JP2003140284A - Method for manufacturing silver halide emulsion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a photosensitive silver halide emulsion containing planar particulate silver halide particles in which the covering rate of an adsorbed dye is high and aggregation of particles are prevented. SOLUTION: The method for manufacturing the photosensitive silver halide emulsion containing a gelatin dispersion medium and silver halide planar particles, is characterized in that a crosslinking agent for the gelatin is added in the period after starting the formation of the silver halide particles and before completing the formation of the particles.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a silver halide emulsion,
Particularly, it relates to a method for producing a silver halide tabular grain emulsion for photography.

[0002]

2. Description of the Related Art Tabular silver halide grains (hereinafter referred to as "tabular grains") have the following photographic characteristics: 1) ratio of surface area to volume (hereinafter referred to as "specific surface area").
Is large and a large amount of sensitizing dye can be adsorbed on the surface, and thus the color sensitizing sensitivity is relatively high with respect to the intrinsic sensitivity. 2) When an emulsion containing tabular grains is coated and dried, the grains are arranged parallel to the surface of the support, so that the thickness of the coating layer can be reduced and the photographic light-sensitive material has good sharpness. 3) In a radiographic system, addition of a sensitizing dye to tabular grains can significantly reduce silver halide crossover light and prevent deterioration of image quality. 4) An image with high resolution can be obtained with little light scattering. 5) Due to its low sensitivity to blue light, the green photosensitive layer or
When used in the red light-sensitive layer, the yellow filter can be removed from the emulsion. Since it has many advantages as described above, it has been conventionally used for high-sensitivity commercial light-sensitive materials. JP-B-6-44132 and JP-B-5-16015 disclose tabular grain emulsions having an aspect ratio of 8 or more. The aspect ratio as used herein is indicated by the ratio of the diameter to the thickness of tabular grains. Further, the diameter of a grain means the diameter of a circle having an area equal to the projected area of the grain when the emulsion is observed with a microscope or an electron microscope. The thickness is indicated by the distance between two parallel planes constituting the tabular silver halide. Further, JP-B-4-36374 discloses that at least one of the green-sensitive emulsion layer and the red-sensitive emulsion layer has a thickness of 0.3.
There is described a color photographic light-sensitive material improved in sharpness, sensitivity and graininess by using tabular grains having a diameter of less than μ and a diameter of 0.6 μ or more.

In recent years, however, silver halide light-sensitive materials have been made highly sensitive and have a small format, and there is a strong demand for color light-sensitive materials having higher sensitivity and improved image quality. Therefore, a silver halide grain emulsion having higher sensitivity and more excellent graininess is required, and the conventional tabular silver halide emulsion is insufficient to meet these demands. Was expected to improve performance.

Since the tabular grains having a larger aspect ratio have a larger specific surface area, the advantages of the tabular grains can be greatly utilized. That is, it is possible to obtain high sensitivity by adsorbing more sensitizing dye on a larger surface area and increasing the amount of light absorption per grain. Like this
It is necessary to adsorb a larger amount of dye to tabular grains having a higher aspect ratio, but in that case, a big problem called aggregation of tabular grains occurs. Aggregation refers to a phenomenon in which two or more tabular grains are aggregated to form secondary particles, and when this aggregation occurs, deterioration of photographic performance such as deterioration of graininess, decrease in density after development, and increase in fog is caused. To do. Aggregation is a phenomenon in which the main surfaces of the tabular grains are attached to each other. The higher the aspect ratio of the tabular grains, the greater the amount of adsorbed dye, that is, the higher the coverage of the adsorbed dye on the grain surface, the more likely it is that aggregation will occur.

EP 603804 discloses acid-processed gelatin with extended chain length. In this patent, the acid-processed gelatin has many low molecular weight components as compared with the alkali-processed gelatin, and it is intended to eliminate the drawback by cross-linking the gelatin molecular chain. In that case, the cross-linking agent is a cross-linking agent that cross-links the amino groups of gelatin, such as bis- (vin
ylsulfonyl) compound. Crosslinking of gelatin was carried out in advance before preparation of silver halide grains.

Japanese Patent Laid-Open No. 11-237704 discloses a molecular weight of 2
A method for producing a tabular grain emulsion in the presence of an alkali-processed gelatin containing 30% or more of 80,000 or more components is disclosed, in which gelatin crosslinking is carried out prior to the preparation of the silver halide grains. Met. By cross-linking gelatin with a cross-linking agent, its molecular weight is substantially increased and therefore its viscosity is rapidly increased. Such a high-viscosity gelatin solution is difficult to handle, and requires special equipment for preparation, feeding and addition. Further, it is considered that the high-viscosity gelatin solution is once dried and made into a powder to facilitate the handling. For this purpose, the viscosity is further increased in the step of concentrating the high-viscosity gelatin solution,
In practice, concentration becomes difficult. In other words, the method of using pre-crosslinked gelatin for the preparation of silver halide grains has a drawback that there is a limit to the strengthening of the crosslinking, that is, there is a limit to the increase in the molecular weight due to the crosslinking of gelatin. There was a limit to the preventive power.
JP-A No. 11-231447 discloses that after any step from the formation of silver halide grains to the end of chemical sensitization,
A method for producing by adding a compound capable of crosslinking with gelatin is disclosed. In the preparation of tabular grains, particularly tabular grains having a high aspect ratio, aggregation is caused during grain formation, and thus the method according to the patent has little effect.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a photosensitive silver halide emulsion containing tabular grain silver halide grains having a high coverage of an adsorbing dye and preventing aggregation of grains. To do.

(1) In a method for producing a photosensitive silver halide emulsion containing a gelatin dispersion medium and silver halide tabular grains, a gelatin crosslinking agent is added from the start of the silver halide grain formation to the end of the grain formation. A method for producing a silver halide emulsion, characterized in that (2) The method for producing a silver halide emulsion according to (1), wherein the tabular grains have an aspect ratio of 10 or more and a sensitizing dye coverage of 60% or more. (3) A silver bromide-containing tabular grain comprising 60% or more of the total projected area of all silver halide grains having a thickness of less than 0.1 μm and an average equivalent circle diameter of 2 μm or more. The method for producing a photosensitive silver halide emulsion according to (1) or (2), wherein the amount is 70 mol% or more. (4) In the tabular grain preparation method comprising the steps of nucleation, ripening and growth, ripening without allowing at least one compound represented by the following general formula (I), (II) or (III) to exist during nucleation In the method for producing a silver halide emulsion to obtain a tabular grain emulsion, the mixer is provided outside the reaction vessel for nucleating silver halide grains and / or grain growth, An aqueous solution of a water-soluble silver salt and an aqueous solution of a water-soluble halide are supplied to the mixer and mixed to form silver halide fine particles, and the fine particles are immediately supplied to a reaction vessel, and the silver halide particles are fed in the reaction vessel. Nucleation and / or growth of
The method for producing a silver halide emulsion according to any one of (1) to (3). (5) In the tabular grain preparation method comprising the processes of nucleation, ripening and growth, ripening without allowing at least one compound represented by the following general formula (I), (II) or (III) to exist during nucleation The method for producing a silver halide emulsion according to any one of (1) to (4), characterized in that a tabular grain emulsion having a (111) plane as a main surface is obtained by allowing it to exist during and during growth.

[0009]

[Chemical 3]

In the 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 substituent. 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, at least one of R ₂ , R ₃ , R ₄ , R _5, and R ₆ represents an aryl group. X ^- represents a counter anion.

[0011]

[Chemical 4]

In the formula, A ₁ , A ₂ , A ₃ and A ₄ each represent a non-metal atom group for completing the nitrogen-containing heterocycle, and they 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, 1 or 2, and when it is an intramolecular salt, n is 0 or 1.

The tabular silver halide grain (hereinafter referred to as "tabular grain") in the present invention has two parallel main surfaces facing each other and has a circle equivalent diameter (the same projected area as the main surface). The diameter of a circle having is larger than the distance of the main surface (that is, the thickness of the particle) by a factor of 2 or more. The average grain diameter / grain thickness ratio (aspect ratio) of the emulsion having tabular grains of the present invention is preferably 3 to 500, more preferably 10 to 500, and further preferably 20 to 500. Here, the average grain diameter / grain thickness can be obtained by averaging the grain diameter / thickness ratios of all tabular grains, but as a simple method, the average diameter of all tabular grains and the average thickness of all tabular grains can be used. It can also be calculated as the ratio of.

The tabular grains of the present invention have an average diameter (corresponding to a circle) of 0.5 to 20 μm, preferably 1.0 to 15 μm, more preferably 1.0 to 10 μm, further preferably 2-1.
It is 0 μm. The particle thickness is 0.2 μm or less, preferably 0.1 μm or less (preferably 0.001 μm or more), and more preferably 0.06 to 0.02 μm. In the present invention, the average particle diameter and the average particle thickness can be measured from electron micrographs of the particles as described in US Pat. No. 4,434,226. That is, the measurement of the thickness of the particles,
It can be easily found by evaporating a 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.

The main surface of the tabular grain of the present invention is (11
It is roughly divided into 1) and (100). The tabular grain having the (111) plane as the main surface is a general term for silver halide grains having one twin plane or two or more parallel twin planes. The twin plane means the (111) plane when ions at all lattice points on both sides of the (111) plane have a mirror image relationship.
The tabular grains have a triangular shape, a hexagonal shape, or a rounded shape when viewed from above. The triangular shape has a triangular shape, and the hexagonal shape has a hexagonal shape. Tabular grains have parallel outer surfaces with rounded corners.

A method for producing (111) main surface type tabular grains is described in US Pat. Nos. 4,434,226 and 4,439,520.
No. 4414310, No. 4433048, No. 44
No. 14306, No. 4459353 and the like disclose the manufacturing method and use technique. In addition, JP-A-6-214331
As disclosed in US Pat.
Tabular grains can also be formed by setting conditions such as Ag and adding silver and a halogen solution and growing them. Further, as one preferable method, tabular grains are formed by adding silver halide fine particles instead of adding a silver salt aqueous solution and a halide aqueous solution to a reaction vessel holding a protective colloid aqueous solution. This method is described in US Pat. No. 4,879,208.
No. 1,183,644, No. 2-4435, No. 2-43535, No. 2-68538, No. 10-23.
The technology is disclosed in 9787. A fine grain silver iodide (grain size of 0.1 μm or less, preferably 0.06 μm or less) emulsion may be added as a method of supplying iodine ions in the formation of tabular grains. It is preferable to use the manufacturing method disclosed in JP-A-10-239787.

In the present invention, it is preferable to use monodisperse tabular grains. Regarding this, Japanese Patent Laid-Open No. 63-11928
JP-B-5-61205 discloses monodisperse hexagonal tabular grains, and JP-A-1-131541 discloses circular monodisperse tabular grains. Further, in JP-A-2-838, 95% or more of the total projected area is occupied by tabular grains having two twin planes parallel to the main surface, and the size distribution of the tabular grains is monodisperse. An emulsion is disclosed. EP 514742A discloses tabular grain emulsions prepared with polyalkylene oxide block copolymers having a grain size variation coefficient of 10% or less.

The silver chloride or the (111) plate having a high content of silver chloride used in the present invention is disclosed in the following patent. U.S. Pat. No. 4,414,306, U.S. Pat. No. 4,400,463, U.S. Pat. No. 4,713,323.
U.S. Pat. No. 4,783,398, U.S. Pat. No. 4,962.
491, US Pat. No. 4,983,508, US Pat. No. 4
804621, US Pat. No. 5,389,509, US Pat. No. 5,217,858, US Pat. No. 5,460,934.

The high silver bromide (111) tabular grains used in the present invention are described in the following patents. U.S. Pat. No. 4,425,425, U.S. Pat. No. 4,425,426,
US Pat. No. 443426, US Pat. No. 4,439,520
U.S. Pat. No. 4,414,310, U.S. Pat. No. 4,433.
048, US Pat. No. 4,647,528, US Pat. No. 4
665012, US Pat. No. 4,672,027, US Pat. No. 4,678,745, US Pat. No. 4,684,607,
U.S. Pat. No. 4,593,964, U.S. Pat. No. 472288.
6, US Pat. No. 4,722,886, US Pat. No. 475.
5617, US Pat. No. 4,755,456, US Pat. No. 4,806,461, US Pat. No. 4,801,522, US Pat. No. 4,835,322, US Pat. No. 4839268,
U.S. Pat. No. 4,914,014, U.S. Pat. No. 4,96201.
5, US Pat. No. 4,977,074, US Pat. No. 498.
5350, US Pat. No. 5,061,609, US Pat. No. 5061616, US Pat. No. 5,068,173, US Pat. No. 5,132,203, US Pat.
U.S. Pat. No. 5,334,469, U.S. Pat. No. 5,334.
495, US Pat. No. 5,358,840, US Pat. No. 5
No. 372927.

Regarding the (100) plate used in the present invention, US Pat. No. 4,386,086 described in the following patents:
156, US Pat. No. 5,275,930, US Pat. No. 5
292632, US Pat. No. 5,314,798, US Pat. No. 5,320,938, US Pat. No. 5,319,635,
US Pat. No. 5,356,764, European Patent No. 569971
No., European Patent No. 737887, JP-A-6-30864
No. 8, JP-A-9-5911.

The halogen composition of the tabular grains is silver iodobromide, silver chloroiodobromide, silver iodochloride, silver iodobromochloride, silver chlorobromide, and silver chloride. Regarding the structure relating to the halogen composition of the tabular grains of the present invention, X-ray diffraction, EPMA (XMA
Method) (a method of scanning silver halide grains with an electron beam to detect the silver halide composition), ESCA
It can be confirmed by combining (method of irradiating X-rays to disperse photoelectrons emitted from the particle surface) and the like. In the present invention, the grain surface means a region up to a depth of about 50 Å from the surface, and its halogen composition is usually ES.
It can be measured by the CA method. The inside of a particle refers to a region other than the above-mentioned surface region.

The gelatin to be crosslinked in the present invention means
Alkali-processed bone gelatin is preferable, and it is particularly preferable to use alkali-processed gelatin which has been subjected to deionization treatment for removing impurity ions and impurities or ultrafiltration treatment. Also,
Acid-processed gelatin can be used as well. As the gelatin used in the present invention, the following various modified alkali-treated bone gelatins can also be used. Such as phthalated gelatin modified with amino group, amber gelatin, trimellitic gelatin, pyromellitic gelatin, esterified gelatin represented by methyl esterified gelatin modified with carboxyl group, amidated gelatin, and ethoxyformylated gelatin. Imidazole group-modified gelatin, low molecular weight gelatin (specific examples of molecular weight of 1,000 to 80,000 include enzyme-decomposed gelatin, acid- and / or alkali-hydrolyzed gelatin, and heat-decomposed gelatin), High molecular weight gelatin (molecular weight 11
10,000 to 300,000) Gelatin having a methionine content of 50 μmol / g or less, gelatin having a tyrosine content of 20 μmol / g or less, oxidized gelatin, and gelatin in which methionine is inactivated by alkylation can be used. In the production method of the present invention, the silver halide grains may be prepared by using one type of gelatin alone, or may be prepared by using two or more types of gelatin in combination. The amount of gelatin used in the grain forming process in the present invention is 1 to 60 g /
Silver moles, preferably 3-40 g. The concentration of gelatin in the chemical sensitization process of the present invention is preferably 1 to 100 g / silver mole, more preferably 1 to 70 g / silver mole.

The gelatin used in the present invention is obtained by decomposing the structure of collagen tissue with an alkali or an acid to impart water solubility. In the case of alkali-treated gelatin, sub-α ( Low molecular weight),
It is composed of α (molecular weight of 100,000), β (molecular weight of 200,000), γ (molecular weight of 300,000) and a large polymer portion (void; molecular weight of more than 300,000). The ratio of each component, that is, the molecular weight distribution is measured by a high performance liquid chromatography method. For details of the method, refer to the "Paggie method" photographic gelatin test method established by the Joint Council for Photographic Gelatin Test Method.
7th edition (1992 edition) pages 31-33. For a measurement example of a general alkali-processed gelatin based on the Paggy method, see Journal of Photography Society, Vol.
Year) It is described in Fig. 6 on page 12. Here, the void component is called the H component. When alkali-treated bone gelatin with an isoelectric point of 5.0 used for photography was measured by this measurement, the molecular weight was 280,000 or more, that is, the ratio of the sum of γ and voids was 21%. In the gelatin of the present invention, the sum of γ and the void component is 50% or less,
It is 1% or more.

In the production method of the present invention, a gelatin crosslinking agent is added to a gelatin solution or a silver halide grain emulsion in a reaction vessel for causing nucleation and / or grain growth, and gelatin intermolecular crosslinking is carried out in the reaction vessel. Wake up. The conditions in the reaction vessel at that time differ depending on each crosslinking agent, but the reaction conditions can be determined by setting a constant reaction temperature and reaction time. At that time, the progress of crosslinking can be traced by measuring the viscosity of the gelatin solution. It is desirable that all of the added cross-linking agent participates in cross-linking, but if it remains uncross-linked, if it is added in the particle forming step, it is removed in the subsequent water washing step. Further, the cross-linking agent which is added after the washing step and does not contribute to cross-linking can be removed by ultrafiltration of the silver halide emulsion. The progress of crosslinking depends on temperature, time, pH of the solution, and the like.

The gelatin cross-linking agent of the present invention may be added at any time from the start of grain formation to the end of grain formation. In the grain forming step, it may be added in any step of nucleation, ripening, and growth, but it is preferable to add it after the nucleation is completed, and it is more preferable to add it before the start of the growth step or during the growth step. . Generally, grain aggregation is more likely to occur as the aspect ratio of tabular grains is higher and the thickness of tabular grains is thinner. This suggests that aggregation of particles is more likely to occur as the surface / volume increases. Aggregation of colloidal particles of small size causes a very large attractive force when the particles come within a certain distance because the van der Waals force (dispersion force) that acts between two particles is inversely proportional to the interparticle distance d. Aggregation will occur. In a silver halide grain emulsion using gelatin, gelatin is adsorbed on the grain surface to form an adsorption layer with a certain thickness, and this adsorption layer prevents grains from approaching each other within a certain distance. The particle agglomeration is prevented to ensure the colloidal stability of the particles. However, when the aspect ratio of the tabular grains increases and the surface / volume increases, aggregation tends to occur, and in order to secure colloidal stability, that is, to prevent grain aggregation, the gelatin adsorption layer on the grain surface should be made thicker. Will be required. Aggregation of particles causes a large amount of the spectral sensitizing dye to be adsorbed on the surface of the particle, and when the coverage exceeds 60%, desorption of gelatin occurs due to the adsorption of the dye, and the gelatin adsorption layer becomes substantially thin. As a result, particle aggregation easily occurs. Also in this case, it is necessary to thicken the adsorbed gelatin layer as described above. In order to make the adsorbed gelatin layer thick, it has been revealed in the present invention that it is essential to significantly increase the molecular weight of gelatin by cross-linking the gelatin in a reaction vessel in which particles are prepared.

Japanese Patent Laid-Open No. 11-237704 discloses a molecular weight of 2
A method for producing a tabular grain emulsion in the presence of an alkali-processed gelatin containing 30% or more of 80,000 or more components is disclosed, in which gelatin crosslinking is carried out prior to the preparation of the silver halide grains. Met. By cross-linking gelatin with a cross-linking agent, its molecular weight is substantially increased and therefore its viscosity is rapidly increased. Such a high-viscosity gelatin solution is difficult to handle, and requires special equipment for preparation, feeding and addition. Further, it is considered that the high-viscosity gelatin solution is once dried and made into a powder to facilitate the handling, but in this case, the viscosity is further increased in the step of concentrating the high-viscosity gelatin solution,
In practice, concentration becomes difficult. In other words, the method of using pre-crosslinked gelatin for the preparation of silver halide grains has a drawback that there is a limit to the strengthening of the crosslinking, that is, there is a limit to the increase in the molecular weight due to the crosslinking of gelatin. There was a limit to the preventive power.
The present invention solves this problem all at once and enables production of tabular grains with a high aspect ratio. That is, the crosslinking can be further strengthened by adding the crosslinking agent to the reaction vessel during the silver halide grain forming step. Although addition of a large amount of cross-linking agent certainly increases the viscosity, especially in the grain forming step, since a large amount of salt is present in the silver halide emulsion in the reaction vessel, the spread of gelatin molecules is suppressed, and the viscosity is reduced. The rise is remarkably alleviated, and the crosslinking can be further strengthened.

There are the following three methods for measuring the degree of aggregation of tabular grains. Filtration pressure method: The tabular grain emulsion is passed through a filter having a pore size of 10 μ or 3 μ, and the rise in filtration pressure at that time is measured. When coagulation occurs, the filtration pressure rises faster. Coating film concentration: A fixed amount of tabular grain emulsion is coated on a film, and after drying, the concentration is measured with visible light (light of wavelength of dye absorption in the case of particles adsorbing dye) specular light. The concentration decreases when the particles agglomerate. Section photography method: A certain amount of tabular grain emulsion is applied to a film, dried, and then the film is prepared into an ultrathin section by a microtome, and its cross section is observed by SEM. From the cross-sectional photograph, the aggregation state of tabular grains can be observed. This method is visually recognizable, but not quantitative.

As the gelatin cross-linking method used in the present invention, all the cross-linking agents which have hitherto been known as thickeners for gelatin can be used. As the thickener, an anionic polymer having an interaction with gelatin can be used. JP-B Nos. 41-12835 and 57-33
777, 59-7724, JP-A-57-1054.
71, 51-81123, 53-39119.
No. 52-67318, No. 55-98746, No. 56-5537, No. 53-13411, No. 55-9.
No. 8745, No. 53-18687, and U.S. Pat. No. 374.
No. 6547, No. 3767410, British Patent No. 142
Compounds described in publications such as 1930 and French Patent No. 2178157 are useful. Preferred examples of the thickener in the present invention include compounds represented by the following general formula (TH-I) to general formula (TH-II). General formula (TH-I)

[0029]

[Chemical 5]

In the formula, A represents a monomer unit obtained by copolymerizing a copolymerizable ethylenically unsaturated monomer, and may contain two or more kinds of monomer units. A of general formula (TH-I)
Examples of ethylenically unsaturated monomers represented by are styrene, hydroxymethylstyrene, α-methylstyrene,
4-vinylpyridine, N-vinylpyrrolidone, 1-vinylimidazole, 2-methyl-1-vinylimidazole, monoethylenically unsaturated ester of fatty acid (eg vinyl acetate), maleic anhydride, ethylenically unsaturated monocarboxylic acid Alternatively, an ester of dicarboxylic acid (for example, n
-Butyl acrylate, N, N-diethylaminoethyl methacrylate, 2-hydroxyethyl acrylate and methacrylate, etc.), ethylenically unsaturated ethers (such as methyl vinyl ether), ethylenically unsaturated monocarboxylic acids, or dicarboxylic acid amides (such as acrylamide). , N- (1,1-dimethyl-3-oxobutyl) acrylamide, N-isopropylacrylamide, {N- (3-acrylamidepropyl)-
N, N-dimethylammonio} acetate betaine). R ¹ represents a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, butyl group, etc.), in which a hydrogen atom,
Or a methyl group is particularly preferable. L is a single bond or 2
It is a valent linking group and may be substituted. Preferably an alkylene group, an arylene group, or these groups

[0031]

[Chemical 6]

It is a divalent group formed by combining one or more bonds represented by. R ² represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aralkyl group. Particularly preferably, L is

[0033]

[Chemical 7]

--CONHC (CH ₃ ) ₂ CH _2- , --CO
_{OCH 2 CH 2 O -, -} COOCH 2 CH 2 OCOCH 2 C
_{H 2 -, - CONHCH 2 CH} 2 O -, - CONHCH 2 C
_{H 2 OCOCH 2 CH 2 -,} - COOCH 2 CH 2 -, - C
ONHCH ₂ CH ₂ —, and a single bond. Q ^n- represents an anionic group, preferably a carboxyl group, a sulfo group or a phosphonic acid group. n is 1 or 2, and Q ^n-
Specified by the type of. (For example, Q ^n- is a sulfo group,
For a carboxyl group or the like, n = 1. ) M ⁺ represents a hydrogen ion, a monovalent metal ion or an ammonium cation, preferably a hydrogen ion, a sodium ion, a potassium ion or an ammonium ion.

[0035]

[Chemical 8]

The monomer unit represented by may be a mixture of two or more different monomer units. x and y represent mole percentages, and x has a value of 0 to 99 and y has a value of 1 to 100. Preferably x is 0 to 75, y
Is 25 to 100. General formula (TH-II)

[0037]

[Chemical 9]

In the formula, A represents a monomer unit obtained by copolymerizing a copolymerizable ethylenically unsaturated monomer. Examples of the ethylenically unsaturated monomer represented by A are styrene, hydroxymethylstyrene, sodium vinylbenzene sulfonate, N, N, N-trimethyl-N-vinylbenzylammonium chloride, α-methylstyrene, 4-vinylpyridine. , N-vinylpyrrolidone, monoethylenically unsaturated esters of aliphatic acids (eg vinyl acetate), ethylenically unsaturated monocarboxylic or dicarboxylic acids and salts thereof (eg acrylic acid, methacrylic acid), maleic anhydride, ethylene Of unsaturated monocarboxylic or dicarboxylic acids (for example, n-butyl acrylate,
N, N-diethylaminoethyl methacrylate, N, N
-Diethyl-N-methyl-N-methacryloyloxyethylammonium-p-toluenesulfonate), amides of ethylenically unsaturated monocarboxylic or dicarboxylic acids (eg acrylamide, 2-acrylamido-
2-methyl propane sulfonic acid sodium, N, N- dimethyl-N'-methacryloyl propane diamine acetate betaine). x and y are mole percentages,
x represents 0 to 99 and y represents 1 to 100. R ³ and R ⁴ have the same definition as R ^{1 in} formula (TH-I), and may be the same or different. R ³ and R ⁴ are preferably hydrogen atoms. X represents a hydrogen atom, a monovalent metal atom or an ammonium salt, preferably a hydrogen atom, a sodium atom or a potassium atom. Y is -O- or -N (R ⁵⁾ - a and (R ⁵ is an alkyl group having a hydrogen atom, or 1 to 10 carbon atoms, an aralkyl group, an aryl group.), - O-is preferred . Z is defined as R ⁵ and Y is —O—
In the case of, a monovalent metal atom or an ammonium salt is represented, and a hydrogen atom, a sodium atom and a potassium atom are preferable. Specific examples of the thickener in the present invention will be given below, but the present invention is not limited thereto.

[0039]

[Chemical 10]

[0040]

[Chemical 11]

As the cross-linking agent used in the present invention, all the cross-linking agents known to date as curing agents can be used. The representative compounds are listed below. A. Inorganic cross-linking agent (inorganic hardener) Cationic chromium complex; as a ligand of the complex, hydroxyl group, oxalic acid group, citric acid group, malonic acid group, lactate salt, tartrate salt, succinate salt, acetate salt, Formate, sulfate,
Chloride, nitrate. Aluminum salt; especially sulfate, potassium alum, ammonium alum. In addition, water-soluble salts of titanium and zirconium. The above compounds crosslink the carboxyl groups of gelatin at relatively low pH.

B. Organic cross-linking agent (organic hardener) 1. Aldehyde cross-linking agent; formaldehyde is the most commonly used. Dialdehyde can also be effectively crosslinked, and examples thereof include glyoxal and succinaldehyde, particularly glutaraldehyde. Diglycolaldehyde and various aromatic dialdehydes, as well as dialdehyde starch and dialdehyde derivatives of plant gums are also used in the crosslinking of the present invention. 2. N-methylol compounds and other protected aldehyde cross-linkers; N-methylol compounds obtained by condensation of formaldehyde with various aliphatic linear or cyclic amides, urea, nitrogen-containing heterocycles. Specifically, a few
-Dihydrochidioxane, dialdehyde and acetic acid ester of hemiacetal thereof, and 2,5-methoxytetrahydrofuran. 3. Ketone cross-linking agent; compounds of diketone and quinones. Well known diketones include 2,3-butanedione,
CH ₃ COCOCH ₃ etc. As the quinone, p-benzoquinone is well known. 4. Sulfonic acid ester and sulfonyl halide; bis (sulfonyl chloride) s and bis (sulfonyl fluoride) s are typical compounds. 5. Active halogen compound; a compound having two or more active halogen atoms. Typical compounds are ketones, esters,
Examples include simple bis-a-chloro or bis-a-bromo derivatives of amides, bis (2-chloroethylurea), bis (2-chloroethyl) sulfone, and phosphoramidic halides. 6. Epoxide; butadiene-oxide is mentioned as a typical compound. 7. Active olefins; many compounds with two or more double bonds, especially unsubstituted vinyl groups activated by adjacent electron withdrawing groups, are effective as gelatin crosslinkers.
Examples of this compound include divinyl ketone, resorcinol bis (vinyl sulfonate), 4,6-bis (vinyl sulfonate), 4,6-bis (vinyl sulfonyl) -m-xylene, bis (vinyl sulfonyl alkyl). Examples thereof include ethers or amines, 1,3,5-triacryloylhexahydro-s-triazine, diacrylamide, and 1,3-bis (acryloyl) urea.

8. s-triazines; the following general formula [H-
A compound represented by I].

[0044]

[Chemical 12]

In the formula, R ¹ is a hydroxyl group, —OM group (M is a monovalent metal atom), alkyl group, —N (R ₂ ) (R ₃ ) group (R ² , R ^3).
Represents an alkyl group and an aryl group, respectively. ), -NH
COR ⁴ (R ⁴ represents a hydrogen atom, an alkyl group, an aryl group, an alkylthio group or an arylthio group) or an alkoxy group. The cyanuric chloride type hardener represented by the general formula (HI) is disclosed in Japanese Examined Patent Publication No.
6151, 47-33380, 54-2541
No. 1 and JP-A-56-130740 have detailed description. Further, JP-B-53-2726 and JP-A-50-61219 having a structure similar to that of the compound of formula (HI).
Nos. 56-27135 and the like are also useful in the present invention.

9. Vinyl sulfone compounds: compounds represented by the following general formula [H-II].

[0047]

[Chemical 13]

In the above general formula, X ¹ and X ² are each-
CH = CH ₂ or is any of -CH ₂ CH ₂ Y, X ¹ and X ² may be the same or different. Y represents a group which is substituted by a nucleophilic group or which can be eliminated by a base in the form of HY (eg, a halogen atom, sulfonyloxy, sulfuric acid monoester, etc.). L is a divalent linking group and may be substituted. Regarding the vinyl sulfone type hardener represented by the general formula (H-II), for example, JP-B-47-24
259, 50-35807, JP-A-49-244.
No. 35, No. 53-41221, No. 59-18944 and the like have detailed description.

10. Carbamoyl ammonium salt; a compound represented by the following general formula [H-III].

[0050]

[Chemical 14]

In the formula, R ¹ and R ² are each an alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, 2-ethylhexyl group, etc.), aryl group having 6 to 15 carbon atoms (eg, phenyl group, naphthyl group). Etc.) or an aralkyl group having 7 to 15 carbon atoms (eg, benzyl group, phenethyl group, etc.), and they may be the same or different. Also R
It is also preferred that ¹ and R ² are bonded to each other to form a heterocycle with a nitrogen atom. R ³ represents a substituent. General formula (H
-III), the detailed description of the carbamoyl ammonium salt type hardener represented by JP-B-56-12853.
No. 58-32699, JP-A-49-51945.
No. 51-59625 and 61-9641.

11. A compound represented by the following general formula [H-IV].

[0053]

[Chemical 15]

[0054] R ^1, R ^2, R ³ and X ^- definition is exactly the same as defined in the general formula (H-III), the compounds detailed in Belgian Patent No. 825,726.

12. Amidinium salt compounds: compounds represented by the following general formula [HV].

[0056]

[Chemical 16]

R ¹ , R ² , R ³ and R ⁴ have 1 to 1 carbon atoms.
It is an alkyl group having 20 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, or an aryl group having 5 to 20 carbon atoms, which may be the same or different. X represents a group capable of leaving when the compound represented by the general formula (HV) reacts with a nucleophile, and preferable examples thereof include a halogen atom, a sulfonyloxy group, a 1-pyridiniumyl group and the like. Y ^-
Represents an anion. The amidinium salt-based hardener represented by the general formula (HV) is disclosed in JP-A-60-2251.
No. 48 has a detailed description.

13. Carbodiimide compounds; compounds represented by the following general formula [H-VI].

[0059]

[Chemical 17]

In the formula, R ¹ is an alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, etc.), a cycloalkyl group having 5 to 8 carbon atoms, an alkoxyalkyl group having 3 to 10 carbon atoms, or a carbon number. It represents an aralkyl group of 7 to 15. R
² is a group defined for R ¹ or -R ³ -N ⁺ ≡ (R ⁴ )
Represents (R ⁵ ) (R ⁶ ) .X ⁻ . R ³ represents an alkylene group having 2 to 4 carbon atoms. R ⁴ and R ⁵ may be the same or different and each represents an alkyl group having 1 to 6 carbon atoms. R ⁶ represents an alkyl group having 1 to ⁶ carbon atoms, but it is also preferably substituted. X ⁻ represents an anion. Regarding these carbodiimide type hardeners, see JP-A-51-
For details, see 126125 and 52-48311.

14. Pyridinium base compounds: compounds represented by the following general formula [H-VII].

[0062]

[Chemical 18]

In the formula, R ¹ is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, or 7 to 1 carbon atoms.
Represents an aralkyl group of 5. These groups may be substituted. R ² and R ³ represent a hydrogen atom, a halogen atom, an acylamido group, a nitro group, a carbamoyl group, a ureido group, an alkoxy group, an alkyl group, an alkenyl group, an aryl group, an aralkyl group and the like, and they are the same. May be different. It is also preferable that R ² and R ³ are bonded to each other to form a condensed ring together with the pyridinium ring skeleton.
X represents a group capable of leaving when the compound represented by the general formula (X-VII) reacts with a nucleophile. Y ^- is represents an anion. For these pyridinium base hardeners,
JP-B-58-50699, JP-A-57-44140
No. 57-46538.

15. Pyridinium salt compounds: compounds represented by the following general formula [H-VIII].

[0065]

[Chemical 19]

In the formula, R ¹ and R ² are defined by the general formula (H-II
The definition of R ¹ and R ² in I) is exactly the same as that of R ³
Represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, or an aralkyl group having 7 to 15 carbon atoms.
X ^- is an anion. The pyridinium salt hardener represented by the general formula (H-VIII) is disclosed in JP-A-52-54.
No. 427 for details.

As the hardener used in the present invention, in addition to the compounds represented by the above general formulas (H-1) to (H-VIII), JP-A-50-38540 and 52- 9
No. 3470, No. 56-43353, No. 58-1139.
The compounds described in U.S. Pat. No. 29 and U.S. Pat. No. 3,321,313 are also preferable. Specific examples of the compound used in the present invention are listed below, but the present invention is not limited thereto.

[0068]

[Chemical 20]

[0069]

[Chemical 21]

As the cross-linking agent used in the present invention, a method of cross-linking gelatin with an enzyme can be used. As a typical method, gelatin crosslinked with transglutaminase will be described. The transglutaminase enzyme can crosslink gelatin by its function of catalyzing the acyl transfer reaction between the γ-carboxamide group of glutamine residue and various primary amines of protein gelatin. The transglutaminase may be animal-derived, plant-derived, or microbial-derived.For example, animal-derived ones include mammalian organs such as guinea pig liver, those extracted from blood, and plant-derived ones from pea. Extracted and derived from microorganisms are extracted from actinomycetes. In the present invention, any origin can be preferably used as long as it exhibits transglutaminase activity.

The transglutaminase of the present invention can be obtained by the method of Clark et al. (Achives of Biochemistry and Bioph).
ysics, 79, 338 [1959]), Connel et al. (J. Bilogi
calChemistry, 246, [1971]), JP-A-4-207149.
Compounds synthesized by any of the methods described in JP-A-6-30770 and JP-A-6-30770 can be preferably used.
Examples of these transglutaminases include Acteva (trade name, manufactured by Ajinomoto Co., Inc.). The transglutaminase activity of the present invention can be measured by reacting benzyloxycarbonyl L-glutaminylglycine with hydroxyamine and determining the amount of hydroxamic acid produced. The transglutaminase activity that produces 1 × 10 ⁻⁶ mol of hydrixamic acid per minute by this measurement is defined as one unit. Although the transglutaminase of the present invention varies depending on the gelatin used, gelatin 1
It is preferable to add 1 x 10 ^-6 mol or more of hydroxamic acid to g, particularly preferably 1 x 1
0 is preferable to produce a ^-5 mol or more hydroxamic acids.

In producing the silver halide emulsion based on the present invention, there is no particular limitation on the additives which can be added from the time of grain formation to the time of coating. Also, any combination of known techniques can be used. Regarding these, the description in the following documents can be referred to.
A silver halide solvent can be used in order to promote the growth during the crystal formation process and to effectively smooth the chemical sensitization during grain formation and / or chemical sensitization. Examples of frequently used silver halide solvents include water-soluble thiocyanates, ammonia, thioethers and thioureas. For example, thiocyanates (US Pat. Nos. 2,222,264, 2,448,534, and 33).
No. 20069 each specification), ammonia, thioether compound (for example, US Pat. Nos. 3,271,157, 357).
No. 4628, No. 3704130, No. 4297439
Nos. 4,276,347 and the like) and thione compounds (for example, JP-A Nos. 53-144319 and 53-824).
No. 08, No. 55-77737, etc.), amine compounds (for example, JP-A No. 54-100717, etc.),
Thiourea derivatives (for example, JP-A-55-2982), imidazoles (JP-A-54-100717), substituted mercaptotetrazoles (JP-A-57-20).
No. 2531).

The silver halide emulsion used in the present invention can be produced by any method known so far. That is, the silver salt aqueous solution and the halogen salt aqueous solution are added to a reaction vessel containing the gelatin aqueous solution under efficient stirring. As a concrete method, P. Glafkides
By Chemie et Phisique Photographique (Paul Montel
(Published in 1967), by GF Duffin, Photographic Emulsion
Chemistry (The Focal Press, 1966), VLZeli
By kman et al Making and Coating Photographic Emuls
ion (published by The Focal Press, 1964) and the like. That is, the acidic method,
The neutral method, the ammonia method, or the like may be used, and the method of reacting the soluble silver salt with the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof. As one type of simultaneous mixing method, a method of keeping pAg constant in a liquid phase in which silver halide is produced,
That is, the so-called controlled double jet method can also be used. Also, British Patent 1535016
Specification, Japanese Patent Publication Nos. 48-36890 and 52-163
No. 64, etc., a method of changing the addition rate of silver nitrate or an alkali halide aqueous solution according to the grain growth rate, US Pat. No. 4,242,445, JP-A-55-158124, etc. It is preferable to grow rapidly in a range not exceeding the critical supersaturation degree by using a method of changing the concentration of the aqueous solution as described in 1. These methods are preferably used because re-nucleation does not occur and silver halide grains grow uniformly.

Instead of adding the silver salt solution and the halogen salt solution to the reaction vessel, finely prepared fine particles are added to the reaction vessel to cause nucleation and / or grain growth to obtain silver halide grains. It is preferred to use the method. Regarding this technique, JP-A-1-183644, JP-A-1-183645, and US Pat.
No. 8, JP-A-2-44335, JP-A-2-43
No. 534 and JP-A-2-43535. According to this method, the distribution of halogen ions in the crystal of emulsion grains can be made completely uniform, and preferable photographic characteristics can be obtained.

Further, in the present invention, emulsion grains having various structures can be used. So-called core / shell double-structured particles composed of the inside (core part) and the outside (shell part) of particles, triple-structured particles as disclosed in JP-A-60-222844, and multilayers of more than that. Structural particles are used. When a structure is provided inside the emulsion grains, not only the wrapping structure described above but also a so-called junction structure can be prepared. Examples of these are disclosed in JP-A-59-133540 and JP-A-58-58.
108526, European Patent 199290A2, JP-B-58-24772, JP-A-59-162.
No. 54, etc. are disclosed. The crystal to be joined is
It can be formed by bonding to the edge, corner, or face of the host crystal with a composition different from that of the host crystal. Such a junction crystal can be formed even if the host crystal has a uniform halogen composition or has a core-shell type structure. In the case of a junction structure, it is naturally possible to combine silver halides with each other. However, if a silver salt compound not having a rock salt structure such as silver rhodan and silver carbonate is combined with silver halide, a junction structure can be used. May be.

In the case of silver iodobromide grains having these structures, for example, in a core-shell type grain, even if the silver iodide content in the core portion is high and the silver iodide content in the shell portion is low, Conversely, grains having a low silver iodide content in the core part and a high silver iodide content in the shell part may be used. Similarly, with respect to the grains having a junction structure, the grains having a high silver iodide content in the host crystal and the silver iodide content in the junction crystal being relatively low, or vice versa. Also,
The boundary portion of the grains having these structures, which have different halogen compositions, may be a clear boundary or an unclear boundary by forming a mixed crystal due to a difference in composition, and it is positively continuous. It may have a structural change. The silver halide emulsion used in the present invention is EP-0096727B1, EP.
-00644B1 Treatments for rounding particles, as disclosed in the respective specifications, or DE-23
The surface may be modified as disclosed in the specification of 06447C2 and JP-A-60-221320.

As the chemical sensitization in the present invention, chalcogen sensitization such as sulfur sensitization, selenium sensitization and tellurium sensitization, and noble metal sensitization and reduction sensitization can be used alone or in combination.

In sulfur sensitization, unstable sulfur compounds were used, and P. Grafkides, Chimie et Physique Photograph was used.
ique (Paul Momtel, 1987, 5th edition), Research
Unstable sulfur compounds described in Disclosure magazine 307, volume 307105 and the like can be used. Specifically, thiosulfates (for example, hypo), thioureas (for example, diphenylthiourea, triethylthiourea, N-
Ethyl-N '-(4-methyl-2-thiazolyl) thiourea, carboxymethyltrimethylthiourea), thioamides (for example, thioacetamide), rhodanines (for example, diethylrhodanine, 5-benzylidene-N-ethyl-). Rhodanine), phosphine sulfides (eg, trimethylphosphine sulfide), thiohydantoins, 4-oxo-oxazolidine-2-thiones, dipolysulfides (eg, dimorpholine disulfide, cystine, hexathiocan-thione), mercapto Compounds (for example, cystine), polythionates, known sulfur compounds such as elemental sulfur, and active gelatin can also be used.

In the sensitization of selenium, an unstable selenium compound is used, and Japanese Patent Publication Nos. 43-13489 and 44-157 are used.
48, JP-A-4-25832 and 4-109240.
Unstable selenium compounds described in Japanese Patent Application No. 3-53693, Japanese Patent Application No. 3-82929 and the like can be used. Specifically, colloidal metal selenium, selenoureas (eg, N, N-dimethylselenourea, trifluoromethylcarbonyl-trimethylselenourea, acetyl-trimethylselenourea), selenamides (eg, selenoacetamide, N, N-diethylphenyl selenamide), phosphine selenides (for example, triphenylphosphine selenide, pentafluorophenyl-triphenylphosphine selenide), selenophosphates (for example, tri-p-tolylselenophosphate) , Tri-n-butylselenophosphate), selenoketones (eg, selenobenzophenone), isoselenocyanates, selenocarboxylic acids,
Selenoesters and diacyl selenides may be used. Furthermore, Japanese Patent Publications Nos. 46-4553 and 52-3.
The relatively stable selenium compounds described in each of the 4492 publications, such as selenious acid, potassium selenocyanide, selenazoles, and selenides, can also be used.

In tellurium sensitization, an unstable tellurium compound was used, and Canadian Patent 800958 and British Patent 129 were used.
Nos. 5462, 1396696, Japanese Patent Application No. 2-
No. 333819, No. 3-53693, No. 3-1315
Unstable tellurium compounds described in JP-A-98 and JP-A-4-129787 can be used. Specifically, telluroureas (for example, tetramethyl tellurourea, N, N'-dimethylethylene tellurourea, N, N'-
Diphenylethylene tellurourea), phosphine tellurides (eg, butyl-diisopropylphosphine telluride, tributylphosphine telluride, tributoxyphosphine telluride, ethoxy-diphenylphosphine telluride), diacyl (di) tellurides. (For example, bis (diphenylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) telluride, bis (ethoxycarbonyl) telluride), isosterocyanate, telluroamide , Tellurohydrazides, telluroesters (eg, butylhexyl telluroester), telluroketones (eg, telluroacetophenone), colloidal tellurium, (di) tellurides, and other tellurium compounds ( Tashiumuterurido, tellurocarbonyl penta isethionate sodium salt) or the like may be used.

Regarding the sensitization of precious metals, P. Grafkides,
Chemie et Physique Photographique (Paul Momtel, 1987, 5th edition), Research Disclosure 307
Noble metal salts such as gold, platinum, palladium and iridium described in Vol. 307105 can be used,
Of these, gold sensitization is particularly preferable. Specifically, in addition to potassium chloroaurate, potassium aurithiocyanate, gold sulfide, gold selenide, US Pat.
No. 5, bis (1,4,5-trimethyl-1,1,
2,4-triazolium-3-thiolate) gold (1) tetrafluoroborate, US Pat. No. 2,642,361,
The gold compounds described in the respective specifications of Nos. 5049484 and 5049485 can also be used. Regarding reduction sensitization, Chemie et Physique Photo by P. Grafkides mentioned above.
graphique (Paul Momtel, 1987, 5th edition), Rese
Known reducing compounds described in arch Disclosure 307, 307105, etc. can be used. Specifically, aminoiminomethanesulfinic acid (also known as thiourea dioxide), borane compound (eg, dimethylamineborane), hydrazine compound (eg, hydrazine, paratolylhydrazine), polyamine compound (eg, diethylenetriamine, triethylenetetramine) , Stannous chloride, silane compounds, reductones (eg, ascorbic acid), sulfites, aldehyde compounds, hydrogen gas and the like may be used. Further, reduction sensitization may be performed in an atmosphere of high pH or excess silver ions (so-called silver ripening).

These chemical sensitizations may be used alone or in combination of two or more kinds. When they are combined, a combination of chalcogen sensitization and gold sensitization is particularly preferable. Further, reduction sensitization is preferably performed at the time of forming silver halide grains. The amount of the chalcogen sensitizer used in the present invention varies depending on the silver halide grains used, chemical sensitization conditions, etc., but is 10 ^-8 to 10 ^-2 mol, preferably 1 mol per mol of silver halide.
About 0 ^{−7 to} 5 × 10 ⁻³ mol is used. The amount of the noble metal sensitizer used in the present invention is 1 per mol of silver halide.
About 0 ^-7 to 10 ^-2 mol is used. The chemical sensitization conditions in the present invention are not particularly limited, but pAg is 6 to 1
1, preferably 7 to 10, with a pH of 4 to 10
Is preferable, and the temperature is 40 to 95 ° C., and further 4
5 to 85 ° C is preferable.

[0083]

EXAMPLES Example 1 Pure silver bromide tabular grain emulsion Emulsion 1-A (comparative) In the system shown in FIG. 2 described in JP-A-10-239787, the system shown in FIG. Tabular grains were prepared in the following manner using a mixer (volume of the mixer: 0.5 ml). In this example, a method of performing nucleation and grain growth using a mixer is shown. In the mixer, add 0.00
250 ml of 29 M silver nitrate aqueous solution and 250 ml of 0.0089 M KBr aqueous solution containing 0.1% by mass of low molecular weight gelatin (average molecular weight 40,000) were continuously added at a constant flow rate for 10 minutes, and the obtained emulsion was continuously added. 10 in the reaction vessel
It was received over a period of time to obtain 500 ml of a nuclear emulsion. The stirring speed of the mixer was 2000 rpm. (Nucleation) After completion of the nucleation, 11 ml of 0.8M KBr solution and 10% by mass of trimellitic gelatin containing 0.1 millimole of the crystal habit controlling agent 1 were stirred while thoroughly stirring the nuclei emulsion in the reaction vessel. Add 200 ml and raise the temperature to 75 ° C. 30
Let stand for a minute. (Aging) After the temperature was set to 90 ° C., 300 ml of a 10 mass% solution of lime-processed bone gelatin in which the ratio of the total of voids and γ parts to the whole was 15% was added, and a 1/50 M crystal habit controlling agent was further added. 60 ml of I was added. After that, the mixture was mixed again with 0.
KBr 0.6 containing 1000 ml of 6M silver nitrate aqueous solution and 90 g of low molecular weight lime-treated bone gelatin (average molecular weight 40,000)
1000 ml of an aqueous solution of M was added over 92 minutes at a constant flow rate. The fine grain emulsion produced in the mixer was continuously added to the reaction vessel. At that time, the stirring speed of the mixer is 2000 rp
It was m. At the same time, 90 ml of a 1/50 M solution of the crystal habit controlling agent I and 92 ml of a 1.45 M KBr solution were continuously added to the reaction vessel at a constant flow rate for 92 minutes. The stirring blade of the reaction vessel was rotated at 800 rpm and well stirred. (Growth) During grain growth, when 70% of silver nitrate was added, IrCl ₆ was added and doped at 8 × 10 ⁻⁸ mol / molAg. Furthermore, the yellow blood salt solution was added to the mixer before the end of particle growth. Yellow blood salt was doped to 3% of the shell portion of the particles (in terms of the amount of added silver) so as to have a local concentration of 3 × 10 ⁻⁴ mol / mol Ag.
After the addition was completed, the emulsion was cooled to 35 ° C, washed with water by the usual flocculation method, and 70 g of lime-treated bone gelatin was added and dissolved to adjust pAg to 8.7 and pH to 6.5, and then stored in a cool and dark place. did. Table 1 shows the characteristics of the obtained tabular grains. Crystal habit control agent I

[0084]

[Chemical formula 22]

Emulsion-B (Comparative) A gelatin solution added after ripening was previously cross-linked with a vinyl sulfone-based cross-linking agent [H-2], and a lime treatment in which the sum of voids and γ portions accounted for 40% of the whole was treated. The procedure of Emulsion A was repeated except that the solution was changed to a 10% by mass solution of gelatin.

Emulsion-C (invention) The same procedure as Emulsion A was carried out except that 60 ml of a 2% solution of an anionic thickener [TH-1] was added 2 minutes after the addition of the gelatin solution added after ripening. . Emulsion-D (Invention) Two minutes after the gelatin solution added after ripening was added, 50 ml of a 2% solution of an anionic thickener [TH-1] was added,
Further, after 30 minutes, the same procedure as in Emulsion A was performed except that 100 ml of the same solution was added. Table 1 shows the characteristics of the obtained tabular grains.

[0087]

[Table 1]

As is clear from the results shown in Table 1, it is understood that tabular grains having a large equivalent circle diameter and a small thickness can be prepared by the method according to the present invention. Tabular grains 1-D have an average aspect ratio of more than 200. Emulsion 1-A, 1-
In B and 1-E, thick tabular grains were mixed with thin tabular grains. The thick tabular grains are aggregates of thin tabular grains during grain growth and grow as one tabular grain. In the method of the present invention, aggregation of the tabular grains was prevented, and thin tabular grains could be grown. Example 2 Filtration Pressure Measurement Emulsions 1-A to 1-E were evaluated for their easiness of filtration by measuring the increase in filtration pressure as follows. (Filtration conditions) Filtration cross-sectional area: 2.27 cm ² Temperature: 40 ° C. Flow rate: 25 ml / min Filter pore size: 10 μm Results showing filterability at the time required for the filtration pressure to reach 0.6 kg / cm ^2. It shows in Table-2.

[0089]

[Table 2]

As can be seen from the results in Table 2, Emulsions 1-A, 1
In -B and 1-E, the filtration time is short, but in the emulsions 1-C and 1-D of the present invention, the filtration time is long, and the aggregation suppression of particles effectively functions in the present invention. I understand that.

Example 3 Evaluation of Photographic Properties of Emulsion Using Coated Samples 1-A, 1-B, 1-C, 1-D obtained in Example 1
The following sensitizing dye, 2.4 × 10 ^-4 mol / mol silver, was added to the emulsion of 1-E, and sodium thiosulfate, potassium chloroaurate and potassium thiocyanate were added to optimize the temperature at 60 ° C. Chemically sensitized. The coverage of the sensitizing dye was 80%.

[0092]

[Chemical formula 23]

A coating sample was prepared by coating an emulsion and a protective layer on a cellulose triacetate film support having an undercoat layer under the following conditions. [Emulsion coating conditions] (1) Emulsion layer / Emulsion Various emulsions (Silver 3.6 × 10 ^-2 mol / m ² ) -Couplers shown below (1.5 × 10 ^-3 mol / m ² ).

[0094]

[Chemical formula 24]

Tricresyl phosphate (1.10 g / m ² ), gelatin (2.30 g / m ² ) (2) protective layer, 2,4-dichloro-6-hydroxy-s-triazine sodium salt (0 .08g / m ²⁾ · gelatin (1.80g / m ²⁾ these samples 40 ° C., the relative humidity of 70% 14
After being left for a time, it was exposed for 1/100 seconds through a yellow filter and a continuous wedge, and the following color development was performed.

[Color Development] Process processing time Processing temperature Color development 2 minutes 00 seconds 40 ° C Bleach-fixing 3 minutes 00 seconds 40 ℃ Washing with water (1) 20 seconds 35 ° C Washing with water (2) 20 seconds 35 ° C Stabilized 20 seconds 35 ℃ Dry 50 seconds 65 ℃ Next, the composition of the treatment liquid is shown. (Color development) (Unit: g)   Diethylenetriamine pentaacetic acid 1-hydroxyethylidene     -1,1-disulfone 2.0   Sodium sulfite 4.0   Potassium carbonate 30.0   Potassium bromide 1.4   Potassium iodide 1.5mg   Hydroxyamine sulfuric acid 2.4   4- [N-ethyl-N-β-hydroxyethylamino] -2-     Methylaniline sulfate 4.5   1.0 liter with water   pH 10.05 (Bleaching fixer) (Unit: g)   Ethylenediaminetetraacetic acid ferric ammonium dihydrate 90.0   Ethylenediaminetetraacetic acid disodium salt 5.0   Sodium sulfite 12.0   Ammonium thiosulfate aqueous solution (70%) 260.0 ml   Acetic acid (98%) 5.0 ml   Bleach accelerator shown below 0.01 mol

[0097]

[Chemical 25]

1.0 liter pH 6.0 (water washing solution) was added water, and tap water was used for H-type cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type anion exchange resin (Amberlite). IR-400) was passed through a mixed bed column to treat calcium and magnesium ions at a concentration of 3 mg / liter or less, and then 20 mg / liter sodium diisocyanurate dichloride and 1.5 g / liter sodium sulfate were added. Was added.

The pH of this liquid is in the range of 6.5 to 7.5. (Stabilizer) (Unit: mg) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization: 10) 0.3 Ethylenediaminetetraacetic acid disodium 0.05 Add water 1.0 Liters PH 5.0-8.0 The obtained results are shown in Table-3. Sensitivity is fogging 0.1
The value is expressed by the relative value of the logarithm of the reciprocal of the exposure amount displayed in lux · second giving the density of

[0100]

[Table 3]

As shown in Table 3, the emulsions 1-C and 1 of the present invention,
-D has higher sensitivity and higher Dmax than Comparative Emulsions 1-A, 1-B and 1-E. This is a result of reflecting that the aggregation of tabular grains is prevented by the technique of the present invention, the tabular grains obtained have a high aspect ratio, and the surface area of the tabular grains is large.

Example 4 Silver chloride doped with yellow blood salt (11
1) Tabular grain emulsion 2-A (comparative) 0.9 g of sodium chloride and 2 g of lime-processed bone gelatin were added to 1.2 liter of water, and 60 ml of an aqueous silver nitrate solution (9 g of silver nitrate was added to a container kept at 35 ° C. with stirring). ) And 60 ml of an aqueous sodium chloride solution (3.1 g of sodium chloride) were added over 1 minute. 1 minute after that, 3 mmol of the following compound, which is a (111) surface control agent, and an aqueous solution of sodium chloride 40
ml (sodium chloride 4g) was added and over 6 minutes 6
The temperature was raised to 0 ° C. After aging for 10 minutes, increase the temperature to 50 ° C.
250 ml of Nishilime-processed bone gelatin aqueous solution (gelatin 3
0 g) was added, and 800 ml of an aqueous silver nitrate solution (silver nitrate 12
0 g) and a sodium chloride aqueous solution were added at an accelerated flow rate over 44 minutes to grow. During this period, the potential was kept at +130 mV by using a silver electrode and a saturated calomel electrode as a reference electrode. Since 78% of the addition of silver nitrate used for growth was over, 0.08% yellow blood salt solution was added so that the yellow blood salt concentration became 4 × 10 ^-4 mol / mol silver with respect to silver. To the above, a fixed amount was added until the addition of silver nitrate was completed. This doped the shell of tabular grains (20% silver) with yellow blood salt. After the growth process is completed, potassium thiocyanate is added at 310 ^-3 mol / mol silver, and the sensitizing dye described below is added.
1, 2 were added, the temperature was raised to 75 ° C., and 15 minutes passed. After the addition was completed, the temperature was adjusted to 40 ° C., an aqueous solution containing an anionic precipitant was added, and sulfuric acid was further added to adjust the pH to 4 for desalting by the coagulation sedimentation method. After that, 80 g of lime-treated bone gelatin and 200 ml of filtered water were added to redisperse the emulsion, and pH was adjusted to 6.2 with NaOH and sodium chloride and pAg of 7.7.
Adjusted to. The silver (111) tabular grains thus obtained had an average equivalent circular diameter of 1.4 μm and an average thickness of 0.11 μm.
It was m. The lime-processed bone gelatin used here is
The gelatin was a gelatin having a molecular weight distribution of 23% in which the components having a molecular weight of 280,000 or more account for the whole.

[0103]

[Chemical formula 26]

[0104]

[Chemical 27]

[0105]

[Chemical 28]

Emulsion 2-B (Comparative) After the temperature was raised to 60 ° C. and ripened for 10 minutes, the temperature was raised to 50 ° C. and 250 ml of the lime-treated bone gelatin aqueous solution was used.
Emulsion 2-A except that lime-treated bone gelatin cross-linked with glutaraldehyde was added in which the sum of voids and γ moieties accounted for 39% in the molecular weight distribution measured by the PAGI method of the present invention. The same was done. The obtained tabular grains had an average equivalent circular diameter of 1.4 μm and an average thickness of 0.11 μm, as in Emulsion 2-A. Emulsion 2-C (invention) After the temperature was raised to 60 ° C. and ripened for 10 minutes, the temperature was adjusted to 50 ° C. and 250 ml of a lime-treated bone gelatin aqueous solution (gelatin 3
2 minutes after the addition of 0 g), an anionic thickener [TH
-1] except that 130 ml of a 2% solution was added.
The same procedure as in A was performed. The resulting tabular grains had an average equivalent circular diameter of 1.4 μm and an average thickness of 0.11 μm, as in Emulsion 2-A.
It was m. Emulsion 2-D (Comparative) 5 minutes after the addition of 44 minutes, the anionic thickener [TH
-1] Emulsion 2A except that 130 ml of 2% solution was added
I went the same way. The obtained tabular grains had an average equivalent circular diameter of 1.4 μm and an average thickness of 0.11 μm, as in Emulsion 2-A.
Met. << Measurement of Filtration Pressure >> Emulsions 2-A, 2-B, 2-C, and 2-D were subjected to measurement of filtration pressure under the same conditions as in Example 1. The results are shown in Table 4.

[0107]

[Table 4]

As is clear from Table 4, Emulsion 2 of the present invention
-C is more excellent in filterability than Comparative Emulsions 2-A, 2-B and 2-D.

[0109]

According to the present invention, it can be seen that a method for producing a light-sensitive silver halide emulsion from tabular grain silver halide grains having a high coverage of an adsorbing dye and preventing aggregation of grains has become possible.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03C 1/12 G03C 1/12

Claims (5)

[Claims] 1. A method for producing a photosensitive silver halide emulsion containing a gelatin dispersion medium and silver halide tabular grains, wherein a gelatin crosslinking agent is added from the start of the silver halide grain formation to the end of the grain formation. A method for producing a silver halide emulsion characterized by: 2. The method for producing a silver halide emulsion according to claim 1, wherein the tabular grains have an aspect ratio of 10 or more and a sensitizing dye coverage of 60% or more. 3. The tabular grains have a silver bromide content of 60% or more of the total projected area of all silver halide grains, a thickness of less than 0.1 μm, and an average equivalent circle diameter of 2 μm or more. 3. The method for producing a silver halide emulsion according to claim 1 or 2, wherein the content is mol% or more. 4. A nucleation and / or grain growth of the silver halide grains is carried out, a mixer is provided outside the reaction vessel, and an aqueous solution of a water-soluble silver salt and an aqueous solution of a water-soluble halide are placed in the mixer. A method of supplying and mixing to form silver halide fine particles, and immediately supplying the fine particles to a reaction vessel to cause nucleation and / or growth of silver halide grains in the reaction vessel. Item 4. A method for producing a silver halide emulsion according to any one of Items 1 to 3. 5. The following general formula (I), (II) or (III)
2. A tabular grain emulsion having a (111) main surface is obtained by allowing at least one compound represented by the formula (1) not to exist during nucleation and to exist during ripening and / or growth. 5. The method for producing a silver halide emulsion according to any one of 4 to 4. [Chemical 1] In 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 substituent. 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, at least one of R ₂ , R ₃ , R ₄ , R _5, and R ₆ represents an aryl group. X ^- represents a counter anion. [Chemical 2] (In the formula, A ₁ , A ₂ , A ₃ and A ₄ each represent a non-metal atom group for completing the nitrogen-containing heterocycle, which 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, 1 or 2, and n is 0 or 1 in the case of an intramolecular salt. is there.