JP2001337408A - Silver halide photographic emulsion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide emulsion that exhibits high efficiency blue absorption and has good sensitivity and fog. SOLUTION: The silver halide emulsion contains silver halide grains, >=70% of the total projected area of the silver halide grains is occupied by flat platy grains, the principal planes of the flat platy grains are 111} faces and the thickness is <=0.04 μm. An epitaxial phase comprising silver halide containing >=97 mol% silver iodide has been joined to the flat platy grains.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a light-sensitive silver halide emulsion, and particularly to a photographic silver halide tabular grain emulsion.

[0002]

2. Description of the Related Art In general, tabular silver halide grains (hereinafter referred to as "tabular grains") have the following photographic characteristics, particularly in a silver halide emulsion having a small thickness: 1) Ratio of surface area to volume (hereinafter referred to as "ratio"). The surface sensitization dye is large, and a large amount of sensitizing dye can be adsorbed on the surface, so that the color sensitization sensitivity is higher than 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 sharpness of the photographic light-sensitive material is good. 3) An image with low light scattering and high resolution can be obtained. 4) Low sensitivity to blue light, green sensitive layer or
When used in the red-sensitive layer, the yellow filter can be removed from the emulsion layer. Because of these advantages, they have been used in commercially available photosensitive materials having high sensitivity. 6-44
No. 132 and JP-B-5-16015 disclose tabular grain emulsions having an aspect ratio of 8 or more. Here, the aspect ratio is indicated by the ratio of the diameter to the thickness of the tabular grains. Furthermore, the diameter of a grain refers to the diameter of a surface having an area equal to the projected area of the grain when the emulsion grain is observed with a microscope or an electron microscope. The thickness is indicated by a distance between two parallel surfaces constituting the tabular silver halide.

Japanese Patent Publication No. 4-36374 discloses that at least one of a green-sensitive emulsion layer and a red-sensitive emulsion layer has a thickness of 0.3 μm.
It describes a color photographic light-sensitive material in which sharpness, sensitivity and graininess are improved by using tabular grains having a diameter of less than m and a diameter of 0.6 μm or more. However, in recent years, the sensitivity and the format of silver halide light-sensitive materials have been increased, and color light-sensitive materials having higher sensitivity and improved image quality have been strongly desired. Therefore, silver halide grain emulsions having higher sensitivity and better graininess are required, but conventional tabular silver halide emulsions are insufficient to meet these demands, and furthermore, Performance improvement was desired.

Further, the tabular grains having a higher aspect ratio have a larger specific surface area, so that the above-mentioned advantages of the tabular grains can be greatly utilized. In order to achieve a high aspect ratio, thin tabular grains having a reduced thickness of tabular grains are required.

However, tabular grains having a thickness of 0.04 μm or less (ultrathin tabular grains) can adsorb more sensitizing dyes and, at the same time, have a disadvantage that they reflect more incident light. It is difficult to obtain the expected increase in light absorption. Further, photographic properties are deteriorated due to aggregation of the emulsion grains.

On the other hand, silver iodide shows a face-centered cubic crystal lattice structure only at a very high pressure level (3,000 to 4,000 times the atmospheric pressure). This form of silver iodide is called sigma-phase silver iodide and is not relevant to silver halide photography. Usually, the most stable silver iodide crystal structure is a hexagonal wurtzite type generally called β-phase silver iodide. A sufficiently stable second silver iodide crystal lattice structure that is photographically useful is a face-centered cubic zinc-blende-type silver iodide crystal structure commonly called gamma-phase silver iodide. It is. Silver iodide emulsions containing each of the β and γ phase crystal structures and mixtures of these phases have been produced. The fourth crystallographic form of silver iodide is the α-phase, the body-centered cubic crystal structure, which is described in James, cited above, "Theory of Photographic Process," page 1, It is stated that a temperature of 146 ° C. is required for its production, but Daubendiek, US Pat.
No. 72,026, "bright yellow"
ellow) Silver iodide is in fact believed to be alpha-phase silver iodide (James pages 1-5 relate to this and the rest of this discussion).

High iodide silver halide grains are more prominent than face-centered cubic crystal lattice structured silver halide grains in that they exhibit a higher intrinsic absorption in the blue region of the short spectrum (400-450 nm). Advantages.
In particular, high iodide silver halide does not exhibit a face-centered cubic crystal structure exhibiting an absorption peak at 425 nm, which is not found in silver chloride or silver bromide. % Iodide (hereinafter referred to as high iodide)
, Ie containing only small amounts of bromide and / or chloride. Maternaghan U.S. Pat. No. 4,184,878 is an illustration of a high iodide silver halide emulsion.

However, high iodide silver halide grains are difficult to sensitize and are difficult to develop with a commercially available developer. Its use is significantly reduced.

In order to simultaneously realize the advantages of the above tabular grains and the high light absorption of silver iodide, and to compensate for the shortcomings of both, halogenated halides having a face-centered hexagonal crystal lattice structure are used. It has occasionally been proposed to bond a high iodide phase on the surface of silver tabular grains.

US Pat. No. 4,471,050 discloses that non-isomorphic silver salts can be selectively deposited on the edges of silver halide host grains without resorting to additional site directors. This non-isomorphous silver salt includes silver thiocyanate, β-phase silver iodide (having a hexagonal wurtz type crystal structure), γ-phase silver iodide (having a zinc-containing crystal structure), and silver phosphate (meta- and pyro- -Including phosphates), and silver carbonate.
None of these non-isomorphic silver salts exhibit the face-centered cubic crystal structure of the type found in photographic silver halide (ie, rock salt-type isomorphous face-centered cubic crystal structure). In practice, the sensitivity gains caused by non-isomorphic silver salt epitaxy were smaller than the gains obtained with comparative isomorphous silver salt epitaxial sensitization.

Japanese Patent Application Laid-Open No. 8-171162 discloses an average thickness of 0.1 mm.
Disclosed is a silver halide emulsion comprising epitaxially bonded projections on the peripheral edge of {111} ultrathin tabular grains of less than 07 μm, wherein the projections have a higher iodide concentration than the tabular grains. Ultrathin tabular grains reduce visible light scattering and achieve low levels of granularity. On the other hand, since the projections have the same face-centered cubic crystal lattice structure as the tabular grains, the iodide content is limited, and conversion with halogen constituting the tabular grains occurs. No advantage as silver halide could be given.

Japanese Patent Application Laid-Open No. 2000-2959 discloses that the thickness is 0.1 μm.
A tabular silver halide grain having a raffle surface composed of fine projections having a projected area diameter of 0.15 μm or less containing 10 mol% or less of iodine on a main plane of a {111} flat plate of not more than m is disclosed. . In the invention, since the specific surface area is increased without reducing the thickness of the tabular grains, it is possible to provide tabular silver halide grains having an increased dye adsorption amount and less light reflection. However, the inclusion of silver iodide in the projections is not intended to improve the light absorption, but is to maintain the morphological stability of the projections, such as high efficiency light absorption of silver iodide. It is hard to say that photographically useful properties are fully exhibited.

US Pat. No. 5,604,086 is an example of an emulsion having high iodide silver halide grains grown epitaxially on the major planes of tabular grains having a rock salt type face centered cubic lattice structure. {111} tabular grains or {10}
A composite grain having a high iodine content epitaxial phase on the main plane of a 0 ° tabular grain. The high iodine epitaxial phase in the grain forms a triangular or hexagonal surface shape, and the high iodine phase absorbs blue light. It is disclosed that the rate is significantly increased. However, the fact that the epitaxial phase is non-uniformly precipitated between grains, that halogen conversion occurs between the host plate and the epitaxial phase, and that the iodine content ratio of the epitaxial phase is relatively low, There was a problem that the sharpness of the image was low because the grains on the host flat plate contained relatively thick grains.

[0014]

That is, high image formation efficiency can be realized by short-wave blue absorption of a high iodide phase while maintaining the superior development characteristics of silver halide grains having a face-centered cubic lattice structure. It is an object of the present invention to do so.

According to the present invention, ideally high iodide epitaxy is located in the major plane of ultrathin tabular grains,
A composite particle structure that produces an overall improvement of each of the two is produced.

[0016]

The object of the present invention has been attained by the following items. (1) Tabular grains account for at least 70% of the total projected area of the silver halide grains, and the main plane of the tabular grains is {11}
On the 1 を plane, the thickness is 0.04 μm or less, and the tabular grains contain silver halide grains in which an epitaxial phase composed of silver halide containing 97 mol% or more of silver iodide is bonded. A characteristic silver halide emulsion. (2) The silver halide emulsion according to (1), wherein at least 60% of the epitaxial phase is silver halide containing 97 mol% or more of silver iodide. (3) The silver halide emulsion according to (1) or (2), wherein the epitaxial phase comprises at least 10 mol% of the total silver. (4) The occupied area of the epitaxial phase bonded to the main plane of the tabular grains is ± 1 of the average occupied area among all grains.
The silver halide emulsion according to any one of (1) to (3), wherein the tabular grains have an equivalent circle diameter of at least 0.7 μm.
m. The silver halide emulsion according to any one of (1) to (4), wherein (6) The tabular grain has a coefficient of variation between grains of 4
The silver halide emulsion according to any one of (1) to (5), which is less than 0%. (7) the tabular grains comprise [1] a core and a shell,
[2] The shell includes one or more dislocation lines reaching the edge or corner of the tabular grain from the interface between the core and the shell,
[3] The halogen according to any one of (1) to (6), wherein the amount of silver used for forming the core is from 0.1% to 10% of the total amount of silver used for forming the grains. Silver halide emulsion. (8) The silver halide emulsion according to any one of (1) to (7), wherein the tabular grains comprise at least 50 mol% of silver chloride. (9) The silver halide emulsion according to any one of (1) to (7), wherein the tabular grains comprise at least 70 mol% of silver bromide. (10) The tabular grains are prepared by not having at least one compound represented by the general formula (I), (II) or (III) at the time of nucleation but at the time of ripening and growing. The silver halide emulsion according to any one of (1) to (9), wherein

[0017]

Embedded image

(Where R₁Is an alkyl or alkenyl group
Or an aralkyl group;_Two, R_Three, R_Four, R_Five, And R
₆Represents a hydrogen atom or a substituent, respectively. R_TwoAnd R_Three,
R_ThreeAnd R _Four, R_FourAnd R_Five, R_FiveAnd R₆May be fused. However
Then R_Two, R_Three, R_Four, R_Five, And R₆At least one of
Represents an aryl group. X^-Represents an anion. )

[0019]

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(A ₁ , A ₂ , A ₃ and A ₄ each represent a group of non-metallic atoms for completing a nitrogen-containing heterocyclic ring, each of which may be the same or different. B is a divalent linking group Represents
m represents 0 or 1. R ₁ and R ₂ each represent an alkyl group. n represents 0, 1 or 2, and X ⁻ represents an anion. (11) A mixing vessel is provided outside the reaction vessel for causing nucleation and / or grain growth of the tabular grains, and an aqueous solution of a water-soluble silver salt and an aqueous solution of a water-soluble halide are supplied into the mixing vessel. To form silver halide fine particles. The fine particles are immediately supplied to the reaction vessel, and nucleation and / or growth of silver halide grains is performed in the reaction vessel to form the tabular grains. The silver halide emulsion according to any one of the above (1) to (10). (12) The silver halide grains are spectrally sensitized with a dye represented by formula (S) (1).
-The silver halide emulsion according to (11). General formula (S)

[0021]

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In the formula (S), Z ₁ and Z ₂ represent a sulfur atom, a selenium atom, an oxygen atom or a nitrogen atom. V ₁ and V ₂ represent a monovalent substituent. However, V ₁ and V ₂ are not bonded to each other by an aromatic group or two or more adjacent groups to form a condensed ring. l ₁ and l ₂ represent 0, 1, 2 or 3. L ₁ , L ₂
And L ₃ represents a methine group. R ₁ and R ₂ represent an alkyl group. n ₁ represents 0, 1 or 2. m ₁ represents a number of 0 or more necessary to neutralize the charge of the molecule. M ₁ represents a charge balancing counter ion.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION The silver halide grains in the present invention are composed of host tabular grains and an epitaxial phase existing on the main plane.

The host tabular grains of the present invention have a main surface of {111} faces. A tabular grain having a {111} plane as a main surface is a general term for silver halide grains having one twin plane or two or more parallel twin planes. What is a twin plane?
This means the {111} plane when ions at all lattice points on both sides of the 1} plane are in a mirror image relationship. These tabular grains have a triangular shape, a hexagonal shape or a rounded shape when viewed from above, and triangular ones are triangular, hexagonal ones are hexagonal, and rounded tabular grains. Have outer surfaces parallel to each other with rounded corners.

Diameter (corresponding to a circle) of the host tabular grains of the present invention
Is 0.7 μm or more (preferably 5 μm or less), preferably 0.9 μm or more and 4.5 μm or less, more preferably 1.2 μm or more and 4 μm or less, with a deviation within 30%,
Furthermore, it is desirable that it is within 20%. The particle thickness is 0.04 μm or less, preferably 0.03 to 0.01
μm. The measurement of the particle diameter and the particle thickness in the present invention can be obtained from an electron micrograph of the particles as in the method described in US Pat. No. 4,434,226.

It is preferable to use tabular grains having a monodisperse circle equivalent diameter as the host tabular grains of the present invention. Regarding this, JP-A-63-11928, Japanese Patent Publication No. 5-612
No. 05 discloses monodisperse hexagonal tabular grains,
No. 541 discloses circular monodisperse tabular grains. JP-A-2-838 discloses that 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 monodispersed. Are disclosed. European Patent 514, 74
No. 2A has a coefficient of variation of 10% for the particle size prepared using the polyalkylene oxide block copolymer.
The following tabular grain emulsions are disclosed:

The method for producing {111} main surface type tabular grains which are host tabular grains used in the present invention is described in US Pat. Nos. 4,434,226 and 4,439,520.
Nos. 4,414,310 and 4,433,048
Nos. 4,414,306 and 4,459,353 disclose the production method and the technology used. Further, as disclosed in JP-A-6-214331, after once forming a seed crystal emulsion by nucleation, conditions such as pH and pAg are set so as to be convenient for growth, Tabular grains can also be formed by adding silver and a halogen solution for growth.

In preparing the host tabular grains of the present invention, silver halide fine particles are added to a reaction vessel holding an aqueous solution of protective colloid instead of adding an aqueous solution of silver salt and an aqueous solution of halide to form nuclei and / or grow. The preferred method is to do so. This method is described in U.S. Pat.
9,208, JP-A-1-183644, 2-44
No. 35, 2-43535 and 2-68538 disclose the technology. As a method for supplying iodine ions in forming tabular grains, a fine grain silver iodide (having a grain size of 0.1 μm or less, preferably 0.06 μm or less) emulsion may be added. It is desirable to use the manufacturing method disclosed in U.S. Pat. No. 4,879,208. In these methods of forming nuclei and / or growing particles by adding fine particles, a stirring blade having no rotating shaft penetrating a stirring tank disclosed in JP-A-10-239787 and JP-A-11-76783 is placed in a stirring tank. It is desirable that fine silver halide grains adjusted by rotation are added to the reaction vessel to adjust the silver halide grains.

In the present invention, {111} is used as the host tabular grain.
When forming main plane type tabular grains, general formula (I),
The compound represented by (II) or (III) (hereinafter referred to as a crystal habit controlling agent) is preferably used.

The ultra-thin tabular grains having a thickness of 0.04 μm or less have a larger specific surface area, so that more sensitizing dyes can be adsorbed per grain. Contains high iodide, so that the amount of blue light absorbed per particle can be increased, and high sensitivity can be obtained. On the other hand, JP-A-6-43605,
As described in JP-A-6-43606, when the thickness of the tabular grains is smaller than 0.1 μm, the degree of reflection of incident light on the main surface of the tabular grains oriented perpendicular to the tabular grains becomes more intense. By thinning the tabular grains to increase the specific surface area and adsorbing more sensitizing dye, the effect of increasing the light absorption of the grains decreases,
A tabular grain emulsion having an aspect ratio of 10 or more and a thickness of 0.14 to 0.17 .mu.m, instead of an ultrathin tabular grain of 0.04 .mu.m or less,
The tabular grains having a thickness of 3 μm are applied to the green photosensitive layer,
It is disclosed that tabular grains having a size of 8 to 0.10 μm are used for a blue photosensitive layer.

In the present invention, means for solving this problem at once are presented. That is, in the present invention, the host tabular grains are ultra-thin tabular grains having a thickness of not more than 0.04 μm, and have a very large specific surface area per grain. Can be increased. On the other hand, the increase in light reflection due to the decrease in the thickness of the tabular grains to 0.04 μm or less is due to the fact that a large number of the epitaxial phases are formed on the main surface of the tabular grains. The thickness of the particles increases, and an increase in light reflection can be prevented. Further, it was found that the effect was increased by the coefficient of variation of the thickness between the particles being less than 40%. Tabular grains of the present invention,
By realizing a large increase in the amount of sensitizing dye adsorbed due to a remarkable increase in specific surface area, and by solving the problem of increased light reflection, the amount of light absorption per tabular grain has been significantly increased. It achieves unprecedented high sensitivity. Since the epitaxial phase is not a continuous layer, this does not directly become the thickness of the tabular grains, but there is no doubt that the tabular grains could be made substantially thicker. This makes it possible to increase the specific surface area and reduce the light reflection at once.

In the present invention, the epitaxial phase (sometimes abbreviated as epi phase) exists on the main plane of the host tabular grains and contains 97 mol% or more of high iodide. Silver iodide has high morphological stability due to low solubility,
It can also gain blue absorption. When a halide other than iodide is contained in an amount of more than 3 mol%, the light absorptivity becomes low. Halides other than iodide are added to the first tabular grain emulsion in the presence of bromide and / or chloride ions in the dispersion medium of the first tabular grain emulsion in equilibrium with the host tabular grains to form silver ions and It is a result of depositing an epitaxial phase by introducing iodide ions. It is effective to minimize the incorporation of halides other than iodide into the epitaxial phase in order to obtain highly efficient light absorption. Further, for the same reason as the halogen composition of the epi phase, it is essential for the present invention that 60% or more of the epi phase is 97 mol% of silver iodide.

When the emulsion of the present invention is exposed to short-wave light of 400 to 450 nm, photons are absorbed not only in tabular grains but also in epitaxial sites existing on the main plane (except in some cases). Since the epitaxial phase exists on the upper side and the lower side of the tabular grains, short-wave blue light can be absorbed in the upper and lower epitaxial portions by 60 to 70% of all photons. When the epitaxial site exists at the fringe portion or the vertex portion of the tabular grain, the number of photons that can be absorbed becomes very small. Therefore, it is ideally desirable that no epitaxial phase is formed outside the main plane.

When a blue dye (a dye sensitive to a wavelength of 400 to 500 nm) is applied to ordinary tabular grains,
A dye having a maximum absorption wavelength in the range of 500 nm and a half width of about 100 nm is ideal. In fact, 10
There is almost no dye exhibiting a half-width of 0 nm, and none of the dyes has the same half-width as the blue spectral wavelength.
The half width in the case of an ordinary blue dye is 50 nm or less.
When one or more dyes having a maximum absorption in the long wavelength region are combined with the emulsion of the present invention, the absorption peak of the epitaxial phase is 427 nm, so that blue absorption with higher efficiency over the entire blue portion of the spectrum can be obtained. can get.

In the absence of a photosensitive dye, short-wave blue photons are absorbed at the epitaxial site, forming photohole and photoelectron pairs. Photoelectrons pass freely through the interface between the host plate and the epitaxial phase and move freely to the host tabular grains, while photoholes are trapped in the epitaxial site.
Therefore, recombination is suppressed by the separation of photoelectrons and photoholes. Thus, the epitaxial phase contributes to many photoelectrons for forming a latent image, and consequently serves to increase the sensitivity of the whole emulsion grain.

In the emulsion of the present invention, no matter what photosensitive dye is used, the sensitivity of the whole emulsion can be increased by the high iodide epitaxial phase. Longer wave photons are in fact absorbed by the photosensitive dye, which injects the absorbed energy directly into the epitaxial site or into the host slab. Photoholes remaining in the dye are trapped in the epitaxial site. Since this mechanism can be applied irrespective of exposure conditions, the epitaxial phase can improve the efficiency of forming a latent image in an emulsion sensitive to green or red spectrum.

The improvement of the short wave blue light absorption efficiency is achieved by increasing the thickness of the epitaxy and increasing the occupied area. In order to further improve the light absorption efficiency, it is desirable to increase the proportion of host tabular grains present on the main plane, and at least 2% on the main plane.
It preferably occupies at least 5%, preferably at least 50%, ideally at least 60%.

The area occupied by the epitaxial phase in one grain is ± 10% of the average area occupied by all the grains.
Is required to be within the range. More preferably, it is desirable to be within ± 8%. Thereby, the sharpness of the image can be further improved.

It has been found that the host tabular grains of the present invention have a further effect by having dislocation lines in the grains. A technique for controlling the introduction of dislocations into silver halide grains is described in JP-A-63-220238. According to this publication, a specific high iodine phase is provided inside a tabular silver halide grain having an average grain diameter / grain thickness ratio of 2 or more, and the outside thereof is covered with a phase having a lower iodine content than the high iodine phase. This can introduce dislocations. By introducing the dislocation, effects such as an increase in sensitivity, an improvement in storage stability, an improvement in latent image stability, and a reduction in pressure fog can be obtained. According to the invention described in this publication, dislocations are mainly introduced into edge portions of tabular grains. Further, with respect to tabular grains having dislocations introduced at the center, US Pat.
No. 96 is described. This publication discloses that silver chloride or silver chlorobromide epitaxy is formed in normal crystal grains, and that the epitaxy can be introduced by physical ripening and / or conversion by halogen. The introduction of such dislocations has the effect of increasing sensitivity and reducing pressure fog. Dislocation lines in silver halide grains are described, for example, in JF Hamilton, Photo. S
ci.Eng. 1967, 11, 57, T. Shinozawa, J. Soc. Photo
JAPAN, 1972, 35, 213, can be observed by a direct method using a transmission electron microscope at low temperature. That is, silver halide grains taken out with care not to apply enough pressure to generate dislocations from the emulsion are placed on a mesh for observation with an electron microscope, and the sample is placed so as to prevent damage (printout) by electron beams. Observation by a transmission method is performed in a cooled state. At this time, the thicker the particle, the more difficult it is for the electron beam to pass therethrough.
The use of an electron microscope (200 keV or more with respect to the thickness of m) enables more clear observation. From the photograph of the particles obtained by such a method, the position and number of dislocation lines for each particle when viewed from a plane perpendicular to the main plane can be obtained.

In the tabular grain of the present invention, the position where the dislocation exists is the shell portion. Dislocations occur at the boundary between the core and the shell and grow as the shell grows. At that time, the direction of the dislocation may be linear and substantially perpendicular to the side of the tabular grain, but if it is linear but not perpendicular to the side, it is curved and substantially perpendicular to the side, or perpendicular to the side. It may not be. Here, the ratio of the core to the shell having dislocations is not particularly limited as long as the amount of silver used for forming the core is 0.1 to 10% of the total silver used for forming the grains.

In the present invention, since the epitaxial phase contains a high proportion of iodine, its solubility is reduced and its form is stably maintained, and the presence of iodide ions on the surface of the epitaxy causes the adsorption of the sensitizing dye. Is strengthened.

In the case of thin tabular grains, agglomeration between grains has been a problem due to the small thickness of the grains. In the present invention, however, it was also found that the presence of the epitaxial phase significantly improved the agglomeration of grains. .

It is considered that the main reason why a large number of epitaxial phases are formed on the main plane of the host tabular grains as in the present invention is caused by a difference in lattice constant between the host grain component and the epitaxial phase component. The lattice constant of the silver halide composition is, for example, THJames "The Theory of the Photograph
ic Process "4th.ed.p.3-4 (1977 MaCmillan N.
Y.). If the lattice constant of the host tabular grains and the lattice constant of the epitaxial phase are significantly different, the growth proceeds in the plane direction of the host plane until the strain of the structure cannot be alleviated, and thereafter or simultaneously grows out of the plane direction. Therefore, it is considered that many epitaxial phases are formed on the main surface of the host tabular grains.

In order to form the epitaxial phase of the present invention on the main surface of the host tabular grains, the phase is formed at a silver potential of not less than +60 mV (reference electrode is a saturated calomel electrode) and not more than +80 mV, preferably not less than +70 mV and not more than +75 mV. Is desirable. The higher the temperature at which the protrusions are formed, the better the temperature is 50 ° C
The temperature is not less than 80 ° C and preferably not more than 55 ° C and not more than 65 ° C. Although a specific production method is described in Examples, a double jet method in which the potential is controlled is preferable. The rate of addition during the formation of the epitaxial phase is 0.1 g / min to 0.7 g / min for AgNO ₃ , and 0.2 g / min to 0.6 g for AgNO _3.
/ Min or less is preferred.

It is desirable that the epitaxial phase of the present invention is deposited on the main plane of the host tabular grains and not at the edge. However, it is common practice in practice to precipitate both on the outer edges and on the major planes of the host tabular grains.

The silver halide grains of the present invention are prepared using gelatin as a protective colloid. For gelatin, alkali treatment is usually often used. In particular, alkali-treated gelatin that has been subjected to deionization treatment or ultrafiltration treatment to remove impurity ions and impurities can be used. In addition to alkali-treated gelatin, acid-treated gelatin, low-molecular-weight gelatin (molecular weight 10
As specific examples of gelatin at 00 to 80,000, gelatin decomposed with an enzyme,
Examples thereof include gelatin hydrolyzed with an acid and / or an alkali, and gelatin decomposed by heat), high-molecular-weight gelatin (molecular weight of 110,000 to 300,000), and a methionine content of 50 μm.
Mol / g or less of gelatin and tyrosine content of 20 μmol / g
g or less, oxidized gelatin having reduced methionine groups, gelatin in which methionine has been inactivated by alkylation, and various modified gelatins described below can be used. Regarding high molecular weight gelatin, see JP-A-11-23.
7704, Japanese Patent Application No. 2000-48166, Japanese Patent Application 200
No. 0-95146. Examples of amino-modified phthalated gelatin, ambered gelatin, trimellit gelatin, pyromellitic gelatin, esterified gelatin represented by carboxyl-modified methyl esterified gelatin, amidated gelatin, ethoxyformylated gelatin, etc. Gelatin modified with imidazole groups. The above-mentioned gelatin may be used alone, or a mixture of two or more kinds may be used. In the present invention, the amount of gelatin used in the particle forming step is 1 to 60 g / mol of silver, preferably 3 to 40 g / mol of silver. The concentration of gelatin in the chemical sensitization step of the present invention is preferably from 1 to 100 g / silver mole, and more preferably from 1 to 70 g / silver mole.

Although not required for the practice of this invention, improvements in photographic performance consistent with the described advantages can be achieved by subjecting the host tabular grains to chemical sensitization. It has also been found that the chemical sensitizer can be introduced together with the epitaxial phase into ultrathin host tabular grains of 0.04 μm or less, while completely avoiding an increase in the thickness of the host tabular grains.

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 the sulfur sensitization, an unstable sulfur compound is used, and P. Grafkides, Chimie et Physique Photograph
ique (Paul Momtel, 1987, 5th edition), Research
Unstable sulfur compounds described in Disclosure, Vol. 307, No. 307105 can be used. Specifically, thiosulfates (eg, hypo), thioureas (eg, diphenylthiourea, triethylthiourea, N-ethyl-
N ′-(4-methyl-2-thiazolyl) thiourea, carboxymethyltrimethylthiourea), thioamides (eg, thioacetamide), rhodanines (eg, diethyl rhodanine, 5-benzylidene-N-ethyl-rhodanine) , Phosphine sulfides (eg, trimethyl phosphine sulfide), thiohydantoins, 4-oxo-oxazolidin-2-thiones, dipolysulfides (eg, dimorpholine disulfide, cystine, hexathiocan-thione), mercapto compounds ( For example, known sulfur compounds such as cysteine), polythionate, elemental sulfur, and active gelatin can also be used.

In the selenium sensitization, an unstable selenium compound is used, and JP-B-43-13489 and JP-B-44-157.
No. 48, JP-A-4-25832, JP-A-4-109240
And labile selenium compounds described in Japanese Patent Application Nos. 3-53693 and 3-82929 can be used. Specifically, colloidal metal selenium, selenoureas (eg, N, N-dimethylselenourea, trifluoromethylcarbonyl-trimethylselenourea, acetyl-trimethylselenourea), selenoamides (eg, selenoacetamide, N, N-diethylphenylselenoamide), phosphine selenides (eg, triphenylphosphine selenide, pentafluorophenyl-triphenylphosphine selenide), selenophosphates (eg, tri-p-tolylselenophosphate) , Tri-n-butylselenophosphate), selenoketones (eg, selenobenzophenone), isoselenocyanates, selenocarboxylic acids,
Selenoesters and diacylselenides may be used. Furthermore, Japanese Patent Publication No. 46-4553 and 52-3
Non-labile selenium compounds described in 4492 publications and the like,
For example, selenous acid, potassium selenocyanide, selenazoles, selenides and the like can be used.

In tellurium sensitization, an unstable tellurium compound is used, and is described in Canadian Patent 800,958, British Patent Nos. 1,295,462 and 1,396,696, and Japanese Patent Application No. 2-333819. No. 3-53693,
Unstable tellurium compounds described in JP-A Nos. 3-131598 and 4-129787 can be used. Specifically, telluroureas (eg, tetramethyltellurourea, N, N′-dimethylethylene tellurourea, N, N′-diphenylethylenetellurourea), phosphine tellurides (eg, butyl-diisopropylphosphine) Telluride, tributylphosphine telluride, tributoxyphosphine telluride, ethoxy-diphenylphosphine telluride, diacyl (di) tellurides (eg, bis (diphenylcarbamoyl) ditelluride, bis (N-phenyl-N-methyl) Carbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) telluride, bis (ethoxycarbonyl) telluride), isosterocyanates, telluramides, tellurohydrazides, telluroesters (for example, butylhexyltelluroester), Roketon compounds (for example,
Telluroacetophenone), colloidal tellurium, (di) tellurides, other tellurium compounds (potassium telluride, telluropentathionate sodium salt) and the like may be used.

The noble metal sensitization is described in P. Grafkide, supra.
s, Chimie et Physique Photographique (Paul Momt
el company, 1987, 5th edition), Research Disclosure 3
Gold, platinum, and the like described in Vol.
Noble metal salts such as palladium and iridium can be used, and gold sensitization is particularly preferable. Specifically, in addition to chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, and gold selenide, U.S. Patent Nos. 2,642,361, 5,049,484, and 5,049,485 Gold compounds described in the specifications of the above publications can also be used. Regarding reduction sensitization, see P. Gr
afkides, Chimie et Physique Photographique (Pau
l Momtel, 1987, 5th edition), Research Disclosur
Known reducing compounds described in e Magazine 307, 307105 and the like can be used. Specifically, aminoiminomethanesulfinic acid (also called thiourea dioxide), borane compound (for example, dimethylamine borane), hydrazine compound (for example, hydrazine, p-tolylhydrazine), polyamine compound (for example, diethylenetriamine, triethylene Tetramine), chloride 1
Tin, silane compounds, reductones (eg, ascorbic acid), sulfites, aldehyde compounds, hydrogen gas, and the like may be used. The reduction sensitization may be performed in an atmosphere having a high pH or an excess of silver ions (so-called silver ripening).

These chemical sensitizations may be used alone or in combination of two or more. When 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 silver halide grains to be used, chemical sensitization conditions, and the like, but is 10 ^-8 to 10 ^-2 mol, preferably 1 to 10 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 to 1 mol of silver halide.
About 0 ^-7 to 10 ^-2 mol is used. The conditions of the chemical sensitization in the present invention are not particularly limited, but the pAg is 6 to 1
1, preferably 7 to 10 and a pH of 4 to 10
Preferably, the temperature is 40 to 95 ° C, and more preferably 4 to 95 ° C.
5-85 ° C is preferred.

The silver halide emulsion preferably contains various compounds for the purpose of preventing fogging during storage of the photographic material during the production process or during photographic processing or stabilizing photographic performance. Examples of such compounds include azoles (eg, benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (especially nitro- or halogen-substituted)), heterocyclic mercapto compounds, Imidazoles (eg, mercaptothiazole, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazole, (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines), carboxy group and sulfone group, etc. The above heterocyclic mercapto compounds having a water-soluble group, thioketo compounds (eg, oxatozinthione), azaindenes (eg, tetrazaindenes, (especially 4-hydroxy-substituted (1,3,3a, 7) Seinden) ,
Includes benzenethiosulfonic acids and benzenesulfinic acid. Generally these compounds are known as antifoggants or stabilizers.

The timing of adding the antifoggant or the stabilizer is as follows.
Usually, it is performed after chemical sensitization. However, it can also be selected during chemical sensitization or at a time before the start of chemical sensitization. That is, during the formation of silver halide emulsion grains, during the chemical sensitization (during the chemical sensitization time, even during the addition of the silver salt solution or between the addition and the start of the chemical sensitization).
Preferably within a period of up to 50% from the start, more preferably within a period of up to 20%).

Next, the spectral sensitizing dye represented by formula (S) used in the present invention will be described. In the general formula (S), Z ₁ and Z ₂ represent a sulfur atom, a selenium atom, an oxygen atom or a nitrogen atom. Preferably, at least one of Z ₁ and Z ₂ is a sulfur atom. For the spectral sensitizing dyes, refer to the compounds described in Japanese Patent Application No. 10-123789.

V ₁ and V ₂ represent a monovalent substituent. However, V ₁ and V ₂ are not bonded to each other by an aryl group or two adjacent groups to form a condensed ring. l ₁ and l ₂
Represents 0, 1, 2, 3, and 4. R ₁ and R ₂ represent an alkyl group. L ₁ , L ₂ and L ₃ represent a methine group. n ₁ represents 0, 1 or 2. M ₁ represents a charge balancing counter ion, and m ₁ represents a number of 0 or more necessary to neutralize the charge of the molecule.

In the formula (S), when n ₁ is 0, at least one of Z ₁ and Z ₂ is a sulfur atom.

In the formula (S), when n ₁ is 0, both Z ₁ and Z ₂ are sulfur atoms.

In the formula (S), when n ₁ is 1, at least one of Z ₁ and Z ₂ is an oxygen atom.

In the formula (S), when n ₁ is 1, both Z ₁ and Z ₂ are oxygen atoms.

In the formula (S), when n ₁ is 2, both Z ₁ and Z ₂ are sulfur atoms.

The layer constitution of the silver halide photographic material is not particularly limited. However, the color photographic material has a multilayer structure for recording blue, green and red light separately. Each silver halide emulsion layer may be composed of two layers, a high sensitivity layer and a low sensitivity layer. Examples of practical layer configurations are listed in (1) to (6) below.

(1) BH / BL / GH / GL / RH / R
L / S (2) BH / BM / BL / GH / GM / GL / RH / R
M / RL / S (3) BH / BL / GH / RH / GL / RL / S (4) BH / GH / RH / BL / GL / RL / S (5) BH / BL / CL / GH / GL / RH / RL / S (6) BH / BL / GH / GL / CL / RH / RL / S

B is a blue-sensitive layer, G is a green-sensitive layer, R is a red-sensitive layer, H is the highest-sensitive layer, M is an intermediate-sensitive layer, L is a low-sensitive layer, S is a support, and CL is a multilayer effect. Layer. Specific photosensitive layers such as a protective layer, a filter layer, an intermediate layer, and an antihalation layer are omitted. The high-sensitivity layer and the low-sensitivity layer having the same color sensitivity may be arranged in reverse. (3) is described in US Pat. No. 4,184,876. Regarding (4), Research Disclosure, Vol. 225, No. 22534, JP-A-59-177551 and JP-A-59-177551.
It is described in each publication of 177552. Further, (5) and (6) are described in JP-A-61-34541. Preferred layer configurations are (1), (2) and (4)
It is. The silver halide photographic light-sensitive material of the present invention may be an X-ray light-sensitive material, a black-and-white photographic light-sensitive material,
The present invention can also be applied to photosensitive materials for plate making and photographic paper.

As the gelatin hardener, for example, an active halogen compound (2,4-dichloro-6-hydroxy-
1,3,5-triazine and its sodium salt, etc.)
And active vinyl compounds (such as 1,3-bisvinylsulfonyl-2-propanol, 1,2-bis (vinylsulfonylacetamido) ethane or a vinyl polymer having a vinylfuronyl group as a chain) rapidly cure hydrophilic colloids such as gelatin. To provide stable photographic characteristics. N-carbamoylpyridinium salts ((1
-Morpholinocarbonyl-3-pyridinio) matansulfonate) and haloamidiniune salts (such as 1- (1-chloro-1-pyridinomethylene) pyrrolidinium 2-naltarene sulphonate) can be preferably used because of their high curing rate.

Various additives of the silver halide emulsion (binder, chemical sensitizer, spectral sensitizer, stabilizer, gelatin, hardener, surfactant, antistatic agent, polymer latex,
Matting agents, color couplers, ultraviolet absorbers, anti-fading agents, dyes), supports for photographic materials and processing methods for photographic materials (eg, coating methods, exposure methods, development processing methods) are described in Reserch Disclosure 176: 17643. Issue (RD-1
7643), 187, 18716 (RD-18716), 225, 2
No. 2534 (RD-22543) can be referred to. The following list in these Research Disclosure magazines shows.

Additive type RD-17643 RD-18716 RD-22534 1 Chemical sensitizer page 23, page 648, right column 24 page 2 Sensitivity enhancer Same as above 3 Same as above 3 Spectral sensitizer page 23-24 page 648, right column 24 to 24 Page 28 to 649 Right column 4 Brightener 24 Page 5 5 Antifoggant 23 to 25 Page 649 Right column 24, Page 31 6 Light absorber 25 to 26 Page 649 Right column Filter dyes Page 650 Left column Ultraviolet Absorbent 7 Stain inhibitor 25 page right column 650 page left column to right column 8 Dye image stabilizer 25 page 32 page 9 Hardener 26 page 651 left column 32 page 10 Binder 26 Same as above 28 page 11 Plasticizer, lubrication Agent 27 page 650 right column 12 Coating aids, pages 26 to 27 Same as above Surfactant 13 Static inhibitor page 27 Same as above 14 Color coupler page 25 page 649 page 31

Color photographic materials are published in Research Disclosure
The development can be carried out by a usual method described in 176, 17643 and 187, 18716. The color photographic light-sensitive material is usually subjected to a washing treatment or a stabilizer treatment after development, bleach-fixing or fixing. In the rinsing process, it is common to use two or more tubs for countercurrent rinsing to save water. As the stabilization treatment, use a method disclosed in
A typical example is a multi-stage AC stabilization process as described in JP-A-8543.

[0070]

EXAMPLE 1 Emulsion T-1 Ultra-thin host tabular grain emulsion In the same system as the system shown in FIG. 3 of JP-A-2-283837, the mixer shown in FIG. 0.5 cc) to prepare host tabular grains as described below. 1.0 liter of distilled water and low molecular weight bone gelatin (average molecular weight 2
10 g of a 0.5 M silver nitrate aqueous solution and 20 cc of a 0.3 M KBr solution were added over 40 seconds while stirring in a solution maintained at 35 ° C. by adding 3 g of 0.5 g of KBr and 0.5 g of KBr. (Nucleation) 22 cc of a 0.8 M aqueous KBr solution and 300 cc of bone gelatin (hereinafter referred to as trimellit gelatin) containing 0.2 mmol of the crystal habit controlling agent 1 and 95 wt% of amino groups trimmed to 95%. Add at 75 ° C over 30 minutes
Temperature. Further aging was performed at 75 ° C. for 5 minutes. (Aging) Then, a 0.60 M silver nitrate aqueous solution 100 was again placed in the mixer.
0cc and low molecular weight gelatin (average molecular weight 20,000) 50
g and KBr 0.603M aqueous solution 1000cc, 1 /
A fixed amount of 150 cc of a 50 M solution of the crystal habit controlling agent 1 was added by a triple jet for 56 minutes. The fine grain emulsion produced in the mixer was continuously added to the reaction vessel. The stirring rotation speed of the mixer was 2000 rpm. The stirring blade of the reaction vessel was rotated at 800 rpm and stirred well. (Growth) During grain growth, IrCl ₆ was added when 70% of silver nitrate was added.
Was added at 8 × 10 ⁻⁸ mol / mol Ag to dope. Before the end of the particle growth, a yellow blood salt solution was added to the mixer. The yellow blood salt was doped into 3% (in terms of the amount of added silver) of the shell portion of the particles so that the local concentration was 3 × 10 ⁻⁴ mol / mol Ag. After the addition was completed, the emulsion was cooled to 35 ° C., washed with normal flocculation, and lime-processed bone gelatin was added in an amount of 5%.
After adding and dissolving 0 g and adjusting the pH to 6.5, the mixture was stored in a cool and dark place. The tabular grains obtained had a circular phase equivalent diameter of 2.9 μm,
Ultra-thin tabular grains having an average thickness of 0.026 μm and a tabular grain ratio of 94% to the total projected area were obtained.

[0071]

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Emulsion E-1 (Invention) 640 cc of distilled water was added to Emulsion T-1 corresponding to 0.3 mol of silver nitrate, the temperature was maintained at 60 ° C., and the pAg was maintained at 7.0.
An aqueous solution of silver nitrate and an aqueous solution of potassium iodide of the same concentration are used so that the silver content of the epitaxial phase is 15% of the total silver content.
It was added at 10.5 cc / min for 30 minutes by the double jet method to form an epitaxial phase on the tabular grains. The obtained emulsion was washed and stored in the same manner as Emulsion T-1. Emulsion E-2 (Invention) Emulsion E-2 was carried out in the same manner as Emulsion E-1, except that the silver content of the epitaxial phase was 25% of the total silver content. Emulsion E-3 (Comparative) The same operation as in Emulsion E-1 was performed except that the addition time was changed to 10 minutes. Emulsion E-4 (Comparative) Emulsion E-4 was carried out in the same manner as Emulsion E-1, except that the temperature at the time of adding the aqueous solution of silver nitrate and the aqueous solution of potassium iodide was changed to 75 ° C. Emulsion E-5 (comparative) Silver iodobromide (3
Emulsion T-1 was shelled by depositing 6 mol% I). By adding a mixture of KBr and KI as a mixed halide salt solution with an aqueous silver nitrate solution by a double jet method, the shell amount is reduced to 1% of the total silver amount for 30 minutes.
It was made to adhere to 5 mol%. Shell deposition is 60
C. at pBr 3.6.

Emulsion T-2 Thin Host Tabular Grain Emulsion In emulsion T-1, 150 cc of a 0.2 mmol solution of crystal habit modifier 1 used for ripening and 150 cc of a solution of crystal habit modifier 1 used during growth were not added, and 2.52M before growth
Of emulsion T-1 except that 100 cc of KBr was added. The obtained tabular grains have a circular phase equivalent diameter of 2.3 μm.
m, the average thickness was 0.060 μm, and the ratio of tabular grains to the total projected area was 96%. Emulsion E-6 (Comparative) The same operation was performed as for Emulsion E-1, except that Emulsion T-2 was used.

The shapes and compositions of the obtained emulsions T-1, 2 and E-1 to 5 are shown in Table 1.

[0075]

[Table 1]

In emulsions E-3 and E-4, halogen conversion occurred, and AgI of 97 mol% or more was not obtained. In particular, the phase precipitated on the main plane of Emulsion E-4 did not have a triangular or hexagonal shape, and precipitation at the fringe portion was conspicuous and was not included in the definition of the present invention. The average thickness of the epitaxy in the emulsion E-1 was 0.011 μm, and that in the emulsion E-2 was 0.013 μm.
μm.

The obtained emulsions E-1 to E-5 and T-1,
To each of T-2, sensitizing dye 1 1.1 × 10 ⁻³ mol / mol silver was added at 40 ° C., and then the temperature was increased to 55 ° C., followed by sodium thiosulfate, potassium chloroaurate, and thiocyanate. Optimum chemical sensitization was performed by adding potassium acid. The obtained emulsion was coated on a cellulose triacetate film support provided with an undercoat layer so as to have a silver content of 18.5 g / m ² . Surfactant 1 was added as appropriate to improve coatability.

[0078]

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[0079]

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On a cellulose triacetate film support provided with an undercoat layer, an emulsion and a protective layer were coated under the following conditions to prepare a coated sample. [Emulsion coating conditions] (1) Emulsion layer Emulsion Various emulsions (silver 3.6 × 10 ⁻² mol / m ² ) Coupler 1 shown below (1.5 × 10 ⁻³ mol / m ² )

[0081]

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• 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 0.08 g / m ² ) · Gelatin (1.80 g / m ² ) These samples were treated under the conditions of 40 ° C. and 70% relative humidity.
After leaving for a period of time, exposure was carried out for 1/100 second through a yellow filter and a continuous wedge, and the following color development was performed.

[Color development] Step Processing time Processing temperature Color development 2 minutes 00 seconds 40 ° C. Bleaching and fixing 3 minutes 00 seconds 40 ° C. Washing with water (2) 20 seconds 35 ° C. Washing with water (1) 20 seconds 35 ° C. Stable 20 seconds 35 ° C. Drying Next, the composition of the processing liquid is shown. (Color development) (unit g) 1-hydroxyethylidene-1,1-disulfone diethylenetriaminepentaacetic acid-1,1-disulfone 2.0 sodium sulfite 4.0 potassium carbonate 30.0 potassium bromide 1.4 potassium iodide 1.5 mg hydroxyamine sulfate 2 4.4 4- [N-ethyl-N-β-hydroxyethylamino] -2-methylaniline sulfate 4.5 Water and 1.0 liter pH 10.05 (Bleaching / fixing solution) (g) Ethylenediamine Ferric ammonium acetate 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 Bleaching accelerator 1 shown below 0.01 mol

[0084]

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Water was added and 1.0 liter, pH 6.0 (washing liquid). Tap water was converted from H-type cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type anion exchange resin (Amberlite). Water is passed through a mixed-bed column packed with (IR-400) to reduce the concentration of calcium and magnesium ions to 3 mg / l or less, and then 20 mg / l of sodium diisocyanurate and 1.5 g / l of sodium sulfate are added. Was added.

This solution has a pH in the range of 6.5 to 7.5. (Stabilizing solution) (Unit: mg) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.3 Disodium ethylenediaminetetraacetate 0.05 Add water 1.0 Liters pH 5.0-8.0

The sensitivity was determined from the exposure amount expressed in lux-second giving a density of 0.1 on the fog, and expressed as a reciprocal logarithmic value with the sample T-1 sensitivity being 100. In addition, the result of the light absorptance measured for the same sample was T-1 of 10
The values are shown in Table 2 with the relative values being 0.

[0088]

[Table 2]

As shown in Table 2, the emulsions E-1 and E
-2 had a high absorptivity of short-wave blue light and low fog. Comparative emulsion E-5 has a lower sensitivity than E-1 and E-2, as shown in Table 1, because light reflection increased due to the large thickness of host tabular grain T-2. Met. E-3 and E-4 have low light absorptance and sensitivity because the number of triangular-shaped silver iodide epitaxial phases precipitated is small.

A cross-sectional electron micrograph of the obtained coated sample was taken in three or more visual fields at a magnification of 3000 times, and the average number of aggregates per visual field was measured. As a result, emulsions T-1 and T
In the case of -2, 40 to 50 aggregates were observed, whereas in the emulsions of the present invention E-1 and E-2, the number of aggregates was reduced to 5 to 10 aggregates. According to the present invention, not only the sensitivity is improved but also the state of aggregation is improved.

Example 2 Emulsion T-3 Ultrathin Host Tabular Grain Emulsion In this example, the mixer described in Preparation of Emulsion T-1 was used for both nucleation and grain growth. 0.02 in the mixer
0.028M KB containing 500cc of 1M silver nitrate aqueous solution and 0.1% by weight of low molecular weight gelatin (average molecular weight 40,000)
500 cc of the aqueous solution was continuously added for 20 minutes, and the obtained emulsion was continuously placed in a reaction vessel for 20 minutes.
A nuclear emulsion of 00 cc was obtained. At that time, the stirring rotation speed of the mixer was 2000 rpm. (Nucleation) After nucleation,
While stirring the nuclear emulsion in the reaction vessel well,
22 cc of the Br solution and 300 cc of 10% by weight trimellit gelatin containing 0.2 mmol of the crystal habit controlling agent 1 were added, and the temperature was raised to 75 ° C. and left for 5 minutes. (Aging) Then, a 0.6M silver nitrate aqueous solution 10
00cc and low molecular weight gelatin (average molecular weight 40,000)
0.6M aqueous solution of KBr containing g and 3 mol% of KI
00 cc was added at a constant flow rate for 56 minutes. The fine grain emulsion produced in the mixer was continuously added to the reaction vessel. At that time, the stirring rotation speed of the mixer was 2000 rpm.
At the same time, 150 cc of a 1/50 M solution of the crystal habit controlling agent 1 was continuously added to the reaction vessel at a constant flow rate. The stirring blade of the reaction vessel was rotated at 800 rpm and was well stirred. (Grain Growth) During the grain growth, IrCl ₆ was added when 70% of silver nitrate was added.
Was added at 8 × 10 ⁻⁸ mol / mol Ag to dope. Before the end of the particle growth, a yellow blood salt solution was added to the mixer. The yellow blood salt was doped into 3% (in terms of the amount of added silver) of the shell portion of the particles so that the local concentration was 3 × 10 ⁻⁴ mol / mol Ag. After the addition was completed, the emulsion was cooled to 35 ° C., washed with normal flocculation, and lime-processed bone gelatin was added in an amount of 5%.
After adding and dissolving 0 g and adjusting the pH to 6.5, the mixture was stored in a cool and dark place. The resulting tabular grains had a circular phase equivalent diameter of 3.0 μm,
Ultra-thin tabular grains having an average thickness of 0.023 μm and a tabular grain ratio of 96% to the total projected area.

Emulsion E-7 (Invention) 640 cc of distilled water was added to Emulsion T-3 corresponding to 0.3 mol of silver nitrate, the temperature was maintained at 60 ° C., and the silver content of the epitaxial phase was 20% of the total silver content. A silver nitrate aqueous solution and a potassium iodide aqueous solution of the same concentration were added by the double jet method while maintaining pBr at 4.0 for 60 minutes. The flow rate was accelerated 10 times from the start to the end of the addition. The obtained emulsion was washed and stored in the same manner as Emulsion T-1. Emulsion E-8 (Invention) Emulsion E-8 was carried out in the same manner as Emulsion E-6, except that the silver content of the epitaxial phase was 10% of the total silver content. Emulsion E-9 (Comparative) Emulsion E-9 was carried out in the same manner as Emulsion E-6, except that the temperature at the time of adding the aqueous solution of silver nitrate and the aqueous solution of potassium iodide was changed to 75 ° C.

Emulsion T-4 Thin Host Tabular Grain Emulsion 0.028M KBr containing 0.1% by weight of low molecular weight gelatin (average molecular weight 40,000) in the nucleation of Emulsion T-3
Emulsion T-3 was performed in the same manner as in emulsion T-3 except that 0.2 mmol of crystal habit controlling agent 1 was added to 500 cc of the aqueous solution, and 0.2 mmol of crystal habit controlling agent 1 after nucleation was not added. . The resulting tabular grains were thin tabular grains having a circular phase equivalent diameter of 2.1 μm, an average thickness of 0.067 μm, and a tabular grain ratio of 82% to the total projected area. Emulsion E-10 (Comparative) The same operation as Emulsion E-7 was performed except that Emulsion T-4 was used.

Table 3 shows the shape and composition of the obtained emulsion.

[0095]

[Table 3]

In particular, the phase precipitated on the main plane of Emulsion E-9 does not have a triangular or hexagonal shape, and precipitates in the fringe portion are conspicuous, and are not included in the definition of the present invention. Was. The average thickness of epitaxy in Emulsion E-7 was 0.012 μm, and in Emulsion E-8 was 0.007 μm.

Emulsions T-3, T-4 and E-7-1 obtained
0 was exposed and developed in the same manner as in Example 1. Table 4 shows the results. Also, the results of the light absorptivity measured for the same sample are shown in Table 4 as relative values with T-3 being 100.

[0098]

[Table 4]

As shown in Table 4, the emulsions E-6 and E
-7 showed better results in sensitivity, fog, and light absorptivity than the other emulsions.

When the coagulated state of the coated sample was observed in the same manner as in Example 1, similar to the result in Example 1, the emulsions E-6 and E-7 of the present invention exhibited host tabular grain emulsions T-3 and T-3.
The state of aggregation was greatly improved as compared with -4.

Example 3 Emulsion E-7 obtained in Example 2 was optimally chemically sensitized and subjected to spectral sensitization, and then subjected to the preparation of sample 201 of Example 2 of JP-A-9-146237. It was used as the emulsion of the third layer, and the same processing as in the example of the same JP-A-Hei Hei 9 was performed, and good results were obtained.

Example 4 Emulsion E-7 obtained in Example 2 was optimally chemically sensitized and subjected to spectral sensitization, and then subjected to the preparation of Sample 110 of Example 1 of JP-A-10-20462. It was used as the emulsion of the third layer, and the same processing as in the example of the same JP-A-Hei Hei 9 was performed, and good results were obtained.

Example 5 Emulsion T-5 Ultra-Thin Host Tabular Grain Emulsion In this example, nucleation was carried out using a reaction vessel and grain growth was carried out with a fine grain prepared using the mixer described in Preparation of Emulsion T-1. Is added to the reaction vessel. 1.0 liter of water and 0.5 g of oxidized bone gelatin (methionine content: 5 μm / g) and 0.38 g of KBr in a reaction vessel
Was added and dissolved in a solution kept at 20 ° C. while stirring.
20 cc of a 9 M KBr aqueous solution was added over 40 seconds. (Nucleation) The temperature was increased from 20 ° C to 75 ° C over 29 minutes,
Let stand for minutes. During the temperature rise, 495 cc of a 10% by weight aqueous solution of trimellit gelatin and KBr were added to adjust the pBr in the reaction vessel to 2.1. Further, 3 minutes after completion of nucleation, 10 ml of 0.02 M crystal habit controlling agent 2 was added to the reaction vessel. (Aging) Then, a 0.53M silver nitrate aqueous solution 942c was added to the mixer.
c, 5% by weight of low molecular weight bone gelatin (average molecular weight: 20,000)
942cc of 0.59M KBr aqueous solution and 0.02
150 ml of an aqueous solution of M crystal habit controlling agent 2 was quantitatively added over 42 minutes. The fine grain emulsion prepared by the mixer was continuously added into the reaction vessel. (Growth) The obtained ultrathin tabular grains had an average thickness of 0.036 nm, a coefficient of variation of the tabular thickness of 86%, and an average equivalent circle diameter of 1.0 nm. The variation coefficient is a value obtained by dividing the standard deviation of the plate thickness by the average plate thickness and multiplying the result by 100.

[0104]

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Emulsion E-11 (Comparative) The same operation as in Emulsion E-1 was carried out except that Emulsion T-5 was used. Emulsion T-6 Ultra-Thin Host Tabular Grain Emulsion Emulsion T- except that 200 cc of a 10% by weight solution of high molecular weight bone gelatin (a component having a molecular weight of 300,000 or more, 16.2%) was added to the reaction vessel before tabular grain growth. Performed in the same manner as 5. The resulting ultrathin tabular grains have an average thickness of 0.033 n
m, coefficient of variation of plate thickness 18%, average circle equivalent diameter 1.3n
m. Emulsion E-12 (Invention) The same operation as in Emulsion E-1 was performed except that Emulsion T-6 was used.

Table 5 shows the grain shapes of the obtained emulsions E-11 and E-12.

[0107]

[Table 5]

Further, the emulsions shown in Table 5 were exposed and developed in the same manner as in Example 1. As a result, emulsion E-
In No. 12, good results were obtained in sensitivity, fogging, and light absorptivity, and it was found that graininess was particularly superior to Emulsion E-11.

Example 6 Emulsion T-7 Thin host tabular grain emulsion (with dislocation) 1205 ml of an aqueous gelatin solution (containing 0.6 g of deionized alkali-treated bone gelatin having a methionine content of about 3 μmol / g and 0.47 g of KBr) was placed in a reaction vessel. ), Keeping the temperature at 20 ° C., and stirring the mixture, by a double jet method, using an Ag-1 solution (containing 5 g of silver nitrate in 100 ml) and X
-1 solution (containing 3.5 g of KBr in 100 ml) of 30
20 ml were added at ml / min. After stirring for 1 minute,
14 ml of 30% KBr aqueous solution was added, and the temperature was raised to 75 ° C. in 24 minutes. Immediately after the start of heating, 350 ml of an aqueous dispersion medium containing 35 g of trimellitated gelatin was added.
Further, immediately after adding the gelatin, 1/50 M (1
11) 10 ml of crystal habit controlling agent 1 was added. After the temperature was raised to 75 ° C., the mixture was allowed to stand for 2 minutes, and 200 ml of an aqueous dispersion medium containing 20 g of trimellitated gelatin was added to 3,6-dithia-1,
10 m of 8-octanediol aqueous solution (1.0% by weight)
1 was added. Ten minutes after the completion of the addition, the Ag-2 solution (100
The flow rate at the start of the addition was 1.0 ml / min, and 9 ml was added while accelerating the flow rate by 0.32 ml / min. During this time, liquid X-2 (16.6 mL of KBr in 100 ml) was maintained so that pBr was maintained at 2.5.
g) were simultaneously added by the CDJ (controlled double jet) method. Further, 10 seconds after the start of the Ag-2 solution addition,
In a well-mixed 0.5 ml capacity mixing container described in JP-A-10-43570, 70.7 ml of Ag-3 solution (containing 1.7 g of silver nitrate in 100 ml) was added at 15.7 ml /
Minutes, X-3 solution (1.7 g of KI in 100 ml, deionized alkali-treated low molecular weight gelatin (average molecular weight 200
00) 5.0 g) to 15.7 ml
Per minute and mixed simultaneously, and the formed fine particle emulsion of AgI was continuously added into the reaction vessel. At that time, the stirring rotation speed of the mixer was 2000 rpm. Two minutes after the completion of the addition of the liquid A-2, the liquid Ag-4 (silver nitrate 2 in 100 ml) was added.
(Including 0.4 g) at a flow rate of 4.3 ml / min and 493 ml while accelerating the flow rate by 0.6 ml / min.
Was added. During this time, X is adjusted so that pBr is maintained at 2.5.
-4 liquid (containing 16.6 g of KBr in 100 ml) is C
Co-added by the DJ (controlled double jet) method.
Further, a flow rate at the start of addition of 1/125 M (111) crystal phase controlling agent 1 was 1.5 ml / min, and 398 ml were added simultaneously with the addition of the Ag-4 solution while accelerating the flow rate by 0.6 ml / min. One minute after the completion of the addition of the Ag-4 solution, the temperature was lowered to 35 ° C., the pH was adjusted to 3.9 by adding sulfuric acid, and the soluble salts were removed by flocculation. Thereafter, the temperature was raised again to 50 ° C.
g and filtered water (130 ml) to redisperse the emulsion.
The pH was adjusted to 5.5 and the pAg to 8.6 by adding OH and KBr. The average equivalent circle diameter of the thus obtained (111) tabular grains is 1.46 μm and the average grain thickness is 0.05.
It was 8 μm. The ratio of the projected area of (111) tabular grains to the total projected area of all grains was 96%.

Emulsion E-13 (Comparative Example) 640 cc of distilled water was added to Emulsion T-7 corresponding to 0.5 mol of silver nitrate, the temperature was kept at 65 ° C., the pAg was kept at 7.02, and the amount of silver in the epitaxial phase was reduced. An aqueous solution of silver nitrate and an aqueous solution of potassium iodide of the same concentration were added in two 10-minute growth segments so that the total silver content was 18%. In the first segment, an aqueous solution of silver nitrate was added at 3.5 to 17.5 cc /
min, while adding KI at 5-25 cc /
min. In the second segment, the addition of the aqueous silver nitrate solution was accelerated to 17.5 to 35 cc / min,
During that time, the addition of KI was accelerated to 25-50 cc / min. The obtained emulsion was washed and stored in the same manner as Emulsion T-1.

Emulsion T-8 Thin host tabular grain emulsion (no dislocation) The same operation as in emulsion T-7 was performed, except that fine particles of AgI formed using Ag-3 solution and X-3 solution were not added. Was. The average equivalent circle diameter of the obtained (111) tabular grains was 1.59 μm, and the average grain thickness was 0.050 μm. The ratio of the projected area of (111) tabular grains to the total projected area of all grains was 98%.

Emulsion E-14 (Comparative Example) Emulsion E-11 was carried out in the same manner as Emulsion E-11, except that Emulsion T-8 was used.

Emulsion T-9 Ultra-thin host tabular grain emulsion (with dislocations)
(Containing 0.6 g of deionized alkali-treated bone gelatin having a methionine content of about 3 μmol / g and 0.47 g of KBr), keeping the temperature at 20 ° C., and stirring the Ag-1 solution (double-jet method). 2. 100 ml of 5 g of silver nitrate and X-1 solution (KBr in 100 ml of 3.
(Including 5 g) was added in 20 ml portions at 30 ml / min. 1
After stirring for 30 minutes, 14 ml of a 30% aqueous KBr solution was added, and the temperature was raised to 75 ° C. in 24 minutes. Immediately after the start of the heating, 3 g of an aqueous dispersion medium containing 35 g of trimellitated gelatin was added.
50 ml was added. Further, immediately after the addition of the gelatin, 10 ml of 1/50 M (111) crystal habit controlling agent 1 was added. After the temperature was raised to 75 ° C., the mixture was allowed to stand for 2 minutes, and then 200 ml of an aqueous dispersion medium containing 20 g of trimellitated gelatin and 10 ml of an aqueous solution of 3,6-dithia-1,8-octanediol (1.0% by weight) were added. End of the addition 10
Minutes later, the Ag-2 solution (containing 20.4 g of silver nitrate in 100 ml) was added at a flow rate of 1.0 ml / min.
9 ml was added while accelerating the flow rate by ml / min. During this time, the X-2 solution (100
ml containing 16.6 g of KBr) in CDJ (controll
ed double jet). Furthermore, Ag-
10 seconds after the start of the two-liquid addition, the Ag was placed in a well-mixed 0.5 ml-volume mixing container described in JP-A-10-43570.
-3 solution (containing 1.7 g of silver nitrate in 100 ml)
0.7 ml at a rate of 15.7 ml / min.
1.7 g of KI and 5.0 g of deionized alkali-treated low molecular weight gelatin (average molecular weight: 20,000) in 1 l
Was added and mixed at a rate of 15.7 ml / min, and the formed fine particle emulsion of AgI was continuously added into the reaction vessel. The stirring rotation speed of the mixer at that time was 200
It was 0 rpm. Two minutes after the completion of the addition of the liquid A-2, 942 ml of the liquid Ag-4 (containing 9.1 g of silver nitrate in 100 ml) was again placed in the mixing vessel at 22.5 ml / min.
Into 00 ml, 942 ml of KBr and 942 ml of deionized alkali-treated low-molecular-weight gelatin (including 5.0 g of average molecular weight 20,000) were simultaneously added at 22.5 ml / min and mixed, and the resulting fine particle emulsion of AgBr was added to the reaction vessel. Was added continuously. At this time, the stirring rotation speed of the mixer is 2
000 rpm. Furthermore, 0.013M (11
1) 213.5 ml of the crystal habit controlling agent 1 was added at a rate of 5.1 ml / min when the fine grain emulsion was added. During the addition of the fine grain emulsion, the temperature in the reaction vessel was set to 75 ° C. and pBr2.
It was kept constant at 5. One minute after completion of the addition of the fine grain emulsion,
The temperature was lowered to 35 ° C., and sulfuric acid was added to adjust the pH to 3.
The mixture was set to 9 to remove soluble salts and the like by a flocculation method. Thereafter, the temperature was raised again to 50 ° C., 75 g of lime-processed bone gelatin and 130 ml of filtered water were added to re-disperse the emulsion, and NaOH and KBr were added to adjust the pH to 5.5 and pAg.
Adjusted to 8.6. (111) thus obtained
The average equivalent circle diameter of the tabular grains was 2.23 μm, and the average grain thickness was 0.034 μm. The ratio of the projected area of (111) tabular grains to the total projected area of all grains is 88.
%Met.

Emulsion E-15 (Invention) The same operation as in Emulsion E-11 was carried out except that Emulsion T-9 was used.

The grain shapes of E-13 to E-15 were all the same, and a triangular or hexagonal epitaxial phase was precipitated on the main plane. According to the X-ray diffraction analysis, all of the deposited epitaxial phases were 97 mol% or more of AgI. Further, these emulsions were optimally chemically sensitized and spectrally sensitized with the following sensitizing dye 2, and exposed and developed in the same manner as in Example 1. The sensitivity was determined from an exposure amount expressed in lux-second giving a density of 0.1 on fog, and expressed as a reciprocal logarithmic value with the sensitivity of sample T-7 being 100. Table 6 shows the results. In addition to the effect of increasing sensitivity by AgI epi, the sensitivity was further improved by introducing dislocations into host tabular grains. Further, the residual color due to the dye after development was greatly improved by the sensitizing dye 2.

[0116]

Embedded image

[0117]

[Table 6]

[0118]

According to the present invention, an ultrathin tabular grain emulsion having high efficiency of blue absorption, good sensitivity and good fog, and having a high iodide epitaxial phase was obtained. Further, in the present invention, agglomeration which has been a problem in ultrathin tabular grain emulsions has also been greatly improved.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 1/035 G03C 1/035 L 1/015 1/015 1/14 1/14

Claims (12)

[Claims] 1. A total of 7 projected areas of silver halide grains.
0% or more are tabular grains, the main plane of the tabular grains is a {111} plane, the thickness is 0.04 μm or less, and 97 mol% or more of silver iodide is added to the tabular grains. A silver halide emulsion comprising silver halide grains joined to an epitaxial phase comprising silver halide. 2. At least 60% of said epitaxial phase
Is a silver halide containing 97 mol% or more of silver iodide. 3. The silver halide emulsion according to claim 1, wherein said epitaxial phase accounts for at least 10 mol% of the total silver. 4. The occupied area of the epitaxial phase bonded to the main plane of the tabular grains is within ± 10% of the average occupied area among all grains.
A silver halide emulsion according to any one of the above. 5. The silver halide emulsion according to claim 1, wherein said tabular grains have an equivalent circle diameter of at least 0.7 μm. 6. The method according to claim 1, wherein the coefficient of variation between the thicknesses of the tabular grains is less than 40%.
A silver halide emulsion according to any one of the above. 7. The tabular grain comprises [1] a core and a shell, and [2] the shell includes at least one dislocation line reaching an edge or a corner of the tabular grain from an interface between the core and the shell, [3]. The silver halide emulsion according to any one of claims 1 to 6, wherein the amount of silver used for forming the core is 0.1% to 10% of the total amount of silver used for forming the grains. 8. A silver halide emulsion according to claim 1, wherein said tabular grains comprise at least 50 mol% of silver chloride. 9. The silver halide emulsion according to claim 1, wherein said tabular grains comprise at least 70 mol% of silver bromide. 10. The tabular grains having the general formula (I) or (II)
Alternatively, at least one of the compounds represented by (III) is a nucleus
Do not exist during formation, but during ripening and growth
10. The method according to claim 1, which is prepared.
The silver halide emulsion as described above. Embedded image(Where R₁Is an alkyl, alkenyl or aralkyl
R_Two, R_Three, R_Four, R_Five, And R₆Are each
Represents a hydrogen atom or a substituent. R_TwoAnd R_Three, R_ThreeAnd R _Four, R
_FourAnd R_Five, R_FiveAnd R₆May be fused. Where R_Two,
R_Three, R_Four, R_Five, And R₆At least one is an aryl group
Represents X^-Represents an anion. )(A₁, A_Two, A_ThreeAnd A_FourCompletes a nitrogen-containing heterocycle
Group of non-metallic atoms for
May be. B represents a divalent linking group. m is 0 or
Represents 1. R₁, R_TwoEach represents an alkyl group. n is
0, 1 or 2 is represented by X^-Represents an anion. ) 11. A mixing vessel is provided outside a reaction vessel for causing nucleation and / or grain growth of the tabular grains, and an aqueous solution of a water-soluble silver salt and an aqueous solution of a water-soluble halide are supplied into the mixing vessel. To form silver halide fine particles. The fine particles are immediately supplied to the reaction vessel, and nucleation and / or growth of silver halide grains is performed in the reaction vessel to form the tabular grains. The silver halide emulsion according to any one of claims 1 to 10, wherein 12. The silver halide emulsion according to claim 1, wherein said silver halide grains are spectrally sensitized by a dye represented by the formula (S). General formula (S) In the formula (S), Z ₁ and Z ₂ represent a sulfur atom, a selenium atom, an oxygen atom or a nitrogen atom. V ₁ and V ₂ represent a monovalent substituent. However, V ₁ and V ₂ are not bonded to each other by an aromatic group or two or more adjacent groups to form a condensed ring. l ₁ and l
₂ represents 0, 1, 2 or 3. L ₁ , L ₂ and L ₃ represent a methine group. R ₁ and R ₂ represent an alkyl group. n ₁ represents 0, 1 or 2. m ₁ represents a number of 0 or more necessary to neutralize the charge of the molecule. M ₁ represents a charge balancing counter ion.