JPH06242530A - Silver halide photographic emulsion and photographic sensitive material using the same - Google Patents

Abstract

PURPOSE:To attain high sensitivity and excellency in pressure resistance in wet state by increasing silver iodide content in the surface layer of a specific silver halide platelike particle than that in the inner part phase adjacent to the surface layer. CONSTITUTION:In the plate like particle having >=3 aspect ratio in >=50% of the total projection area of the silver halide particle and made by introducing >=10 dislocation lines per one of particles, the surface layer of the particle has higher silver halide content than the inner part phase adjacent to the surface layer. The surface layer is an outermost layer of the particle including the uppermost surface of the silver halide particle and contains the part up to a 5th atomic layer when an atomic layer forming the uppermost surface of the particle is defined as a 1st atomic layer and each of the atomic layers toward inside thereof is defined successively as a 2nd atomic layer, a 3rd atomic layer... toward the inside direction. The silver halide content in the surface layer is preferably >=3mol.% to <30mol.%. The inner part phase adjacent to the surface layer is a phase forming the outermost phase of the particle in the case of excluding the surface layer. The silver halide content in the inner part phase is preferably <20mol.% from the view point of developing property.

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 and a silver halide photographic light-sensitive material using the same, and more specifically to a silver halide photographic emulsion having high sensitivity and excellent pressure resistance and a silver halide photographic emulsion containing the same. The present invention relates to a silver halide color photographic light-sensitive material used.

[0002]

2. Description of the Related Art The technical progress of silver halide color light-sensitive materials for photography (including color negatives and color reversal light-sensitive materials; hereinafter simply referred to as "color negatives") has continued unabated, and it has been possible to obtain conventional high-sensitivity films. The so-called ISO speed 400 class light-sensitive material has come to be used as a regular film for general users.

Many studies have been conducted to achieve high sensitivity and high image quality. For example, JP-A-58-113
No. 930, No. 58-113934, No. 59-1193.
No. 50 discloses a multi-layer color photographic light-sensitive material in which a tabular silver halide emulsion having an aspect ratio of 8 or more is used in a high-sensitivity layer and which has high sensitivity and improved graininess, sharpness and color reproducibility. Materials are disclosed. Since tabular silver halide grains have a large surface area in the same volume as cubic, octahedral or agglomerate grains, a large amount of sensitizing dye can be used and light absorption can be increased. It is advantageous to achieve high sensitivity and high image quality.

Various pressures are applied to a photographic light-sensitive material coated with a silver halide emulsion. For example, a general-purpose negative film is folded in a cartridge or loaded in a camera, or is pulled for feeding a frame. In the development process, for example, in an automatic development process such as roller conveyance, pressure may be applied during conveyance in the developing solution or rubbing with suspended matter in the developing solution. Therefore, the pressure resistance of a photographic emulsion is a very important characteristic not only in a dry and dry state but also in a wet state.

Although the above-mentioned tabular silver halide emulsion is advantageous for high sensitivity, it is also known that it has poor pressure resistance in a dry and dry state, and a method for improving it has been studied. There is. For example, JP-A-63-220238 discloses a method of introducing dislocation lines on the outer periphery of tabular grains.

It is also known that the introduction of dislocation lines into tabular grains has an influence on photographic characteristics and can achieve high sensitivity. For example, there is a description to that effect in JP-A-3-237450.

The present inventor has introduced dislocation lines on the outer circumference disclosed in JP-A-63-220238 for the purpose of achieving high sensitivity and high image quality and improving the pressure fog in the dry state. A light-sensitive material was prepared using the flat silver halide emulsion, and various evaluations for practical use were performed. Among them, the pressure resistance in the dry state was certainly improved, but significant fogging occurred in the wet state corresponding to the pressure resistance in the developing solution, and as it is, it has not reached the level practical for commercial use. It became clear.

As described above, in the conventional technology, it has not been possible to achieve both high sensitivity and pressure resistance in a wet state.

[0009]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a silver halide photographic emulsion having high sensitivity and excellent pressure resistance in a wet state, and a silver halide photographic light-sensitive material using the same. Is.

[0010]

As a result of earnest studies to achieve the above object, the present inventor has found that the object is (1) 50% or more of the total projected area of silver halide grains is
In a tabular grain having an aspect ratio of 3 or more and having 10 or more dislocation lines introduced per grain, the surface layer of the grain has a higher silver iodide content than the internal phase adjacent to the surface layer. Characteristic silver halide photographic emulsion.

(2) The above-mentioned (1), wherein the silver halide phase on the surface layer of the silver halide grain is formed by using an iodide ion-releasing agent and controlling the iodide ion-releasing rate. Silver halide photographic emulsion.

(3) In a photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least 50% of the total projected area of silver halide grains in the silver halide emulsion layer is at least 50% of the above (1). ) Or (2), the photographic light-sensitive material comprising tabular silver halide grains. It was confirmed that

The present invention resides in controlling the introduction of dislocation lines and the iodine content of the surface layer and the internal phase adjacent thereto, whereby the pressure resistance in the wet state is improved for the first time. However, it is not always clear why such an effect is obtained at the present time when there is very little knowledge about pressure resistance in a wet state.

The contents of the present invention will be described in detail below.

The surface layer in the present invention is the outermost layer of the grain including the outermost surface of the silver halide grain, and the layer of atoms forming the outermost surface of the grain is the first atomic layer, and is located inside thereof. The second atomic layer, the third atomic layer, ...
Is the portion up to the fifth atomic layer (thus, for example, in the case of cubic silver bromide grains, the portion from the surface to 14.4 A). Further, in the present invention, it preferably refers to the fourth atomic layer, and more preferably to the third atomic layer. As the surface layer becomes thicker than this, desensitization due to dispersion of chemically sensitized nuclei and deterioration in developability become more remarkable.

In the present invention, the surface layer must have a higher silver iodide content than the internal phase adjacent to the surface layer.
The silver iodide content of the surface layer is preferably 3 mol% or more and less than 30 mol%, more preferably 5 mol% or more and less than 10 mol%. Here, the internal phase adjacent to the surface layer means a phase forming the outermost part of the particles when the surface layer is excluded. The silver iodide content of the internal phase is preferably less than 20 mol% in view of developability.

The halogen composition of such a surface layer is ISS.
It can be measured by a surface analysis method such as (ion scattering spectroscopy).

Regarding the ISS, for example, T. M. Buc
“Methods of Surface An” by k
alysis, ed A .; IV. Czanderna
(Elsevier, Amsterdam, 197
5) ”or Masakazu Aono“ Vacuum 26 (1983), 1
36 ".

In the present invention, there is no particular limitation on the time for increasing the surface iodide, and it may be during grain formation or after grain formation. After formation is preferable.

As a method for increasing the iodide content of the surface layer after grain formation, there is, for example, a method of adding an aqueous halide solution or silver iodide fine grains, but the method is not particularly limited thereto. When the surface layer is made to have a high iodine level after grain formation, it is possible to add a reagent capable of making the surface layer highly iodine at any stage after the grain formation. For example, when an aqueous solution of halide or fine silver iodide grains is added, the aqueous solution or fine grains may be prepared in a silver halide emulsion preparation step (thus, after desalting / washing / mid / after washing), Sensitization process (hence before / after chemical sensitization),
Alternatively, it may be added at any stage of the coating emulsion preparation process.

When addition is carried out after desalting and washing with water after grain formation and before chemical sensitization, silver iodide fine particles or silver halide fine particles having a high silver iodide content are used rather than using an aqueous iodide solution. It is preferable to use the emulsion because the change in pAg of the emulsion is small.

When an aqueous iodide solution is used in the above process, pAg changes greatly, which may greatly affect chemical sensitization.

The treatment for increasing the iodine level on the grain surface may be carried out once, or may be carried out twice or more in a plurality of times.

In the present invention, the surface layer referred to in the present invention does not have to cover the entire surface of the particle, and the effect of the present invention can be exhibited if at least a part of the surface is covered with the surface layer. It is preferable that 10% or more of the particle surface is covered with the surface layer. Furthermore, the effect of the present invention is remarkable when 20% or more is covered with the surface layer of the present invention,
It is particularly preferable that 30% or more is covered. It is also possible to use a crystal habit control agent in combination in order to increase the iodide content of only a specific portion of the surface layer.

As described above, in the present invention, a method of adding a halide aqueous solution or silver iodide fine particles can be used, but for the following reasons, silver iodide fine particles or silver halide fine particles having a high silver iodide content is used. Is preferably used. Most preferably, the iodide ion-releasing agent and the method for controlling the iodide ion-releasing rate described below are used.

When an aqueous solution of iodide is added, a difference in solubility between silver iodide and silver bromide or silver chloride causes halogen conversion (conversion) on the surface of the silver halide grain, and the grain surface layer is made highly iodine. However, since the conversion reaction proceeds faster than the iodide ion concentration becomes uniform in the emulsion solution, the grain surface layer and the high iodine layer between grains become non-uniform. Further, since this reaction easily proceeds to the inside of the grain, it is difficult to control the thickness, and for example, it is difficult to increase the iodine of only the surface layer to obtain the silver halide grain of the present invention.

On the other hand, when silver iodide fine grains or silver halide grains having a high silver iodide content are added, the grain surface layer becomes high after dissolution of the silver halide fine grains and recrystallization on the grain surface. Be iodized. In this reaction, the dissolution of the silver halide fine grains to be added is rate-determining, so that recrystallization occurs uniformly in the emulsion solution, and each grain can be made more homogeneous and have a higher iodine. Also, since it is not a rapid reaction like the conversion reaction, the grain surface layer can be made more uniform and highly iodine,
Further, the control of the thickness is easier than in the case of adding the iodide aqueous solution. However, in this method, the rate-determining process of releasing iodide ions is dissolution of silver halide fine particles, and it is extremely difficult to control this on a large scale. Therefore, it is desirable to use the method for controlling the iodide ion release rate using the iodide ion release agent described below.

The iodide ion eluent will be described below.

The iodide ion-releasing agent used in the present invention is represented by the formula (I) shown in the chemical formula 1 below.
No. 68538 partially overlaps with the compound used to make the halogen composition uniform within and between individual silver halide grains.

However, by rapidly forming iodide ions in the presence of the iodide ion-releasing agent represented by the formula (I) to form silver halide grains, a fog is low and a high-sensitivity silver halide emulsion is obtained. The present inventors have unexpectedly found that the above is obtained.

The iodide ion-releasing agent represented by the following formula (I) used in the present invention will be described in detail.

[0032]

[Chemical 1] In the formula (I), R represents a monovalent organic residue that releases an iodine atom in the form of iodide ion by reaction with an iodide ion releasing agent (base and / or nucleophile).

Explaining the compound represented by the formula (I) in more detail, R is, for example, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or 2 to 2 carbon atoms.
3 alkynyl group, C 6-30 aryl group, C 7-30 aralkyl group, C 4-30 heterocyclic group, C 1-30 acyl group, carbamoyl group, C 2-30 Is preferably an alkyl or aryloxycarbonyl group, an alkyl or arylsulfonyl group having 1 to 30 carbon atoms, or a sulfamoyl group.

As R, the above groups having 20 or less carbon atoms are preferable, and the above groups having 12 or less carbon atoms are particularly preferable.

Further, R is preferably substituted, and preferable substitutions include the following. Any of the substituents described below may be further substituted with another substituent.

Typical substituents are listed below: halogen atom (eg fluorine, chlorine, bromine, iodine), alkyl group (eg methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, cyclopentyl, cyclohexyl). ), An alkenyl group (eg, allyl, 2-butenyl, 3-pentenyl), an alkynyl group (eg, propargyl, 3-pentynyl), an aralkyl group (eg, benzyl, phenethyl), an aryl group (eg, phenyl, naphthyl, 4-methylphenyl). , Heterocyclic groups (eg pyridine, furyl, imidazolyl, piperidyl, morpholyl), alkoxy groups (eg methoxy, ethoxy, butoxy), aryloxy groups (eg phenoxy, naphthoxy), amino groups (eg unsubstituted amino, dimethylamino, ethyl) Amino, Ani No), an acylamino group (for example, acetylamino, benzoylamino), a ureido group (for example, unsubstituted ureido, N-methylureido, N-phenylureido), a urethane group (for example, methoxycarbonylamino, phenoxycarbonylamino), a sulfonylamino group ( For example, methylsulfonylamino, phenylsulfonylamino), a sulfamoyl group (eg, sulfamoyl, N-methylsulfamoyl, N-phenylsulfamoyl), a carbamoyl group (eg, carbamoyl, diethylcarbamoyl, phenylcarbamoyl),
Sulfonyl group (eg methylsulfonyl, benzenesulfonyl), sulfinyl group (eg methylsulfinyl, phenylsulfinyl), alkyloxycarbonyl group (eg methoxycarbonyl, ethoxycarbonyl), aryloxycarbonyl group (eg phenoxycarbonyl), acyl group (eg acetyl) , Benzoyl, formyl, pivaloyl), acyloxy groups (eg acetoxy, benzoyloxy), phosphoramide groups (eg N, N-diethyl phosphoramide), alkylthio groups (eg methylthio, ethylthio), arylthio groups (eg phenylthio), A cyano group, a sulfo group, a carboxyl group, a hydroxy group, a phosphono group, and a nitro group.

Among the above substituents, a halogen atom, an alkyl group, an aryl group, a 5-membered or 6-membered heterocyclic group containing at least one O, N or S, an alkoxy group, an aryloxy group, Acylamino group, sulfamoyl group,
A carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an aryloxycarbonyl group, an acyl group, a sulfo group, a carboxyl group, a hydroxy group or a nitro group is preferable. Further, when it is substituted with an alkylene group, a hydroxy group, a carbamoyl group, an alkylsulfonyl group having 1 to 5 carbon atoms or a sulfo group (including salts thereof; the same applies hereinafter) is particularly preferable, and when substituted with a phenylene group, a sulfo group. Is particularly preferable.

The compounds of formula (I) used in the present invention are
Preferred are compounds represented by the formula (II) or the formula (III) shown below.

The compound represented by the formula (II) used in the present invention will be described.

[0040]

[Chemical 2] In the formula (II), R ₂₁ represents an electron withdrawing group, and R ₂₂ represents a hydrogen atom or a substitutable group.

N ₂ represents an integer of 1 to 6, and a plurality of R _{22 s} in the molecule may be the same or different.

The electron withdrawing group represented by R ₂₁ is preferably an organic group having a Hammett's σ _p or σ _m or σ _I value of greater than 0.

The Hammett's σ _p value or σ _m value is “Structure-activity relationship of drugs” (published by Nankodo), page 96 (1979).
Also, the σ _I value is described on page 105 of the same, and can be selected based on this table.

R ₂₁ is preferably a halogen atom (eg fluorine, chlorine, bromine), trichloromethyl group, cyano group, formyl group, carboxylic acid group, sulfonic acid group, carbamoyl group (eg unsubstituted carbamoyl, diethylcarbamoyl), acyl. Groups (eg acetyl, benzoyl),
Oxycarbonyl group (eg methoxycarbonyl, ethoxycarbonyl), sulfonyl group (eg methanesulfonyl, benzenesulfonyl), sulfonyloxy group (eg methanesulfonyloxy), carbonyloxy group (eg acetoxy), sulfamoyl group (eg unsubstituted sulfamoyl, dimethyl) Sulfamoyl), a heterocyclic group (eg, 2-thienyl, 2-benzoxazolyl, 2
-Benzothiazolyl, 1-methyl-2-benzimidazolyl, 1-tetrazolyl, 2-quinolyl). When R ₂₁ is a group containing carbon, the total sum thereof is preferably 1 to 20.

As examples of the substitutable group represented by R ₂₂ , those enumerated as the substituents of R are directly applicable.

It is preferable that more than half of R ₂₂ contained in the compound of the formula (II) is a hydrogen atom.

N ₂ is preferably an integer of 1 to 3, and 1 or 2 is particularly preferable.

R ₂₁ and R ₂₂ may be further substituted, and preferable substituents include those enumerated as the substituents of R.

R ₂₁ and R ₂₂ , or two or more R
₂₂ may combine to form a 3- to 6-membered ring.

Next, the compound represented by the formula (III) used in the present invention will be explained.

[0051]

[Chemical 3] In formula (III), R ₃₁ is R ₃₃ O— group, R ₃₃ S— group, (R ₃₃ ).
₂ N-group, (R ₃₃ ) ₂ P-group or phenyl,
R ₃₃ is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 3 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms. Represents a heterocyclic group having 4 to 30 carbon atoms.

R ₃₁ is a (R ₃₃ ) ₂ N-group, and (R ₃₃ ) ₂ P-
When representing groups, each two R ₃₃ groups may be the same or different. R ₃₂ and n ₃ have the same meaning as R _{22 in} formula (II), and a plurality of R ₃₂ may be the same or different. R ₃₁ is preferably an R ₃₃ O— group.

As the examples of the substitutable group represented by R ₃₂ , those enumerated as the substituents of R are directly applicable.

N _3, preferably 1, 2, 4 or 5 is 2
Is particularly preferable.

R ₃₁ and R ₃₂ may be further substituted, and preferable substituents include those enumerated as the substituents for R.

R ₃₁ and R ₃₂ , or two or more R
₃₂ may combine with each other to form a ring.

Specific examples of the iodide ion-releasing agent of the present invention are shown in Chemical Formulas 4 to 10 below, but the compounds of the present invention are not limited thereto.

[0058]

[Chemical 4]

[0059]

[Chemical 5]

[0060]

[Chemical 6]

[0061]

[Chemical 7]

[0062]

[Chemical 8]

[0063]

[Chemical 9]

[0064]

[Chemical 10] The iodide ion-releasing agent used in the present invention can be synthesized according to the following synthetic method.

J. Am. Chem. Soc. , 76 , 3
227-8 (1954), J. Org. Chem. , 1
6 , 798 (1951), Chem. Ber. , 97 ,
390 (1964), Org. Synth. , V. 47
8 (1973), J. Am. Chem. Soc. , 1951 ,
1851, J.M. Org. Chem. , 19 , 1571
(1954), J. Chem. Soc. , 1952 , 1
42, J. Chem. Soc. , 1955 , 1383,
Angew, Chem. , Int. Ed. , 11 , 22
9 (1972), Chem. Commu. , 1971 ,
1112.

The iodide ion-releasing agent used in the present invention releases an iodide ion by a reaction with an iodide ion-releasing regulator (base and / or nucleophile). Preferably includes the following chemical species. For example, hydroxide ion, sulfite ion, hydroxylamine, thiosulfate ion, metabisulfite ion, hydroxamic acids, oximes, dihydroxybenzenes, mercaptans, sulfinates, carboxylates, ammonia, amines, alcohols And ureas, thioureas, phenols, hydrazines, hydrazides, semicarbazides, phosphines, and sulfides.

As the base, alkali hydroxide is preferable.

In the present invention, the iodide ion-releasing rate and timing can be controlled by controlling the concentrations of the iodide ion-releasing agent and the iodide ion-releasing regulator, the addition method, or the temperature of the reaction solution. In order to rapidly generate iodide ions, 1 × 1 of iodide ion-releasing agent and iodide ion-releasing regulator should be used.
It is preferably used in a concentration range of 0 ^{-7 to} 20 M, and 1 ×
The range of 10 ^{−5 to} 10 M is particularly preferable. Moreover, a preferable temperature range is 30 to 80 ° C., and 35 to 75 ° C. is particularly preferable.

In the present invention, when a base is used for releasing iodide ions, a change in liquid pH may be used.

At this time, the pH may be controlled in the range of 2 to 12 to control the release rate and timing of iodide ions. The preferred range of pH change is 3 to 1
1, particularly preferably 5 to 10. The preferred pH range after adjusting the release of iodide ions is 7.5-10.0.
Is.

Further, a nucleophile and a base may be used in combination,
At this time, the pH may be controlled within the above range to control the iodide ion release rate and timing. In addition, the hydroxide ion determined by the ionic product of water functions as a regulator even under neutral conditions of pH 7.

The amount of iodide ions released from the iodide ion-releasing agent is preferably in the range of 1 to 10 mol%, more preferably 1 to 8 mol%, based on the total amount of silver halide.
Is.

When iodine atoms are released from the iodide ion releasing agent in the form of iodide ions, all iodine atoms may be released or some of them may remain without being decomposed.

The iodide ion release rate from the iodide ion release agent will be specifically described.

What is important is to rapidly generate iodide ions so as not to cause locality (non-uniform distribution) of iodide ions in the grain forming container. When an iodide ion-releasing agent or an iodide ion-releasing regulator used in combination with it is added to the reaction solution in the grain forming vessel, iodide is added to the locality of the local concentration of the additive generated near the addition port. If the ion-releasing reaction is too fast, a region where iodide ion has a high locality is formed. The time for the iodide ions to deposit on the host grains is extremely fast, and grain growth occurs in the region near the addition port where the iodide ion has a high locality, so uneven grain growth occurs between grains. Therefore, an iodide ion release rate must be selected so that iodide ion locality does not occur in the grain forming container. In the conventional method (eg, adding an aqueous solution of potassium iodide), iodide ions are added in a free state even if the aqueous solution of potassium iodide is diluted and added, so that the locality of iodide ions is reduced. There was a limit. Therefore, it has been difficult to form particles without unevenness among particles by the conventional method.

However, in the present invention, since the iodide ion releasing rate of the iodide ion releasing agent can be controlled, the locality of iodide ions can be reduced as compared with the conventional method.

In the present invention, a preferable iodide ion release rate is a rate at which 100 to 50% of the iodide ion releasing agent present in the reaction solution in the grain forming container completes the release of iodide ion within 180 seconds after the formation. And more preferably 100 to 70% is the rate at which the release of iodide ions is completed within 180 consecutive seconds. If it exceeds 180 seconds, the release rate is generally slow, the use conditions are limited, and the same is true even if it is less than 50%. The iodide ion release rate can be determined by controlling the temperature and the concentrations of the iodide ion releasing agent and the iodide ion release controlling agent as described above.

When the reaction for rapidly forming iodide ions is represented by a secondary reaction which is substantially proportional to the concentration of the iodide ion-releasing agent and the concentration of the iodide ion-releasing agent, it is preferable in the present invention. Second-order reaction rate constant is 1,000
To 5 × 10 ^-3 (M ^-1 · sec ^-1 ), more preferably 100 to 5 × 10 ^-2 (M ^-1 · sec ^-1 ), and particularly preferably 10 to 0.1 (M). ^-1 sec
^-1 ) (in water, 40 ° C).

The term "substantially second-order reaction" means that the correlation coefficient is 1.0 to 0.8.

The iodide ion releasing agent has a concentration of 10 ^-4 to 10 ^-5 M, and the iodide ion regulator has a concentration of 10 ^-1 to 1 M.
A typical second-order reaction rate constant k (M ^-1 · sec ^-1 ) measured in water in the range of 0 ^-4 M under the condition of being regarded as a pseudo first-order reaction under the condition of 40 ° C is as follows. Compound number Iodide ion modifier k 11 Hydroxide ion 1.3 1 Sulfite ion 1 × 10 ⁻³ or less 2 Ibid 0.29 58 Ibid 0.49 63 Ibid 1.5 22 Hydroxide ion 720 k When it exceeds 1,000, the release is too fast to control, and when it is less than 5 × 10 ⁻³ , the release is too slow to obtain the effect of the present invention.

The following method is preferable for controlling the release of iodide ions in the present invention.

That is, by changing the pH, the concentration of the iodide ion release controlling agent, the temperature, etc. from the already uniformly distributed iodide ion releasing agent added to the reaction solution in the grain forming container (usually low). This is a method of releasing iodide ions while controlling the iodide ion to be uniform throughout the reaction solution by changing the pH from high to high.

The alkali for increasing the pH at the time of releasing iodide ions and the iodide ion release controlling agent used in combination are preferably added in a state where the iodide ion releasing agent is evenly distributed throughout.

The halogen composition of the surface layer of the particles is preferably uniform among the particles, and the halogen composition of the entire particles is also preferably uniform among the particles. The present invention, as described above, can achieve particle-to-particle homogeneity not reached by the prior art.

By the way, the emulsion of the present invention has an aspect ratio of 3
The above tabular silver halide grains are an emulsion in which 50% or more of the total projected area of all silver halide grains in the emulsion is present.
Here, tabular silver halide grains are a general term for silver halide grains having one twin plane or two or more parallel twin planes.

The twin plane is defined as (11) when ions at all lattice points on both sides of the (111) plane have a mirror image relationship.
1) A surface. When viewed from above, tabular grains having such twin planes have a triangular shape, a hexagonal shape or a rounded circular shape, and the triangular shape is a triangular shape or a hexagonal shape. Have hexagonal and circular ones have circular outer surfaces parallel to each other.

In the present invention, the aspect ratio of tabular grains means a value (aspect ratio) obtained by dividing the grain diameter by the thickness. The thickness of the particles can be easily calculated by evaporating the metal from the oblique direction of the particles together with the latex for reference, measuring the shadow length on an electron micrograph, and calculating by referring to the shadow length of the latex. Can be measured.

The grain diameter in the present invention is the diameter of a circle having an area equal to the projected area of the parallel outer surface of the grain.

The projected area of the particles can be obtained by measuring the area on an electron micrograph and correcting the area with a photographing magnification.

The diameter of the tabular grains is 0.3 to 5.0.
It is preferably μm. The thickness of the tabular grains is preferably 0.05 to 0.5 μm.

The proportion of the tabular grains of the present invention in the emulsion is preferably 50% or more, particularly preferably 80% or more of the projected area of all silver halide grains in the emulsion. Further, more preferable results may be obtained by using monodisperse tabular grains. The structure and manufacturing method of the monodisperse tabular grains are described, for example, in JP-A-63-151618. In this monodisperse tabular grain, 70% or more of the total projected area of the silver halide grain has a ratio of the side having the maximum length to the length of the piece having the minimum length of 2 or less. The hexagonal tabular silver halide grains are rectangular and are occupied by tabular silver halide having two parallel outer surfaces, and the coefficient of variation of the grain size distribution of the hexagonal tabular silver halide grains The value obtained by dividing the variation (standard deviation) of the particle size represented by the formula by the average particle size] has a monodispersity of 20% or less.

Further, the tabular grains of the present invention have dislocations. The dislocations of tabular grains are described, for example, in J. F. Ham
ilton, Photo. Sci. Eng. , 11 , 5
7, (1967) and T.S. Shiozawa, J .; So
c. Photo. Sci. Japan, 35 , 213,
It can be observed by a direct method using a transmission electron microscope at low temperature described in (1972). In other words, the silver halide grains taken out carefully so as not to apply pressure enough to cause dislocations in the grains from the emulsion are placed on a mesh for electron microscope observation, and the sample is placed to prevent damage (printout, etc.) due to electron beams. Observation is carried out by the transmission method in the cooled state. In this case, the thicker the particles, the more difficult it is for the electron beam to pass therethrough. Therefore, it is possible to more clearly observe using a high-voltage electron microscope (200 kV or more for particles having a thickness of 0.25 μ). .

The particles of the present invention have an average of 10 particles per particle.
Although more than two dislocation lines have been introduced, more preferably,
It is 20 or more, and more preferably 50 or more.

The dislocation lines can be introduced into the tabular grains of the present invention as follows.

That is, it is the epitaxial growth of silver halide on the edges of the tabular grains (also referred to as host grains) serving as the base, and the introduction of dislocation lines by the subsequent formation of the silver halide shell.

The silver iodide content of the host grains is preferably 0.
˜12 mol%, more preferably 0 to 10 mol%.

The silver halide epitaxially grown on the host grains may be any of silver iodide, silver iodobromide, silver chloroiodobromide and silver chloroiodide, but silver iodide or silver iodobromide (iodinated The silver content is preferably 10 to 40 mol%,
More preferably, it is silver iodide.

The amount of the halogen compound added at this time is preferably 0.1 to 20 mol% of the host particles in terms of halogen, more preferably 0.5 to 10 mol%, and most preferably 1 to 5 mol%.

Thereafter, AgNO ₃ and a halogen compound are added to grow a silver halide shell, and dislocation lines are introduced.

Epitaxial growth of silver halide and formation of a shell (surface layer) on the edge are particularly preferably carried out by using the above-mentioned iodide ion-releasing agent and controlling the iodide ion-releasing rate. In particular, it is preferable to form a silver halide phase containing silver halide containing silver iodide at the edge of the grain by this method in order to introduce dislocation lines at a high density. In this case, if the time for forming the silver halide layer containing silver iodide on the edge of the grain is too long, the silver halide containing silver iodide is redissolved during that time, and the density of dislocation lines is reduced.

The silver iodide content of the silver halide shell is preferably 0 to 12 mol%, more preferably 0 to 10 mol%, and most preferably 0 to 3 mol%.

Preferred p in the above dislocation line introduction process
Ag is in the range of 6.4 to 10.5 and the preferred temperature is 30 to 80 ° C.

The emulsion used in combination with the emulsion of the present invention is described below.

The silver halide grains used in the present invention are silver chloroiodide, silver iodobromide and silver chloroiodobromide. Other silver salts such as silver rhodanide, silver sulfide, silver selenide, silver carbonate, silver phosphate and silver organic acid may be contained as separate grains or as a part of silver halide grains.

In the case of silver halide grains in which two or more silver halides exist as a mixed crystal or have a structure, it is important to control the halogen composition distribution between the grains. The method for measuring the halogen composition distribution between grains is described in JP-A-60-254032. A uniform halogen distribution between grains is a desirable property. In particular, a highly uniform emulsion having a variation coefficient of 20% or less is preferable.
Another preferred form is an emulsion where there is a correlation between grain size and halogen composition. For example, there may be a case where the larger size particles have a higher iodine content, while the smaller size particles have a lower iodine content. Depending on the purpose, an inverse correlation or a correlation with another halogen composition can be selected. For this purpose, it is preferable to mix two or more emulsions having different compositions.

It is important to control the halogen composition near the surface of the grain. Increasing the silver iodide content in the vicinity of the surface or increasing the silver chloride content is desirable because the adsorbability of the dye and the developing rate can be changed. When changing the halogen composition in the vicinity of the surface, it is possible to select either a structure that encloses the entire grain or a structure that adheres only to a part of the grain. For example, the halogen composition may be changed only on one surface of a tetrahedral grain composed of (100) planes and (111) planes, or the halogen composition may be changed on one of the main plane and the side surface of a tabular grain.

The silver halide grains which can be used in the present invention include those of normal crystals not containing twin planes, edited by The Photographic Society of Japan, Fundamentals of Photography Industry, Silver Salt Photography (Corona Publishing Co.), P.P. 1
63, eg single twin containing one twin plane, parallel multiple twin containing two or more parallel twin planes, non-parallel containing two or more non-parallel twin planes. It can be selected and used from multiple twins and the like according to the purpose. Also, particles having different shapes can be mixed, but this example is disclosed in US Pat. No. 4,865,964, and this method can be selected as necessary. In the case of a normal crystal, a cube having a (100) plane, an octahedron having a (111) plane, JP-B-55-42737, and JP-A-60-22.
12 composed of (110) plane disclosed in No. 2842
Faced grains can be used. Furthermore, Journa
30 of of Imaging Science
Page 247 as reported in 1986 (2
(H11) plane particles typified by (11) plane, (hh1) plane particles typified by (331) plane, (hk0) plane particles typified by (210) plane, and (321) plane typified (hk)
1) Planar particles can also be used according to the purpose, though the preparation method requires some devise. A tetrahedral grain in which (100) plane and (111) plane coexist in one grain, and (100) plane and (11) plane
Particles in which (0) faces coexist, or (111) faces and (11) faces
Particles in which two surfaces or a large number of surfaces coexist, such as particles in which 0) surfaces coexist can be used according to the purpose.

As the protective colloid used in the preparation of the emulsion of the present invention and as the binder for other hydrophilic colloid layers, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol. Use of various synthetic hydrophilic polymer substances such as homo- or copolymers such as polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole. You can

Examples of gelatin include lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci. Ph
oto. Japan. NO. 16. P30 (1966)
You may use the enzyme-treated gelatin as described in,
Further, a hydrolyzate or an enzymatic hydrolyzate of gelatin can also be used.

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

During preparation of the emulsion of the present invention, for example, during grain formation,
In the desalting step, during chemical sensitization, it is preferable to allow a salt of a metal ion to exist before coating, depending on the purpose. When the particles are doped with a salt of a metal ion, the salt of a metal ion may be added after the particle is formed and before the completion of the chemical sensitization when the salt of the metal ion is used as a modification of the particle surface or as a chemical sensitizer. preferable. The salt of the metal ion may be doped not only in the entire particle, but also in the core portion of the particle, only the shell portion, only the epitaxial portion, or only the base particle. Examples of metal ions include Mg, Ca, Sr, Ba, Al, Sc,
Y, La, Cr, Mn, Fe, Co, Ni, Cu, Z
n, Ga, Ru, Rh, Pd, Re, Os, Ir, P
t, Au, Cd, Hg, Tl, In, Sn, Pb, Bi
Can be used. These metal ions may be, for example, ammonium salts, acetates, nitrates, sulfates, phosphates, hydrates or hexacoordinated complex salts, tetracoordinated complex salts,
Any salt form can be used as long as it can be dissolved during grain formation. As such salt, for example, CdB
_{r 2, CdCl 2, Cd (} NO 3) 2, Pb (NO 3)
₂ , Pb (CH ₃ COO) ₂ , K ₃ [Fe (C
N) ₆ ], (NH ₄ ) ₄ [Fe (CN) ₆ ], K ₃ Ir
Cl ₆ , (NH ₄ ) ₃ RhCl ₆ , K ₄ Ru (CN) ₆
And so on. The ligand of the coordination complex can be selected from, for example, halo, aco, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo and carbonyl. These metal ion salts may be used alone or in combination of two or more kinds.

The metal ion salt is preferably added after being dissolved in water or a suitable solvent such as methanol or acetone. Aqueous hydrogen halide solution (eg HCl, HBr) or alkali halide (eg KCl, NaCl, KBr, NaBr) to stabilize this solution.
Can be added. If necessary, for example, acid or alkali may be added. The metal ion salt may be added to the reaction vessel before grain formation or during grain formation. In addition, a metal ion salt is used as a water-soluble silver salt (for example, AgN).
O ₃ ) or an alkali halide aqueous solution (eg Na
Cl, KBr, KI) and continuously added during the formation of silver halide grains. Further, a solution of a metal ion salt may be prepared independently of the water-soluble silver salt and the alkali halide, and this solution may be continuously added at an appropriate time during grain formation. It is also preferable to combine various addition methods.

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

The silver halide grain of the present invention is subjected to at least one of sulfur sensitization, selenium sensitization, gold sensitization, palladium sensitization or other noble metal sensitization and reduction sensitization in any of the steps for producing a silver halide emulsion. Can be applied in the process of. It is preferable to combine two or more sensitizing methods. Various types of emulsions can be prepared depending on which step is chemically sensitized. A type in which chemically sensitized nuclei are embedded in the grains,
There is a type that is embedded at a shallow position from the grain surface, or a type that creates a chemically sensitized nucleus on the surface. In the emulsion of the present invention, the location of the chemically sensitized nucleus can be selected according to the purpose, but it is generally preferable that at least one type of chemically sensitized nucleus is formed near the surface.

One of the chemical sensitizations which can be preferably carried out in the present invention is chalcogen sensitization and noble metal sensitization, either alone or in combination, and these chemical sensitizers can be used in James (TH Jame).
s), The Photographic Process, 4th Edition,
Published by Macmillan, 1977, (TH James,
The Theory of the Photogr
apic Process, 4th ed, Macm
illan, 1977) 67-76 and using active gelatin, and Research Disclosure, 120, 1974, 4
Mon, 20088; Research Disclosure, 34.
Vol., June 1975, 13452, U.S. Pat. No. 2,64.
No. 2,361, No. 3,297,446, No. 3,7
72,031, No. 3,857,711, No. 3,9
01,714, 4,266,018, and 3,904,415, and British Patent 1,31.
PAg 5-10, pH as described in 5,755
5 to 8 and a temperature of 30 to 80 ° C., sulfur, selenium,
Tellurium, gold, platinum, palladium, iridium or combinations of these sensitizers can be used. In noble metal sensitization, salts of noble metals such as gold, platinum, palladium and iridium can be used as a sensitizer, and as the noble metal sensitizer, gold sensitization, palladium sensitization and a combination of both are preferable. In the case of gold sensitization, known gold sensitizers such as chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide and gold selenide can be used. The palladium sensitizer is a divalent or tetravalent palladium salt. A preferred palladium sensitizer is represented by R ₂ PdX ₆ or R ₂ PdX ₄ . Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom and represents a chlorine, bromine or iodine atom. Specifically, K ₂ PdC
l ₄ , (NH ₄ ) ₂ PdCl ₆ , Na ₂ PdCl ₄ ,
(NH ₄ ) ₂ PdCl ₄ , Li ₂ PdCl ₄ , Na ₂ P
dCl ₆ or K ₂ PdBr ₄ are preferred.

The gold sensitizer and palladium sensitizer are preferably used in combination with thiocyanate or selenocyanate.

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

As sulfur sensitizers, hypo, thiourea compounds, rhodanine compounds and US Pat. No. 3,857,
711, 4,266,018 and 4,0.
The sulfur-containing compounds described in No. 54,457 can be used. The amount of the sulfur sensitizer used for the silver halide grains of the present invention is preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻⁷ mol, and more preferably 1 × 10 ⁻⁵ to 1 mol per mol of the silver halide. It is 5 × 10 ⁻⁷ mol.

The chemical sensitization can be performed in the presence of a so-called chemical sensitization aid. Useful chemical sensitization aids include azaindene, azapyridazine, azapyrimidine, and other compounds known to suppress fog and increase sensitivity during the chemical sensitization process. Examples of the chemical sensitization aid modifier are described in US Pat. Nos. 2,131,038 and 3,311.
411, 914, 3,554, 757, JP-A-58-126526 and the above-mentioned Duffin "Photographic Emulsion Chemistry", pages 138-143.

Selenium sensitization is a preferable sensitizing method for the emulsion of the present invention. In the selenium sensitization, a known unstable selenium compound is used, and specifically, colloidal metal selenium, selenoureas (for example, N, N-dimethylselenourea, N, N-diethylselenourea, etc.), selenoketone And selenium compounds such as selenoamides can be used. In some cases, it is preferable to use selenium sensitization in combination with sulfur sensitization, precious metal sensitization, or both.

During grain formation of the silver halide emulsion of the present invention,
It is preferable to carry out reduction sensitization after grain formation and before or during chemical sensitization, or after chemical sensitization.

The reduction sensitization is carried out by a method of adding a reduction sensitizer to a silver halide emulsion, pAg1 called silver ripening.
Either the method of growing or aging in a low pAg atmosphere of 7 or the method of growing or aging in a high pH atmosphere of pH 8 to 11 called high pH aging 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 reduction sensitizers include stannous salts, ascorbic acid and its derivatives, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid,
Silane compounds and borane compounds are known. These known reduction sensitizers can be used in the reduction sensitization of the invention, and two or more kinds of compounds can be used in combination. As reduction sensitizers, stannous chloride, thiourea dioxide, dimethylamine borane, ascorbic acid and its derivatives are preferred compounds. The addition amount of the reduction sensitizer depends on the emulsion production conditions, and therefore it is necessary to select the addition amount accordingly, but the range of 10 ^-7 to 10 ^-3 mol per mol of silver halide is suitable.

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

It is preferable to use an oxidizing agent for silver during the process of producing the emulsion of the present invention. What is an oxidizing agent for silver?
It refers to a compound that acts on metallic silver to convert it into silver ions. In particular, a compound that can convert extremely fine silver grains, which are a by-product in the process of forming silver halide grains and the process of chemical sensitization, into silver ions is effective. The silver ion generated here may form a water-insoluble silver salt such as silver halide, silver sulfide, and silver selenide.
An easily soluble silver salt may be formed in water such as silver nitrate. The oxidizing agent for silver may be an inorganic substance or an organic substance. Examples of the inorganic oxidant include ozone, hydrogen peroxide and its adducts (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 (eg 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 (e.g., KMnO _4), chromates (e.g.,
Oxyacid salts such as K ₂ Cr ₂ O ₇ ), halogen elements such as iodine and bromine, perhalogenates (eg potassium periodate), salts of high valent metals (eg hexacyanoferric acid) Potassium) and thiosulfonate.

As the organic oxidant, quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (for example, N-
Bromsuccinimide, chloramine T, chloramine B)
Is given as an example.

Preferred oxidizing agents of the present invention 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 that the reduction sensitization described above and the oxidizing agent for silver are used in combination. In this case, any of a method of using an oxidant and then reduction sensitization, a reverse method thereof, and 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 may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. That is, thiazoles (for example, benzothiazolium salt), nitroimidazoles,
Nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles ( In particular, 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines, mercaptotriazines (e.g., thioketo compounds such as oxadrinethione), azaindenes [e.g., triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted ( 1,3,3a, 7) Tetraazaindenes), pentaazaindenes]] known as antifoggants or stabilizers It can be. As such a compound,
For example, US Pat. Nos. 3,954,474 and 3,98.
Nos. 2,947 and 52-28660 can be used. One of the preferred compounds is the compound described in JP-A-63-212932.
Antifoggants and stabilizers are used before particle formation, during particle formation,
After grain formation, washing step, dispersion after washing, before chemical sensitization,
It can be added during chemical sensitization, after chemical sensitization, and at various times before coating, depending on the purpose. In addition to expressing the original antifoggant and stabilizing effects by adding during emulsion preparation, controlling the crystal habit of grains, reducing the grain size,
It can be used for many purposes such as reducing the solubility of grains, controlling chemical sensitization, and controlling the arrangement of dyes.

The photographic emulsion of the present invention is preferably spectrally sensitized with methine dyes and the like in order to exert the effects of the present invention. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes,
Included are styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes.
These dyes may contain any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus. As such a nucleus, for example, a pyrroline nucleus, an oxazoline nucleus, a thiozoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus,
A tetrazole nucleus, a pyridine nucleus; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, that is, an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, Examples thereof 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.

The merocyanine dye or the complex merocyanine dye has as a nucleus having a ketomethylene structure a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidin-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, and a rhodanine. It may have a 5- or 6-membered heterocyclic nucleus such as a nucleus or a thiobarbituric acid nucleus.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Typical examples thereof are US Pat. Nos. 2,688,545 and 2,972.
7,229, 3,397,060, 3,52
No. 2,052, No. 3,527,641, No. 3,61
7,293, 3,628,964, 3,66
6,480, 3,672,898, 3,67
9,428, 3,703,377 and 3,76
9,301, 3,814,609, 3,83
No. 7,862, No. 4,026,707, British Patent Nos. 1,344,281, 1,507,803, Japanese Patent Publication No. 43-4936, No. 53-12,375, and Japanese Unexamined Patent Publication No. 52-375. -110,618 and 52-109,925.

Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion.

The timing of adding the sensitizing dye to the emulsion may be at any stage in the emulsion preparation which has heretofore been known to be useful. Most commonly, it is carried out after the completion of chemical sensitization and before coating, but it is described in US Pat. No. 3,62.
It is also possible to add spectral sensitization simultaneously with chemical sensitization by adding it at the same time as the chemical sensitizer as described in JP-A-58-11.
It can be carried out prior to chemical sensitization as described in US Pat. No. 3,928, or it can be added before the completion of silver halide grain precipitation to initiate spectral sensitization. Furthermore, the addition of these sensitizing dyes separately as taught in U.S. Pat. No. 4,225,666, i.e. adding some of these sensitizing dyes prior to chemical sensitization, It is also possible to add the rest after chemical sensitization,
It may be at any time during silver halide grain formation, including the method disclosed in U.S. Pat. No. 4,183,756.

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

The light-sensitive material produced by using the silver halide emulsion obtained in the present invention comprises a silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer on a support. It suffices that at least one layer is provided, and there is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. As a typical example, at least one color-sensitive layer (unit light-sensitive layer) consisting of a plurality of silver halide emulsion layers having substantially the same color-sensitivity but different sensitivities is typically provided on a support. The silver halide photographic light-sensitive material has a unit light-sensitive layer having a color sensitivity to any of blue light, green light and red light. In a multilayer silver halide color photographic light-sensitive material, the unit light-sensitive layers are generally arranged in order of the red-sensitive layer, the green-sensitive layer and the blue-sensitive layer from the support side. However, even if the above installation order is reversed depending on the purpose,
Further, the order of installation may be such that different photosensitive halogenated emulsion layers are sandwiched in the same color-sensitive layer.

Non-photosensitive layers such as various intermediate layers may be provided between the above silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

For the intermediate layer, JP-A-61-43748 is used.
No. 59-113438, No. 59-113440
No. 61-20037, No. 61-20038, a coupler as described in the specification, a DIR compound may be contained, and a color mixing inhibitor may be contained as is usually used.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are a high sensitivity emulsion layer and a low sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer constitution of emulsion layers can be preferably used. In general, it is preferable that the layers are arranged so that the photosensitivity is gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also,
JP-A-57-112751, JP-A-62-200350
Nos. 62-206541 and 62-206543, a low-sensitivity emulsion layer may be provided on the side farther from the support and a high-sensitivity emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support, a low-sensitivity blue photosensitive layer (BL) / a high-sensitivity blue photosensitive layer (B
H) / high-sensitivity green photosensitive layer (GH) / low-sensitivity green photosensitive layer (GL) / high-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH
/ RL, or BH / BL / GH / GL / RL / R
It can be installed in the order of H.

Further, as described in JP-B-55-34932, the blue-sensitive layer / GH / RH / GL / RL may be arranged in this order from the side farthest from the support. Also, JP-A-56-25738 and 62-6393.
As described in the specification No. 6, it is also possible to provide the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

As described in JP-B-49-15495, a silver halide emulsion layer having the highest photosensitivity in the upper layer, a silver halide emulsion layer having a lower photosensitivity in the middle layer, and a lower layer than the middle layer. Further, an arrangement can be applied in which a silver halide emulsion layer having a lower photosensitivity is arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side remote from the support in the same color-sensitive layer. Layers / high-speed emulsion layers / low-speed emulsion layers may be arranged in this order.

In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, 4
In the case of more than one layer, the arrangement may be changed as described above.

As described above, various layer structures and arrangements can be selected according to the purpose of each photosensitive material.

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

More specifically, these additives are described in Research Disclosure Item 17643 (1978).
December 18), Item 18716 (1 January 1979)
January) and Item 308119 (December 1989), and the corresponding parts are shown in Table A below.
Are summarized in.

Table A Additive type RD17643 RD18716 RD308119 1 Chemical sensitizer page 23 648 page right column 996 page 2 Sensitivity enhancer same as above 3 Spectral sensitizer, page 23-24 page 648 right column to page 996 right column ~ Supersensitizer page 649 right column page 998 right column 4 brightener page 24 page 647 right column page 998 right column 5 antifoggant, pages 24 to 25 page 649 right column page 998 right column and stabilizer page 1000 right Column 6 Light absorber, page 25 to 26, page 649, right column to page 1003, left column ~ Filter dye, page 650, left column 1003, right column UV absorber 7 Stain inhibitor, page 25, right column 650, left to right column 8 Dye image Stabilizer page 25 9 Hardener page 26 651 page left column 1004 page right column to page 1005 left column 10 Binder page 26 same as above page 1003 right column to page 1004 right column 11 Plasticizers and lubricants page 27 650 page right column Page 1006 Left column to Page 1006 Right column 12 Coating aid, pages 26 to 27 Ibid.Page 1005 Left column to Surfactant page 1006 Left column 13 Static Page 27 same as above Page 1006 Right column to Anti-static agent Page 1007 Left column Also, formaldehyde gas In order to prevent deterioration of photographic performance due to a black matrix, a compound capable of being immobilized by reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503 is added to a light-sensitive material. Is preferred.

Various color couplers can be used in the present invention, and specific examples thereof include Research Disclosure No. 17643, VII-CG, and No. 17643. 307105, VII-C to G.

Examples of yellow couplers include US Pat. Nos. 3,933,501 and 4,022,620.
Issue No. 4,326,024, No. 4,401,75
No. 2, No. 4,248,961, Japanese Patent Publication No. 58-107.
39, British Patent Nos. 1,425,020 and 1,4
76,760, U.S. Pat. Nos. 3,973,968, 4,314,023, 4,511,649,
Those described in European Patent No. 249,473A and the like are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897 are preferred.
No., EP 73,636, US Pat. No. 3,06
No. 1,432, No. 3,725,067, Research
Disclosure No. 24220 (June 1984)
Mon.), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, 61-72238 and 60.
-35730, 55-118034, 60-1
Those described in US Pat. No. 8,5951, US Pat. Nos. 4,500,630, 4,540,654, 4,556,630 and International Publication WO88 / 04795 are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers, and US Pat.
No. 52,212, No. 4,146,396, No. 4,
No. 228,233, No. 4,296,200, No. 2,369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826,
No. 3,772,002, No. 3,758,308
No. 4,334,011, No. 4,327,17
3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A, 249,453A, U.S. Patents 3,446,622, 4,333,999.
Issue No. 4,775,616, No. 4,451,55
No. 9, No. 4,427, 767, No. 4, 690, 8
No. 89, No. 4,254,212, No. 4,296,
Those described in JP-A No. 199 and JP-A No. 61-42658 are preferable.

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820 and 4,084.
No. 0,211, No. 4,367,282, No. 4,4
09,320, 4,576,910, British Patent 2,102,137, European Patent 341,188A.
No. etc.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570,
Those described in West German Patent (Publication) No. 3,234,533 are preferable.

Colored couplers for correcting unwanted absorption of color forming dyes are available from Research Disclosure N.
o. 17643, Item VII-G, ibid. Of 307105
Item VII-G, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-39413, U.S. Pat. No. 4,004,929.
No. 4,138,258, British Patent No. 1,14.
Those described in 6,368 are preferable. Further, a coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in US Pat. No. 4,774,181 and a reaction with a developing agent described in US Pat. No. 4,777,120. It is also preferable to use a coupler having as a leaving group a dye precursor group capable of forming a dye.

Compounds that release a photographically useful residue upon coupling are also preferably used in the present invention.
DIR couplers that release development inhibitors are described in RD1 above.
7643, Item VII-F and No. 307105, VII
Patents described in section F, JP-A-57-151944
No. 57-154234, No. 60-184248.
No. 63-37346, No. 63-37350, and U.S. Pat. Nos. 4,248,962 and 4,782,01.
Those described in No. 2 are preferable.

As a coupler capable of releasing a nucleating agent or a development accelerator in an image form during development, British Patent No. 2,092
7,140, 2,131,188, JP-A-59
Those described in Nos. 157638 and 59-170840 are preferable. Further, JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and JP-A-1-4940.
Compounds releasing a fog agent, a development accelerator, a silver halide solvent and the like by an oxidation-reduction reaction with an oxidized product of a developing agent described in JP-A-45687 are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
Competitive couplers described in U.S. Pat. No. 4,283,4
No. 72, No. 4,338,393, No. 4,310,
No. 618 and the like, multiequivalent couplers, JP-A-60-18.
5950, DI described in JP-A-62-24252, etc.
R redox compound-releasing coupler, DIR coupler-releasing coupler, DIR coupler-releasing redox compound or DIR redox-releasing redox compound, coupler releasing a dye that recolors after separation described in European Patent Nos. , RD. No.
11449, 24241, JP-A-61-201247.
Bleach accelerator releasing couplers described in U.S. Pat.
Examples thereof include ligand releasing couplers described in U.S. Pat. No. 555,477, couplers releasing a leuco dye described in JP-A-63-75747, and couplers releasing a fluorescent dye described in U.S. Pat. No. 4,774,181. .

The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers.

The color photographic light-sensitive material according to the present invention has the RD. No. 17643, pages 28-29, ibid.
18716, 651 left column to right column, and the same No. 307
Development processing can be carried out by a usual method described on page 880-881.

The silver halide light-sensitive material of the present invention is described in US Pat. No. 4,500,626 and JP-A-60-1334.
No. 49, No. 59-218443, No. 61-23805.
It is also applicable to the photothermographic materials described in No. 6, European Patent No. 210,660A2, and the like.

The silver halide light-sensitive material of the present invention is more effective when applied to a film unit with a lens (light-sensitive material packaging unit) described in JP-B-2-32615, JP-B-3-39784 and the like. It is easy to develop and effective.

Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step.

In the processing using the automatic processor, when each processing solution described above is concentrated by evaporation, it is preferable to add water to correct the concentration.

Various processing solutions used in the present invention are 10 ° C. to 5 ° C.
Used at 0 ° C. Normally, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature is used to accelerate the processing to shorten the processing time, and conversely, a lower temperature is used to improve the image quality and improve the stability of the processing liquid. be able to.

The silver halide photographic light-sensitive material of the present invention is described in, for example, US Pat. No. 4,500,626, JP-A-60-133449, JP-A-59-218443, and JP-A-59-218443.
It can also be applied to the photothermographic materials described in Nos. 1-238056 and EP 210,660A2.

[0168]

EXAMPLES Examples of the present invention will be described in detail below, but the embodiments of the present invention are not limited thereto. Example 1 (1) Preparation of emulsion Emulsion a 6 g of potassium bromide and 27 g of inert gelatin were added to distilled water 3.
While well stirring the solution dissolved in 7 liters, a 14% aqueous solution of potassium bromide and a 20% aqueous solution of silver nitrate were added at a constant flow rate over 1 minute at 55 ° C. and pBr of 1.0 by the double jet method. This addition consumed 2.4% of the total silver). After this (i) ~ (iii)
Were sequentially performed.

(I) Gelatin aqueous solution (17%, 300c
c) was added, and after stirring at 55 ° C., a 20% aqueous silver nitrate solution was added at a constant flow rate until pBr reached 1.4 (this addition consumed 5.0% of the total silver amount). (Ii)
5% potassium iodobromide solution (KBr _1-x I _x : X =
0.01) and 33% aqueous silver nitrate solution were added by the double jet method over 43 minutes (this addition consumed 50.0% of the total silver). (Iii) After adding an aqueous solution containing 8.3 g of potassium iodide, a 20% potassium bromide solution and a 33% silver nitrate solution were added by the double jet method over 39 minutes. (This addition consumed 42.6% of total silver.) The amount of silver nitrate used in this emulsion was 425 g. Then, after desalting by the usual flocculation method and adding gelatin, pH
5.8 and pAg 8.8.

After raising the temperature to 62 ° C., the sensitizing dye ExS
−1 is 2.0 × 10 ⁻⁴ mol / mol Ag, ExS-2 is 0.1 × 10 ⁻⁴ mol / mol Ag, ExS-3 is 3.0 ×.
10 ⁻⁴ mol / mol Ag, sodium thiosulfate 0.8 × 1
0 ⁻⁵ mol / mol Ag, chloroauric acid 1.5 × 10 ⁻⁵ mol / mol Ag, potassium thiocyanide 1.6 × 10 ⁻³ mol / mol Ag, N, N-dimethylselenourea 0.4 × 10 ⁻ Optimal chemical sensitization was performed by sequentially adding ⁵ mol / mol Ag.

As described above, the aspect ratio is 3 to 8
A silver iodobromide emulsion (emulsion a) having 70% of the total projected area, the equivalent spherical diameter of 1.10 μm and a coefficient of variation of 16% was prepared.

When these grains were observed with a transmission electron microscope, 10 or more dislocation lines were observed in 70% or more of all grains. Emulsion b In the step (iii) of preparing Emulsion a, 8.3 g of potassium iodide was added by a double jet method of an aqueous solution of silver nitrate and an aqueous solution of potassium bromide to the aqueous solution of potassium bromide to obtain potassium iodide ( 8.3 g) was mixed and added. Emulsion b was prepared in the same manner as Emulsion a except for the above.

When these particles were observed with a transmission electron microscope, no particles showed dislocation lines of 10 or more. Emulsion c In the step (iii) of preparation of emulsion a, 8.3 g of potassium iodide was added by a double jet method of an aqueous solution of silver nitrate and an aqueous solution of potassium bromide. 8.3 g) are mixed and added, and 1 g of potassium iodide is added after the grain formation and before desalting.
Was dissolved in 100 cc for 1 minute, and the surface layer was highly iodized.
Was prepared.

When these particles were observed with a transmission electron microscope, no particles showed dislocation lines of 10 or more. Emulsion d In the preparation of emulsion a, after the grain formation was completed and before desalting, a solution in which 1 g of potassium iodide was dissolved in 100 cc was added for 1 minute, and the surface layer was highly iodized in the same manner as in emulsion a. Emulsion d was prepared. Emulsion e In the preparation of emulsion a, after the grain formation was completed and before desalting,
06μ ultrafine silver iodide emulsion (AgI 1.42
(including g) was added for 1 minute, and emulsion e was prepared in the same manner as emulsion a except that the surface layer was highly iodized. Emulsion f In the preparation of Emulsion a, p-
A sodium iodoacetamidobenzenesulfonate (1.5 g) aqueous solution was added, and then a 0.8 M sodium sulfite aqueous solution (7.5 cc) was added to adjust the pH to 9.0.
Emulsion f was prepared in the same manner as Emulsion a, except that the surface layer was increased to 5.6 and held at 5.6 for higher iodine.

Next, pBr during grain growth of emulsions a to f
By changing the ratio, the aspect ratio of the tabular emulsion was controlled to obtain emulsions g to r shown in Table 1. However, the amount of sensitizing dye is
The sensitivity was adjusted to the maximum.

[0176]

[Table 1] (2) Preparation of Coating Samples Emulsion layers and protective layers as shown in Table 2 were coated on a teriacetylcellulose film support having an undercoat layer to prepare samples 101 to 118 shown in Table 1.

[0177]

[Table 2] After dipping these samples in distilled water for 1 minute, a weight of 4 g was added with a needle having a thickness of 0.1 mmφ under the same atmosphere, and 1c was added.
I scratched at a speed of m / sec.

After the sample was naturally dried, it was developed under the conditions shown in Table 3 below, and the density was measured with an aperture of 25 μmφ.

Then, these samples were subjected to sensitometric exposure according to a conventional method, and after developing under the conditions shown in Table 3, the density was measured to calculate the sensitivity change.

The results are shown in Table 1 above.

From Table 1, the sample of the present invention in which dislocation lines are introduced and the surface layer is highly iodinated has high sensitivity, little increase in fogging due to scratching, and excellent pressure resistance even in a wet state. I understand.

Table 3 (Processing method) Process Processing time Processing temperature Color development 3 minutes 15 seconds 38 ° C Bleaching 3 minutes 00 seconds 38 ° C Water washing 30 seconds 24 ° C Settling 3 minutes 00 seconds 38 ° C Water washing (1) 30 S 24 ℃ Washing with water (2) 30 s 24 ℃ Stabilization 30 s 38 ℃ Dry 4 min 20 s 55 ℃ Next, describe the composition of the treatment liquid. (Color developer) (Unit: g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1. 5 mg hydroxylamine sulfate 2.4 4- [N-ethyl-N- (β-hydroxyethyl) 4.5 amino] -2-methylaniline sulfate Water was added to 1.0 liter pH (potassium hydroxide and sulfuric acid 10.05 (bleaching solution) (unit g) ferric ethylenediaminetetraacetate 100.0 sodium trihydrate disodium ethylenediaminetetraacetic acid 10.0 3-mercapto-1,2,4-triazole 0. 03 Ammonium bromide 140.0 Ammonium nitrate 30.0 Ammonia water (27%) 6.5 ml Add water 1.0 liter pH (adjusted with ammonia water and nitric acid) 6.0 (fixer) (unit g) ethylenediaminetetraacetic acid disodium salt 0.5 ammonium sulfite 20.0 ammonium thiosulfate aqueous solution 295.0 ml (700 g / L) Acetic acid (90%) 3.3 Water was added to 1.0 L pH (adjusted with ammonia water and acetic acid) 6.7 (Stabilizing liquid) (Unit: g) Sodium p-toluenesulfinate 0.03 Polyoxy Ethylene-p-monononylphenyl 0.2 ether (average degree of polymerization 10) ethylenediaminetetraacetic acid disodium salt 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazole- 1-0.75 ylmethyl) piperazine Water was added to 1.0 liter pH 8.5 Example 2 On acid cellulose film support,
Each layer having the composition shown below was applied in multiple layers to prepare a sample 201 which is a multilayer color light-sensitive material. (Photosensitive layer composition) The main materials used for each layer are classified as follows: ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer. (Sample 201) First layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin 1.40 ExM-1 0.18 ExF-1 2.0 × 10 ⁻³ HBS-1 0.20 Second layer (intermediate) Layer) Emulsion G Silver 0.065 2,5-di-t-pentadecylhydroquinone 0.18 ExC-2 0.020 UV-1 0.060 UV-2 0.080 UV-3 0.10 HBS-10 .10 HBS-2 0.020 Gelatin 1.04 Third layer (low-sensitivity red-sensitive emulsion layer) Emulsion A Silver 0.25 Emulsion C Silver 0.25 ExS-1 4.5 × 10 ^-4 ExS-2 1. 5 × 10 ⁻⁵ ExS-3 4.5 × 10 ⁻⁴ ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.0050 ExC-7 0.0050 ExC-8 0. 020 Cpd-2 0.025 HBS 1 0.10 Gelatin 0.87 Fourth Layer (medium-sensitivity red-sensitive emulsion layer) Emulsion D silver ^{0.80 ExS-1 3.0 × 10 -4} ExS-2 1.2 × 10 -5 ExS-3 4. 0 × 10 ⁻⁴ ExC-1 0.15 ExC-2 0.060 ExC-4 0.11 ExC-7 0.0010 ExC-8 0.025 Cpd-2 0.023 HBS-1 0.10 Gelatin 0. 75 Fifth layer (high-sensitivity red-sensitive emulsion layer) Emulsion a Silver 1.40 ExS-1 2.0 × 10 ^-4 ExS-2 1.0 × 10 ^-5 ExS-3 3.0 × 10 ^-4 ExC- 1 0.095 ExC-3 0.040 ExC-6 0.020 ExC-8 0.007 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.10 Gelatin 1.20 6th layer (intermediate layer) ) Cpd-1 0.10 HBS-1 0.50 gelatin 1.10 7 layers (low-sensitivity green-sensitive emulsion layer) Emulsion A Silver 0.17 Emulsion B Silver 0.17 ExS-4 4.0 × 10 ⁻⁵ ExS-5 1.8 × 10 ⁻⁴ ExS-6 6.5 × 10 ^-4 ExM-1 0.010 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73 8th layer (medium sensitivity green feeling) Emulsion layer) Emulsion D Silver 0.80 ExS- ⁴ 2.0x10 ^-5 ExS-5 1.4x10 ^-4 ExS-6 5.4x10 ^-4 ExM-2 0.16 ExM-3 0. 045 ExY-1 0.01 ExY-5 0.030 HBS-1 0.16 HBS-3 8.0 × 10 ^-3 Gelatin 0.90 9th layer (high-sensitivity green-sensitive emulsion layer) Emulsion E Silver 1.25 ^{ExS-4 3.7 × 10 -5 ExS} -5 8.1 × 10 -5 ExS-6 3.2 × 10 -4 ExC-1 0.010 ExM-1 0.015 ExM-4 0.040 ExM-5 0.019 Cpd-3 0.020 HBS-1 0.25 HBS-2 0.10 Gelatin 1.20 10th layer (yellow filter layer) Yellow colloidal silver Silver 0.010 Cpd-1 0.16 HBS-1 0.60 Gelatin 0.60 11th layer (low-sensitivity blue emulsion layer) Emulsion C Silver 0.25 Emulsion D Silver 0.40 ExS-7 8 0.0 × 10 ⁻⁴ ExY-1 0.030 ExY-2 0.55 ExY-3 0.25 ExY-4 0.020 ExC-7 0.01 HBS-1 0.35 Gelatin 1.30 12th layer ( High-sensitivity blue-sensitive emulsion layer) Emulsion F Silver 1.38 ExS-7 3.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 HBS-1 0.070 Gelatin 0.86 13th layer (third layer) 1 protective layer) Agent G silver 0.20 UV-4 0.11 UV-5 0.17 HBS-1 5.0 × 10 -2 Gelatin 1.00 14th layer (second protective layer) H-1 0.40 B-1 (Diameter 1.7 μm) 5.0 × 10 ⁻² B-2 (Diameter 1.7 μm) 0.10 B-3 0.10 S-1 0.20 Gelatin 1.20 Further, the storability is properly stored in each layer. W to improve processability, pressure resistance, antifungal and antibacterial properties, antistatic properties and coating properties.
-1 to W-3, B-4 to B-6, F-1 to F-17, and iron salt, lead salt, gold salt, platinum salt, iridium salt, palladium salt, and rhodium salt.

[0183]

[Table 4] In Table 4, (1) Emulsions A to F were reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938. (2) Emulsions A to F were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. Has been done. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. (4) Dislocation lines as described in JP-A-3-237450 are observed in the tabular grains by using a high voltage electron microscope.

[0184]

[Chemical 11]

[0185]

[Chemical 12]

[0186]

[Chemical 13]

[0187]

[Chemical 14]

[0188]

[Chemical 15]

[0189]

[Chemical 16]

[0190]

[Chemical 17]

[0191]

[Chemical 18]

[0192]

[Chemical 19]

[0193]

[Chemical 20]

[0194]

[Chemical 21]

[0195]

[Chemical formula 22]

[0196]

[Chemical formula 23]

[0197]

[Chemical formula 24]

[0198]

[Chemical 25] For the sample 201 prepared as described above, the fifth layer emulsion a
Was changed as shown in Table 5 to prepare samples 202 to 218.

[0199]

[Table 5] Samples 201 to 218 were evaluated for pressure resistance and photographic performance in the same manner as in Example 1, and the results shown in Table 5 were obtained.

From Table 5, the sample of the present invention in which a dislocation line was introduced and the surface layer was highly iodized has high sensitivity, little increase in fogging due to scratching, and excellent pressure resistance even in a wet state. I understand. As described above, the effect of the present invention was confirmed even in a multilayer coating photosensitive material.

Claims (3)

[Claims] 1. 50% of the total projected area of silver halide grains
In the tabular grains having an aspect ratio of 3 or more and having 10 or more dislocation lines introduced per grain, the surface layer of the grains has a silver iodide content higher than that of the internal phase adjacent to the surface layer. A silver halide photographic emulsion characterized by high price. 2. The halogen according to claim 1, wherein the silver halide phase on the surface layer of the silver halide grain is formed by using an iodide ion releasing agent and controlling the iodide ion releasing rate. Silver halide photographic emulsion. 3. A photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein at least 50% of the total projected area of silver halide grains in the silver halide emulsion layer is at least 50%. A photographic light-sensitive material characterized by being occupied by tabular silver halide grains described in 2.