JPH095911A - Silver halide emulsion and silver halide photosensitive material using the emulsion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide emulsion good in anisotropic growth, very slow in a growth speed in the thickness direction, superior in uniformity among silver halide grains, sensitivity, graininess, and spectral sensitization characteristics, and to provide a photosensitive material using this emulsion. SOLUTION: The emulsion has a silver chloride content of 30-100mol% and >=30% of the projection areas of the total silver halide grains are flat silver halide grains satisfying the following conditions (1)-(5) at the same time: (1) A principal face is a face 100}; (2) an aspect ratio (corresponding circle diameter/thickness) is 2-25; (3) an average thickness is 20-300nm; (4) an adjacent side ratio is 1-5; and (5) when the grain is observed from the direction perpendicular to the principal face, 2 dislocation lines extending from the nucleus at the time of nucleus formation exist on the grain having grown to 75% of the average projection areas of the completed grain and an angle formed between the 2 dislocation lines is 5 deg.-85 deg..

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide (hereinafter sometimes referred to as "AgX") emulsion useful in the field of photography and a silver halide light-sensitive material using the same. The present invention relates to an AgX emulsion containing tabular grains of 100} plane and a silver halide light-sensitive material using the same.

[0002]

2. Description of the Related Art When a tabular AgX emulsion particle is used in a photographic light-sensitive material, color sensitization, sharpness, light scattering characteristics, covering power, development progress, graininess, etc. are improved as compared with a non-tabular AgX particle. You. For this reason, tabular grains having twin planes parallel to each other and having a principal plane of {111} plane have come to be used frequently.

However, when a large amount of a sensitizing dye is adsorbed on AgX grains, grains having {100} faces are usually
Good color sensitization characteristics. Therefore, development of tabular grains having a {100} major plane is desired. The {100} tabular grains whose main plane has a shape of a right-angled parallelogram are disclosed in JP-A-51-8.
No. 8017, Japanese Examined Patent Publication No. 64-8323, European Patents 0,5
34,395A1, U.S. Pat. No. 5,292,632.
No. 5,264,337, No. 5,320,938
And JP-A-6-59360. However, in these patents, there is no description that it is particularly preferable to grow while leaving the acute-angled dislocation lines of the present invention in terms of anisotropic growth, sensitivity, and fogging. Further, even if additional tests of the examples of these patents are carried out, even if the average of the projected areas of the dislocation lines of the present invention is 75% or more of the average of the projected areas of the finished particles, the total projected area of It was not possible to confirm more than 30%.

Further, the description that particles grow by dislocation is
Journal of Crystal Growth 23 (1974) 207-
213, but the dislocation lines here are orthogonal,
It is different from the dislocation line of the grain of the present invention. When anisotropic growth of particles occurs at two dislocation lines that are orthogonal to each other and extend in the {100} direction, when the dislocation lines are orthogonal to each other, the shape of the grain is 1
It becomes a fan shape with two rounded corners, and when dislocation lines are not orthogonal to each other, it becomes acicular grains, and in both cases, {100} tabular grain formation is inferior.

[0005]

The object of the present invention is that the anisotropic growth is good, the growth speed in the thickness direction is very slow, the intergranular uniformity is more excellent, and the sensitivity, graininess and spectral sensitization characteristics are improved. An object is to provide a more excellent AgX emulsion and a photographic light-sensitive material using the same.

[0006]

The objects of the present invention have been achieved by the following items.

(1) In a silver halide emulsion having at least a dispersion medium and silver halide grains, the silver chloride content of the emulsion is 30 mol% or more and 100 mol% or less, and the projected area of the silver halide grains is A silver halide emulsion characterized in that 30% or more of the total is composed of tabular silver halide grains satisfying the following conditions at the same time. The main plane is the {100} plane. The aspect ratio (equivalent circle diameter / thickness) is 2.0 or more and 25 or less. The average thickness is 0.02 μm or more and 0.3 μm or less. The average of adjacent side ratios is 1 or more and 5 or less. When observed from a direction perpendicular to the main plane, the average projected area of the grains grew to 75% of the average projected area of the finished grains, and there were two dislocation lines extending from the nuclei at the time of nucleation, and The angle formed by the two dislocation lines is 5 ° or more and 85 ° or less.

(2) The silver halide emulsion according to (1), wherein the dislocation lines are present in grains grown to an average projected area of 85% of the average projected area of finished grains.

(3) The silver halide emulsion according to (1), wherein the dislocation lines are present in grains grown to an average projected area of 99% of the average projected area of finished grains.

(4) The silver halide emulsion according to (1), wherein the dislocation lines are present in the grains coated on the silver halide light-sensitive material.

(5) When observed from a direction perpendicular to the main plane, the angle formed by the two dislocation lines is 30 ° or more and 75 ° or more.
The silver halide emulsion according to any one of (1) to (4), characterized in that

(6) When observed from a direction perpendicular to the main plane, the angle formed by the two dislocation lines is 45 ° or more and 75 ° or more.
The silver halide emulsion according to any one of (1) to (4), characterized in that

(7) The tabular silver halide grains are present in an amount of 45% or more of the total projected area (1).
The silver halide emulsion according to any one of (6).

(8) The tabular silver halide grains are present in an amount of 60% or more of the total projected area (1).
The silver halide emulsion according to any one of (7).

(9) The silver halide grains have a silver chloride content of 50.
It is characterized in that it is not less than mol% and not more than 100 mol%
The silver halide emulsion according to any one of (1) to (8).

(10) The silver halide grains have a silver chloride content of 80.
% Or more and 100 mol% or less (1)
The silver halide emulsion according to any one of (8).

(11) When the tabular silver halide grains are observed from a direction perpendicular to the principal plane, they are within the range of 0.001% to 10% of the projected area including one corner. The silver halide emulsion according to any one of (1) to (10), which is a grain in which nuclei are present during nucleation.

(12) The silver halide emulsion according to any one of (1) to (11), which is sensitized with gold and / or chalcogen.

(13) A silver halide photographic material comprising at least one of the emulsions described in any one of (1) to (12) on at least one side of a support.

(14) A silver halide photographic material comprising at least one of the emulsions described in any one of (1) to (12) on both sides of a support.

(15) The silver halide photosensitive material according to (14), which is used in combination with a fluorescent intensifying screen which emits light by X-ray exposure having a peak in the range of 200 nm to 400 nm.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION In the present specification, the projected area of silver halide grains means a state in which AgX emulsion grains do not overlap with each other, and a tabular silver halide grain has a main plane parallel to a substrate surface. The area of particles observed from the direction perpendicular to the main plane when placed on the substrate. The equivalent circle diameter of a tabular silver halide grain means the diameter of a circle having an area equal to the projected area of the grain when the grain is observed with an electron microscope. The thickness means the distance between the main planes of tabular silver halide grains. The aspect ratio refers to a value obtained by dividing the equivalent circle diameter (diameter) of tabular silver halide grains by the thickness. The average thickness is 2 or more and the aspect ratio is 2 or more.
Refers to the average thickness of tabular silver halide grains of 5 or less,
0.02 μm or more and 0.3 μm or less is preferable,
The thickness is more preferably μm or more and 0.25 μm or less, still more preferably 0.05 or more and 0.25 μm or less. The circle-equivalent projected grain size of the tabular silver halide grains having an aspect ratio of 2 or more and 25 or less is preferably 0.1 μm or more and 8 μm or less, more preferably 0.2 μm or more and 5 μm or less, and further preferably 0.3 μm or more and 2 μm or less. The equivalent circle diameter distribution is preferably monodisperse, and the coefficient of variation (standard deviation / average diameter) of the distribution is preferably 0 or more and 0.4 or less, more preferably 0 or more and 0.3 or less, and 0 or more and 0.2 or less. Is more preferable. Further, the shape of the main plane of the tabular grains having an aspect ratio of 2 or more and 25 or less is a right-angled parallelogram, and the adjacent side ratio [(long side length / short side length) of one grain is indicated. ] Is 1 or more and 5 or less, preferably 1 or more and 3 or less, and more preferably 1 or more and 2 or less.

The AgX emulsion of the present invention is an AgX emulsion having at least a dispersion medium and AgX grains, and the amount of the projected area of the AgX grains is 30% or more, preferably 45% or more, more preferably 60% or more. It is a tabular silver halide grain that satisfies the above conditions (simply referred to as a tabular grain). The aspect ratio is preferably 2 or more and 20 or less, more preferably 2 or more and 15 or less. The AgX composition of the AgX particles of the present invention has a silver chloride content of 30 mol%.
Or more and 100 mol% or less, preferably 50 mol% or more and 100 mol% or less, and more preferably 80 mol% or more and 100 mol% or less.

In the present specification, the projected area of grains during the growth of tabular grains means X% of the projected area of finished grains and is 1%.
00 × average of projected area of growing tabular grains (interim sampling) (fine particles are not counted) / average of projected area of finished grains.

In order to form tabular grains, it is necessary that crystal defects such as screw dislocations are incorporated during nucleation to promote growth in a specific direction. Although the crystal defects have not been determined to be screw dislocations, it is considered that the crystal defects may be screw dislocations from the anisotropic growth conditions of grains. Further, since this dislocation serves as a driving force for growth, it is preferable that this dislocation line does not disappear during grain formation.

In the present specification, the corner of the tabular grain means a portion where the side faces of the {100} flat plate intersect. Usually the tabular grains have four corners. The core portion of the tabular grains refers to a portion where a grain having no anisotropic growth property becomes anisotropic growth for the first time due to a halogen gap due to different halogens and / or impurities. The anisotropic growth property is often imparted because dislocations or the like are introduced into the grains. The core of the particles of the present invention is characterized by being present in the range of 0.001% or more and 10% or less, more preferably 0.001% or more and 7% or less of the square of the projected area including one corner. Is. In many cases, lattice distortion is observed and the location of the nucleus can be confirmed by a direct method low-temperature transmission electron microscope photograph image (hereinafter referred to as a “direct TEM image”). The nuclei preferably have different halogens such as I ⁻ and / or Br ^{− with} respect to the amount of added silver, preferably 0.01
Mol% or more and 5 mol% or less, more preferably 0.05 mol%
Or more and 3 mol% or less, more preferably 0.1 mol% or more 1
A method in which the growth history is entered by a method of adding less than or equal to mol% and a low-temperature luminescence is directly observed in the case of TEM image or I ⁻ [eg Journal of Imaging Science, Vol. 31, 15
~ 26 (1987) can be referred to]
If the location of the nucleus can be indirectly confirmed by
The lattice distortion of the nucleus may not be observed in the EM image. The composition of the core of the particles of the present invention is often different from the composition other than the composition of the core, but the composition is not necessarily different.
However, in this case as well, it is necessary to confirm the existence position of the nucleus by including the history of growth in the nucleus.

The tabular grains of the present invention are direct TEM images,
It is characterized by having two dislocation lines extending from the nucleus when observed from the direction perpendicular to the principal plane. The dislocation lines preferably have a projected area of growing tabular grains of up to 75% of the projected area of finished grains, more preferably up to 85%, and even up to 99%. Is particularly preferred. In addition, dislocation lines often extend directly from the nucleus at the time of nucleation, but even if a part of the dislocation line is lost, if the extension of the dislocation line reaches the nucleus at the time of nucleation, the present invention Particles. Further, the angle formed by the dislocation lines is characterized by 5 ° or more and 85% or less when observed from a direction perpendicular to the main plane, preferably 30 ° or more and 75 ° or less, and 45 ° or more. 75 °
It is more preferred that: The feature is that dislocation lines are often introduced in the (31n) direction when the side faces of the tabular grains are {100}.

The characteristic feature of forming grains of the structure is that the dislocation lines introduced by nucleation do not disappear. In {100} tabular grains, it is observed that dislocation lines introduced by nucleation disappear during grain formation, for example, during physical ripening and grain growth, resulting in thickening of grains. Therefore, the ripening is performed in the presence of fine particles, for example, and the dislocation lines should not disappear along with the dissolution of each corner of the tabular grain.
In addition, the growth must be performed from the state where the dislocation lines remain. Furthermore, in order to make the dislocation lines stably exist,
The introduced dislocation line needs to be pinned.
For that purpose, the growth is not limited to a single halogen composition, but different halogens are preferably contained in an amount of 0.1 mol% or more and 25 mol% or less,
More preferably 0.5 mol% or more and 10 mol% or less, particularly preferably 0.7 mol% or more and 7 mol% or less mixed halogen method, and impurities such as yellow blood salt are preferably 0.1
A method of growing with a halogen solution having a single halogen composition containing mol% or more and 20 mol% or less, and more preferably 0.2 mol% or more and 10 mol% or less, and lowering the growth temperature so that pinning of dislocation lines does not easily come off. Preferably 30 ° C
There is a method of growing at 75 ° C. or higher and more preferably at 35 ° C. or higher and 65 ° C. or lower, and any one of these methods may be used or used in combination. By the way, in order to grow while maintaining the anisotropic growth property, low supersaturation of Ag ⁺ salt solution and X ^- salt solution may be added.

An example of the direct TEM method is shown below. 1. Sample preparation An emulsion during grain formation and / or after grain formation was treated with a grain deformation inhibitor-1 or phenylmercaptotetrazole (1 × 10 ⁻³ to 1 × 10) so as not to cause grain deformation.
^-2 mol / mol Ag) in methanol solution,
The particles were taken out by centrifugation, dropped on a sample support (mesh) for observing an electron microscope having a carbon support film attached in advance, and dried to obtain a sample.

2. Observation of particles The prepared sample was subjected to an electron microscope JEM-20 manufactured by JEOL Ltd.
00FXII, acceleration voltage 200kV, magnification 5000x ~
50000 times, sample cooling holder gatan 626
Observation temperature using -300 Cryostation-
Observation was performed at 120 ° C. For particles for which dislocation lines could not be observed, the sample was tilted and observed to confirm the presence or absence of dislocations.

[0031]

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The aging and / or growth of the grains is carried out with pCl
It is preferably formed under the condition of 2.8 or less and 1.6 or more, preferably pCl 2.5 or less and 1.6 or more. Also in the case of grains having other halogen composition structures, it is preferable to form them at the Cl ⁻ concentration. This is because it is preferable that the tabular grain formation is carried out under the cubic grain formation condition, and the Cl ^- concentration condition corresponds to the cubic grain formation condition. The excess Cl ⁻ can be regarded as a kind of crystal habit controlling agent.

The silver halide grains of the present invention can be anisotropically grown by AgX fine particles. It is preferable that the added fine particles have the smallest degree of supersaturation of the system, and thus it is preferable to use particles having the largest size that can be eliminated.
Since the size of the erasable grains varies depending on the size of the growing {100} tabular grains, it is preferable to gradually increase the added fine particles during the growth. Tabular grains are grown by Ostwald ripening using the AgX fine particles. The fine grain emulsion can be added continuously or intermittently. The fine grain emulsion can be continuously prepared by supplying the AgNO ₃ solution and the X ⁻ salt solution by a mixer provided near the reaction vessel, and can be immediately added to the reaction vessel immediately or in another vessel in advance. And then added continuously or intermittently. The fine grain emulsion can be added in a liquid form or as a dry powder. The fine particles preferably do not substantially contain multiple twin particles.
Here, the multiple twin particles refer to particles having two or more twin planes per particle. The term "substantially free" means that the number ratio of multiple twin crystal grains is 0% or more and 5% or less, preferably 0% or more and 1% or less, and more preferably 0% or more and 0.1% or less. Further, it is preferable that substantially no single twin particles are contained. Further, it is preferable that the composition does not substantially include a screw dislocation. Here, "substantially not included" complies with the above-mentioned rules. The halogen composition of the fine particles is preferably 0.1 mol% or more and 25 mol% or less, more preferably 0.5 mol% or more and 10 mol% or less, and particularly preferably 0.
AgCl, AgBr containing 7 mol% or more and 7 mol% or less,
AgBrI (I ⁻ content is preferably 0 mol% or more and 20 mol% or less, more preferably 0 mol% or more and 10 mol% or less), a mixed crystal of two or more kinds, or impurities such as yellow blood salt is preferably 0.1. AgCl, Ag containing not less than mol% and not more than 20 mol%, more preferably not less than 0.2 mol% and not more than 10 mol%
Br, AgBrI (I ^- content is 0 mol% to 20 mol%
The following are preferable, 0 mol% or more and 10 mol% or less are more preferable), and two or more kinds of mixed crystals.

Next, a method for preparing the particles will be described in detail. First, the nucleation process will be described in order. Forming a by reacting with first host silver halide nuclei AgX ₁ nucleus ^- (1) Nucleation at least a dispersion medium and Ag ⁺ and halide dispersion medium solution with water (X _1). Then different X ₂ ^- is added a solution or impurities (yellow prussiate, etc.), substantially forms a dislocation as the tabular grain formation caused. In order to form the dislocations of the present invention, the reaction condition must be a {100} plane forming atmosphere. Further, since the formation of dislocations of the present invention is usually slow, a new addition is not made for a certain period of time (preferably 3 minutes or more and 100 minutes or less, more preferably 7 minutes or more and 60 minutes or less) after addition of the heterogeneous X ^- solution or impurities. It is necessary to keep it as it is.

As the crystal habit controlling agent necessary for nucleation, in addition to the compounds described in European Patent 0,534,395A1, gelatin having a high methionine content (preferably 10) is used.
μmol / g or more and 300 μmol / g or less, more preferably 30 μmol / g or more and 200 μmol / g or less),
Known water-soluble dispersion media for AgX emulsions (research disclosure, volume 307, item 3071 for general).
05, the description of November 1989 can be referred to, especially Japanese Patent Publication No. 52-16365 and Japanese Patent Laid-Open No. 59-86.
04, Journal of Imaging Science, Volume 31, 148.
To 156 (1987) are more preferable).

The nucleation temperature is preferably 20 ° C. or higher and 80 ° C. or lower, more preferably 25 ° C. or higher and 50 ° C. or lower. The smaller the size of the nucleus, the easier the ripening proceeds, and the more convenient it is to make thin particles. Therefore, it is preferable to perform nucleation at a low temperature. However, energy is required to form the dislocations of the present invention. In order to satisfy both of them, the formation of AgX nuclei is set to a low temperature, and at the time of dislocation formation, preferably 2 ° C. or higher and 30 ° C. or lower, more preferably 5 ° C.
The temperature may be increased by 30 ° C. or less. After introducing the dislocations of the present invention and before aging, it is preferable to add an Ag ⁺ solution and a Cl ⁻ solution. The introduction of the dislocations of the present invention can be stopped by the addition of this halogen.

Dislocations are introduced into the grains due to a halogen gap or impurities. When the number of dislocations introduced into the grains is more than 3, the grains finally obtained were promoted to grow in the x, y and z axis directions. Thick particles with a low aspect ratio will be produced. Here, the x and y axes are parallel to and orthogonal to the main plane, and the z axis is perpendicular to the main plane. Therefore, the amount of dislocation formation may be controlled so that the frequency of thick grain generation is low and the frequency of tabular grain generation is high. In order to control it, the halogen species and the added amount of X ₂ for forming dislocations, and the impurity species and the added amount can be appropriately selected by trial and error. Further, the aging and the addition of the halogen used for stopping the introduction of the dislocations of the present invention, the halogen species and the addition amount can be appropriately selected by trial and error.

(2) Aging It is difficult to prepare only tabular grain nuclei separately during nucleation. Therefore, grains other than tabular grains are eliminated by Ostwald ripening in the next ripening process. The temperature is preferably 10 ° C. or more and 60 ° C. or less higher than the nucleation temperature, and usually 50 ° C. or more and 80 ° C. or less is used. Non-tabular nuclei disappear by aging and deposit on tabular grains. It is preferable that fine particles having a composition and a size that are more soluble than the flat plate are present in the early stage of the ripening so that the flat plate does not easily disappear in the early stage of the ripening. In addition, it is desirable that new dislocations are not introduced during the ripening. For that purpose, a different halogen is added by adding a halogen having the same composition as AgX ₁ to the equilibrium state by allowing sufficient time after the addition of the different halogen or impurities. , And it is preferable to make the influence of impurities as small as possible.

Aging is preferably not performed until all the fine particles have disappeared. This is because if all the fine particles are eliminated, the corners of the tabular grains will be dissolved, dislocation lines will disappear, and there will be grains in which the anisotropic growth property of the grains is deteriorated. Therefore, it is necessary to start the growth while the fine particles are present and the dislocation lines are present.

(3) Growth After the aging, the particles can be further grown to a desired size, if necessary. In this case, (1) an ion addition method in which an Ag ⁺ salt solution and an X ⁻ salt solution are added at low supersaturation to grow (2) a particle addition method in which AgX particles are formed in advance and the particles are added to grow (3) ) A combination method of both can be mentioned. In either case, it is necessary to grow in the presence of impurities such as yellow blood salt or to grow with mixed halogen. In any case, it is preferable that the fine particles are always present.

The conditions for chemical sensitization in the present invention are as follows:
Although not particularly limited, pAg is 6 or more and 11 or less, preferably 7 or more and 10 or less, and the temperature is 40 ° C or more and 95 ° C or less, preferably 45 ° C or more and 85 ° C or less.

In the present invention, it is preferable to use a noble metal sensitizer such as gold, platinum, palladium or iridium together. In particular, it is preferable to use a gold sensitizer in combination, and specific examples thereof include chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, gold selenide, etc., and 10 ^-7 mol / Ag mol or more 10 It can be used at about ^-2 mol / Ag mol or less. In the present invention, it is also preferable to use a sulfur sensitizer together. Specifically, thiosulfates (e.g., hypo), thioureas (e.g., diphenyl thiourea, triethyl urea, allyl thiourea), a known unstable sulfur compounds, such as rhodanine and the like, 10 ^-7 mol / It can be used in an amount of Ag mol or more and about 10 ^-2 mol / Ag mol or less.

In the present invention, it is also preferable to use a selenium sensitizer in combination. For example, Japanese Patent Publication No. 44-1574
The unstable selenium sensitizer described in No. 8 is preferably used. Specifically, colloidal selenium, selenoureas (eg, N, N-dimethylselenourea, selenoureas, tetramethylselenourea), selenamides (eg, selenacetamide, N, N-dimethyl-selenobenzamide), Selenoketones (eg, selenoacetone, selenobenzophenone), selenides (eg, triphenylphosphine selenide, diethyl selenide), selenophosphates (eg, tri-p-tolyl selenophosphate), selenocarboxylic acid and Esters,
Compounds such as isoselenocyanates are listed, and 10
^-8 mol / Ag mol or more and 10 ^-3 mol / Ag mol or less can be used.

In the present invention, tellurium sensitization is preferably carried out in the presence of a silver halide solvent. Specifically, thiocyanates (for example, potassium thiocyanate) and thioether compounds (for example, US Pat. No. 3,0).
21,215, 3,271,157
-30571, compounds described in JP-A-60-136736, etc., particularly, for example, 3,6-dithia-1,8-octanediol, tetra-substituted thiourea compounds (for example, JP-B-59-11892, U.S.A. Patent No. 4,221,863
Compounds such as tetramethylthiourea), thione compounds described in JP-B-60-11341, mercapto compounds described in JP-B-63-29727, and compounds described in JP-B-60-163042. Examples thereof include mesoionic compounds, selenoether compounds described in U.S. Pat. No. 4,782,013, telluroether compounds described in JP-A-2-118566, and sulfites. Particularly, among these, thiocyanate, thioether compound, tetrasubstituted thiourea compound and thione compound can be preferably used. The amount used is 10 ^-5 mol / A
It can be used in an amount of not less than g mol and not more than about 10 ^-2 mol / Ag mol.

Particularly preferred examples of their use and compounds are described in, for example, JP-A-3-116132 and 5-1136.
No. 35, No. 5-165136, No. 5-165137
No. 5-134345 and the like. Particularly preferred selenium sensitizers include selenium compounds -I to -X. Examples of the tellurium sensitizer include tellurium compounds-I to -X.

[0046]

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[0047]

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The emulsion of the present invention is preferably subjected to reduction sensitization. As a method of reduction sensitization, JP-A-2-
191938, JP-A-2-136852, JP-B-5
As described in JP-A No. 7-33572, ascorbic acid and its derivative, thiourea dioxide, stannous chloride, aminoiminomethanesulfinic acid, hydrazine derivative, borane compound, silane compound, polyamine compound are used as a reducing agent. You can feel it. The pH of the emulsion should be 7
Reduction sensitization can be carried out by keeping the above or pAg at 8.3 or less and aging. Further, reduction sensitization can be performed by introducing a single addition portion of silver ions during grain formation.

However, in order to reduce the influence of grain formation and crystal growth and to carry out controlled reduction sensitization,
It is preferable to carry out reduction sensitization using ascorbic acid and its derivative, or thiourea dioxide. The amount of reduction sensitizer used varies depending on the reducing agent species, but an amount of 10 ⁻⁷ to 10 ⁻² mol / Ag mol is preferably used. The reduction sensitization may be performed anywhere during grain formation and at any time after grain formation and before chemical sensitization.

Since most of the grains are {100} planes,
The adsorption group of gelatin (eg, methionine group) is strongly adsorbed to Ag ⁺ on the surface of the grain. Therefore, the adsorption of the spectral sensitizing dye, the antifoggant and other photographic additives may be excluded. In this case, the dispersion medium gelatin having the optimum methionine content can be selected. Specifically, the photosensitive material AgX
The average methionine content of gelatin in the emulsion layer is preferably 0 to 50 μmol / g, and more preferably 3 to 30 μmol / g. The chemical sensitizer can be added to the AgX emulsion at 10 ^-2 to 10 ^-8 mol / mol AgX, and the sensitizing dye can be added at a saturated adsorption amount of preferably 5 to 100% for sensitization.

The obtained particles may be used as host particles, and epitaxial particles may be formed at the edges and / or corners of the particles for use. Further, particles having dislocation lines inside may be formed using the particles as a core. Alternatively, the particles may be used as a substrate, and AgX layers having a different halogen composition from the substrate may be laminated to produce various known particles having various particle structures. Regarding these, it is possible to refer to the description of the literature described later. Also,
Usually, a chemically sensitized nucleus is provided to the obtained emulsion grains. In this case, it is preferable that the location of the chemically sensitized nuclei and the number / cm ² are controlled. Regarding this, JP-A-2
-838, 2-146033, 1-20165
No. 1, 3-121445, JP-A-64-74540.
No. 3, Japanese Patent Application No. 3-73266, No. 3-140712,
Reference can be made to the description in JP-A-3-115872.

The AgX emulsion grains produced by the method of the present invention can also be used as a blend with one or more other AgX emulsions. The blending ratio can be appropriately selected and used in the range of 1.0 to 0.01 (molar ratio). The AgX emulsion grains produced by the method of the present invention can be used in any photographic light-sensitive material.

In the photographic light-sensitive material of the present invention, the following phosphors are used as a fluorescent intensifying screen, and X-ray photography can be preferably carried out. Blue emitting phosphor Y ₂ O ₂ S: Tb, LaOBr: Tb, BaFCl: E
u Green light emitting phosphor Gd ₂ O ₂ : Tb, LaO ₂ S: Tb

As a method of forming an image using the light-sensitive material of the present invention, there is a method of forming an image in combination with a phosphor having a main peak at 400 nm or less. More preferably, a method of forming an image by combining with a phosphor having a main peak at 380 nm or less is preferable. A screen having a main emission peak at 400 nm or less is disclosed in JP-A-6-11804,
The screen described in WO93 / 01521 is used, but the screen is not limited to this. The emission wavelength of the phosphor preferably used in the present invention is 400 nm or less, more preferably 370 nm or less.

Typical phosphors are M'phase YTaO.
₄ alone or Gd, Bi, Pb, Ce, Se, Al,
Compounds to which Rb, Ca, Cr, Cd, Nb, etc. are added,
A compound obtained by adding Gd, Tm, Gd and Tm, Gd and Ce, Tb to LaOBr, a compound obtained by adding an oxide of HfZr alone or an alkali metal such as Ge and Ti,
A compound containing Y ₂ O ₃ alone or containing Gd and Eu,
_There are a compound in which Gd is added to ₂ O ₂ S, a compound in which Gd, Tl, and Ce are used as an activator in a host of various phosphors. Particularly preferred compounds include M′-phase YTaO ₄ alone or a compound obtained by adding Gd and Sr, LaOBr to which Gd, Tm, Gd and Tm are added, HfZ
An oxide of r or a compound to which an alkali metal such as Ge or Ti is added. The particle size of the phosphor is 1 μm or more and 20 μm
The following is preferable, but it can be changed depending on the required sensitivity and manufacturing problems. The coating amount is 400 g / mm ² or more and 2000 g / mm
^{A value of 2} or less is preferable, but it cannot be said unconditionally depending on the required sensitivity and image quality. A single intensifying screen may be used to provide a particle size distribution from the vicinity of the support to the surface.
In this case, it is generally known that particles on the surface are enlarged. The space filling ratio of the phosphor is 40% or more, preferably 60% or more.

When the phosphor layers are provided on both sides of the light-sensitive material for photographing, the phosphor coating amount on the X-ray incident side and the opposite side can be changed. In general, it is known to reduce the coating amount of the intensifying screen on the X-ray incident side, especially when a high-sensitivity system is required for shielding by the intensifying screen on the X-ray incident side. The support used for the screen used in the present invention includes paper, metal plate, polymer sheet, and the like.
Generally, a flexible sheet such as polyethylene terephthalate is used. The support may be added with a reflecting agent or a light absorbing agent, if necessary, or may be provided as a separate layer on the surface.

If necessary, the surface of the support may be slightly uneven, or an adhesive layer for increasing the adhesion to the phosphor layer or a conductive layer may be provided as an undercoat. Examples of the reflecting agent include zinc oxide, titanium oxide, barium sulfate, etc., but titanium oxide and barium sulfate are preferable because the phosphor has a short emission wavelength. The reflecting agent may be present not only in the support or between the support and the phosphor layer, but also in the phosphor layer. When it is present in the phosphor layer, it is preferred that it is localized near the support. Examples of the binder used in the screen of the present invention include proteins such as gelatin, polysaccharides such as dextran and corn starch, and natural polymer substances such as gum arabic; polyvinyl butyral, polyvinyl acetate, polyurethane, polyalkyl acrylate, vinylidene chloride, nitro. Examples thereof include synthetic polymeric substances such as cellulose, fluorine-containing polymers, polyesters, and mixtures and copolymers thereof. As a preferable binder, as basic performance,
It can be said that it has a high transmittance for the light emitted from the phosphor. In this respect, gelatin, corn starch, an acrylic polymer, a fluorine-containing olefin polymer, a polymer containing a fluorine-containing olefin as a copolymer component, a styrene / acrylonitrile copolymer and the like can be mentioned. These binders may have functional groups that are crosslinked by the crosslinking agent. Further, depending on the required image quality performance, an absorber for light emission from the phosphor may be added to the binder, or a binder having a low transmittance may be used. Examples of the absorbent include a pigment, a dye, and an ultraviolet absorbing compound. The ratio of phosphor to binder is generally 1: 5 to 50: 1 by volume, preferably 1: 1 to 15: 1. The ratio between the phosphor and the binder may be uniform or non-uniform in the thickness direction.

The phosphor layer is usually formed by a coating method using a coating liquid in which the phosphor is dispersed in a binder solution.
Examples of the solvent for the coating liquid include water or alcohols, chlorine-containing hydrocarbons, organic solvents such as ketones, esters and ether aromatic compounds, and mixtures thereof.
Phosphoric acid, stearic acid,
A dispersion stabilizer such as caproic acid and a surfactant, and a plasticizer such as a phosphate, a phthalate, a glycolate, a polyester, and a polyethylene glycol may be added.

In the screen used in the present invention, a protective layer can be provided on the phosphor layer. As the protective layer, a method of coating on the phosphor layer or a method of separately forming a protective layer film and laminating is used. In the coating method, the coating may be performed simultaneously with the phosphor layer, or may be performed after the phosphor layer is coated and dried. The protective layer may be the same substance as the binder of the phosphor layer or a different substance. Examples of the substance used for the protective layer include the substances listed as the binder for the phosphor layer, as well as cellulose derivatives, polyvinyl chloride, melamine, phenol resins and epoxy resins.
Preferred materials include gelatin, corn starch, acrylic polymers, fluorine-containing olefin polymers, polymers containing fluorine-containing olefins as copolymer components, and styrene / acrylonitrile copolymers. The thickness of the protective layer is generally 1 μm or more and 2 μm or more.
0 μm or less, preferably 2 μm or more and 10 μm or less,
It is more preferably from 6 μm to 6 μm. It is preferable to emboss the surface of the protective layer of the present invention. Further, a matting agent may be present in the protective layer, or a substance having a light-scattering property for light emission depending on the image to be obtained, such as titanium oxide may be present.

The protective layer of the screen used in the present invention may have surface slipperiness. Examples of preferable slip agents include polysiloxane skeleton-containing oligomers and perfluoroalkyl group-containing oligomers. You may give electroconductivity to the protective layer of this invention. Examples of the conductivity imparting agent include white and transparent inorganic conductive substances and organic antistatic agents. As a preferable inorganic conductive substance, Z
Examples thereof include nO powder, whiskers, SnO ₂ and ITO.

There are no particular restrictions on the various additives used in the light-sensitive material of the present invention. For example, JP-A-2-6853.
No. 9 can be used as described in the following sections. Item Applicable section 1. Silver halide emulsion and JP-A-2-68539, page 8, lower right column, lower column, 6 from its manufacturing line, to page 10, upper right column, 12th column. 2. Chemical sensitization method, page 10, upper right column, line 13 to lower left column, line 16 3. Antifoggant / Stable From page 10, lower left column, line 17 to page 11, upper left column 7, agent line and from page 3, lower left column, line 2 to page 4, lower left column. 4. Spectral sensitizing dyes, page 4, lower right column, line 4 to page 8, lower right column. 5. Surfactant / Electrostatic Protection Line 11 on page 11, upper left column to line 9, Stopper on page 12, upper left column. 6. Matting agent, slip agent, page 12, top left column, line 10 to top right column, line 10. Plasticizer Same as page 14, lower left column, line 10 to lower right column, line 1. 7. Hydrophilic colloid, page 12, line 11, upper right column to line 16, lower left column. 8. Hardener From page 12, lower left column, line 17 to page 13, upper right column, line 6; 9. Support, page 13, upper right column, lines 7 to 20. 10. Dyes / mordanting agents, page 13, lower left column, line 1 to page 14, lower left column, line 9

[0062]

EXAMPLES The present invention will now be described in more detail by way of examples, but the embodiments of the present invention are not limited thereto. Example 1 Preparation of Emulsion A of the Present Invention 1582 ml of gelatin aqueous solution (gelatin-1) was placed in a reaction vessel.
(Deionized alkali-treated bone gelatin having a methionine content of about 40 μmol / g) 19.5 g, HNO ₃ IN solution 7.
8 ml, pH 4.3), NaCl-1 solution (100 ml
13 ml of NaCl (containing 10 g of NaCl therein),
While maintaining the temperature at 0 ° C., the Ag-1 solution (AgNO
₃ containing 20 g) and X-1 solution (NaCl in 100 ml)
(Including 7.05 g) was simultaneously mixed and added at 62.4 ml / min in 15.6 ml portions. After stirring for 3 minutes, solution X-2 (10
28.2 ml of 80.6 ml / min of KBr (1.1 g in 0 ml) was added. After stirring for 3 minutes, 46.8 ml of the Ag-1 solution and 46.8 ml of the X-1 solution were simultaneously mixed and added at 62.4 ml / min. After stirring for 2 minutes, 203 ml of gelatin aqueous solution
(Gelatin-1 13 g, NaCl 1.3 g, pH
NaOH 1N solution to make 6.5)
After adjusting Cl to 1.75, the temperature was raised to 65 ° C.
It was aged for 3 minutes according to 11.95. Then Ag-2
Liquid (containing 50 g of AgNO _{3 in} 100 ml) and liquid X-3 (16.9 g of NaCl in 100 ml, KBr 1.4).
CDJ (controlled double jet)
The g-3 solution was added at a constant flow rate for 20 minutes until the added amount reached 182 ml. Add precipitant, lower temperature to 35 ° C,
Washed down. Add gelatin aqueous solution, pH at 60 ℃
Adjusted to 6.0. A TEM image of a replica of the particles was observed. The resulting emulsion contained AgBr of 3.
It was a silver chlorobromide {100} tabular grain containing 94 mol%.
The shape characteristic value of the particles is

[(Aspect ratio 2 or more and 25 or less {10
0} total projected area of tabular grains / sum of projected areas of all AgX grains) × 100] = a ₁ = 91 [average aspect ratio (average aspect ratio) of {100} tabular grains having an aspect ratio of 2 or more and 25 or less) ] = A ₂ =
12.1 (average diameter of {100} tabular grains having an aspect ratio of 2 or more and 25 or less) = a ₃ = 1.45 μm (average main surface edge length ratio of {100} tabular grains having an aspect ratio of 2 or more and 25 or less) ) = A ₄ = 1.21 (average thickness of {100} tabular grains having an aspect ratio of 2 or more and 25 or less) = a ₅ = 0.12 μm [thickness of {100} tabular grains having an aspect ratio of 2 or more and 25 or less Coefficient of thickness distribution (standard deviation of thickness / average thickness)]
= A ₆ = 0.13 [({100} tabular grains having an aspect ratio of 2 or more and 25 or less and the average projected area is 75% of the average projected area of the finished grains.
%, The total projected area of grains in which two dislocation lines can be observed / the total projected area of all AgX grains) × 100] = a
₇ = 85 (average angle formed of two dislocation lines above) = a ₈ = 57
Further, when the tabular grains were directly observed by a TEM image, it was possible to observe the dislocation lines of the present invention in grains having 75% of the projected area even in the emulsion after coating.

Preparation of Emulsion B of the Present Invention In the emulsion A of the present invention, pCl after the temperature was raised to 70 ° C. was 1.7.
5 and then kept constant, instead of adding Ag-2 solution and X-3 solution, AgBrCl fine grain emulsion (E-1)
(Average particle diameter 0.1 μm, Br content 4 mol%)
It was added at a rate of 68 × 10 ^-2 mol / min AgCl for 20 minutes. A TEM image of a replica of the particles was observed. The resulting emulsion contained 3.94 mol% AgBr based on silver.
The contained silver chlorobromide {100} tabular grains. The shape characteristic values of the particles are a ₁ = 91, a ₂ = 12.7, a ₃ = 1.
51 μm, a ₄ = 1.22, a ₅ = 0.11 μm, a ₆
= 0.13 was _{a 7 = 90, a 8 =} 59 °. Further, even in the emulsion after coating, the dislocation lines of the present invention could be observed in grains having 79% of the projected area.

Preparation of Emulsion C of the present invention In Emulsion A of the present invention, instead of adding Solution X-3, Solution X-4 (NaCl 17.4 g, KBr 0.4 in 100 ml) was added.
(including g) was added to prepare. A TEM image of a replica of the particles was observed. The resulting emulsion was silver chlorobromide {100} tabular grains containing 1.32 mol% of AgBr based on silver. The shape characteristic value of the particles is a ₁ = 91, a
_{2 = 9.6, a 3 = 1.34μm} , a 4 = 1.35, a
_{5 = 0.14μm, a 6 = 0.16} , a 7 = 78, a 8
= 56 °. The projected area of the emulsion after coating is 6
The dislocation line of the present invention could be observed in 4% of the grains.

Preparation of Inventive Emulsion D In Inventive Emulsion B, instead of adding AgBrCl fine grain emulsion (E-1), AgBrCl fine grain emulsion (E-2).
Preparation was carried out by adding (average particle diameter 0.1 μm, Br content 1 mol%). A TEM image of a replica of the particles was observed. The resulting emulsion had an AgBr of 1.3 based on silver.
It was a silver chlorobromide {100} tabular grain containing 2 mol%. The shape characteristic values of the particles are a ₁ = 91, a ₂ = 10.7, a
_{3 = 1.39μm, a 4 = 1.30} , a 5 = 0.13μ
m, a ₆ = 0.13, a ₇ = 83, and a ₈ = 57 °. Further, even in the coated emulsion, the dislocation lines of the present invention could be observed in the grains of 71% of the projected area.

Preparation of Emulsion E of the present invention In Emulsion A of the present invention, instead of adding Solution X-3, Solution X-5 was used.
(NaCl 17.6 g, yellow blood salt 1 mol% in 100 ml)
Was added) to prepare. T of the particle replica
The EM image was observed. The resulting emulsion is A based on silver
Silver chlorobromide {100} tabular grains containing 0.44 mol% of gBr
Was a child. The shape characteristic value of the particles is a ₁= 91, a₂
= 9.8, a_Three= 1.33 μm, a_Four= 1.41, a_Five
= 0.14 μm, a₆= 0.15, a₇= 77, a₈=
It was 57 °. The projected area of the coated emulsion is 6
The dislocation line of the present invention can be observed in 6% of the grains.
Was.

Preparation of Emulsion F of the Present Invention In the emulsion B of the present invention, instead of adding the AgBrCl fine particle emulsion (E-1), the AgCl fine particle emulsion (E-3) (average particle diameter 0.1 μm, yellow blood salt 1 mol%) was used. Was added) to prepare. A TEM image of a replica of the particles was observed. The resulting emulsion had an AgBr of 1.3 based on silver.
It was a silver chlorobromide {100} tabular grain containing 2 mol%. The shape characteristic values of the particles are a ₁ = 91, a ₂ = 11.1, a
₃ = 1.41 μm, a ₄ = 1.30, a ₅ = 0.13 μm
m, a ₆ = 0.12, was _{a 7 = 80, a 8 =} 59 °. Further, even in the coated emulsion, the dislocation lines of the present invention could be observed in the grains of 71% of the projected area.

Preparation of Comparative Emulsion G Preparation of Emulsion A of the present invention was carried out by adding Solution X-6 (containing 17.6 g of NaCl in 100 ml) instead of Solution X-3. A TEM image of a replica of the particles was observed. The obtained emulsion had AgBr of 0.4 based on silver.
It was a silver chlorobromide {100} tabular grain containing 4 mol%. The shape characteristic values of the particles are a ₁ = 82, a ₂ = 6.7, a ₃
= 1.20 μm, a ₄ = 1.65, a ₅ = 0.18 μm
, A ₆ = 0.17, a ₇ = 7, a ₈ = 57 °.

Preparation of Comparative Emulsion H In the emulsion B of the present invention, AgCl fine grain emulsion (E-4) (including average grain diameter of 0.1 μm) was added in place of AgBrCl fine grain emulsion (E-1). went. A TEM image of a replica of the particles was observed. The resulting emulsion was silver chlorobromide {100} tabular grains containing 0.44 mol% of AgBr based on silver. The shape characteristic values of the particles are a ₁ = 91, a ₂ = 7.2, a ₃ = 1.23 μm,
a ₄ = 1.57, a ₅ = 0.17 μm, a ₆ = 0.1
4, a ₇ = 8, a ₈ = 57 °.

Chemical sensitization Each emulsion prepared as described above was stirred at 60
Chemical sensitization was performed while the temperature was kept at ℃. First, thiosulfonic acid compound-I was added in an amount of 10 ^-4 mol per mol of silver halide, and then thiourea dioxide was added in an amount of 1 × 10 ^-6 mol / mol Ag, and the mixture was kept for 22 minutes to carry out reduction sensitization. did. Next, 4-hydroxy-6-methyl-1,3,3
a, 7-tetraazaindene at 3 × 10 ⁻⁴ mol / mol A
g and sensitizing dyes-1 and 2 were added respectively. Further calcium chloride was added. Then sodium thiosulfate (6 × 10 ⁻⁶ mol / mol Ag) and selenium compound-I
(4 × 10 ⁻⁶ mol / mol Ag) was added. Chloroauric acid 1 × 10 ⁻⁵ mol / mol Ag and potassium thiocyanate × 10 ⁻³ mol / mol Ag were further added, and 40 minutes later, 35
Cooled to ° C. Thus, the preparation (chemical ripening) of the emulsion was completed.

[0072]

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(Preparation of Emulsion Coating Layer) An emulsion coating solution was prepared by adding the following chemicals to 1 mol of silver halide to the chemically sensitized emulsion.・ Gelatin (including gelatin in emulsion) 111 g ・ Dextran (average molecular weight 39,000) 21.5 g ・ Sodium polyacrylate (average molecular weight 400,000) 5.1 g ・ Sodium polystyrene sulfonate (average molecular weight 600,000) 1.2g-Hardener 1,2-bis (vinylsulfonylacetamide) ethane Addition amount was adjusted so that the swelling ratio would be 230% -Compound-I 42.1mg-Compound-II 10.3g-Compound- III 0.11 g-Compound-IV 8.5 mg-Compound-V 0.43 g-Compound-VI 0.004 g-Compound-VII 0.1 g-Compound-VIII 0.1 g NaOH adjusted to pH 6.1.

[0074]

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[0075]

[Chemical 6]

Dye Emulsion A was added to the above coating solution such that Dye-I was 10 mg / m ² per side.

[0077]

[Chemical 7]

(Preparation of Dye Emulsion A)
0 g, 62.8 g of the following high boiling organic solvent-I, 62.8 g of the high boiling organic solvent-II and 333 g of ethyl acetate were dissolved at 60 ° C. Next, 65 ml of a 5% aqueous solution of sodium dodecyl sulfonate, 94 g of gelatin and 581 ml of water were added, and the mixture was emulsified and dispersed by a dissolver at 60 ° C. for 30 minutes. Next, 2 g of the following compound-IX and 6 l of water were added, and the temperature was lowered to 40 ° C. Next, using Asahi Kasei ultrafiltration laboratory module ACP1050, the total amount was concentrated to 2 kg, and 1 g of the compound-IX was added to the dye emulsion A.
And

[0079]

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(Preparation of Coating Solution for Surface Protective Layer) A coating solution for surface protective layer was prepared so that each component had the following coating amount.・ Gelatin 0.780 g / m ²・ Sodium polyacrylate (average molecular weight 400,000) 0.035 g / m ²・ Sodium polystyrene sulfonate (average molecular weight 600,000) 0.0012 g / m ²・ Polymethyl methacrylate (average particle size) 3.7μm) 0.072g / m ² · coating aids -I 0.020g / m ² · coating aids -II 0.037g / m ² · coating aids -III 0.0080g / m ² · coating aids -IV 0.0032 g / m ² · Coating aid-V 0.0025 g / m ² · Compound-X 0.0022 g / m ² · Proxel 0.0010 g / m ² (pH adjusted to 6.8 with NaOH)

[0081]

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(Preparation of Support) (1) Preparation of Dye Dispersion B for Undercoat Layer The following Dye-II was ball-milled by the method described in JP-A-63-197943.

[0083]

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434 ml water and Triton X200
(Registered trademark) surfactant (TX-200 (registered trademark))
And 791 ml of a 6.7% aqueous solution of was added to a 2 liter ball mill. 20 g of the dye were added to this solution. 400 ml (2 mm diameter) beads of zirconium oxide (ZrO ₂ ) were added, and the contents were ground for 4 days. Thereafter, 160 g of 12.5% gelatin was added. After defoaming, Zr is filtered
O ₂ beads were removed. Observing the obtained dye dispersion, the particle size of the crushed dye is 0.05 or more and 1.15.
It has a wide range of fields up to and including μm, and the average particle size was 0.37 μm. Furthermore, dye particles having a size of 0.9 μm or more were removed by centrifugation. Thus, a dye dispersion B was obtained.

(2) Preparation of Support Corona discharge was performed on a biaxially stretched polyethylene terephthalate film having a thickness of 175 μm, and the first undercoating liquid having the following composition was applied at an amount of 4.9 ml / m ^2. Thus, it was applied by a wire converter and dried at 185 ° C. for 1 minute. Next, a first undercoat layer was similarly provided on the opposite surface. The polyethylene terephthalate used is a dye-
The one containing 0.04% by weight of I was used. * Butadiene-styrene copolymer latex solution (solid content 40% butadiene / styrene weight ratio = 31/69) 158 ml * 2,4-dichloro-6-hydroxy-s-triazine sodium salt 4% solution 41 ml * Distilled water 801 ml * The latex solution contains the following compounds as emulsifying dispersants in an amount of 0.4 wt% based on the latex solids.

[0086]

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(3) Coating of undercoat layer A second undercoat layer having the following composition was coated on the first undercoat layer on both sides so that the coating amount would be as described below. To the wire bar coder method,
It was dried at 155 ° C.・ Gelatin 80 mg / m ²・ Dye dispersion B (as dye solid content) 8 mg / m ²・ Coating aid-VI 1.8 mg / m ²・ Compound-XI 0.27 mg / m ²・ Mat agent Average particle size 2 0.5 μm polymethylmethacrylate 2.5 mg / m ²

[0088]

[Chemical 12]

(Preparation of photographic material) On the support prepared as described above, the above emulsion layer and the surface protective layer were combined and coated on both sides by the simultaneous extrusion method. The coated silver amount per one side was 1.75 g / m ² .

(Evaluation of Photographic Performance) A photographic material was changed to Du Po.
Ultravision first detail manufactured by nt was used to bring them into close contact with both sides, and an exposure of 0.05 seconds was applied from both sides, and X-ray sensitometry was performed. To adjust the exposure amount,
It was performed by changing the distance between the X-ray tube and the cassette. After the exposure, the sensitivity was evaluated using the following automatic developing machine and processing solution. The sensitivity is expressed as the logarithm of the reciprocal of the exposure required to give a density of fog +0.1, and the sensitivity of emulsion A is 1
The other values are represented as 00.

(Processing) Automatic processor: CEPROS3 manufactured by FUJIFILM Corporation
0 was used, and Dry to Dry was set to 30 seconds. Preparation of Concentrated Solution <Developer> Part Agent A Potassium hydroxide 330 g Potassium sulfite 630 g Sodium sulfite 255 g Potassium carbonate 90 g Boric acid 45 g Diethylene glycol 180 g Diethylenetriaminepentaacetic acid 30 g 1- (N, N-diethylamine) ethyl-5-mercaptotetrazole 0. 75 g Hydroquinone 450 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 60 g Water was added to 4125 ml.

Part Agent B Diethylene glycol 525 g 3,3 ′ Dithiobishydrocinnamic acid 3 g Glacial acetic acid 102.6 g 2-Nitroindazole 3.75 g 1-Phenyl-3-pyrazolidone 34.5 g Water 750 ml

Parts agent C Glutaraldehyde (50 wt / vol%) 150 g Potassium bromide 15 g Potassium metabisulfite 105 g Water was added to obtain 750 ml.

<Fixer> Ammonium thiosulfate (70 wt / vol%) 3000 ml Ethylenediaminetetraacetic acid / disodium dihydrate 0.45 g Sodium sulfite 225 g Boric acid 60 g 1- (N, N-diethylamine) -ethyl-5-mercapto Tetrazole 15 g Tartaric acid 48 g Glacial acetic acid 675 g Sodium hydroxide 225 g Sulfuric acid (36N) 58.5 g Aluminum sulfate 150 g Water was added to it 6000 ml pH 4.68

(Preparation of Processing Solution) The above-mentioned concentrated solution of the developing solution was filled into the following containers for each part. In this container, the respective partial containers of the parts agents A, B, and C are connected together by the container itself. Further, the above-mentioned fixing solution concentrate was also filled in the same kind of container. First, 300 ml of an aqueous solution containing 54 g of acetic acid and 55.5 g of potassium bromide was added as a starter in the developing tank. Insert the processing agent container upside down and insert it into the perforation blade of the processing liquid stock tank mounted on the side of the automatic processing machine, break the sealing film of the cap, and transfer each processing agent in the container to the stock tank. Filled. These processing agents were filled in the developing tank and the fixing tank of the automatic processing machine at the following ratios by operating the pumps respectively installed in the automatic processing apparatus. In addition, every time 8 sheets of the photosensitive material were processed in terms of quarter size, the processing agent stock solution and water were mixed at this ratio and replenished in the processing tank of the developing machine.

Developer solution Parts solution A 51 ml Parts solution B 10 ml Parts solution C 10 ml Water 125 ml pH 10.50 Fixer concentrate 80 ml water 120 ml pH 4.62 The washing tank was filled with tap water.

As a water stain preventive agent, 0.4 g of actinomycetes supported on perlite having an average particle size of 100 μm and an average pore size of 3 μm was covered with a polyethylene bottle (the bottle opening was covered with a 300-mesh nylon cloth. Prepare three pieces filled with water and fungi from the cloth), two of them at the bottom of the washing tank, and one at the bottom of the stock tank for washing water (liquid volume 0.2 liters). I sunk each. Processing speed and processing temperature Current image 35 ° C 8.8 seconds Fixed temperature 32 ° C 7.7 seconds Water washing 17 ° C 3.8 seconds Squeeze 4.4 seconds Dry 58 ° C 5.3 seconds Total 30 seconds Replenishment amount Developer 25 ml / 10 x 12 inch fixer 25 ml / 10 x 12 inch

The obtained light-sensitive material of the present invention was used in Japanese Patent Laid-Open No. 6-118.
When an image was formed by X-ray exposure using a phosphor screen having a peak intensity in the range of 320 to 380 nm described in No. 04, it was confirmed that a good X-ray image was formed.

Surprisingly, when the shape characteristic values of the grains of Emulsions A to F of the present invention and the grains of Comparative Emulsions G and H were compared, the grains of Emulsions A to F of the present invention were higher than those of Comparative Emulsions G and H. It can be seen that it is the aspect ratio. This means that the grains of the emulsion of the present invention are very excellent in anisotropic growth property as compared with the grains of Comparative Emulsions G and H. Further, when comparing the grains of Emulsions A to F of the present invention with the grains of Comparative Emulsions G and H, the variation coefficient of the thickness distribution is also very large in the grains of Emulsions A to F of the present invention as compared with the grains of Comparative Emulsions G and H. It turns out to be small. These facts are surprising when the direct TEM image of the particles is observed.
Corresponding to the results that in Emulsions A to F of the present invention, many of the dislocation lines of the present invention can be confirmed, while in Comparative Emulsions G and H, the dislocation lines are hardly confirmed.

The results of the sensitivity of photographic light-sensitive materials of Emulsions A to F of the present invention and Comparative Emulsions G and H are shown in Table 1. (The sensitivity of Emulsion H is 1
00. )

[0101]

[Table 1]

As is clear from Table 1, the light-sensitive material of the present invention has high sensitivity and low fog in rapid processing.

Example 2 Emulsions A to H were chemically sensitized by using tellurium compound-I instead of selenium compound-I. Others were the same as in Example 1.

Similar to the selenium compound, the emulsions A to G of the present invention were high in sensitivity and low in fog in the rapid processing with the tellurium compound.

[0105]

The emulsion of the present invention is excellent from the viewpoints of high aspect ratio, high sensitivity and low fog.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G03C 5/17 G03C 5/17 // G21K 4/00 G21K 4/00 A G03C 1/035 C

Claims (15)

[Claims] 1. A silver halide emulsion having at least a dispersion medium and silver halide grains, wherein the emulsion has a silver chloride content of 30 mol% or more and 100 mol% or less, and a total projected area of the silver halide grains. 30% or more of the silver halide emulsions are tabular silver halide grains satisfying the following conditions (1) to (5) at the same time. The main plane is the {100} plane. The aspect ratio (equivalent circle diameter / thickness) is 2.0 or more and 25 or less. The average thickness is 0.02 μm or more and 0.3 μm or less. The average of adjacent side ratios is 1 or more and 5 or less. When observed from a direction perpendicular to the main plane, the average projected area of the grains grew to 75% of the average projected area of the finished grains, and there were two dislocation lines extending from the nuclei at the time of nucleation, and The angle formed by the two dislocation lines is 5 ° or more and 85 ° or less. 2. The silver halide emulsion according to claim 1, wherein the dislocation lines are present in grains grown to an average projected area of 85% of the average projected area of finished grains. 3. The silver halide emulsion according to claim 1, wherein the dislocation lines are present in grains grown to have an average projected area of 99% of the average projected area of finished grains. 4. The silver halide emulsion according to claim 1, wherein the dislocation lines are present in the grains coated on the silver halide light-sensitive material. 5. When observed from a direction perpendicular to the main plane, the angle formed by the two dislocation lines is 30 ° or more and 75 ° or less, wherein The silver halide emulsion according to item 1. 6. The angle formed by the two dislocation lines is 45 ° or more and 75 ° or less when observed from a direction perpendicular to the main plane. The silver halide emulsion according to item 1. 7. The tabular silver halide grain is present in an amount of 45% or more of the total projected area.
7. The silver halide emulsion according to any one of 6 to 6. 8. The tabular silver halide grain is present in an amount of 60% or more of the total projected area.
7. A silver halide emulsion according to any one of items 7 to 7. 9. The silver halide emulsion according to claim 1, wherein the silver halide grains have a silver chloride content of 50 mol% or more and 100 mol% or less. 10. The silver halide grains have a silver chloride content of 80.
% Or more and 100 mol% or less, The silver halide emulsion according to claim 1, wherein 11. When the tabular silver halide grains are observed from a direction perpendicular to a principal plane, the tabular silver halide grains are in a range of 0.001% to 10% of a projected area including one corner, The silver halide emulsion according to any one of claims 1 to 10, which is a grain having nuclei at the time of nucleation. 12. The silver halide emulsion according to claim 1, which is sensitized with gold and / or chalcogen. 13. A silver halide photographic material comprising at least one of the emulsions according to claim 1 on at least one side of a support. 14. A silver halide photosensitive material comprising at least one of the emulsions according to claim 1 on both sides of a support. 15. The silver halide light-sensitive material according to claim 14, which is used in combination with a fluorescent intensifying screen that emits light by X-ray exposure having a peak in the range of 200 nm to 400 nm.