JP3415933B2 - Method for producing silver halide photographic emulsion - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a silver halide photographic emulsion. The present invention particularly relates to a method for producing a tabular silver halide grain photographic emulsion.

[0002]

2. Description of the Related Art US Pat. No. 4,9,947 discloses the introduction of dislocation lines into tabular grain emulsions to increase the sensitivity of silver halide photographic emulsions.
No. 56,269 and the like are known. Regarding the method of introducing the dislocation lines, it is also known in JP-A-3-213845 that the silver iodide fine grain emulsion is added during the growth of the tabular grain emulsion. However, in the case where a silver iodide fine grain emulsion is added during the growth of a tabular grain emulsion, the effect of the structure of the tabular grain emulsion during the growth on its characteristics has not been known at all.

[0003]

SUMMARY OF THE INVENTION The present invention provides a method for producing a silver halide photographic emulsion excellent in sensitivity / fog ratio and sensitivity / granularity ratio. The present invention further provides a method for producing a silver halide photographic emulsion having excellent pressure characteristics and reciprocity law characteristics.

[0004]

The object of the present invention can be achieved by the following method for producing a silver halide photographic emulsion or a light-sensitive material.

(1) An emulsion in which 50% or more of the total projected area is occupied by host tabular grains composed of silver iodobromide or silver bromide having an aspect ratio of 3 or more with parallel main planes being (111) planes, 75% or less of the side faces of the host tabular grains are composed of (111) faces in the step of adding an emulsion containing silver halide grains which are less soluble than the host tabular grains. Method for producing photographic emulsion (2) An emulsion in which 50% or more of the total projected area is occupied by silver iodobromide host tabular grains having a parallel main plane of (111) planes and an aspect ratio of 3 or more. In the step of adding an emulsion containing a less soluble silver halide grain, the host tabular grain has a structure inside the grain,
Method for producing a silver halide photographic emulsion, characterized in that the outermost layer of the host tabular grains is substantially composed of silver bromide (3) Iodine having a parallel main plane of (111) and an aspect ratio of 3 or more An emulsion in which 50% or more of the total projected area is occupied by silver bromide or host tabular grains made of silver bromide,
In the step of introducing dislocation lines by rapidly adding an emulsion of fine silver iodide grains, 75% or less of the side faces of the host tabular grains are composed of (111) faces. Method for producing photographic emulsion (4) The parallel main plane is the (111) plane, and 50% or more of the total projected area is occupied by host tabular grains made of silver iodobromide or silver bromide having an aspect ratio of 5 or more. In the step of introducing dislocation lines by rapidly adding an emulsion containing fine silver iodide grains to the emulsion, 70% or less of the side faces of the host tabular grains are composed of (111) faces. Method for producing silver halide photographic emulsion (5) Milk in which 50% or more of the total projected area is occupied by host tabular grains made of silver iodobromide having a parallel main plane of (111) planes and an aspect ratio of 3 or more. In the step of introducing dislocation lines by rapidly adding an emulsion containing fine silver iodide grains, the host tabular grain has a structure inside the grain, and the outermost layer of the host tabular grain is substantially brominated. A method for producing a silver halide photographic emulsion characterized by comprising silver (6) A host tabular grain composed of silver iodobromide having a parallel principal plane of (111) planes and an aspect ratio of 3 or more In the step of introducing dislocation lines by rapidly adding an emulsion containing fine silver iodide grains to an emulsion occupying 50% or more, the host tabular grains have a structure inside the grains, and (7) A method for producing a silver halide photographic emulsion, characterized in that the outer layer consists essentially of silver bromide, and 75% or less of the side surfaces are composed of (111) planes. ) Face and ass In the method of introducing dislocation lines by rapidly adding an emulsion containing fine silver iodide grains to an emulsion in which 50% or more of the total projected area is occupied by host tabular grains made of silver iodobromide having a cut ratio of 5 or more, The host tabular grains have a structure inside the grains, the outermost layer of the host tabular grains consists essentially of silver bromide, and 70% or less of the side faces are constituted by (111) faces. The method for producing a silver halide photographic emulsion according to any one of (8), (1) to (7) above, further including the step of adding an emulsion containing hardly soluble silver halide grains or silver iodide fine grains. Then, a photographic emulsion produced by the production method according to any one of (9), (1) to (8) above, which is a method for producing a silver halide photographic emulsion for growing a region made of silver bromide or silver iodobromide. Fewer emulsion layers containing Silver halide photographic light-sensitive material having a single-layer support

The present invention will be described in detail below. In the present invention, a sparingly soluble silver halide emulsion is added to a silver iodobromide or silver bromide host tabular grain emulsion, and thereafter, an aqueous silver nitrate solution and / or an aqueous halide solution is added, preferably a dislocation line is added to the tabular grain emulsion. Is about how to introduce.

Host tabular grain emulsions face (111)
It is composed of a main surface and side surfaces connecting the main surface. The host tabular grain emulsion comprises silver iodobromide or silver bromide. Although it may contain silver chloride, the silver chloride content is preferably 8 mol% or less, more preferably 3 mol% or less, or 0 mol%. In the case of silver iodobromide, the variation coefficient of the grain size distribution of the tabular grain emulsion is preferably 25% or less, and therefore the silver iodide content is preferably 20 mol% or less. By reducing the silver iodide content, it becomes easy to reduce the variation coefficient of the grain size distribution of the tabular grain emulsion. In particular, the variation coefficient of the grain size distribution of the host tabular grain emulsion is preferably 20% or less, and the silver iodide content is preferably 10 mol% or less. The variation coefficient of the distribution of silver iodide content between grains is 2
It is preferably 0% or less, particularly preferably 10% or less.

When the host tabular grain emulsion is silver iodobromide, it is preferable that the tabular grain emulsion has a structure within the grain in terms of silver iodide distribution. In this case, with respect to the silver iodide distribution, the grain structure may have a double structure, a triple structure, a quadruple structure or more. In any case, it is particularly preferable that the outermost layer of the structure is silver bromide which does not substantially contain silver iodide. The term "silver bromide substantially free of silver iodide" means that the silver iodide content of the outermost layer is 3 mol% or less, and most preferably 1 mol% or less. The effect of the present invention on the silver iodide content of the outermost layer will be described in detail in Examples. A preferred structure of the host tabular grain emulsion is, for example, a triple structure grain composed of silver bromide / silver iodobromide / silver bromide. Other higher order structures are also preferred as long as the outermost layer is substantially silver bromide. The boundary of the silver iodide content between the structures may be clear or may have a continuous and gradual change. Usually, the measurement of the silver iodide content using the powder X-ray diffraction method does not show two distinct peaks having different silver iodide contents, and the tail is drawn toward the high silver iodide content. Such an X-ray diffraction profile is shown. In the present invention, it is preferable that the silver iodide content of the inner layer than the outermost layer is higher than the silver iodide content of the outermost layer, and the silver iodide content of the inner layer is preferably 3 or more. Mol%
that's all. The efficiency of the invention becomes remarkable when the content is more preferably 5 mol% or more.

Host tabular grain emulsion comprises 50% of total projected area
The above is occupied by particles having an aspect ratio of 3 or more. Here, the projected area and aspect ratio of the tabular grains can be measured from an electron micrograph by a carbon replica method in which a shadow is cast together with a latex sphere for reference. When viewed from above, tabular grains usually have a hexagonal, triangular or circular shape, and the aspect ratio is the value obtained by dividing the equivalent diameter of a circle having the same area as the projected area by the thickness.
The tabular grain shape is preferably such that the ratio of hexagons is higher, and the ratio of the lengths of adjacent sides of the hexagons is preferably 1: 2 or less. The higher the aspect ratio, the more remarkable the effect of the present invention is obtained. Therefore, 50% or more of the total projected area of the host tabular grain emulsion is preferably occupied by grains having an aspect ratio of 5 or more. More preferably, the aspect ratio is 8 or more, but if the aspect ratio becomes too large, the coefficient of variation of the particle size distribution described above tends to increase, so the aspect ratio is usually preferably 20 or less.

In the present invention, the host tabular grain emulsion comprises (111) major surfaces facing each other and side faces connecting the major surfaces. At least one twin plane is included between the main surfaces. Two twin planes are usually observed in the host tabular grain emulsion of the present invention. The distance between these two twin planes is US5.
It can be less than 0.012μ as described in 219,720. Furthermore, JP-A-5-249585
It is also possible that the value obtained by dividing the distance between the (111) main surfaces by the twin plane spacing is 15 or more as described in (1).

In the present invention, the side faces connecting the (111) major surfaces facing each other of the host tabular grain emulsion account for 75% of all the side faces.
It is remarkably preferable that the following is composed of the (111) plane. The effect will be described in detail in Examples. Here, 75% or less of all side faces are composed of (111) faces means that crystallographic planes other than the (111) faces are present at a ratio higher than 25% of all side faces. Usually, the plane can be understood as a (100) plane, but it can also include other planes, that is, a (110) plane and a plane with a higher index. In the present invention, the effect is remarkable when 70% or less of all the side faces are composed of (111) faces.

Whether or not 70% or less of all side faces are composed of (111) faces can be easily judged from an electron micrograph by a carbon replica method in which the host tabular grain is shadowed. Usually, 75% or more of the side surface is (11
In the case of the hexagonal tabular grains in the case of 1) planes, the six side faces directly connected to the (111) main surface are alternately connected to the (111) main surface at an acute angle and an obtuse angle. On the other hand, when 70% or less of all side faces are composed of (111) faces, in hexagonal tabular grains, (1
11) All six sides directly connected to the main surface are connected to the (111) main surface at an obtuse angle. By applying shadowing at an angle of 50 ° C. or less, the obtuse angle and the acute angle of the side surface with respect to the main back surface can be determined. Preferably, shadowing at an angle of 30 ° or less and 10 ° or more makes it easy to determine an obtuse angle and an acute angle.

Further, a method using adsorption of a sensitizing dye is effective as a method for obtaining the ratio of the (111) plane to the (100) plane. Journal of the Chemical Society of Japan, 1984, Volume 6, Page 94
The ratio of the (111) plane to the (100) plane can be quantitatively obtained by using the method described in Nos. 2-947.
It is possible to calculate the ratio of (111) planes on all side faces by using the ratio and the equivalent circle diameter and thickness of the tabular grains described above. In this case, tabular grains are assumed to be cylindrical using the equivalent circle diameter and thickness. By this assumption, the ratio of the side surface to the total surface area can be obtained. The value obtained by dividing the ratio of the (100) plane obtained by adsorption of the above-mentioned sensitizing dye by the ratio of the above-mentioned side surfaces and multiplying by 100 is the ratio of the (100) plane on all the side surfaces. If the value is subtracted from 100, the ratio of (111) planes on all side surfaces can be obtained. In the present invention, (111) in all aspects
More preferably, the ratio of the faces is 65% or less.

In the present invention, a method of making 75% or less of all side surfaces of the host tabular grain emulsion into (111) planes will be described. Most commonly, the ratio of the (111) faces to the side faces of a silver iodobromide or silver bromide host tabular grain emulsion can be determined by pBr at the time of preparation of the host tabular grain emulsion. Where pB
r is the logarithm of the reciprocal of the Br ⁻ ion concentration of the system. When the total silver amount of the host tabular grain emulsion is 100, preferably the ratio of the (111) faces on the side faces decreases after at least 50% or more of the total silver amount is added, that is, (100) on the side faces.
The pBr is set so that the ratio of the faces increases. Most preferably, pBr is set so that the ratio of (100) faces on the side faces increases after at least 65% of the total silver amount is added. It is not preferable to set the pBr so that the ratio of (100) faces on the side surface increases before 50% of the total silver amount is added, because the aspect ratio of the host tabular grain emulsion is lowered. When pBr is set so that the ratio of (100) faces on the side faces increases after 95% or more of the total silver amount is added, the (100) face ratio on the side faces for achieving the effect of the present invention is achieved. Becomes difficult.
Therefore, most preferably, pBr is set so that the ratio of (100) faces on the side surface increases between the time when 70% or more of the total silver amount is added and the time when 90% or less of the total silver amount is added. Then, the effect of the invention is remarkably obtained. However, as an alternative, after the total silver amount has been added,
It is also possible to increase the ratio by setting pBr such that the ratio of the (100) plane on the side surface increases and aging.

The pBr that increases the ratio of the (100) plane on the side surface means the temperature of the system, the pH, the kind and concentration of the protective colloid agent such as gelatin, the presence or absence of the silver halide solvent, and the kind.
The value can vary widely depending on the concentration and the like. Usually, the pBr is preferably 2.0 or more and 5 or less. More preferably, pBr is 2.5 or more and 4.5 or less. However,
As described above, the pBr value can be easily changed by the presence of a silver halide solvent or the like. It is preferable not to use a silver halide solvent in the present invention.

As the silver halide solvent which can be used in the present invention, US Pat. Nos. 3,271,157, 3,531,289, 3,574,628 and JP-A-54-1019 are known. (A) Organic thioethers described in JP-A No. 54-158917 and JP-A No. 53-824.
No. 08, No. 55-77737, No. 55-2982 and the like, (b) thiourea derivative, JP-A-53-14.
4319 (c) a silver halide solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom, (d) imidazoles described in JP-A-54-100717, ( Examples include e) sulfite, (f) ammonia, (g) thiocyanate and the like.

Particularly preferred solvents are thiocyanate, ammonia and tetramethylthiourea. The amount of solvent used varies depending on the type, but in the case of thiocyanate, the preferred amount is silver halide 1.
It is 1 × 10 ⁻⁴ mol or more and 1 × 10 ⁻² mol or less per mol.

EP 515894A1 and the like can be referred to as a method of changing the plane index of the side surface of the host tabular grain emulsion. Further, the polyalkylene oxide compounds described in US Pat. No. 5,252,453 can also be used.
US4680254, US46802 as effective method
55, US4680256 and US4684607.
The surface index modifiers described in JP-A No. 1994-2000 can be used. Ordinary photographic spectral sensitizing dyes can also be used as a modifier having the same surface index as above.

The effect of the present invention is most remarkably obtained. The host tabular grain emulsion is silver iodobromide, and in the silver iodide distribution structure of the tabular grains, the outermost layer is substantially free of silver iodide. It is silver bromide, and 75% or less of the side faces are composed of (111) faces. Therefore, pBr may be selected so that the ratio of the (100) faces on the side faces increases when the substantially outermost silver iodide-free silver bromide layer of the host tabular grain emulsion is formed. Alternatively, by adding a silver halide solvent and / or a surface index modifier,
It suffices to increase the ratio of the 0) plane.

In the present invention, the silver iodobromide or silver bromide host tabular grain emulsion can be prepared by various methods as long as the above requirements are satisfied. Preparation of a host tabular grain emulsion usually consists of three basic steps of nucleation, ripening and growth. In the step of nucleation, use of gelatin having a low methionine content described in US4713320 and US4942120, U
It is extremely effective in the nucleation step of the host tabular grain emulsion of the present invention to perform nucleation with high pBr described in S4914014 and to perform nucleation in a short time described in JP-A-2-222940. US in the aging process
It may be effective in the ripening step of the host tabular grain emulsion of the present invention to carry out in the presence of a low-concentration base described in US Pat. No. 5,254,453 and at a high pH described in US Pat. US in the growth process
Grow at low temperature described in No. 5248587, U
The use of silver iodide fine particles described in S4672027 and US Pat. No. 4,693,964 is particularly effective in the step of growing the host tabular grain emulsion of the present invention.

In the present invention, a sparingly soluble silver halide emulsion is added to the above-described silver iodobromide or silver bromide host tabular grain emulsion. Here, the slightly soluble silver halide emulsion means that the halogen composition is less soluble than the host tabular grain emulsion.

In the present invention, dislocation lines are preferably introduced by rapidly adding a silver iodide fine grain emulsion to the above-described silver iodobromide or silver bromide host tabular grain emulsion. This step consists essentially of two steps, a step of rapidly adding a silver iodide fine grain emulsion to a host tabular grain emulsion, and a step of thereafter growing silver bromide or silver iodobromide to introduce dislocation lines. Is. These two steps may be carried out completely separately, or may be duplicated and carried out at the same time. It is preferably performed separately. The step of rapidly adding the silver iodide fine grain emulsion to the first host tabular grain emulsion will be described.

Rapid addition of a silver iodide fine grain emulsion means that
It is preferable to add the silver iodide fine grain emulsion within 10 minutes. More preferably, it means addition within 7 minutes. These conditions may vary depending on the temperature of the system to be added, pBr, pH, type and concentration of protective colloid agent such as gelatin, presence or absence of silver halide solvent, type and concentration, but as described above, shorter conditions are preferable. It is preferable that substantially no aqueous silver salt solution such as silver nitrate is added at the time of addition.
The temperature of the system during addition is preferably 40 ° C or higher and 90 ° C or lower,
It is particularly preferably 50 ° C. or higher and 80 ° C. or lower. As for pBr, there is no particular limitation on pBr at the time of adding the silver iodide fine grain emulsion as long as the conditions of the host tabular grain emulsion described above are satisfied.

The silver iodide fine grain emulsion may be substantially silver iodide and may contain silver bromide and / or silver chloride as long as it can form a mixed crystal. Preferably 100%
It is silver iodide. In its crystal structure, silver iodide has β-form and γ-form.
The body and the α-form or α-form-analogous structure can be present as described in US Pat. No. 4,672,026. In the present invention, the crystal structure is not particularly limited, but a mixture of β-form and γ-form, more preferably β-form, is used. The silver iodide fine grain emulsion may be one formed immediately before addition as described in US Pat. Used. The silver iodide fine grain emulsion can be easily formed by the method described in the above-mentioned US Pat. No. 4,672,026. A double jet addition method of an aqueous silver salt solution and an aqueous iodide salt solution, which carries out grain formation with a constant pI value during grain formation, is preferred. Here, pI is the logarithm of the reciprocal of the I ⁻ ion concentration of the system. The temperature, pI, pH, type and concentration of protective colloid agent such as gelatin, presence / absence of silver halide solvent, type and concentration are not particularly limited, but the grain size is 0.1 μm or less, more preferably 0. 07 μm
The following are convenient for the present invention. The shape of the particles cannot be completely specified because they are fine particles, but the variation coefficient of the particle size distribution is preferably 25% or less. Especially when it is 20% or less, the effect of the present invention is remarkable. Here, the size and size distribution of the silver iodide fine grain emulsion are determined by placing the silver iodide fine grains on a mesh for electron microscope observation and directly observing by a transmission method instead of the carbon replica method. This is because the particle size is small and the measurement error is large in the observation by the carbon replica method. Grain size is defined as the diameter of a circle with a projected area equal to the observed grain. The particle size distribution is also calculated using the same projected area circle diameter. The most effective silver iodide fine particles in the present invention have a grain size of 0.06 μm or less and 0.02 μm or less.
Above, the coefficient of variation of the particle size distribution is 18% or less.

After the above-mentioned grain formation, the silver iodide fine grain emulsion is preferably washed with water and adjusted in the usual manner as described in US Pat. Be seen. pH is 5
It is preferably 7 or more and 7 or less. The pI value is preferably set to a pI value at which the solubility of silver iodide becomes the minimum or a pI value higher than the pI value. As the protective colloid agent, normal gelatin having an average molecular weight of about 100,000 is preferably used.
A low molecular weight gelatin having an average molecular weight of 20,000 or less is also preferably used. Further, it may be convenient to mix and use the above gelatins having different molecular weights. The amount of gelatin per kg of emulsion is preferably 10 g or more and 100 g or less. It is more preferably 20 g or more and 80 g or less. The silver amount in terms of silver atoms per kg of emulsion is preferably 10 g or more and 100
g or less. It is more preferably 20 g or more and 80 g or less. The amount of gelatin and / or the amount of silver is preferably selected to a value suitable for rapidly adding the silver iodide fine grain emulsion.

The addition amount of the silver iodide fine grain emulsion is preferably 1 mol% or more and 1 in terms of silver amount with respect to the host tabular grain emulsion.
It is 0 mol% or less. Most preferably, it is 3 mol% or more and 7 mol% or less. By selecting this addition amount, dislocation lines described later are preferably introduced, and the effect of the invention becomes remarkable. The silver iodide fine grain emulsion is usually dissolved in advance and added, but it is necessary to sufficiently enhance the stirring efficiency of the system at the time of addition. Preferably, the stirring rotation speed is set higher than usual. The addition of an antifoaming agent is effective in preventing the generation of bubbles during stirring. Specifically, US 5,275,929
The defoaming agent described in Examples of No. 1 is used.

After the silver iodide fine grain emulsion is rapidly added to the host tabular grain emulsion, silver bromide or silver iodobromide is grown to preferably introduce dislocation lines. Although the growth of silver bromide or silver iodobromide may be started before or at the same time as the addition of the silver iodide fine grain emulsion, it is preferable to add silver bromide or silver iodobromide after the addition of the silver iodide fine grain emulsion. Start growing. The time from the addition of the silver iodide fine grain emulsion to the start of the growth of silver bromide or silver iodobromide is preferably within 10 minutes and 1 second or more. More preferably, it is within 5 minutes and 3 seconds or more. More preferably, it is within 1 minute. The shorter this time interval, the more preferable, but it is better before the start of silver bromide or silver iodobromide growth.

Growth after addition of the silver iodide fine grain emulsion is preferably silver bromide. In the case of silver iodobromide, the silver iodide content is preferably within 5 mol% with respect to the layer. It is more preferably within 3 mol%. The amount of silver in the layer grown after the addition of this silver iodide fine grain emulsion is preferably 20 or more and 70 or less when the amount of silver in the host tabular grain emulsion is 100. Most preferably, it is 25 or more and 65 or less. The temperature, pH and pBr for forming this layer are not particularly limited, but a temperature of 40 ° C. or higher and 90 ° C. or lower and a pH of 2 or higher and 9 or lower are usually used. More preferably, 50 ° C. or higher and 80 ° C. or lower, and pH is 3 or higher and 7 or lower. Regarding pBr, in the present invention, it is preferable that pBr at the end of formation of the layer is higher than pBr at the beginning of formation of the layer.
Preferably, the pBr at the beginning of formation of the layer is 2.9 or less and the pBr at the end of formation of the layer is 1.7 or more. More preferably, the pBr at the beginning of formation of the layer is 2.5 or less, and the pBr at the end of formation of the layer is 1.9 or more. Most preferably, pBr at the initial stage of formation of the layer is 2.3 or less and 1 or more. Most preferably, the pBr at the end of the layer is 2.1 or more and 4.5 or less. The dislocation line in the present invention is preferably introduced by the above method.

In the present invention, the tabular grains preferably have dislocation lines. The dislocation lines of tabular grains are described in, for example, J. F. H
amilton, Photo. Sci. Eng. , 11,
57, (1967) and T.W. Shiozawa, J .; So
c. Photo. Sci. Japan, 35, 213,
It can be observed by a direct method using a transmission electron microscope at low temperature described in (1972). In other words, the silver halide grains taken out carefully so that dislocation lines are not generated on the grains from the emulsion are placed on the mesh for electron microscope observation, and the sample to prevent damage (printout etc.) due to electron beams In the cooled state, observation is performed by the transmission method. At this time, the thicker the particles, the more difficult it is for the electron beam to pass therethrough. Therefore, it is possible to more clearly observe using a high-voltage electron microscope (200 kV or more for particles having a thickness of 0.25 μm). . From the photograph of the grain obtained by such a method, the position and number of dislocation lines for each grain when viewed from the direction perpendicular to the main plane can be obtained.

The number of dislocation lines is preferably 10 or more on average per grain. More preferably 20 on average per particle
More than a book. When dislocation lines are densely present, or when dislocation lines are observed intersecting with each other, the number of dislocation lines per grain may not be clearly counted. However, even in these cases, it is possible to count to about 10, 20, or 30 lines, and it is possible to clearly distinguish from the case where there are only a few lines. The average number of dislocation lines per grain is calculated as the number average by counting the number of dislocation lines for 100 grains or more.

Dislocation lines can be introduced, for example, in the vicinity of the outer periphery of tabular grains. In this case, the dislocations are almost perpendicular to the outer circumference, and dislocation lines are generated starting from the position of x% of the length of the distance from the center of the tabular grain to the side (outer circumference) and reaching the outer circumference. The value of x is preferably 10 or more and less than 100, more preferably 30 or more and less than 99, and most preferably 50 or more and less than 98. At this time, the shape formed by connecting the start positions of the dislocation lines is similar to the particle shape, but it is not a perfect similar shape and may be distorted. This type of dislocation number is not found in the central region of the grain.
The dislocation lines are crystallographically in the (211) direction, but they are often meandering and may intersect with each other.

Further, the dislocation lines may be substantially uniform over the entire outer circumference of the tabular grain, or may be locally located on the outer circumference. That is, taking hexagonal tabular silver halide grains as an example, the dislocation lines may be limited only in the vicinity of the six vertices, or the dislocation lines may be limited in the vicinity of only one of the vertices. On the contrary, it is possible that the dislocation lines are limited only to the sides excluding the vicinity of the six vertices.

Further, dislocation lines may be formed over a region including the centers of two parallel main planes of tabular grains. When dislocation lines are formed over the entire main plane, the direction of the dislocation lines may be crystallographically approximately (211) when viewed from a direction perpendicular to the main plane, but (110) or In some cases, they are randomly formed, and the length of each dislocation line is also random. In some cases, they are observed as short lines on the main plane, and in other cases, they are observed as long lines reaching the side (outer periphery). is there. Dislocation lines are often straight or meandering. Also, they often intersect with each other.

The position of the number of dislocations may be limited to the outer circumference, the main plane or a local position as described above, or may be formed by combining these.
That is, they may exist on the outer circumference and the main plane at the same time.

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

As gelatin, in addition to lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci. Photo. Japan. No.
16, enzyme-treated gelatin as described in P30 (1966) may be used, and a hydrolyzate or an enzymatic hydrolyzate of gelatin may also be used.

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

During preparation of the emulsion of the present invention, for example, during grain formation,
In the desalting step, during chemical sensitization, it is preferable to allow a salt of a metal ion to exist before coating, depending on the purpose. When the grains are doped, they are preferably added during grain formation, after grain formation, or before chemical sensitization, when grain surface modification or as a chemical sensitizer is used. A method of doping the entire grain, a method of doping only the core portion of the grain, only the shell portion, only the epitaxial portion, or only the base grain can be selected. Mg, Ca, Sr, Ba, Al, S
c, Y, LaCr, Mn, Fe, Co, Ni, Cu, Z
n, Ga, Ru, Rh, Pd, Re, Os, Ir, P
t, Au, Cd, Hg, Tl, In, Sn, Pb, Bi
Etc. can be used. These metals can be added in the form of salts such as ammonium salts, acetates, nitrates, sulfates, phosphates, hydrates, hexacoordinated complex salts and tetracoordinated complex salts which can be dissolved at the time of grain formation. For example CdB
_{r 2, CdCl 2, Cd (} NO 3) 2, Pb (NO 3) 2,
Pb (CH ₃ COO) ₂ , K ₃ [Fe (CN) ₆ ], (NH
₄ ) ₄ [Fe (CN) ₆ ], K ₃ IrCl ₆ , (NH ₄ ) ₃ R
Examples include hCl ₆ , K ₄ Ru (CN) _{6, and the} like. The ligand of the coordination compound can be selected from halo, aco, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo and carbonyl. These may use only one type of metal compound, but may use two types or a combination of three or more types.

The metal compound is preferably added by dissolving it in water or a suitable solvent such as methanol or acetone.
Aqueous hydrogen halide solution (eg HC to stabilize the solution)
l, HBr, etc. or alkali halide (eg KC)
1, NaCl, KBr, NaBr, etc.) can be used. If necessary, acids and alkalis may be added. The metal compound may be added to the reaction vessel before grain formation or during grain formation. Further, it may be added to a water-soluble silver salt (eg AgNO ₃ ) or an alkali halide water-soluble (eg NaCl, KBr, KI) and continuously added during the formation of silver halide grains. Further, a solution independent of the water-soluble silver salt and the alkali halide may be prepared and continuously added at an appropriate time during grain formation. It is also preferable to combine various addition methods.

The method of adding a chalcogenide compound as described in US Pat. No. 3,772,031 during emulsion preparation may be useful. In addition to S, Se, and Te, cyanates, thiocyanates, selenocyanates, carbonates,
Phosphate and acetate may be present.

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

One of the chemical sensitizations which can be preferably carried out in the present invention is chalcogenide sensitization and noble metal sensitization, alone or in combination, by TH James, The Photographic Process, 4th Edition, Macmillan Company. Published, 1977
Year, (TH James, The Theoryof the Photographic Proc
ess, 4th ed, Macmillan, 1977) 67-76, using active gelatin, and Research Disclosure 120, 19
Apr. 1974, 12008; Research Disclosure, Vol. 34, June 1975, 13452, U.S. Pat. Nos. 2,642,361, 3,297,446, 3,772,031, 3,3. 857,711, 3,901,714, 4,266,018, and 3,904,415, and British Patent No. 1,31.
PAg 5-10, pH as described in 5,755
5 to 8 and a temperature of 30 to 80 ° C., sulfur, selenium,
It can be tellurium, gold, platinum, palladium, iridium or combinations of these sensitizers. In the noble metal sensitization, noble metal salts such as gold, platinum, palladium and iridium can be used, and among them, gold sensitization, palladium sensitization and a combination of both are preferable. In the case of gold sensitization, known compounds such as chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide and gold selenide can be used. The palladium compound means a divalent or tetravalent palladium salt. Preferred palladium compounds are represented by R ₂ PdX ₆ or R ₂ PdX ₄ . Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom and represents a chlorine, bromine or iodine atom.

Specifically, K ₂ PdCl ₄ , (NH ₄ ) ₂
PdCl ₆ , Na ₂ PdCl ₄ , (NH ₄ ) ₂ PdC
l ₄ , Li ₂ PdCl ₄ , Na ₂ PdCl ₆ or K ₂
PdBr ₄ is preferred. The gold compound and the palladium compound are preferably used in combination with thiocyanate or selenocyanate. As sulfur sensitizers, hypo, thiourea compounds, rhodanine compounds and US Pat.
57,711, 4,266,018 and 4,
The sulfur-containing compounds described in 054,457 can be used. It is also possible to carry out chemical sensitization in the presence of a so-called chemical sensitization aid. Useful chemical sensitization aids include azaindene, azapyridazine, azapyrimidine, and other compounds known to suppress fog and increase sensitivity during the chemical sensitization process. Examples of chemical sensitization aid modifiers are described in US Pat. No. 2,131,038,
No. 3,411,914, No. 3,554,757, JP-A-58-126526 and the above-mentioned Daffin's "Photographic Emulsion Chemistry", pages 138-143.

The emulsion of the present invention is preferably combined with gold sensitization. The amount of the gold sensitizer is preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻⁷ mol, and more preferably 1 × 10 ^{−5 to} 5 × 10 ⁻⁷ mol, per mol of silver halide. The preferable range of the palladium compound is 1 × 10 ⁻³ to 5 × 10 ⁻⁷ . The preferred range of the thiocyan compound or selenocyan compound is 5 × 10 ^-2 to 1 × 10 ^-6 . The preferred amount of sulfur sensitizer used for the silver halide grains of the present invention is from 1 × 10 ⁻⁴ to 1 × 10 ⁴ per mol of silver halide.
^-7 mol, more preferably 1 × 10 ^{-5 to} 5 × 1
It is ^0-7 mol.

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

During grain formation of the silver halide emulsion of the present invention,
It is preferable to carry out reduction sensitization after grain formation and before or during chemical sensitization, or after chemical sensitization. Here, the reduction sensitization is a method of adding a reduction sensitizer to a silver halide emulsion, a method of growing in a low pAg atmosphere of pAg 1 to 7 called silver ripening, or a method of ripening, and a pH 8 to 11 called high pH ripening. Any method of growing or aging in a high pH atmosphere can be selected.
Also, two or more methods can be used in combination. The method of adding a reduction sensitizer is a preferable method because the level of reduction sensitization can be finely adjusted. Known reduction sensitizers include stannous salt, ascorbic acid and its derivatives, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds and borane compounds. For the reduction sensitization of the present invention, these known reduction sensitizers can be selected and used, or two or more kinds of compounds can be used in combination. As reduction sensitizers, stannous chloride, thiourea dioxide, dimethylamine borane, ascorbic acid and its derivatives are preferred compounds. Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount, but the range of 10 ^-7 to 10 ^-3 mol is suitable per mol of silver halide. The reduction sensitizer is dissolved in water or a solvent such as alcohols, glycols, ketones, esters and amides and added during grain growth. It may be added to the reaction vessel in advance, but it is preferable to add it at an appropriate time during grain growth. Further, a reduction sensitizer may be added in advance to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide, and the silver halide grains may be precipitated using these aqueous solutions. Further, it is also a preferable method to add the solution of the reduction sensitizer in several times as the grains grow, or to continuously add the solution for a long time.

It is preferable to use an oxidizing agent for silver during the process of producing the emulsion of the present invention. What is an oxidizing agent for silver?
It refers to a compound that acts on metallic silver to convert it into silver ions. In particular, a compound that can convert extremely fine silver grains, which are a by-product in the process of forming silver halide grains and the process of chemical sensitization, into silver ions is effective. The silver ions generated here may form a poorly soluble silver salt such as silver halide, silver sulfide, or silver selenide, or may form a readily soluble silver salt such as silver nitrate. Good. The oxidizing agent for silver may be an inorganic substance or an organic substance. Examples of the inorganic oxidant include ozone, hydrogen peroxide and its adducts (for example, NaBO ₂ · H ₂ O ₂ · 3H ₂ O and 2Na).
_{CO 3 · 3H 2 O 2,} Na 4 P 2 O 7 · 2H 2 O 2, 2
Na ₂ SO ₄ .H ₂ O ₂ .2H ₂ O), peroxy acid salts (eg K ₂ S ₂ O ₈ , K ₂ C ₂ O ₆ , K ₂ P ₂ O ₈ ),
Peroxy complex compound (for example, K ₂ [Ti (O ₂ ) C ₂
O ₄ ] ・ 3H ₂ O, 4K ₂ SO ₄・ Ti (O ₂ ) OH ・ S
_{O 4 · 2H 2 O, Na} 3 _{[VO (O 2) (C 2} H 4) 2 · 6
H ₂ O), permanganate (eg KMnO ₄ ), chromate (eg K ₂ Cr ₂ O ₇ ), etc. Potassium iodate) salts of high valence metals (eg potassium hexacyanoferrate) and thiosulfonates. Examples of organic oxidants include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (for example, N-bromosuccinimide, chloramine T, chloramine B). ) Is mentioned as an example.

Preferred oxidizing agents of the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, thiosulfonate inorganic oxidizing agents and quinones of organic oxidizing agents.
It is a preferable embodiment to use the reduction sensitization and the oxidizing agent for silver in combination. It can be selected from the method of using an oxidant and then the reduction sensitization, the reverse method thereof, or the method of coexisting both. These methods can be selectively used in the grain forming step and the chemical sensitization step.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or stabilizing the photographic performance. . That is, thiazoles, such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes, for example tria Theindenes, tetraazaindenes (particularly 4-hydroxy-substituted (1,
Many compounds known as antifoggants or stabilizers such as 3,3a, 7) tetraazaindenes), pentaazaindenes, etc. can be added. For example, U.S. Pat. Nos. 3,954,474 and 3,982,9
No. 47 and Japanese Patent Publication No. 52-28660 can be used. Japanese Patent Application Sho 6
There are compounds described in 2-47225. Antifoggants and stabilizers can be used at various times before particle formation, during particle formation, after particle formation, in the washing step, during dispersion after washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added depending on the purpose. In addition to adding the effect of preventing fog and stabilizing during the preparation of the emulsion, the crystal wall of the grain is controlled, the grain size is reduced, the solubility of the grain is reduced, and the chemical sensitization is controlled. It can be used for various purposes such as controlling the arrangement of dyes.

The photographic emulsion used in the present invention is preferably spectrally sensitized with a methine dye or the like in order to exert the effects of the present invention. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiozoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of
That is, indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, a thiazolidine-2,4-
A 5-6 membered heterocyclic nucleus such as a dione nucleus, a rhodanine nucleus or a thiobarbituric acid nucleus can be applied. These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. A typical example thereof is US Pat.
8,545, 2,977,229, 3,39
7,060, 3,522,052, 3,52
No. 7,641, No. 3,617,293, No. 3,62
8,964, 3,666,480, 3,67
2,898, 3,679,428, 3,70
No. 3,377, No. 3,769,301, No. 3,81
4,609, 3,837,862, 4,02
6,707, British Patents 1,344,281, 1,507,803, and Japanese Patent Publication Nos. 43-4936 and 5
3-12,375, JP-A-52-110,618,
52-109,925.

Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion. The sensitizing dye may be added to the emulsion at any stage in the emulsion preparation which has heretofore been known to be useful. Most commonly, it is carried out after the completion of chemical sensitization and before coating, but it is described in US Pat. No. 3,628,969.
No. 4,225,666, and spectral sensitization can be carried out simultaneously with chemical sensitization by adding it at the same time as the chemical sensitizer. It can also be carried out prior to the chemical sensitization as described in 1), or can be added before the completion of silver halide grain precipitation to start the spectral sensitization. It is also possible to add these said compounds separately, as taught in U.S. Pat. No. 4,225,666, i.e. to add some of these compounds prior to chemical sensitization and the rest to chemical sensitization. It is also possible to add it after the feeling, and it is possible to add it after the sensation.
It may be at any time during the formation of silver halide grains, including the method disclosed in US Pat. No. 3,756.

The addition amount is 4 × per mol of silver halide.
It can be used in an amount of 10 ⁻⁶ to 8 × 10 ⁻³ mol, but in the case of a more preferable silver halide grain size of 0.2 to 1.2 μm, about 5 × 10 ⁻⁵ to 2 × 10 ⁻³ mol is more effective. Is. The above-mentioned various additives are used in the light-sensitive material of the present technology, but various additives other than the above can be used depending on the purpose. These additives are described in more detail in Research Disclosure Item 17643 (1
December 1978), Item 18716 (December 1979, 1)
January) and Item 308119 (December 1989)
Month), and the relevant parts are summarized in the table below.

[0054]   Additive type RD17643 RD18716 RD308119 1 Chemical sensitizer Page 23 Page 648 Right column Page 996 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, pages 23-24, page 648, right column-996 right-998 right     Supersensitizer, page 649, right column 4 Whitening agents 24 pages 998 Right 5 Antifoggant page 24 to 25 page 649 right column 998 right to 1000 right     And stabilizers 6 Light absorbers, pages 25-26, page 649, right column-1003 left-1003 right     Filter dye page 650, left column     UV absorber 7 Anti-stain agent Page 25 Right column 650 Left to right column 1002 Right 8 Dye image stabilizer 25 pages 1002 right 9 Hardener 26 pages 651 left column 1004 right to 1005 left 10 Binder page 26 Same as above 1003 right to 1004 right 11 Plasticizer, Lubricant Page 27 Page 650 Right column 1006 Left to 1006 Right 12 Coating aid, pages 26-27 Same as above 1005 left to 1006 left     Surfactant 13 Static 27 pages Same as above 1006 right to 1007 left     Preventive agent 14 Matting agent 1008 left to 1009 left

Techniques such as layer arrangement which can be used for the emulsion of the present invention and photographic light-sensitive materials using the emulsion, silver halide emulsions, dye-forming couplers, functional couplers such as DIR couplers, various additives and the like. , And the development processing are described in European Patent No. 0565096A1 (published on October 13, 1993) and the patents cited therein. Below, each item and the corresponding description place are listed.

1. Layer structure: page 61, lines 23-35, page 61, line 41-page 62, line 2. Middle layer: p. 61, lines 36-40, 3. Multilayer effect imparting layer: p. 62, lines 15-18, 4. Silver halide halogen composition: p. 62, lines 21-25, 5. Crystal habit of silver halide grains: p. 62, lines 26-30, 6. Silver halide grain size: p. 62, lines 31-34, 7. Emulsion production method: Page 62, lines 35-40, 8. Silver halide grain size distribution: 62-page 41-42
Line, 9. Tabular grains: p. 62, lines 43-46, 10. Internal structure of particles: p. 62, lines 47-53, 11. Emulsion latent image forming type: page 62 line 54-page 63 5
Line, 12. Physical and chemical ripening of emulsion: page 63, lines 6-9, 13. Mixed use of emulsion: page 63, lines 10-13, 14. Fogging emulsion: p. 63, lines 14-31, 15. Non-photosensitive emulsion: page 63, lines 32-43, 16. Silver coating amount: Page 63, lines 49-50, 17. Photographic Additives: Research Disclosure (R
D) Item17643 (December 1978), Item18
716 (November 1979) and Item 307105.
(November, 1989), and each item and related description are shown below.

Types of Additives RD17643 RD18716 RD307105 1 Chemical sensitizer page 23 648 page right column 866 page 2 Sensitivity enhancer page 648 right column 3 Spectral sensitizer, page 23-24 page 648 right column page 866-868 strong Color sensitizer: page 649, right column 4, whitening agent, page 24, 647 page, right column, page 868, 5 antifoggant, page 24, 25, page 649, right column, page 868, 870, stabilizer 6, light absorber, page 25, 26, 649 Page right column page 873 filter dye, ~ 650 page left column UV absorber 7 stain inhibitor page 25 right column 650 left column ~ right column 872 page 8 dye image stabilizer page 25 650 page left column 872 page 9 hardener 26 Page 651 page left column 874 to 875 page 10 binder 26 page 651 page left column 873 to 874 page 11 plasticizer, lubricant page 27 650 page right column 876 page 12 coating aid, page 26 to page 650 page right column 875 ... Page 876 Surfactant 13 Static Page 27 Page 650 Right column 876-877 Page 14 Inhibitor 14 Matt agent 878-879 18. Formaldehyde scavenger: 64 pages 54-5
7th line, 19. Mercapto-based antifoggant: page 65, lines 1-2, 20. Release agents such as fogging agents: Page 65, lines 3-7, 21. Dye: Page 65, lines 7-10, 22. Color couplers in general: Page 65, lines 11-13, 23. Yellow, magenta and cyan couplers: p. 65 1
Lines 4-25, 24. Polymer coupler: page 65, lines 26-28, 25. Diffusible dye-forming coupler: p. 65, lines 29-31, 26. Colored coupler: p. 65, lines 32-38, 27. Functional couplers in general: Page 65, lines 39-44, 28. Bleach accelerator releasing coupler: page 65 lines 45-48, 29. Development accelerator releasing coupler: p. 65, lines 49-53, 30. Other DIR couplers: Page 65, Line 54-Page 66, 4
Line, 31. Coupler dispersion method: Page 66, lines 5-28, 32. Preservatives and fungicides: p. 66, lines 29-33, 33. Kind of sensitive material: page 66, lines 34-36, 34. Photosensitive layer film thickness and swelling speed: page 66 line 40-page 1
Line, 35. Back layer: Page 67, line 3-8, 36. General development processing: Page 67, lines 9-11, 37. Developer and developer: Page 67, lines 12-30, 38. Developer additive: Page 67, lines 31-44, 39. Inversion processing: Page 67, lines 45-56, 40. Treatment liquid aperture ratio: Page 67, line 57-Page 68, line 12, 41. Development time: Page 68, lines 13-15, 42. Bleach-fix, bleach-fix: page 68 line 16-69 31
Line, 43. Automatic processor: Page 69, lines 32-40, 44. Rinse, rinse, stabilize: p. 69 line 41-p. 70
Line, 45. Replenishment and reuse of processing liquid: p. 70, lines 19-23, 46. Built-in developer sensitive material: Page 70, lines 24-33, 47. Development processing temperature: p. 70, lines 34-38, 48. Use in a film with a lens: page 70, lines 39-41, and 2-ferric carboxylic acid or 2,6-pyridinedicarboxylic acid and ferric salts such as ferric nitrate described in EP 602600. And a bleaching solution containing persulfate can also be preferably used. In the use of this bleaching solution, it is preferable to interpose a stopping step and a water washing step between the color developing step and the bleaching step. Use an organic acid such as acetic acid, succinic acid or maleic acid as the stopping solution. Is preferred. Further, the bleaching solution may contain an organic acid such as acetic acid, succinic acid, maleic acid, glutaric acid, adipic acid in the range of 0.1 to 2 mol / liter for the purpose of adjusting pH and bleaching fog. preferable.

[0058]

EXAMPLES Examples of the present invention will be shown below. However, it is not limited to this embodiment. (Example 1) In the method of introducing dislocation lines using a silver iodide fine grain emulsion, the effects of the surface index of the host tabular grain emulsion and the silver iodide content of the outermost layer on the sensitivity / fogging ratio will be described.

(Preparation of seed emulsion a) Aqueous solution 16 containing 4.5 g of KBr and 7.9 g of gelatin having an average molecular weight of 15,000.
00 ml was kept at 40 ° C. and stirred. AgNO ₃ (8.9g)
An aqueous solution and an aqueous KBr (6.2 g) solution containing 6.3% by weight of KI were added by the double jet method over 40 seconds. After adding 38 g of gelatin, the temperature was raised to 58 ° C. AgN
After adding an O ₃ (5.6 g) aqueous solution, ammonia 0.1
Mole was added and 15 minutes later, the mixture was neutralized with acetic acid to adjust the pH to 5.0. An AgNO ₃ (219 g) aqueous solution and a KBr aqueous solution were added over 40 minutes while accelerating the flow rate by the double jet method. At this time, the silver potential was changed with respect to the saturated calomel electrode −
It was kept at 10 mV. After desalting, 50 g of gelatin was added and adjusted to pH 5.8 and pAg 8.8 at 40 ° C. to prepare a seed emulsion. This seed emulsion contains 1 Ag per 1 kg of emulsion.
Contains 80 g of mol and gelatin, and has an equivalent circle diameter of 0.6
2 μm, coefficient of variation of equivalent circle diameter 16%, average thickness 0.1
The tabular grains had a thickness of 03 μm and an average aspect ratio of 6.0.

(Production Method of Emulsion A) 134 g of seed emulsion a, K
1200 ml of an aqueous solution containing 1.9 g Br and 38 g gelatin
Was kept at 78 ° C. and stirred. After adding 2 mg of thiourea dioxide, 1 part of KI was added with an aqueous solution of AgNO ₃ (130.3 g).
A KBr aqueous solution containing 7.9% by weight was added over 60 minutes while accelerating the flow rate by the double jet method. At this time, the silver potential was kept at -40 mV against the saturated calomel electrode.
The silver potential was adjusted to -80 mV by adding 44 mg of sodium ethylthiosulfonate and a KBr aqueous solution. A silver iodide fine grain emulsion having an average equivalent circle diameter of 0.025 μm and a coefficient of variation of equivalent circle diameter of 18% was converted into AgNO ₃ amount of 7.1 g within 5 seconds.
After 30 seconds from the sudden addition, AgNO ₃ (66.4 g)
The aqueous solution was metered in over 8 minutes. The silver potential after the addition was -10 mV. Normal washing with water was performed, gelatin was added, and the pH was adjusted to 5.8 and pAg 8.8 at 40 ° C. This emulsion was designated as Emulsion A.

(Production Method of Emulsion B) 134 g of seed emulsion a, K
1200 ml of an aqueous solution containing 1.9 g Br and 38 g gelatin
Was kept at 78 ° C. and stirred. After adding 2 mg of thiourea dioxide, an aqueous solution of AgNO ₃ (87.7 g) and KI was added to 17.9.
A KBr aqueous solution containing wt% was added over a period of 46 minutes while accelerating the flow rate by the double jet method. At this time, the silver potential was kept at -40 mV against the saturated calomel electrode. Then, an AgNO ₃ (42.6 g) aqueous solution and a KBr aqueous solution containing 17.9% by weight of KI were added by the double jet method over 17 minutes. At this time, the silver potential was kept at +40 mV against the saturated calomel electrode. The silver potential was adjusted to -80 by adding 44 mg of sodium ethylthiosulfonate and KBr aqueous solution.
Adjusted to mV. A silver iodide fine grain emulsion having an average equivalent circle diameter of 0.025 μm and a variation coefficient of equivalent circle diameter of 18% was rapidly added in an amount of 7.1 g in terms of AgNO ₃ amount within 5 seconds, and after 30 seconds, AgNO ₃ (66. 4 g) Aqueous solution was metered in over 8 minutes. The silver potential after the addition was -10 mV. Normal washing was performed, gelatin was added, and the pH was adjusted to 5.
8, the pAg was adjusted to 8.8. This emulsion was designated as Emulsion B.

(Production Method of Emulsion C) 134 g of seed emulsion a, K
1200 ml of an aqueous solution containing 1.9 g Br and 38 g gelatin
Was kept at 78 ° C. and stirred. After adding 2 mg of thiourea dioxide, an aqueous solution of AgNO ₃ (87.7 g) and KI was added to 17.9.
A KBr aqueous solution containing wt% was added over a period of 46 minutes while accelerating the flow rate by the double jet method. At this time, the silver potential was kept at -40 mV against the saturated calomel electrode. afterwards,
An AgNO ₃ (42.6 g) aqueous solution and a KBr aqueous solution were added by the double jet method over 17 minutes. At this time, the silver potential was kept at -40 mV against the saturated calomel electrode. The silver potential was adjusted to -80 mV by adding 44 mg of sodium ethylthiosulfonate and a KBr aqueous solution. A silver iodide fine grain emulsion having an average equivalent circle diameter of 0.025 μm and a variation coefficient of equivalent circle diameter of 18% was rapidly added in an amount of 7.1 g in terms of AgNO ₃ amount within 5 seconds, and after 30 seconds, AgNO ₃ (66. 4 g) Aqueous solution was metered in over 8 minutes. The silver potential after the addition was -10 mV. Normal washing with water was performed, gelatin was added, and the pH was adjusted to 5.8 and pAg 8.8 at 40 ° C.
This emulsion was designated as Emulsion C.

(Production Method of Emulsion D) 134 g of seed emulsion a, K
1200 ml of an aqueous solution containing 1.9 g Br and 38 g gelatin
Was kept at 78 ° C. and stirred. After adding 2 mg of thiourea dioxide, an aqueous solution of AgNO ₃ (87.7 g) and KI was added to 17.9.
A KBr aqueous solution containing wt% was added over a period of 46 minutes while accelerating the flow rate by the double jet method. At this time, the silver potential was kept at -40 mV against the saturated calomel electrode. afterwards,
An AgNO ₃ (42.6 g) aqueous solution and a KBr aqueous solution were added by the double jet method over 17 minutes. At this time, the silver potential was kept at +40 mV against the saturated calomel electrode. The silver potential was adjusted to -80 mV by adding 44 mg of sodium ethylthiosulfonate and a KBr aqueous solution. A silver iodide fine grain emulsion having an average equivalent circle diameter of 0.025 μm and a variation coefficient of equivalent circle diameter of 18% was rapidly added in an amount of 7.1 g in terms of AgNO ₃ amount within 5 seconds, and after 30 seconds, AgNO ₃ (66. 4 g) Aqueous solution was metered in over 8 minutes. The silver potential after the addition was -10 mV. Normal washing with water was performed, gelatin was added, and the pH was adjusted to 5.8 and pAg 8.8 at 40 ° C.
This emulsion was designated as Emulsion D.

Emulsion A was a tabular grain having an average equivalent circular diameter of 1.17 μm, a variation coefficient of equivalent circular diameter of 26%, an average thickness of 0.23 μm, an average aspect ratio of 5.1, and an average equivalent spherical diameter of 0.78 μm. Further, particles having an aspect ratio of 5 or more occupied 60% or more of the total projected area. Emulsions B, C and D also showed almost the same grain shape as Emulsion A.

[0065]

[Table 1]

Table 1 summarizes the structural characteristics of Emulsions A, B, C and D. Electron micrographs of the emulsions A, B, C and D obtained by the carbon replica method just before the addition of the silver iodide fine grain emulsion are shown in FIG. Shadowing was done at 20 °. From the shadows of the electron micrographs, emulsions A and C have six sides alternately connecting the (111) main surface with the (111) main surface at an acute angle and an obtuse angle. That is, the side surface has a high (111) plane ratio. On the other hand, in Emulsions B and D, all six side faces connecting the (111) major surface intersect with the (111) major surface at an obtuse angle. That is, obviously, 30% or more of all side faces are (100) faces. In other words, 70% or less of all side faces are composed of (111) faces. Emulsions A, B, C and D were heated to 60 ° C., and dipotassium iridium hexachloride, sensitizing dye I shown below,
Optimum chemical sensitization was performed by adding potassium thiocyanate, chloroauric acid, sodium thiosulfate and N, N-dimethylselenourea.

[0067]

[Chemical 1]

Emulsions A, B, C and D, which had been chemically sensitized as described above, were coated on a cellulose triacetate film support having an undercoat layer under the coating conditions shown in Table 2 below with a protective layer. , Sample Nos. 1, 2, 3 and 4 were prepared.

[0069]

[Table 2]

These samples were left for 14 hours under the conditions of 40 ° C. and 70% relative humidity. Then, it was exposed for 1/100 second through a gelatin filter SC-39 manufactured by FUJIFILM Corporation and a continuous wedge.

Using the negative processor FP-350 manufactured by Fuji Photo Film Co., Ltd., the treatment was carried out by the method described below (until the cumulative replenishment amount of the liquid became 3 times the capacity of the mother liquor tank). (Processing method) Process processing time Processing temperature Replenishment amount Color development 3 minutes 15 seconds 38 ° C. 45 ml Bleach 1 minute 00 seconds 38 ° C. 20 ml Bleach solution overflows into bleach-fixing tank 3 minutes 15 seconds 38 ° C. 30 ml Washing with water (1) 40 seconds 35 ° C Countercurrent piping system from (2) to (1) Washing with water (2) 1 minute 00 seconds 35 ° C 30 ml Stability 40 seconds 38 ° C 20 ml Drying 1 minute 15 seconds 55 ℃ * Replenishment amount is 35 mm width 1.1 m per length (equivalent to 24 Ex. 1) Next, the composition of the treatment liquid is described. (Color developer) Tank liquid (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 2.0 Sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide 1.4 0.7 Potassium iodide 1.5 mg-hydroxylamine sulfate 2.4 2.8 4- [N-ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline sulfate 4.5 5.5 Add water 1.0 liter 1.0 liter pH (to potassium hydroxide and sulfuric acid 10.05 10.10 (bleaching solution) Common for tank solution and replenisher (unit: g) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 100.0 Ammonium nitrate 10.0 Bleaching accelerator 0.005 mol (CH _{3) 2 N-CH 2 -CH} 2 -SS-CH 2 -CH 2 -N (CH 3) 2 · 2HCl aqueous ammonia (27%) 15.0 ml water 1.0 liter pH (adjusted with ammonia water and nitric acid) 6.3 (bleach-fixer) tank solution (g) replenisher (g) ethylenediaminetetraacetic acid ammonium ferric dihydrate 50.0-ethylenediaminetetraacetic acid disodium salt 5.0 2.0 Sodium sulfite 12.0 20.0 Ammonium thiosulfate aqueous solution (700 g / liter) 240.0 ml 400.0 ml Ammonia water (27%) 6.0 ml-1.0 liter 1.0 liter by adding water pH (adjusted with ammonia water and acetic acid) 7.2 7.3 (wash solution) A mixed bed type column in which tap water common to tank liquid and replenisher is filled with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH type anion exchange resin (Amberlite IR-400). Water concentration to reduce calcium and magnesium ion concentration to 3 mg / liter or less Treated, followed by the addition of sodium isocyanurate dichloride 20mg / liter and sodium 0.15 g / l of sulfuric acid. The pH of this liquid was in the range of 6.5 to 7.5. (Stabilizer) Tank liquid and replenisher are common (unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization 10) 0.2 Ethylenediaminetetraacetic acid disodium salt 0.05 1,2,4 -Triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added and 1.0 liter pH 8.5 A sample that had been treated was measured for concentration with a green filter. The results obtained are shown in Table 3 below. Sensitivity is fog density plus 0.
The relative values of 2 and 1.5 are displayed.

[0072]

[Table 3]

As is clear from Table 3, the ratio of (111) planes on the side surface of the host tabular grain emulsion to the comparison emulsion A was 7
When the content is 0% or less, the fog is lowered as in Emulsion B, and particularly the sensitivity at the shoulder of the characteristic curve (fog plus 1.5)
Has risen. Compared with Comparative Emulsion A, the composition of the outermost layer of the host tabular grain emulsion was changed to silver bromide to reduce fog as in Emulsion C. Sensitivity (fog plus 1.5) increased. Compared with Comparative Emulsion A, the composition of the outermost layer of the host tabular grain emulsion was changed to silver bromide, and the side surface (111) ratio was set to 70% or less, whereby the fog was remarkably reduced as in Emulsion D. Sensitivity of feet (fogging plus 0.
2) and shoulder sensitivity (fogging plus 1.5) increased significantly. That is, according to the present invention, the sensitivity / fog ratio of the tabular grain emulsion was remarkably improved. Emulsions C and D
Was observed at a liquid nitrogen temperature using a 200 kV transmission electron microscope, and it was found that dislocation lines were present at a high density in the fringe portion of the tabular grains in all the grains.

Example 2 It will be described that the emulsion of the present invention is superior in pressure characteristics to the conventional emulsion.

(Preparation of Emulsion E) Instead of adding the silver iodide fine grain emulsion in the preparation of Emulsion A, an aqueous AgNO ₃ solution (AgNO ₃ 7.1 g) and an aqueous KI solution (KI 6.9) are used.
Emulsion E was prepared in the same manner except that g) was added by the double jet method over 5 minutes.

(Production Method of Emulsion F) Instead of adding the silver iodide fine grain emulsion in the production method of Emulsion D, AgNO ₃ aqueous solution (AgNO ₃ 7.1 g) and KI aqueous solution (KI 6.9 g) are used.
Emulsion F was prepared in the same manner except that was added by the double jet method over 5 minutes.

Emulsions E and F were chemically sensitized as in Example 1. Coating and film hardening were carried out in the same manner as in Example 1. After the emulsion-coated surface was scratched with a fine needle having a diameter of 50 μm applied with a load of 4 g, exposure and treatment were carried out in the same manner as in Example 1.
Compared with Emulsion D of the present invention, increase in fog density due to sensitivity, fog and fine needle scratching and decrease in image density are shown in Table 4.
Shown in.

[0078]

[Table 4]

As is clear from Table 4, Emulsion D of the present invention showed a smaller increase in fog due to fine needle scratching, and image density due to fine needle scratching, as compared with Emulsions E and F not using the silver iodide fine grain emulsion. The decrease in is completely gone.
That is, a remarkable improvement effect on the pressure characteristics is recognized. Further, as is clear from the comparison between Emulsions E and F, when the silver iodide fine grain emulsion is not used, the composition of the outermost layer of the host tabular grain emulsion is silver bromide, and (111) on the side surface.
The effect of making the surface ratio 70% or less is small. That is, this effect is particularly remarkable when a silver iodide fine grain emulsion is used. 200 for emulsions E and F
Observation at a liquid nitrogen temperature using a transmission electron microscope of kV revealed that dislocation lines were present at high density in the fringe portion of the tabular grains in all the grains. From that point of view, the mechanism of the significant effect of the present invention on the pressure characteristics is unknown.

(Example 3) The results of a more detailed examination of the (111) face ratio of the side faces of the host tabular grain emulsion will be described.

(Preparation of seed emulsion b) 1500 ml of an aqueous solution containing 0.75 g of gelatin was kept at 35 ° C. and stirred. Adjust the silver potential to -10 mV against saturated calomel electrode and adjust the pH.
Was adjusted to 1.90. An aqueous solution of AgNO ₃ (0.85 g) and an aqueous solution of KBr (0.59 g) were mixed by a double jet method.
Added over 5 seconds. After the temperature was raised to 60 ° C., 8.3 g of gelatin was added. After adjusting the pH to 5.5, the silver potential was adjusted to -20 mV against a saturated calomel electrode.
An AgNO ₃ (227.1 g) aqueous solution and a KBr aqueous solution were added over 45 minutes while accelerating the flow rate by the double jet method. At this time, the silver potential is -2 with respect to the saturated calomel electrode.
It was kept at 0 mV. After desalting, add 50 g of gelatin,
The seed emulsion was prepared by adjusting the pH to 5.8 and pAg 8.8 at 40 ° C. This seed emulsion contains 1 mol of Ag and 80 g of gelatin per 1 kg of emulsion, and has an average equivalent circle diameter of 0.71 μm.
m, coefficient of variation of equivalent circle diameter 17%, average thickness 0.081μ
It was a tabular grain having m and an average aspect ratio of 8.8.

(Production Method of Emulsion G) 134 g of seed emulsion b, K
1200 ml of an aqueous solution containing 1.9 g Br and 38 g gelatin
Was maintained at 65 ° C and stirred. After adding 4 mg of sodium benzenethiosulfonate, an aqueous AgNO ₃ (87.7 g) solution and an aqueous KBr solution containing 9.0 wt% of KI were added over 46 minutes while accelerating the flow rate by the double jet method. At this time, the silver potential was -20 m with respect to the saturated calomel electrode.
Kept at V. Then, AgNO ₃ (42.6 g) aqueous solution and K
The Br aqueous solution was added by the double jet method over 17 minutes. At this time, the silver potential was set to −40 with respect to the saturated calomel electrode.
kept at mV. An aqueous KBr solution was added to adjust the silver potential to -80.
Adjusted to mV. A silver iodide fine grain emulsion having an average equivalent circle diameter of 0.025 μm and a coefficient of variation of equivalent circle diameter of 18% was rapidly added in an amount of 8.5 g in terms of AgNO ₃ within 5 seconds, and after 30 seconds, AgNO ₃ (66.4 g) was added. ) The aqueous solution was added over a 4 minute period at a reduced flow rate. The silver potential after the addition was -10 mV. Wash with normal water, add gelatin, 40 ℃
The pH was adjusted to 5.8 and pAg 8.8. This emulsion was designated as Emulsion G.

(Preparation of Emulsion H) Emulsion H was prepared in the same manner as in preparation of Emulsion G except that the silver potential was kept at -40 mV and the potential at which the AgBr layer was provided was changed to -10 mV.

(Production Method of Emulsion I) Emulsion I was prepared in the same manner as in the production method of Emulsion G except that the silver potential was kept at -40 mV and the potential at which the AgBr layer was provided was changed to +20 mV.

(Production Method of Emulsion J) Emulsion J was prepared in the same manner as in the production method of Emulsion G, except that the silver potential was kept at -40 mV and the potential at which the AgBr layer was provided was changed to +50 mV.

(Production Method of Emulsion K) An emulsion K was prepared in the same manner as in the production method of Emulsion G, except that the silver potential was kept at -40 mV and the potential at which the AgBr layer was provided was changed to +80 mV.

Emulsion G was a tabular grain having an average equivalent circle diameter of 1.40 μm, a variation coefficient of equivalent circle diameter of 19%, an average thickness of 0.159 μm, an average aspect ratio of 8.8, and an average equivalent spherical diameter of 0.78 μm. Further, particles having an aspect ratio of 8 or more occupied 60% or more of the total projected area. Emulsions H, I, and J were in the order of decreasing average aspect ratio in this order, but had almost the same grain shape as Emulsion G. Emulsion K is 6
The corners were rounded, and the aspect ratio was clearly reduced.

Emulsions G, H, I, J and K were sampled immediately before the addition of the silver iodide fine grain emulsion, and electron micrographs and the Chemical Society of Japan, 1984, Vol.
Using the method described on pages 942 to 947, the ratio of the (111) plane to the (100) plane on the side surface of the tabular grain was determined. Table 5 shows the (100) plane and the (111) plane on the side surface of the tabular grain.
The ratio of faces is shown.

[0089]

[Table 5]

Emulsions G, H, I, J and K were heated to 60 ° C. and dipotassium iridium hexachloride, sensitizing dye II,
Optimum chemical sensitization was carried out by adding III and IV, potassium thiocyanate, chloroauric acid, sodium thiosulfate and N, N-dimethylselenourea.

[0091]

[Chemical 2]

[0092]

[Chemical 3]

[0093]

[Chemical 4]

Coating, exposure and development were carried out in the same manner as in Example 1. However, the filter for exposure is FUJIFILM Corporation.
A gelatin filter SC50 manufactured by KK was used. Further, the exposure time was also evaluated at 10 seconds. The results are shown in Table 6.

[0095]

[Table 6]

As is clear from Table 6, when the ratio of the (111) faces on the side faces of the host tabular grain emulsion is 75% or less, a large increase in sensitivity is recognized. In particular, the effect is remarkable when the ratio of the side surface (111) plane of the host tabular grain emulsion is 70% or less. What is more remarkable is that this effect is 1/10
That is, the exposure for 10 seconds is larger than the exposure for 0 seconds. That is, the reciprocity law characteristic is improved by the present invention. In the present invention, a monodisperse tabular grain emulsion having a high aspect ratio is used, and the effect of the present invention is remarkable.

Example 4 The effect of the grain size and distribution of the silver iodide fine grain emulsion will be described.

(Preparation of silver iodide fine grain emulsion a) 2000 ml of an aqueous solution containing 10 g of gelatin having an average molecular weight of 15,000 was kept at 20 ° C and stirred. The silver potential was adjusted to -240 mV and the pH was adjusted to 2.0 with respect to the saturated calomel electrode.
An AgNO ₃ (100 g) aqueous solution and a KI aqueous solution were added over 5 minutes while accelerating the flow rate by the double jet method. At this time, the silver potential was -240 mV against the saturated calomel electrode.
Kept at. After desalting, gelatin was added and pH was adjusted to 40 ℃.
It was adjusted to 5.8 and pAg10. This silver iodide fine grain emulsion a had an average equivalent circle diameter of 0.038 μm and a variation coefficient of 16% of the equivalent circle diameter. According to the measurement using the X-ray diffraction method, this silver iodide was found to have almost 100% of β-form.

(Preparation of silver iodide fine grain emulsion b) Gelatin 2
2000 ml of an aqueous solution containing 0 g was kept at 35 ° C. and stirred.
The silver potential was adjusted to -60 mV against a saturated calomel electrode. An AgNO ₃ (100 g) aqueous solution and a KI aqueous solution were added over 5 minutes while accelerating the flow rate by the double jet method. At this time, the silver potential was -60 m with respect to the saturated calomel electrode.
Kept at V. After desalting, add gelatin and p at 40 ℃
It was adjusted to H5.8 and pAg10. This silver iodide fine grain emulsion b had an average equivalent circle diameter of 0.025 μm and a variation coefficient of 18% of the equivalent circle diameter. From the measurement using the X-ray diffraction method, this silver iodide contained 20% of the γ-form and the rest was the β-form. This silver iodide fine grain emulsion was used in Examples 1, 2 and 3.

(Preparation of silver iodide fine grain emulsion c) Gelatin 2
2000 ml of an aqueous solution containing 0 g and 98 g of KI was kept at 35 ° C. and stirred. An aqueous solution of AgNO ₃ (100 g) was added in a fixed amount. After desalting, gelatin was added and pH was adjusted to 40 ℃.
It was adjusted to 5.8 and pAg10. This silver iodide fine grain emulsion c had an average equivalent circle diameter of 0.070 μm and a variation coefficient of equivalent circle diameter of 28%. From the measurement using the X-ray diffraction method, this silver iodide contained 20% of the γ-form and the rest was the β-form.

(Production Method of Emulsion L) An emulsion L was prepared in the same manner as in the production method of Emulsion D in Example 1 except that the silver iodide fine grain emulsion was changed from b to a.

(Production Method of Emulsion M) An emulsion M was prepared in the same manner as in the production method of Emulsion D in Example 1 except that the silver iodide fine grain emulsion was changed from b to c.

(Production Method of Emulsion N) In the production method of Emulsion L, 30 seconds after addition of the silver iodide fine grain emulsion, AgNO ₃ (6
6.4 g) aqueous solution and KBr aqueous solution with silver potential of -80 mV
Emulsion N was prepared in the same manner except that the amount was quantitatively added over 8 minutes while maintaining the above.

(Preparation of Emulsion O) Emulsion O was prepared in the same manner as preparation of Emulsion L except that silver iodide fine grain emulsion was added and then AgNO ₃ (66.4 g) aqueous solution was added for 30 minutes.

Emulsions D, L, M, N and O were chemically sensitized in the same manner as in Example 1 and then coated, exposed and developed. The results are shown in Table 7.

[0106]

[Table 7]

As is clear from the comparison of emulsions D, L and M in Table 7, the effect of the present invention is greatly influenced by the grain size and distribution of the silver iodide fine grain emulsion used. Further, comparison of emulsions D, N, and O shows that the influence of time and potential history after addition of the silver iodide fine grain emulsion is large. The most effective silver iodide fine grains in the present invention have a grain size of 0.06 μm or less 0.0
2 μm or more, the coefficient of variation of particle size distribution is 18%
It is the following. Furthermore, it is preferable that the pause time until the silver bromide is grown after the addition of the silver iodide fine grain emulsion is short. In silver bromide growth, pBr at the end of formation is preferably higher than pBr at the beginning of formation.

(Example 5) By using the emulsions of the present invention described in Examples 1, 2, 3 and 4 in the photographic materials shown below, the sensitivity / fog ratio, the sensitivity / granular ratio, the pressure characteristic and the reciprocal relation were obtained. A photographic light-sensitive material having excellent law characteristics was obtained.

On the undercoated cellulose triacetate film support, each layer having the composition shown below was coated in multiple layers to prepare Sample 101, which is a multilayer color light-sensitive material. (Photosensitive layer composition) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin Hardening agent ExS: Number corresponding to each component of the sensitizing dye indicates the coating amount expressed in g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Sample 101) First layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin 1.40 ExM-1 0.11 ExF-1 3.4 × 10 ^-3 HBS-1 0.16

Second layer (intermediate layer) ExC-2 0.030 UV-1 0.020 UV-2 0.020 UV-3 0.060 HBS-1 0.05 HBS-2 0.020 Polyethyl acrylate latex 0.080 Gelatin 0.90

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Emulsion A Silver 0.23 Emulsion B Silver 0.23 ExS-1 5.0 × 10 ^-4 ExS-2 1.8 × 10 ^-5 ExS-3 5.0 × 10 ^-4 ExC-1 0.050 ExC-3 0.030 ExC-4 0.14 ExC-5 3.0 x 10 ^-3 ExC-7 1.0 x 10 ^-3 ExC-8 0.010 Cpd-2 0.005 HBS-1 0.10 Gelatin 0.90

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Emulsion C Silver 0.70 ExS-1 3.4 × 10 ^-4 ExS-2 1.2 × 10 ^-5 ExS-3 4.0 × 10 ^-4 ExC-1 0.15 ExC-2 0.060 ExC-4 0.050 ExC-5 0.010 ExC-8 0.010 Cpd-2 0.023 HBS-1 0.11 Gelatin 0.60

Fifth layer (high-sensitivity red-sensitive emulsion layer) Emulsion D Silver 1.62 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-5 ExS-3 3.0 × 10 ^-4 ExC-1 0.10 ExC-3 0.050 ExC-5 2.0 × 10 ^-3 ExC-6 0.010 ExC-8 0.010 Cpd-2 0.025 HBS-1 0.20 HBS-2 0.10 Gelatin 1.30

Sixth layer (intermediate layer) Cpd-1 0.090 HBS-1 0.05 Polyethyl acrylate latex 0.15 Gelatin 1.10

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Emulsion E Silver 0.24 Emulsion F Silver 0.24 ExS-4 4.0 × 10 ^-5 ExS-5 1.8 × 10 ^-4 ExS-6 6.5 × 10 ^-4 ExM-1 5.0 × 10 ^-3 ExM-2 0.28 ExM-3 0.086 ExM-4 0.030 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.85

Eighth Layer (Medium Sensitivity Green Sensitive Emulsion Layer) Emulsion G Silver 0.94 ExS-4 2.0 × 10 ^-5 ExS-5 1.4 × 10 ^-4 ExS-6 5.4 × 10 ^-4 ExM-2 0.14 ExM-3 0.045 ExM-5 0.020 ExY-1 7.0 × 10 ^-3 ExY-4 2.0 × 10 ^-3 ExY-5 0.020 HBS-1 0.16 HBS-3 8.0 × 10 ^-3 Gelatin 0.80

Ninth layer (high-sensitivity green-sensitive emulsion layer) Emulsion H Silver 1.29 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.020 ExM-4 0.050 ExM-5 0.020 ExY-4 5.0x10 ^-3 Cpd-3 0.050 HBS-1 0.20 HBS-2 0.08 Polyethyl acrylate latex 0.26 Gelatin 1.45

10th layer (yellow filter layer) Yellow colloidal silver Silver 7.5 × 10 ^-3 Cpd-1 0.13 Cpd-4 7.5 × 10 ^-3 HBS-1 0.60 Gelatin 0.60

Eleventh layer (low-sensitivity blue-sensitive emulsion layer) Emulsion I Silver 0.25 Emulsion J Silver 0.25 Emulsion K Silver 0.10 ExS-7 8.0 × 10 ^-4 ExC-7 0.010 ExY-1 5.0 × 10 ^-3 ExY-2 0.40 ExY-3 0.45 ExY-4 6.0 × 10 ^-3 ExY-6 0.10 HBS-1 0.30 Gelatin 1.65

Twelfth layer (high-sensitivity blue-sensitive emulsion layer) Emulsion L Silver 1.30 ExS-7 3.0 × 10 ^-4 ExY-2 0.15 ExY-3 0.06 ExY-4 5.0 × 10 ^-3 Cpd-2 0.10 HBS-1 0.070 Gelatin 1.20

Thirteenth layer (first protective layer) UV-2 0.10 UV-3 0.12 UV-4 0.30 HBS-1 0.10 Gelatin 2.50

14th layer (second protective layer) Emulsion M Silver 0.10 H-1 0.37 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.15 B-3 0.05 S-1 0.20 Gelatin 0.70

Further, in order to improve storage stability, processability, pressure resistance, antifungal / bacteriostatic property, antistatic property and coating property, each layer may be provided with W-1 to W-3, B-4 to B-. 6, F
-1 to F-17 and iron salt, lead salt, gold salt, platinum salt,
It contains iridium salt, palladium salt, and rhodium salt. Cpd-4 was dispersed in a solid state according to the method described in International Patent No. 88-4794.

[0125]

[Table 8]

In Table 8, (1) Emulsions I to L were prepared according to the examples of JP-A-2-91938.
It is reduction-sensitized during grain preparation using thiourea dioxide and thiosulfonic acid. (2) Emulsions A to L were prepared according to the examples of JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization are performed in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A 1-158426. (4) In the tabular grains, dislocation lines as described in JP-A-3-237450 are observed using a high voltage electron microscope.

The couplers and additives of each layer were dispersed in a gelatin solution by the method shown in Table 9. The addition method for each layer is shown in Table 10.

[0128]

[Table 9]

[0129]

[Table 10]

[0130]

[Chemical 5]

[0131]

[Chemical 6]

[0132]

[Chemical 7]

[0133]

[Chemical 8]

[0134]

[Chemical 9]

[0135]

[Chemical 10]

[0136]

[Chemical 11]

[0137]

[Chemical 12]

[0138]

[Chemical 13]

[0139]

[Chemical 14]

[0140]

[Chemical 15]

[0141]

[Chemical 16]

[0142]

[Chemical 17]

[0143]

[Chemical 18]

[0144]

[Chemical 19]

Example 6 When the sample of Example 5 was evaluated in the same manner except that the treatment method was changed as follows, the same effect as that of Example 5 was confirmed. (Processing method) Process processing time Processing temperature Replenishment amount ^{* 1} Tank capacity Color development 3 minutes 15 seconds 38 ℃ 22 ml 40 liter Stop 1 minute 38 ℃ 10 ml 20 liter Water wash (1) 1 minute 24 ℃ 200 ml 20 liter Bleach 3 minutes 38 ℃ 10ml 40liters ^{* 3} Washing with water (2) 1 minute 24 ℃ 200ml 20liters Settling 3 minutes 38 ℃ 15ml 40liters Washing with water (3) 1 minute 24 ° C * 2 20liters Washing (4) 1 minute 24 ℃ 200 ml 20 liters Stability 1 minute 38 ℃ 15 ml 20 liters Dry 4 minutes 55 ℃ * 1 Replenishment amount is 35mm width 1m per length * 2 Countercurrent piping from washing (4) to (3) Supply by method * 3 The bleaching solution tank was equipped with an aeration device, and air was aerated at 1 liter per minute.

Next, the composition of the treatment liquid will be described. (Color developer) Tank liquid (g) Replenisher (g)   Diethylenetriamine pentaacetic acid 1.0 1.2   1-hydroxyethylidene-1,1-diphosphonic acid                                              2.0 2.2   Sodium sulfite 4.0 4.8   Potassium carbonate 30.0 39.0   Potassium bromide 1.4 0.3   Potassium iodide 1.5 mg −   Hydroxylamine sulfate 2.4 3.1   4- [N-ethyl-N- (β-hydroxyethyl) amino]     -2-Methylaniline sulfate 4.5 6.0   1.0 liter with water added 1.0 liter   pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.15

[0147] (Stop solution)                                         Tank liquid (g) Replenisher (g)   Acetic acid (90%) 40 60   1.0 liter with water added 1.0 liter   Adjust pH with potassium hydroxide 4.0 3.0 (Bleaching solution)                                         Tank liquid (g) Replenisher (g)   2,6-Pyridinedicarboxylic acid 4.6 6.9   Ferric nitrate (9-hydrate) 5.1 7.7   Acetic acid (90%) 67.0 100.0   Sodium persulfate 30.0 45.0   Sodium chloride 8.7 13.0   Ammonia water (27%) 38.0 ml 50.0 ml   1.0 liter with water added 1.0 liter   pH 4.0 3.7

[0148] (Fixer) Tank liquid (g) Replenisher (g)   Ethylenediaminetetraacetic acid disodium salt 0.5 0.7   Ammonium sulfite 20.0 22.0   Ammonium thiosulfate aqueous solution (700 g / liter)                                   295.0 ml 320.0 ml   Acetic acid (90%) 3.3 4.0   1.0 liter with water added 1.0 liter   pH (adjusted with aqueous ammonia and acetic acid) 6.7 6.8

[0149] (Stabilizer) Tank / replenisher common (g)   p-Nonylphenoxypolyglycidol 0.2   (Glycidol average degree of polymerization 10)   Ethylenediaminetetraacetic acid 0.05   1,2,4-triazole 1.3   1,4-bis (1,2,4-triazole-1-     Ilmethyl) piperazine 0.75   Hydroxyacetic acid 0.02   Hydroxyethyl cellulose 0.1   (Daicel Chemistry HEC SP-200)   1,2-benzisothiazolin-3-one 0.05   1.0 liter with water   pH 8.5

[Brief description of drawings]

FIG. 1 is an electron micrograph of a silver halide grain structure produced in Example 1. The magnification is 16,000 times.

FIG. 2 is an electron micrograph of the silver halide grain structure produced in Example 1. The magnification is 16,000 times.

FIG. 3 is an electron micrograph of a silver halide grain structure produced in Example 1. The magnification is 16,000 times.

FIG. 4 is an electron micrograph of a silver halide grain structure produced in Example 1. The magnification is 16,000 times.

─────────────────────────────────────────────────── ─── Continuation of front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) G03C 1/015 G03C 1/035 G03C 1/06 502

Claims (8)

(57) [Claims] 1. An emulsion in which 50% or more of the total projected area is occupied by host tabular grains composed of silver iodobromide or silver bromide having an aspect ratio of 3 or more with parallel main planes being (111) planes, A silver halide photograph characterized in that, in the step of adding an emulsion containing a silver halide grain which is less soluble than the host tabular grain, 75% or less of the side face of the host tabular grain is composed of (111) faces. Emulsion manufacturing method. 2. An emulsion in which parallel major planes are (111) planes and silver iodobromide host tabular grains having an aspect ratio of 3 or more occupy 50% or more of the total projected area is more difficult than the host tabular grains. In the step of adding an emulsion containing a soluble silver halide grain, the host tabular grain has a structure inside the grain, and the outermost layer of the host tabular grain consists essentially of silver bromide. Method for producing silver halide photographic emulsion. 3. An emulsion in which 50% or more of the total projected area is occupied by tabular grains of silver iodobromide or silver bromide having an aspect ratio of 3 or more, whose parallel main planes are (111) planes, A silver halide photograph characterized in that, in the step of introducing dislocation lines by rapidly adding an emulsion composed of silver halide fine grains, 75% or less of the side faces of the host tabular grains are composed of (111) faces. Emulsion manufacturing method. 4. The parallel principal planes are (111) planes,
Dislocation lines are introduced by rapidly adding an emulsion containing fine silver iodide grains to an emulsion in which silver iodobromide having an aspect ratio of 5 or more or host tabular grains made of silver bromide occupies 50% or more of the total projected area. 70% or less of the side surfaces of the host tabular grains in the step of (1) are composed of (111) planes. 5. A silver iodide fine grain is added to an emulsion in which 50% or more of the total projected area is occupied by host tabular grains made of silver iodobromide having a parallel main plane of (111) plane and an aspect ratio of 3 or more. In the step of introducing dislocation lines by rapidly adding an emulsion containing the host tabular grains, the host tabular grains have a structure inside the grains, and the outermost layer of the host tabular grains consists essentially of silver bromide. A method for producing a silver halide photographic emulsion. 6. A silver iodide fine grain is added to an emulsion in which 50% or more of the total projected area is occupied by host tabular grains composed of silver iodobromide having a parallel main plane of (111) planes and an aspect ratio of 3 or more. In the step of introducing dislocation lines by abruptly adding the emulsion containing the host tabular grains, the host tabular grains have a structure inside the grains, and the outermost layer of the host tabular grains consists essentially of silver bromide. A method for producing a silver halide photographic emulsion, characterized in that 75% or less is composed of (111) planes. 7. A silver iodide fine grain is added to an emulsion in which 50% or more of the total projected area is occupied by host tabular grains made of silver iodobromide having a parallel main plane of (111) planes and an aspect ratio of 5 or more. In the method of introducing a dislocation line by rapidly adding an emulsion containing the host tabular grains have a structure inside the grains, the outermost layer of the host tabular grains consists essentially of silver bromide, and A method for producing a silver halide photographic emulsion, which comprises 70% or less of (111) planes. 8. The method according to claim 1, wherein the silver bromide or iodo odor is added following the step of adding an emulsion containing hardly soluble silver halide grains or silver iodide fine grains. A method for producing a silver halide photographic emulsion, in which a region made of silver halide is grown.