JPH0980659A - Manufacture of silver halide emulsion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high silver chloride emulsion that causes little fog and provides high spectral sensitivity so that it is suited for rapid processing by forming specific silver halide particles in the presence of a cationic crystal phase controlling agent, and washing and demineralizing them in the absence of an anionic settling agent. SOLUTION: Silver halide particles, at least 50mol% of which are silver chloride, with 30% or more of their surface area consisting of a (111) face, are formed in the presence of a cationic crystal phase controlling agent, and are washed and demineralized thereafter in the absence of an anionic settling agent. The crystal phase controlling agent may be added anytime from nucleation to physical aging of the silver halide particles to particle growth. After the addition the (111) face starts to form. The crystal phase controlling agent may be added into a reaction vessel beforehand, or may be put into the reaction vessel as the particles grow, so as to increase their concentration. With the use of the crystal phase controlling agent, normal-crystal (octahedron to tetradecahedrom) and flat particles having the (111) face can be manufactured.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a silver halide emulsion for photography. In particular, (11
1) A process for producing a photographic silver halide emulsion comprising a tetrahedral, octahedral or tabular silver chloride having a face or silver chlorobromide, silver chloroiodide or silver chloroiodobromide having a high silver chloride content It is about.

[0002]

2. Description of the Related Art In recent years, the photographic industry has been eagerly desired to shorten the access time, and there is an urgent need to develop a silver halide photographic light-sensitive material suitable for rapid processing. Increasing the silver chloride content increases water solubility, achieves development and fixing in a shorter time, and provides a silver halide suitable for rapid processing. Silver halide grains having a high silver chloride content (hereinafter referred to as "high silver chloride grains") tend to be cubic grains generally composed of (100) faces, and grains other than cubic grains, specifically (111) faces are Considerable effort is required to obtain regular crystal grains such as octahedrons and tetrahedral grains and tabular grains.

A method for producing tabular grains of silver chlorobromide is already known. For example, as described in JP-B-64-8324, a chloride and silver salt solution is dispersed by a double jet method in the presence of ammonia. A method of simultaneously introducing into a medium, a method of reacting an aqueous solution of a silver salt with an aqueous solution of a chloride salt containing a chloride in the presence of an aminoazaindene and a peptizer containing a thioether condensation, as described in JP-B-64-8326, JP-A-58-111
936, the molar ratio of chloride ion to bromide ion in the reaction vessel is 1.6: 1 to 25.
A method of simultaneously introducing silver, chloride and bromide salts while keeping the total concentration of halogen ions in the range of 0.10 to 0.90, while maintaining the ratio of 8: 1.
No. 2-163046, at least 0.5 molar chloride ion, and 30 μg per gram.
Method of introducing silver ions into a dispersion medium containing a gelatino-peptizer produced from less than methionine, JP-A-63-
No. 281149, a method of contacting a chloride salt containing a chloride with an aqueous silver salt in the presence of a dispersion medium in the presence of a crystal phase change amount of aminozapyridine and a salt thereof. As described in JP-A-62-218959 and JP-A-63-213836, a method of mixing a halide and a silver salt solution in the presence of thiourea or a thiourea derivative, a method of using a gold compound, Further, as described in JP-A-63-2043, a method of forming particles in the presence of a compound containing a sulfur atom in a heterocycle, as described in JP-A-63-41845, A method of forming particles in the presence of a carbonyl compound containing a sulfur atom in the molecule or a sulfone compound is known.

Among these, the silver chloride content in tabular grains is limited to 40 mol% and is not suitable for the production of high silver chloride grains. Alternatively, it is difficult to make thin tabular grains due to the solvent action of ammonia, and the pH during the grain formation is inevitably high, which increases the fog of a high silver chloride emulsion sensitive to fog. Often, the conditions for forming the particles are significantly limited. Such thiourea derivatives have the drawback that fog is likely to occur during aging. Uses a synthetic polymer as a peptizer, and gelatin has a reduced methionine content as a peptizer. However, it is difficult to obtain a copolymer with good reproducibility, or the polymerization initiator contains photographically harmful impurities. However, there are many drawbacks from an industrial point of view because the cost is high and the desalting process becomes complicated and the adverse effects are eliminated. Again, there is a problem in cost increase and reproducibility associated with using special gelatin. Synthetic crystal phase control agents such as and are difficult to remove by a simple method because they are still adsorbed on the silver chloride grains even after the grain formation. Met.

JP-A-3-288143 discloses that in a high silver chloride tabular plate using adenine as a crystal habit-controlling agent, the emulsion is washed with water at pH 3.7 or below after grain formation, or with a sensitizing dye at the same time as washing with water. It is described that the addition of the above compound can increase the adsorption of the sensitizing dye and improve the spectral sensitization. However, adenine has a pH that allows crystal phase control.
Is limited to a relatively high range, and
The high silver chloride flat plate formed within the range had a problem of high fog and high internal sensitivity. Also, European Patent No. 584811
And No. 584817 disclose a method for producing a high silver chloride emulsion using 2-hydroaminoazines (the aforementioned adenine is also included therein) as a (111) plane morphological stabilizer. By lowering it, the morphological stabilizer is protonated and desorbed from the silver halide grains to the dispersion medium, and instead, a photographically useful compound having a specific structure is adsorbed,
It is stated that by removing the desorbed morphological stabilizer from the dispersion medium, it is possible to improve the photographic sensitivity while maintaining the morphology of a high silver chloride tabular plate. However, these morphological stabilizers that can be removed by protonation, including adenine, have a pH below the pH (pKa) at which they are protonated.
In that case, since the adsorption force to particles, that is, the morphological stabilization action of the (111) plane is significantly weakened, the essential problem is that the pH at the time of particle formation capable of forming the (111) plane is limited to pKa or more. Have a

In Japanese Patent Application No. 6-333780, a pyridinium salt or the like is used as a crystal habit-controlling agent, so that the spectral sensitizing dye of It has been shown that the adsorption is improved. According to this technique, although the adsorption of the spectral sensitizing dye was certainly improved, the crystal habit controlling agent remained in the emulsion. As a result of investigating the influence of the remaining crystal habit controlling agent by the present inventors, it was found that it has a function of suppressing the development process, and therefore, the advantages of the high silver chloride emulsion suitable for rapid processing are sufficiently utilized by these techniques. Was difficult.

In Japanese Patent Application No. 6-181940, by setting the washing temperature of the emulsion higher than the grain forming temperature, the removal of the crystal habit controlling agent from the emulsion is promoted and the adsorption of the spectral sensitizing dye is improved. It has been shown that However, even with this technique, due to the partial remaining of the crystal habit controlling agent,
Development inhibition was observed.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a high silver chloride emulsion suitable for rapid processing, which has low fog and high spectral sensitization sensitivity. The problem to be solved in order to achieve the object is, firstly, high chloride having a (111) face on the outer surface using a crystal habit controlling agent capable of controlling the crystal habit even in an acidic region where the occurrence of fog is easily suppressed. In a method for producing a silver emulsion, a technique of desorbing from the grain the crystal phase control agent that inhibits the adsorption of a photographically useful compound such as a dye and suppresses the development and remove it from the emulsion is established. It is to develop a technique for suppressing the morphological change of high silver chloride grains due to the desorption of the phase control agent.

[0009]

The objects of the present invention have been achieved by the following. That is, 1. After forming silver halide grains having at least 50 mol% of silver chloride and 30% or more of the surface area of (111) faces in the presence of a cationic crystal habit controlling agent, the absence of an anionic precipitating agent A method for producing a silver halide emulsion, which comprises washing with water and desalting underneath. 2. The method for producing a silver halide according to the above 1, wherein the cationic crystal habit-controlling agent is any one of compounds represented by the following general formula (I), general formula (II) and general formula (III). And a method for producing a silver halide emulsion. General formula (I)

[0010]

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In the general formula (I), R ₁ represents an alkyl group, an alkenyl group or an aralkyl group, and R ₂ , R ₃ ,
R ₄ , R ₅ and R ₆ each represent a hydrogen atom or a group capable of substituting it. R ₂ and R ₃ , R ₃ and R ₄ , R ₄ and R ₅ , and R ₅ and R ₆ may be condensed. However, R ₂ , R
_At least one of ₃ , R ₄ , R ₅ and R ₆ represents an aryl group. X ^- represents a counter anion. General formula (II)

[0012]

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General formula (III)

[0014]

[Chemical 6]

In the general formula (II) and general formula (III), A ₁ and A
₂ , A ₃ and A ₄ represent a non-metal atom group for completing the nitrogen-containing heterocycle, and each may be the same or different. B represents a divalent linking group. m represents 0 or 1. R ₁ and R ₂ each represent an alkyl group. X represents an anion. n represents 0 or 1, and when the salt is an intramolecular salt, n is 0.
It is. 3. 1. A chemically modified gelatin capable of washing and desalting an emulsion by a precipitation method in the absence of an anionic precipitant is used as at least a part of a dispersion medium.
Alternatively, the method for producing a silver halide emulsion as described in 2 above. 4. 4. The method for producing a silver halide emulsion, wherein the chemically modified gelatin described in 3 above is phthalated gelatin. 5. 5. The method for producing a silver halide emulsion as described in 1 to 4 above, wherein a photographically useful compound having a stabilizing effect on the grain morphology adsorbed on the grains is added before washing and desalting. 6. 6. The method for producing a silver halide emulsion as described in 5 above, wherein the photographically useful compound is a spectral sensitizing dye.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Preferred embodiments of the method for producing a photographic silver halide emulsion of the present invention are as follows. The method for producing a photographic silver halide emulsion as described in 2 above, wherein in the general formula (I), R ₄ represents an aryl group.
3. The method for producing a photographic silver halide emulsion as described in 2 above, wherein in the general formula (I), R ₁ represents an aralkyl group.

The general formula (I) used in the present invention will be described in detail. In the general formula (I), R ₁ has 1 to ₁ carbon atoms.
20 linear, branched or cyclic alkyl groups (eg methyl group, ethyl group, isopropyl group, t-butyl group, n
-Octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group), alkenyl group having 2 to 20 carbon atoms (e.g., allyl group, 2-butenyl group, 3-pentenyl group), 7 carbons
Preferred are 20 aralkyl groups (eg, benzyl group, phenethyl group). Each group represented by R ₁ may be substituted. Examples of the substituent include the substitutable groups represented by R _{2 to} R ₆ below.

R ₂ , R ₃ , R ₄ , R ₅ and R _{6, which} may be the same or different, each represents a hydrogen atom or a group capable of substituting it. Examples of the substitutable group include the following. A halogen atom (for example,
Fluorine atom, chlorine atom, bromine atom, etc.), alkyl group (eg, methyl group, ethyl group, n-propyl group, isopropyl group, t-butyl group, n-octyl group, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (For example,
Allyl group, 2-butenyl group, 3-pentenyl group, etc., alkynyl group (eg, propargyl group, 3-pentynyl group, etc.), aralkyl group (eg, benzyl group, phenethyl group, etc.), aryl group (eg, phenyl group) , Naphthyl group, 4-methylphenyl group, etc.), heterocyclic group (for example,
Pyridyl group, furyl group, imidazolyl group, piperidyl group, morpholino group etc.), alkoxy group (eg methoxy group, ethoxy group, butoxy group etc.), aryloxy group (eg phenoxy group, 2-naphthyloxy group etc.),
Amino group (eg, unsubstituted amino group, dimethylamino group, ethylamino group, anilino group, etc.), acylamino group (eg, acetylamino group, benzoylamino group, etc.), ureido group (eg, unsubstituted ureido group, N- Methylureido group, N-phenylureido group, etc.), urethane group (eg, methoxycarbonylamino group, phenoxycarbonylamino group, etc.), sulfonylamino group (eg, methylsulfonylamino group, phenylsulfonylamino group, etc.), sulfamoyl group ( For example, unsubstituted sulfamoyl group, N, N-dimethylsulfamoyl group, N-
Phenylsulfamoyl group etc.), carbamoyl group (eg unsubstituted carbamoyl group, N, N-diethylcarbamoyl group, N-phenylcarbamoyl group etc.), sulfonyl group (eg mesyl group, tosyl group etc.), sulfinyl group ( For example, methylsulfinyl group, phenylsulfinyl group, etc.), alkyloxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.), acyl group (eg, acetyl group, Benzoyl group, formyl group, pivaloyl group etc.), acyloxy group (eg acetoxy group, benzoyloxy group etc.), phosphoric acid amide group (eg N, N-diethyl phosphoric acid amide group etc.), alkylthio group (eg methylthio) Group, ethylthio group, etc.), aryl Thio group (for example, phenylthio group), cyano group, sulfo group, carboxy group, hydroxy group, phosphono group, nitro group, sulfino group, ammonio group (for example, trimethylammonio group), phosphonio group, hydrazino group, etc. is there. These groups may be further substituted. When there are two or more substituents, they may be the same or different. R ₂ and R ₃ , R ₃ and R ₄ ,
R ₄ and R ₅ , R ₅ and R ₆ may be condensed to form a quinoline ring, an isoquinoline ring or an acridine ring.

[0019] X ^- represents a counter anion. Examples of the counter anion include a halogen ion (a chloride ion and a bromine ion), a nitrate ion, a sulfate ion, a p-toluenesulfonic acid ion, and a trifluoromethanesulfonic acid ion.

In the general formula (I), preferably R ₁ represents an aralkyl group, and R ₂ , R ₃ , R ₄ , R ₅ and R
_At least one of ₆ represents an aryl group. General formula (I)
More preferably, R ₁ represents an aralkyl group,
R ₄ represents an aryl group, and X ⁻ represents a halogen ion.

The general formulas (II) and (III) will be described in more detail below. A ₁ , A ₂ , A ₃ and A ₄ represent a non-metal atom group for completing a nitrogen-containing heterocycle, and may contain an oxygen atom, a nitrogen atom or a sulfur atom, and even if the benzene ring is condensed. I don't care. The hetero ring composed of A ₁ , A ₂ , A ₃ and A ₄ may have a substituent, and each may be the same or different. As the substituent, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfo group, a carboxy group, a hydroxy group, an alkoxy group, an aryloxy group, an amide group. , Sulfamoyl group, carbamoyl group, ureido group, amino group, sulfonyl group, cyano group, nitro group, mercapto group, alkylthio group and arylthio group. Preferred examples are A ₁ , A ₂ , A ₃ and A
₄ is a 5- to 6-membered ring (for example, a pyridine ring, an imidazole ring, a thiozole ring, an oxazole ring, a pyrazine ring, a pyrimidine ring and the like), and a more preferred example is a pyridine ring.

B represents a divalent linking group. The divalent linking group means alkylene, arylene, alkenylene, -S
_{O 2 -, - SO -,} - O -, - S -, - CO -, - NR
_3- (R ₃ represents an alkyl group, an aryl group or a hydrogen atom) is used alone or in combination.
Preferred examples of B include alkylene and alkenylene.

R ₁ and R ₂ represent an alkyl group having 1 to 20 carbon atoms. R ₁ and R ₂ may be the same or different. The alkyl group represents a substituted or unsubstituted alkyl group, and the substituents are the same as those described as the substituents for A ₁ , A ₂ , A ₃ and A ₄ . As a preferred example, R ₁ and R ₂ each have 4 to 10 carbon atoms.
Represents an alkyl group. A further preferred example is a substituted or unsubstituted aryl-substituted alkyl group. X represents an anion. For example, chlorine ion, bromine ion,
It represents iodine ion, nitrate ion, sulfate ion, p-toluenesulfonate, and oxalate. n represents 0 or 1, and in the case of an inner salt, n is 0.

Specific examples of the compounds represented by the general formulas (I) to (III) are shown below, but the cationic crystal habit controlling agent in the present invention is not limited thereto.

[0025]

[Chemical 7]

[0026]

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The crystal habit controlling agent used in the present invention is 6 × 10 ^{−5 to} 6 × 10 ⁵ mol per mol of silver halide in the finished emulsion.
It can be used in the range of ^-6 mol, but is preferably 6 x 10 ^-4 mol to 6 x 10 ^-2 mol. The crystal habit controlling agent may be added at any time from the nucleation of silver halide grains to the physical ripening or the middle of grain growth. After addition (111)
The surface begins to form. The crystal habit-controlling agent may be added in advance in the reaction vessel, or may be added in the reaction vessel along with grain growth to increase its concentration. Using the crystal habit controlling agent of the present invention, a normal crystal having a (111) plane (octahedral to 14
It is possible to produce surface grains) and tabular grains. The selection of both is mainly dependent on the nucleation method and the addition timing and amount of the crystal habit controlling agent. The nucleation method is described below.

When Producing Normal Crystal Grains It is preferable not to allow a crystal habit controlling agent to be present during nucleation.
The chloride concentration at the time of nucleation is 0.6 mol / liter or less, preferably 0.3 mol / liter or less, and particularly preferably 0.1 mol / liter or less. When producing tabular grains Tabular grains are obtained by forming two parallel twin planes. The formation of twin planes depends on temperature, dispersion medium (gelatin),
These appropriate conditions must be set because they depend on the halogen concentration and the like. When the crystal habit controlling agent is present at the time of nucleation, the gelatin concentration is 0.1% to 10%,
It is preferably 0.15% to 5%. The chloride concentration is 0.
The amount is 01 mol / liter or more, preferably 0.03 mol / liter or more. When the crystal habit controlling agent is not used during nucleation, the gelatin concentration is 0.03% to 10%, preferably 0.05% to 1.0%. Chloride concentration is 0.001
Mol / l to 1 mol / l, preferably 0.0
It is from 03 mol / liter to 0.1 mol / liter. The nucleation temperature can be any temperature from 2 ° C to 90 ° C, but 5 ° C
-80 ° C is preferable, and 5 ° C-40 ° C is particularly preferable.

Next, when the formed nuclei are grown in the presence of a crystal habit-controlling agent by physical ripening and addition of a silver salt and a halide, the chloride concentration is 5 mol / liter or less, preferably 0.08. ~ 2 mol / l. The temperature during grain growth can be selected in the range of 10 ° C to 90 ° C, but 30 ° C to
A range of 60 ° C. is preferred. If the amount of the dispersion medium used at the time of nucleation is insufficient for growth, it is necessary to supplement the amount by addition. It is preferred that 10 g / l to 60 g / l of gelatin be present for growth. The pH at the time of particle formation is arbitrary, but is preferably in a neutral to acidic range.

The high silver chloride grains referred to in the present invention are grains having a silver chloride content of at least 50 mol% or more. It is preferably 80 mol% or more, and particularly preferably 95% or more. The portion other than silver chloride consists of silver bromide and / or silver iodide. The silver iodobromide layer can be localized on the grain surface. This is preferred for sensitizing dye adsorption. Also, so-called core / shell type particles may be used. The content of silver iodide is 20 mol% or less, preferably 10 mol%
It is particularly preferably 3 mol% or less.

The silver halide grains of the present invention are (111)
It has a surface composed of planes, and at least 30% or more, preferably 40% or more, and particularly preferably 60% or more of the total surface area is (111) planes. The (111) plane can be quantified from an electron micrograph of the silver halide grains formed.

When the silver halide grains of the present invention are normal crystals, the average grain size is not particularly limited, but is 0.1 μm to 5 μm.
m, preferably 0.2 μm to 3 μm. When the silver halide grain of the present invention is a tabular grain, the diameter / thickness ratio thereof is preferably 2 or more, more preferably 2 or more 2.
It is 0 or less, and particularly preferably 3 or more and 10 or less.
Here, the diameter of silver halide grains means the diameter of a circle having an area equal to the projected area of the grains in an electron micrograph.
In the present invention, the tabular silver halide grains have a diameter of 0.
3 to 5.0 μm, preferably 0.5 to 3.0 μm
It is. The thickness is 0.4 μ or less, preferably 0.3
It is not more than μm, particularly preferably not more than 0.2 μm. The volume average volume of particles is preferably 2 μm ³ or less, and 1 μm
Particularly preferred is ³ or less. Generally, tabular silver halide grains are tabular having two parallel planes, and thus "thickness" in the present invention is represented by the distance between two parallel planes constituting the tabular silver halide grain. . The grain size distribution of the silver halide grains of the invention may be polydisperse or monodisperse, but more preferably monodisperse.

The silver halide emulsion of the present invention may be an internal latent image type emulsion or a surface latent image type emulsion.

A silver halide solvent may be used during the production of the silver halide grains of the present invention. As the silver halide solvent often used, for example, thiocyanate (for example, US Pat. Nos. 2,222,264 and 2,448,
534, 3,320,069, etc.), thioether compounds (for example, US Pat. No. 3,271,157,
No. 3,574,628, No. 3,704,130,
Nos. 4,297,439, 4,276,347, etc.), thione compounds and thiourea compounds (for example, JP-A Nos. 53-144319, 53-82408 and 5).
5-77737) and amine compounds (for example, JP-A-54-100717).
These can be used. Ammonia can also be used as long as it does not have any adverse effect.

In the process of silver halide grain formation or physical ripening, even if cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or iron complex salt, etc. are present together. Good. Particularly, an iridium salt or a rhodium salt is preferable.

During the production of the silver halide grains of the present invention, a silver salt solution (eg AgN) is added to accelerate the grain growth.
A method of increasing the addition rate, the addition amount, and the addition concentration of the O ₃ aqueous solution) and the halide solution (for example, NaCl aqueous solution) according to the addition time is preferably used.

Regarding these methods, for example, British Patent No. 1,335,925 and British Patent No. 3,672,900.
No. 3, No. 3,650,757, No. 4,242,44
5, JP-A-55-142329 and JP-A-55-1581.
No. 24, No. 58-113927, No. 58-11392
No. 8, No. 58-111934, No. 58-111936
No. etc. can be referred to.

The present invention is characterized in that washing and desalting are carried out without using an anionic precipitant. Rinse the emulsion by precipitating the emulsion only by adjusting the pH without the presence of an anionic precipitant and removing the supernatant.
For desalting, it is preferable to use chemically modified gelatin as a dispersion medium. When gelatin in which the positive charge of the amino group is changed to no charge or negative charge is used as the dispersion medium, the emulsion can be precipitated only by lowering the pH of the emulsion, and the anionic precipitant is not required. .
Examples of such gelatin include acetylated, deaminated, benzoylated, dinitrophenylated, trinitrophenylated, carbamylated, phenylcarbamylated, succinylated, succinated, and phthalated gelatins. There is. In the present invention, the case where phthalated gelatin is used is preferable.

As another example of the water washing / desalting method without using an anionic precipitating agent, a method of adding an inorganic salt such as sodium sulfate or chrome alum to the emulsion to coagulate the emulsion and remove the supernatant Examples thereof include a method using ultrafiltration, a method of precipitating an emulsion by centrifugation and then removing a supernatant thereof, a method of washing with noodles, a method of using a synthetic polymer as a dispersion medium, and the like. Regarding these, RESEARCH DISCLOSUR (discussed below)
The description of the cited document can be referred to in E).

The purpose of desalting is to remove the crystal habit controlling agent from the emulsion. The crystal habit controlling agent can be removed by any desalting method which does not use the above-mentioned anionic precipitation agent.

The most commonly used desalting method in the art is the so-called flocculation method. In the flocculation method, usually, an anionic organic compound is added to the emulsion as a precipitating agent, and then the emulsion is allowed to settle by lowering the pH of the emulsion, and the supernatant is removed to carry out desalting. The reason why the emulsion precipitates is that the anionic precipitant binds to the positive charge of gelatin (mainly consisting of amino groups) to neutralize the positive charge, and
This is because by lowering H, the negative charge of gelatin (mainly consisting of a carboxyl group) is protonated and neutralized, and the water solubility of gelatin is reduced. Gelatin precipitates with the silver halide grains and the emulsion separates into a liquid portion and a solid portion. The salt dissolved in the liquid portion is removed together with the liquid portion to allow desalting of the emulsion.

However, as a result of intensive studies conducted by the present inventors, it is quite surprising that the anionic precipitant added in the desalting step by the most commonly used flocculation method described above has a cationic property. It was found that the removal of the crystal habit-controlling agent shown from the emulsion was inhibited, and that the crystal habit-controlling agent could be easily desorbed from the grains and removed from the emulsion by washing with water without using the anionic precipitation agent.

It can be said that the crystal habit-controlling agent having a cationic property interacts with the anionic sedimentation agent.
It is difficult to predict that the crystal habit control agent added with the intention of adsorbing to the particles and the precipitation agent added with the intention of binding with gelatin affect each other. there were. Furthermore, it was totally unexpected that the crystal habit controlling agent adsorbed on the particles would be easily desorbed by washing with water without using the anionic precipitation agent.

Desorption of the crystal habit-controlling agent from the emulsion can be easily carried out by any washing / desalting method using no anionic precipitant, but the industrially preferable method is to use the precipitant-free method. This is a method in which chemically modified gelatin, which can be washed with water by the flocculation method, is used as the dispersion medium. It is also possible to use ordinary gelatin in combination with these chemically modified gelatins as long as they can be washed and desalted by the flocculation method without using an anionic precipitation agent.

The temperature of water washing / desalting is not particularly limited, but it is preferable to carry out water washing at a high temperature to the extent that it promotes desorption of the crystal habit controlling agent. In the present invention, the preferred washing / desalting temperature is in the range of 30 ° C to 80 ° C.

The grains after desorption of the crystal habit-controlling agent are likely to cause grain deformation because the (111) surface of the outer surface is unstable for high silver chloride, but the deformation causes the outer surface to be completely (111). The present invention can be effective even for an emulsion composed of non-faced grains. For example, an emulsion composed of tabular grains whose outer surface cannot be called a perfect (111) surface due to deformation resulting in unevenness on the main plane or rounded corners has a large specific surface area. The present invention is sufficiently effective in an emulsion in which the characteristics of the granular shape remain.

The deformation of particles due to the desorption of the crystal habit controlling agent can be suppressed by adding the photographically useful compound adsorbed to the particles as described above. It is more preferred for the present invention to prevent particle deformation by adsorption of photographically useful compounds.
The photographically useful compound for stabilizing the morphology of the (111) plane is not particularly limited, but a spectral sensitizer, an antifoggant, a stabilizer and the like can be preferably used. Regarding these, Research Disclosure magazine (RESEARC
H DISCLOSURE) can be referred to.

In the present invention, the desorption of the crystal habit controlling agent is carried out at pH.
It is a major feature of the present invention that the pH at the time of desorption of the crystal habit-controlling agent can be freely set because it does not depend on the above operation. It is possible to select a pH that is convenient for the adsorption of photographically useful compounds for preventing particle deformation, which is an advantage over the prior art in which the crystal habit controlling agent is desorbed by pH control. At the same time, it is preferable to set the pAg of the emulsion to a condition convenient for adsorption of a photographically useful compound.

Further, a preferable mode in the present invention is a case where a spectral sensitizing dye is used as a photographically useful compound for preventing grain deformation, and a spectral sensitizing dye which forms a J-aggregate and is adsorbed on the grain is particularly preferable.

The enhanced adsorption of the spectral sensitizing dye means that
It is preferable for promoting desorption of the crystal habit controlling agent. Inorganic salts such as calcium, bromine ions, iodine ions, thiocyanate ions and the like can be preferably added to the emulsion before washing and desalting.

The photographically useful compound added for the purpose of stabilizing the morphology needs to be added at the latest after the desorption of the crystal habit controlling agent and before the particles are deformed. The particles after desorption of the crystal habit controlling agent do not always cause particle deformation immediately, and the particle deformation can be suppressed to some extent by selecting the temperature after desorption and pAg. Therefore, even if a photographically useful compound is added for the purpose of stabilizing the shape after desalting, the particle shape can be retained. However, in order to ensure the retention of the particle morphology, it is preferable to add it at the latest before washing with water. The preferable amount of the photographically useful compound added for the purpose of stabilizing the shape depends on the grain size, but is in the range of 1 × 10 ⁻⁴ to 1 × 10 ⁻² mol per mol of the halogen compound.

The silver halide grains of the present invention may be left unchemically sensitized, but may be chemically sensitized if necessary. The chemical sensitization may be performed after the desalting agent, after the desalting, or during the desalting, and before or after the addition of the photographically useful compound added for the purpose of stabilizing the shape. But good.

As the chemical sensitization method, a so-called gold compound sensitization method (for example, US Pat. No. 2,448,060) is used.
No. 3,320,069) or iridium, platinum,
Sensitization method using metals such as rhodium and palladium (for example, US Pat. Nos. 2,448,060 and 2,566,245)
No. 2,566,263) or a sulfur sensitization method using a sulfur-containing compound (for example, US Pat. No. 2,222,264).
), A selenium sensitization method using a selenium compound, or a reduction sensitization method using tin salts, thiourea dioxide, polyamine or the like (for example, U.S. Pat. Nos. 2,487,850 and 2,51).
8,698, 2,521,925), or a combination of two or more of these.

Particularly, the silver halide grains of the present invention are preferably gold-sensitized or sulfur-sensitized, or a combination thereof. The emulsion layer of the silver halide photographic light-sensitive material of the present invention may contain ordinary silver halide grains in addition to the silver halide grains of the present invention. In the photographic emulsion of the present invention containing the high silver chloride grains according to the present invention, the high silver chloride grains account for 50% or more, preferably 70% or more, particularly preferably 70% or more, of the projected area of all silver halide grains in the emulsion. Preferably, it is present at 90% or more.

When the photographic emulsion of the present invention and other photographic emulsions are used in combination, it is preferable to use the high silver chloride grains of the present invention in an amount of 50% or more in the emulsion after mixing. Further, when the photographic emulsion of the present invention and another photographic emulsion are mixed and used, the mixed emulsion is more preferably a high silver chloride emulsion in which 50 mol% or more is silver chloride.

The emulsion of the present invention may be spectrally sensitized with methine dyes and 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. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes.

That is, a pyrroline nucleus, an oxazoline nucleus,
Tinazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc .; nuclei in which alicyclic hydrocarbon rings are fused to these nuclei; and aromatic hydrocarbon rings in these nuclei Are fused, i.e., indolenine nucleus, benzindolenin nucleus, indole nucleus, benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applied. it can. These nuclei may be substituted on carbon atoms.

The merocyanine dye or the complex merocyanine dye has a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidin-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, and a rhodanin as a nucleus having a ketomethylene structure. 5 such as nucleus and thiobarbituric acid nucleus
~ 6-membered heterocyclic nuclei can be applied. For example, the Research Disclosure item. 17643, page 23, page IV (December 1978) or the compounds described in the cited documents can be used.

The dye may be added to the emulsion at any stage known to be useful in the preparation of the emulsion. Most commonly, it is performed after completion of chemical sensitization but before coating, but US Pat. No. 3,628,9.
As described in JP-A-58-113,92 and JP-A-58-11392, spectral sensitization can be performed simultaneously with chemical sensitization by adding a chemical sensitizer at the same time as described in JP-A Nos.
As described in No. 8, it can be carried out prior to chemical sensitization, or it can be added before completion of precipitation of silver halide grains to start spectral sensitization.

Furthermore, US Pat. No. 4,225,666
It is also possible to add these compounds separately, as taught in US Pat. Yes, any time during silver halide grain formation, including the method taught in U.S. Pat. No. 4,183,756. However, when these dyes are added for the purpose of also stabilizing the particle morphology, it is preferable to add them at the latest before washing and desalting as described above.

The addition amount is 4 × per mol of silver halide.
Although it can be used in an amount of 10 ^{−6 to} 1.5 × 10 ⁻² mol,
In the case of a more preferable silver halide grain size of 0.2 to 3 μm, about 5 × 10 ⁻⁵ to 8 × 10 ⁻³ mol is more effective.

The silver halide emulsion prepared according to the present invention can be used in either a color photographic light-sensitive material or a black-and-white photographic light-sensitive material. Examples of the color photographic light-sensitive material include color paper, color photographic film, color reversal film, and black-and-white photographic light-sensitive material include X-ray film, general photographic film, and printing light-sensitive material film.

There are no particular restrictions on other additives to the photographic light-sensitive material to which the emulsion of the present invention is applied. For example, RESEARCH DISCLOSURE 17
6 volumes, Item 17643 (RD17643) and 1
87, Item 18716 (RD18716) can be referred to. RD17643 and RD1
Listed locations of various additives in 8716 are listed below.

Additive type RD17643 RD18716 1 Chemical sensitizer, page 23, page 648, right column 2 Sensitivity enhancer, same as above 3 Spectral sensitizer, supersensitizer, page 23 to page 648, right column to page 649, right column 4 increase Whitening agent page 24 5 Antifoggants and stabilizers 24 to 25 pages 649 right column 6 Light absorbers, filter dyes 25 to 26 pages 649 right column to UV absorbers 650 left column

7 Anti-Staining Agent, page 25, right column, page 650, left-right column, 8 dye image stabilizer, page 25, 9 hardening agent, page 26, page 651, left column 10, binder, page 26, same 11 plasticizer, lubricant, page 27, page 650, right Column 12 Coating aids, surface-active agents, pages 26 to 27, ibid. 13 Antistatic agents, page 27, ibid.

Of the above additives, antifoggants and stabilizers are azoles (eg, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, nitroindazoles, Benzotriazoles, aminotriazoles, etc .; mercapto compounds {eg mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-
Phenyl-5-mercaptotetrazole), mercaptopyrimidines, mercaptotriazines and the like; thioketo compounds such as oxadrinethione; azaindenes such as triazaindenes and tetraazaindenes (especially 4-hydroxy-substituted (1, 3,3a, 7) tetraazaindenes, pentaazaindenes, etc .;
Benzenethiosulfones, benzenesulfinic acid, benzenesulfonamide and the like can be preferably used.

The color coupler is preferably a non-diffusible type having a hydrophobic group called a ballast group in the molecule, or a polymerized type. The coupler may be either 4-equivalent or 2-equivalent to silver ion.
Further, a colored coupler having a color correcting effect or a coupler releasing a development inhibitor upon development (so-called DIR coupler) may be contained. It may also include a colorless DIR coupling compound that is colorless in the product of the coupling reaction and releases a development inhibitor.

Examples of magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, pyrazolotetrazole couplers, cyanoacetylcoumarone couplers, and open-chain acylacetonitrile couplers, and yellow couplers include acylacetamide couplers. (For example, benzoylacetanilides, pivaloylacetanilides), and the like, and cyan couplers include naphthol couplers and phenol couplers.

As a cyan coupler, US Pat. No. 377 is used.
No. 2002, No. 2772162, No. 3758308
Nos. 4126396, 4334011, 43
Nos. 27173, 3446622 and 4333999
Phenol couplers having an ethyl group at the meta-position of the phenol nucleus, 2,5-diacylamino-substituted phenol couplers having a phenylureido group at the 2-position, and a phenol coupler having a phenylureido group at the 5-position described in JP-A Nos. 4451559 and 4427767. Phenolic couplers having an acylamino group, couplers in which sulphonatemid, amide, etc. are substituted at the 5-position of naphthol, etc. are preferred because of their excellent image fastness.

The above-mentioned couplers and the like can be used in combination of two or more kinds in the same layer in order to satisfy the characteristics required for the light-sensitive material, and the same compound can be added in two or more different layers, as a matter of course. Absent.

As the anti-fading agent, hydroquinone, 6
-Hydroxychromans, 5-hydroxycoumarins,
Spirochroman, p-alkoxyphenols, hindered phenols, mainly bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines and the phenolic hydroxyl groups of these compounds were silylated and alkylated. Ether or ester derivatives are typical examples.
Further, a metal complex represented by (bissalicylaldoximato) nickel complex and (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

Photographic processing of a light-sensitive material using the present invention includes
Any known method can be used, and a known processing solution can be used. The treatment temperature is usually selected from 18 ° C to 50 ° C, but it may be lower than 18 ° C or higher than 50 ° C. Depending on the purpose, any of a developing process for forming a silver image (black-and-white photographic process) and a color photographic process including a developing process for forming a dye image can be applied.

Known black-and-white developers include dihydroxybenzenes (eg hydroquinone), 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone), aminophenols (eg N-methyl-p-aminophenol) and the like. The developing agents can be used alone or in combination.

The color developing solution generally comprises an alkaline aqueous solution containing a color developing agent. Color developing agents are known primary aromatic amine developers such as phenylenediamines (eg 4-amino-N, N-diethylaniline, 3-
Methyl-4-amino-N, N-diethylaniline, 4-
Amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N
-Ethyl-N-β-methanesulfamidoethylaniline, 4-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.) can be used.

Besides this, L. F. A. Messon, Photographic Processing Chemistry, Focal
Presses (1966), pages 226 to 229, U.S. Pat. Nos. 2,193,015 and 2,592,364, and JP-A-48-64933 may be used.

Other developers include pH buffers such as alkali metal sulfites, carbonates, borates, and phosphates, development inhibitors such as bromides, iodides, and organic antifoggants, or antifoggants. Agents and the like can be included.
If necessary, water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol, polyethylene glycol, quaternary ammonium salts, development inhibitors such as amines, dye-forming couplers, competitive couplers, Fogging agents such as sodium boron hydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity improvers, U.S. Pat. No. 4,083,723
No. 2, the polycarboxylic acid chelating agent disclosed in West Germany (O
LS) No. 2,622,950.

When color photographic processing is performed, the photographic light-sensitive material after color development is usually subjected to bleaching processing. The bleaching process may be performed simultaneously with the fixing process, or may be performed individually. Examples of bleaching agents include iron (III) and cobalt (III)
Compounds of polyvalent metals such as chromium, chromium (VI) and copper (II), peracids, quinones, nitroso compounds and the like are used. For example, ferricyanide, dichromate, organic complex salts of iron (III) or cobalt (III), such as ethylenediamine tetracomplex, nitrilotriacetic acid, aminopolycarboxylic acids such as 1,3-diamino-2-propanoltetraacetic acid, or Complex salts of organic acids such as citric acid, tartaric acid and malic acid; persulfates, permanganates; nitrosophenol and the like can be used. Of these, potassium ferricyanide, ethylenediaminetetracomplex iron (III) sodium salt and ethylenediaminetetracomplex iron (III) ammonium salt are particularly useful. The ethylenediamine tetra-complex salt iron (III) complex salt is useful both in the independent bleaching solution and in the one-bath bleach-fixing solution.
Bleaching or bleach-fixing solutions are described in US Pat.
No. 20, No. 3,241,966, Japanese Patent Publication No. 45-850
Various additives can be added in addition to the bleaching accelerators described in JP-B No. 6-45, 88-36, and the thiol compounds described in JP-A-53-65732. After the bleaching or the bleaching / fixing treatment, a washing treatment or a stabilizing bath treatment may be used.

[0078]

【Example】

Example 1 (Preparation of pure silver chloride normal crystal grains) To 1.17 liters of water were added 4 g of sodium chloride and 18 g of inert gelatin, and 6
600 mg of silver nitrate aqueous solution with stirring in a container kept at 0 ° C
cc (silver nitrate 21.3g) and sodium chloride aqueous solution 600
cc (7.74 g of sodium chloride) was added by the double jet method in 20 minutes. Four minutes after the addition was completed, 1.2 mmol of the crystal habit controlling agent-1 was added to the emulsions shown in Table 1 below.

[0079]

Embedded image

Next, 300 cc of silver nitrate aqueous solution (silver nitrate 11
2.5 g) and 300 cc of aqueous sodium chloride solution (sodium chloride 40.14 g) were added over 60 minutes to complete the particle formation. From an electron microscopic observation, the emulsion to which the crystal habit-controlling agent was added was an octahedral emulsion in which almost 100% consisted of (111) faces. After the completion of the addition of the aqueous silver nitrate solution and aqueous sodium chloride solution, as photographically useful compound for holding a particulate form, spectral sensitizing dyes 1 and potassium thiocyanate, respectively 7.7 × 10 ^-4 mol / mol Ag and 4 × 10 ^{- 3} mol /
Molar silver was added to some emulsions.

[0081]

Embedded image

54 g of phthalated gelatin was added to all emulsions, the temperature was lowered to 35 ° C., and some emulsions (shown in Table 1) were added.
2 g of anionic precipitating agent-1 shown below was added to the solution, and the pH was lowered with sulfuric acid until the silver halide was precipitated. Next, about 3 liters of the supernatant was removed (first washing with water). An additional 3 liters of distilled water was added and then sulfuric acid was added until the silver halide had settled. Again, 3 liters of the supernatant was removed (second washing with water). The same operation as the second water washing was repeated once (third water washing) to complete the water washing / desalting process.

[0083]

Embedded image

80 g of gelatin, 85 cc of phenol (5%) and 242 cc of distilled water were added to the emulsion after washing and desalting. PH 6.2, pAg with caustic soda and silver nitrate solution
Adjusted to 7.5. Thus, pure silver chloride particles having an average equivalent spherical diameter of 0.55 μm were obtained. The particle shape is shown in Table 1.

[0085]

[Table 1]

From Table 1, it can be seen that the emulsion washed with water without adding the anionic precipitant had a rounded grain morphology after washing with water.
It can be seen that the crystal habit-controlling agent can be removed and that the grain deformation can be prevented by adding the spectrally sensitizing dye, which is a photographically useful compound, before washing with water. In addition, in an emulsion in which an anionic precipitant was added before washing with water, the grain morphology remained octahedral after washing with water without adding a spectral sensitizing dye before washing with water, and the crystal habit controlling agent remained after washing with water. You can see that it is still done. Carbon replica transmission electron micrographs of Emulsion 1, Emulsion 2 and Emulsion 4 are shown in FIGS. The shadow in the photograph was given by vapor deposition of gold and palladium at an angle of about 45 degrees with respect to the particles. The magnification of the photograph is about 10,000 times.

Emulsions 3 to 6 were kept at 60 ° C., and 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene was added at 6 × 10 ^-4 mol / mol silver. Further, a calcium chloride aqueous solution was added. Subsequently, sodium thiosulfate and chloroauric acid were added to carry out optimum chemical sensitization for 30 minutes, and the emulsion was cooled to 35 ° C.

Antifoggant; 1-phenyl-5-mercaptotetrazole, sodium dodecylbenzene sulfonate, tricresyl phosphate, and gelatin were sequentially added to prepare a coating solution.

This solution was coated on a triacetylcellulose film having an undercoat layer, together with a protective layer containing 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium and gelatin, to obtain a coated sample. A to sample D were obtained.

(Evaluation of Dye Adsorption) Table 2 shows the absorption rates of the coated samples A to D. Absorption rate is U made by Hitachi
It measured using the 3400 type spectrophotometer. The sensitizing dye used in this example is a green-sensitive dye.
Form the J band at 0 nm.

[0091]

[Table 2]

Table 2 shows that the absorption rate of the dye does not change in the cubic emulsion in the presence or absence of the precipitating agent, although the absorption rate of the dye decreases in the octahedral emulsion by the addition of the precipitating agent. Has been done. This is considered to indicate that the sedimentation agent itself did not inhibit the dye adsorption. That is, it is considered that the inhibition of the dye adsorption in the octahedron is a result of the sedimentation agent interfering with the desorption of the crystal habit controlling agent having the dye adsorption inhibiting effect.

The samples were exposed to a wedge of 550 nm using an interference filter, and then subjected to RDIII treatment designated by Fuji Photo Film Co., Ltd. to compare the photographic properties. The results are shown in Table 2. Exposure was performed for 1/100 second. The sensitivity was represented by the relative value of the reciprocal of the exposure amount required to give a density of fog + 0.2, and the sensitivity when the sample D was developed for 90 seconds was 100.

As shown in Table 2, it can be seen that the samples of the present invention have high sensitivity from the stage of short development time and fast development. It is considered that the reason why the rapid progress of development was achieved in the sample of the present invention is that the crystal habit-controlling agent having a development-inhibiting effect was removed more from the sample of the present invention.

Example 2 (Preparation of pure silver chloride tabular grains) To 1.2 liters of water, 4.8 g of sodium chloride and 1.8 g of inactive gelatin were added, and the mixture was stirred in a container kept at 27 ° C. with silver nitrate. Aqueous solution 6
0cc (silver nitrate 9g) and sodium chloride aqueous solution 60cc (sodium chloride 3.15g) 1 by double jet method
Minutes. One minute after the completion of the addition, 1.5 mmol of the crystal habit controlling agent-2 of the present invention was added, and 1 minute later, 288 g of a 10% gelatin aqueous solution was added. Here, an aqueous solution of phthalated gelatin was used for emulsions 6 and 7, and an inert gelatin which was not phthalated was used for emulsions 8 and 9. The temperature of the reaction vessel was raised to 75 ° C. in the next 22 minutes. After aging at 75 ° C for 14 minutes, an aqueous solution of silver nitrate 74
1.5 cc (111.2 g of silver nitrate) and aqueous sodium chloride solution were added at an accelerated flow rate over 40 minutes. During this period, the potential was kept at +125 mV against the saturated calomel electrode. In this way, tabular grains having an average equivalent spherical diameter of 0.85 μm and an average thickness of 0.2 μm and substantially 100% of (111) faces were obtained from pure silver chloride.

[0096]

[Chemical 12]

After the addition of the aqueous silver nitrate solution and the aqueous sodium chloride solution, as a photographically useful compound which retains the grain morphology,
Spectral sensitizing dye-2 and potassium thiocyanate were added to some emulsions at 1 × 10 ⁻³ mol / mol silver and 4 × 10 ⁻³ mol / mol silver, respectively.

[0098]

Embedded image

The temperature of the emulsion was lowered to 35 ° C. and the pH was lowered with sulfuric acid until the silver halide precipitated. Here, the following anionic precipitating agent-2 was added to emulsions 7 and 8 before lowering the pH. Next, about 3 liters of the supernatant was removed (first washing with water). An additional 3 liters of distilled water was added and then sulfuric acid was added until the silver halide had settled. Again 3
L of supernatant was removed (second water wash). Repeat the same operation as the second water washing once more (3rd water washing)
The desalination process was completed. 80 g gelatin and phenol (5
%) And 242 cc of distilled water were added. The pH was adjusted to 6.2 and pAg 7.5 with caustic soda and silver nitrate solution. The particle shape is shown in Table 3.

[0100]

Embedded image

[0101]

[Table 3]

From Table 3, the emulsion washed with water without the addition of the anionic precipitant showed a deformation in the grain morphology after washing with water,
It can be seen that the crystal habit-controlling agent can be removed and that the grain deformation can be prevented by adding the spectrally sensitizing dye, which is a photographically useful compound, before washing with water. In addition, in the emulsion in which the anionic precipitant was added before washing with water, the grain morphology was retained even after washing with water without adding the spectral sensitizing dye before washing with water, and the crystal habit controlling agent remained after washing with water. It can be seen that it is. Carbon replica transmission electron micrographs of Emulsion 7, Emulsion 8 and Emulsion 10 are shown in FIGS.
The shadow in the photograph was given by depositing gold and palladium at an angle of about 15 degrees with respect to the particles. The magnification of the photograph is about 7,000 times.

While maintaining the emulsions 9 and 10 at 60 ° C. with stirring, 4-hydroxy-6-methyl-1,3,3 was added.
After the addition of 6 × 10 ⁻⁴ mol / mol silver of 3a, 7-tetraazaindene, optimum chemical sensitization was performed with sodium thiosulfate, chloroauric acid and selenium compound-1 shown below.

[0104]

[Chemical 15]

(Preparation of emulsion coating layer) Coupler-1, antifoggant shown below; 1-phenyl-5-mercaptotetrazole, sodium dodecylbenzenesulfonate,
Tricresyl phosphate and gelatin were sequentially added to obtain a coating solution.

[0106]

Embedded image

This solution was applied together with a protective layer containing 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium and gelatin on a triacetyl cellulose film having an undercoat layer, to give a coated sample. E and sample F were obtained.

Wedge exposure of 550 nm was applied to the sample using an interference filter, and then CN16 treatment by Fuji Photo Film was performed to compare the photographic properties, and the results are shown in Table 4. Exposure was performed for 1/100 second. Sensitivity is cover +
Expressed as a relative value of the reciprocal of the exposure amount required to give a density of 0.2, the sensitivity when the sample E was developed for 90 seconds was set to 100.

[0109]

[Table 4]

As shown in Table 4, it can be seen that the samples of the present invention have high sensitivity from the stage of short development time and fast development. In the sample of the present invention, fast development was achieved because the crystal phase having a development inhibitory effect was obtained as a result of washing and desalting without the presence of an anionic precipitant which interferes with the removal of the cationic crystal habit controlling agent. It is believed that more of the control agent was removed from the samples of the invention.

[Brief description of drawings]

FIG. 1 is an electron micrograph (magnification: about 10,000 times) showing a crystal structure of grains of emulsion 1.

FIG. 2 is an electron micrograph (magnification: about 10,000 times) showing the crystal structure of grains of emulsion 2.

FIG. 3 is an electron micrograph showing the crystal structure of grains of emulsion 4 (magnification: about 10,000 times).

FIG. 4 is an electron micrograph (magnification: about 7,000 times) showing a crystal structure of grains of emulsion 7.

FIG. 5 is an electron micrograph (magnification: about 7,000 times) showing a crystal structure of grains of emulsion 8.

FIG. 6 is an electron micrograph (magnification: about 7,000 times) showing a crystal structure of grains of emulsion 10.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] January 9, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0085

[Correction method] Change

[Correction contents]

[0085]

[Table 1]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name]

[Correction method] Change

[Correction contents]

The temperature of the emulsion was lowered to 35 ° C. and the pH was lowered with sulfuric acid until the silver halide precipitated. Here, the following anionic precipitant-2 was added to Emulsions 7 and 9 before lowering the pH. Next, about 3 liters of the supernatant was removed (first washing with water). An additional 3 liters of distilled water was added and then sulfuric acid was added until the silver halide had settled. Again 3
L of supernatant was removed (second water wash). Repeat the same operation as the second water washing once more (3rd water washing)
The desalination process was completed. 80 g gelatin and phenol (5
%) And 242 cc of distilled water were added. The pH was adjusted to 6.2 and pAg 7.5 with caustic soda and silver nitrate solution. The particle shape is shown in Table 3.

Claims (6)

[Claims] 1. At least 50 mol% is silver chloride,
In addition, silver halide grains having at least 30% of its surface area consisting of (111) faces are formed in the presence of a cationic crystal habit controlling agent, and then washed and desalted in the absence of an anionic precipitating agent. And a method for producing a silver halide emulsion. 2. The halogen according to claim 1, wherein the cationic crystal habit modifier is any one of compounds represented by the following general formula (I), general formula (II) and general formula (III). Method for producing silver halide emulsion. General formula (I) In general formula (I), R ₁ represents an alkyl group, an alkenyl group or an aralkyl group, and R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each represent a hydrogen atom or a group capable of substituting it. R ₂ and R ₃ , R ₃ and R ₄ , R ₄ and R ₅ , R ₅ and R ₆
May be condensed. However, at least one of R ₂ , R ₃ , R ₄ , R ₅ and R ₆ represents an aryl group. X ^- represents a counter anion. General formula (II) General formula (III) In the general formulas (II) and (III), A ₁ , A ₂ , A ₃ and A ₄ represent a non-metal atom group for completing the nitrogen-containing heterocycle, and may be the same or different. B is 2
Represents a valent linking group. m represents 0 or 1. R ₁ , R ₂
Each represents an alkyl group. X represents an anion. n is 0
Alternatively, it represents 1, and n is 0 in the case of an inner salt. 3. A chemically modified gelatin capable of washing and desalting an emulsion by a precipitation method in the absence of an anionic precipitation agent is used as at least a part of a dispersion medium. Alternatively, the method for producing a silver halide emulsion according to claim 2. 4. The method for producing a silver halide emulsion according to claim 3, wherein the chemically modified gelatin is phthalated gelatin. 5. The production of a silver halide emulsion according to claim 1, wherein a photographically useful compound having a stabilizing effect on the grain morphology adsorbed on the grains is added before washing and desalting. Method. 6. The method for producing a silver halide emulsion according to claim 5, wherein the photographically useful compound is a spectral sensitizing dye.