JPH11125878A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the silver halide photographic sensitive material capable of forming an image superior in sharpness and graininess and high in image quality by incorporating, in the silver halide emulsion layer, silver halide grains having an average grain size of <= a specified value and each grain having the corners and/or ridges to which the epitaxial parts of fine silver halide grains attach. SOLUTION: The silver halide grains contained in the silver halide grains have an average grain size of <=0.1 μm and the corners and/or ridges combining with the fine silver halide epitaxial parts. These fine silver halide grains of the epitaxial parts have an average grain size <=0.05 μm. These fine grains have cubic crystal forms. After these fine silver halide grains have been formed, growth of the epitaxial parts is continued. The hosts of these fine silver halide grains are silver chloride and the epitaxial parts comprise silver iodide or silver iodobromide or silver bromide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material containing fine silver halide particles.

[0002]

2. Description of the Related Art The factors that determine the image quality of a silver halide photographic light-sensitive material include sharpness caused by the optical characteristics of the photographic film and graininess, which is noise caused by the fine structure of the photographic film.

That is, as a result of light scattering by silver halide grains contained in a light-sensitive material, an incident light beam spreads as it enters the film, which causes deterioration in sharpness. Further, the developed silver is arranged at random, and due to the random pattern, even if individual points are far enough apart to be invisible, density fluctuation over a long distance is perceived as granularity.

[0004] "The Theory of the
Photographic Process, Four
According to "The Edition (by TH James)", the light scattering factor exhibits a particle size dependence, and as shown in FIGS. 20.7 and 20.8 of the same document, when the particle size becomes extremely small, (0.1 μm or less) Light scattering is significantly reduced, resulting in improved sharpness.

[0005] As shown in Fig. 21.72 of the same document, the graininess is improved as the particle size is reduced.

The above “The Theory of the th
According to "e Photographic Process", the covering power (ratio of optical density to silver mass per unit area) increases as the particle size decreases.

In the field of graphic arts, when a light-sensitive material for a bright room having a low sensitivity is to be obtained, for example, Japanese Patent Application Laid-Open No.
JP-A-83038 and JP-A-60-162246 disclose silver halide photosensitive materials containing a water-soluble rhodium salt, but when a sufficient amount of rhodium salt is added to lower the sensitivity, the hydrazine compound increases the contrast. Is not alienated and a desired image cannot be obtained. In the first place, in a silver halide photographic emulsion, the sensitivity decreases with a decrease in the grain size. .

As described above, there is a demand for ultra-fine particles having a smaller size. As a technique for obtaining ultra-fine particles having a smaller size, for example, the above-mentioned “The Theory of t”
he Photographic Process ", and a" Lipmann emulsion "having silver bromide fine particles of 0.05 μm.

A "Lipmann emulsion" is usually a photographic plate or film having an average grain size of 0.05 to 0.1 μm and having particularly high resolution, such as a microphotograph, an astrophotograph, or a mask used for producing an electronic integrated circuit. It is particularly important in holography and the like.

Attempts have been made to change the operating conditions during the precipitation of silver halide in order to obtain ultrafine grains having an average grain size of 0.05 μm or less. In a system in which a silver salt aqueous solution and a halide aqueous solution are added to a protective colloid aqueous solution in a reaction vessel, it is important to generate a large number of nuclear particles at the time of nucleation at the start of the addition. However, the subsequent addition of the aqueous silver nitrate solution and the aqueous halide solution always results in the growth of these core particles, so that the size is 0.05 μm
It is in principle difficult to obtain very small ultrafine particles. On the other hand, Japanese Patent Application Laid-Open No. 1-183417 has an aqueous solution of protective colloid, and a mixer is provided outside a reaction vessel for causing crystal growth of silver halide grains. The mixer is provided with an aqueous solution of silver salt and an aqueous solution of halide. Silver halide grains, characterized in that silver halide fine particles are formed by supplying and mixing a colloid aqueous solution, and the fine particles are immediately supplied to a reaction vessel, and crystal growth of the silver halide fine grains is performed in the reaction vessel. Is disclosed, in which the size of particles discharged from the mixer is 0.0
It is shown to be less than 5 μm. If the nuclei are formed in the mixer and discharged immediately, very small ultrafine particles can be obtained. However, the fine particles formed in the mixer have extremely high solubility because of their extremely small size, and as a result, so-called Ostwald ripening occurs between the fine particles, and the particle size increases.

In other words, according to the above-mentioned method, once formed extremely fine particles undergo Ostwald ripening in the washing step, redispersion step and re-dissolution step, and the particle size increases.

In US Pat. Nos. 3,661,592 and 3,704,130, a protective colloid aqueous solution and a particle growth inhibitor are added to a reaction vessel, and then a silver salt aqueous solution and a halide aqueous solution are added. To obtain fine particles of a smaller size than Lippmann emulsions. This method attempts to prevent the particle size from increasing by preventing particle growth after nucleation in the reaction vessel. It is difficult to completely eliminate grain growth. The average size of the fine particles shown in the examples of these two specifications is 0.05 to 0.03 μm in silver bromide. Although it is possible to obtain fine particles having a smaller size than the Lippmann emulsion, it is extremely difficult to obtain fine particles having a smaller size.

Under these circumstances, it has been demanded to obtain an ultrafine grain emulsion much smaller in size than the Lippmann emulsion, but this has not been realized by the prior art.

[0014]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to make it possible to obtain an ultrafine grain emulsion having a very small size without increasing the grain size, and to produce such an ultrafine grain emulsion stably. It is an object of the present invention to provide a silver halide photographic light-sensitive material containing an ultra-fine particle emulsion having a very small size.

It is a further object of the present invention to provide a silver halide photographic light-sensitive material containing an ultrafine grain emulsion having a very small size, thereby providing a high-quality image excellent in sharpness and graininess. Is to provide the material.

[0016]

The object of the present invention has been attained by the following means. (1) In a silver halide photographic material having a support and at least one silver halide emulsion layer coated on at least one side of the support, at least one of the silver halide emulsion layers has an average grain size. A silver halide photographic light-sensitive material having a size of 0.1 μm or less and having silver halide fine grains having corners and / or edges and having silver halide epitaxy portions at the corners and / or edges. material. (2) The average size of the silver halide fine particles is 0.0
The silver halide photographic light-sensitive material according to the above (1), which has a size of 5 μm or less. (3) The silver halide photographic material as described in the above item (1) or (2), wherein the fine silver halide particles are cubic. (4) After the grain formation of the silver halide fine grains is completed, the epitaxy portion is continuously grown.
The silver halide photographic light-sensitive material according to any of (3). (5) The halogenation according to any one of (1) to (4), wherein the host part of the silver halide fine particles is silver chloride, and the epitaxy part is silver iodide, silver iodobromide or silver bromide. Silver photographic photosensitive material. (6) The silver halide fine grains have an epitaxy part of silver iodobromide, and the silver halide fine grains have a silver iodide content of 2 mol% or more and 20 mol% or less, and combine silver bromide and silver iodide. Content is 10 mol% or more and 20 mol%
The following silver halide photographic light-sensitive material according to any one of the above (1) to (5).

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The silver halide photographic light-sensitive material of the present invention has an average grain size of 0.1 μm or less, has corners and / or edges, and has silver halide epitaxy portions at the corners and / or edges. Having a silver halide emulsion layer. By using such a fine grain emulsion, a silver halide photographic material having excellent sharpness and granularity and excellent resolution can be obtained. In the case of a heat-developable silver halide photosensitive material in which an image is formed by heating, image turbidity can be further prevented.

The size of the silver halide fine particles of the present invention is as follows:
The fine particles are placed on a mesh and can be confirmed by a transmission electron microscope as it is, and the magnification is preferably 20 to 40,000 times. The average size of the fine particles of the present invention is 0.005 μm to 0.1 μm
And more preferably 0.005 μm to 0.05.
μm, more preferably 0.005 μm to 0.0
3 μm, and most preferably 0.005 μm to 0.05 μm.
2 μm. The grain size in the present invention refers to the length of the edge of the silver halide grains when the silver halide grains are cubic, octahedral or dodecahedral so-called normal crystals. In the case where the silver halide grains are tabular grains, the diameter refers to a diameter when converted into a circular image having the same area as the projected area of the main surface. Other non-normal crystals, for example, spherical particles,
In the case of needle-like grains, rod-like grains, etc., it refers to the diameter of a sphere equivalent to the volume of silver halide grains.

The crystal form of the silver halide fine grains of the present invention is not particularly limited, and may be cubic, octahedral, dodecahedral, tabular, acicular, etc., but normal crystals are preferable to twins.
Particularly preferred is a cube.

The silver halide fine grains of the present invention have an epitaxy portion grown at a specific selected site by epitaxy of silver halide. That is, coarse growth due to Ostwald ripening of the fine particles is prevented by epitaxially growing silver halide having a halogen composition having a lower solubility at the growth active point of the fine particles.

The epitaxy part of the silver halide fine grains of the present invention is a growth active point of the fine grains, specifically, a corner and / or a ridge of a crystal, preferably a corner of a crystal.

The halogen composition of the silver halide fine grains of the present invention is not particularly limited, but the halogen composition is preferably high silver chloride from the viewpoint of processability and the like, and particularly the halogen composition of the host part is high silver chloride. Is preferred. The epitaxy part preferably has a halogen composition having a lower solubility than the host part from the viewpoint of preventing coarsening of the fine particles. More preferably, the host portion is silver chloride and the epitaxy portion is silver iodide, silver iodobromide, or silver bromide.

The epitaxy part of the silver halide fine grains of the present invention is preferably silver iodide from the viewpoint of preventing coarsening of the fine grains, but from the viewpoint of processability and the like, the silver iodide content of the silver halide fine grains is as small as possible. Is preferred.

As a result of investigations by the present inventors, the amount of silver iodide used in the epitaxy part for preventing the coarsening of fine particles is minimized by using silver iodobromide mixed crystal instead of pure silver iodide. It became clear that it can be suppressed to the limit.

In the silver halide fine grains of the present invention, when epitaxial growth is performed, it is preferable that halogen conversion be performed uniformly between grains, and it is preferable that the composition and size of the epitaxy part be uniform.

The halogen composition of the silver halide fine grains of the present invention preferably has a silver iodide content of 2 mol% to 20 mol%.
And the total content of silver bromide and silver iodide is 1
0 mol% or more and 20 mol% or less, more preferably the silver iodide content is 4 mol% or more and 15 mol% or less, and the total content of silver bromide and silver iodide is 15 mol% or more and 20 mol% or less, most preferably. The silver iodide content is 6 mol% or more and 12 mol% or less, and the total content of silver bromide and silver iodide is 18 mol% or more and 20 mol% or less.

A method for producing a silver halide ultrafine grain emulsion constituting the emulsion layer in the light-sensitive material of the present invention will be described.

In the emulsion of the present invention, an aqueous solution of protective colloid, an aqueous solution of a water-soluble silver salt and an aqueous solution of a water-soluble halide are supplied into a reaction vessel, mixed and stirred to form a host portion of silver halide fine particles. After discharging from the reaction vessel, the mixture is further introduced into a stirrer, and halogen conversion is performed by adding an aqueous solution of a halogen salt having a desired halogen composition to form an epitaxy portion. Is removed. In order to prepare a coating solution, it is usually concentrated to an appropriate concentration, and further redispersed in a hydrophilic colloid aqueous solution to obtain a silver halide emulsion coating solution. However, it is not limited to these. In the emulsion of the present invention, the grain structure of silver halide having an epitaxy part is maintained even in a coating solution. The particle structure can be confirmed by a direct transmission electron microscope.

As the protective colloid for preparing the silver halide fine particles of the present invention, gelatin or a protective colloid polymer is preferable.

The above gelatin or protective colloid polymer may be added in the form of an aqueous solution of a water-soluble silver salt and / or an aqueous solution of a water-soluble halide salt, or may be added as another aqueous solution.

The protective colloid polymer is selected from gelatin, other natural polymers and synthetic polymers. In particular, the protective colloid polymer suppresses physical ripening (coalescing ripening and Ostwald ripening) of fine silver halide particles. Is preferably used. Specific examples are shown below.

(1) Gelatin having a high degree of physical inhibition Gelatin containing a large amount of adenine and guanine. (2) Polyvinylpyrrolidone Homopolymer of vinylpyrrolidone, French Patent 203
1396. A copolymer of acrolein and pyrrolidone. (3) Polyvinyl alcohol Homopolymer of vinyl alcohol, US Patent 30007
An organic acid monoester of vinyl alcohol according to No. 14,
Maleic acid esters described in U.S. Pat. No. 3,236,653;
A copolymer of polyvinyl alcohol and polyvinyl pyrrolidone described in U.S. Pat. No. 3,479,189. (4) Polymer having thioether US Pat. Nos. 3,615,624, 3,860,428 and 3,
A polymer having a thioether group described in No. 706564. (5) Polyvinyl imidazole Homopolymer of polyvinyl imidazole, copolymer of polyvinyl imidazole and polyvinyl amide, Shoko 4
No. 3-7561, German Patent No. 20120195, No. 20
No. 12970 terpolymer of acrylamide, acrylic acid and vinylimidazole.

(6) Polyethylene imine (7) Acetal polymer Water-soluble polyvinyl acetal described in US Pat. No. 2,358,836, polyvinyl acetal having a carboxyl group described in US Pat. No. 3,0038,879, British Patent 77115
5. The polymer according to item 5. (8) Amino polymer US Pat. Nos. 3,345,346, 3,706,504 and 4,
No. 350759, amino polymers described in German Patent 2,138,872, British Patent No. 1413125, U.S. Pat.
No. 4,258,836, polymers having an amino group and a carboxyl group described in US Pat. No. 3,511,818, and polymers described in US Pat. No. 3,832,185. (9) Polyacrylamide polymer Homopolymer of acrylic amide, US Pat. No. 25414
No. 74, copolymer of polyacrylamide and imidized polyacrylamide, German Patent No. 120213
No. 2, copolymer of acrylamide and methacrylamide, partially aminated acrylamide polymer described in U.S. Pat. No. 3,284,207, Japanese Patent Publication No. 45-1
No. 4031, U.S. Pat. Nos. 3,713,834 and 37,465.
No. 48, the substituted acrylamide polymer described in British Patent 788,343. (10) Polymer having hydroxyquinoline The polymer having hydroxyquinoline described in U.S. Pat. Nos. 4,030,929 and 4,152,161. (11) Others A vinyl polymer having an azaindene group described in JP-A-59-8604, a polyalkylene oxide derivative described in U.S. Pat. No. 2,976,150, a polyvinylamine imide polymer described in U.S. Pat.
No. 94920, No. 4089688, polyvinyl pyridine described in U.S. Pat. No. 2,484,456, vinyl polymer having imidazole group described in U.S. Pat. No. 3,520,857, vinyl polymer having triazole group described in JP-B-60-658, Zeitschrift Bisenshaftrich Photography 45, 43 (1
950) The water-soluble polyalkyleneaminotriazoles according to the above.

For a specific apparatus for forming ultrafine particles according to the present invention, see, for example, Japanese Patent Application No. 63-318382.
No. 63-318381, No. 63-325797
And the ultrafine particle forming method described in JP-A-63-322171 can be referred to. The constitution of the mixer is disclosed in Japanese Patent Application No. 63-322169, and the desalting and thickening of the ultrafine grain emulsion by a functional film is disclosed in Japanese Patent Application No. 63-3259.
No. 80 etc. can be referred to.

For the preparation of the ultrafine particles according to the present invention, a stirrer (pipeline mixer) used in the method for producing silver halide fine particles described in Japanese Patent Application No. 8-207219 can be particularly preferably used.

FIG. 1 shows an example of the stirring device (pipeline mixer). This stirring device is provided with a stirring tank provided with a predetermined number of liquid supply ports through which a liquid to be stirred is introduced and a liquid discharge port through which the liquid after the stirring process is discharged, and is separated into two opposing positions in the stirring tank. It is characterized by comprising a pair of stirring blades arranged and driven to rotate in opposite directions to each other.

As shown in FIG. 1, the stirrer 10 has three liquid supply ports 11, 12 through which the liquid to be stirred flows.
13, a cylindrical stirring tank 18 provided with a liquid discharge port 16 for discharging the mixed liquid after the stirring process,
A pair of agitating blades 21, which are agitating means for controlling the agitating state of the liquid in the agitating tank 18 by being rotationally driven in the
22.

The stirring tank 18 is composed of a cylindrical tank body 19 whose central axis is directed in the vertical direction, and a seal plate 20 serving as a tank wall for closing upper and lower open ends of the tank body 19. Further, the stirring tank 18 and the tank main body 19 are formed of a non-magnetic material having excellent magnetic permeability.

The three liquid supply ports 11, 12, and 13 are provided at positions near the lower end of the tank body 19,
Is provided at a position near the upper end of the tank body 19. In the case of this embodiment, the liquid supply port 11 provided at the lowermost end is for supplying the liquid of the main component to be agitated, and the liquid supply ports 12 and 13 provided above the liquid supply port 11 are added to the liquid of the main component. It is for supplying an additive liquid to be uniformly stirred and mixed with the liquid of the main component.

The pair of agitating blades 21 and 22 are spaced apart from each other at upper and lower ends in the agitating tank 18 and are driven to rotate in opposite directions.

Each of the stirring blades 21 and 22 is
A magnetic coupling C is formed with an external magnet 26 disposed outside the tank wall (seal plate 20) in which the adjacent magnet 22 is located. That is, the stirring blades 21 and 22 are connected to the respective external magnets 26 by magnetic force, and the respective external magnets 26 are rotationally driven by independent motors 28 and 29 to be rotated in opposite directions.

In the stirring device 10 described above, the pair of stirring blades 21 and 22 opposed to each other in the tank 18 are respectively arranged as shown by a dashed arrow (X) and a solid arrow (Y) in FIG. Stirring flows having different directions are formed in the tank 18.

According to this production method, an aqueous solution of a water-soluble silver salt and an aqueous solution of a water-soluble halide are supplied to and mixed with the stirring layer having an inner volume of several ml to form silver halide fine particles. By discharging the fine particles from the agitating layer, it is possible to prevent the fine particles from growing and increasing in size, and to obtain silver halide fine particles having a very small size.

The size of the silver halide fine particles obtained by the above-mentioned production method strongly depends on the number of rotations of the stirring. In order to obtain fine particles having a smaller size, generally, the higher the number of rotations of the stirring, the better.
If the stirring is insufficient, the particles become coarse due to coalescence aging (contact and adhesion of fine particles). The preferred stirring rotation speed is selected in the range of 500 to 10000 rpm, and more preferably in the range of 1000 to 10000 rpm.

The size of the silver halide fine grains obtained by the above-mentioned production method strongly depends on the residence time of the fine grain emulsion in the mixing vessel. In order to obtain small-sized fine grains, the shorter the residence time, the better. Here, the residence time is defined below.

T = c / v t: fine particle emulsion residence time (sec) c: internal volume of mixing vessel (ml) v: total amount of liquid added to mixing vessel per unit time (ml · s)
ec ^-1 )

In the present invention, the preferred residence time t is 60
Seconds or less, more preferably 10 seconds or less, and most preferably 2 seconds or less.
Seconds or less. The lower limit of the residence time t is not particularly limited, but is about 0.1 second.

In the method for epitaxially growing silver halide fine grains of the present invention, halogen conversion can be uniformly performed between grains by, for example, the same method as disclosed in Japanese Patent Application No. 8-20721.
The stirring apparatus used in the method for producing silver halide fine grain emulsion described in No. 9 can be preferably used.

That is, the silver halide fine grain emulsion is introduced into the stirring device immediately after the preparation, and a halogen salt aqueous solution having a desired halogen composition is added thereto, whereby uniform halogen conversion can be achieved.

The silver halide fine particles of the present invention are freed of excess water-soluble salts by a known method, but desalting by ultrafiltration is particularly preferable. The specific apparatus is described in, for example, JP-A-2-172816. There is a description in the issue.

The silver halide fine grain emulsion of the present invention can be spectrally sensitized.

As the spectral sensitizing dye used in the present invention, a methine dye is usually preferably used.

The methine dyes include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, hemioxonol dyes, and the like.

As the above-mentioned dyes, any of nuclei usually used for cyanine dyes can be applied as basic heterocyclic nuclei, that is, a pyrroline nucleus, an oxazoline nucleus,
Thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc., and nuclei obtained by fusing alicyclic hydrocarbon rings to these nuclei and aromatic hydrocarbon rings Nuclei fused with, i.e., indolenine nucleus, benzindolenin nucleus, indole nucleus, benzoxadol nucleus, naphthoxadol nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. Where applicable, these nuclei may be substituted on carbon atoms.

The merocyanine dye or the complex merocyanine dye includes, as nuclei having a ketomethylene structure, pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidin-2,4-dione nucleus, and thiazolidine-2,4-nucleus.
5 such as dione nucleus, rhodanine nucleus and thiobarbituric acid nucleus
A 6-membered heterocyclic nucleus can be applied.

The silver halide fine grain emulsion of the present invention can be chemically sensitized.

More specifically, a sulfur sensitization method using a compound containing a sulfur capable of reacting with active gelatin or silver, for example, thiosulfate, thioureas, mercapto compounds, rhodanins, etc .; Tin salts, amines,
Reduction sensitization using hydrazine derivatives, formamidine sulfines, silane compounds and the like, and noble metal sensitization using noble metal compounds such as gold complex salts and complex salts of metals such as Pt, Ir, and Pd alone or in combination can be used. it can.

The silver halide fine grain emulsion of the present invention can contain various compounds for the purpose of preventing fog and stabilizing photographic performance.

That is, azoles (for example, benzothiazolium salts, nitroindazoles, triazoles,
Benzotriazoles, benzimidazoles (particularly nitro or halogen-substituted)), heterocyclic mercapto compounds (eg, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles,
Mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines, the above heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group, thioketo compounds (for example, oxazoline), Azaindenes (for example, tetraazaindenes (especially 4-
Many compounds known as antifoggants or stabilizers can be added, such as hydroxy-substituted (1,3,3a, 7) tetraazaindenes), benzenethiosulfonic acids, benzenesulfines and the like.

Various additives of the silver halide fine grain emulsion of the present invention, for example, a binder, a chemical sensitizer, a spectral sensitizer,
Stabilizer, gelatin hardener, surfactant, antistatic agent, polymer latex, matting agent, color coupler, ultraviolet absorber, anti-fading agent, support for dye and photosensitive material, coating method, exposure method, development method, etc. Is not particularly limited, for example, Research Disclosure Volume 176,
Item 17643 (RD-17643), 187
Volume, Item 18716 (RD-18716) and 225, Item 22534 (RD-22534). The following is a part of the description.

Additive type RD17643 RD18716 RD22534 1) Chemical sensitizer page 23, page 648, right column, page 24 2) Sensitivity enhancer Same as above 3) Spectral sensitizer, strong color, pages 23-24, page 648, right column, pages 24-28 Sensitizer 〜 Right column on page 649 4) Whitening agent page 24 5) Antifoggant and page 24 -25 Right column on page 24, page 31 Stabilizer 6) Light absorber, fill 25-26 on page 649 right column Ter dyes, ultraviolet rays 頁 Page 650 Left column Absorbent 7) Stain inhibitor 25 Page Right column 650 8) Dye image stabilizer 25 Page 32 9) Hardener 26 Page 651 Left column 28 10) Binder 26 Same as above 11) Plasticizer, lubricant page 27, page 650, right column 12) Coating aid, surface activity 26 to 27 Same as above 13) Antistatic agent 27 page Same as above 14) Color coupler 25 page 649 page 31

In the present invention, two silver halide emulsion layers
When it has more than one layer, it is preferred that all of the layers contain the silver halide emulsion of the present invention.

The excellent sharpness possessed by the silver halide photographic light-sensitive material of the present invention is a property exhibited regardless of the exposure method. In order to make effective use of this excellent sharpness, the resolution of the image recording method itself is required. Is also preferably high. As a preferable example of the exposure method for performing such high-resolution image recording, use of a light source having a short wavelength (for example, a light source having a short wavelength ultraviolet component such as a mercury lamp, and X-rays as a short-wave electromagnetic wave) is used. Use of a light source having high directivity (laser or the like), and exposure with an electron beam may be considered.

In holographic image recording, interference fringes of light generated by interference between light (object wave) from a subject and a reference wave are recorded on a recording surface of a photographic light-sensitive material, and at the time of image reproduction, the recorded interference fringes are used. In order to reproduce a stereoscopic image corresponding to the original object wave, the quality of a holographic image is greatly influenced by how faithfully the photographic material can record interference fringes of light generated as described above. Therefore, the high sharpness realized by the silver halide photographic light-sensitive material of the present invention is extremely useful for holographic image recording.

Regarding the implementation of holographic image recording, see, for example, M. Smith ed. "Hologr
aphic Recording Material
s "Springer Verlag 1977 and the like can be referred to.

The resolving power of image recording by a single light source can be enhanced by using a light source having a short wavelength as described above or by using a light source having a high directivity. Except for a special case using the interference of light, it is in principle impossible to obtain a resolving power below the wavelength using light. There are restrictions on the light sources that can be used practically, and the resolution of image recording by light is naturally limited.

In order to obtain a higher resolution, an image recording using an electron beam has been attempted as a means to overcome the above-mentioned limit. Since the wavelength of the electron beam becomes shorter as the accelerating voltage becomes higher, the resolution of image recording by this is easily increased as compared with the case of using light, but when a conventional silver halide photographic material is used as a recording medium, the photosensitive material itself is used. Resolution was a constraint. Therefore, the high sharpness achieved by the silver halide photographic light-sensitive material of the present invention is extremely useful for electron beam image recording.

Regarding the above-mentioned electron beam exposure for the purpose of obtaining a high resolution, see, for example, “Electron / Ion Beam Handbook (2nd edition)” edited by the 132nd Committee of the Japan Society for the Promotion of Science.
Nikkan Kogyo Shimbun 1986 or the like can be referred to.

In the case of electron beam image recording, an electron beam applied to a recording medium during recording forms energy by forming a latent image on silver halide crystals in the film or diffusing the film through the film. Although the electrons lose energy and become low energy electrons, they gradually accumulate charges on the film surface, causing deflection of an electron beam for image recording that comes later, resulting in distortion of the recorded image.
As a means for preventing this phenomenon and performing image recording without distortion, it is possible to impart conductivity to a photosensitive material for electron beam recording and prevent charge accumulation. The silver halide fine particles in the silver halide photographic light-sensitive material of the present invention have relatively low sensitivity due to their small size, and the electron beam irradiation amount tends to be large when performing electron beam image recording. Is particularly preferable. For the specific method for producing this conductive layer, see, for example, the descriptions in the specifications and publications of US Pat. No. 3,336,596, British Patent No. 1340403, JP-B-49-24282, and JP-A-64-70742, and references cited therein. Can be

As described above, the silver halide photographic light-sensitive material of the present invention has relatively low sensitivity due to the small size of the silver halide fine particles contained therein. Is relatively increased. On the other hand, when an image is recorded at a high density on the order of several microns to sub-microns, pattern exposure through a mask is performed, but scanning exposure capable of precisely controlling image recording is also preferably performed. Either type of image recording method can be preferably applied to the silver halide photographic light-sensitive material of the present invention, but the latter image recording method by scanning exposure is particularly preferably used for the silver halide photographic light-sensitive material of the present invention.

Since image recording by scanning exposure is performed by moving a fine spot-like light beam on a recording medium, the exposure time of each part is short. In order to expose the silver halide grains, a certain amount or more of exposure is required, so that the illuminance of the exposed part is generally high so that the required amount of exposure is given in a short time in the exposure for scanning exposure. . In such high-illuminance short-time exposure, the decrease in sensitivity due to the use of the silver halide photographic light-sensitive material of the present invention is relatively small. This is presumably because the silver halide fine particles of the present invention are extremely small and thus have low sensitivity, but are less likely to cause a latent image dispersion which tends to become apparent at high illuminance.

The silver halide fine grain emulsion of the present invention can be used for a photographic material having an arbitrary layer constitution. Further, the present invention can be applied to a color photosensitive material, a photosensitive material for X-rays, a photosensitive material for black-and-white photography, a photosensitive material for plate making, a photographic paper, and the like.

The silver halide fine grain emulsion of the present invention can be used for a heat-developable silver halide photosensitive material. The heat-developable silver halide light-sensitive material comprises a light-sensitive silver halide emulsion, an organic silver salt, a reducing agent for the organic silver salt, a binder, and if necessary, a color tone agent, and the like.
It is developed by applying heat of 200 ° C. Such photosensitive materials are disclosed in US Pat. No. 4,258,129,
-160166 and the like.

Further, the present invention can be applied to a heat-developable silver halide color light-sensitive material.
And Nos. 6-337510 and 5-127334.

[0075]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited to these examples. Example 1 (Preparation of silver halide fine grain emulsion) Silver chloride fine grain emulsion (1-1) (comparative example) In this example, the pipeline mixer shown in FIG. 1 was used. The mixing vessel of this pipeline mixer has an internal volume of 2
It is a closed cylinder of ml and has stirring blades that can rotate at high speed in the opposite direction above and below inside.

A 0.5N silver nitrate aqueous solution and a 0.5N sodium chloride aqueous solution were added at 25 ml / min and 30 ml / min, respectively, and simultaneously a protective colloid aqueous solution was added at 50 ml / min. 300
It contains 15 g of low molecular weight gelatin dissolved in 15 g per liter of aqueous solution.

The above solution was stirred in a mixing vessel at a rotational speed of 200 rpm.
The mixture was vigorously stirred at 0 rpm and mixed quickly and uniformly to obtain a silver halide fine grain emulsion. This emulsion stays in the mixing vessel for about 1 second and is immediately discharged out of the vessel. The emulsion is introduced directly into an ultrafiltration membrane to remove excess water-soluble salts and concentrated to an appropriate concentration for preparing a coating solution. did. The concentrated emulsion was redispersed in an aqueous gelatin solution, resulting in an emulsion 100
A silver halide fine grain emulsion having a silver amount of 45 g per 0 g was obtained.

When the silver halide fine particles were observed at a magnification of 20,000 with a direct method transmission electron microscope (direct method TEM), the silver halide fine particles immediately after preparation by the pipeline mixer had an average particle size of 0.02 μm. However, as a result of the increase in particle size after concentration and re-dispersion, spherical particles having an average particle size of 0.10 μm were obtained. Incidentally, the halogen composition of the obtained spherical particles is AgCl10
It was 0 mol%.

Silver Chloride Fine Particle Emulsion (1-2) (Comparative Example) A silver halide fine particle emulsion was prepared in the same manner as in the above (1-1). However, the emulsion stayed in the mixing vessel for about 1 second, was immediately discharged out of the vessel, and was introduced into a second stirring device similar to the stirring device. Here, 25% of 0.04N potassium iodide aqueous solution was used for halogen conversion.
Added at ml / min. The emulsion was retained in the second mixing vessel for about 1 second, immediately discharged out of the vessel, introduced into an ultrafiltration membrane to remove excess water-soluble salts, and concentrated. The emulsion was redispersed in an aqueous gelatin solution, resulting in an emulsion 100
A silver halide fine grain emulsion having a silver amount of 45 g per 0 g was obtained.

When the silver halide fine particles were observed at a magnification of 20,000 with a direct transmission electron microscope, the silver halide fine particles immediately after preparation and before concentration and redispersion had an average particle size of 0.01.
It was a cube having an epitaxy part at a corner of 5 μm, but after concentration and redispersion, an average particle size of 0.06 μm
Of amorphous particles. The halogen composition of the obtained irregular-shaped particles was 92 mol% of AgCl and 8 mol% of AgI.

Silver chloride fine grain emulsion (1-3) (Invention) A silver halide fine grain emulsion was prepared in the same manner as in the above (1-2). However, the water-soluble halide aqueous solution added to the second stirring device for halogen conversion is 0.01
An aqueous solution of potassium bromide N and an aqueous solution of potassium iodide 0.06N were added at 25 ml / min. The emulsion was concentrated and redispersed in the same manner as in the above (1-2), and as a result, a silver halide fine grain emulsion having a silver amount of 45 g per 1000 g of the emulsion was obtained.

When the silver halide fine particles were observed at a magnification of 20,000 with a direct transmission electron microscope, the silver halide fine particles immediately after preparation and before concentration and redispersion had an average particle size of 0.02.
After concentration and redispersion, the particles were cubic particles having an epitaxy part at a corner having an average particle size of 0.03 μm. The halogen composition after concentration and redispersion of the obtained particles was 86 mol% of AgCl, 2 mol% of AgBr, and 12 mol% of AgI, and the ratio of the epitaxy portion to the whole particles was about 14 vol%. TEM photographs corresponding to these fine particles are shown in FIGS.

Silver chloride fine grain emulsion (1-4) (Invention) A silver halide fine grain emulsion was prepared in the same manner as in the above (1-3). However, the water-soluble halide aqueous solution added to the second stirring device for halogen conversion is 0.05
An N aqueous potassium bromide solution and a 0.05 N aqueous potassium iodide solution were added at 25 ml / min. The emulsion was concentrated and redispersed in the same manner as in the above (1-3), and as a result, a silver halide fine grain emulsion having a silver amount of 45 g per 1000 g of the emulsion was obtained.

When the silver halide fine particles were observed at a magnification of 20,000 with a direct transmission electron microscope, the silver halide fine particles immediately after preparation and before concentration and dispersion had an average particle size of 0.015.
Even after concentration and redispersion, the particles were cubic particles having an epitaxy part at a corner having an average particle size of 0.015 μm. The halogen composition after concentration and re-dispersion of the obtained particles was 80 mol% of AgCl, 10 mol% of AgBr, and 10 mol% of AgI, and the ratio of the epitaxy portion to the whole particles was about 20% by volume. TEM photographs corresponding to these fine particles are shown in FIGS.

The average grain size of the above emulsion is summarized below. Emulsion Size immediately after preparation / μm Size after concentration / redispersion / μm 1-1 (Comparative Example) 0.02 0.1 1-2 (Comparative Example) 0.015 0.06 1-3 (Invention) 0.0250 .03 1-4 (the present invention) 0.015 0.015

As described above, silver chloride fine particles have high solubility, and an increase in the particle size is usually unavoidable in the process of concentration and redispersion. However, the iodine conversion or iodobromo conversion immediately after the preparation of the fine particles increases the particle size. And a stable silver halide fine grain emulsion having a very small size can be obtained.

Example 2 (Application to Holographic Image Recording) Emulsions 1-1 to 4 were each heated and dissolved at 40 ° C., and spectral sensitizing dye V-5 was added in an amount of 0.044 mol per mol of silver halide. did.

Further, a surfactant, a hardening agent and a preservative were added and the temperature was kept at 40 ° C., and this was coated on an undercoated cellulose triacetate film support with a thickness of 7 μm and a coated silver amount of 5 g / m 2.
² to prepare silver halide photographic light-sensitive materials, which were designated as Samples 2-1 to 4-2, respectively.

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With respect to Samples 2-1 to 4-2, light having a wavelength of 488 nm of an Ar laser was divided into two light beams by a half mirror, and interference fringes (interval of 0. 0 to 1 in a prism in which xylene was interposed between the samples and closely adhered to each other). 2 μm) and record,
A phase hologram was produced.

The exposure was performed at the optimum exposure amount at which the diffraction efficiency was maximized for each sample.

The sample after exposure was processed with the following steps and a processing solution having the following formulation. Development 20 ° C. 3 minutes Stop 20 ° C. 1 minute Bleaching 20 ° C. 10 minutes Rinse 20 ° C. 2 minutes KI bath 20 ° C. 2 minutes Rinse 20 ° C. 10 minutes Natural drying Developer formulation Pyrogallol 6.0 g L-ascorbic acid 6.0 g Sodium carbonate 30 Make up to 1 liter with water. Stop solution formulation 0.5% acetic acid aqueous solution Bleach solution formulation Ethylenediaminetetraacetate sodium salt 100 g KBr 10 g Make up to 1 liter with water. KI bath formula KI 2.5 g Make up to 1 liter with water.

The values of the diffraction efficiency of each sample at the optimum exposure dose are shown below. Sample Diffraction efficiency (%) 2-1 (comparative example) 10 2-2 (comparative example) 25 2-3 (present invention) 55 2-4 (present invention) 60 As described above, the silver halide photographic light-sensitive material of the present invention The material has an extremely high resolving power, and by using this, the diffraction efficiency (brightness of a reproduced image) at the time of image reproduction is remarkably improved.

Example 3 (Application to Electron Beam Image Recording) In the preparation of Samples 2-1 to 4-2, the spectral sensitizing dye was changed to IV.
−9, and as a support, Japanese Patent Publication No. 49-24282.
Sample 3 using a polyethylene terephthalate film provided with an RbAg ₂ I ₃ discharge film having a nitrocellulose protective film shown in FIG. 2 (b) and having a coating thickness of 1 μm and a coating silver amount of 0.7 g / m ^2. -1 to -4 were produced.

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A parallel line test pattern at an interval of 0.20 μm was recorded on the sample by an electron beam having a beam diameter of 0.10 μm at an acceleration voltage of 70 kV.

The sample after exposure was treated with the following steps and a processing solution having the following formulation. Development 20 ° C 5 minutes Stop 20 ° C 1 minute Fixing 20 ° C 5 minutes Washing 20 ° C 10 minutes Natural drying Developer formulation Metol 2.5 g L-ascorbic acid 10.0 g Nabox 35.0 g KBr 1.0 g To 1 liter with water I do.

Stop solution formulation 0.5% acetic acid aqueous solution Fixing solution formulation Sodium thiosulfate 50.0 g Acetic acid 2.0 g Make up to 1 liter with water.

The results of observation of the developed sample obtained as described above with a high-resolution electrolytic emission scanning electron microscope (Hitachi S-900) are shown below. The evaluation was performed on “constant line width” and “uniformity of line connection”, and was evaluated as × (notably bad), Δ
(Slightly poor), （(good), ◎ (very good).

Sample Developed silver size / μm Line width uniformity Line connection uniformity 3-1 (Comparative example) 0.1 ×× 3-2 (Comparative example) 0.06 ×× 3-3 (Invention) 03 ○ ○ 3-4 (the present invention) 0.015 ◎ ◎

As described above, in the comparative example, since the size of the developed silver is close to the line width of the test pattern, the line width of the test pattern is not constant, and the density of the connection of the lines is conspicuous. In contrast, in the sample of the present invention, the developed silver size was sufficiently smaller than the line width of the test pattern, the line width of the test pattern was constant, and the connection of the lines was uniform.

Example 4 Preparation of Silver Halide Emulsions A-1 to 4 Each of the above emulsions 1-1 to 4 was heated and dissolved at 55 ° C., and 44 mg of sodium thiosulfate and 74 mg of chloroauric acid were added thereto to chemically sensitize the emulsions. And after 60 minutes 4-hydroxy-6-
Methyl-1,3,3a, 7-tetraazaindene 4.4
g and 32 g of the following compound [II] were added, followed by quenching and solidification, and these were designated as emulsions A-1 to A-4, respectively.

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Preparation of Emulsion Coating Solutions A-1 to E-4 Each of the above emulsions A-1 to A-4 was heated and dissolved at 40 ° C., and the following additives were added to obtain emulsion coating solutions. Silver halide fine grain emulsion 1000 g Spectral sensitizing dye [I] 2.6 mmol Supersensitizer [I] 18 mmol Storage stability improver [I] 22 mmol Polyacrylamide (molecular weight 40,000) 8.8 g Trimethylolpropane 1.9 g Polystyrene Sodium sulfonate (molecular weight 600,000) 2.8 g Poly (ethyl acrylate / methacrylic acid) latex 19 g N, N'-ethylenebis- (vinylsulfone acetamide) 1.4 g Spectral sensitizing dye [I], supersensitizer The structural formulas of [I] and the storage stability improving agent [I] are as follows.

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The above were designated as emulsion coating solutions A-1 to A-4.

Preparation of silver halide emulsion B (comparative example) 32 g of gelatin was dissolved in 1 liter of water, and 5 g of sodium chloride and 0.3 g of potassium bromide were placed in a vessel heated to 43 ° C.
g and 46 mg of the compound [I], 400 g of an aqueous solution containing 80 g of silver nitrate and 415 ml of an aqueous solution containing 40 g of potassium bromide and 8 g of sodium chloride were added over 25 minutes by a double jet method, and then 80 g of silver nitrate were added. Of water containing 400 g of potassium bromide, 40 g of potassium bromide, 8 g of sodium chloride and hexachloroiridium (III)
415 ml of an aqueous solution containing potassium acidate (10 ^-7 mol / silver mol)
Was added by the double jet method to prepare cubic, monodisperse (coefficient of variation of projected area diameter: 10%) silver halide grains having an average grain size of 0.2 μm.

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After desalting the above emulsion, 60 g of gelatin was added to adjust the pH to 6.5 and the pAg to 7.5.

Thereafter, the temperature was raised to 55 ° C., and 2 mg of sodium thiosulfate and 3.4 mg of chloroauric acid were added to perform chemical sensitization.
After 60 minutes, 4-hydroxy-6-methyl-1,3,3
250 mg of a, 7-tetraazaindene and compound [II]
After adding 1.8 g, the mixture was quenched and solidified.

Preparation of Emulsion Coating Solution B (Comparative Example) Emulsion B was heated and dissolved at 40 ° C., and additives were added by the following method to prepare an emulsion coating solution. The above was designated as emulsion coating solution B.

Preparation of Emulsion Layer Surface Protective Layer The container was heated to 40 ° C., and additives were added according to the following formulation to prepare a coating solution. Gelatin 100 g Polyacrylamide (molecular weight 40,000) 10 g Sodium polystyrene sulfonate (molecular weight 600,000) 0.6 g N, N'-ethylenebis- (vinyl sulfone acetamide) 1.5 g Polymethacrylate fine particles (average particle size 2.5 μm) 2 1.2 g sodium t-octylphenoxyethoxyethanesulfonate 1.2 g C ₁₆ H ₃₃ O- (CH ₂ CH ₂ O) ₁₀ -H 2.7 g sodium polyacrylate 4 g C ₈ F ₁₇ SO ₃ K 70 mg C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ CH ₂ O) ₄ (CH ₂ ) ₄ -SO ₃ Na 70 mg NaOH (1N) 4 ml Methanol 60 ml Compound [III] 60 mg

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Preparation of Back Layer Coating Solution The container was heated to 40 ° C., and additives were added according to the following formulation to prepare a back layer coating solution. Gelatin 80 g Dye [I] 3.1 g Sodium polystyrene sulfonate 0.6 g Poly (ethyl acrylate / methacrylic acid) latex 15 g N, N'-ethylenebis- (vinylsulfone acetamide) 2.0 g Dye [II] Oil dispersion described in JP-A 61-285445 250 mg as dye itself Surfactant dispersion as described in JP-A-61-28544 of dye [III] 50 mg Compound [III] 60 mg Dye [I] to [III] The structural formula is as shown below.

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Preparation of Back Surface Protective Layer The container was heated to 40 ° C., and additives were added according to the following formulation to prepare a coating solution. Gelatin 80 g Sodium polystyrene sulfonate 0.3 g N, N'-ethylenebis- (vinylsulfone acetamide) 1.7 g Polymethyl methacrylate fine particles (average particle size 3.5 μm) 4 g Sodium t-octylphenoxyethoxy ethanesulfonate 3.6 g NaOH (1N) 6 ml sodium polyacrylate _{2g C 16 H 33 O- (CH} 2 CH 2 O) 10 -H 3.6g C 8 F 17 SO 3 K 50mg C 8 F 17 SO 2 N (C 3 H 7) (CH ₂ CH ₂ O) ₄ (CH ₂ ) ₄ -SO ₃ Na 50 mg Methanol 130 ml Compound (III) 60 mg

Preparation of Coated Samples A-1 to A-4 The back layer coating solution was coated together with the back layer surface protective layer coating solution on one side of a blue-colored polyethylene terephthalate support by a back layer having a gelatin coating amount of 2 g. /
m ² , the gelatin coating amount of the surface protective layer of the back layer is 1 g /
It was applied as a m ^2. Subsequently, on the opposite side of the support, the above-mentioned emulsion coating solutions A-1 to A-4 and the coating solution for the surface protective layer were applied, and the silver coating amount was 0.4 g / m ² and the gelatin coating amount of the surface protective layer was not enough. Each was applied so as to be 1 g / m ² . The above were used as coating samples A-1 to A-4.

Preparation of Coated Sample B (Comparative Example) The above-mentioned back layer coating solution was coated on one side of a blue-colored polyethylene terephthalate support together with the back layer surface protective layer coating solution, and the back layer gelatin coating amount was 2 g. /
m ² , the gelatin coating amount of the surface protective layer of the back layer is 1 g /
It was applied as a m ^2. Subsequently, the emulsion coating solution B and the surface protective layer coating solution described above were coated on the opposite side of the support with a coating amount of 2.2 g / m ² and a gelatin coating amount of the surface protective layer of 1 g / m ^2. It applied so that it might become. The above was designated as coating sample B.

Coated samples A-1 to A-4 prepared as described above
And B were kept at 25 ° C. and 60% temperature and humidity for 7 days after application, and a 780 nm semiconductor laser (FCR7000 Laser Im, manufactured by Fuji Photo Film Co., Ltd.) was used at room temperature.
age Printer type CR-LP414)
Scanning exposure using, the following developer [I],
Development processing was performed with the fixing solution [I].

Developer [I] Composition Potassium hydroxide 24 g Sodium sulfite 40 g Potassium sulfite 50 g Diethylenetriaminepentaacetic acid 10 g Boric acid 10 g Hydroquinone 35 g Diethylene glycol 11 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 6 g 5-methyl Benzotriazole 60 mg Potassium bromide 2 g Acetic acid 1.8 g Compound [IV] 0.3 g Compound [V] 0.2 g Compound [VI] 0.12 g Make up to 1 liter with water. pH adjustment 10.5 The structural formulas of compounds [IV] to [VI] are as shown below.

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Fixer [I] Composition: Ammonium thiosulfate 140 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid disodium dihydrate 25 mg Sodium hydroxide 6 g Make up to 1 liter with water. pH adjustment 5.10 The measurement results of RMS and MTF are shown below.

The RMS is an RMS value when the density of a sample exposed at an exposure amount giving a density of 2.0 is measured by using a 48 μm aperture.

The measurement of MTF is described in “Journal of Applied Photographic Engineering”, No. 6.
Volume (1) 1 to 8 (1980). M
The value of TF was expressed as a relative value when the value of 30 lines / mm of sample B was taken as 100.

Sample RMS MTF A-1 (Comparative Example) 0.021 112 A-2 (Comparative Example) 0.020 118 A-3 (Invention) 0.018 135 A-4 (Invention) 0.017 141 B (Comparative Example) 0.041 100

As described above, it can be seen that the silver halide photographic light-sensitive material of the present invention has extremely good graininess and sharpness.

Example 5 Preparation of Silver Halide Particles C-1 to 4 Each of the emulsions 1-1 to 4 was heated and dissolved at 60 ° C., and 85 μmol of sodium thiosulfate and 2, 3, 4, 5 11-mol of 2,6-pentafluorophenyldiphenylphosphine selenide, tellurium compound 1
15 μmol, chloroauric acid 3.3 μmol, thiocyanic acid 25
After adding 0 μmol and aging for 120 minutes with stirring, the mixture was quenched and solidified, and these were used as silver halide grains C-1 to C-4, respectively.

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Preparation of Silver Halide Grain D (Comparative Example) 22 g of phthalated gelatin and 30 mg of potassium bromide were dissolved in 700 ml of water, the pH was adjusted to 5.0 at a temperature of 35 ° C., and 18.6 g of silver nitrate was obtained. And an aqueous solution of potassium bromide and potassium iodide in a molar ratio of (92/8) were added over 10 minutes by a control double jet method while maintaining the pAg at 7.7. Then, silver nitrate 5
476 ml of an aqueous solution containing 5.4 g, potassium bromide and K
_An aqueous solution containing 0.3 mg of ₂ IrCl ₆ was added over 30 minutes by a control double jet method while maintaining the pAg at 7.7. After completion of the addition, the pH was lowered to cause coagulation sedimentation and desalting treatment, and then 0.1 g of phenoxyethanol was added.
The pH was adjusted to 5.9 and pAg to 8.2. Then 60 ° C
To 85 μmol of sodium thiosulfate per mol of silver
And 2,3,4,5,6-pentafluorophenyldiphenylphosphine selenide in 11 μmol, 15 μmol of tellurium compound 1, 3.3 μmol of chloroauric acid, and 2 of thiocyanic acid
After adding 50 μmol and aging for 120 minutes with stirring, the mixture was rapidly cooled and solidified at 30 ° C. to obtain silver halide grains D.

The silver halide grains D had a silver iodide content of 8 mol% inside the grains, an average of 2 mol%, and an average grain size of 0.1 mol%.
It was 11 μm silver iodobromide fine particles.

Preparation of Organic Fatty Acid Silver Emulsions C-1 to C-4 and D Stearic acid 7 g, arachidic acid 4 g, behenic acid 36
g, 850 ml of distilled water at 90 ° C. while stirring vigorously with 1N
187 ml of an aqueous solution of NaOH was added and reacted for 60 minutes;
After adding 65 ml of 1N-nitric acid, the temperature was lowered to 50 ° C.

Next, the silver halide grains C-1 to C-4 and D prepared in advance were added so that the amount of silver halide was 6.2 mmol. Further, 125 ml of an aqueous solution of 21 g of silver nitrate was added over 100 seconds, and stirring was continued for 10 minutes. Thereafter, 1.24 g of N-bromosuccinimide was added, the mixture was allowed to stand for 10 minutes, and the temperature was lowered to 30 ° C. or lower.

While stirring the aqueous mixture thus prepared, 150 g of butyl acetate was added thereto, followed by stirring. All the organic fatty acid silver salts were poured into the butyl acetate phase, and the aqueous phase was removed together with the salts contained therein. Further, the butyl acetate phase was desalted and dehydrated until the conductivity of the finally removed water became 50 μS / cm. To this, polyvinyl butyral (Electrical Chemical Industry Co., Ltd.)
2.5% by weight of Denka Butyral # 3000-K)
-80 g of butanone solution was added and stirred. Further, 200 g of 2-butanone and 59 g of polyvinyl butyral (BUTVAR ^™ B-76 manufactured by Monsanto) were added, and the mixture was stirred with a homogenizer for 80 minutes. Thereafter, 0.5 mmol of pyridinium hydrobromide perbromide (PHP) was added, and the mixture was stirred for 30 minutes. The above were silver organic fatty acid emulsions C-1 to C-4 and D, respectively.

Preparation of Emulsion Layer Coating Solutions C-1 to 4 and D Each of the organic fatty acid silver emulsions C-1 to 4 and D prepared as described above was prepared by adding the following chemicals to 1 mol of the organic fatty acid silver. A layer coating solution was prepared. CaBr ₂ 6.5 mmol of 2-mercapto-5-methylbenzimidazole 7.65mmol Sensitizing dye A 0.5 mmol 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethyl Hexane 0.27 mol Antifoggant compound II-2 0.025 mol 4-chlorobenzophenone-2-carboxylic acid 0.053 mol Tetrachlorophthalic acid 5.8 mmol Color tone compound I-16 0.04 mol Sumidur-N3500 (Sumitomo Bayer Urethane ( 3.7 g of sensitizing dye A, antifoggant compound II-2, and color tone compound I-16 are as follows.

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The above were used as emulsion layer coating solutions C-1 to C-4 and D, respectively.

Preparation of Surface Protective Layer Coating Solution A surface protective layer coating solution was prepared as follows. Cellulose acetate butyrate 7.5 g 2-butanone 80 g methanol 10 g 4-methylphthalic acid 0.3 g 4,6-ditrichloromethyl-2-phenyltriazine 0.07 g Megafax F-176P (manufactured by Dainippon Ink and Chemicals, Inc.) 2.5 g Preparation of Coating Solution for Backing Layer (Back Layer) A coating solution for the backing layer was prepared as follows. Polyvinyl butyral (10 wt% 2-butanone solution) 150 ml Antihalation dye 1 0.05 g Megafax F-176P (Fluorine surfactant manufactured by Dainippon Ink and Chemicals, Inc.) 0.5 g Sildex H121 (manufactured by Dokai Chemical Co., Ltd.) 0.4 g Sildex H51 (average 5 μm spherical silica manufactured by Dokai Chemical Co., Ltd.) 0.4 g

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The backing layer coating solution prepared as described above was applied to a biaxially stretched blue colored 175 μm thick polyethylene terephthalate film so that the absorbance at 810 nm was higher than that of the polyethylene terephthalate film by 1.2. .

Preparation of Coating Sample Each of the emulsion layer coating liquids C-1 to C-4 and D was coated on the opposite side of the polyethylene terephthalate film coated with the backing layer so that the coated silver amount was 1.8 g / m ^2. And dried. Thereafter, the coating solution for the surface protective layer was applied so that the cellulose acetate butyrate was 2.5 g / m ² . Each of the above was applied sample C-1
4 and D.

Evaluation of photographic performance The coating samples C-1 to 4 and D were imagewise exposed using a semiconductor laser of 810 nm by modifying FCR7000 manufactured by Fuji Photo Film Co., Ltd. The exposure laser angle was set to 80 degrees. Heat treatment is 1
The mixture was uniformly heated at 20 ° C. for 20 seconds.

The results of measurement of RMS and MTF in the same manner as in Example 4 are shown below.

The cloudiness after image formation was visually evaluated. The results were evaluated on a 5-point scale, with 5 being the best level at which virtually no cloudiness was perceivable, 3 being a level with some cloudiness, 1 being the worst and unacceptably severe cloudiness level, and 4 being 5 and 3 Is between 3 and 1.

Sample RMS MTF Cloudy C-1 (Comparative Example) 0.018 105 2 C-2 (Comparative Example) 0.017 107 3 C-3 (Invention) 0.014 120 5 C-4 (Invention) 0.012 125 5 D (Comparative Example) 0.021 100 1 As described above, it can be seen that the photothermographic material of the invention has extremely good graininess and sharpness, and does not have white turbidity after image formation.

Example 6 Preparation of Silver Halide Particles E-1 to E-4 Each of the emulsions 1-1 to 4 was heated and dissolved at 60 ° C., and 85 μmol of sodium thiosulfate and 2, 3, 4, 5 , 6-pentafluorophenyldiphenylphosphine selenide, 6 μmol, tellurium compound 1 1.7 μmol, chloroauric acid 3.9 μmol, thiocyanic acid 22
0 μmol was added and the mixture was aged for 120 minutes. Thereafter, the temperature was changed to 50 ° C., and 0.5 mmol of sensitizing dye C and 0.2 mmol of sensitizing dye D were added to 1 mol of silver halide with stirring. Further, 3.7 mol of potassium iodide is added to silver.
1%, stirred for 30 minutes and quenched and solidified at 30 ° C. These were used as silver halide grains E-1 to E-4. The structural formulas of the sensitizing dyes C and D are as follows.

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Preparation of silver halide grains F (Comparative Example) After dissolving 22 g of phthalated gelatin and 30 mg of potassium bromide in 700 ml of water and adjusting the pH to 5.0 at a temperature of 40 ° C., 18.6 g of silver nitrate was added. An aqueous solution containing 159 ml of an aqueous solution containing potassium bromide and potassium iodide at a molar ratio of 92: 8 was added over 10 minutes by a controlled double jet method while maintaining a pAg of 7.8. Then silver nitrate 5
476 ml of an aqueous solution containing 5.4 g and an aqueous solution containing 6 μmol / l of dipotassium hexachloroiridate and 1 mol / l of potassium bromide were added over 30 minutes by a controlled double jet method while maintaining the pAg at 7.6. Then pH
Then, the solution was subjected to coagulation and sedimentation for desalting, and 0.2 g of phenoxyethanol was added to adjust the pH to 5.9 and the pAg to 8.0. Cubic grains having a silver iodide content of 8 mol% of the core, an average of 2 mol%, and a grain size of 0.12 μm were obtained.

The temperature of the silver halide grains was raised to 60 ° C., and 85 μmol of sodium thiosulfate and 2,3,4,5,6-pentafluorophenyldiphenylphosphine selenide were added per mol of silver. 6 μmol, 1.7 μmol of tellurium compound 1, 3.9 μmol of chloroauric acid and 220 μmol of thiocyanic acid were added, and the mixture was aged for 120 minutes.
Thereafter, the temperature was changed to 50 ° C., and sensitizing dye C was 0.5 mmol and sensitizing dye D was 0.2 mmol per 1 mol of silver halide.
l Added with stirring. Further, 3.7 mol% of potassium iodide was added to silver, and the mixture was stirred for 30 minutes and rapidly cooled to 30 ° C. to obtain silver halide grains F.

Preparation of Organic Acid Silver Microcrystal Dispersion B 40 g of behenic acid, 7.3 g of stearic acid and 500 ml of water were stirred at a temperature of 90 ° C. for 20 minutes, and 187 ml of 1N NaOH was added.
Was added over 15 minutes, 61 ml of a 1N aqueous nitric acid solution was added, and the temperature was lowered to 50 ° C. Next, 1N silver nitrate aqueous solution 124
ml was added over 2 minutes, and the mixture was stirred for 40 minutes.
Thereafter, the solid content was separated by centrifugal filtration, and the conductivity of the filtrate was 30%.
The solid content was washed with water until it reached μS / cm. The solid thus obtained was handled as a wet cake without drying, and 12 g of polyvinyl alcohol and 150 ml of water were added to a wet cake equivalent to 33.4 g of dry solid, and mixed well to form a slurry. This slurry was charged into a dispersing machine (trade name: Microfluidizer M110E / H, manufactured by Microfluidics Corporation, wall collision type chamber) to perform a dispersion operation. The pressure at the time of the collision at this time was 500 kg / cm ² . In this way, the preparation of the microcrystal dispersion B of the silver salt of an organic acid, which is needle-like particles having an average minor axis of 0.04 μm and an average major axis of 0.8 μm by electron microscopy, was completed.

Preparation of Dispersion of Solid Fine Particles of Reducing Agent 1.5 g of hydroxypropylmethylcellulose and water 8 were added to 10 g of 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane.
8.5 ml was added, and the mixture was stirred well and left as a slurry for 3 hours. Then, 0.5 mm zirconia beads 36
0 g was prepared, put into a vessel together with the slurry, and dispersed with a disperser (機 G sand grinder mill: manufactured by Imex Co., Ltd.) for 3 hours to prepare a reducing agent solid fine particle dispersion. As for the particle diameter, 80% by weight of the particles were 0.3 μm or more and 1.0 μm or less.

Preparation of Antifoggant Solid Fine Particle Dispersion 1.5 g of hydroxypropylmethylcellulose and 88.5 g of water were added to 10 g of the antifoggant compound II-24, and the mixture was stirred well and left as a slurry for 3 hours. Thereafter, a solid fine particle dispersion of the antifoggant was prepared in the same manner as the preparation of the reducing agent solid fine particle dispersion. Particle size is 70
wt% was 0.3 μm or more and 1.0 μm or less.

[0161]

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Preparation of Dispersion of Solid Fine Particles of Toning Agent 1.5 g of hydroxypropylmethylcellulose and 88.5 g of water were added to 10 g of the toning compound I-10.
The mixture was added, stirred well, and left for 5 hours. Thereafter, a solid fine particle dispersion of a color tone agent was obtained in the same manner as in the preparation of the reducing agent solid fine particle dispersion. As for the average particle diameter, 60 wt% was 0.3 μm or more and 1.0 μm or less.

[0163]

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Preparation of Solid Fine Particle Dispersion of Development Accelerator To 5 g of 3,4-dihydro-4-oxo-1,2,3-benzotriazine, 0.7 g of hydroxypropylmethylcellulose and 94.3 ml of water may be added. Stir, 2
Left for hours. Thereafter, a solid fine particle dispersion of a development accelerator was prepared in the same manner as in the preparation of the reducing agent solid fine particle dispersion. 70% by weight of average particle size is 0.4μm or more and 1.0μm
It was below.

Preparation of Emulsion Layer Coating Solutions E-1 to E-4 and F With respect to 1 mol of silver in the organic acid silver microcrystal dispersion B, the silver halide grains E-1 to E-4 and F were respectively An emulsion coating solution was prepared by adding 10 mol% of silver halide / 1 mol of organic acid silver and the following polymer latex and raw materials.

LACSTAR 3307B (manufactured by Dainippon Ink and Chemicals, Inc .: SBR latex) 431 g 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane (solid fine particle dispersion) 94g Antifoggant compound II-24 (solid fine particle dispersion) 0.05 mol 3,4-dihydro-4-oxo-1,2,3-benzotriazine (solid fine particle dispersion) 4.6 g Layer coating solutions E-1 to E-4 and F were used.

Preparation of Coating Solution for Emulsion Surface Protective Layer For 10 g of inert gelatin, 0.2 g of surfactant A was added.
6 g, 0.10 g of surfactant B, 1.0 g of silica fine particles (average particle size 2.5 μm), 0.4 g of 1,2- (bisvinylsulfonylacetamide) ethane, and solid fine particle dispersion I- 10 to 0.04 mol per mol of silver
And an amount of 66 g of water was added to form a surface protective layer. The structural formulas of the surfactants A and B are as follows.

[0168]

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[0169]

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Preparation of Coloring Agent Dispersion Compounds 1 and 2 were added to 35 g of ethyl acetate in 2.
5 g and 7.5 g were added and dissolved by stirring. 50 g of a 10% by weight solution of polyvinyl alcohol dissolved in advance was added to the solution, and the mixture was stirred with a homogenizer for 5 minutes. Thereafter, the ethyl acetate was volatilized by removing the solvent, and finally diluted with water to prepare a color former dispersion. The structural formulas of compounds 1 and 2 are as follows.

[0171]

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[0172]

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Preparation of Back Surface Coating Solution For 30 g of polyvinyl alcohol, 51 g of the color former dispersion prepared above, 20 g of Compound 3, 250 g of water and Sildex H121 (Spherical silica manufactured by Dokai Chemical Co., average size 12 μm) 2.0 g was added to obtain a back surface coating solution.

[0174]

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Preparation of Coating Samples E-1 to E-4 and F Emulsion layer coating solutions E-1 to E-4 and F prepared as described above
Was coated on a 175 μm polyethylene terephthalate support tinted with a blue dye so that the coating amount of silver was 1.8 g / m ^2, and the emulsion surface protective layer coating solution was coated on the emulsion coating layer with a gelatin coating amount of 1 g / m ^2. 0.8 g / m ² . After drying, a coating solution for the back side was coated on the surface opposite to the emulsion layer so as to have an optical density of 0.7 at 650 nm.
And

Evaluation of photographic performance Kr laser sensitometer of 647 nm (maximum output 500 m
After exposing each of the coated samples at an angle of 30 degrees with respect to the normal line in W), each coated sample was developed at 120 ° C. for 20 seconds. Hereinafter, the measurement results of RMS and MTF measured by the same method as in Example 4 are shown.

The white turbidity after image formation was visually evaluated. The results were evaluated on a five-point scale, where 5 was the best level at which practically no white turbidity was practically perceived, 3 was the level at which white turbidity was a little, and 1 was the most Bad and unacceptably high levels of cloudiness, 4 indicating a level between 5 and 3 and 2 indicating a level between 3 and 1.

Sample RMS MTF white turbidity E-1 (comparative example) 0.019 103 2 E-2 (comparative example) 0.018 105 3 E-3 (present invention) 0.013 124 5 E-4 (present invention) 0.012 127 5 F (Comparative Example) 0.024 100 1 As described above, it is found that the heat developable photosensitive material of the present invention has extremely good graininess and sharpness, and does not have white turbidity after image formation. .

[0179]

As described above, the silver halide photographic light-sensitive material of the present invention makes it possible to record high-quality images excellent in graininess and sharpness.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram of a stirring device used in the present invention.

FIG. 2 is a drawing substitute photograph showing a grain structure, which is a direct method TEM photograph of silver halide fine particles.

FIG. 3 is a drawing substitute photograph showing a grain structure, and is a direct method TEM photograph of silver halide fine particles.

FIG. 4 is a drawing substitute photograph showing a grain structure, and is a direct method TEM photograph of silver halide fine particles.

FIG. 5 is a drawing substitute photograph showing a grain structure, and is a direct method TEM photograph of silver halide fine particles.

[Explanation of symbols]

 Reference Signs List 10 Stirring device 11, 12, 13 Liquid supply port 16 Liquid discharge port 18 Stirring tank 19 Tank main body 20 Seal plate 21, 22 Stirring blade 26 External magnet 28, 29 Motor

Claims (6)

[Claims] 1. A silver halide photographic material comprising a support and at least one silver halide emulsion layer coated on at least one side of the support, wherein at least one of the silver halide emulsion layers comprises: A silver halide having an average grain size of 0.1 μm or less, having silver halide grains having corners and / or edges and having silver halide epitaxy portions at the corners and / or edges. Photosensitive material. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the average size of the silver halide fine particles is 0.05 μm or less. 3. The silver halide photographic material according to claim 1, wherein said silver halide fine particles are cubic. 4. The method according to claim 1, wherein after the grain formation of said silver halide fine grains is completed, the epitaxy portion is continuously grown.
3. The silver halide photographic material according to any one of 3. 5. The silver halide according to claim 1, wherein the host part of the silver halide fine grains is silver chloride, and the epitaxy part is silver iodide, silver iodobromide or silver bromide. Photosensitive material. 6. The silver halide fine grains whose epitaxy part is silver iodobromide, the silver halide fine grains have a silver iodide content of 2 mol% to 20 mol%, and silver bromide and silver iodide. Is 10 mol% or more 2
The silver halide photographic material according to any one of claims 1 to 5, wherein the content is 0 mol% or less.