization and spectral sensitization in such a way as to satisfy at least one of the following requirements (1) and (2). (1) Spectral sensitization is carried out by adding a spectral sensitizing dyestuff under <=500 ppm Ca, Mg and Sr, a water-soluble salt of at least one metal selected from Ca, Mg and Sr is added so as to ensure 100-25,000 ppm Ca, Mg and Sr and then the chemical sensitization is started. (2) The chemical sensitization and spectral sensitization are carried out in the presence of alkali-treated bone gelatin containing >=30% component whose molecular weight is >=280,000 in the molecular weight distribution measured by the PAGI method.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic emulsion. In particular, the present invention provides a tabular silver halide grain photographic emulsion which is excellent in photographic sensitivity and granularity, has little fluctuation in photographic performance after storage, and has little fog, a method for producing the same, and a halogen containing such an emulsion. The present invention relates to a silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art As a method of improving the sensitivity / granularity ratio of a silver halide photographic emulsion, for example, a method of increasing the aspect ratio or monodispersing tabular grains is well known to those skilled in the art. Furthermore, as described in JP-A-6-332093, it is known that sensitivity is improved by combining selenium sensitization with a monodisperse high aspect ratio flat plate. However, the high aspect ratio flat plate has a problem in that the particles are likely to aggregate, which deteriorates the granularity. Therefore, the sensitivity / granularity ratio, which is important for image quality, was not satisfactory. JP-A-6-11782 describes an example in which silver iodobromide tabular grains having a high aspect ratio (= 15) are combined with selenium sensitization. Time, desalination process,
It is described that the presence of a metal ion salt before chemical sensitization and before coating is desirable depending on the purpose. Specific metal ions include Mg, Ca, Sr, Ba, Al, S
Although numerous metal ions such as c are described, Mg, Mg,
There is no description about the granular improvement effect specifically exerted by adding Ca and Sr, and it is not at all distinguished from other metal ions.

[0003] In silver halide photographic materials, high sensitivity is demanded, and the importance of high aspect ratio emulsions is increasing. With the increase in sensitivity, photographic properties tend to increase due to storage after the production of photosensitive materials,
It is desired to suppress this, and in particular, a technique for suppressing fog is required.

In this regard, the addition of a palladium compound such as a palladium complex of ethylenediamine for the purpose of suppressing fog is disclosed in US Pat. No. 2,552,229, US Pat. No. 2,566,263, and JP-A-5-333480. This has the effect of actually suppressing an increase in fog during storage.

[0005] JP-A-8-234341 (US Pat. No. 5,614,360) discloses that when a palladium compound of ethylenediamine is used,
It is disclosed that there is an advantage that the viscosity does not increase even under a high gelatin concentration. However, when stored under tropical conditions of high temperature and high humidity, the effect of suppressing fog is not sufficient, and further improvement has been desired. (For fog stored under such tropical conditions, data is described in US Pat. No. 2,552,229. It is shown.).

In the examination of the present invention, it has been found that the use of the Pd complex described in the above-mentioned JP-A-8-234341 (US Pat. No. 5,614,360) has a problem that the fluctuation of photographic properties in running processing is increased. In the production of silver halide photographic light-sensitive materials, it is also desired that fluctuations in photographic properties during running processing are small, and it is desired to suppress both fluctuations in photographic properties during storage and fluctuations in photographic properties before and after running processing. ing.

We have found that these problems can be solved by using a specific palladium complex in the present invention, but there is no example disclosing the use of such a palladium compound so far. Further, there is no example in which this is applied to the photosensitive silver halide emulsion of the present invention.

On the other hand, JP-A-4-16838 describes the use of a mercaptotetrazole compound having a water-soluble group for the purpose of suppressing fog during storage.
Further, it is disclosed that storage stability is improved by using a combination of a mercaptotetrazole compound and a mercaptothiadiazole compound.

However, in the emulsion of the present invention (tabular silver halide grains having an aspect ratio of 8 or more account for 50% or more of the total projected area of silver halide grains, and the average iodine content of all grains is 2 mol % Or more, and wherein the tabular grains contain 10 or more dislocation lines per grain so that the emulsion satisfies at least one requirement selected from the following (1) and (2): A light-sensitive silver halide emulsion characterized by chemical sensitization and spectral sensitization {(1) spectral sensitization by adding a spectral sensitizing dye in a state where calcium, magnesium and strontium are 50 ppm or less; Done, then calcium,
100 to 2500p for magnesium and strontium
A water-soluble salt of at least one metal selected from calcium, magnesium and strontium is added so as to obtain pm, and then chemical sensitization is started. (2)
Chemical sensitization and spectral sensitization were carried out by measuring components having a molecular weight of 280,000 or more in the molecular weight distribution measured by the PAGI method.
% In the presence of alkali-treated bone gelatin. ) Does not disclose the use of｝ with a water-soluble mercapto compound. Further, it does not disclose the excellent effects obtained by using water-soluble mercaptotetrazole and water-soluble mercaptotriazole in the emulsion as in the present invention.

We have studied the application of various compounds known as water-soluble mercapto compounds to the emulsion of the present invention having a high sensitivity / granularity ratio, but most of them were accompanied by a decrease in sensitivity. After various studies, it has been found that storage stability can be improved without lowering sensitivity by using a specific combination, that is, water-soluble mercaptotetrazole and water-soluble mercaptotriazole in combination.

[0011] Thiocyanate ions are useful for producing high-sensitivity emulsions. It is well known to those skilled in the art that reducing the amount leads to a decrease in sensitivity. However, there is no specific example showing that the required amount of thiocyanate ion in the above-mentioned emulsion of the present invention is lower than the conventionally known level and at the same time that the storage stability can be improved.

It is effective to reduce the surface silver iodide content for the purpose of suppressing fog during aging. However, those which attempted to lower the silver iodide content on the ultra-surface by adding and dissolving silver iodobromide fine grains having a lower silver iodide content than the surface silver iodide content of the host grains during post-ripening are disclosed in US Pat. Not until now.

The inclusion of a metal complex having a cyan ligand in emulsion grains for the purpose of increasing the quantum sensitivity is described, for example, in JP-A-4-306664. However, in the emulsion of the present invention, tabular silver halide grains having an aspect ratio of 8 or more account for 50% or more of the total projected area of the silver halide grains, and the average iodine content of all grains is 2 mol%.
In the photosensitive silver halide emulsion wherein the tabular grains contain 10 or more dislocation lines per grain, the emulsion should satisfy at least one requirement selected from the following (1) and (2). Photosensitive silver halide emulsion characterized by chemical sensitization and spectral sensitization (1) Spectral sensitization is carried out by adding a spectral sensitizing dye in a state where calcium, magnesium and strontium are not more than 50 ppm. Thereafter, a water-soluble salt of at least one metal selected from calcium, magnesium and strontium is added so that the content of calcium, magnesium and strontium becomes 100 to 2500 ppm, and thereafter chemical sensitization is started. (2) Chemical sensitization and spectral sensitization are performed in the presence of an alkali-treated bone gelatin containing 30% or more of a component having a molecular weight of 280,000 or more in a molecular weight distribution measured by the PAGI method. ) There is no specific description that the sensitivity / granularity ratio is further improved by combining｝ with the inclusion of a metal complex having a cyanide ligand, and an increase in fog during storage is suppressed. By adding the hexacyanoiron (II) complex and the hexacyanoruthenium complex to the above emulsion during grain formation, it is possible for the first time by the present inventors that not only the sensitivity / granularity ratio can be improved but also the fog during storage can be improved. Was found.

[0014]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide photographic emulsion and a silver halide color photographic light-sensitive material which are excellent in sensitivity / fogging ratio and sensitivity / granularity ratio. SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic emulsion and a silver halide color photographic light-sensitive material having significantly improved storage stability. Still another object of the present invention is to provide a method for producing the above-mentioned emulsion.

[0015]

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

(Embodiment I) When at least 50% of the total projected area of the silver halide grains is occupied by tabular silver halide grains having an aspect ratio of 8 or more, and the average iodine content of all grains is 2 mol% or more, In a light-sensitive silver halide emulsion in which the tabular grains contain 10 or more dislocation lines per grain, the emulsion is chemically enhanced so as to satisfy at least one requirement selected from the following (1) and (2). A light-sensitive silver halide emulsion characterized by sensitivity and spectral sensitization.

(1) Spectral sensitization is performed by adding a spectral sensitizing dye in a state where calcium, magnesium and strontium are 50 ppm or less, and thereafter, calcium, magnesium and strontium are added in an amount of 100 to 250 ppm.
A water-soluble salt of at least one metal selected from calcium, magnesium and strontium is added so as to be 0 ppm, and then chemical sensitization is started.

(2) Chemical sensitization and spectral sensitization were carried out using PAGI
The molecular weight distribution measured by the
Performed in the presence of alkali treated bone gelatin containing 30% or more of more than 10,000 components.

(Embodiment II) The photosensitive silver halide emulsion of Embodiment I, wherein the twin plane spacing of the silver halide grains is 0.017 μm or less.

(Embodiment III) In the crystal growth process of the above silver halide grains, fine silver halide grains containing 95 mol% or more of silver iodide are provided outside a reactor for crystal growth. In the prepared mixer, an aqueous solution of a water-soluble silver salt and an aqueous solution of a water-soluble halide are mixed, and the mixture is supplied to the reaction vessel immediately after the formation and used for crystal growth. A light-sensitive silver halide emulsion according to embodiment I or II.

(Embodiment IV) The above-mentioned photosensitive silver halide emulsion is produced by adding a silver iodobromide emulsion prepared in advance, dissolving and shelling the emulsion during chemical sensitization. The light-sensitive silver halide emulsion according to any one of the embodiments I to III.

(Embodiment V) The above-mentioned photosensitive silver halide emulsion was produced by adding at least one selected from the group consisting of a hexacyanoiron (II) complex and a hexacyanoruthenium complex during grain formation. The light-sensitive silver halide emulsion according to any one of Embodiments I to IV, characterized in that:

(Embodiment VI) A blue-sensitive silver halide emulsion layer containing a yellow coupler, a green-sensitive silver halide emulsion layer containing a magenta coupler, a red-sensitive silver halide emulsion layer containing a cyan coupler on a support, And a silver halide color photographic light-sensitive material having at least one hydrophilic protective colloid layer, the coating amount of calcium ion, magnesium ion and strontium ion in the light-sensitive material is 8.0 × 10 ^-2 per g of gelatin in terms of atomic weight.
g or less, and at least one of the emulsions used in the emulsion layer is a photosensitive silver halide emulsion according to any one of Embodiments I to V. material.

(Embodiment VII) A halide comprising a silver halide emulsion according to any one of Embodiments I to V, which satisfies at least one requirement selected from the following (1) to (3): Silver photographic photosensitive material.

(1) It contains at least one Pd (II) complex represented by the following general formula (I-1).

General formula (I-1)

Embedded image In the formula, X ₁ and X ₂ are each independently -S (R ₁₁ )-, -N (R ₁₂ ) (R
_{13) -, - O (R} 14) - represents, Y _1, Y ₂ are each independently -S (R
_{21) -, - N (R} 22) (R 23) -, - O (R 24) - represents, Z _1, Z ₂
Each independently represents an alkylene group, an arylene group, or a divalent heterocyclic residue; L ₁ and L ₂ each independently represent a single bond, an alkylene group, —CO—, or —SO ₂ —; M represents an integer of 0 to 4; Where X ₁ ,
When X ₂ is each independently -N (R ₁₂ ) (R ₁₃ )-and Y ₁ and Y ₂ are each independently -N (R ₂₂ ) (R ₂₃ )-, L ₁ and L ₂ are each independently -CO -, - SO ₂ - represents a. R ₁₁ , R ₁₄ , R
₂₁ and R ₂₄ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or a heterocyclic group, and R ₁₂ , R ₁₃ , R
₂₂ and R ₂₃ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkyl Represents a sulfonyl group or an arylsulfonyl group. When R ₁₂ or R ₂₂ is a hydrogen atom, N
The proton may be dissociated and coordinated to Pd (II).

(2) at least one water-soluble mercaptotetrazole compound represented by the following general formula (II-1) and at least one water-soluble mercaptotriazole compound represented by the following general formula (II-2) contains.

General formula (II-1)

Embedded image

In the general formula (II-1), R ₅ is —SO
₃ represents M, -COOM, an organic residue substituted with both one least member selected from the group consisting of -OH and -NHR _2,
M represents a hydrogen atom, an alkali metal atom, or a quaternary ammonium group or a quaternary phosphonium group, R ₂ represents a hydrogen atom,
Alkyl group having 1 to 6 carbon atoms, a -COR _3, -COOR ₃ or -SO ₂ R _3. R ₃ represents a hydrogen atom, an alkyl group, or an aryl group.

Formula (II-2)

Embedded image

In the general formula (II-2), R ₆ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and R ₅ represents —SO ₃ M,
COOM, at least selected from the group consisting of -OH and -NHR ₂ represents an organic residue substituted by one, M is a hydrogen atom, an alkali metal atom or represents a quaternary ammonium group or a quaternary phosphonium group , R ₂ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, -COR _3, -COOR ₃ or -
Represents SO ₂ R ₃ . R ₃ represents a hydrogen atom, an alkyl group, or an aryl group.

(3) The thiocyanate ion in the photosensitive material is not more than 2.5 × 10 ^-3 mol per mol of silver.

(Embodiment VIII) Pd (I) which satisfies the requirement (1) described in the embodiment VII and is represented by the general formula (I-1) of the requirement
I) The silver halide photographic material of Embodiment VII, wherein the complex is represented by the following general formula (I-2).

[0034]

Embedded image

[0035] In the formula, Z _1, Z ₂ represents an alkylene group, an arylene group or a divalent heterocyclic group each independently, R _1,
R ₂ is each independently a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group,
Represents an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group or an arylsulfonyl group.
X ₁₁ , X ₁₂ , X ₁₃ and X ₁₄ each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

(Embodiment IX) The silver halide photographic material of Embodiment VII, which satisfies the requirement (2).

(Embodiment X) Tabular silver halide grains having an aspect ratio of 8 or more occupy 50% or more of the total projected area of the silver halide grains, and the average iodine content of all the grains is 2 mol% or more. In the method for producing a photosensitive silver halide emulsion in which the tabular grains contain 10 or more dislocation lines per grain, the emulsion may satisfy at least one requirement selected from the following (1) and (2). A method for producing a light-sensitive silver halide emulsion, characterized by chemically sensitizing and spectrally sensitizing the emulsion.

(1) Spectral sensitization is carried out by adding a spectral sensitizing dye in a state where calcium, magnesium and strontium are 50 ppm or less, and thereafter, calcium, magnesium and strontium are added in an amount of 100 to 250 ppm.
A water-soluble salt of at least one metal selected from calcium, magnesium and strontium is added so as to be 0 ppm, and then chemical sensitization is started.

(2) Chemical sensitization and spectral sensitization were carried out using PAGI
The molecular weight distribution measured by the
Performed in the presence of alkali treated bone gelatin containing 30% or more of more than 10,000 components.

(Embodiment XI) The method for producing a photosensitive silver halide emulsion according to Embodiment X, wherein the twin plane spacing of the silver halide grains is 0.017 μm or less.

(Embodiment XII) In the above-mentioned crystal growth process of silver halide grains, fine silver halide grains containing 95 mol% or more of silver iodide were provided outside a reaction vessel for crystal growth. Embodiment X or Embodiment wherein the mixture is formed by mixing an aqueous solution of a water-soluble silver salt and an aqueous solution of a water-soluble halide in a mixer, and is supplied into the reaction vessel immediately after the formation to be used for crystal growth. A method for producing a photosensitive silver halide emulsion of XI.

(Embodiment XIII) An embodiment X is characterized in that a silver iodobromide emulsion prepared in advance is added, dissolved and shelled at the time of chemical sensitization of the photosensitive silver halide emulsion.
And a process for producing a photosensitive silver halide emulsion according to any one of the embodiments XII to XII.

(Embodiment XIV) An embodiment X characterized by adding at least one member selected from the group consisting of a hexacyanoiron (II) complex and a hexacyanoruthenium complex during the formation of the grains of the photosensitive silver halide emulsion. Or a process for producing a photosensitive silver halide emulsion according to any one of the embodiments XIII to XIII.

(Embodiment XV) The silver halide photographic material of Embodiment VII, which satisfies all of the requirements (1) to (3).

Hereinafter, the present invention will be described in detail. The emulsion of the present invention relates to a silver iodobromide or silver chloroiodobromide tabular grain emulsion.

In the tabular silver halide grains (hereinafter also referred to as tabular grains), the aspect ratio means the ratio of the diameter to the thickness of the silver halide. That is, it is a value obtained by dividing the diameter of each silver halide grain by the thickness. Here, the diameter refers to the diameter of a circle having an area equal to the projected area of the silver halide grains when the grains are observed with a microscope or an electron microscope. Therefore, that the aspect ratio is 8 or more means that the diameter of the circle is 8 times or more the thickness of the particle. In the tabular silver halide grains of the present invention, grains having an aspect ratio of 8 or more occupy 50% or more of the projected area of all silver halide grains, and preferably 60% or more.

In the present invention, the average aspect ratio is an average value of the aspect ratios of all tabular grains in the emulsion, and the tabular grains are grains having an aspect ratio of 2 or more. The average aspect ratio of the tabular grains of the present invention is preferably 8 or more.
The above is further preferred, and the value of 16 or more is particularly preferred. The aspect ratio is preferably 50 or less.

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

The shape of the tabular grains in the present invention is usually
Hexagon. The hexagonal shape means that the shape of the main plane of the tabular grain is hexagonal and the adjacent side ratio (maximum side length / minimum side length) is 2 or less. Preferably, the adjacent side ratio is 1.6 or less, more preferably, the adjacent side ratio is 1.
2 or less. It goes without saying that the lower limit is 1.0. Particularly in high aspect ratio grains, triangular tabular grains increase in tabular grains. Triangular tabular grains appear when Ostwald ripening has progressed too much. In order to substantially obtain hexagonal tabular grains, it is preferable to shorten the time for ripening as much as possible. For that purpose, it is necessary to devise a method of increasing the ratio of tabular grains by nucleation. As described in JP-A-63-11928 by Saito, when silver ions and bromide ions are added to a reaction solution by a double jet method, silver ions must be added to the reaction solution in order to increase the probability of generation of hexagonal tabular grains. Preferably, one or both of the aqueous solution and the aqueous bromide ion solution contains gelatin.

The hexagonal tabular grains used in the present invention have nucleation and
It is formed by the Ostwald ripening and growing process. Each of these steps is important in suppressing the spread of the particle size distribution, but it is impossible to narrow the spread of the size distribution generated in the step described on the left in the subsequent steps. Care must be taken that the distribution does not spread. An important point in the nucleation process is the relationship between the nucleation time at which silver ions and bromide ions are added to the reaction solution by the double jet method to cause precipitation, and the temperature of the reaction solution. JP-A 63-63 by Saito
No. 92942 describes that the temperature of the reaction solution during nucleation is preferably in the range of 20 to 45 ° C. in order to improve the monodispersibility. Further, Japanese Patent Laid-Open Publication No.
No. 40 states that the preferred temperature during nucleation is 60 ° C. or less.

Monodisperse flat plate with large aspect ratio
Add gelatin during particle formation to obtain particles
There are cases. At this time, the gelatin used is described in
Phthalic anhydride and carboxylic anhydride described in
Use of gelatin modified by succinic acid is preferred
No. Furthermore, Japanese Patent Application Laid-Open Nos.
Chemically modified gelatin described in 1-143002
(-NH in gelatin _TwoWhen a group is chemically modified,
Gelatin having at least two COOH groups)
It is also preferred to use. This chemically modified gelatin is
When the amino group in the amino acid is chemically modified,
Characterized in that at least two groups have been introduced.
Although it is ratine, the use of trimellitized gelatin is
preferable. These gelatins are added before the growth step
Preferably, but more preferably added immediately after nucleation
Good to do. The amount added is the weight of the entire dispersion medium during particle formation.
60% or more, preferably 80% or more,
More preferably, it is 90% or more.

The tabular grain emulsion comprises silver iodobromide or silver chloroiodobromide. Although silver chloride may be contained, the silver chloride content is preferably 8 mol% or less, more preferably 3 mol% or less, or 0 mol%. Regarding the silver iodide content, the coefficient of variation of the grain size distribution of the tabular grain emulsion is preferably 30% or less, so that the silver iodide content was 20 mol%.
The following is preferred. By reducing the silver iodide content, the coefficient of variation of the grain size distribution of the tabular grain emulsion can be easily reduced. In particular, the coefficient of variation of the distribution of the equivalent circle diameter of the tabular grain emulsion is preferably 20% or less, and the silver iodide content is preferably 10% by mol or less.

It is preferable that the tabular grain emulsion has a structure within the grains with respect to the silver iodide distribution. In this case, the structure of the silver iodide distribution may be a double structure, a triple structure, a quadruple structure, or even a higher structure.

In the present invention, tabular grains have dislocation lines. Dislocation lines of tabular grains are described, for example, in JF Hamilton, Phot.
i.Eng., 11, 57, (1967) and T. Shiozawa, J. Soc. Phot. Sci. Jap
An, 35, 213, (1972) can be observed by a direct method using a transmission electron microscope at a low temperature. That is, the silver halide grains taken out from the emulsion so as not to apply enough pressure to generate dislocation lines on the grains are placed on a mesh for observation with an electron microscope, and the sample is prepared so as to prevent damage (printout, etc.) by the electron beam. Observation is performed by a transmission method in a state of cooling. At this time, the thicker the particle, the more difficult it is for the electron beam to penetrate. Therefore, a clearer image can be observed by using a high-pressure electron microscope (200 kV or more for a particle having a thickness of 0.25 μm). . From the photograph of the particles obtained by such a method, the position and the number of dislocation lines for each particle when viewed from the direction perpendicular to the main plane can be obtained.

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

Dislocation lines can be introduced, for example, near the outer periphery of tabular grains. In this case, the dislocation is almost perpendicular to the outer periphery, and a dislocation line is generated from the position of x% of the length from the center of the tabular grain to the side (outer periphery) to the outer periphery. The value of x is preferably 10 or more and less than 100, more preferably 30 or more and less than 99, and most preferably 50 or more and less than 98. At this time, the shape formed by connecting the start positions of the dislocation lines is similar to the particle shape, but may not be a perfect similar shape and may be distorted. This type of dislocation number is not found in the central region of the grain.
The direction of the dislocation lines is approximately (211) crystallographically, but often meanders, and may intersect each other.

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

Further, dislocation lines may be formed over a region including the center of two parallel main planes of the tabular grains. When dislocation lines are formed over the entire area of the main plane, the direction of the dislocation lines may be approximately (211) crystallographically when viewed from a direction perpendicular to the main plane, but may be in the (110) direction or In some cases, the dislocation lines are formed randomly, and the length of each dislocation line is also random. In some cases, the dislocation lines are observed as short lines on the main plane, and in other cases, they are observed as long lines reaching the side (outer circumference). is there. Dislocation lines are sometimes straight or meandering. They also often intersect with each other.

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

The introduction of dislocation lines into tabular grains can be achieved by providing a specific high silver iodide phase inside the grains.
In this case, a high silver iodide phase may be provided with a high silver iodide region discontinuously. Specifically, the high silver iodide phase inside the grains is obtained by preparing a base grain, providing a high silver iodide phase, and covering the outside with a phase having a lower silver iodide content than the high silver iodide phase. Can be The silver iodide content of the tabular grains of the base is lower than that of the high silver iodide phase, preferably 0 to 20 mol%, more preferably 0 to 15 mol%.

The high silver iodide phase inside the grains means a silver halide solid solution containing silver iodide. As silver halide in this case, silver iodide, silver iodobromide and silver chloroiodobromide are preferable, but silver iodide or silver iodobromide (iodide relative to silver halide contained in the high silver iodide phase) is preferable. The silver halide content is more preferably 10 to 40 mol%). The high silver iodide phase inside the grain (hereinafter, referred to as the internal silver iodide high phase) is defined on the side, corner,
It is desirable to control the conditions for forming the base grains, the conditions for forming the internal silver iodide-rich phase, and the conditions for forming the phase covering the outside thereof, in order to selectively exist at any place on the surface. The conditions for forming the base particles are pA
The important factors are g (the logarithm of the reciprocal of silver ion concentration) and the presence, type, amount and temperature of the silver halide solvent. By controlling the pAg during the growth of the base grains to 8.5 or less, more preferably 8 or less, the internal high silver iodide phase is formed in the vicinity of the apex of the base grains or at the surface when the internal high silver iodide phase is formed later. It can be selectively present above. On the other hand, by performing the pAg at the time of growing the base grains at 8.5 or more, more preferably at 9 or more,
An internal silver iodide-rich phase can be present on the side of the base grain. These pAg thresholds change up and down depending on the temperature and the presence / absence, type and amount of the silver halide solvent. When, for example, thiocyanate is used as the silver halide solvent, the threshold value of the pAg shifts toward a higher value. Particularly important as the pAg during growth is the pAg at the end of the growth of the base particle. On the other hand, even when the pAg at the time of growth does not satisfy the above value, the pAg is adjusted to the pAg after the growth of the base particles, and the maturation is performed.
It is also possible to control the selection position of the internal silver iodide-rich phase. At this time, ammonia, amine compounds, thiourea derivatives, and thiocyanate salts are effective as silver halide solvents. The formation of the internal silver iodide-rich phase can use a so-called conversion method. In this method, during the grain formation, there is a method of adding a halogen ion having a lower solubility of a salt for forming a silver ion than a halogen ion forming a grain or a vicinity of the surface of the grain at that time. In the present invention, it is preferable that the amount of the added halogen ions having low solubility is not less than a certain value (related to the halogen composition) with respect to the surface area of the particles at that time. For example, it is preferable to add a certain amount or more of KI to the surface area of the silver halide grains at that time during grain formation. Specifically, it is preferable to add 8.2 × 10 ⁻⁵ mol / m ² or more of iodide salt.

A more preferred method for forming an internal silver iodide-rich phase is to add an aqueous silver salt solution simultaneously with the addition of an aqueous halide salt solution containing an iodide salt.

For example, AgNO is added simultaneously with the addition of the KI aqueous solution.
₃ Add the aqueous solution by double jet. At this time, the addition start time and the addition end time of the KI aqueous solution and the AgNO ₃ aqueous solution may be shifted from each other and may be changed. The addition molar ratio of the AgNO ₃ aqueous solution to the KI aqueous solution is preferably 0.1 or more, more preferably 0.5 or more. More preferably, it is 1 or more. The total added molar amount of the AgNO ₃ aqueous solution may be in the silver excess region with respect to the halogen ions and the added iodine ions in the system. It is preferable that the pAg at the time of addition of the halide aqueous solution containing iodide ions and the addition of the silver salt aqueous solution by the double jet decrease with the addition time by the double jet. The pAg before the start of addition is
It is preferably 6.5 or more and 13 or less. More preferably 7.0
It is preferably 11 or more and 11 or less. The pAg at the end of the addition is 6.5
More preferably, it is at most 10.0.

In carrying out the above method, it is preferable that the solubility of the mixed silver halide is as low as possible. Therefore, the temperature of the mixed system for forming a high silver iodide phase is preferably 30 ° C. or more and 80 ° C. or less, more preferably 30 ° C. or more and 7 ° C. or less.
0 ° C. or less.

More preferably, the formation of the internal high silver iodide phase can be carried out by adding fine grain silver iodide, fine grain silver iodobromide, fine grain silver chloroiodide, or fine grain silver chloroiodobromide. In particular, it is preferable to add fine grain silver iodide.
These fine particles usually have a particle size of 0.01 μm or more and 0.1 μm or less, but 0.01 μm or less or 0.1 μm or less.
Fine particles having a particle size of m or more can also be used.
The methods for preparing these fine silver halide grains are described in JP-A-1-183417, JP-A-2-44335,
No. 183644, No. 1-183645, No. 2-435
No. 34 and No. 2-43535 can be referred to. An internal high silver iodide phase can be provided by adding and ripening these fine grain silver halides. When the fine particles are dissolved by ripening, the above-mentioned silver halide solvent can be used. It is not necessary that all of the added fine particles dissolve and disappear immediately, and it is sufficient that the fine particles dissolve and disappear when the final particles are completed.

Further, as another method for introducing dislocation lines into tabular grains, there is a method using an iodide ion releasing agent as described in JP-A-6-11782, which is preferably used.

It is also possible to introduce dislocation lines by appropriately combining the method of introducing dislocation lines with the above-described method of introducing dislocation lines.

The position of the internal silver iodide-rich phase is measured from the center of the hexagon or the like on which the grains are projected, and is preferably in the range of 5 mol% or more and less than 100 mol% based on the silver amount of the whole grains. Preferably 20 mol% or more and less than 95 mol%,
In particular, the content is preferably in the range of 50 mol% or more and less than 90 mol%. The amount of silver halide forming these internal high silver iodide phases is not more than 50 mol%, more preferably not more than 20 mol% of the silver amount of the whole grains in terms of silver amount. These high silver iodide phases are the prescription values for the production of silver halide emulsions, not the values obtained by measuring the halogen composition of the final grains by various analytical methods. The internal silver iodide-rich phase often disappears in the final grain due to recrystallization or the like in the shelling process, and the above-mentioned silver content is all related to the prescribed value.

Accordingly, in the final grain, dislocation lines can be easily observed by the above-mentioned method. However, in the internal silver iodide phase introduced for introducing dislocation lines, the silver iodide composition at the boundary changes continuously. For this reason, it is often not possible to confirm it as a clear phase. Regarding the halogen composition of each part of the grain, X-ray diffraction, EPMA (also known as XMA) method (a method of detecting silver halide composition by scanning silver halide grains with an electron beam), and ESCA (also known as XPS) ) Method (a method of irradiating X-rays and dispersing photoelectrons coming out of the particle surface) and the like.

The outer phase covering the internal high silver iodide phase is lower than the silver iodide content of the high silver iodide phase, and preferably the silver iodide content is contained in the outer phase to be covered. 0 to 30 mol%, more preferably 0 to 30 mol% based on the amount of silver halide
It is 20 mol%, most preferably 0 to 10 mol%.

The temperature and pAg at the time of forming the outer phase covering the inner silver iodide-rich phase are arbitrary, but the preferred temperature is 3
0 ° C. or higher and 80 ° C. or lower. Most preferably, it is 35 ° C or more and 70 ° C or less. Preferred pAg is 6.5 or more and 1
1.5 or less. In some cases, it is preferable to use the above-mentioned silver halide solvent, and the most preferable silver halide solvent is a thiocyanate salt.

The coefficient of variation of the intergranular iodine distribution of the silver halide grains used in the present invention is preferably 25% or less. It is more preferably at most 15%, particularly preferably at most 10%. If the coefficient of variation of the iodine content distribution of each silver halide is greater than 25%, the contrast is not so high, and the decrease in sensitivity when pressure is applied is undesirably large.

The method of producing silver halide grains having a narrow intergranular iodine distribution used in the present invention can be carried out by any known method, for example, a method of adding fine particles as disclosed in JP-A-1-183417 and the like. A method using an iodide ion releasing agent as described in JP-A-2-68538 can be used alone or in combination.

The silver halide grains of the present invention preferably have a coefficient of variation of iodine distribution between grains of 25% or less. The most preferred method for monodispersing the iodine distribution between grains is described in JP-A-3-213845. The method described can be used. That is, fine silver halide grains containing 95 mol% or more of silver iodide are mixed with an aqueous solution of a water-soluble silver salt and a water-soluble halide (95 mol% or more of iodine) in a mixer provided outside the reaction vessel. (I.e., containing an ion) is formed by mixing, and is supplied into the reaction vessel immediately after the formation, whereby a monodispersed interparticle iodine distribution can be achieved. Here, the reaction vessel refers to a vessel that causes nucleation and / or crystal growth of tabular silver halide grains.

As described in Japanese Patent Application Laid-Open No. 3-213845, the following three techniques can be used for the method of addition prepared and added in a mixer.

After the fine particles are formed in the mixer, they are immediately added to the reaction vessel. Strong and efficient stirring is performed in the mixer. Injection of the aqueous protective colloid solution into the mixer.

The protective colloid used above may be injected into the mixer alone, or may be mixed with an aqueous solution of a halogen salt or an aqueous solution of silver nitrate containing the protective colloid. The concentration of the protective colloid is 1% by weight or more, preferably 2 to 5% by weight. Examples of the polymer compound having a protective colloid action on silver halide grains used in the present invention include polyacrylamide polymer, amino polymer, polymer having thioether group, polyvinyl alcohol, acrylic acid polymer, polymer having hydroxyquinoline, and cellulose. , Starch, acetal, polyvinylpyrrolidone, terpolymer and the like, but it is preferable to use low molecular weight gelatin. The molecular weight of the low molecular weight gelatin is preferably 30,000 or less, more preferably 10
000.

The grain forming temperature at the time of preparing fine silver halide grains is preferably 35 ° C. or lower, particularly preferably 25 ° C. or lower. The temperature of the reaction vessel to which the fine silver halide grains are added is 50 ° C. or higher, preferably 60 ° C. or higher,
More preferably, it is 70 ° C. or higher.

The grain size of the fine silver halide grains used in the present invention can be confirmed by placing the grains on a mesh and using a transmission electron microscope as it is. The size of the fine particles of the present invention is 0.3 μm or less, preferably 0.1 μm or less, particularly preferably 0.01 μm or less. The fine silver halide may be added at the same time as the addition of other halide ions and silver ions, or only the fine silver halide may be added. Fine silver halide grains are mixed in an amount of 0.005 to 20 mol%, preferably 0.01 to 10 mol%, based on the total silver halide.

The silver iodide content of each grain can be measured by analyzing the composition of each grain using an X-ray microanalyzer. The coefficient of variation of the intergranular iodine distribution is defined as the standard deviation of the silver iodide content and the average iodine content when the silver iodide content of at least 100, more preferably 200 and particularly preferably 300 or more emulsion grains is measured. It is a value defined by a relational expression (standard deviation / average silver iodide content) × 100 = coefficient of variation using silver halide content. The measurement of the silver iodide content of the individual grains is described, for example, in EP 147,868. There may or may not be a correlation between the silver iodide content Yi (mol%) of each grain and the sphere equivalent diameter Xi (microns) of each grain, but it is desirable that there is no correlation. Regarding the structure relating to the silver halide composition of the grains of the present invention,
For example, X-ray diffraction, EPMA (also referred to as XMA) method (a method of scanning silver halide grains with an electron beam to detect silver halide composition), and ESCA (also referred to as XPS) method (X-ray (A method of irradiating photoelectrons emitted from the particle surface by irradiating the particles). In measuring the silver iodide content in the present invention, the grain surface means a region having a depth of about 50 ° from the surface, and the inside of the grain means a region other than the above surface. Such a halogen composition on the surface of a grain usually has a
It can be measured by the CA method.

In one embodiment of the silver halide emulsion of the present invention, spectral sensitization is carried out by adding a spectral sensitizing dye in a state where calcium, magnesium and strontium are not more than 50 ppm, and thereafter calcium, magnesium and strontium are added. Is a water-soluble salt of at least one metal selected from calcium, magnesium and strontium so as to be 100 to 2500 ppm, and thereafter chemical sensitization is started.

In the present invention, calcium, magnesium and strontium in the emulsion after the desalting step and before the spectral sensitization and the chemical sensitization are applied are substantially absent.
Substantially absent means that the lower the content of calcium, magnesium and strontium, the better. Specifically, the content of calcium, magnesium and strontium is 50 ppm or less,
More preferably 35 ppm or less, further preferably 20 ppm
ppm or less. Here, that the content of calcium, magnesium, and strontium is 50 ppm or less means that the content of calcium, magnesium, and strontium is within a specified range.
The contents of calcium, magnesium and strontium are calcium ions, magnesium ions, strontium ions, calcium salts, magnesium salts, strontium salts, etc., for all compounds containing calcium, magnesium and strontium, calcium atoms, magnesium atoms, and strontium. It is represented by the weight in terms of atoms, and is represented by the concentration per unit weight of the emulsion.

The method for quantifying calcium, magnesium and strontium can be determined, for example, by ICP emission spectroscopy.

Next, calcium added after the spectral sensitization,
The addition of the water-soluble salt of at least one metal selected from magnesium and strontium will be described.

First, the timing of the addition of the water-soluble metal salt will be described. After the spectral sensitizing dye is added to the emulsion, it is adsorbed on the surface of the emulsion grains and eventually reaches an equilibrium state. In the present invention, a water-soluble salt of at least one metal selected from calcium, magnesium and strontium can be added after the spectral sensitizing dye is sufficiently adsorbed on the particle surface. It is preferably added when at least 80% or more of the dye is adsorbed on the particle surface of the spectral sensitizing dye in the equilibrium state, and more preferably 90% or more.

The adsorption amount of the spectral sensitizing dye was determined by separating the solid layer and the liquid layer by centrifugation and measuring the difference between the amount of the spectral sensitizing dye added first and the amount of the spectral sensitizing dye in the supernatant. The amount of the adsorbed spectral sensitizing dye can be determined.

In the present invention, the amount of the water-soluble salt of at least one metal selected from calcium, magnesium and strontium added after the spectral sensitizing dye is sufficiently adsorbed and before the start of chemical sensitization is: The content of calcium, magnesium and strontium in the emulsion after the addition is 100 to 2500 ppm, preferably 20 to 2500 ppm.
0 to 2500 ppm. Of the metals added, calcium is most preferred, followed by strontium and magnesium.

The water-soluble salt of calcium in the present invention is preferably, for example, calcium nitrate or calcium chloride, and the water-soluble salt of magnesium is preferably magnesium nitrate, magnesium chloride or magnesium chloride.
Magnesium nitrate is most preferred, and strontium nitrate is preferred as the water solubility of strontium.

In the present invention, the start of chemical sensitization refers to the time when at least one of the chemical sensitizers is added to the emulsion.

Next, the high molecular weight gelatin used in the present invention will be described.

The high-molecular-weight gelatin used in the present invention refers to an alkali-treated bone gelatin containing 30% or more of a component having a molecular weight of 280,000 or more in a molecular weight distribution measured by the PAGI method. Gelatin used in the present invention contains three components having a molecular weight distribution of 280,000 or more.
It is an alkali-treated bone gelatin containing 0% or more, preferably 35% or more. Gelatin is a collagen tissue whose structure is decomposed with alkali or acid to impart water solubility. In the case of alkali-treated gelatin, sub-α (low molecular weight), α (molecular weight of about 10
10,000), β (molecular weight of about 200,000), γ (molecular weight of about 300,000) and a large polymer portion (void; molecular weight of more than about 300,000). The ratio of the components, ie the molecular weight distribution, is determined by the internationally defined PAGI method. PA
The GI method is a method of estimating a molecular weight distribution by obtaining a chromatogram of a gelatin aqueous solution by a gel filtration method using high performance liquid chromatography. In the gelatin of the present invention, the sum of the γ and the void component is 30% or more,
It is preferably at least 35%, more preferably at least 37%.

The method for producing such gelatin is roughly classified into the following two methods. 1. A method that does not crosslink gelatin.

[0093] The alkali-treated gelatin is produced by removing calcium from the raw material bone, immersing in lime treatment to loosen the collagen structure, and then extracting with warm water and drying. In general, extraction is performed by setting the extraction temperature in 1 to 7 stages, and the extraction temperature increases with the number of extractions. At that time, the molecular weight distribution of the resulting gelatin can be controlled by adjusting the extraction temperature and time. The gelatin of the present invention can be prepared by examining the extraction conditions.

2. A method using a gelatin crosslinking agent. The gelatin used in the present invention is obtained by crosslinking gelatin. As the crosslinking method, there are two methods: a method of crosslinking between gelatin molecules by an enzyme, and a method of adding a crosslinking agent to form a chemical bond between gelatin molecules and crosslinking the gelatin molecules.

As a typical method of the enzyme method used in the present invention, gelatin crosslinked with transglutaminase will be described. The transglutaminase enzyme can crosslink gelatin by a function of catalyzing an acyl transfer reaction between a γ-carboxamide group of a glutamine residue and various primary amines of gelatin, which is a protein. Transglutaminase is derived from animals, plants, and microorganisms.For example, animal-derived ones include mammalian organs such as guinea pig liver, those extracted from blood, and plant-derived ones derived from pea. Extracted and derived from microorganisms are extracted from actinomycetes. In the present invention, any source having transglutaminase activity can be preferably used.

The transglutaminase that can be used in the present invention can be obtained, for example, by the method of Clark et al. (Archives of Biochemis).
try and Biophysics, 79, 338 (1959)), the method of Connel et al. (J. Biological Chemistry, 246, (1971)), the method described in JP-A-4-207149, and the method described in JP-A-6-3077.
Those synthesized by any of the methods described in No. 0 can be preferably used. Examples of these transglutaminases include Acteva (trade name, manufactured by Ajinomoto Co., Inc.).
The transglutaminase activity that can be used in the present invention can be measured by reacting benzyloxycarbonyl L-glutaminylglycine with hydroxyamine and determining the amount of hydroxamic acid produced. By this measurement, 1
The transglutaminase activity producing 1 × 10 ⁻⁶ mol of hydrixamic acid per minute is defined as 1 unit.
The transglutaminase of the present invention varies depending on the gelatin used, but 1 × 10 ^{−6 /} g of gelatin.
It is preferable to add an amount that produces at least 1 mol of hydroxamic acid, and it is particularly preferable to produce at least 1 × 10 ⁻⁵ mol of hydroxamic acid.

As the cross-linking agent used in the cross-linked gelatin used in the present invention, any cross-linking agent which has hitherto been known as a hardening agent for gelatin can be used. The typical compounds are shown below.

A. Inorganic crosslinking agent (inorganic hardener) Cationic chromium complex; ligands of the complex include hydroxyl group, oxalic acid group, citric acid group, malonic acid group, lactate, tartrate, succinate, acetate, Formate, sulfate,
Chloride, nitrate.

Aluminum salts; especially sulfates, potassium alum, ammonium alum.

The above compounds crosslink the carboxyl groups of gelatin.

B. Organic crosslinking agent (organic hardener) Aldehyde-based crosslinkers; the most commonly used is formaldehyde. Effective cross-linking can also be achieved with dialdehyde, for example, glyoxal and succinaldehyde, particularly glutaraldehyde. Diglycolaldehyde, various aromatic dialdehydes, dialdehyde starch, and dialdehyde derivatives of vegetable gums are also used in the crosslinking of the present invention.

2. N-methylol compounds and other protected aldehyde crosslinkers; N-methylol compounds obtained by condensation of formaldehyde with various aliphatic linear or cyclic amides, ureas and nitrogen-containing heterocycles. Specific examples include 2,3-dihydroxidioxane, acetate esters of dialdehydes and hemiacetals thereof, and 2,5-dimethoxytetrahydrofuran.

3. Ketone crosslinking agents; compounds of diketones and quinones. Well-known diketones include 2,3-butanedione, CH ₃ COCOCH _{3 and the} like. As quinone, p-benzoquinone is well known.

4. Sulfonate and sulfonyl halide; bis (sulfonyl chloride) as a typical compound
And bis (sulfonyl fluoride) s.

5. Active halogen compound; a compound having two or more active halogen atoms. Representative compounds include simple bis-α-chloro or bis-α-bromo derivatives of ketones, esters, and amides, bis (2-chloroethylurea), bis (2-chloroethyl) sulfone, and phosphoramidic halides. .

6. Epoxide; butadioxide is a typical compound.

7. Activated olefins; Many compounds having two or more double bonds, especially unsubstituted vinyl groups activated by adjacent electron-withdrawing groups, are effective as gelatin crosslinkers. Examples of this compound include divinyl ketone, resorcinol bis (vinyl sulfonate),
4,6-bis (vinylsulfonate), 4,6-bis (vinylsulfonyl) -m-xylene, bis (vinylsulfonylalkyl) ether or amine, 1,3,5-triacryloylhexahydro-s-triazine, Diacrylamide, 1,3-bis (acryloyl) urea and the like.

8. Others JP-A-62-215272, page 475, line 8 to 50
The hardener described on page 8, line 3 (general formula (HI)
To (H-VIII)) can also be used.

In the production of the crosslinked gelatin used in the present invention, the crosslinking agents mentioned above are added to a gelatin solution to cause gelatin intermolecular crosslinking.
The conditions at that time differ depending on each crosslinking agent,
The reaction conditions can be determined by setting a constant reaction temperature and reaction time and measuring the molecular weight distribution of gelatin by the PAGI method. At that time, the progress of crosslinking can be monitored by measuring the viscosity of the gelatin solution. It is desirable that all of the added cross-linking agent be reacted, but if it remains unreacted, after the cross-linking reaction, the gelatin solution can be subjected to ultrafiltration to remove the remaining cross-linking agent. The molecular weight distribution of the present invention is measured according to the measurement method of the PAGI method,
The conditions for the crosslinking reaction can be set. That is, the temperature and time of the crosslinking reaction, the pH of the solution, and the like.

The gelatin used in the present invention may be added at any point during grain formation, but is preferably added at least after nucleation. The addition amount is at least 10%, preferably 3%, based on the total dispersion medium during the formation of the particles.
0%, more preferably 50% or more. Further, the gelatin used in the present invention has an effect even if it is added as a dispersed gelatin added after washing the emulsion with water. The addition amount is at least 10%, preferably at least 30%, more preferably at least 50% of the dispersed gelatin added after washing with water.
Further, the gelatin of the present invention is effective even if added before coating. The addition amount is 10% or more of the dispersion medium added before coating,
It is preferably at least 30%, more preferably at least 50%.

The emulsion of the present invention is preferably chemically sensitized with a selenium sensitizer. The selenium sensitization used in the present invention will be described below.

As the selenium sensitizer used in the present invention, selenium compounds disclosed in conventionally known patent application specifications and the like can be used. Usually, the unstable selenium compound and / or the non-unstable selenium compound is used by adding the selenium compound and stirring the emulsion at a high temperature, preferably at 40 ° C. or higher for a certain period of time. Examples of unstable selenium compounds include JP-B-44-15748 and JP-B-43-157.
No. 13489, JP-A-4-25832, JP-A-4-1
It is preferable to use the compounds described in JP 09240A and the like.

Specific examples of unstable selenium sensitizers include, for example, isoselenocyanates (for example, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenoamides, and selenocarboxylic acids ( For example, 2-selenopropionic acid, 2-
Selenobutyric acid), selenoesters, diacylselenides (eg, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, and colloidal metal selenium.

While the preferred types of unstable selenium compounds have been described above, they are not intended to be limiting. Speaking of an unstable selenium compound as a sensitizer of a photographic emulsion, the structure of the compound is not very important as long as selenium is unstable, and the organic portion of the selenium sensitizer molecule carries selenium, It is generally understood by those skilled in the art that it has no role other than to be present in the emulsion in an unstable form. In the present invention, an unstable selenium compound having such a broad concept is advantageously used.

Examples of the non-labile selenium compound used in the present invention include JP-B-46-4553 and JP-B-52-3.
No. 4,492, and JP-B-52-34491. As a non-labile selenium compound,
For example, selenous acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenide, diaryl diselenide, dialkyl selenide, dialkyl diselenide, 2-selenazolidinedione, 2-selenooxazolidinthione and these Derivatives.

Of these selenium compounds, the following general formulas (A) and (B) are preferred.

General formula (A)

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In the formula, Z ₁ and Z ₂ may be the same or different and each represents an alkyl group (eg, methyl, ethyl, t-butyl, adamantyl, t-octyl), an alkenyl group (eg, vinyl, propenyl) Aralkyl group (eg, benzyl, phenethyl), aryl group (eg, phenyl, pentafluorophenyl, 4-chlorophenyl, 3-nitrophenyl, 4-octylsulfamoylphenyl, α-naphthyl), heterocyclic group (eg, 2-pyridyl, 3-thienyl, 2-furyl, 2-imidazolyl), -NR ₁ (R ₂ ), -OR ₃ or -SR ₄
Represents

R ₁ , R ₂ , R ₃ and R ₄ may be the same or different and each represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, a heterocyclic group or an acyl group. Alkyl group, an aralkyl group, the aryl group or heterocyclic group, the same examples as Z ₁ and the like. However, R ₁ and R ₂ are a hydrogen atom or an acyl group (for example,
Acetyl, propanoyl, benzoyl, heptafluorobutanoyl, difluoroacetyl, 4-nitrobenzoyl, α-naphthoyl, 4-trifluoromethylbenzoyl).

[0120] In formula (A), preferably, Z ₁ represents an alkyl group, an aryl group, or -NR ₁ a (R _2), Z ₂
Represents -NR ₅ (R _6). R ₁ , R ₂ , R ₅ and R ₆ may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group, or an acyl group.

The general formula (A) is more preferably N, N
-Dialkylselenourea, N, N, N'-trialkyl-N'-acylselenourea, tetraalkylselenourea, N, N-dialkyl-arylselenoamide, N-
Represents an alkyl-N-aryl-arylselenoamide.

General formula (B)

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In the formula, Z ₃ , Z ₄ and Z ₅ may be the same or different and each represents an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heterocyclic group,
—OR ₇ , —NR ₈ (R ₉ ), —SR ₁₀ , —SeR ₁₁ ,
X represents a hydrogen atom.

R ₇ , R ₁₀ and R ₁₁ are an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group,
R ₈ and R ₉ represent an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heterocyclic group or a hydrogen atom, and X represents a halogen atom.

In the general formula (B), Z ₃ , Z ₄ , Z ₅ ,
The alkyl group, alkenyl group, alkynyl group and aralkyl group represented by R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ are a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group, aralkyl group ( For example, methyl, ethyl, n
-Propyl, isopropyl, t-butyl, n-butyl,
n-octyl, n-decyl, n-hexadecyl, cyclopentyl, cyclohexyl, allyl, 2-butenyl, 3
-Pentenyl, propargyl, 3-pentynyl, benzyl, phenethyl).

In the general formula (B), Z ₃ , Z ₄ , Z ₅ ,
The aryl group represented by R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a monocyclic or condensed aryl group (for example, phenyl,
Pentafluorophenyl, 4-chlorophenyl, 3-sulfophenyl, α-naphthyl, 4-methylphenyl).

In the general formula (B), Z ₃ , Z ₄ , Z ₅ ,
The heterocyclic group represented by R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a saturated or unsaturated 3- to 10-membered ring containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. Heterocyclic groups (eg, 2-pyridyl, 3-thienyl, 2-
Furyl, 2-thiazolyl, 2-imidazolyl, 2-benzimidazolyl) and may be condensed.

In formula (B), the cation represented by R ₇ , R ₁₀ and R ₁₁ represents an alkali metal atom or ammonium. The halogen atom represented by X is
For example, it represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

In the general formula (B), preferably,
Z ₃ , Z ₄ or Z ₅ represents an alkyl group, an aryl group, or —OR ₇ , and R ₇ represents an alkyl group or an aryl group.

The formula (B) more preferably represents a trialkylphosphine selenide, a triarylphosphine selenide, a trialkylselenophosphate or a triarylselenophosphate.

Specific examples of the compounds represented by formulas (A) and (B) are shown below, but the present invention is not limited to these.

[0132]

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[0133]

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[0134]

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[0135]

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[0136]

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[0137]

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[0138]

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These selenium sensitizers are dissolved in water or an organic solvent such as methanol or ethanol alone or in a mixed solvent, and added during chemical sensitization. Preferably, it is added before the start of chemical sensitization. The selenium sensitizer used is 1
The selenium sensitizer is not limited to the species, and two or more of the above selenium sensitizers can be used in combination. A combination of an unstable selenium compound and a non-unstable selenium compound is preferred.

Addition amount of selenium sensitizer used in the present invention
Indicates the activity of the selenium sensitizer used and the type of silver halide
And size, aging temperature and time, etc.,
Preferably, 1 × 10 5 per mol of silver halide^-8Less than mole
Above. More preferably 1 × 10^-7More than a mole,
Particularly preferably 2.5 × 10^-6More than mol and 5 × 10 ^-Five
Mol or less. Chemical sensitization with selenium sensitizer
Is preferably 40 ° C. or higher, and 80 ° C. or lower.
Below. pAg and pH are arbitrary. For example, pH
About the effect of the present invention in a wide range from 4 to 9
can get.

The selenium sensitization is more effectively achieved by performing the sensitization in the presence of a silver halide solvent.

Examples of the silver halide solvent usable in the present invention include, for example, US Pat. Nos. 3,271,157 and 3,5
No. 31,289, No. 3,574,628, JP-A-54-1019
(A) organic thioethers described in JP-A-53-158917, for example, JP-A-53-82408, JP-A-5-158917;
(B) Thiourea derivatives described in JP-A-5-77737 and JP-A-55-2982, and (c) Thiocarbonyl sandwiched between an oxygen or sulfur atom and a nitrogen atom described in JP-A-53-144319. A silver halide solvent having a group,
Examples thereof include (d) imidazoles, (e) sulfites, and (f) thiocyanate described in JP-A-54-100717.

Particularly preferred silver halide solvents include:
There are thiocyanate and tetramethylthiourea. The amount of the solvent to be used varies depending on the kind. For example, in this case, the preferable amount is 1 × per mol of silver halide.
It is not less than 10 ^-4 mol and not more than 1 × 10 ^-2 mol.

As the gold sensitizer for gold sensitization, the oxidation number of gold may be +1 or +3, and a gold compound usually used as a gold sensitizer can be used. Representative examples include, for example, chloroaurate, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodooleate, tetracyano auric acid, ammonium aurothiocyanate, pyridyl trichlorogold, gold sulfide, gold selenide No. Although the amount of the gold sensitizer to be added varies depending on various conditions, the standard is 1 × per mole of silver halide.
It is preferably 10 ^-7 mol or more and 5 × 10 ^-5 mol or less.

The emulsion of the present invention is desirably used in combination with sulfur sensitization in chemical sensitization.

Sulfur sensitization is usually carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature, preferably at 40 ° C. or higher, for a certain period of time.

For the above-mentioned sulfur sensitization, known sulfur sensitizers can be used. Examples include thiosulfate, allyl thiocarbamide thiourea, allyl isothiocyanate, cystine, p-toluene thiosulfonate, rhodanine and the like. Others, for example, U.S. Pat.
No. 4,944, No. 2,410,689, No. 2,278,947, No. 2,7
No. 28,668, No. 3,501,313, No. 3,656,955, German Patent 1,422,869, JP-B-56-24937
And a sulfur sensitizer described in JP-A-55-45016. The addition amount of the sulfur sensitizer may be an amount sufficient to effectively increase the sensitivity of the emulsion. This amount varies over a considerable range under various conditions such as pH, temperature, silver halide grain size, etc., but is not less than 1 × 10 ⁻⁷ mol per mol of silver halide and not less than 5 × 10 ⁻⁷ mol.
It is preferably at most 10 ^-5 mol.

During the grain formation of the silver halide emulsion of the present invention,
Reduction sensitization can also be performed after grain formation and before or during chemical sensitization, or after chemical sensitization.

As the reduction sensitization, a method of adding a reduction sensitizer to a silver halide emulsion, a pAg 1
7, a method of growing or ripening in a low pAg atmosphere;
Either a method of growing or ripening in a high pH atmosphere of pH 8 to 11 called high pH ripening can be selected. Also, two or more methods can be used in combination.

The method of adding a reduction sensitizer is a preferable method because the level of reduction sensitization can be finely adjusted.

Examples of the reduction sensitizer include stannous salts, ascorbic acid and its derivatives, amines and polyamines, hydrazine derivatives, formamidine sulfinic acid,
Silane compounds, borane compounds and the like are known. For the reduction sensitization of the present invention, these known reduction sensitizers can be selected and used, and two or more compounds can be used in combination. Stannous chloride, thiourea dioxide as reduction sensitizer,
Dimethylamine borane, ascorbic acid and its derivatives are preferred compounds. Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount, but an appropriate range is from 10 ^-7 to 10 ^-3 mol per mol of silver halide.

The reduction sensitizer is dissolved in water or an organic solvent such as alcohols, glycols, ketones, esters, and amides and added during grain growth. Although it may be added to the reaction vessel in advance, it is preferable to add it at an appropriate time during grain growth. Further, a reduction sensitizer may be added in advance to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide, and silver halide grains may be precipitated using these aqueous solutions. It is also a preferred method to add the solution of the reduction sensitizer in several portions as the grains grow, or to add the solution continuously for a long time.

It is preferable to use an oxidizing agent for silver during the production process of the emulsion of the present invention. The oxidizing agent for silver is
A compound which acts on metallic silver to convert it into silver ions. In particular, a compound that converts extremely fine silver grains by-produced during the formation process of silver halide grains and the chemical sensitization process into silver ions is effective.
The silver ions generated here may form a silver salt that is hardly soluble in water, such as silver halide, silver sulfide, and silver selenide.
Further, a silver salt easily soluble in water such as silver nitrate may be formed.
The oxidizing agent for silver may be inorganic or organic. As the inorganic oxidizing agent, ozone, hydrogen peroxide and additives thereof (for example, NaBO ₂ .H ₂ O ₂ .3H _{2
O, 2NaCO 3 · 3H 2 O} 2, Na 4 P 2 O 7 · 2H 2 O 2,
_{2Na 2 SO 4 · H 2 O} 2 · 2H 2 O), peroxy acid salts (e.g., _{K 2 S 2 O 8, K} 2 C 2 O 6, K 2 P 2 O 8), peroxy complex compounds (e.g., K ₂ [Ti (O ₂ ) C ₂ O ₄ ] ·
_{3H 2 O, 4K 2 SO 4} · Ti (O 2) OH · SO 4 · 2H 2
O, Na ₃ [VO (O ₂ ) (C ₂ H ₄ ) ₂ .6H ₂ O), permanganate (eg, KMnO ₄ ), chromate (eg, K ₂ Cr ₂ O ₇ ) Oxygenates, halogens such as iodine and bromine, perhalates (eg, potassium periodate), salts of high valent metals (eg, potassium hexacyanoferric acid), and thiosulfonates. is there.

Examples of the organic oxidizing agent include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds which release active halogen (for example, N-
Bromsuccinimide, chloramine T, chloramine B) are mentioned by way of example.

In the present invention, preferred oxidizing agents are ozone, hydrogen peroxide and its adducts, halogen elements, inorganic oxidizing agents such as thiosulfonates, and organic oxidizing agents such as quinones.

It is a preferred embodiment to use the above-described reduction sensitization and an oxidizing agent for silver in combination. A method of using an oxidizing agent followed by reduction sensitization, a reverse method thereof, or a method of coexisting both can be used. These methods can be applied to both the grain formation step and the chemical sensitization step.

The photographic emulsion of the present invention exerts the effects of the present invention preferably by being spectrally sensitized with methine dyes or the like. The dyes used include cyanine dyes,
Merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes are included. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and compound merocyanine dyes. These dyes may contain any nucleus commonly used in cyanine dyes as a basic heterocyclic nucleus. Such nuclei include, for example, a pyrroline nucleus, an oxazoline nucleus, a thiazoline 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, an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, Examples include a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, and a quinoline nucleus. 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, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidin-2,4-dione nucleus, and a thiazolidine-2,4-nucleus.
It can have a 5-6 membered heterocyclic nucleus such as a dione nucleus, a rhodanine nucleus, a thiobarbituric acid nucleus.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. Representative examples are U.S. Pat.Nos. 2,688,545, 2,977,229 and 3,39.
7,060, 3,522,052, 3,527,641, 3,617,293
No. 3,628,964, 3,666,480, 3,672,898,
3,679,428, 3,703,377, 3,769,301, 3,8
No. 14,609, 3,837,862, 4,026,707, UK Patent No.
No. 1,344,281, No. 1,507,803, JP-B-43-4936
No. 53-12375, JP-A-52-110618
And No. 52-109925.

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

The sensitizing dye may be added to the emulsion at any stage in the preparation of the emulsion which has hitherto been known to be useful. Most commonly, it is performed after completion of chemical sensitization and before coating, but US Pat. No. 3,628,969
As described in JP-A-58-113928, addition of a chemical sensitizer and simultaneous addition of a chemical sensitizer to perform spectral sensitization simultaneously with chemical sensitization as described in JP-A No. 4,225,666 can also be used. Can be added prior to chemical sensitization, or can be added before completion of silver halide grain precipitation to start spectral sensitization. Furthermore, U.S. Pat.No.4,225,66
Separate addition of these sensitizing dyes as taught in No. 6, i.e. some of these sensitizing dyes are added prior to chemical sensitization and the rest are added after chemical sensitization It is also possible at any time during the formation of the silver halide grains, including the method disclosed in U.S. Pat. No. 4,183,756.

The sensitizing dye was used in an amount of 4 per mole of silver halide.
It can be used in an amount of from × 10 ^-6 to 8 × 10 ^-3 mol, but a more preferable silver halide grain size is from 0.2 to 1.2 μm.
Is about 5 × 10 ^-5 to 2 × per mol of silver halide.
10 ^-3 mol is more effective.

The silver halide grains of the present invention preferably have a twin plane spacing of 0.017 μm or less. It is more preferably 0.007 to 0.017 μm, and particularly preferably 0.007 to 0.015 μm.

The twin plane spacing is the distance between two twin planes in a particle having two twin planes in the particle.
In the case of grains having three or more twin planes, it refers to the longest distance among twin plane intervals.

The method for measuring the twin plane spacing is described in JP-A-63-16 / 1988.
3451. That is, the twin plane can be observed with a transmission electron microscope. Specifically, a sample in which tabular grains are arranged substantially parallel to the support is prepared by coating an emulsion of tabular grains on a support, and the sample is cut with a diamond knife to obtain a thickness. Make 0.1 μm sections. By observing this section with a transmission electron microscope, the twin plane of the tabular grains can be detected. When the electron beam passes through the twin plane, a phase shift occurs in the electron wave, so that its existence is recognized.

The silver halide emulsion of the present invention can improve fog during aging by adding a silver iodobromide emulsion prepared in advance at the time of chemical sensitization, dissolving the resulting emulsion, and shelling it to host grains. The timing of addition may be any time during chemical sensitization, but it is preferable to first add and dissolve the silver iodobromide emulsion, and then add the sensitizing dye and the chemical sensitizer in that order. The silver iodobromide emulsion to be used is a silver iodobromide emulsion having an iodine content lower than the surface iodine content of the host grains, and preferably a pure silver bromide emulsion. The size of the silver iodobromide emulsion is not limited as long as it can be completely dissolved, but is preferably 0.1 μm or less, more preferably 0.05 μm or less. The addition amount of the silver iodobromide emulsion varies depending on the host grains to be used, but is preferably from 0.005 to 5 mol%, more preferably from 0.1 to 1 mol%, per mol of silver. is there.

Hexacyanoiron (II) complex used in the present invention
And hexacyanoruthenium complex (hereinafter simply referred to as “metal complex
) Is added per mole of silver halide
10 ^-7Mol or more and 10^-3Preferably less than mole
1.0 × 10 5 per mole of silver halide^-FiveMole
Above and 5 × 10^-FourMore preferably less than a mole
No.

The metal complex used in the present invention may be added and contained at any stage before the preparation of silver halide grains, that is, before and after nucleation, growth, physical ripening, and chemical sensitization. Further, it may be added and contained by dividing it several times. However, it is preferable that 50% or more of the total content of the metal complex contained in the silver halide grains is contained in a layer whose silver content is within １ ／ from the outermost surface of the silver halide grains used. A layer containing no metal complex may be provided further outside the layer containing a metal complex described here.

These metal complexes are dissolved in water or a suitable solvent and added directly to the reaction solution at the time of forming silver halide grains, or in a silver halide aqueous solution for forming silver halide grains. It is preferable to add them in an aqueous solution or another solution to form particles. Further, it is also preferable to add and dissolve silver halide fine particles containing a metal complex in advance and to deposit on a separate silver halide particle to contain these metal complexes.

When these metal complexes are added, the hydrogen ion concentration in the reaction solution is preferably pH 1 or more and 10 or less, more preferably pH 3 or more and 7 or less.

The silver halide color photographic light-sensitive material of the present invention contains a blue-sensitive silver halide emulsion layer containing a yellow coupler, a green-sensitive silver halide emulsion layer containing a magenta coupler, and a cyan coupler on a support. It has at least one red-sensitive silver halide emulsion layer and at least one hydrophilic protective colloid layer, and at least one of the emulsions used in the emulsion layer is the silver halide emulsion of the present invention. The calcium ions, magnesium ions and strontium ions contained in the emulsion of the present invention may diffuse from the emulsion layer to other layers due to water solubility, and may flow out into the processing solution during processing, causing trouble.
For this purpose, the amount of calcium ion, magnesium ion and strontium ion contained in the silver halide color photographic light-sensitive material of the present invention is 8.0 × 10 ^-2 g or less in terms of atomic weight per 1 g of total gelatin contained in the light-sensitive material. Is more preferable, and particularly preferably 4.0 × 10 ⁻² g or less.

Here, the amount of calcium ion, magnesium ion and strontium ion means the amount obtained by adding the amount of calcium ion, magnesium ion and strontium ion.

Next, the Pd compound represented by formula (I-1) will be described in detail.

In the general formula (I-1), X ₁ and X ₂ each independently represent -S (R ₁₁ )-, -N (R ₁₂ ) (R ₁₃ )-or -O (R ₁₄ )-. . R ₁₁ and R ₁₄ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group,
Represents an aralkyl group, an aryl group, or a heterocyclic group. In R ₁₁ and R ₁₄ , the alkyl group, cycloalkyl group, alkenyl group, alkynyl group, and aralkyl group preferably have 1 to 30 carbon atoms, particularly 1 to 10 carbon atoms.
Straight-chain or branched alkyl group, cycloalkyl group,
An alkenyl group, an alkynyl group and an aralkyl group, for example, methyl, ethyl, propyl, butyl, isopropyl, cyclopropyl, allyl, propargyl and benzyl. In R ₁₁ and R ₁₄ , the aryl group preferably has 6 to 30 carbon atoms, and particularly preferably has 6 to 12 carbon atoms.
Is a monocyclic or condensed aryl group, for example, phenyl and naphthyl. In R ₁₁ and R ₁₄ , the heterocyclic group is at least one of a nitrogen atom, an oxygen atom and a sulfur atom.
It is a 3- to 10-membered saturated or unsaturated heterocyclic group including one. These may be monocyclic or may form a condensed ring with another aromatic ring. The heterocyclic ring is preferably a 5- to 6-membered aromatic heterocyclic ring.
Pyridyl, 2-imidazolyl, 2-quinolyl, 2-benzimidazolyl, 4-pyrimidyl, 3-pyrazolyl, 2-isoquinolyl, 2-thiazolyl, 2-thienyl, 3-furyl, 2-benzothiazolyl.

R ₁₂ and R ₁₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, Represents a carbamoyl group, an alkylsulfonyl group, or an arylsulfonyl group. An alkyl group for R ₁₂ and R ₁₃ ,
Cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heterocyclic group have the same meanings as R ₁₁ and R ₁₄ of X _1, X _2. An acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group for R ₁₂ and R ₁₃ ,
The carbamoyl group, alkylsulfonyl group, and arylsulfonyl group preferably have 1 to 20 carbon atoms, such as acetyl, benzoyl, formyl, methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, mesyl, and tosyl.

In the general formula (I-1), R ₁₁ , R ₁₂ , R ₁₃ and R
Each group represented by ₁₄ may be substituted, and examples of the substituent include the following. The carbon number of each group described above includes the carbon number of the following substituents.

Halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, ammonium group (for example, trimethylammonio), phosphonio group, sulfo group (including salt), sulfino group (salt) ), A carboxy group (including a salt), a phosphono group (including a salt), a hydroxy group, a mercapto group, a hydrazino group, an alkyl group (e.g., 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 group ( For example, phenyl, naphthyl, 4-methylphenyl), a heterocyclic group (eg, pyridyl Furyl, imidazolyl,
Piperidyl, morpholino), alkoxy groups (eg, methoxy, ethoxy, butyloxy), aryloxy groups (eg, phenoxy, 2-naphthyloxy), alkylthio groups (eg, methylthio, ethylthio), arylthio groups (eg, phenylthio), amino Groups (eg, unsubstituted amino, methylamino, dimethylamino,
Ethylamino, alinino), acyl group (eg, acetyl, benzoyl, formyl, pivaloyl), alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl), aryloxycarbonyl group (eg,
Phenoxycarbonyl), carbamoyl group (for example, unsubstituted carbamoyl, N, N-dimethylcarbamoyl,
N-ethylcarbamoyl, N-phenylcarbamoyl), acyloxy group (eg, acetoxy, benzoyloxy), acylamino group (eg, acetylamino, benzoylamino), alkoxycarbonylamino group (eg, methoxycarbonylamino), aryloxycarbonylamino Groups (eg, phenoxycarbonylamino), ureido groups (eg, unsubstituted ureido,
N-methylureido, N-phenylureido), alkylsulfonylamino group (eg, methylsulfonylamino), arylsulfonylamino group (eg, phenylsulfonylamino), alkylsulfonyloxy group (eg, methylsulfonyloxy), arylsulfonyloxy Groups (eg, phenylsulfonyloxy), alkylsulfonyl groups (eg, mesyl), arylsulfonyl groups (eg, tosyl), alkoxysulfonyl groups (eg, methoxysulfonyl), aryloxysulfonyl groups (eg, phenoxysulfonyl), sulfamoyl groups (For example, unsubstituted sulfamoyl, N-methylsulfamoyl, N, N-dimethylsulfamoyl,
N-phenylsulfamoyl), alkylsulfinyl group (eg, methylsulfinyl), arylsulfinyl group (eg, phenylsulfinyl), alkoxysulfinyl group (eg, methoxysulfinyl), aryloxysulfinyl group (eg, phenoxysulfinyl), phosphorus Acid amide group (for example, N, N-diethyl phosphoric 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 (I-1), Z ₁ and Z ₂ each independently represent an alkylene group, an arylene group or a divalent heterocyclic residue. Examples of the alkylene group include methylene, ethylene, propylene, cyclopentylene, and cyclohexylene; examples of the arylene group include phenylene and naphthalene; examples of the heterocycle of a divalent heterocyclic residue include pyridine, imidazole, and quinoline. , Pyrimidine,
Thiazole, thiophene, furan, morpholine, piperazine, piperidine and the like. Further, Z ₁ and Z ₂ are R
_11, R _12, those listed as the substituent for R ₁₃ and R ₁₄ may be substituted.

In the general formula (I-1), Y ₁ and Y ₂ each independently represent -S (R ₂₁ )-, -N (R ₂₂ ) (R ₂₃ )-or -O (R ₂₄ )-.
R ₂₁ and R ₂₄ each independently have the same meaning as R ₁₁ and R ₁₄ in X ₁ and X ₂ . R ₂₂ and R ₂₃ each independently have the same meaning as R ₁₂ and R ₁₃ in X ₁ and X ₂ .

In formula (I-1), L ₁ and L ₂ each independently represent a single bond, an alkylene group, —CO— or —SO ₂ —. However, X _1, X ₂ is NR ₁₂ R _13, when Y _1, Y ₂ is _{NR 2 2 R 23, L 1} , L 2 is -CO -, - SO ₂
Represents-. Examples of the alkylene group include methylene, ethylene,
Propylene, cyclopentylene, cyclohexylene and the like are mentioned, and these alkylene groups may be substituted by those mentioned as the substituents of R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ .

In the general formula (I-1), X ₁ and X ₂ , Y ₁ and Y
₂ , L ₁ and L ₂ and Z ₁ and Z ₂ may be the same or different. X ₁ and Z ₁ , X ₁ and L ₁ , Y
₁ and Z ₁ or Y ₁ and L ₁ may be linked to form a saturated or unsaturated heterocyclic ring, X ₂ and Z ₂ , X ₂ and L ₂ , Y ₂ and Z ₂ or Y ₂ and L _{2 Two} may be linked to form a saturated or unsaturated heterocycle. Further, X ₁ and X ₂ or / and Y ₁ and Y ₂ may be linked to form a compound which coordinates with a palladium ion in one molecule.

In the general formula (I-1), Q represents an anionic ion. Halogen ion, nitrate ion, carbonate ion, hydrogen carbonate ion, sulfate ion, sulfite ion, cyano ion, cyanate ion, isocyanate ion, thiocyanate ion, borate ion, phosphonate ion, perchlorate ion, organic carboxylic acid Ions (e.g., formate ion, acetate ion, oxalate ion, etc.), organic sulfonic acid ions (e.g., methane sulfonic acid ion, benzene sulfonic acid ion, p-toluene sulfonic acid ion, 2,
6-naphthalene-disulfonate ion).
Preferred are halogen ions (chloro ions, bromo ions), nitrate ions, sulfate ions, sulfite ions, cyanate ions, and perchlorate ions.

In the general formula (I-1), m represents an integer of 0 to 4.

Here, the compound of the general formula (I-1) is in a complex formation equilibrium between the ligand and Pd (II) in a solution. Therefore, the two ligands of the general formula (I-1) can have either a trans or cis structure in a solution. In the present invention, for convenience, only one isomer is described.

In the general formula (I-1), preferably, X ₁ and X
₂ , Y ₁ and Y ₂ , L ₁ and L ₂ , and Z ₁ and Z ₂ are the same, and X ₁ is -S (R ₁₁ ), -N (R ₁₂ ) (R ₁₃ )- , Z ₁ is substituted or unsubstituted alkylene group, an arylene group, Y ₁ is _{-N (R 22) (R 2} 3) - a is, L ₁ is a single bond, -CO-, R ₁₁ is Hydrogen atom, unsubstituted or hydrophilic group (for example, sulfo, sulfino, carboxy,
Phosphono, hydroxy, carbamoyl groups (for example, unsubstituted carbamoyl, N, N-dimethylcarbamoyl, N
-Ethylcarbamoyl, N-phenylcarbamoyl),
Acylamino group (eg, acetylamino, benzoylamino), alkoxycarbonylamino group (eg, methoxycarbonylamino), ureido group (eg, unsubstituted ureido, N-methylureido, N-phenylureido), alkylsulfonylamino group ( For example, methylsulfonylamino), a sulfamoyl group (for example, unsubstituted sulfamoyl, N-methylsulfamoyl, N,
N- dimethylsulfamoyl, substituted alkyl groups of N- phenylsulfamoyl), etc.), an aryl _{group, R 12, R 13, R} 22, and R ₂₃ is a hydrogen atom, an unsubstituted or a hydrophilic group ( the hydrophilic group is a substituted alkyl group having a hydrophilic group as defined) of R _11, an aryl group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group (preferably be of 1 to 20 carbon atoms, e.g. Acetyl, formyl, methoxycarbonyl, ethoxycarbonyl, mesyl).

In the present invention, the compounds represented by the general formula (I-2) are more preferable than the above preferable compounds.

Next, Z ₁ , Z ₂ , R ₁ and R 2 in the general formula (I-2)
R ₂ , X ₁₁ , X ₁₂ , X ₁₃ and X ₁₄ will be described.

In the formula (I-2), Z ₁ and Z ₂ each independently represent an alkylene group (methylene, ethylene, propylene, cyclopentylene, cyclohexylene, etc.), an arylene group (phenylene, naphthalene, etc.), A divalent heterocyclic group (pyridine, imidazole,
Quinoline, pyrimidine, thiazole, thiophene, furan, morpholine, piperazine, piperidine, etc.).

In the formula (I-2), R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group , An alkylsulfonyl group or an arylsulfonyl group, wherein the alkyl group represented by R ₁ or R ₂ preferably has 1 to 30 carbon atoms, and particularly has a straight-chain, branched or It is a cyclic alkyl group, for example, methyl, ethyl, propyl, cyclopropyl. In the present specification, the definition of the number of carbon atoms is, for example, that the alkyl group represented by R ₁ or R ₂ is
In the case of having a substituent described later, the term also includes the number of carbon atoms of the substituent. The same applies to other groups. The aryl group represented by R ₁ and R ₂ preferably has 6 to 30 carbon atoms, particularly a monocyclic or condensed aryl group having 6 to 12 carbon atoms, such as phenyl and naphthyl. It is. The heterocyclic group represented by R ₁ and R ₂ is
It is a 3- to 10-membered saturated or unsaturated 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 ring. As the heterocycle, preferably 5 to 6
Membered aromatic heterocycle, for example, 2-pyridyl,
2-imidazolyl, 2-quinolyl, 2-benzimidazolyl,
4-pyrimidyl, 3-pyrazolyl, 2-isoquinolyl, 2-thiazolyl, 3-thienyl, 2-furyl, 2-benzothiazolyl and the like.

The acyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, alkylsulfonyl and arylsulfonyl groups of R ₁ and R ₂ are
It preferably has 1 to 20 carbon atoms, such as acetyl, benzoyl, formyl, methoxycarbonyl,
Ethoxycarbonyl, phenoxycarbonyl, mesyl,
Such as Tosyl.

In the general formula (I-2), independently of each other, X
_11, X _12, represented by X ₁₃ and X _14, a hydrogen atom, an alkyl group, an aryl group, and heterocyclic group, a hydrogen atom represented by R _1, R _2, an alkyl group, an aryl group, and heteroaryl Synonymous with ring group.

In the general formula (I-2), R ₁ , R ₂ and X
_11, X _12, each group represented by X _13, X ₁₄ and Z _1, Z ₂ may be substituted, the substituent include the following.

A halogen atom (fluorine, chlorine, bromine, iodine), a cyano group, a nitro group, an ammonio group (for example, a trimethylammonio group), a phosphonio group, a sulfo group (including a salt), and a sulfino group (including a salt) ), Carboxy group (including salt), phosphono group (including salt), 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 group (eg, pyridyl, furyl, imidazolyl, piperidyl, morpholino), alkoxy group (eg, methoxy, ethoxy, butyloxy), aryloxy group (eg, phenoxy, 2-naphthyloxy) An alkylthio group (eg, methylthio, ethylthio), an arylthio group (eg, phenylthio), an amino group (eg, an unsubstituted amino group, methylamino, dimethylamino, ethylamino,
Alinino), acyl groups (eg, acetyl, benzoyl, formyl, pivaloyl), alkoxycarbonyl groups (eg, methoxycarbonyl, ethoxycarbonyl), aryloxycarbonyl groups (eg, phenoxycarbonyl), carbamoyl groups (eg, unsubstituted carbamoyl) Groups, N, N-dimethylcarbamoyl, N-ethylcarbamoyl, N-phenylcarbamoyl), acyloxy groups (eg, acetoxy, benzoyloxy), acylamino groups (eg, acetylamino, benzoylamino), alkoxycarbonylamino groups (eg, Methoxycarbonylamino), an aryloxycarbonylamino group (for example, phenoxycarbonylamino), a ureido group (for example, an unsubstituted ureido group, N-
Methylureido, N-phenylureido), alkylsulfonylamino group (eg, methylsulfonylamino), arylsulfonylamino group (eg, phenylsulfonylamino), alkylsulfonyloxy group (eg, methylsulfonyloxy), arylsulfonyloxy group ( For example, phenylsulfonyloxy), alkylsulfonyl group (eg, mesyl), arylsulfonyl group (eg, tosyl), alkoxysulfonyl group (eg, methoxysulfonyl), aryloxysulfonyl group (eg, phenoxysulfonyl), sulfamoyl group (eg, Unsubstituted sulfamoyl group, N-methylsulfamoyl, N, N-dimethylsulfamoyl, N-phenylsulfamoyl), alkylsulfinyl group (for example, Finiru), arylsulfinyl group (e.g., phenylsulfinyl), alkoxysulfinyl sulfinyl group (e.g., methoxysulfinyl), an aryloxy sulfinyl group (e.g., phenoxy cis sulfinyl), phosphoric acid amide groups (e.g., N, N
-Diethyl phosphoric acid amide). These groups may be further substituted. When there are two or more substituents, they may be the same or different.

In the general formula (I-2), the two ligands may be the same or different. X ₁₁
And X ₁ may be linked and / or X ₁₄ and Z ₂ may be linked to form a ring. Further, X ₁₁ and X ₁₃ may be linked, or R ₁ and R ₂ may be linked to form a compound which coordinates with a palladium ion in one molecule.

In the compound of the formula (I-2), the two ligands can have either a trans or cis structure.

The compound preferably used in the present invention is a compound represented by formula (I-2).

In formula (I-2), preferably, Z ₁ and Z ₂ each represent an alkylene group, and R ₁ and R ₂ each represent a hydrogen atom, an alkyl group, an acyl group, a carbamoyl group, an alkylsulfonyl group, Represents an arylsulfonyl group. X ₁₁ , X ₁₂ , X
₁₃ and X ₁₄ represent a hydrogen atom or an alkyl group.

In the general formula (I-2), more preferably, X ₁₁ ,
X ₁₂ represents an alkylene group; R ₁ and R ₂ each represent a hydrogen atom or an alkyl group; X ₁₁ , X ₁₂ , X ₁₃ and X ₁₄
Represents a hydrogen atom or an alkyl group.

In formula (I-2), most preferably, Z₁, Z
_TwoEach represents a methylene group;₁, R _TwoAre each a hydrogen atom and
And hydrophilic groups (for example, sulfo groups, carboxy groups,
Droxy group, amino group, ammonium group, carbamoyl
Group, a sulfamoyl group) having 1 to 6 carbon atoms
X represents an alkyl group;₁₁, X₁₂, X₁₃And X₁₄Is hydrogen field
And a hydrophilic group (for example, a sulfo group,
Group, hydroxy group, amino group, ammonium group, carba
Moyl group, sulfamoyl group), having 1 carbon atom
Represents an alkyl group of 1 to 6.

Next, specific examples of the compounds represented by formulas (I-1) and (I-2) are shown, but the compounds of the present invention are not limited thereto.

[0201]

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[0202]

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[0203]

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The ligands represented by formula (I-1) (for example, X ₁
-L ₁ -Z ₁ -Y ₁ ) is easily available as a commercially available drug or as a compound synthesized from a commercially available drug by a known method.

The palladium compound represented by the general formula (I-1) can be synthesized from a corresponding ligand and an organic or inorganic palladium compound by a known method. The synthesis method is described in J. Inorg. Nucl. Chem., 41, 4
29 (1979), Inorg. Chim. Acta, 7, 8
8 (1973), Acta Crystallogr., Sect. B, 2
9, 762 (1973), Inorganic Chemistry, 7, 1447 (1968), Journal of Inorganic Chemistry, 8,
P. 304 (1963), ibid., 23, 561 (19
1978).

Examples of the palladium compound used in the synthesis of the general formula (I-1) include, for example, Gmelin Handbook (Gmel
in Handbook TEIL 65 (published in 1942) and Supplment
vol.B2 (published in 1989)).
Synthetic products and in situ synthetic products.

Specific examples of useful palladium compounds include palladium (II) chloride, palladium (II) bromide, palladium (II) hydroxide, palladium (II) sulfate, palladium (II) thiocyanate, tetrachloropalladium ( I
I) acid salts (sodium salt, potassium salt, ammonium salt), hexachloropalladium (IV) salt, tetrabromopalladium (II) salt, hexabromopalladium (I
V), bis (salicylate) palladium (II), bis (dithiooxalate-S, S ') palladium (II), trans-dichlorobis (thioether) palladium (II), tetraamminepalladium (II) salt,
Examples include dichlorodiaminepalladium (II), dibromodiaminepalladium (II), oxalatediaminepalladium (II), and bis (glycinate) palladium (II).

In the present invention, as a method for adding the compound represented by the general formula (I-1) to a silver halide photographic light-sensitive material, a method generally used for adding an additive to a photographic light-sensitive material is applied. . For example, a water-soluble compound is an aqueous solution having an appropriate concentration, and a compound that is insoluble or hardly soluble in water is an appropriate organic solvent that is miscible with water, for example, alcohols, glycols, ketones, esters, and amides. Can be dissolved in a solvent that does not adversely affect photographic properties, and added as a solution. The compound represented by the general formula (I-1) may be a compound synthesized and isolated by the method described in the above literature, or may be used without isolation to form a mixed solution of a palladium compound and a ligand. May be added to the silver halide photographic material.

In the present invention, a solution of the palladium compound represented by the formula (I-1) can be added to at least one of a photosensitive emulsion layer, an intermediate layer, an antihalation layer, and a surface protective layer. Furthermore, the general formula (I-1) of the present invention
May be newly provided as a separate layer together with the binder. Preferably, an intermediate layer,
It is added to the antihalation layer and the surface protection layer. When added to these layers, they are added to the coating solution of these layers,
Any case from the time of preparation of the coating liquid to immediately before the coating may be used. When it is added to the photosensitive emulsion layer, it may be added immediately after grain formation of the silver halide emulsion, but is preferably added after chemical sensitization.

In the present invention, the content of the palladium compound represented by the general formula (I-1) is 1 × / m ² of the light-sensitive material.
It is in the range of 10 ^-7 mol to 1 × 10 ^-3 mol. It is preferably in the range of 1 × 10 ^-6 mol to 1 × 10 ^-4 mol.

Next, the water-soluble mercaptotetrazole compound of the present invention represented by the formula (II-1) will be described.

In the general formula (II-1), R ₅ represents —SO
₃ M, -COOM, an organic residue substituted with at least one member selected from the group consisting of -OH and -NHR _2,
The organic residue specifically indicates an alkyl group having 1 to 10 carbon atoms (eg, methyl, ethyl, propyl, hexyl, cyclohexyl) and an aryl group having 6 to 14 carbon atoms (eg, phenyl, naphthyl).

Each group represented by R ₅ in formula (II-1) may be further substituted, and examples of the substituent include the following.

A halogen atom (fluorine, chlorine, bromine, iodine), a cyano group, a nitro group, an ammonio group (for example, trimethylammonio), a phosphonio group, a sulfo group (including a salt), a sulfino group (including a salt), Carboxy group (including salt), phosphono group (including salt), hydroxy group, mercapto group, hydrazino group, alkyl group (for example, methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, cyclopentyl, Cyclohexyl), alkenyl group (for example, allyl, 2-butenyl,
3-pentenyl), alkynyl group (eg, propargyl, 3-pentynyl), aralkyl group (eg, benzyl, phenethyl), aryl group (eg, phenyl, naphthyl, 4-methylphenyl), heterocyclic group (eg,
Pyridyl, furyl, imidazolyl, piperidyl, morpholino), alkoxy groups (eg, methoxy, ethoxy,
Butyloxy), an aryloxy group (e.g., phenoxy, 2-naphthyloxy), an alkylthio group (e.g.,
Methylthio, ethylthio), arylthio group (for example,
Phenylthio), an amino group (eg, unsubstituted amino,
Methylamino, dimethylamino, ethylamino, alinino), acyl group (eg, 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), acyloxy group (eg, acetoxy, benzoyloxy), acylamino group (eg, acetylamino, benzoylamino) , An alkoxycarbonylamino group (eg, methoxycarbonylamino), an aryloxycarbonylamino group (eg, phenoxycarbonylamino), a ureido group (eg, unsubstituted Id, N-methylureido, N-phenylureido), alkylsulfonylamino group (eg, methylsulfonylamino), arylsulfonylamino group (eg, phenylsulfonylamino), alkylsulfonyloxy group (eg, methylsulfonyloxy), aryl A sulfonyloxy group (eg, phenylsulfonyloxy), an alkylsulfonyl group (eg, mesyl), an arylsulfonyl group (eg, tosyl), an alkoxysulfonyl group (eg, methoxysulfonyl), an aryloxysulfonyl group (eg, phenoxysulfonyl), Sulfamoyl group (for example, unsubstituted sulfamoyl, N-methylsulfamoyl, N, N-dimethylsulfamoyl, N-phenylsulfamoyl), alkylsulfinyl group (for example, Methylsulfinyl), arylsulfinyl group (e.g., phenylsulfinyl), alkoxysulfinyl sulfinyl group (e.g., methoxysulfinyl), an aryloxy sulfinyl group (e.g., phenoxy cis sulfinyl)
And a phosphoric acid amide group (for example, N, N-diethylphosphoric acid amide). These groups may be further substituted. When there are two or more substituents, they may be the same or different.

Here, the substituent of R ₅ --SO ₃ M, --COO
M, may say be the same when the -OH and -NHR ₂ there are two or more.

In the general formula (II-1), R ₂ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, —COR ₃ , —CO ₂ R
₃ or —SO ₂ R ₃ , where R ₃ is a hydrogen atom, carbon number 1
Represents an alkyl group (eg, methyl, ethyl, propyl, hexyl, cyclohexyl, dodecyl, octadecyl) and an aryl group (eg, phenyl, naphthyl). These groups may be substituted by the substituents mentioned as the substituent of R ₅ .

In the general formula (II-1), M represents a hydrogen atom, an alkali metal atom (for example, lithium, sodium,
A quaternary ammonium group (eg, ammonium, tetramethylammonio, benzyltrimethylammonio, tetrabutylammonio) or a quaternary phosphonium group (eg, tetramethylphosphonio).

In the general formula (II-1), preferably, R ₅
Is phenyl substituted with one or two —SO ₃ M, —COO
Phenyl substituted with 1 or 2 M, phenyl substituted with 1 or 2 —NHR ₂ , alkyl group having 1 to 4 carbon atoms substituted with 1 or 2 —SO ₃ M, 1 or 2 —COOM
Pieces substituted alkyl group having from 1 to 4 carbon atoms is,, R ₂
Is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, -COR ₃
R ₃ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms substituted with a hydrophilic group (eg, carboxyl, sulfo, hydroxy), and M is a hydrogen atom or a sodium atom. More preferably R ₅ is phenyl phenyl which -SO ₃ M is substituted, -COOM is substituted.

Specific examples of the compound represented by formula (II-1) are shown below, but the present invention is not limited thereto.

[0220]

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[0221]

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[0222]

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Next, general formula (II-2) will be described.
M in the general formula (II-2) and R ₅ represent M in the general formula (II-1)
And R ₅ are synonymous.

In the general formula (II-2), R ₆ is a hydrogen atom,
An alkyl group having 1 to 10 carbon atoms (eg, methyl, ethyl, propyl, hexyl, cyclohexyl);
To 15 aryl groups (for example, phenyl and naphthyl), and the alkyl group or the aryl group may be substituted with the substituents listed as the substituent for R _{5 in} formula (II-1).

In the general formula (II-2), preferably, R ₆
Is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or phenyl, and R ₅ is phenyl substituted by one or two —SO ₃ M;
Phenyl substituted with one or two -COOM, -NHR ₂
Is 1 or 2 substituted phenyl, -SO ₃ M is 1 or 2
R ₂ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, and -COOM having 1 or 2 substituents.
COR ₃ , wherein R ₃ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms substituted with a hydrophilic group (eg, carboxyl, sulfo, hydroxy), and M is a hydrogen atom or a sodium atom. More preferably, R ₆ is a hydrogen atom, and R ₅ is phenyl substituted with one —SO ₃ M and phenyl substituted with one —COOM.

Specific examples of the compound represented by formula (II-2) are shown below, but the present invention is not limited to these.

[0227]

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[0228]

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[0229]

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The compound represented by formula (II-1) or (II-2) is known, and can be synthesized by the method described in the following literature.

"The Chemistry of Heterocyclic Chemistry", edited by John A. Montogomery, 1,
2,4-triazole (“The Chemistry of Heterocyc
lic Chemistry ”1,2,4-triazole), JOHN WILEY &
SONS (1981), pp. 404-442, SR Sandler,
W. Karo, “Organic Functional Group Prevation” (“Organic Functional Gro
up Preparation ”) Academic Press (1968) 3
Pages 12-5, edited by Kevin T. Pott, "Comprehensive
Heterocyclic compounds ”(“ COMPREHENSI
VE HETEROCYCLIC COMPOUNDS "), PERGAMON PRESS,
Volume 5, pages 761-784, pages 825-834, Ro
edited by bert C. Elderfield, "Heterocyclic Compounds"("HETEROCYCLICCOMPOUNDS"), JOHN WILE
Y & SONS (1961), 425-445, Frederic
R. Benson ed., "THE HIGH NITROGEN COMPOUNDS" JOHN WIL
EY & SONS (1984), pages 640 to 653.

The compound represented by the formula (II-1) or (II-2) can be a silver halide emulsion layer, a hydrophilic colloid layer (intermediate layer, surface protective layer, yellow filter layer, antihalation layer, etc.). Is preferably contained in the silver halide emulsion layer or an adjacent layer thereof. Furthermore, it is most preferable that the compound be contained in an emulsion layer corresponding to any one of the embodiments I to VI.

The compound of the general formula (II-1) and the compound of the general formula (II-2)
Is preferably added to the same layer or an adjacent layer, and most preferably to the same emulsion layer.

The method of adding this compound to an emulsion may be in accordance with the usual method of adding a photographic emulsion additive. For example, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, dissolved in water or a mixed solvent thereof,
It can be added as a solution.

The compound represented by the general formula (II-1) or (II-2) can be added and used in any step of the production process of a photographic emulsion. It can be added at any stage and used. In the preferred addition step in the present invention, it is effective to add during the chemical sensitization step after completion of the formation of silver halide grains.

The compound represented by formula (II-1) or (II-2) may be added in an amount of 1 × 10 ^-6 mol to 1 × per mol of usually selenium-sensitized silver halide. 1
It is used in an amount of 0 ^-1 mol, preferably 5 x 10 ^-6 mol to 5 x 10 ^-3 mol. A compound of the general formula (II-1)
The combination molar ratio of the compound of -2) is arbitrary, but is preferably from 99.5: 0.5 to 50:50. In particular, it is preferable to use a small amount of the compound (II-2) in a proportion of 99: 1 to 70:30.

In the present invention, the compounds represented by the general formulas (II-1) and (II-1)
When used in combination with the compound represented by -2), the compound represented by the general formula (II-1)
And the compound represented by formula (II-2) may be added at the same time or at different times. For example, the compound represented by the general formula (II-2) is added after completion of the formation of silver halide grains and before the completion of the chemical sensitization step, and the compound represented by the general formula (II-1) is terminated. It may be added just before post-coating. The opposite is also possible, but the former is preferred.

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

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

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

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

In addition, a high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or a low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer may be arranged in this order. The arrangement may be changed as described above even in the case of four or more layers.

As a means for improving color reproducibility, it is preferable to use an interlayer suppression effect.

In order to provide the above-mentioned layering effect on the red-sensitive layer in a specific wavelength region, it is preferable to provide a layering effect donor layer separately containing predetermined spectrally sensitized silver halide grains.

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

The size and shape of the silver halide grains used in the layer giving the layering effect to the red-sensitive layer are not particularly limited. For example, tabular grains having a high aspect ratio and monodispersed emulsions having a uniform grain size are provided. Silver iodobromide grains having a layered structure of iodine are preferably used.
In order to enlarge the exposure latitude, it is preferable to mix two or more emulsions having different grain sizes.

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

The donor layer which gives the red-sensitive layer a multilayer effect is preferably closer to the support than the green-sensitive layer, more preferably farther from the support than the red-sensitive layer, and is closer to the support of the green-sensitive layer. Most preferably, it is located adjacent to the side. In this case, “adjacent” means that no intermediate layer or the like is interposed.

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

The emulsion used in the light-sensitive material of the present invention may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which a latent image is formed inside a grain, or a type having a latent image on both the surface and the inside. However, it is necessary that the emulsion be a negative emulsion. Of the internal latent image type,
The emulsion may be a core / shell type internal latent image type emulsion described in No. 0, and its preparation method is described in JP-A-59-133542. The thickness of the shell of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

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

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

The silver halide grains having a fogged surface described in US Pat. No. 4,082,553, US Pat. No. 4,626,498, JP-A-59-21
It is preferable to apply silver halide grains or colloidal silver having the inside of the grains described in 4852 to a light-sensitive silver halide emulsion layer and / or a substantially light-insensitive hydrophilic colloid layer. The term "silver halide particles having a fogged interior or surface" refers to silver halide grains that can be uniformly (non-imagewise) developed regardless of unexposed portions and exposed portions of the photosensitive material. Its preparation is described in US Pat. No. 4,626,498 and JP-A-59-214852. The silver halide forming the internal nucleus of the core / shell type silver halide grain having the inside of the grain fogged may have a different halogen composition. As the silver halide having the inside or surface of the grain fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The average grain size of these fogged silver halide grains is 0.01 to 0.
75 μm, particularly preferably 0.05 to 0.6 μm, is preferred. The grains may be regular grains or polydisperse emulsions, but may be monodisperse (at least 95% of the weight or the number of silver halide grains has a grain size within ± 40% of the average grain size). Is preferable.

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

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

The coated silver amount of the light-sensitive material of the present invention was 8.0 g / m ^2.
The following is preferred.

The above-mentioned various additives are used in the light-sensitive material according to the present technology, but other various additives can be used according to the purpose.

These additives are described in more detail in Research Disclosure Item 17643 (Dec. 1978).
), Item 18716 (November 1979) and Item 308119 (December 1989), and the relevant locations are summarized in the table below.

Additive type RD17643 RD18716 RD308119 1 Chemical sensitizer page 23, page 648, right column, page 996 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, page 23-24, page 648, right column-996 right-998 right Super strong Sensitizer page 649 right column 4 Brightener 24 page 998 right 5 Antifoggant page 24-25 page 649 right column 998 right-1000 right and stabilizer 6 light absorber, page 25-26 page 649 right column 1003 Left to 1003 right Filter dye 650 page left column UV absorber 7 Stain inhibitor 25 page right column 650 left to right column 1002 right 8 Dye image stabilizer 25 page 1002 right 9 Hardening agent 26 page 651 left column 1004 right to 1005 left 10 Binder 26 Same as above 1003 right to 1004 right 11 Plasticizer, lubricant page 27 650 right column 1006 left to 1006 right 12 Coating aid, page 26 to 27 Same as above 1005 left to 1006 left Surfactant 13 Static page 27 Same as above 1006 right to 1007 left Inhibitor 14 matting agent 1008 left to 1009 left.

Techniques such as layer arrangement and the like which can be used for the emulsions of the present invention and photographic materials using the emulsions, functional couplers such as silver halide emulsions, dye-forming couplers and DIR couplers, various additives, etc. And development processing are described in EP 056596 A1 (published October 13, 1993) and the patents cited therein. The following is a list of each item and the corresponding places.

[0261] 1. 1. Layer structure: page 61, lines 23 to 35, page 61, line 41 to page 62, line 14, 2. Intermediate layer: page 61, lines 36 to 40, 3. Multilayer effect imparting layer: page 62, lines 15 to 18, 4. Silver halide composition: page 62, lines 21 to 25; 5. Silver halide grain habit: page 62, lines 26 to 30, 6. Silver halide grain size: page 62, lines 31 to 34, 7. Emulsion production method: page 62, lines 35 to 40, Silver halide grain size distribution: page 62, 41 to 42
Row, 9. Tabular grains: page 62, lines 43 to 46,10. 10. Internal structure of particle: page 62, lines 47 to 53, Emulsion latent image forming type: page 62, line 54 to page 63, 5
Line, 12. 12. Physical ripening and chemical sensitization of emulsion: p. 63, lines 6 to 9, 13. Mixed use of emulsion: page 63, lines 10-13, 14. Fogged emulsion: p. 63, lines 14 to 31, Non-light-sensitive emulsion: page 63, lines 32-43, 16. 16. Silver coating amount: page 63, lines 49 to 50; Photographic additives: Research Disclosure (R
D) Item 17643 (December 1978), Item 18
716 (November 1979) and Item 307105
(November, 1989), and each item and a description place related thereto are shown 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, page 23-24, page 648, right column 866-868 Color sensitizer ~ page 649 right column 4 Brightening agent page 24 page 647 right column page 868 5 antifoggant, page 24-25 page 649 right column 868-870 page stabilizer 6 light absorber, page 25-26 649 Page right column 873 page Filter dye, ~ 650 page left column UV absorber 7 Stain inhibitor 25 page right column 650 left column to right column 872 8 Dye image stabilizer 25 page 650 left column 872 9 Hardener 26 Page 651, left column 874-875 10 Binder page 26, page 651 left column 873-874 11 Plasticizer, lubricant 27 page 650 right column 876 page 12 Coating aid, page 26-27 page 650 right column 875- Page 876 Surfactant 13 Static Page 27 Page 650 Right column Pages 876 to 877 Inhibitor 14 Matting agent 878 to 879.

[0263] 18. Formaldehyde scavenger: 6
Page 4, lines 54-57; 20. Mercapto antifoggant: page 65, lines 1 and 2, Release agent such as fogging agent: page 65, lines 3-7, 21. Dye: page 65, lines 7-10, 22. General color couplers: p. 65, lines 11 to 13, 23. Yellow, magenta and cyan couplers: page 65, 1
Lines 4 to 25, 24. Polymer coupler: page 65, lines 26 to 28, 25. Diffusible dye-forming couplers: p. 65, lines 29 to 31, 26. Colored coupler: page 65, lines 32-38, 27. General functional couplers: p. 65, lines 39 to 44, 28. Bleach accelerator releasing coupler: page 65, lines 45-48, 29. Development accelerator releasing coupler: page 65, lines 49 to 53, 30. Other DIR couplers: page 65, line 54 to page 66, 4
Line, 31. Coupler dispersion method: page 66, lines 5-28, 32. Preservatives / fungicides: page 66, lines 29-33, 33. Type of photosensitive material: page 66, lines 34 to 36, 34. Photosensitive layer thickness and swelling speed: page 66, line 40 to page 67, 1
Row, 35. Back layer: page 67, lines 3 to 8, 36. Overall development processing: page 67, lines 9-11, 37. Developer and developer: page 67, lines 12 to 30, 38. 39. Developer additive: page 67, lines 31 to 44, Reverse processing: page 67, lines 45 to 56, 40. Processing solution opening ratio: page 67, line 57 to page 68, line 12, 41. Developing time: page 68, lines 13 to 15, 42. Bleach-fixing, bleaching, fixing: page 68, 16 lines-page 69, 31
Row, 43. Automatic developing machine: page 69, lines 32 to 40, 44. Rinsing, rinsing, stabilization: page 69, line 41 to page 70, line 18
Row, 45. Processing solution replenishment, reuse: page 70, lines 19-23, 46. 47. Built-in developer sensitive material: page 70, lines 24-33, Developing temperature: 70, lines 34-38, 48. Use for film with lens: page 70, lines 39-41.

A bleaching solution described in EP-A-602600 containing a 2-pyridinecarboxylic acid or 2,6-pyridinedicarboxylic acid, a ferric salt such as ferric nitrate, and a persulfate is also used. It can be used preferably. In the use of this bleaching solution, it is preferable to interpose a stopping step and a washing step between the color developing step and the bleaching step,
It is preferable to use an organic acid such as acetic acid, succinic acid, and maleic acid for the stop solution. In addition, this bleaching solution contains p
Organic acids such as acetic acid, succinic acid, maleic acid, glutaric acid, adipic acid, etc.
It is preferable to contain the compound in a range of 2 mol / liter (hereinafter, liter is referred to as “L”).

Preferred color reversal film treating agents having the above contents include E-6 manufactured by Eastman Kodak Company.
And a processing agent and CR-56 processing agent of Fuji Photo Film Co., Ltd.

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

The magnetic recording layer preferably used in the present invention is a layer in which an aqueous or organic solvent-based coating liquid in which magnetic particles are dispersed in a binder is provided on a support.

The magnetic particles used in the present invention are γFe ₂ O
₃ , ferromagnetic iron oxide such as ₃ , Co-coated γFe ₂ O ₃ , Co-coated magnetite, Co-containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy, hexagonal Ba ferrite, Sr ferrite, Pb ferrite , Ca ferrite and the like can be used. Co-coated ferromagnetic iron oxide, such as Co-coated γFe ₂ O _3, is preferred. The shape may be any of needle shape, rice grain shape, spherical shape, cubic shape, plate shape and the like. Preferably at least 20 m ² / g in S _BET is the specific surface area, and particularly preferably equal to or greater than 30 m ² / g.

The saturation magnetization (σs) of the ferromagnetic material is preferably from 3.0 × 10 ^{4 to} 3.0 × 10 ⁵ A / m, particularly preferably 4.0 × 10 ⁵ A / m.
10 ^{4 to} 2.5 × 10 ⁵ A / m. The ferromagnetic particles may be subjected to a surface treatment with silica and / or alumina or an organic material. Further, the surface of the magnetic particles may be treated with a silane coupling agent or a titanium coupling agent as described in JP-A-6-161032. JP-A-4-25
No. 9911, the surface described in 5-81652 is inorganic,
Magnetic particles coated with an organic substance can also be used.

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

As a method for dispersing the above-mentioned magnetic substance in the above-mentioned binder, a kneader, a pin type mill, an annular type mill and the like are preferably used, as in the method described in JP-A-6-35092. 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 to 3 μm. The weight ratio between the magnetic particles and the binder is preferably 0.
5: 100-60: 100, more preferably 1: 100-30: 100
It is. The coating amount of the magnetic particles is 0.005 to 3 g / m ² , preferably 0.01 to ² g / m ² , and more preferably 0.02 to 0.5 g / m ² . The transmission yellow density of the magnetic recording layer is preferably from 0.01 to 0.50, more preferably from 0.03 to 0.20, and particularly preferably from 0.04 to 0.15. The magnetic recording layer may be provided on the entire back surface of the photographic support by coating or printing, or in a stripe shape. As a method for applying the magnetic recording layer, an air doctor, a blade, an air knife, a squeeze, an impregnation, a reverse roll, a transfer roll, a gravure, a kiss, a cast, a spray, a dip, a bar, an extrusion, and the like can be used. The coating solution described in 341436 is preferred.

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

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

Next, the polyester support has a curl.
The heat treatment temperature should be 40 ° C or higher and lower than Tg to reduce
More preferably, the heat treatment is performed at Tg-20 ° C. or higher and lower than Tg.
The heat treatment may be performed at a constant temperature within this temperature range,
The heat treatment may be performed while cooling. This heat treatment time is 0.
1 hour or more and 1500 hours or less, more preferably 0.5 hour or more
 Less than 200 hours. The heat treatment of the support is performed in roll form.
Or may be carried out while being transported in web form.
Good. The surface is made uneven (for example, SnO_TwoAnd Sb_TwoO _Five Etc.
(Apply conductive inorganic fine particles.)
No. Also, knurling is applied to the end and only the end is raised slightly.
To prevent cuts in the core
It is desirable. These heat treatments are performed on the surface after forming the support.
After treatment, after coating the back layer (antistatic agent, slip agent, etc.)
It may be carried out at any stage after the application. Preferred
Is after the application of the antistatic agent.

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

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

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

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

The most preferred antistatic agent is Zn
O, TiO_Two, SnO_Two, Al_TwoO_Three, In_TwoO_Three, SiO _Two, MgO, BaO, Mo
O_Three, V_TwoO_FiveAt least one type of volume resistivity selected from
Ten⁷Ωcm or less, more preferably 10^FiveGrains that are Ω · cm or less
0.001 to 1.0 μm crystalline metal oxide or
Fine particles of these composite oxides (Sb, P, B, In, S, Si, C, etc.),
Furthermore, sol-like metal oxides or composite oxides thereof
Particles.

The content in the light-sensitive material is from 5 to 500 mg / m^TwoBut
Preferably particularly preferably 10 to 350 mg / m ^TwoIt is. Conductivity
Of the amount of the crystalline oxide or the composite oxide thereof and the binder
The ratio is preferably 1/300 to 100/1, more preferably 1/100 to 1
00/5.

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

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

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

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

Preferred plastic materials are polystyrene, polyethylene, polypropylene, polyphenyl ether and the like. Further, the patrone of the present invention may contain various antistatic agents, and carbon black, metal oxide particles, nonionic, anionic, cationic and betaine surfactants or polymers can be preferably used. These antistatic patrones are disclosed in
No. 12537 and No. 1-312538. Particularly, the resistance at 25 ° C. and 25% RH is preferably 10 ¹² Ω or less. Usually, a plastic patrone is manufactured using a plastic into which carbon black, a pigment, or the like is kneaded to impart light-shielding properties. Patrone size is now
It is also possible to keep the 135 size, or to reduce the size of the camera, it is effective to reduce the diameter of the current 135 size 25 mm cartridge to 22 mm or less. The volume of the patrone case is
It is preferably 30 cm ³ or less, more preferably 25 cm ³ or less.
The weight of the plastic used for the patrone and the patrone case is preferably 5 g to 15 g.

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

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

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

(1) Reception (exposed cartridge film received from customer) (2) Detach step (transfer film from cartridge to intermediate cartridge for development step) (3) Film development (4) Retouch step (development (Return the used negative film to the original cartridge.) (5) Printing (Continuous automatic printing of C / H / P3 type print and index print on color paper (preferably SUPER FA8 made by FUJIFILM)) (6) Verification and shipping (collating cartridges and index prints with ID numbers and shipping with prints).

These systems include Fujifilm Minilab Champion Super FA-298 / FA-278 / FA-258 / F
A-238 and Fujifilm Digital Lab System Frontier are preferred. FP922AL / FP562B / FP562B, AL / FP362B / FP as a minilab champion film processor
362B, AL, and the recommended treatment chemicals are Fujicolor Justit CN-16L and CN-16Q. PP3008AR / PP3008A / PP1828AR / PP1828A /
PP1258AR / PP1258A / PP728AR / PP728A are the recommended treatment chemicals. Fujicolor Justit CP-47L and CP-4
0FAII. In the frontier system, a scanner & image processor SP-1000 and a laser printer & paper processor LP-1000P or a laser printer LP-1000W are used. The detacher used in the detaching process and the rear toucher used in the rear touching process are Fujifilm's DT200 / DT100 and AT200 / AT1 respectively.
00 is preferred.

The AP system can also be enjoyed by a photo joy system centered on the Fuji Film Aladdin 1000 digital image workstation. For example, Aladdin 1000 can be directly loaded with developed AP system cartridge film, or it can be used to transfer negative, positive, and print image information to a 35mm film scanner FE.
The digital image data obtained by inputting using the -550 or the flat head scanner PE-550 can be easily processed and edited. The data is stored in a digital color printer NC-550AL using a light fixing type thermal color printing system and a pictograph 3000 using a laser exposure thermal development transfer system.
Or as prints by existing laboratory equipment through a film recorder. The Aladdin 1000 can also output digital information directly to a floppy (registered trademark) disk or Zip disk, or to a CD-R via a CD writer.

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

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

[0294]

Examples of the present invention will be described below. However, the present invention is not limited to this embodiment.

Example 1 (Proof of Aspect I) (Preparation of Em-1) Low molecular weight gelatin having a molecular weight of 15,000
Aqueous solution 1200 containing 1.0 g, KBr and 1.0 g
The mL was kept at 35 ° C. and stirred vigorously. AgNO_Three,
30 mL of an aqueous solution containing 1.9 g, 1.5 g of KBr and molecules
Aqueous solution containing 0.7 g of low molecular weight gelatin having a weight of 15,000
Add 30 mL by double jet method over 30 seconds and add nuclei
The formation was performed. At this time, the excess concentration of KBr was kept constant.
Was. After adding 5.0 g of KBr, the temperature was raised to 75 ° C. and the mixture was aged.
Was. After ripening, 35 μmol of methionine / g
Having a molecular weight of 100,000 and a phthalation rate of 97%.
35 g of tall gelatin were added. Adjust pH to 5.6
did. AgNO_Three, 150 mL of an aqueous solution containing 30 g and K
Br aqueous solution is added over 16 minutes by double jet method
(Growth step 1). At this time, the silver potential is changed to a saturated calomel electrode.
0 mV. Furthermore, AgNO _Three, 110
aqueous solution containing 3.8 g and KBr water containing 3.8 mol% KI
Solution (15% by weight) with double jet method, the final flow rate is the first
15 minutes by accelerating the flow rate to 1.2 times the initial flow rate
Migrated addition (growth step 2). At this time, the silver potential was set to 0 mV.
Kept. AgNO_Three, Aqueous solution 13 containing 35 g
2mL and KBr aqueous solution are passed for 7 minutes by the double jet method.
Was added. So that the potential at the end of the addition is +20 mV
The addition of the aqueous KBr solution was adjusted. Benzenethiosulfo
Sodium salt, 2 mg, then KBr
The silver potential was adjusted to -20 mV with AgNO._Three, 6.8g
Solution containing 100 mL of aqueous solution containing 7.1 g of KI and 9 g of aqueous solution containing 7.1 g of KI
00 mL by the double jet method over 10 minutes
Was. Immediately after the addition is completed, AgNO_ThreeWater containing 70g
250 mL of liquid and 170 mL of aqueous solution containing 50 g of KBr
Added over 0 minutes. After washing with water, 45 g of gelatin
The mixture was adjusted to pH 5.8 and pAg 8.7 at 40 ° C.

(Preparation of Em-2) Em-2 was prepared in the same manner as Em-1, except that the silver potential in growth step 1 and growth step 2 was changed to -20 mV.

(Preparation of Em-3) In the preparation of Em-2, a dispersion gelatin (alkaline-treated bone gelatin containing 28% or more of a component having a molecular weight of 280,000 or more) added after washing with water was used.
Em-3 was prepared in the same manner as Em-2, except that the alkali-treated bone gelatin containing 40% of 80,000 or more components was changed to the method described in the detailed description, which was prepared by a method without cross-linking of gelatin. .

(Preparation of Em-4) In the preparation of Em-2, the KI in the growth step 2 was changed to 0 mol%, and AgNO ₃ added by a double jet after the growth step 2 was used.
Em-4 was prepared in the same manner as Em-2 except that the amounts of and KI were changed to 1.0 g and 1.1 g, respectively.

(Preparation of Em-5) 1200 mL of an aqueous solution containing 1.0 g of low molecular weight gelatin having a molecular weight of 15000, 1.0 g of KBr was maintained at 35 ° C., and vigorously stirred. A
gNO ₃ , 30 mL of an aqueous solution containing 1.9 g, KBr1.
30 mL of an aqueous solution containing 5 g and 0.7 g of low molecular weight gelatin having a molecular weight of 15,000 was added by a double jet method over 30 seconds to form nuclei. At this time, the excess concentration of KBr was kept constant. 5.0 g of KBr was added, and the temperature was raised to 75 ° C. to ripen. After the ripening, the phthalation ratio of 100,000 containing 35 μmol of methionine per gram and having a molecular weight of 100,000 was measured.
35 g of 7% phthalated gelatin was added. pH 5.
Adjusted to 6. Aqueous solution 150 containing 30 g of AgNO ₃
mL and an aqueous KBr solution were added by a double jet method over 16 minutes (growth step 1). At this time, the silver potential was kept at -20 mV with respect to the saturated calomel electrode. Furthermore, AgN
An aqueous solution containing 110 g of O ₃ and a KBr aqueous solution (15% by weight) containing 9.9 mol% KI were accelerated by a double jet method so that the final flow rate was 1.2 times the initial flow rate, and over 15 minutes. (Growth step 2). At this time, the silver potential was kept at -20 mV. AgNO ₃ , 35g
And an aqueous KBr solution were added over 7 minutes by the double jet method. +2 potential at the end of addition
The addition of the aqueous KBr solution was adjusted to be 0 mV. After adding 2 mg of sodium benzenethiosulfonate, KBr was added to adjust the silver potential to -20 mV.
250 mL of an aqueous solution containing 76.8 g of gNO ₃ and KBr
170 mL of an aqueous solution containing 54.9 g was added over 20 minutes. After washing with water, add 45 g of gelatin and p
H5.8 and pAg8.7 were adjusted.

(Preparation of Em-6) 1200 mL of an aqueous solution containing 1.0 g of low molecular weight gelatin having a molecular weight of 15,000, 1.0 g of KBr was maintained at 35 ° C., and vigorously stirred.
30 mL of an aqueous solution containing 1.9 g of AgNO ₃ , KBr
1.5 g and low molecular weight gelatin having a molecular weight of 15,000 0.7
30 mL of an aqueous solution containing g was added for 30 seconds by a double jet method to form nuclei. At this time, the excess concentration of KBr was kept constant. 5.0 g of KBr was added, and 75 ° C.
And aged. After ripening, 35 μmo per g
1 g of methionine, 15 g of trimellitated gelatin having a molecular weight of 100,000 and a trimellitation ratio of 98%, 10 g of succinated gelatin, and 10 g of oxidized gelatin were added. The pH was adjusted to 5.6. 150 mL of an aqueous solution containing 30 g of AgNO ₃ and an aqueous KBr solution were added over 16 minutes by a double jet method. At this time, the silver potential was kept at -30 mV with respect to the saturated calomel electrode. Furthermore, Ag
An aqueous solution containing 110 g of NO ₃ and an aqueous KBr solution were added over a period of 15 minutes by a double jet method while accelerating the flow rate so that the final flow rate was 1.2 times the initial flow rate. At this time, an AgI fine grain emulsion having a size of 0.03 μm was simultaneously added at an accelerated flow rate such that the silver iodide content became 3.8%, and the silver potential was kept at -30 mV. 132 mL of an aqueous solution containing 35 g of AgNO ₃ and an aqueous KBr solution were added over 7 minutes by the double jet method. The potential at the end of the addition is -20
The addition of the aqueous KBr solution was adjusted to be mV. After the temperature was adjusted to 40 ° C., sodium p-iodoacetamidobenzenesulfonate (compound 1) was converted to KI by 7.1.
g and then 64 mL of a 0.8 M aqueous sodium sulfite solution. Further, by adding an aqueous solution of NaOH,
H was raised to 9.0 and maintained for 4 minutes to rapidly generate iodide ions, and then the pH was returned to 5.5. 75 ℃
After returning to, sodium benzenethiosulfonate, 2m
g was added, and 13 g of gelatin was further 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 keeping the potential at 0 mV. After washing with water, add 45 g of gelatin and add
It adjusted to pH5.8 and pAg8.7 at ℃, and was set to Em-6.

Compound 1

Embedded image

According to transmission electron microscopy observations at liquid nitrogen temperatures of Em-1 to Em-6, dislocation lines were observed at high density in the fringe portion of each of the emulsions except for Em-5. It had more than 20 lines. Also, E
ratio of particles occupying an aspect ratio of 8 or more of m-1 to 6;
Table 1 shows the average aspect ratio and the average iodine content.

[0303] The calcium, magnesium and strontium concentrations of Em-1 to 6 were examined by ICP emission spectroscopy.
m, magnesium 2ppm and strontium 0ppm
Met.

[0304]

[Table 1]

(Chemical sensitization and spectral sensitization) (Preparation of solid fine dispersion of sensitizing dye) Solid fine dispersions of sensitizing dyes 1 to 3 were prepared as follows. As shown in Table 2, the preparation conditions are shown by dissolving an inorganic salt in ion-exchanged water, adding a sensitizing dye, and dispersing the mixture at 2000 rpm for 20 minutes using a dissolver blade at 60 ° C. Solid fine dispersions of dyes 1 to 3 were prepared.

[0306]

[Table 2]

(Preparation of Em-1-A, 2-A, 3-A)
Em-1 to 3 were heated to 56 ° C. Sensitizing dyes 1, 2, 3
In a molar ratio of 58: 36: 1, respectively, and in the form of a finely divided solid. Then potassium thiocyanate,
Chloroauric acid, sodium thiosulfate, and N, N-dimethylselenourea were added for optimal chemical sensitization. The amounts of chloroauric acid and N, N-dimethylselenourea are shown in Table 3. At the end of the chemical sensitization, compound 2 was added and Em-1-
A, 2-A and 3-A were prepared.

[0308]

[Table 3]

Sensitizing dye 1

Embedded image

Sensitizing dye 2

Embedded image

Sensitizing dye 3

Embedded image

Compound 2 = Exemplified Compound II-1-1.

(Em-1-B, 2-B, 4-A, 5-
A, Preparation of 6-A) Em-1 to 2, 4 to 6 were heated to 56 ° C. Sensitizing dyes 1, 2, and 3 were added at 58: 36: 1, respectively.
And in the form of a fine solid dispersion, and when the sensitizing dye had adsorbed 90% of the equilibrium adsorption amount, calcium nitrate was added so as to be 180 ppm with respect to the emulsion. Thereafter, potassium thiocyanate, chloroauric acid, sodium thiosulfate, and N, N-dimethylselenourea were added and the mixture was aged and optimally chemically sensitized. Chloroauric acid and N, N-
Table 3 shows the amount of dimethylselenourea added. At the end of chemical sensitization, compound 2 was added, and Em-1-
B, 2-B, 4-A, 5-A and 6-A were prepared.

(Em-2-BA, Em-2-BB, Em
Preparation of 2-BC) Em-2-B was prepared in the same manner as in Em-2-B, except that calcium nitrate was added when the sensitizing dye had adsorbed 50% of the equilibrium adsorption amount. -2-BA was prepared. In the preparation of Em-2-B, Em-2-BB was prepared in the same manner as Em-2-B except that calcium nitrate was added at the end of chemical sensitization.
Was prepared. Em-2-BC was prepared in the same manner as Em-2-B except that calcium nitrate was added before adding the sensitizing dye in the preparation of Em-2-B.

(Em-2-BD, Em-2-BE, Em
Preparation of 2-BF) In the preparation of Em-2-B, calcium concentrations were 50, 1800, and 3000 ppm, respectively.
Em-2 except that calcium nitrate was added so that
Em-2-BD and Em-2
-BE, Em-2-BF were prepared.

(Preparation of Em-2-C, 2-D, 2-E)
In the preparation of Em-2-B, instead of calcium nitrate, magnesium nitrate, strontium nitrate, and zinc nitrate were added in such an amount that the concentration in the emulsion became the same as the concentration of calcium nitrate. , 2-D, 2
-E was prepared.

A cellulose triacetate film support provided with an undercoat layer was subjected to the above-described chemically sensitized emulsions Em-1-A to 6-A under the coating conditions shown in Table 4 below, and a protective layer was provided thereon. It was applied to prepare a sample. In Em-2-BF, the surface of the coated sample was poor due to a large amount of Ca, and photographic properties could not be evaluated.

[0318]

[Table 4]

These samples were left under the conditions of 40 ° C. and 70% relative humidity for 14 hours. Thereafter, exposure was performed for 1/100 second through a continuous wedge with a gelatin filter SC-50 manufactured by FUJIFILM Corporation.

Using a negative processor FP-350 manufactured by Fuji Photo Film Co., Ltd., processing was carried out by the method described below (until the cumulative replenishment amount of the liquid became three times the mother liquid tank capacity).

(Processing method) Process Processing time Processing temperature Replenishment amount Color development 3 minutes 15 seconds 38 ° C. 45 milliliters (milliliters are described as “mL”) Bleaching 1 minute 00 seconds 38 ° C. 20 mL Bleach liquid overflow is bleaching The entire amount flows into the fixing tank. Bleaching and fixing 3 minutes 15 seconds 38 ° C 30 mL Rinse with water (1) 40 seconds 35 ° C Countercurrent piping system from (2) to (1) Rinse with water (2) 1 minute 00 seconds 35 ° C 30 mL Stable 40 seconds 38 ° C. 20 mL Drying 1 minute 15 seconds 55 ° C. * Replenishment amount per 35 mm width 1.1 m length (corresponding to 24 Ex. 1 line) Next, the composition of the processing solution is described.

(Color developing solution) Tank solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 2.0 Sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide 1.4 0.7 Iodine 1.5 mg potassium hydroxide-hydroxylamine sulfate 2.4 2.8 4- [N-ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline sulfate 4.5 5.5 Add water and add 1.0 L 1.0 L pH (potassium hydroxide And adjusted with sulfuric acid) 10.05 10.10.

(Bleaching solution) Common to tank solution and replenisher (unit: g) Ethylenediaminetetraacetic acid ammonium ferric ammonium dihydrate 20.0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 100.0 Ammonium nitrate 10.0 Bleaching accelerator 0.005 mol (CH ₃ ) _{2 N-CH 2 -CH 2 -SS} -CH 2 -CH 2 -N (CH 3) 2 · 2HCl aqueous ammonia (27%) 15.0 mL water to make 1.0 L pH (adjusted with aqueous ammonia and nitric acid) 6.3 .

(Bleaching / fixing solution) Tank solution (g) Replenisher (g) Ethylenediaminetetraacetate ammonium dihydrate 50.0-Ethylenediaminetetraacetic acid disodium salt 5.0 2.0 Sodium sulfite 12.0 20.0 Aqueous ammonium thiosulfate (700 g / L) 240.0 mL 400.0 mL Ammonia water (27%) 6.0 mL-Add water 1.0 L 1.0 L pH (adjusted with ammonia water and acetic acid) 7.2 7.3.

(Washing solution) Common tank water and replenisher tap water is H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co.) and OH type anion exchange resin (Amberlite IR-400) The mixture was passed through a mixed-bed column packed with to treat the calcium and magnesium ion concentrations at 3 mg / L or less, and then 20 mg / L of sodium isocyanurate dichloride and 0.15 g / L of sodium sulfate were added. The pH of this solution is 6.5-
It was in the range of 7.5.

(Stabilizing solution) Common to tank solution and replenisher (unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.2 Disodium ethylenediaminetetraacetate 0.05 1, 2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to make 1.0 L pH 8.5.

The density of the treated sample was measured with a green filter. The sensitivity was represented by the relative value of the reciprocal of the exposure required to give a density of fog plus 0.2. Also, RM
The S granularity is uniformly exposed with a light amount giving a density of 0.2, and after performing the above-described development processing, the “Theory of the Photographic Process” published by Macramin Co., Ltd.
It was measured by the method described on page 619. Table 1 shows the obtained results. In addition, Em-
The sensitivity and RMS granularity of 1-A were each set to a standard level.

As apparent from Table 1, the aspect ratio of 8
The proportion of the particles occupying the above exceeds 50%, the iodine content of the particles is 2 mol% or more, has dislocation lines, and the time and amount of calcium to be added are within the specified range, or the molecular weight is 280,000 or more. It can be seen that high sensitivity and good granularity can be obtained when a dispersed gelatin containing 30% or more of the component is used. Further, it can be seen that good granularity is obtained when calcium nitrate, magnesium nitrate and strontium nitrate are used, but that the effect of the present invention is not obtained when zinc nitrate is used. In addition, it can be seen that when the proportion occupied by particles having an aspect ratio of 8 or more increases, further improvements in sensitivity and granularity can be obtained.

As described above, the sensitivity and granularity of tabular grains were improved by the present invention.

Example 2 (Proof of Aspect II) (Preparation of Em-7) In the nucleation of Em-2 described in Example 1, gelatin having a molecular weight of 15,000 was converted to 3.0.
g-7 was changed to an aqueous solution containing 2.0 g of KBr, and the growth potential was further reduced so that the proportion of particles having an aspect of 8 or more was about the same as Em-2, thereby preparing Em-7.

(Preparation of Em-8) Em described in Example 1
In the nucleation at -2, an aqueous solution containing 9.0 g of gelatin having a molecular weight of 15,000 and 5.0 g of KBr was changed, and the growth potential was further reduced so that the proportion of particles having an aspect of 8 or more was about the same as Em-2. Thus, Em-8 was prepared.

When the twin plane spacing of Em-2, Em-7 and Em-8 was measured, the twin plane spacing was 0.01
5, 0.0165 and 0.018 μm.

(Preparation of Em-7-A, 8-A) Em-7
To 8 were subjected to chemical sensitization and spectral sensitization in the same manner as in Em-2-B described in Example 1 to give Em-7-A, 8-
A was prepared.

The photographic properties were evaluated in the same manner as described in Example 1. The granularity was evaluated in the same manner as in Example 1 except that the exposure was uniformly performed with a light amount giving a density of fog + 2.0.

[0335]

[Table 5]

As is clear from Table 5, the emulsions having the twin plane spacing of 0.018 μm and the emulsions having the twin plane spacing of 0.015 μm and 0.0165 μm are superior in sensitivity and granularity.

Example 3 (Proof of Aspect III) (Preparation of Em-9) An aqueous solution 1200 containing 1.0 g of low-molecular-weight gelatin having a molecular weight of 15,000, 1.0 g of KBr, and 1.0 g of KBr
The mL was kept at 35 ° C. and stirred vigorously. AgNO ₃ ,
30 mL of an aqueous solution containing 1.9 g and 30 mL of an aqueous solution containing 1.5 g of KBr and 0.7 g of low-molecular-weight gelatin having a molecular weight of 15,000 were added over 30 seconds by a double jet method to form nuclei. At this time, the excess concentration of KBr was kept constant. 5.0 g of KBr was added, and the temperature was raised to 75 ° C. to ripen. After completion of ripening, trimellitization rate of 98,000 containing methionine at a molecular weight of 100,000 per g was 98.
% Of trimellitated gelatin, 10 g of succinated gelatin, and 10 g of oxidized gelatin were added. The pH was adjusted to 5.6. Aqueous solution 1 containing 30 g of AgNO ₃
50 mL and an aqueous KBr solution were added by a double jet method over 16 minutes. At this time, the silver potential was kept at -30 mV with respect to the saturated calomel electrode. Further, AgNO ₃ , 11
An aqueous solution containing 0 g 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, the size is 0.03
μm AgI fine grain emulsion was simultaneously added at a flow rate acceleration of 3.8% so that the silver iodide content became 3.8%.
It was kept at 30 mV. Aqueous solution 1 containing 35 g of AgNO ₃
32 mL and an aqueous KBr solution were added over 7 minutes by the double jet method. The addition of the aqueous KBr solution was adjusted so that the potential at the end of the addition became -20 mV. Further, KBr was added to adjust the potential to −60 mV, and then 2 mg of sodium benzenethiosulfonate and 7 g of gelatin were added. After the addition was completed, an aqueous solution of low molecular weight gelatin having a molecular weight of 15,000, an aqueous solution of AgNO _{3 and an} aqueous solution of KI were added to JP-A-10-435.
In a separate chamber having a magnetic coupling induction type stirrer described in No. 70, 7.1 g of an AgI fine grain emulsion having a grain size of 0.008 μm prepared by mixing immediately before addition was added while continuously adding 7.1 g of KI equivalent. ₃ , 250 mL of an aqueous solution containing 70 g and a KBr aqueous solution were added over 20 minutes. After washing with water, 45 g of gelatin was added and adjusted to pH 5.8 and pAg 8.7 at 40 ° C. to obtain Em-9.

(Preparation of Em-9-A) Em-9 was subjected to chemical sensitization and spectral sensitization in the same manner as Em-6-A to prepare Em-9-A.

Photographic properties and granularity were evaluated in the same manner as described in Example 2.

[0340]

[Table 6]

As is clear from Table 6, Em-9-A is more excellent in sensitivity and granularity than Em-6-A.

Example 4 (Evidence of Aspect IV) In Em-9-A of Example 3, a fine grain emulsion of pure AgBr having a size of 0.05 μm at the start of spectral sensitization and chemical sensitization was added to host grains. Em-9-B was prepared in the same manner as Em-9-A except that 0.5 mol% was added,
Photographic properties and granularity were evaluated in the same manner as described in Example 1. Furthermore, the change over time of the exposed sample (storability)
Was stored for 7 days at 50 ° C. and 60% relative humidity.

[0343]

[Table 7]

As is clear from Table 7, the emulsion to which fine AgBr fine particles were added at the start of spectral sensitization and chemical sensitization was
It can be seen that the sensitivity and the granularity are the same and the storage stability is excellent as compared with the emulsion to which pure AgBr fine particles are not added.

Example 5 (Evidence of Aspect V) In Em-9 described in Example 3, in the final addition during grain formation, yellow blood salt was added to 1 mol of silver,
Em-9 was obtained in the same manner as Em-9 except that potassium hexacyanoruthenate was added in an amount of 1.0 × 10 ⁻⁵ mol.
-10 to 11 were prepared. Further, Em-10 to 11 were each subjected to chemical sensitization and spectral sensitization in the same manner as Em-9-B to prepare Em-10-A and Em-11-A, respectively, and described in Example 4. Photographic properties in the same way as
The granularity and storability were evaluated.

[0346]

[Table 8]

As is evident from Table 8, the addition of yellow blood salt and potassium hexacyanoruthenate has excellent sensitivity and granularity, and can suppress an increase in fog during storage.

Example 6 (Proof of Aspect VII (2) -1 (Single Layer Coating System)) Using Em-2 used in Example 1, chemical sensitization was carried out in the same manner, and Em-2-B was used again. It was adjusted. Also, Em-2-B
At the end of the chemical sensitization of Example 2, a mercapto compound shown in Table 9 was added instead of using Compound 2, and Em-2-BG was converted to Em-
-2-BN was adjusted.

The photographic properties of the prepared emulsion were evaluated in the same manner as in Example 1. In order to evaluate the storage stability, the unexposed sample was stored at 50 ° C. and a relative humidity of 60% for 2 weeks. This sample and a sample stored at 5 ° C. for 2 weeks were subjected to exposure, development processing and density measurement in the same manner as in Example 1,
The difference (Δfog) between the fog value of the sample stored at 5 ° C. and the fog value stored at 5 ° C. was determined. The results are shown in the table below.

[0350]

[Table 9]

Comparative compound STO-A (JP-A-4-16838)
Compounds described in

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As is evident from Table 9, the fog increase during storage is better when the two compounds of the present invention are used together than when the conventionally known compound 2 (exemplified compound II-1-1) is used. Could be suppressed. At this time, the sensitivity is reduced and R
It was found that deterioration of MS granularity did not occur.

On the other hand, Japanese Patent Laid-Open No.
It has been clarified that the combination use of the exemplified compound II-1-1 described in 838 and the comparative compound STO-A causes a reduction in sensitivity in a high-speed emulsion like the present invention.

Further, Em-6 was used in place of Em-2-B, and only the mercapto compound to be added at the end of post-ripening was changed in the same manner as in the above-mentioned experiment to obtain the same post-ripening as in Em-6-A. Yielded Em-6-AA to Em-6-AH. Similarly, using Em-9, the same post-ripening as in Em-9-A gave E
Em-9-BA to Em-9-BH were obtained by post-ripening in the same manner as m-9-AA to Em-9-AH and Em-9-B. Similarly, using Em-10, Em-10-AA to Em-10-AH were obtained by post-ripening in the same manner as Em-10-A. For these, the above-mentioned Em-2-B and Em-2-B
When the same experiment was performed from G to Em-2-BN,
From m-2-B and Em-2-BG, results similar to those of Em-2-BN were obtained.

Example 7 A silver halide emulsion Em-A to Em-A was prepared in the following manner.
Em-P was prepared from D and Em-F.

(Production method of Em-A) A phthalated low molecular weight gelatin having a phthalation rate of 97% and a molecular weight of 15,000 31.
7g and 42.2L of an aqueous solution containing 31.7g of KBr were added to 35
The mixture was kept at 0 ° C and stirred vigorously. 1583 mL of an aqueous solution containing 316.7 g of AgNO ₃ and 1583 mL of an aqueous solution containing 52.7 g of low molecular weight gelatin having a molecular weight of 15,000 and 221.5 g of KBr were added over 1 minute by the double jet method. Immediately after the addition is completed, 52.8 g of KBr is added,
2485 mL of an aqueous solution containing 398.2 g of AgNO ₃ and 2581 mL of an aqueous solution containing 291.1 g of KBr were added over 2 minutes by a double jet method. Immediately after the addition was completed, 44.8 g of KBr was added. Thereafter, the temperature was raised to 40 ° C. and the product was aged. After ripening, 923 g of phthalated gelatin having a phthalation rate of 97% and a molecular weight of 100,000 and K
After adding 79.2 g of Br, 15947 mL of an aqueous solution containing 5103 g of AgNO ₃ and an aqueous KBr solution were added by a double jet method over 10 minutes while accelerating the flow rate so that the final flow rate was 1.4 times the initial flow rate. At this time, the silver potential was kept at -60 mV with respect to the saturated calomel electrode. After washing with water, gelatin was added to adjust the pH to 5.7, the pAg to 8.8, the weight in terms of silver per kg of the emulsion to 131.8 g, and the gelatin weight to 64.1 g to obtain a seed emulsion. Phthalation rate 97
% Aqueous solution containing 46 g of phthalated gelatin and 1.7 g of KBr was maintained at 75 ° C. and stirred vigorously. After adding 9.9 g of the seed emulsion described above, 0.3 g of modified silicone oil (L7602 manufactured by Nippon Unicar Co., Ltd.) was added.
Was added. After adjusting the pH to 5.5 by adding H ₂ SO ₄ , the final flow rate is 5.1 times the initial flow rate by a double jet method using 67.6 mL of an aqueous solution containing 7.0 g of AgNO ₃ and an aqueous KBr solution. The flow rate was accelerated as described above and added over 6 minutes. At this time, the silver potential was -2 with respect to the saturated calomel electrode.
It was kept at 0 mV. Sodium benzenethiosulfonate,
After adding 2 mg and 2 mg of thiourea dioxide, AgNO
₃ , 328 mL of an aqueous solution containing 105.6 g and an aqueous KBr solution were subjected to a double jet method so that the final flow rate was 3.7, which was the initial flow rate.
The flow rate was accelerated so as to double the amount and added over 56 minutes.
At this time, an AgI fine grain emulsion having a grain size of 0.037 μm was simultaneously added at an accelerated flow rate such that the silver iodide content became 27 mol%, and the silver potential was kept at −50 mV with respect to the saturated calomel electrode. 121.3 mL of an aqueous solution containing 45.6 g of AgNO ₃ and an aqueous KBr solution were added by a double jet method over 22 minutes. At this time, the silver potential was kept at +20 mV with respect to the saturated calomel electrode. After the temperature was raised to 82 ° C. and KBr was added to adjust the silver potential to −80 mV, the above AgI fine grain emulsion was converted to a KI weight of 6.
33 g were added. Immediately after the addition, AgNO ₃ , 6
206.2 mL of an aqueous solution containing 6.4 g was added over 16 minutes. During the initial 5 minutes of the addition, the silver potential was kept at -80 mV with an aqueous KBr solution. After washing with water, add gelatin and add
The pH was adjusted to 5.8, pAg, and 8.7 at 0 ° C. After adding compounds 3 and 4, the temperature was raised to 60 ° C. After addition of sensitizing dyes 4 and 5 in the form of a solid fine dispersion, potassium thiocyanate, chloroauric acid, sodium thiosulfate,
N, N-dimethylselenourea was added for optimal chemical sensitization. At the end of the chemical sensitization, compound 5 and compound 6 were added. Here, optimal chemical sensitization means that the sensitizing dye and each compound are selected from the added amount range of 10 ^-1 to 10 ^-8 mol per mol of silver halide.

[0357]

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[0358]

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[0359]

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[0360]

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[0361]

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[0362]

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(Production method of Em-B) Low molecular weight gelatin
1192 mL of an aqueous solution containing 96 g, KBr, 0.9 g
Maintained at 40 ° C. and stirred vigorously. AgNO_Three, 1.49
37.5 mL of aqueous solution containing 1.0 g of KBr
Transfer 37.5 mL of aqueous solution for 30 seconds by double jet method
Was added. After adding 1.2 g of KBr, the temperature was raised to 75 ° C.
Warm and matured. After aging, the amino group is trimellitic acid
Trimeritase with a molecular weight of 100,000 chemically modified with
35 g of ratine was added and the pH was adjusted to 7. Dioxide
6 mg of thiourea was added. AgNO_Three, Including 29g
116mL of aqueous solution and KBr aqueous solution by double jet method
Accelerate the flow rate so that the final flow rate is three times the initial flow rate
Added. At this time, the silver potential is-with respect to the saturated calomel electrode.
It was kept at 20 mV. AgNO _ThreeContaining water, 110.2 g
Double jet method of 440.6 mL of solution and KBr aqueous solution
Accelerate the flow rate so that the final flow rate is 5.1 times the initial flow rate
And added over 30 minutes. At this time, the preparation of Em-A
The silver iodide content of the AgI fine grain emulsion used in 15.
At the same time, accelerate the flow rate to 8 mol% and add.
The silver potential was kept at 0 mV with respect to the saturated calomel electrode.
AgNO_Three96.5 mL of an aqueous solution containing 24.1 g and K
Br aqueous solution is added for 3 minutes by double jet method
Was. At this time, the silver potential was kept at 0 mV. Ethylthiosul
After adding 26 mg of sodium phonate, the temperature was lowered to 55 ° C.
Warm, add KBr aqueous solution and adjust silver potential to -90mV
did. 7. The above AgI fine grain emulsion is converted to KI weight by 8.
5 g were added. Immediately after the addition is completed, AgNO_Three, 57g
Was added over 5 minutes. this
And KBr such that the potential at the end of the addition becomes +20 mV.
Adjusted with aqueous solution. Washed in almost the same way as Em-A,
I was sensitized.

(Production method of Em-C) 35 μmol / g
1.02 g of phthalated gelatin having a phthalation rate of 97% and a molecular weight of 100,000 containing 1.02 g of methionine, KBr.
1192 mL of an aqueous solution containing 9 g was kept at 35 ° C. and stirred vigorously. AgNO ₃ , aqueous solution containing 4.47 g, 42
42 mL of an aqueous solution containing 3.16 g of mL and KBr was added over 9 seconds by the double jet method. 2.6 KBr
After the addition of g, the mixture was heated to 63 ° C. and aged. After aging, 41.2 g of trimellitated gelatin having a molecular weight of 100,000 used in the preparation of Em-B and NaCl, 18.5 were used.
g was added. After adjusting the pH to 7.2, dimethylamine borane, 8 mg, was added. 203 mL of an aqueous solution containing 26 g of AgNO ₃ and an aqueous KBr solution were added by a double jet method so that the final flow rate was 3.8 times the initial flow rate. At this time, the silver potential was set to -30 with respect to the saturated calomel electrode.
mV. 440.6 mL of an aqueous solution containing 110.2 g of AgNO ₃ and an aqueous KBr solution were added over a period of 24 minutes by a double jet method while accelerating the flow rate so that the final flow rate was 5.1 times the initial flow rate. At this time, the AgI fine grain emulsion used in the preparation of Em-A was adjusted to have a silver iodide content of 2.3 mol.
At the same time, the flow rate was increased to 1%, and the silver potential was kept at -20 mV with respect to the saturated calomel electrode. 1
After adding 10.7 mL of an aqueous solution of potassium thiocyanate N, 153.5 aqueous solution containing 24.1 g of AgNO ₃ .
mL and KBr aqueous solution were added by a double jet method over 2 minutes and 30 seconds. At this time, the silver potential was kept at 10 mV.
An aqueous KBr solution was added to adjust the silver potential to -70 mV. The above-mentioned AgI fine grain emulsion was converted to a KI weight of 6.4.
g was added. Immediately after the addition was completed, 404 mL of an aqueous solution containing 57 g of AgNO ₃ was added over 45 minutes. At this time, KBr is adjusted so that the potential at the end of the addition becomes -30 mV.
Adjusted with aqueous solution. It was washed with water and chemically sensitized almost in the same manner as Em-A.

(Method for Producing Em-D) In the preparation of Em-C, the amount of AgNO ₃ added during nucleation was changed to 2.3 times.
Then, the final aqueous solution 404 containing 57 g of AgNO ₃
KB so that the potential at the end of the addition of mL becomes +90 mV.
It changed so that it may adjust with r aqueous solution. Otherwise Em-
Prepared in substantially the same manner as for C.

(Production method of Em-F) 1200 mL of an aqueous solution containing 0.75 g of low molecular weight gelatin having a molecular weight of 15,000, and 0.9 g of KBr was maintained at 39 ° C., the pH was adjusted to 1.8, and the mixture was vigorously stirred. An aqueous solution containing 1.85 g of AgNO ₃ and an aqueous KBr solution containing 1.5 mol% of KI were added over 16 seconds by a double jet method. At this time, KB
The excess concentration of r was kept constant. The temperature was raised to 54 ° C. and ripened. After completion of ripening, 20 g of phthalated gelatin having a molecular weight of 100,000 and a phthalation rate of 97%, containing 35 μmol of methionine per gram were added. After adjusting the pH to 5.9, 2.9 g of KBr was added. AgNO ₃ , 2
288 mL of an aqueous solution containing 7.4 g and an aqueous KBr solution were added by a double jet method over 53 minutes. At this time, an AgI fine grain emulsion having a grain size of 0.03 μm was simultaneously added so that the silver iodide content became 4.1 mol%, and the silver potential was kept at −60 mV with respect to the saturated calomel electrode.
After adding 2.5 g of KBr, AgNO ₃ , 87.7
The aqueous solution containing g and the aqueous KBr solution were added by a double jet method over a period of 63 minutes while accelerating the flow rate so that the final flow rate was 1.2 times the initial flow rate. At this time, the above AgI fine grain emulsion was simultaneously added at an accelerated flow rate such that the silver iodide content became 10.5 mol%, and the silver potential was kept at -70 mV. 132 m of aqueous solution containing 41.8 g of AgNO ₃
L and KBr aqueous solution were added by a double jet method over 25 minutes. The addition of the aqueous KBr solution was adjusted so that the potential at the end of the addition was +20 mV. The pH was adjusted to 7.3 and 1 mg of thiourea dioxide was added. After KBr was added to adjust the silver potential to -70 mV, 5.73 g of the above-mentioned AgI fine grain emulsion was added in terms of KI weight. Immediately after the addition is completed, an aqueous solution 60 containing 66.4 g of AgNO _{3 is} added.
9 mL was added over 10 minutes. During the initial 6 minutes of the addition, the silver potential was kept at -70 mV with an aqueous KBr solution. After washing with water, gelatin was added, pH 6.5 at 40 ° C., pAg 8.
Adjusted to 2.

After adding Compounds 3 and 4, the temperature was raised to 56 ° C. Sensitizing dyes 6, 7, 8 were added in the form of a fine solid dispersion. Thereafter, potassium thiocyanate, chloroauric acid, sodium thiosulfate, N, N
-Dimethylselenourea was added and ripened for optimal chemical sensitization. Compounds 5 and 6 were added at the end of chemical sensitization.

[0368]

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[0370]

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(Production method of Em-G) 0.70 g of low molecular weight gelatin having a molecular weight of 15,000, KBr, 0.9 g, KI,
An aqueous solution (1200 mL) containing 0.175 g and the modified silicone oil (0.2 g) used in the preparation of Em-A was kept at 33 ° C., the pH was adjusted to 1.8, and the mixture was vigorously stirred. AgN
An aqueous solution containing 1.8 g of O ₃ and an aqueous KBr solution containing 3.2 mol% of KI were added by a double jet method over 9 seconds. At this time, the excess concentration of KBr was kept constant. 6
The temperature was raised to 2 ° C. and ripened. After ripening, 35μ / g
27.8 g of trimellitated gelatin containing mol methionine and chemically modifying amino groups having a molecular weight of 100,000 with trimellitic acid was added. After adjusting the pH to 6.3, 2.9 g of KBr was added. AgNO ₃ , 2
270 mL of an aqueous solution containing 7.58 g and an aqueous KBr solution were added by a double jet method over 37 minutes. At this time, an aqueous solution of low molecular weight gelatin having a molecular weight of 15,000 and AgNO ₃
A particle size of 0.00 prepared by mixing the aqueous solution and the KI aqueous solution immediately before the addition in another chamber having a magnetic coupling induction type stirrer described in JP-A-10-43570.
An 8 μm AgI fine grain emulsion having a silver iodide content of 4.1 m
ol%, and the silver potential was kept at -60 mV with respect to the saturated calomel electrode. KBr, 2.
After the addition of 6 g, an aqueous solution containing 87.7 g of AgNO ₃ and an aqueous KBr solution were added by a double jet method at a flow rate acceleration of 3.1 times the initial flow rate over a period of 49 minutes. At this time, the AgI fine grain emulsion prepared by mixing immediately before the above-mentioned addition was added with a silver iodide content of 7.9 mol%.
At the same time so that the silver potential is -70 m
Kept at V. After adding 1 mg of thiourea dioxide, A
Gno _3, an aqueous solution containing 41.8 g 132 mL of KBr
The aqueous solution was added by the double jet method over 20 minutes.
The addition of the aqueous KBr solution was adjusted so that the potential at the end of the addition was +20 mV. After the temperature was raised to 78 ° C. and the pH was adjusted to 9.1, KBr was added to adjust the potential to −60 mV. The AgI fine grain emulsion used in the preparation of Em-A was KI
5.73 g in terms of weight was added. Immediately after the addition,
321 mL of an aqueous solution containing 66.4 g of gNO ₃ was added over 4 minutes. The silver potential was maintained at −60 mV with an aqueous KBr solution for 2 minutes at the beginning of the addition. It was washed with water and chemically sensitized almost in the same manner as Em-E.

(Production method of Em-H) 17.8 g of ion-exchanged gelatin having a molecular weight of 100,000, KBr, 6.2
g, KI and an aqueous solution containing 0.46 g were maintained at 45 ° C. and vigorously stirred. An aqueous solution containing 11.85 g of AgNO ₃ and an aqueous solution containing 3.8 g of KBr were mixed with an aqueous solution containing 45 g by a double jet method.
Added over seconds. After the temperature was raised to 63 ° C., 24.1 g of ion-exchanged gelatin having a molecular weight of 100,000 was added and ripened. After aging, an aqueous solution containing 133.4 g of AgNO ₃ and an aqueous KBr solution were added over 20 minutes by a double jet method so that the final flow rate was 2.6 times the initial flow rate. At this time, the silver potential is increased by +4 with respect to the saturated calomel electrode.
It was kept at 0 mV. 10 minutes after the start of addition, K ₂ IrCl ₆
Was added. After adding 7 g of NaCl, A
An aqueous solution containing 45.6 g of gNO ₃ and an aqueous KBr solution were added by a double jet method over 12 minutes. At this time, the silver potential was kept at +90 mV. Further, 100 mL of an aqueous solution containing 29 mg of yellow blood salt was added over 6 minutes from the start of the addition. After 14.4 g of KBr was added, 6.3 g of the AgI fine grain emulsion used in the preparation of Em-A was added in terms of KI weight. Immediately after the addition was completed, an aqueous solution containing 42.7 g of AgNO ₃ and an aqueous KBr solution were added over 11 minutes by a double jet method. At this time, the silver potential was kept at +90 mV. It was washed with water and chemically sensitized almost in the same manner as Em-E.

(Preparation method of Em-I) Em-H was prepared in substantially the same manner as in Em-H except that the temperature during nucleation was changed to 35 ° C.

(Production method of Em-J) 1200 mL of an aqueous solution containing 0.75 g of low molecular weight gelatin having a molecular weight of 15,000, KBr and 0.9 g was maintained at 39 ° C., the pH was adjusted to 1.8, and the mixture was vigorously stirred. An aqueous solution containing 0.45 g of AgNO ₃ and an aqueous KBr solution containing 1.5 mol% of KI were added by a double jet method over 16 seconds. At this time, KB
The excess concentration of r was kept constant. The temperature was raised to 54 ° C. and ripened. After completion of ripening, 20 g of phthalated gelatin having a molecular weight of 100,000 and a phthalation rate of 97%, containing 35 μmol of methionine per gram were added. After adjusting the pH to 5.9, 2.9 g of KBr was added. Thiourea dioxide, 3 mg, was added, and 3,5-disulfocateco-
After adding 1.5 g of rudisodium salt, AgNO ₃ ,
288 mL of an aqueous solution containing 28.8 g and an aqueous KBr solution were added over 53 minutes by a double jet method. At this time, an AgI fine grain emulsion having a grain size of 0.03 μm was simultaneously added so that the silver iodide content became 4.1 mol%, and the silver potential was kept at −60 mV with respect to the saturated calomel electrode. After adding 2.5 g of KBr, AgNO ₃ , 8
An aqueous solution containing 7.7 g and a KBr aqueous solution were added over 63 minutes by a double jet method while accelerating the flow rate so that the final flow rate was 1.2 times the initial flow rate. At this time, the above AgI
The fine grain emulsion was added at the same time with the flow rate accelerated so that the silver iodide content became 10.5 mol%, and the silver potential was -70.
mV. Aqueous solution 1 containing 41.8 g of AgNO ₃
32 mL and an aqueous KBr solution were added over 25 minutes by the double jet method. The addition of the aqueous KBr solution was adjusted so that the potential at the end of the addition was +20 mV. After adding 2 mg of sodium benzenethiosulfonate, KBr was added to adjust the silver potential to -70 mV, and then the above AgI was added.
5.73 g of the fine grain emulsion was added in terms of KI weight. Immediately after the addition, an aqueous solution 6 containing 66.4 g of AgNO ₃
09 mL was added over 10 minutes. During the initial 6 minutes of the addition, the silver potential was kept at -70 mV with an aqueous KBr solution. After washing with water, gelatin was added and pH 6.5 at 40 ° C., pAg,
Adjusted to 8.2.

The temperature was raised to 56 ° C. Sensitizing dyes 9, 10, 1
In the form of a fine solid dispersion of 5.3 × 10 ^-4 mol, 2.1 × 10 ^-4 mol, ^1.1 mol per mol of silver halide, respectively.
0 × 10 ^-4 mol was added. Thereafter, 3.3 × 10 ⁻³ mol of potassium thiocyanate, 2.9 × 10 ⁻⁶ mol of chloroauric acid, 3.4 × of sodium thiosulfate per mol of silver halide.
10 ^-6 mol, N, N-dimethylselenourea 3.1 × 1
0 ^-6 mol was added and aged optimum chemical sensitization. At the end of chemical sensitization, 2.6 × 10 ^-4 mol and 6.0 × 10 ^-6 mol of Compound 7 and Compound 8 were added per mol of silver halide, respectively.

Sensitizing Dye 9

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Sensitizing dye 10

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Sensitizing Dye 11

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Compound 7

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Compound 8

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(Production method of Em-K) 1200 mL of an aqueous solution containing 4.9 g of low molecular weight gelatin having a molecular weight of 15,000 and 5.3 g of KBr was kept at 60 ° C. and stirred vigorously. AgN
5. 27 mL of an aqueous solution containing 8.75 g of O ₃ and KBr, 6.
36 mL of an aqueous solution containing 45 g was added by the double jet method over 1 minute. After the temperature was raised to 75 ° C., AgNO ₃ ,
21 mL of an aqueous solution containing 6.9 g was added over 2 minutes. NH ₄ NO ₃ , 26 g, 1N, NaOH, 56 mL were sequentially added, followed by aging. After ripening, the pH is 4.8
Was prepared. Aqueous solution 438 containing 141 g of AgNO ₃
mL and 458 mL of an aqueous solution containing 102.6 g of KBr were added by a double jet method so that the final flow rate was four times the initial flow rate. After cooling to 55 ° C., AgNO ₃ , 7.1
g and an aqueous solution containing 6.46 g of KI were added over 5 minutes by the double jet method. KBr
Was added, and 4 mg of sodium benzenethiosulfonate and 0.05 mg of K ₂ IrCl ₆ were added.
177 mL of an aqueous solution containing 57.2 g of AgNO ₃ and KB
223 mL of an aqueous solution containing 40.2 g of r was added by the double jet method over 8 minutes. It was washed with water and chemically sensitized almost in the same manner as Em-J.

(Preparation method of Em-L) Except that the temperature during nucleation was changed to 40 ° C. in the preparation of Em-K, it was prepared in substantially the same manner.

(Preparation of Em-M, N, O) Prepared in substantially the same manner as Em-H or Em-I. However, the chemical sensitization was performed in substantially the same manner as in Em-J.

(Production method of Em-P)
The emulsion was prepared in the same manner as in the emulsion of the layer of Example No. 237450, which gives a layering effect to the red-sensitive layer.

Table 10 summarizes the characteristic values of the silver halide emulsions Em-A to Em-O.

[0386]

[Table 10]

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

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

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

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

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

3-2) Coating of Magnetic Recording Layer Cobalt-γ-iron oxide coated with 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) (specific surface area 43 m ²⁾ / G, major axis 0.14 μm, single axis 0.03 μm, saturation magnetization 89 emu
/ G, Fe ^{+ 2} / Fe ⁺³ = 6/94, surface treated with silicon oxide aluminum oxide at 2% by weight of iron oxide) 0.06
g / m ² to diacetyl cellulose 1.2 g / m ² (dispersion of iron oxide was carried out with an open kneader and a sand mill),
_{C 2 H 5 C (CH 2} OCONH-C 6 H 3 as a curing agent (C
0.3 g / m ² of H ₃ ) NCO) ₃ was applied with a bar coater using acetone, methyl ethyl ketone and cyclohexanone as a solvent to obtain a magnetic recording layer having a thickness of 1.2 μm. 10 mg each of an abrasive aluminum oxide (0.15 μm) coated with silica particles (0.3 μm) and 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) as a matting agent / M
² was added. Drying was carried out at 115 ° C. for 6 minutes (all rollers and conveying devices in the drying zone were 115 ° C.).
° C). X- write saturation magnetization moment 4.2 emu / g to about 0.1, and the magnetic recording layer color density increment of D ^B of the magnetic recording layer in the (blue filter), the coercive force 7.3 ×
10 ⁴ A / m and the squareness ratio were 65%.

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

4) Coating of Photosensitive Layer Next, on the side opposite to the back layer obtained above, layers having the following compositions were applied in a multi-layered manner to prepare a color negative film.

(Composition of photosensitive layer) The main materials used for each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow Coupler H: Gelatin hardener ExS: Sensitizing dye (Specific compounds are described below, numbers are added after symbols, and chemical formulas are listed after the numbers.) The number corresponding to each component is g / g. The coating amount is shown in m ² unit. For silver halide, the coating amount is shown in terms of silver. However, for the sensitizing dye, the coating amount is shown in mol units with respect to 1 mol of silver halide in the same layer.

First layer (first antihalation layer) Black colloidal silver silver 0.155 (silver iodobromide emulsion) silver 0.01 gelatin 0.87 ExC-1 0.002 ExC-3 0.002 ExC-9 0.002 Cpd-2 0.001 HBS-1 0.004 HBS-2 0.002.

Second Layer (Second Antihalation Layer) Black Colloidal Silver Silver 0.066 Gelatin 0.407 ExM-1 0.050 ExF-1 2.0 × 10 ^-3 HBS-1 0.074 Solid Disperse Dye ExF -2 0.015 solid disperse dye ExF-3 0.020 solid disperse dye ExF-9 0.020.

Third layer (intermediate layer) 0.07 μm AgBrI (2) 0.020 ExC-2 0.022 polyethyl acrylate latex 0.085 gelatin 0.294.

Fourth layer (low-sensitivity red-sensitive emulsion layer) Em-M silver 0.065 Em-N silver 0.097 Em-O silver 0.162 ExC-1 0.109 ExC-3 0.022 ExC-4 0.072 ExC-5 0.011 ExC-6 0.003 ExC-9 0.022 Cpd-2 0.025 Cpd-4 0.025 HBS-1 0.17 Gelatin 0.80.

Fifth Layer (Medium Speed Red Sensitive Emulsion Layer) Em-K silver 0.35 Em-L silver 0.47 ExC-1 0.14 ExC-2 0.026 ExC-3 0.010 ExC-40 .12 ExC-5 0.016 ExC-6 0.007 ExC-9 0.010 Cpd-2 0.036 Cpd-4 0.028 HBS-1 0.16 Gelatin 1.18.

Sixth layer (high-sensitivity red-sensitive emulsion layer) (Emulsions prepared in Examples 1 to 6) Silver 1.47 ExC-1 0.18 ExC-3 0.035 ExC-6 0.029 ExC-7 0.010 ExC-9 0.035 ExY-5 0.008 Cpd-2 0.046 Cpd-4 0.077 HBS-1 0.25 HBS-2 0.12 Gelatin 2.12.

Seventh layer (intermediate layer) Cpd-1 0.089 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl acrylate latex 0.83 Gelatin 0.84.

Eighth Layer (Layer Which Gives Layered Effect to Red Sensitive Layer) Em-P Silver 0.560 ExS-6 1.7 × 10 ^-4 ExS-10 4.6 × 10 ^-4 Cpd-4 0.030 ExC-10 0.021 ExM-2 0.096 HBS-1 0.085 HBS-3 0.003 Gelatin 0.58.

Ninth layer (low-sensitivity green-sensitive emulsion layer) Em-G silver 0.44 Em-H silver 0.29 Em-I silver 0.29 ExM-2 0.36 ExM-3 0.045 HBS-1 0.14 HBS-3 0.01 HBS-4 0.27 HBS compound-20 0.14 Cpd-5 0.01 Gelatin 1.39.

Tenth Layer (Medium Speed Green Sensitive Emulsion Layer) Em-F Silver 0.28 Em-G Silver 0.17 ExC-6 0.0045 ExC-10 0.0045 ExM-2 0.031 ExM-30 0.029 ExY-1 0.006 ExM-4 0.028 HBS-1 0.032 HBS-3 2.1 × 10 ^-3 HBS compound-20 0.032 Cpd-5 0.004 Gelatin 0.44.

Eleventh Layer (High Sensitive Green Sensitive Emulsion Layer) Em-J Silver 0.99 ExC-6 0.002 ExC-10 0.002 ExM-1 0.016 ExM-3 0.036 ExM-40 020 ExM-5 0.004 ExY-5 0.003 ExM-2 0.013 Cpd-3 0.004 Cpd-4 0.007 Cpd-5 0.01 HBS-1 0.09 HBS compound-20 0.09 Polyethyl acrylate latex 0.099 gelatin 1.11.

12th Layer (Yellow Filter Layer) Yellow Colloidal Silver Silver 0.047 Cpd-1 0.16 Solid Disperse Dye ExF-5 0.010 Solid Disperse Dye ExF-6 0.010 Solid Disperse Dye ExF-8 020 Oil soluble dye ExF-7 0.010 HBS-1 0.082 Gelatin 1.057.

Thirteenth layer (low-sensitivity blue-sensitive emulsion layer) Em-B silver 0.15 Em-C silver 0.15 Em-D silver 0.15 ExC-1 0.041 ExC-8 0.012 ExY-1 0.035 ExY-2 0.47 ExY-3 0.10 ExY-4 0.005 ExY-7 0.30 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-1 0.24 Gelatin 1.41.

Fourteenth layer (high-sensitivity blue-sensitive emulsion layer) Em-A Silver 0.75 ExC-1 0.013 ExY-2 0.31 ExY-3 0.05 ExY-6 0.062 Cpd-2 075 Cpd-3 1.0 × 10 ^-3 HBS-1 0.10 Gelatin 0.91.

15th layer (first protective layer) 0.07 μm AgBrI (2) silver 0.30 UV-1 0.21 UV-2 0.13 UV-3 0.20 UV-4 0.025 F- 18 0.009 HBS-1 0.12 HBS-4 5.0 × 10 ^-2 gelatin 2.3.

Sixteenth layer (second protective layer) H-1 0.40 B-1 (1.7 μm in diameter) 5.0 × 10 ^-2 B-2 (1.7 μm in diameter) 0.15 B-30 .05 S-1 0.20 synthetic mica 0.25 pullulan 0.25 gelatin 0.75.

Further, in order to improve the storability, processability, pressure resistance, fungicide / antibacterial properties, antistatic properties and coatability of each layer, W-1 to W-5, B-4 to B -6, F
-1 to F-17, and lead salts, platinum salts, iridium salts, and rhodium salts.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 of the first layer was dispersed by the following method. That is, water 2
1.7 mL and 5 mL of 5% aqueous solution of sodium p-octylphenoxyethoxyethoxyethanesulfonic acid 3 mL and 5 mL
A 0.5% aqueous solution of p-octylphenoxypolyoxyethylene ether (degree of polymerization 10) was placed in a 700 mL pot mill, and 5.0 g of the dye ExF-2 and 500 mL of zirconium oxide beads (1 mm in diameter) were added. Was dispersed for 2 hours. For this dispersion, a BO type vibration ball mill manufactured by Chuo Koki was used. After dispersing, take out the contents,
It was added to 8 g of a 12.5% aqueous gelatin solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the fine dye particles was 0.44 μm.

Similarly, ExF-3, ExF-4, E
A solid dispersion of xF-6, ExF-8 and ExF-9 was obtained. The average particle size of the fine dye particles is 0.24 μm, respectively.
0.28 μm, 0.45 μm, 0.52 μm and 0.4
It was 9 μm. ExF-5 is disclosed in European Patent No. 549,48.
9A, Microprec described in Example 1
The mixture was dispersed by a dispersion method. The average particle size was 0.06 μm.

The compounds used for forming each layer are shown below.

[0416]

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[0417]

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[0418]

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[0419]

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[0420]

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[0421]

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[0422]

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[0423]

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[0424]

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[0425]

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[0426]

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[0427]

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[0428]

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[0429]

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[0430]

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[0431]

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[0432]

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(Preparation of Samples 101 to 107) Sample 101
To 106 are emulsions Em-2-A, Em-2-B, Em-6-A and Em prepared in Examples 1 to 5, respectively, in the sixth layer.
-9-A, Em-9-B, and Em-10-A were applied and produced. Sample 107 was coated with an emulsion Em-10-B prepared by increasing the amount of calcium nitrate added during the preparation of the emulsion Em-10-A. Ca of samples 101 to 107
When the amount of ions was measured, only 107 g of gelatin was 1 g.
It was found to be more than 8.0 × 10 ^-2 g.

These samples were passed through a continuous wedge with a gelatin filter SC-39 manufactured by FUJIFILM Corporation.
/ 100 seconds. The development was performed as follows using an automatic developing machine FP-360B manufactured by Fuji Photo Film Co., Ltd.
The remodeling was performed so that the overflow solution of the bleaching bath was not discharged to the post-bath but was entirely discharged to the waste liquid tank. This FP-36
OB incorporates the evaporation correction means described in Hatsumei Kyokai Disclosure Technique No. 94-4992.

The processing steps and the composition of the processing solution are shown below.

(Processing step) Process Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 37.8 ° C 20 mL 11.5L Bleaching 50 seconds 38.0 ° C 5 mL 5L Fixing (1) 50 seconds 38.0 ° C-5L Fixing ( 2) 50 seconds 38.0 ℃ 8 mL 5L water washing 30 seconds 38.0 ℃ 17 mL 3L stable (1) 20 seconds 38.0 ℃-3L stable (2) 20 seconds 38.0 ℃ 15 mL 3L drying 1 minute 30 seconds 60.0 ℃ * replenishment amount Is per 35 m of photosensitive material and 1.1 m in width (equivalent to 24 Ex. 1 line)

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

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

The composition of the processing solution is shown below.

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

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

(Fixing (1) tank liquid) A 5/95 (volume ratio) mixture of the above bleaching tank liquid and the following fixing tank liquid (pH:
6.8).

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

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

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

The concentration of the treated sample was measured with a red filter. The sensitivity was read by the relative value of the reciprocal of the exposure required to give a density of fog plus 0.2. In addition, in order to evaluate the time-dependent change (preservability) of the exposed sample, 50
C. and 60% relative humidity for 4 weeks. As a result, the same results as those of Examples 1 to 5 were obtained for the samples 101 to 106. In addition, it was found that normal treatment could not be performed on sample 107 due to precipitation of Ca salt.

Example 8 (Evidence of Aspect VII (2) -2 (Multilayer Coating System)) The emulsion of the sixth layer of Sample 102 used in Example 7 was prepared using the Em-2-BG prepared in Example 6 Samples 221 to 223 were prepared in the same manner as in Example 7, except that Em-2-BI was used. Each sample was exposed and developed in the same manner as in Example 7. The concentration of the treated sample was measured with a red filter. The sensitivity was read as a relative value of fog density plus 0.2.

The time-dependent change (preservation) of the exposed sample
The sample was stored at 50 ° C. and a relative humidity of 60% for 3 weeks in order to evaluate.

[0449]

[Table 11]

As is clear from Table 11, the increase in fog during storage was better when the two compounds of the present invention were used together than when the conventionally known compound 2 (exemplified compound II-1-1) was used. Could be suppressed. At this time, the sensitivity decreases, and
It was found that deterioration of RMS granularity did not occur. On the other hand, the conventionally known combination use of the exemplified compound II-1-1 described in JP-A-4-16838 and the comparative compound STO-A causes a reduction in sensitivity in a high-sensitivity emulsion as in the present invention. It became clear.

Further, the sixth sample of Sample 103 used in Example 7 was used.
The emulsions of the layers were the Em-6-AA to Em prepared in Example 6.
Samples 231 to 233 were prepared in the same manner as in Example 7, except that -6-AC was used.

[0452] The sixth sample 104 used in Example 7 was used.
The emulsions of the layers were em-9-AA to em-9 prepared in Example 6.
Samples 241 to 243 were prepared in the same manner as in Example 7, except that -9-AC was used.

[0453] The sixth sample of Sample 105 used in Example 7 was used.
The emulsions of the layers were the Em-9-BA to Em prepared in Example 6.
Samples 251 to 253 were prepared in the same manner as in Example 7, except that the sample was changed to -9-BC.

Also, the sixth sample of Sample 106 used in Example 7 was used.
The emulsions of the layers were Em-10-AA to E-E prepared in Example 6.
Samples 261 to 261 were prepared in the same manner as in Example 7, except that m-10-AC was used.

[0455] These samples were used as samples 102, 221-222.
When an experiment similar to that of Example 3 was performed, the same result as the above result was obtained.

Example 9 (Proof of Aspect VII (1)) The compounds shown in Table 12 were added to the seventh layer of Sample 102 used in Example 7 to prepare each sample.
Further, two 2 mm square perforations are provided at a distance of 5.8 mm at a position 0.7 mm from the width direction on one side in the length direction of the photosensitive material. 32 sets of these two sets
mm is provided at intervals of mm.
No. 6,887. 1 to FIG. 7 was housed in a plastic film cartridge.

Using a magnetic recording head with a head gap of 5 μm, a number of turns of 50, and a Permalloy (registered trademark) material, a digital recording medium having a recording wavelength of 50 μm and a feed speed of 100 mm / sec was applied to the sample from the side of the magnetic recording layer coating surface. A saturation recording was performed.

The sample described above was prepared at a color temperature of 4800K for 5 days.
A cine-type automatic developing machine was used to perform the following development processing, and a photographic material of 2 m ² per day was further subjected to a running processing for 5 days. It was stored again in the original plastic film cartridge.

[0459] (process) step processing time processing temperature Replenishment rate Tank capacity color developing 3 min 05 sec 38.0 ℃ 390 mL / m ² 17L Bleaching 50 sec 38.0 ℃ 130 mL / m ² 5L fixing (1) 50 sec 38.0 ° C. - 5L fixing (2) 50 seconds 38.0 ℃ 260 mL / m ² 5L washing 30 seconds 38.0 ℃ 500 mL / m ² 3.5L stable (1) 20 sec 38.0 ° C. - 3L stability (2) 20 seconds 38.0 ° C. 500 mL / m ² 3L drying 90 seconds 60 ℃.

The stabilizing solution and the fixing solution were of a countercurrent type from (2) to (1), and the overflow of the washing water was all introduced into the fixing bath. The amount of the color developer brought into the bleaching process,
Amount carried to the fixing step of the bleaching solution, bring volume to the washing step of the fixer photosensitive material 35mm wide 1 m ² per each 65 mL, 50 mL, 50 mL, was 50 mL. The crossover time is 6 seconds in each case, and this time is included in the processing time of the previous step.

The composition of the processing solution is shown below. (Color developing solution) Tank solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 3.0 3.0 Tiron 0.3 0.3 Sodium sulfite 3.9 5.3 Potassium carbonate 39.0 39.0 Disodium- N, N-bis (2-sulfonatoethyl) hydroxylamine 10.0 13.0 Potassium bromide 1.25 0.4 Potassium iodide 1.3 mg-4-Hydroxy-6-methyl-1,3,3a, 7 -Tetrazaindene 0.05-2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 4.5 6.5 Add water and add 1.0 L 1.0 L pH ( (Adjusted with potassium hydroxide and sulfuric acid) 10.05 10.18.

(Bleaching solution) Tank solution (g) Replenisher (g) 1,3-propanediaminetetraacetic acid iron (III) ammonium salt 113.0 170.0 ammonium bromide 70.0 105.0 ammonium nitrate 14.0 21.0 Succinic acid 34.0 51.0 Maleic acid 28.0 42.0 Water was added to 1000 mL 1000 mL pH (adjusted with aqueous ammonia and nitric acid) 4.6 4.0.

(Fixing (1) tank liquid) A 5/95 (volume ratio) mixture of the above bleaching tank liquid and the following fixing tank liquid (pH
6.8).

(Fixer (2)) Tank solution (g) Replenisher (g) Ammonium thiosulfate aqueous solution (750 g / L) 240.0 mL 720.0 mL Ammonium methanethiosulfonate 5.0 15.0 Ammonium methanesulfinate 10 0.0 30.0 Ethylenediaminetetraacetic acid 13.0 39.0 Imidazole 7.0 21.0 Add water 1000 mL 1000 mL pH (adjusted with aqueous ammonia and acetic acid) 7.4 7.5.

(Washing water) Common to tank liquid and replenisher tap water is H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co.) and OH type strongly basic anion exchange resin (Amberlite IRA) -4
The mixture was passed through a mixed-bed column filled with (00) to reduce the calcium and magnesium ion concentrations to 3 mg / L or less, and then 20 mg / L of sodium diisocyanurate and 150 mg / L of sodium sulfate were added. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizing solution) Common to tank solution and replenisher 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 g 1,2,4-triazole 1.3 g Polyoxyethylene-p -Monononylphenyl ether 0.2 g (average degree of polymerization 10) Ethylenediaminetetraacetic acid disodium salt 0.05 g Sodium p-toluenesulfinate 0.03 g 1,2-Benzoisothiazolin-3-one. Sodium 0.10 g Gentamicin 0.01 g Water was added to adjust 1 L pH (adjusted with aqueous ammonia and nitric acid) 8.5.

The following preservation evaluation experiment was performed without performing the running process in order to evaluate the preservability. The unexposed sample was stored at 50% relative humidity and 50 ° C. for 4 weeks. The same sample stored at 5 ° C. for 4 weeks was subjected to a color temperature of 4800.
Exposure for sensitometry was given for 1/100 second through a continuous wedge at ° K to perform the color development described above.
Next, the concentration was measured, and the difference between the fog value of the sample stored at 50 ° C. and the fog value of the sample stored at 5 ° C. (Δfog1)
I asked.

Further, a sample stored at 50 ° C. and a relative humidity of 80% for 4 weeks and a sample stored at 5 ° C. for 4 weeks were treated in the same manner to determine a difference in fog value (Δfog2). Table 2 shows the results.

The photosensitive material that had been subjected to the above-mentioned running processing was evaluated for the minimum cyan density change before and after the running of the developing processing by the following method.

<Measurement of Minimum Density of Cyan> Regarding the gradation measurement of the light-sensitive material, the minimum density change of cyan was read from the characteristic curves at the beginning and after the running, and the density difference was obtained.

(ΔDmin) = (Minimum density of cyan after running) − (Minimum density of cyan at the beginning of running) The larger the plus value, the higher the density.

The results are shown in Table 12 together with the results of the storage stability.

[0473]

[Table 12]

From Table 12 above, the following can be seen regarding the storage stability. It is found that the use of the compound represented by the general formula (I-1) of the present invention can suppress storage fog over time (samples 301 and 308 to 319).

The effect was improved by the conventionally known effect of improving the storage stability of Comparative Compounds A, B, C, D and E (Samples 302 to 302).
306). Especially under high humidity conditions
Comparative compounds A, B, C, D, and E could not suppress fog during storage, whereas the compounds of the present invention showed a remarkable storage stability improving effect.

Incidentally, the viscosity of the gelatin solution of the seventh layer before coating was applied.
Is a compound of the present invention I-1-1, I-1-3, I-2-2, I-2-3, I-2-5
It was examined whether it changed with the addition of
Did not. On the other hand, Na_TwoPdCl_Four(See JP-A-5-333480.
Described compound) in 6 × 10 ^-6mol / m^TwoThe amount corresponding to the seventh
When added to the coating solution for the layer, the viscosity increases sharply,
And a uniform coating solution can be adjusted.
I didn't come. This Na _TwoPdCl_FourMeans that the added amount is 2 × 10^-6mol /
m^TwoCould be applied, but the effect of suppressing storage fog
Fruit is small (sample 307), viscosity rise problem and storage stability
The improvement cannot be compatible.

The structures of Comparative Compounds A to E in Table 12 (compounds described in JP-A-8-234341) are shown below.

[0478]

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[0479]

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From Table 12, the following can be seen with respect to the minimum cyan density change before and after the running of the development processing.

It can be seen that when the compound of the present invention was used, there was no increase in the minimum cyan density after running in the development processing.
(Samples 301, 308-319).

On the other hand, when the conventionally known comparative compounds A to E were used, the cyan minimum density after running increased. (Samples 302-306).

Further, similarly to the above experiment, the compounds shown in Table 12 were added to the seventh layer of Samples 103 to 106 used in Example 7 to prepare each sample, and the same storage stability and running experiment as in the above experiment were performed. went. As a result, a result similar to the above result was obtained.

Example 10 A 135-format sample was prepared using the cellulose triacetate film support in place of the PEN support in the sample of Example 7, and the practical evaluation was performed in the same manner as in Example 7. . As a result, a result similar to that of Example 7 was obtained.

Example 11 In Examples 7 and 8, the amount of thiocyanate ion added to the light-sensitive material was 2.3 × 10 ⁻³ mol per mol of silver. In this example, a sample (sample 401) was prepared in which the addition amount of thiocyanate ion in all emulsion layers was 1.2 times to be 2.53 × 10 ⁻³ mol / mol silver. Similarly, a sample (sample 402) was prepared in which the amount of addition was 0.75 times to 1.73 × 10 ⁻³ mol / mol silver.

These samples were evaluated in the same manner as in Example 8 together with the sample 2222 prepared in Example 8. Table 1 shows the results
3 is shown.

[0487]

[Table 13]

From Table 13, it is found that Sample 222 in which the amount of thiocyanate ion added was 2.3 × 10 ⁻³ mol per mol of silver was:
It can be seen that the fog increase during storage is smaller than that of the sample 401 having an added amount of 2.53 × 10 ⁻³ mol / mol silver. Also, 1.
Sample 402 at 73 × 10 ⁻³ mol / mole silver was prepared as sample 222
It was found that the storage stability was even better.

Example 12 In Example 7, instead of using HBS-1 to HBS-4,
A sample was prepared and processed in the same manner as in Example 7 using the following compound, and as a result, a result similar to that in Example 7 was obtained.

[0490]

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[0490]

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[0492]

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[0493]

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[0494]

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[0495]

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[0496]

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[0497]

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[0498]

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[0499]

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[0500]

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[0501]

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[0502]

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[0503]

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[0504]

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[0505]

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[0506]

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[0507]

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Example 13 Samples similar to Samples 301, 307 to 313 of Example 9 were prepared in the same manner except that the undercoated support was changed to the following.

1) First Layer and Undercoat Layer For a polyethylene naphthalate support having a thickness of 90 μm, a treatment atmosphere pressure of 0.2 Torr was applied to both surfaces of each support.
r, partial pressure of H ₂ O in atmosphere gas 75%, discharge frequency 30
The glow discharge treatment was performed at a frequency of 2500 kHz, an output of 2500 W, and a treatment intensity of 0.5 kV · A · min / m ² . A coating solution having the following composition was applied as a first layer on the support at a coating amount of 5 mL / m ² using a bar coating method described in Japanese Patent Publication No. 58-4589.

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

Further, after the first layer was applied, it was wound around a stainless steel core having a diameter of 20 cm, heated at 110 ° C. (Tg of the PEN support: 119 ° C.) for 48 hours, subjected to heat history, and annealed. Thereafter, a coating solution having the following composition was applied to the side opposite to the first layer side as an undercoat layer for the emulsion at a coating amount of 10 mL / m ² by using a bar coating method.

Gelatin 1.01 part by weight Salicylic acid 0.30 part by weight Resorcin 0.40 part by weight Poly (degree of polymerization 10) oxyethylene nonylphenyl ether 0.11 part by weight Water 3.53 parts by weight Methanol 84.57 parts by weight n -Propanol 10.08 parts by weight.

Further, a second layer and a third layer, which will be described later, are sequentially applied on the first layer, and finally, a color negative photosensitive material having a composition, which will be described later, is overlaid on the opposite side to form a silver halide emulsion. A transparent magnetic recording medium with a layer was produced.

2) Second layer (transparent magnetic recording layer) Dispersion of magnetic material Co-coated 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:
77.1 emu / g, σr: 37.4 emu / g) 11
Then, 00 parts by weight, 220 parts by weight of water and 165 parts by weight of a silane coupling agent [3- (poly (degree of polymerization: 10) oxyethynyl) oxypropyl trimethoxysilane] were added and kneaded well with an open kneader for 3 hours. The coarsely dispersed viscous liquid was dried at 70 ° C. for 24 hours to remove water, and then heat-treated at 110 ° C. for 1 hour to produce surface-treated magnetic particles.

[0515] Further, the mixture was kneaded again in an open kneader for 4 hours according to the following formulation.

The above-mentioned surface-treated magnetic particles 855 g, diacetyl cellulose 25.3 g, methyl ethyl ketone 136.3 g, cyclohexanone 136.3 g.

[0517] Furthermore, a sand mill (1/1 /
(4G sand mill) at 2,000 rpm for 4 hours. As the medium, glass beads having a diameter of 1 mm were used.

The above kneading liquid 45 g diacetyl cellulose 23.7 g methyl ethyl ketone 127.7 g cyclohexanone 127.7 g Further, a magnetic substance-containing intermediate liquid was prepared according to the following formulation.

Preparation of Intermediate Liquid Containing Magnetic Substance 674 g of the above magnetic substance fine dispersion liquid 24280 g (solid content: 4.34%, solvent: methyl ethyl ketone / cyclohexanone = 1/1) cyclohexanone 46 g After mixing these, The mixture was stirred with a disper to prepare a "magnetic substance-containing intermediate liquid".

An α-alumina abrasive dispersion of the present invention was prepared according to the following formulation. [A] Sumicorundum AA-1.5 (average primary particle diameter 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 (Shinetsu Silico 0.48 g Diacetyl cellulose solution 227.52 g (solid content 4.5%, solvent: methyl ethyl ketone / cyclohexanone = 1/1) Using a ceramic-coated sand mill (1 / 4G sand mill) according to the above formulation. 80
Finely dispersed at 0 rpm for 4 hours. As the media, zirconia beads having a diameter of 1 mm were used.

[B] Colloidal silica particle dispersion (fine particles) “MEK-ST” manufactured by Nissan Chemical Industries, Ltd. was used.

This is a colloidal silica dispersion having an average primary particle diameter of 0.015 μm using methyl ethyl ketone as a dispersion medium, and has a solid content of 30%.

Preparation of Second Layer Coating Solution The above magnetic substance-containing intermediate solution 19053 g Diacetyl cellulose solution 264 g (solid content: 4.5%, solvent: methyl ethyl ketone / cyclohexanone = 1/1) Colloidal silica dispersion “MEK-ST” [Dispersion b] 128 g (solid content 30%) AA-1.5 dispersion [Dispersion a] 12 g Millionate MR-400 (manufactured by Nippon Polyurethane Co., Ltd.) diluent 203 g (solid content 20%, diluent solvent) : Methyl ethyl ketone / cyclohexanone = 1/1) methyl ethyl ketone 170 g cyclohexanone 170 g.

[0524] was applied so the coating liquid by mixing and stirring the a wire bar, the coating amount of 29.3 mL / m ^2. Drying was performed at 110 ° C. The thickness of the dried magnetic layer was 1.0 μm.

3) Third Layer (Higher Fatty Acid Ester Slip Agent-Containing Layer) Preparation of Dispersion Solution of Slip Agent The following solution A was heated and dissolved at 100 ° C., added to Solution A, dispersed with a high-pressure homogenizer, and dispersed in a high-pressure homogenizer. Was prepared.

[0526] A solution following compound 399 parts by weight of _{C 6 H 13 CH (OH)} (CH 2) 10 COOC 50 H 101 The following compound 171 parts by weight of _{n-C 50 H 101 O (} CH 2 CH 2 O) 16 H Cyclohexanone 830 Part by weight A Liquid cyclohexanone 8600 parts by weight Preparation of spherical inorganic particle dispersion A spherical inorganic particle dispersion [c1] was prepared according to the following formulation.

Isopropyl alcohol 93.54 parts by weight Silane coupling agent KBM903 (manufactured by Shin-Etsu Silicone) Compound 1-1: (CH ₃ O) ₃ (Si) — (CH ₂ ) ₃ —NH ₂ 5.5 parts by weight Parts Compound 2-1 2.93 parts by weight

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Seahoster KEP50 88.00 parts by weight (amorphous spherical silica, average particle diameter 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 weight of diacetone alcohol The above liquid was cooled with ice and stirred, while an ultrasonic homogenizer “SONIFIER450 (BRANSON CORPORATION) was used.
)) For 3 hours to obtain a spherical inorganic particle dispersion c1.
Was completed.

Preparation of Spherical Organic Polymer Particle Dispersion A spherical organic polymer particle dispersion [c2] was prepared according to the following formulation.

XC99-A8808 (manufactured by Toshiba Silicone Co., Ltd., spherical crosslinked polysiloxane particles, average particle size 0.9 μm) 60 parts by weight Methyl ethyl ketone 120 parts by weight Cyclohexanone 120 parts by weight (solid content 20%, solvent: methyl ethyl ketone / cyclohexanone) = 1/1) While cooling with ice and stirring, the ultrasonic homogenizer “SONI
FIER450 (manufactured by BRANSON Co., Ltd.) "for 2 hours to complete a spherical organic polymer particle dispersion c2.

Preparation of Third Layer Coating Solution The following was added to 542 g of the above-mentioned slip agent dispersion stock solution to prepare a third layer coating solution.

Diacetone alcohol 5950 g Cyclohexanone 176 g Ethyl acetate 1700 g The above-mentioned Seahosta KEP50 dispersion liquid [c1] 53.1 g The above-mentioned spherical organic polymer particle dispersion liquid [c2] 300 g FC431 2.65 g (3M Corporation) BYK310 5.3 g (manufactured by BYK Chemi Japan KK, solid content 25%).

The above third layer coating solution was coated on the second layer by 10.3
It was applied at a coating amount of 5 mL / m ² , dried at 110 ° C., and further dried at 97 ° C. for 3 minutes.

The samples obtained above were evaluated in the same manner as in Example 9. As a result, the same result as in Example 9 was obtained.

Example 14 Emulsions Em-2-A and Em-2- produced in Examples 1 to 5
B, Em-6-A, Em-9-A, Em-9-B, Em
-10-A, Emulsions Em2BA to Em prepared in Example 7
2BC was used for the sixth layer of the sample 201 described in Example 2 of JP-A-9-5912 to prepare a silver halide color reversal photographic material, which was used in Example 1 of JP-A-9-5912. If the described color reversal process is performed, the same effects as shown in the first to fifth and seventh embodiments can be obtained.

Example 15 Each sample was prepared by adding the compounds shown in Table 12 to the seventh layer of the silver halide color reversal photographic light-sensitive material shown in Example 14, and the examples were described in JP-A-9-5912. If the color inversion processing described in No. 1 is performed, the same result as in the ninth embodiment can be obtained.

Example 16 Emulsions Em-2-A and Em-2- produced in Examples 1 to 5
B, Em-6-A, Em-9-A, Em-9-B, Em
-10-A, Emulsions Em2BA to Em prepared in Example 7
2BC was used for the emulsion layer of photographic material 9 described in Example 1 of JP-A-8-240877 to prepare a silver halide photosensitive material for X-ray, and Example 1 of JP-A-8-240877 was used. By performing the processing described in Example 1,
To 5, and the same effects as shown in the seventh embodiment can be obtained.

Example 17 Each sample was prepared by adding the compounds shown in Table 12 to the intermediate layer in the silver halide photographic material for X-ray shown in Example 16, and the examples were described in JP-A-8-240877. By performing the processing described in No. 1, a result similar to that of the ninth embodiment can be obtained.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 1/047 G03C 1/047 1/09 1/09 1/34 1/34 (72) Inventor Hiroshi Takeuchi Fuji Photo Film Co., Ltd. (72) Inventor Shunichi Aida 210 Nakanakanuma, Minami Ashigara City, Kanagawa Prefecture Fuji Photo Film Co., Ltd. F-term (reference) 2H023 BA01 BA02 BA04 BA05 CA01 CA02 CA04 CA06 CC04 CC05 DB05

Claims (15)

[Claims] (1) 50% of the total projected area of silver halide grains
The above is occupied by tabular silver halide grains having an aspect ratio of 8 or more, and the average iodine content of all grains is 2 mol% or more.
A photosensitive silver halide emulsion containing at least one of the above, which has been subjected to chemical sensitization and spectral sensitization so as to satisfy at least one requirement selected from the following (1) and (2): Silver halide emulsion. (1) Spectral sensitization is performed by adding a spectral sensitizing dye in a state where calcium, magnesium and strontium are 50 ppm or less, and thereafter, calcium, magnesium and strontium are adjusted so that calcium, magnesium and strontium become 100 to 2500 ppm. Is added, followed by the start of chemical sensitization. (2) Chemical sensitization and spectral sensitization are performed in the presence of an alkali-treated bone gelatin containing 30% or more of a component having a molecular weight of 280,000 or more in a molecular weight distribution measured by the PAGI method. 2. The photosensitive silver halide emulsion according to claim 1, wherein the twin plane spacing of the silver halide grains is 0.017 μm or less. 3. Fine silver halide grains containing 95 mol% or more of silver iodide are provided outside a crystal growth reaction vessel during the crystal growth process of the silver halide grains. In the mixer, an aqueous solution of a water-soluble silver salt and an aqueous solution of a water-soluble halide are mixed and formed, and immediately after the formation, supplied into the reaction vessel and used for crystal growth. Item 3. The photosensitive silver halide emulsion according to item 1 or 2. 4. The method according to claim 1, wherein said photosensitive silver halide emulsion is prepared by adding a silver iodobromide emulsion prepared in advance during the chemical sensitization, dissolving and adding a shell. The photosensitive silver halide emulsion according to claim 1, wherein the emulsion is a silver halide emulsion. 5. The photosensitive silver halide emulsion is produced by adding at least one selected from the group consisting of a hexacyanoiron (II) complex and a hexacyanoruthenium complex during grain formation. 5. The light-sensitive silver halide emulsion according to claim 1, wherein 6. A blue-sensitive silver halide emulsion layer containing a yellow coupler, a green-sensitive silver halide emulsion layer containing a magenta coupler, a red-sensitive silver halide emulsion layer containing a cyan coupler, and a hydrophilic material on a support. Silver halide color photographic light-sensitive material having at least one protective protective colloid layer, the coating amount of calcium ion, magnesium ion and strontium ion in the light-sensitive material is 8.0 × 10 ^-2 g or less per g of gelatin in terms of atomic weight A silver halide color photographic light-sensitive material, characterized in that at least one of the emulsions used in the emulsion layer is the light-sensitive silver halide emulsion according to any one of claims 1 to 5. 7. A silver halide photographic light-sensitive material comprising the silver halide emulsion according to claim 1, which satisfies at least one requirement selected from the following (1) to (3): material. (1) At least one kind of P represented by the following general formula (I-1)
Contains d (II) complex. General formula (I-1) In the formula, X ₁ and X ₂ are each independently -S (R ₁₁ )-, -N (R ₁₂ ) (R
_{13) -, - O (R} 14) - represents, Y _1, Y ₂ are each independently -S (R
_{21) -, - N (R} 22) (R 23) -, - O (R 24) - represents, Z _1, Z ₂
Each independently represents an alkylene group, an arylene group, or a divalent heterocyclic residue; L ₁ and L ₂ each independently represent a single bond, an alkylene group, —CO—, or —SO ₂ —; M represents an integer of 0 to 4; Where X ₁ ,
When X ₂ is each independently -N (R ₁₂ ) (R ₁₃ )-and Y ₁ and Y ₂ are each independently -N (R ₂₂ ) (R ₂₃ )-, L ₁ and L ₂ are each independently -CO -, - SO ₂ - represents a. R ₁₁ , R ₁₄ , R
₂₁ and R ₂₄ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or a heterocyclic group, and R ₁₂ , R ₁₃ , R
₂₂ and R ₂₃ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkyl Represents a sulfonyl group or an arylsulfonyl group. When R ₁₂ or R ₂₂ is a hydrogen atom, N
The proton may be dissociated and coordinated to Pd (II). (2) at least one water-soluble mercaptotetrazole compound represented by the following general formula (II-1);
It contains at least one water-soluble mercaptotriazole compound represented by 2). General formula (II-1) In the general formula (II-1), R ₅ is —SO ₃ M, —COO
M, at least selected from the group consisting of -OH and -NHR ₂ represents an organic residue substituted by one, M is a hydrogen atom, an alkali metal atom or represents a quaternary ammonium group or a quaternary phosphonium group , R ₂ is a hydrogen atom, having 1 to 1 carbon atoms
6, an alkyl group of —COR ₃ , —COOR ₃ or —SO
₂ represents R ₃ . R ₃ represents a hydrogen atom, an alkyl group, or an aryl group. General formula (II-2) In the general formula (II-2), R ₆ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and R ₅ represents —SO ₃ M, —COOM, —O
At least selected from the group consisting of H and -NHR ₂ 1
Represents an organic residue substituted with a species, M represents a hydrogen atom, an alkali metal atom, or a quaternary ammonium group or a quaternary phosphonium group, R ₂ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, —COR ₃ represents a -COOR ₃ or -SO ₂ R _3. R ₃ represents a hydrogen atom, an alkyl group, or an aryl group. (3) The thiocyanate ion in the photosensitive material is not more than 2.5 × 10 ⁻³ mol per mol of silver. 8. A requirement (1) according to claim 7 is satisfied,
The silver halide photographic light-sensitive material according to claim 7, wherein the Pd (II) complex represented by the general formula (I-1) is represented by the following general formula (I-2). Embedded image In the formula, Z ₁ and Z ₂ each independently represent an alkylene group, an arylene group or a divalent heterocyclic group, and R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. ,
Represents an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group or an arylsulfonyl group. X ₁₁ , X ₁₂ , X ₁₃ and X ₁₄ each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. 9. The silver halide photographic material according to claim 7, which satisfies requirement (2). 10. The total projected area of the silver halide grains is 50.
% Or more are occupied by tabular silver halide grains having an aspect ratio of 8 or more, and the average iodine content of all grains is 2 mol% or more, and the tabular grains have dislocation lines of 1% or more per grain.
In a method for producing a photosensitive silver halide emulsion containing 0 or more emulsions, the emulsion is subjected to chemical sensitization and spectral sensitization so as to satisfy at least one requirement selected from the following (1) and (2). Of producing a photosensitive silver halide emulsion. (1) Spectral sensitization is performed by adding a spectral sensitizing dye in a state where calcium, magnesium and strontium are 50 ppm or less, and thereafter, calcium, magnesium and strontium are adjusted so that calcium, magnesium and strontium become 100 to 2500 ppm. Is added, followed by the start of chemical sensitization. (2) Chemical sensitization and spectral sensitization are performed in the presence of an alkali-treated bone gelatin containing 30% or more of a component having a molecular weight of 280,000 or more in a molecular weight distribution measured by the PAGI method. 11. The silver halide grain according to claim 1, wherein the twin plane spacing is 0.017 μm or less.
0. The method for producing a photosensitive silver halide emulsion as described in 0. 12. A mixer in which fine silver halide grains containing 95 mol% or more of silver iodide are provided outside a reactor for crystal growth during the crystal growth process of the silver halide grains. The method according to claim 10 or 11, wherein the aqueous solution is formed by mixing an aqueous solution of a water-soluble silver salt and an aqueous solution of a water-soluble halide, and is supplied into the reaction vessel immediately after the formation to be used for crystal growth. A method for producing a photosensitive silver halide emulsion as described in the above. 13. The method according to claim 10, wherein, during the chemical sensitization of the photosensitive silver halide emulsion, a previously prepared silver iodobromide emulsion is added, dissolved and shelled. 2. The method for producing a photosensitive silver halide emulsion according to item 1. 14. The method according to claim 1, wherein at the time of forming the grains of the photosensitive silver halide emulsion, at least one selected from the group consisting of a hexacyanoiron (II) complex and a hexacyanoruthenium complex.
The method for producing a photosensitive silver halide emulsion according to any one of claims 10 to 13, wherein a seed is added. 15. The silver halide photographic material according to claim 7, wherein all of the requirements (1) to (3) are satisfied.