JPH07128778A - Silver halide photographic emulsion and silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the silver halide photographic emulsion high in sensitivity and low in fog and improved in pressure desensitization and graininess, and the silver halide color photographic sensitive material. CONSTITUTION:(l) The silver halide emulsion characterized by containing, in an amount of >=50 numerical % in a dispersing medium, the silver halide grains which contain multivalent metal ions of group 13 and/or 14 in the periodic table in an amount of 10<-9> to/10<-1>mol/mol of silver halide and have >=10 transition lines in average in one grain, and (2) the silver halide color photographic sensitive material characterized by having the multivalent metal described in (l) added before 50% 96 of the substantial growth of the silver halide grains have been finished.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material having high sensitivity, low fog and improved pressure desensitization, pressure fog and graininess. Materials and silver halide photographic emulsions.

[0002]

2. Description of the Related Art In recent years, with the increase in sensitivity of silver halide color photographic light-sensitive materials, there has been a strong demand for color photographic light-sensitive materials having higher sensitivity and excellent performances such as graininess. In order to produce a light-sensitive material having high sensitivity and excellent graininess, it is desirable to reduce inefficiency in the light-sensing process and increase quantum sensitivity. Factors of inefficiency related to quantum sensitivity include recombination, latent image dispersion, electron traps derived from structural defects, and the like. Photoelectrons in silver halide grains, by doping the silver halide emulsion with polyvalent metal compounds,
Attempts to improve hole motion and modify its photographic properties have been previously investigated.

Japanese Patent Laid-Open No. 2-20853 discloses a doping technique for a cyano complex of rhenium, ruthenium, and osmium as a technique for attaining high sensitivity by doping metal ions. Further, Japanese Patent Application Laid-Open No. 1-121844 discloses a technique of doping divalent iron ions into the minimum part of the band gap in silver halide grains.

As described above, various techniques have been tried, but in addition to the sufficient effect for achieving high sensitivity and high image quality, the pressure desensitization has been remarkably deteriorated. .

In connection with the trend toward higher sensitivity and higher image quality, the demand for improvement of pressure resistance in silver halide photographic light-sensitive materials has been increasing more than ever before.

Various pressures are generally applied to a photographic light-sensitive material coated with a silver halide emulsion. For example, a negative film for general photography is bent or rubbed when it is wound in a cartridge or loaded in a camera, and is also subjected to great pressure during cutting and processing.

As described above, it is generally known that various pressures are applied to the photographic light-sensitive material, and the photographic performance is changed, and a photographic material that does not change the photographic performance in response to these pressures is provided. There is a strong desire to do so.

As means for improving the pressure characteristics, a method of incorporating a plasticizer such as a polymer or an emulsion or a method of reducing the silver halide / gelatin ratio of a silver halide emulsion is used to reach the pressure. It is known to prevent it. However, at present, it is difficult to achieve a sufficient effect by any of the methods.

In response to the demand for improved pressure characteristics, emulsions comprising core / shell type silver halide grains having a silver iodobromide layer having a high silver iodide content have been actively studied. As an example of high sensitivity and improvement of pressure resistance, an emulsion having a high silver iodide content inside the grain is disclosed in JP-A-59-99433 and JP-A-59433.
No. 60-35726 and JP-A No. 60-147726. However, when these examples were additionally tested, the effect of improving pressure resistance was insufficient.

Further, an example of achieving high sensitivity and low pressure fog by continuously changing the iodide content in the grain instead of a clear core / shell in the composition of silver halide grains is disclosed in JP-A-2-94.
No. 3 is disclosed. As a result, the effect of improving the pressure fog was obtained, but the pressure desensitization was significantly deteriorated.

Further, JP-A-63-220238 and JP-A-1
-201649 discloses a technique in which dislocations are intentionally controlled and introduced into tabular silver halide grains, and high sensitivity and improved graininess, pressure fog, and exposure illuminance dependency are improved. However, in these conventional techniques, the pressure desensitization is rather deteriorated, and the various performances of the silver halide emulsion are still unsatisfactory.

[0012]

In order to solve the above problems, an object of the present invention is to improve the above problems and improve the sensitivity, low fog, pressure desensitization, pressure fog and graininess. To provide a silver halide photographic emulsion and a silver halide color photographic light-sensitive material.

[0013]

As a result of earnest research, the present inventors have found that the object of the present invention can be achieved by the following.

(1) In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one layer in the light-sensitive material contains a silver halide photographic emulsion described below. A silver halide color photographic light-sensitive material characterized in that In a silver halide emulsion containing silver halide grains in a dispersion medium, polyvalent metal ions of Group 13 and / or Group 14 of the periodic table are contained in the silver halide grains in an amount of 10 ^-9 mol per mol of silver halide. More than 10
^-1 mol or less and grains having an average of 10 or more dislocation lines are 50% (number) or more of the silver halide grains contained in the silver halide emulsion. Silver halide photographic emulsion.

(2) With respect to the distance L from the center of the silver halide grain to the outer surface, 0.5L to L from the center of the grain
The silver halide color photographic light-sensitive material according to item (1), which contains a silver halide emulsion in which dislocation lines are concentrated in the region (1).

(3) The polyvalent metal ion described in item (1) is
A silver halide color photographic light-sensitive material, which is added before the substantial growth of silver halide is completed at 50% in terms of silver halide amount.

(4) A silver halide color photographic light-sensitive material characterized in that the region where the dislocation lines described in (2) are concentrated is 0.8 L to 0.98 L from the center of the grain.

The present invention will be described in detail below.

In the present invention, the center of silver halide means
The silver halide microcrystals are dispersed in methacrylic resin and solidified, and ultrathin sections are obtained with a microtome, and the section sample with the maximum cross-sectional area or a cross-sectional area of 90% or more is observed. Is the center of the circle when the smallest circumscribed circle is drawn.

In the present invention, the distance L from the center to the outer surface is defined as the distance between the center of the circle and the point intersecting the outer circumference of the particle when a straight line is drawn from the center of the circle to the outside.

The emulsion of the present invention preferably has a more uniform iodine content between grains.

The silver halide grains according to the present invention preferably have a more uniform iodide content between grains.
When the iodide content distribution between grains is measured by the EPMA method, the relative standard deviation is preferably 35% or less, more preferably 20% or less.

The preferred halogen composition of the silver halide grains of the present invention is as follows. The average silver iodide content of the core portion is preferably 10 to 40 mol%, more preferably 15 to 40 mol%, and further preferably 20 to 40 mol%.

The average iodine content in the shell is 10 mol%
The following is preferable, and 5 mol% or less is more preferable.
The distribution of silver iodide in the shell part may be uniform or nonuniform.

The silver iodide content of the surface layer of the silver halide emulsion can be measured by XPS (X-ray photoelectron spectroscopy).

In the silver halide grains according to the present invention, when the silver iodide content of the surface layer of the silver halide emulsion is high, the chemically sensitized nuclei are dispersed, so that the storage stability is adversely affected. Therefore, in the silver halide grains according to the present invention, the silver iodide content of the surface layer of the silver halide emulsion is preferably 6 mol% or less, more preferably 4 mol% or less, and further preferably 2 mol% or less. .

Here, the surface layer of silver halide refers to a portion having a depth of about 50Å analyzed by X-ray photoelectron spectroscopy (XPS).

The silver halide grains according to the present invention are preferably composed of silver iodobromide having an average silver iodide content of 1 to 20 mol%, particularly preferably 3 to 15 mol%.

Further, silver chloride can be contained within a range that does not impair the effects of the present invention.

The amount of KI used for introducing dislocations according to the present invention is preferably 0.01 to 5 mol%, more preferably 0.5 to 3 mol% with respect to the host particles.

The dislocations of the silver halide grains according to the present invention are described, for example, in JF Hamilton, Phot.Sci.Eng., Vol11,
57 (1967), T.Shiozawa, J.Soc.Phot.Sci.Japan, vol3
It can be observed by a direct method using a transmission electron microscope at low temperature described in 5, 213 (1972). In other words, the silver halide grains taken out carefully so as not to apply pressure enough to cause dislocation to the grains from the emulsion are placed on a mesh for electron microscope observation, and a sample is taken to prevent damage (printout etc.) due to electron beams. Observation is carried out by the transmission method in the state of being cooled. 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 grains obtained by such a method, the position and the number of dislocations of each grain when viewed from the direction perpendicular to the main plane can be obtained.

The positions of dislocations in the silver halide grain according to the present invention may be concentrated only in the central portion of the grain, may be evenly distributed inside the grain, or may be present only in the surface layer of the grain. . Further, it may be concentrated only in the intermediate portion of the grain, but in order to effectively bring out the effect of the present invention, it is generated in the region from 0.5 L to L from the center to the outer surface of the silver halide grain. Preferably, and more preferably 0.
It occurs in the area of 80L to 0.98L.

The direction of the dislocation lines is approximately the direction from the center toward the outer surface, but it often meanders. Note that the concentration of dislocation lines means that 50% (number) or more of grains having 10 or more dislocation lines obviously exist in that portion.

Regarding the number of dislocations in the silver halide grains according to the present invention, 50% (number) of grains containing 10 or more dislocations are included.
It is preferable that these exist. More preferably 80% (number) or more of particles containing 10 or more dislocations, and particularly preferably
It is preferable that 80% (number) or more of grains containing 20 or more dislocations are present.

In order to contain a polyvalent metal ion in the silver halide grain according to the present invention, a solution containing the metal ion may be added directly to the silver halide emulsion preparation solution.
The metal compound may be added in advance to the solution containing halide ions.

The solution containing the metal compound may be added instantaneously at an arbitrary point, or may be continuously added using an arbitrary function. Further, silver halide fine particles containing a polyvalent metal ion may be added to cause nucleation and / or crystal growth to allow the silver halide fine particles to be contained in any portion.

The position where the polyvalent metal ion is added to the silver halide grain according to the present invention may be at the time of nucleation,
It may be the central part of the particle or the outermost surface of the particle. Moreover, you may add uniformly in a particle. Preferably, the polyvalent metal ion is added before the substantial growth of silver halide reaches 50% by the amount of silver halide, and more preferably before the substantial growth is started. preferable. In the present invention, the silver halide amount of 50% means that the silver halide grains in the present invention are grown in an aqueous solution containing a protective colloid from the start to the end of the substantial growth of the silver halide grains. Of the total amount of silver halide formed in
Say 50%.

When the silver halide grains in the silver halide emulsion of the present invention are substantially grown, the halide ion and the silver ion are water-soluble in the aqueous solution containing the protective colloid in which the silver halide grain is grown. Supplied as a water-soluble alkali halide and water-soluble silver salt or as fine silver halide grains, and from the start of nucleation of silver halide grains to the end of the growth of the silver halide grains, the production of silver halide emulsion The process does not include a process for producing a silver halide emulsion after the desalting process after the growth of the silver halide grains.

In the silver halide emulsion of the present invention, when the silver halide grains contained in the silver halide emulsion are grown from the seed grains, the term "substantially growing" of the silver halide grains means that the grains on the seed grains are Is a silver halide emulsion manufacturing process from the start to the end of the growth of the silver halide grains by the deposition of silver halide on the silver halide grains, and the halogen after the desalting process after the end of the growth of the silver halide grains. It does not include the manufacturing process of silver halide emulsion.

In the present invention, "substantially starting the growth" means that silver ions added to the dispersion medium after the completion of nucleation,
It means that the deposition of silver halide is started on the surface of the nucleus by the aqueous solution containing the halide ion or the silver ion and the halide ion supplied from the silver halide fine particles onto the surface of the nucleus. When the silver halide grains according to the present invention are produced using seed grains, an aqueous solution containing silver ions and halide ions added to the dispersion medium, or silver halide fine particles are supplied onto the seed grain surface. It refers to the initiation of silver halide deposition on the grain surface by the generated silver ions and halide ions.

The addition amount of the polyvalent metal ion according to the present invention is preferably 10 ^-9 mol or more and 10 ^-1 mol or less, more preferably 10 ^-7 mol or more and 10 ^-2 mol or less, and more It is preferably 10 ⁻⁶ mol or more and 10 ⁻³ mol or less. Moreover, the polyvalent metal ion to be added may be one kind,
You may mix 2 or more types.

The metal ions used in the present invention are group 13 (B, Al, Ga, In, Tl) and group 14 (Si,
Ge, Sn, Pb) are preferred, with Group 13 being particularly preferred. In addition, the expression of the family of the periodic table is Chemical and Eng.
Based on ineering News P26 (1985.2.4).

These can be added in the form of salts such as chlorides, bromides and cyano complexes. These polyvalent metal compounds are preferably dissolved in a suitable solvent such as water or ethanol and then added.

The shape of the silver halide grains according to the present invention may be a normal crystal such as a cube, an octahedron or a tetrahedron, or a twin crystal. When using tabular silver halide grains, the aspect ratio (average grain size / grain thickness ratio) is 1.3 to 20.
Is preferable, and particularly preferably 3-12.

The silver halide grains according to the present invention may be arbitrary such as a polydisperse emulsion having a wide grain size distribution and a monodisperse emulsion having a narrow grain size distribution. It may be a mixture of several emulsions. When a light-sensitive material is prepared using the silver halide grains of the present invention, it is preferably a monodisperse emulsion.

As the monodisperse silver halide emulsion, the weight of silver halide contained in the grain size range of ± 20% around the average grain size r is 60% or more of the total weight of silver halide grains. A certain amount is preferable, more preferably 70% or more, further preferably 80% or more. Here, the average particle size r is
It is defined as the particle size ri when the product ni × ri of the frequencies ni and ri of the particles having the particle size ri is the maximum (three significant figures and the least significant figure are rounded off to the nearest four). The term "particle size" as used herein means the diameter of spherical silver halide grains, and the diameter of grains having a non-spherical shape when the projected image is converted into a circular image having the same area.

The particle size can be obtained, for example, by taking an image of the particles with an electron microscope at a magnification of 10,000 times to 50,000 times and measuring the particle diameter on the print or the area at the time of projection (measurement). The number of particles shall be indiscriminately 1000 or more).

Particularly preferred highly monodisperse emulsions of the present invention are those having a standard distribution of (standard deviation / average grain size) × 100 = amount of distribution (%) of 20% or less. It is more preferably 15% or less. Here, the average particle diameter and the standard deviation are obtained from the particle diameter ri defined above.

The silver halide grains according to the present invention may be those obtained by any of the acidic method, the neutral method and the ammonia method, and the method of reacting a soluble silver salt with a soluble silver halide is a side mixture. Any of a method, a simultaneous mixing method, and a combination thereof may be used.

A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one type of simultaneous mixing method, a method of keeping pAg constant in a liquid layer in which silver halide is produced, that is, a so-called controlled double jet method can be used.

Further, two or more kinds of silver halides formed separately may be mixed and used.

The silver halide grains according to the present study were nucleated and / or nucleated by adding finely prepared fine grain silver halide grains to a reaction vessel for nucleating and / or crystallizing the grains. Alternatively, crystals may be grown.

In the present invention, as a method for obtaining a monodisperse emulsion, two kinds selected arbitrarily from a water-soluble silver salt solution and a water-soluble halide solution in a gelatin solution containing seed particles, and silver halide fine particles are used. The reaction elements above are pAg and p
It can be obtained by adding under the control of H 2.
In determining the addition rate, reference can be made to JP-A-54-48521 and JP-A-58-49938.

As a method for obtaining a more advanced monodisperse emulsion, the growth method in the presence of tetrazaindene disclosed in JP-A-60-122935 can be applied. A known silver halide solvent such as ammonia, thioether or thiourea may be present during the production of the silver halide grains according to the present invention, or the silver halide solvent may not be used.

An oxidizing agent may be present during the production of the silver halide grains according to the present invention. Here, the oxidizing agent refers to a compound that acts on metallic silver to convert it into silver ions. In particular, a compound capable of converting extremely minute silver atoms generated in the process of forming silver halide grains into silver ions is effective. A preferable oxidizing agent is a halogen element, and more preferable is iodine. The addition amount of the oxidizing agent to 1 mol of silver is preferably selected from the range of 10 ^-7 to 10 ^-1 mol. It is preferably in the range of 10 ⁻⁶ to 10 ⁻² mol, and more preferably 10 ⁻⁵ to 10 ⁻³ mol.

The oxidizing agent may be added in the reaction vessel before the grain growth, or may be added at any time after the grain growth until the chemical ripening. As a more preferable time, it is preferable to allow the particles to exist in the reaction vessel immediately before grain growth until desalting.

In the present invention, in order to add the oxidizing agent during the production process, a method usually used when adding the additive to the photographic emulsion can be applied. For example, photographic performance may be adversely affected by dissolving in water to form an aqueous solution having an appropriate concentration, or by using an appropriate organic solvent that can be mixed with water, such as alcohols, glycols, ketones, esters, and amides. You may melt | dissolve in the solvent which does not reach and may add as a solution. Alternatively, the solid may be added directly. The oxidizing agent may be added by rush addition, constant rate addition, or functional addition. The silver halide grains according to the present invention are produced in the presence of a dispersion medium, that is, in a solution containing the dispersion medium.

Here, the aqueous solution containing a dispersion medium refers to an aqueous solution in which a protective colloid is formed by a substance that can be a binder such as gelatin or a substance that can form a hydrophilic colloid, and is preferably a colloidal form. An aqueous solution containing protected gelatin.

When gelatin is used as the protective colloid in carrying out the present invention, the gelatin may be either lime-treated or acid-treated. Details of the method for producing gelatin are described in Arthur Guice, The Macromolecular Chemistry of Gelatin, (Academic Press, 1964).

Hydrophilic colloids other than gelatin that can be used as protective colloids include, 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, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacryl Acid, polymethacrylic acid,
There are various types of synthetic hydrophilic polymeric substances such as polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole, and other single or copolymers.

In the case of gelatin, it is preferable to use one having a jelly strength of 200 or more in the Paggy method.

The silver halide grain according to the present invention may be either a grain in which a latent image is mainly formed on the surface or a grain in which the latent image is mainly formed. The size of silver halide is 0.05 to 5.0. μm, preferably 0.1
~ 3.0 μm. The silver halide grains according to the present invention may be those in which unnecessary soluble salts have been removed after the growth of the silver halide grains has been completed, or the grains may be contained as they are.

Further, as in the method described in JP-A-60-138538, it is possible to carry out desalting at any point of silver halide growth. The removal of the salts can be carried out according to the method described in Research Disclosure (hereinafter abbreviated as RD) No. 17643, Item II. More specifically, in order to remove the soluble salts from the emulsion after the formation of a precipitate or after the physical ripening, a Nudel water washing method performed by gelling gelatin may be used,
Alternatively, a precipitation method (flocculation) using an inorganic salt, an anionic surfactant, an anionic polymer (for example, polystyrene sulfonic acid), or a gelatin derivative (for example, acylated gelatin, carbamoylated gelatin, etc.) may be used.

The silver halide grains according to the present invention can be chemically sensitized by a conventional method. That is, a sulfur sensitization method, a selenium sensitization method, a reduction sensitization method, a noble metal sensitization method using a gold or other noble metal compound can be used alone or in combination.

The silver halide grain according to the present invention can be optically sensitized to a desired wavelength region by using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more kinds. A dye that does not have a spectral sensitizing effect by itself with a sensitizing dye, or a compound that does not substantially absorb visible light, and that contains a supersensitizer that enhances the sensitizing effect of the sensitizing dye is included in the emulsion. May be.

Antifoggants, stabilizers and the like can be added to the silver halide grains according to the present invention. It is advantageous to use gelatin as the binder. The emulsion layer and other hydrophilic colloid layers may be hardened and may contain a plasticizer and a dispersion (latex) of a water-insoluble or soluble synthetic polymer.

A coupler is used in the emulsion layer of the color light-sensitive material. Further, by a coupling with a competing coupler having an effect of color correction and an oxidized product of a developing agent, a development accelerator, a developer, a silver halide solvent, a toning agent, a hardener, a fogging agent, an antifoggant, Compounds that release photographically useful fragments such as chemical sensitizers, spectral sensitizers and desensitizers can be used.

The light-sensitive material may be provided with auxiliary layers such as a filter layer, an antihalation layer and an anti-irradiation layer. In these layers and / or in the emulsion layers, dyes which may be bleached or bleached from the light-sensitive material during development processing may be contained.

Matting agents, lubricants, image stabilizers, formalin scavengers, ultraviolet absorbers, optical brighteners, surfactants, development accelerators and development retarders can be added to the light-sensitive material.

As the support, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate or the like can be used.

[0072]

EXAMPLES Next, the present invention will be described more specifically by way of examples, but the present invention is not limited thereto.

Example 1 (Preparation of silver halide emulsion) (Preparation of twin seed emulsion T-1)
A seed emulsion T-1 having parallel twin planes was prepared.

(Solution A) Oscein gelatin 80.0 g Potassium bromide 47.4 g Polyisopropylene-polyethyleneoxy-disuccinate sodium salt 10% methanol solution 0.48 ml Water 8000.0 ml (Solution B) 3.5N ammoniacal silver nitrate aqueous solution (However, pH was adjusted to 9.0 with ammonium nitrate) (Solution C) Ocein gelatin 32.2 g Potassium bromide 790.0 g Potassium iodide 70.34 g Water 1600.0 ml (Solution D) Ammonia water 470.0 ml A stirred vigorously at 40 ° C A The liquid B and the liquid C were added to the liquid by the double jet method for 7.7 minutes to generate nuclei.
During this period, pBr was kept at 1.60.

Thereafter, the temperature was lowered to 20 ° C. over 30 minutes. Furthermore, the liquid D was added in 1 minute, and a 3.5N potassium bromide aqueous solution was additionally added, followed by aging for 5 minutes. The KBr concentration during aging was 0.10 mol / l and the ammonia concentration was 0.66 mol / l.

After completion of aging, the pH was adjusted to 6.0 and desalting was carried out according to a conventional method. When the seed emulsion grains were observed with an electron microscope, they were hexagonal tabular grains having an average grain size of 0.238 μm, a thickness of 0.12 μm and two twin planes parallel to each other.
(The ratio of two parallel twin planes is 75% in the total number of grains).

(Preparation of Silver Halide Emulsion and Introduction of Dislocation Line into the Emulsion) (Solution E) Ocein gelatin 61.0 g Distilled water 1963.0 ml Polyisopropylene-polyethyleneoxy-succinic acid ester sodium salt 10% Methanol Solution 2.5 ml Seed emulsion (T-1) 0.345 mol 28% by weight aqueous ammonia solution 308.0 ml 56% by weight aqueous acetic acid solution 358.0 ml Distilled water to 20000.0 ml.

(However, containing a predetermined amount of InCl ₃ .4H ₂ O) (Solution F) 3.5N ammoniacal silver nitrate aqueous solution (however, pH was adjusted to 9.0 with ammonium nitrate) (Solution G) 3.5N potassium bromide aqueous solution ( Solution H) 3% by weight of gelatin and silver iodide grains (average grain size)
The method for preparing 1.40 molar fine grain emulsion (*) * consisting of 0.05 μm) is shown below.

6.0% by weight containing 0.06 mol of potassium iodide
2000 ml of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide were added to 5000 ml of the gelatin solution of 10 ml over 10 minutes. The pH during fine particle formation is 2.0 using nitric acid.
The temperature was controlled at 40 ° C. After forming the particles, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution.

(Solution I) Fine grains composed of silver iodobromide grains (average grain size 0.04 μm) containing 2 mol% of silver iodide prepared in the same manner as the silver iodide fine grain emulsion described in Solution H. emulsion
However, the temperature during fine particle formation was controlled at 30 ° C.

(Solution J) 1.75N aqueous solution of potassium bromide (Solution K) 56% by weight aqueous acetic acid solution E was kept at 70 ° C. with vigorous stirring in a reaction vessel.
Solution F, solution G and solution H are added thereto by the simultaneous mixing method.
After adding for 103 minutes, solution I was continuously added at a constant rate for 7 minutes to grow a seed crystal.

Here, the addition rates of the solution F and the solution G were changed in a function-like manner with respect to time so as to be commensurate with the critical growth rate, and a large number of small particles other than the growing seed crystal were generated and Ostwald ripening was performed to increase the number. It was added at an appropriate addition rate so as not to disperse. The solution H, that is, the silver iodide fine grain emulsion is supplied by changing the rate ratio (molar ratio) with the aqueous ammoniacal silver nitrate solution with respect to the grain size (addition time) as shown in Table 1. Silver iodobromide emulsion EM having composition
-1 was created. Immediately before the addition of the aqueous ammoniacal silver nitrate solution, 33.7 ml of a methanol solution containing 450 mg of iodine (1 × 10 ⁻⁴ mol / mol silver) was added by rush.

By using the solutions J and K,
The pAg and pH during crystal growth were controlled as shown in Table 1.
The pAg and pH were measured using a silver sulfide electrode and a glass electrode according to a conventional method.

After the grain formation, desalting treatment was carried out according to the method described in Japanese Patent Application No. 3-41314, gelatin was then added and redispersed, and pH was adjusted to 5.80 and pAg was adjusted to 8.06 at 40 ° C. From the scanning electron micrograph of the obtained emulsion grains, the average grain size was 1.
26 μm, thickness 0.22 μm (aspect ratio 5.7), width of distribution is 1
It was confirmed to be a tabular monodisperse emulsion of 3.6%. Further, crystals were grown from the seed emulsion T-1 by the same preparation method as the emulsion EM-1, and when the addition to the solution H was completed, 100 ml of an aqueous solution containing 29.3 g of potassium iodide was added at a constant rate over 1 minute. Then, after ripening for 5 minutes, Solution E was added in the same manner as Emulsion EM-1 to prepare Emulsion EM-2 of the present invention.

Further, the rate ratio (molar ratio) of the solution H and the aqueous ammoniacal silver nitrate solution at the time of forming the core was changed so that the amount of potassium iodide in the aqueous potassium iodide solution was 2.93 g, and the solution E was prepared.
Emulsion E except that Pb (NO ₃ ) ₂ was used as InCl ₃ .4H ₂ O contained in
Emulsion EM-3 of the present invention was prepared in the same manner as M-1.

Further, crystals were grown from seed emulsion T-1 by the same preparation method as for emulsion EM-1, and when the grain size reached 0.933 μm, addition of solutions F, G and H was stopped and potassium iodide was added. Slowly add 100 ml of an aqueous solution containing 2.93 g over 1 minute,
Then, after aging for 5 minutes, the solutions F, G, and H are re-sized.
(Emulsion EM) of the present invention by adding solution I in the same manner as emulsion EM-1.
-4 was created. In this case, the silver iodide content in Solution I was 4 mol%. InCl ₃ .4H ₂ O was added to solution G instead of solution E. It should be noted that iodine was not added immediately before the start of addition of the ammoniacal silver nitrate aqueous solution.

Next, Emulsion E was prepared in the same manner as Emulsion EM-2 except that InCl ₃ .4H ₂ O contained in Solution E was made free.
M-5 was prepared.

Further, crystals were grown from the seed emulsion T-1 by the same preparation method as for the emulsion EM-1, and when the grain size reached 0.933 μm, addition of the solutions F, G and H was stopped and potassium iodide was added. 100 ml of an aqueous solution containing 2.93 g was added at a constant rate over 1 minute, followed by aging for 5 minutes, and then solutions F, G, and H were added again while changing the particle size (addition time), and then
A solution I having a silver iodide content of 4 mol% as in Emulsion 4
Was added to prepare a comparative emulsion EM-6. In this case, the iodine solution was not added.

Further, the solution E was maintained at 70 ° C. in the reaction vessel with vigorous stirring, and the solution F, the solution G and the solution H were added thereto.
And the rate ratio (molar ratio) with the ammoniacal silver nitrate aqueous solution is 8.
After adding for 103 minutes by the simultaneous mixing method while keeping at 0, solution I having a silver iodide content of 8 mol% was added independently for 7 minutes at a constant rate for comparison. Emulsion E
Created M-7. Also in this case, the iodine solution was not added. Also, InCl ₃ .4H ₂ O is not solution E but solution G
Was added to.

[0090]

[Table 1]

The emulsions EM-1 to EM-7 were directly observed for dislocations using a transmission electron microscope. The electron microscope is JEM-2000FX manufactured by JEOL Ltd., and the acceleration voltage is 200K.
It was observed at V and temperature of -120 ° C.

The preparation conditions of the emulsions EM-1 to EM-7 and the obtained results are summarized in Table 2.

[0093]

[Table 2]

As can be seen from Table 2, generation of dislocation lines was found in the emulsion treated with potassium iodide during the growth of silver halide grains. The emulsion EM-2 of the present invention has a content of 0.
20 or more dislocation lines are generated in the 93L to 0.97L region. Emulsion EM-3 of the present invention has 10 or more dislocation lines in the region of 0.92L to 0.97L and EM-4 in the region of 0.62L to 0.96L.

Also in the comparative emulsions, EM-5 and EM-6.
As described above, generation of dislocation lines was found.

Example 2 (Preparation of Light-Sensitive Material Sample) Emulsions EM-1 to EM-7 were optimally subjected to gold-sulfur sensitization, and these emulsions were used to show the following on a triacetyl cellulose film support. Each layer having such a composition was sequentially formed from the support side to prepare a multilayer color photographic light-sensitive material.

In all the following descriptions, the addition amount in the silver halide photographic light-sensitive material is 1 m ² unless otherwise specified.
The number of grams per unit is shown. Further, silver halide and colloidal silver are shown in terms of silver, and sensitizing dyes are shown in the number of moles per mole of silver halide.

The constitution of the multilayer color photographic light-sensitive material sample-1 (using the emulsion EM-1 of the present invention) is as follows.

1st layer; antihalation layer Black colloidal silver 0.16 UV absorber (UV-1) 0.30 gelatin 1.70 2nd layer; Intermediate layer (1L-1) gelatin 0.80 3rd layer; Low sensitivity red-sensitive layer (R- L) Silver iodobromide emulsion (average grain size 0.30 μm) 0.40 Sensitizing dye (S-1) 1.2 × 10 ⁻⁴ Sensitizing dye (S-2) 0.2 × 10 ⁻⁴ Sensitizing dye (S-3) 2.0 × 10 ^-4 Sensitizing dye (S-4) 1.2 × 10 ^-4 Cyan coupler (C-1) 0.33 Colored cyan coupler (CC-1) 0.05 High boiling point solvent (Oil-1) 0.30 Gelatin 0.55 Fourth layer; Medium Sensitive red-sensitive layer (RM) Silver iodobromide emulsion (average grain size 0.4 μm) 0.48 Sensitizing dye (S-1) 1.5 × 10 ^-4 Sensitizing dye (S-2) 0.2 × 10 ^-4 Sensitizing Dye (S-3) 2.5 × 10 ^-4 Sensitizing dye (S-4) 1.5 × 10 ^-4 Cyan coupler (C-1) 0.30 Colored cyan coupler (CC-1) 0.05 High boiling point solvent (Oil-1) 0.40 Gelatin 0.60 Fifth layer; high-sensitivity red-sensitive layer (RH) Silver iodobromide emulsion (average grain size 0.55 μm) 0.66 Sensitizing dye (S-1) 1.0 × 10 ⁻⁴ Sensitizing dye (S-2 ) 0.2 × 10 ^-4 sensitizing dye (S-3) 1.7 × 10 ^-4 sensitizing dye (S-4) 1.0 × 10 ^-4 Cyan coupler (C-2) 0.10 Colored cyan coupler (CC-1) 0.01 DIR Compound (D-1) 0.02 High boiling point solvent (Oil-1) 0.15 Gelatin 0.53 Sixth layer; Intermediate layer (1L-2) Gelatin 0.80 Seventh layer; Low sensitivity green sensitive layer (GL) Silver iodobromide emulsion (Average grain size 0.40 μm) 0.60 Silver iodobromide emulsion (Average grain size 0.30 μm) 0.40 Sensitizing dye (S-1) 0.6 × 10 ⁻⁴ Sensitizing dye (S-5) 5.1 × 10 ⁻⁴ Magenta coupler ( M-1) 0.55 Colored magenta coupler (CM-1) 0.17 DIR compound (D-2) 0.03 High boiling point solvent (Oil-2) 0.70 Gelatin 1.56 8th layer; High sensitivity green sensitive layer (G H) Silver iodobromide emulsion (emulsions of the invention EM-1) 0.60 Sensitizing dye (S-6) 1.5 × 10 -4 Sensitizing dye (S-7) 1.5 × 10 -4 Sensitizing dye (S-8) 1.5 × 10 ^-4 Magenta coupler (M-1) 0.06 Magenta coupler (M-2) 0.02 Colored magenta coupler (CM-2) 0.02 DIR compound (D-3) 0.002 High boiling point solvent (Oil-2) 0.15 Gelatin 0.45 9 layers; yellow filter layer (YC) yellow colloidal silver 0.12 HS-1 0.20 HS-2 0.14 high boiling point solvent (Oil-2) 0.18 gelatin 0.80 10th layer; low sensitivity blue sensitive layer (BL) silver iodobromide Emulsion (average particle size 0.4 μm) 0.18 Silver iodobromide emulsion (average particle size 0.3 μm) 0.35 Sensitizing dye (S-9) 5.1 × 10 ^-4 Sensitizing dye (S-10) 2.0 × 10 ^-4 Yellow coupler (Y-1) 0.58 Yellow coupler (Y-2) 0.30 High boiling point solvent (Oil-2) 0.15 Gelatin 1.20 11th layer; High sensitivity Sensitive layer (B-H) Silver iodobromide emulsion (average grain size 0.65 .mu.m) 0.45 Sensitizing dye (S-9) 2.8 × 10 -4 Sensitizing dye (S-10) 1.0 × 10 -4 Yellow coupler (Y -1) 0.10 High boiling point solvent (Oil-2) 0.04 Gelatin 0.50 12th layer; 1st protective layer (Pro-1) Silver iodobromide emulsion (average particle size 0.07 μm) 0.30 Ultraviolet absorber (UV-1) 0.07 Ultraviolet absorber (UV-2) 0.10 High boiling point solvent (Oil-2) 0.07 High boiling point solvent (Oil-3) 0.07 HS-1 0.25 Gelatin 0.80 13th layer; 2nd protective layer (Pro-2) Alkali-soluble matting agent (Average particle size 2 μm) 0.13 Polymethylmethacrylate (Average particle size 3 μm) 0.02 Gelatin 0.50 In addition to the above composition, a coating aid Su-1, a dispersion aid Su-2, a film hardener H-1, H-2, Dyes AI-1, AI
-2 was added appropriately.

The structures of the compounds used in the above samples are shown below.

[0101]

[Chemical 1]

[0102]

[Chemical 2]

[0103]

[Chemical 3]

[0104]

[Chemical 4]

[0105]

[Chemical 5]

[0106]

[Chemical 6]

[0107]

[Chemical 7]

[0108]

[Chemical 8]

As for emulsions EM-2 to EM-7, as shown below, by using each of these emulsions in place of the emulsion EM-1 of sample-1, the multilayer color photographic light sensitive material samples-2 to Created 7.

Sample name 2 3 4 5 6 7 Emulsion used EM-2 EM-3 EM-4 EM-5 EM-6 EM-7 Each of the obtained samples was subjected to wedge exposure using green light (G). After that, the following development processing was performed to evaluate relative sensitivity, fog, pressure fog, pressure desensitization and graininess.

<Processing Step> 1. Color development 3 minutes 15 seconds 38.0 ± 0.1 ° C 2. Bleach 6 minutes 30 seconds 38.0 ± 3.0 ° C 3. Water washing 3 minutes 15 seconds 24-41 ° C 4. Fixation 6 minutes 30 Second 38.0 ± 3.0 ℃ 5. Washing with water 3 minutes 15 seconds 24-41 ℃ 6. Stability 3 minutes 15 seconds 38.0 ± 3.0 ℃ 7. Drying 50 ℃ or less The composition of the processing solution used in each processing step is as follows. is there.

<Color developer> 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline / sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine / 1/2 sulfate 2.0 g anhydrous Potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Water is added to make 1 liter, and the pH is adjusted to 10.1.

<Bleach> Ethylenediaminetetraacetic acid iron ammonium salt 100.0g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0g
Adjust to = 6.0.

<Fixer> Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water is added to make 1 liter, and pH is adjusted to 6.0 using acetic acid.

<Stabilizer> Formalin (37% aqueous solution) 1.5 ml Conidax (Konica Corporation) 7.5 ml Water is added to make 1 liter.

The relative sensitivity is the relative value of the reciprocal of the exposure dose giving a density of Dmin (minimum density) +0.15, and is shown as a value with the sensitivity of Sample-1 as 100 (values for 100 are The larger the value, the higher the sensitivity).

The relative fog is a relative value of the reciprocal of the exposure amount giving the density of Dmin, and is shown as a value with the fog of Sample-1 being 100 (the higher the value, the higher the fog). Is shown).

Regarding the pressure resistance, a scratch strength tester (manufactured by Shinto Scientific Co., Ltd.) was used under the conditions of 23 ° C. and 55% (relative humidity).
After scanning at a constant speed with a load of 5 g on a needle with a radius of curvature of 0.025 mm at the tip, exposure and development processing is performed, and for pressure fog, the density change (ΔDpk) of the part where the load is applied at the density of Dmin. For pressure desensitization, the density change (ΔDpg) in the part where a load is applied at the density of Dmin + 0.4
Was determined and shown as a value with each of ΔDpk and ΔDpg of Sample-1 being 100 (the smaller the value with respect to 100, the more improved).

The graininess was indicated by the relative value of the standard deviation (RMS value) of the fluctuation of the density value produced when the density of Dmin + 0.5 was scanned by a microdensitometer having an opening scanning area of 250 μm ² . The smaller the RMS value, the better the graininess, and the more effective it is. The RMS value of Sample-1 was shown as 100.

[0120]

[Table 3]

As is clear from the results shown in Table 3, the samples-2, 3 and 4 of the present invention containing the emulsions EM-2, 3 and 4 according to the present invention have high sensitivity, improved fog and pressure. Fog and pressure desensitization are improved, and the graininess is also improved. Among these, the sample-2 using the emulsion EM-2 which satisfies the best combination of the present invention is particularly excellent.

[0122]

According to the present invention, a silver halide photographic emulsion and a silver halide color photographic light-sensitive material having high sensitivity, low fog, improved pressure desensitization, pressure fog and graininess can be provided. .

Claims (4)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
A silver halide color photographic light-sensitive material, characterized in that at least one layer in the light-sensitive material contains a silver halide photographic emulsion described below. In a silver halide emulsion containing silver halide grains in a dispersion medium, polyvalent metal ions of Group 13 and / or Group 14 of the periodic table are contained in the silver halide grains in an amount of 10 ^-9 mol per mol of silver halide. Characterized in that the number of grains containing 10 ^-1 mol or less and having an average of 10 or more dislocation lines per grain is 50% (number) or more of the silver halide grains contained in the silver halide emulsion. And a silver halide photographic emulsion. 2. A silver halide emulsion in which dislocation lines are concentrated in a region of 0.5 L to L from the center of the grain with respect to the distance L from the center of the silver halide grain to the outer surface. The silver halide color photographic light-sensitive material according to claim 1, which is characterized in that 3. A silver halide color photographic light-sensitive material characterized in that the polyvalent metal ion according to claim 1 is added before the substantial growth of silver halide is completed at 50% of the silver halide amount. . 4. The silver halide color photographic light-sensitive material according to claim 2, wherein the region where dislocation lines are concentrated is 0.8 L to 0.98 L from the center of the grain.