JPH10197977A - Manufacture of silver halide emulsion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the method for manufacturing the silver halide emulsion having a high content of flat silver halide grains and a high silver chloride content and a superior sensitivity to graininess ratio and principal (100) faces. SOLUTION: The silver halide emulsion composed mainly of flat silver halide grains having principal faces (100) and a silver chloride content of >=30mol% is prepared by forming first fine grains in a seed crystal forming process and forming further hardly soluble silver salts by conversion to form halogen gap faces, and by controlling a molar ratio of silver salt in a solution to be added to that in a silver halide solution on the receiving side to 0-0.8, and a molar ratio of the total ions of chloride, bromine, and iodine to 0.05 to 10<4> and extinguishing most of nonflat grains present in 5-70% at the end of the first ripening process by raising the chlorine concentration to 1.5-300 times in the second ripening process.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide (hereinafter referred to as "AgX") emulsion useful in the field of photography, and particularly to tabular grains having {100} major planes.
The present invention relates to a method for producing an AgX emulsion.

[0002]

2. Description of the Related Art AgX emulsions containing tabular grains which have been reported so far are described in JP-A-51-88017, EP-A-0534395A1, JP-A-63-271335 and JP-A-5-281.
No. 640, No. 5-313273, No. 6-59360, No. 6-30864
No. 8, No. 7-146522, and No. 7-234470 can be referred to. Tabularization ratio of the emulsion of the example [ratio of tabular emulsion having a {100} major plane and an aspect ratio (diameter / thickness) of 2.0 to 50 to the total projected area of the silver chloride grains] and ( (Sensitivity / granularity) was not sufficient.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a high AgCl having a better flattening rate and a higher (sensitivity / granularity).
The purpose of the present invention is to provide a {100} tabular grain emulsion having a content.

[0004]

The object of the present invention has been attained by the following items. (1) 50 to 100% of the total projected area of all silver halide grains
Has a principal plane of {100} plane and aspect ratio (diameter / thickness)
Are 2.0 to 50 tabular grains, and the entire tabular grain has a Cl ^- content of 3
0 to 99.99 mol% in a method for producing a silver halide emulsion, the production method includes at least each of a seed crystal forming step, a first ripening step, a growing step and a second ripening step, and the following a A) a method for producing a silver halide emulsion having the features of b) and c). a) the seed crystal forming process forms first fine particles (AgX ₁ ), and then a halide salt solution (Xc) or a silver salt solution with Xc is added;
A halogen conversion reaction is caused to the fine particles, and a silver salt (Ag
X ₂ ) layer, and a step of forming a halogen composition gap plane of (AgX ₁ | AgX ₂ ), and [(moles of Ag ^{+ in} the added silver salt solution) / (the Xc 0 to 0.8 and the Xc has the following formula: [(mol number of Cl ⁻ )
/ (Total mole number of Br ⁻ and I ⁻ )] is 0.05 to 10 ⁴ . b) At the end of the first ripening, the projected area of all AgX particles was 5.0
About 70% are nontabular grains having an aspect ratio of 1.5 or less. c) Cl in 1.5 to 300 times the growth year in the second ripening process ^-
By increasing the concentration and aging, 40 to 100% of the non-tabular grains present in the total non-tabular grains having an aspect ratio of 1.5 or less disappear.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The AgX emulsion formed in the present invention
50-100% of the total imaging area of AgX particles, preferably 80-1
00%, more preferably 90-100%, even more preferably 95-100
% Is a tabular grain having a {100} major plane, and the tabular grain has an average aspect ratio of 2.0 or more, preferably 2.0 to 2.0%.
50, more preferably 3.0 to 30. Here, the aspect ratio refers to the (diameter / thickness) of a tabular grain, and the diameter is an area equal to the projected area of a grain when the main plane of the grain is placed on a substrate surface and its projected shape is observed with an electron microscope. Refers to the diameter of the circle with The thickness indicates the distance between the main planes of the tabular grains. The thickness is preferably 0.5 μm or less, 0.02 to 0.3
μm is more preferred, and 0.03-0.2 μm is even more preferred. The average aspect ratio indicates an average value of aspect ratios of all the tabular grains. The projected outline shape of the tabular grains (the outline shape of the edge surface in the top view) is a shape in which one or more of four corners of a right-angled parallelogram and a right-angled parallelogram are non-equivalently missing (details are particularly described). (Refer to the description of Japanese Unexamined Patent Publication Nos. Hei 5-313273 and Hei 7-146522), in which the four corners are equivalently missing [the corner of the main plane within one particle (the maximum missing part). Area / minimum missing area) <2].
In the above case, the shape of the missing portion is approximated by an isosceles triangle. The side length ratio of the equilateral side is preferably 1 to 40%, more preferably 3 to 30% with respect to the side length of the right-angled parallelogram (supplementary quadrilateral) formed when the missing portion is refilled. , 5 to 20%. The adjacent side ratio (length of long side / length of short side) of the right-angled parallelogram and the supplementary quadrangle is 1 to 6, preferably 1 to 4, more preferably 1 to 4.
2.

The tabular grains have a projected circle equivalent particle diameter of 0.15 to 10
μm is preferred, and 0.2-5 μm is more preferred. The overall composition of the tabular grains has a Cl ^- content of 30 to 99.99%, preferably 50 to 99.99%, and more preferably 70 to 99.99%. The diameter distribution of the tabular grains is preferably monodisperse, and the coefficient of variation [(standard deviation × 100) / average diameter] of the distribution is preferably 0 to 40%, more preferably 5 to 30%.
10-20% is most preferred. The molar yield of AgX after the formation of the particles is 0.05 to 2 mol / l, preferably 0.1 to 2 mol / l.
１1 mol / liter.

The production method of the present invention is a method for producing a silver halide emulsion having at least the steps of a seed crystal forming step, a first ripening step, a growing step and a second ripening step in this order. explain. 1) Seed crystal formation process AgNO ₃ solution and halide salt (hereinafter, referred to as X ^- salt) solution are added to a dispersion medium solution containing at least a dispersion medium and water by stirring at the same time by a simultaneous mixing method to obtain first fine particles. (AgX ₁ ) is formed. The concentration of the added AgNO ₃ solution is preferably from 1 to 1000 g / l, more preferably from 10 to 300 g / l. The X
^- halogen composition of salts, Cl ^- molar content: 50 to 100 mol%
Is preferably 70 to 100 mol%, more preferably 95 to 100 mol%.
Molar% is more preferred. Next, a halogen salt solution of Xc or a silver salt solution of Xc is added to cause a halogen conversion reaction on the fine particles, and a silver salt AgX ₂ layer which is more insoluble than the fine particles is formed on the fine particles. A halogen composition gap of (AgX ₁ | AgX ₂ ) is formed. In order to form the defect, it is necessary to set the reaction condition to a {100} plane forming atmosphere. The details can be referred to the description in JP-A-6-308648. When this gap is formed,
By reducing the amount of added Ag ⁺ mole, uniformity among particles in defect formation can be increased. Therefore, the added silver salt solution is [((mol number of Ag ^{+ in} the added silver salt solution) /
(The number of moles of halogen ions in the Xc)] = 0 to 0.8, preferably 0 to 0.4, more preferably 0 to 0.2.

If the gap formation (defect formation amount (C ₁ ) / particle) is too large, the particles finally obtained will be x, y, z
Thick grains having a low aspect ratio, whose growth is promoted in the axial direction, increase, and if too small, non-tabular grains having no defect increase. It is difficult to separately produce only tabular grains whose growth has been promoted only in the x and y axes during the formation of the gap. However, since the non-tabular grains can be eliminated by ripening, the defect formation amount (C ₁ ) is suppressed at the time of forming the gap, and the existence ratio of the tabular grains is reduced by decreasing the proportion of grains promoted in the x, y, and z-axis directions. Can be enhanced. Here, the x and y axes are parallel to and perpendicular to the main plane, and the z axis is perpendicular to the main plane. The defect formation amount increases as increases the halogen composition gap difference AgX ₁ and AgX ₂ is also the molar ratio of (AgX ₂ / AgX ₁₎ increases.

The formation of the defect is controlled by the halogen salt Xc.
When the halogen composition in the solution is [(Cl^-Moles) / (Br^-When
I^-= 0.05 or more, preferably 0.2 to 10
^ThreeIs more preferable, and 0.5 to 10^TwoIs more preferred. Cl^-of
Contains AgX₁And AgX_TwoTo reduce the halogen gap difference
This is for suppressing generation of many defects in the particle nucleus.
Halogen added to perform the conversion reaction
Br in salt solution Xc^-And I ^-Of the host nucleus AgX₁
Is preferably 0.005 to 0.5 times the total silver molar amount of 0.01 to 0.3.
Double is more preferred. Gap plane AgX_TwoLayer thickness is 0.1 atom
Or more layers, more preferably 0.5 to 20 atomic layers. The
AgX₁The size of the nucleus is preferably 0.01 to 0.20 μm, and 0.02 to 0.
1 μm is more preferred, and 0.02 to 0.06 μm is even more preferred.
No.

[0010] After formation of the manner in to (AgX ₁ / AgX ₂₎ particles, but then it is also possible to enter the aging process, further AgNO ₃ solution or AgNO ₃ solution and X _3, ^- the addition of salt solution, (AgX ₁ / Ag
It is more preferable to form X ₂ / AgX ₃ ) particles. X ₃ ^- Shioeki refers to halogen salt solution capable of forming a AgX ₃ layers. here
AgX ₁ and AgX ₃ preferably have substantially the same halogen composition. Here, “substantially the same” means that the content difference between Cl ⁻ , Br ⁻ and I ⁻ is preferably within 30 mol%, more preferably 0 to 0%.
10% by mole. It is the next aging process,
This is because it is possible to substantially prevent the deposition of AgX ₂ from concentrating on the tabular grains and generating more defects in the tabular grains. Here, "substantially" means preferably 50% or less of the existing defect amount, more preferably 0 to 20%, and still more preferably 0 to 10%. The total molar silver added of AgX _{3 is the same as} the total molar silver added of AgX ₁ .
It is preferably 0.01 to 20 times, more preferably 0.1 to 10 times, and 2
~ 5 times is more preferred.

The temperature and pCl at the time of forming the seed crystal can be referred to Table 1. The smaller the size of the nucleus, the easier the first ripening process proceeds. From that point, it is preferable to perform nucleation at a low temperature. On the other hand, in order to cause a halogen conversion reaction and to form the defect, energy is required and high temperature is required. In order to satisfy both, the formation of the AgX ₁ nucleus and the addition of the Xc salt solution may be carried out at a low temperature, and then the temperature may be raised preferably by 2 ° C or higher, more preferably by 5 to 50 ° C.

[0012]

[Table 1]

2) First Ripening Step In the first ripening step, it is preferable to partially eliminate nontabular grains by Ostwald ripening to increase the ratio of tabular grains. Non-tabular grains that have disappeared due to ripening are deposited on tabular grains. In this case, the ripening is preferably performed to such an extent that defects introduced into the tabular grains are not lost. Therefore, it is preferable that 40 to 95%, more preferably 60 to 90%, of the total projected area of the non-tabular grains be eliminated in the first ripening step. In other words, at the end of the first ripening, the total projected area of AgX particles is 5
A preferred embodiment is that the non-flat fine particles account for 6060%, preferably 10-40%. The temperature and pCl value at the time of ripening can also be referred to Table 1. The ripening time can be appropriately selected depending on the amount of nontabular grains that disappear. The first ripening step is a point at which the temperature has risen by 1 ° C. or more from the temperature at the end of the seed crystal forming step, which is the ripening starting point, and indicates the point immediately before the growth step.

In addition, the following method can be preferably used. A method in which an AgX fine grain emulsion is added to form the AgX _three layers. And / or aging while adding an AgNO ₃ solution and a halogen salt solution to form the AgX ₃ layer.

3) Growth Step The tabular grain ratio is increased during the ripening step, and then the grains are grown to a desired size. In this case, 1) AgNO ₃ solution and X ₄ ^- ion addition method to grow with the addition of salt solution, 2) are formed in advance AgX ₄ microparticles, microparticles addition method to grow with the addition of fine particles, 3) both Combination methods may be mentioned. X ₄ ^- Shioeki refers to halogen salt solution capable of forming a AgX ₄ layers. To grow the tabular grains preferentially in the edge direction, the grains may be grown under low supersaturation conditions. Here, the low supersaturation condition means preferably 35% or less, more preferably 2 to 20% at the time of critical addition. The temperature and pCl value of the growth process can also be referred to in Table 1. Regarding the halogen composition structure in the tabular grains, see JP-A-6-308648.
You can refer to the description of the issue. The growth process to X ₄ are added ^- halogen composition or AgX ₄ halogen composition of the fine particles of salt, Cl ^- content: it is preferably 50 to 100 mol%, 70
100 mol% is more preferable, and 95 to 100 mol% is still more preferable.

[0016] (1) ion addition method AgNO ₃ solution and X ₄ ^- salt solution added simultaneously mixing method at a rate of addition that does not substantially generate new nuclei grow tabular grains. Here, “substantially” means that the projected area ratio of the new nucleus is preferably 0 to 10%, more preferably 0 to 1%, and further preferably
Indicates 0%. By selecting the pAg, pH, temperature, supersaturation concentration, etc. of the solution during grain growth, the growth ratio of tabular grains in the thickness direction and edge direction can be selected. When growing under a low supersaturation degree, it grows preferentially in the edge direction. Here, the low degree of supersaturation is 70% or less of the critical addition rate, preferably 5 to 5%.
It refers to the state where the addition is performed at 0% addition rate. The critical addition rate refers to an addition rate at which a new nucleus starts to form when a solute is added at a higher addition rate.

[0017] (2) fine grain emulsion addition method diameter 0.15 [mu] m, preferably 0.01 to 0.1 [mu] m, more preferably by adding AgX ₄ fine grain emulsion 0.02～0.06Myuemu, growing the tabular grains by Ostwald ripening. The fine grain emulsion can be added continuously or intermittently. The fine grain emulsion is continuously prepared by supplying an Ag ⁺ salt solution and an X ₄ ^- salt solution by a mixer provided in the vicinity of the reaction vessel, and can be immediately and continuously added to the reaction vessel, or separately. And then added continuously or intermittently. The fine grain emulsion can be added in a liquid form or as a dry powder. The fine particles preferably do not substantially contain multiple twin particles. Here, the multiple twin particles refer to particles having two or more twin planes per particle. The term "substantially free" means that the proportion of multiple twin grains is 5% or less, preferably 1% or less, more preferably 0 to 0.1% or less. Further, it is preferable that substantially no single twin particles are contained. Further, it is preferable that the composition does not substantially include a screw dislocation. Here, "substantially not included" complies with the above-mentioned rules.

4) Second aging process In the seed crystal forming process, the amount of defect formation (C ₁ ) is suppressed, and x
By reducing the proportion of grains whose growth is promoted in the y, y, and z axis directions, the proportion of tabular grains can be increased. In this case, the proportion of nontabular grains increases. It is difficult to eliminate all of the non-tabular grains only in the first ripening step and the growing step without losing the introduced defects, and the non-tabular grains disappear in the second ripening step after the growing step. It is preferable to erase 40 to 100%, preferably 70 to 100%, more preferably 90 to 100% of the projected area meter of non-tabular grains by the second ripening step, and to further increase the tabular ratio.

As in the first ripening, the non-tabular grains are deposited on the tabular grains by the second ripening step. As the aging pCl value becomes higher, the non-tabular grains are preferentially deposited in the x and y directions of the tabular grains, and tabular grains having a high aspect ratio are obtained. However, as the ripening pCl value increases or the proportion of nontabular grains increases, the ripening time increases to completely eliminate nontabular grains. Therefore, in order to eliminate the non-tabular grains in the second ripening process, the Cl ⁻ concentration is set to 1.5 to 1.5 in the early stage of growth.
300 times, preferably 5 to 100 times, more preferably 10 to 50 times
It is preferable to carry out the second ripening step. Cl for the increase ^- but the addition of salt, timing of addition is after completion of the addition of the total silver in growth late or growth process. The pre-growth period refers to a period during which 1 to 49% of the total amount of added silver in the growth process is added, and the Cl ⁻ concentration in the pre-growth period is the average of the addition period of 1 to 49% of the total added silver amount in the growth process. Cl ^- refers to the concentration. Here, the average Cl ^- concentration is a formula indicating the weighted average of the added silver amount.
It is represented by (1).

[0020]

(Equation 1)

The late stage of growth refers to the time when 50 to 100%, preferably 80 to 100% or more, and more preferably 100%, of the total silver content during the growth process is added. The second ripening time can be appropriately selected depending on the amount of nontabular grains that disappear, but is usually 1 to 120 minutes, preferably 3 to 60 minutes. The temperature and pCl value during the second aging are shown in Table 1.

In each of the above steps, the dispersion medium concentration (% by weight)
) Is usually 0.05 to 10%, preferably 0.1 to 5%. There is no particular limitation on the pH of the container solution, but usually the pH is 1 to 1
2, preferably pH 2-7 is used. The most preferable pH value can be selected and used according to the combination of the excess X ^- concentration, temperature, and the like.

5) Others The tabular grains thus obtained may be used as host grains and epitaxial grains may be formed on the grains. Epitaxial grains can be formed on the main plane, side faces, ridges, one or more corners of tabular grains, and can be formed on one or more types of surfaces thereof. It can be formed over 0.1 to 100%, preferably 1 to 50% of the particle surface area. (Solubility of the tabular grains−solubility of the epitaxial grains) can take a positive aspect or a negative aspect. (As silver mole of silver amount mol / total epitaxial particles in the host particles) is preferably 0.3 to 10 ^3, more preferably 1.0 to 10 ^2. See Jou for these details.
rnal of Imaging Science, 32, 160-177 (1988), Journal of Colloid and Interface
Science, 140, 335-361 (1990)
Year), R. D. (1994), EP 69994
Nos. 4A1 to 699951A1 and the documents described below can be referred to.

For example, KBr or A
It is preferable to add gBr fine particles to form epi, preferably corner epi, on the surface of the particles for the purpose of increasing the sensitivity.
Is added, Br ^- amount is preferably 0.1 to 10 ^-6 mol per host grain silver amount 1 mol, 0.03 to 10 ^-5 mol is more preferable. For details, reference can be made to the description in European Patent No. 584815.

Metal doping, metal complex doping, chemical sensitization, spectral sensitization,
Regarding the color material, the layer structure, and the development processing for the color light-sensitive material, European Patent Nos. 699944A1 to 699995
Nos. 1A1 and 701164A to 701165A can be referred to.

Forming or raffling epitaxial grains on the main plane of the tabular grains to break the flatness (main plane modification) is effective in the following points. 1) The total surface area of the tabular grains is further increased. 2) The interference effect of the tabular grains because the perfection of the parallel plate surface is broken (this is described in “Re
search Disclosure Magazine, Item 255330, May 1985 ").
Therefore, in the case of a multi-layered light-sensitive material, the work of adjusting the particle thickness for reducing the interference effect can be reduced. 3) The so-called light piping effect, in which light is reflected multiple times within the tabular grains and exits from the edge surfaces of the tabular grains, is reduced. Therefore, the light diffusion amount of the incident light in the horizontal direction due to the effect is reduced, and the sharpness of the generated image is improved. 4) Since the electric field vector directions of the light incident on the surface of the tabular grain and the light reflected on the surface are usually in opposite directions, the two interfere with each other, the light intensity decreases, and the spectral sensitization existing on the surface occurs. The excitation light intensity of the dye decreases. When the modification increases the diffuse reflection ratio and reduces the interference effect, the light intensity increases and the light absorption of the dye increases. Therefore, this embodiment can be preferably used.

The degree of modification of the main plane is reduced to 0 to 70%, preferably 0 to 30%, more preferably 0 to 10% when the interference effect of unmodified tabular grains is defined as 100%. The degree is preferred. The modification can be performed on the main plane at various levels and at uneven levels to achieve the object. The light piping effect can be observed using a microspectroscope (for example, the description of a microspectroscope manufactured by Olympus or Hitachi can be referred to). It can be quantitatively determined by taking the observed photograph with a camera and comparing the photographic densities at the edges and the center of the tabular grains with the calibration curve densities. Regarding the modification method,
European Patent No. 215612B1, a document on the above-mentioned epitaxial particles, European Patent Nos. 699944A1 to 69999
Reference can be made to the description of No. 1A1. The parallel plate interference effect is particularly effective in the case of tabular grains having a thickness of 0.075 to 0.30 μm, preferably 0.08 to 0.25 μm. This is because the tabular grains having such a thickness have a large wavelength dependence of the interference effect.

The area ratio of the epitaxial grain forming portion on the main plane is preferably 5 to 100% of the total area of the main plane, more preferably 40 to 90%, and still more preferably 56 to 90%. The height of the epitaxial grains is preferably 0.2 to 5 times, more preferably 0.4 to 2 times the thickness of the tabular grains. In addition, the average AgI content of the side faces of the tabular grains was −
When the average AgI content of the main plane is from 1 to 30 mol%, preferably from 3.5 to 20 mol%, the following advantages are obtained and are preferred. When the tabular grains have the light piping effect, the reflectivity of the edge surface is further increased, and the amount of light exiting the grains from the edge surface is reduced. In addition, since the amount of the adsorbed spectral sensitizing dye on the edge surface is increased, light that goes out from the edge portion is efficiently absorbed by the adsorbed dye. Therefore, this embodiment can also be preferably used. The average AgI content refers to the average AgI content of the layer from the surface to a thickness of 1/10 of the thickness of the tabular grains and the average AgI content of the layer from the edge surface to 0.02 μm.

These tabular grains may be used as cores to form grains having dislocation lines therein. In this regard, JP-A-63-220238 and U.S. Pat.
JP-A-8-62754, JP-A-7-270952,
Nos. 6-230491, 4-166926, 6-
No. 230491 can be referred to. Alternatively, the grains may be used as a substrate, and an AgX layer having a halogen composition different from that of the substrate may be laminated to form various known grain structures. Regarding these, JP-A-1-201651, JP-A-2-28638,
2-943, 3-121445, 5-457
No. 57 and JP-A-60-143331 can be referred to. The change in the halogen composition between layers having different halogen compositions includes a rapid change type and a gradual change type. Further, a shallow inner latent emulsion may be formed using the tabular grains as a core. Further, it is also possible to form a core / shell type inner latent particle. See R. D. (1
994), JP-A-59-133542, 63-1.
No. 51618, U.S. Pat. Nos. 3,206,313, 3,317,322, 3,761,276, 4,269,927, and 3,367,778. be able to.

The tabular grain emulsion is usually provided with a chemical sensitizing nucleus. In this case, it is preferable that the location of the chemical sensitization nucleus and (number / cm ² ) are controlled. Regarding this, JP-A-2-838, JP-A-2-14633,
JP-A-1-201651, JP-A-3-121445, JP-A-64-74540, and the descriptions of the following documents can be referred to.

The AgX emulsion grains produced by the method of the present invention may be used by blending with one or more other AgX emulsions, or two or more of the emulsion grains of the present invention having different particle sizes may be blended and used. Can also. The blend ratio (moles of guest AgX emulsion / moles of AgX emulsion after blending) is preferably in the range of 0.99 to 0.01, and an appropriate ratio can be appropriately selected and used. There are no particular restrictions on the additives that can be added to the emulsion of the present invention during the period from the grain formation to the coating step, and the amounts thereof can be added, and any conventionally known photographic additives can be added in optimal amounts. For example, an AgX solvent, a dopant for AgX particles (for example, a Group 8 noble metal compound, another metal compound, a chalcogen compound, an SCN compound, etc.), a dispersion medium, an antifoggant, a sensitizing dye (blue, green,
Red, infrared, panchromatic, orthorectified, etc., supersensitizers, chemical sensitizers (sulfur, selenium, tellurium, gold and 8th noble metal compounds, phosphorus compounds, rhodan compounds, reduction sensitizers alone and Two or more of these), fogging agents, emulsion sedimenting agents, surfactants, hardeners, dyes, color image forming agents, color photographic additives, soluble silver salts, latent image stabilizers, developers (hydroquinone System compounds), a pressure desensitizing agent, a matting agent, an antistatic agent, a dimensional stabilizer, and the like.

The AgX emulsion prepared by the method of the present invention can be used for all conventionally known photographic light-sensitive materials. For example, black-and-white silver halide photographic light-sensitive materials [for example, X-ray light-sensitive materials, printing light-sensitive materials, photographic paper, negative films, microfilms, direct positive light-sensitive materials, ultrafine dry plate light-sensitive materials (for LSI photomasks, shadow masks) , Liquid crystal masks)], color photographic light-sensitive materials (eg, negative film, photographic paper, reversal film, direct positive color light-sensitive material, silver dye bleaching method, etc.)
Can be used. In addition, diffusion transfer photosensitive materials (for example, color diffusion transfer elements, silver salt diffusion transfer elements), photothermographic materials (black and white, color), high-density digital recording photosensitive materials,
Examples include holographic materials. The preferable amount of the coated silver is 0.01 to 50 (g / m ² ). AgX emulsion production method (particle formation, desalting, chemical sensitization, spectral sensitization, addition method of photographic additive, etc.) and apparatus, AgX particle structure, support, undercoat layer, surface protective layer, constitution of photographic light-sensitive material (E.g., layer composition, silver / color former molar ratio, silver content ratio between layers, etc.) and product form and storage method,
There is no limitation on the emulsification and dispersion of the photographic additive, the exposure method, the development method, and the like, and any technique or mode known in the art or known in the future can be used. For details of these, the description of the following literature can be referred to.

[0033] Research Disclosure
Disclosure), 176 volumes (item 17643) (19
December, '78, Volume 501 (item 36544, 1
Sept. 994), Duffin, Photographic Emulsion Chemistry, Focal Press, N.
ew York (1966), Bill (EJ Birr), Stabilization of Photographic Silver Halide Emulsion
graphic Silver Halide Emulsion, Focal Press, London (1974), James James (TH James), Theory of Photographic Process (The Theory of
Photographic Process) 4th Edition, Macmilla
n), New York (1977)

Grafkides, Chemie et Physique Photographique, 5th edition.
Edition, edition da lysine nouvelle (Edition del,
Usine Nouvelle, Paris (1987), 2nd edition, Paul Montell, Paris (1957), Zelikman et al. (VL Zelikman et al.), Preparation and coating of photographic emulsions (Ma
king and Coating Photographic Emulsion), Focal Pr
ess (1964), KR Hollister, Journal of Imaging Science (Journal)
of Imaging Science), vol. 31, p. 148-156
(1987), JE Maskasky, Vol. 30, P247-254 (1986), Vol. 32, 1
60-177 (1988), 33 volumes, 10-13
(1989),

Ed. Freezer et al., Basics of the Silver Halide Photography Process (Die Grundlagen Der Photographischen Prozesse)
Mit Silverhalogeniden), Akademische Verlaggesellschaf
t), Frankfurt (1968). JCIA Monthly Report 19
1984, December issue, p. 18-27, Journal of the Photographic Society of Japan,
49, 7-12 (1986), 52, 144-
166 (1989), 52, 41-48 (198
9), JP-A-58-113926 to 113939, JP-A-59-90841, JP-A-58-111936, and JP-A-62-118.
99751, 60-143331, 60-1433
32, 61-14630, 62-6241,

JP-A-1-131541, JP-A-2-838,
2-146033, 3-155539, 3-20
0952, 3-246534, 4-34544, 2-28638, 4-109240, 2-73334
6, Japanese Patent Application Nos. 2-326222 and 6-215513,
Other Japanese patents, US patents, European patents, world patents, journals of imaging science, journals in the AgX photography field
Of Photographic Science (Journal of P
hotographic Science), Photographic Science and Engineering
and Engineering), Journal of the Photographic Society of Japan, Abstracts of the Photographic Society of Japan, International Congress of Photographic S
cience and The International East-West Symposium
on the Factors Influencing Photographic Sensitivit
Summary of y's presentation. Japanese Patent Application Nos. 6-104065 and 5-32
4502. The emulsion of the present invention is disclosed in JP-A-62-269958.
Nos. 62-266538 and 63-220238
No. 63-305343, JP-A-8-12295
4, JP-A-8-212522, JP-A-59-142439.
No. 62-253159, JP-A-1-131541
No. 1-297649, No. 2-42, No. 1-15
No. 8429, No. 3-226730, No. 4-15164
9, Japanese Patent Application No. 4-179951, European Patent 05083
It can be preferably used as a constituent emulsion of the coating sample of Example of No. 98A1.

[0037]

Next, the present invention will be described in more detail by way of examples, but embodiments of the present invention are not limited to these examples. Example 1 A reaction vessel containing 1200 cc of H ₂ O, 25 g of gelatin (deionized alkali-treated bone gelatin having a methionine content of about 40 μmol / g), 1 g of NaCl, and 4.5 cc of an HNO ₃ 1N solution was used, and the pH was 4.5.
And kept at 40 ° C. Ag-1 solution (AgNO ₃ 0.2 g / cc) and X-1 solution (NaC
l 0.069 g / cc) was added at 48 cc / min for 12 seconds. 3 minutes later, X-2 solution (mixture of KBr 0.012g / cc and NaCl 0.0014g / cc)
Was added at 62 cc / min for 13 seconds. After 3 minutes, the Ag-1 solution (AgN
O ₃ 0.2g / cc) and X-1 solution (NaCl 0.069g / cc) at 48cc / min.
The co-mixing addition was performed for seconds. Further, as the first aging process, 1
Minutes later, an aqueous gelatin solution (H ₂ O 120 cc, gelatin 10 g, NaOH
7 cc of 1N solution and 1.7 g of NaCl] were added. After 4 minutes, the temperature was raised to 75 ° C. in 12 minutes, and after aging for 25 minutes, Ag-1 solution (AgNO ₃ 0.2 g / cc) and X-1 solution (NaCl 0.069 g / cc) were flowed in the growth process. Simultaneous additions were made for 36 minutes with a linear increase from 7 cc / min to 8.8 cc / min while maintaining pCl at 2.36. The Cl as the second ripening ^- in preparing the pCl to 1.21, was further aged for 20 minutes, improved completely disappeared flattened rate non-tabular grains striking 12% of the projected area meter of all AgX grains. Additive-1 was added, the temperature was lowered to 35 ° C, and the precipitate was washed by settling. An aqueous gelatin solution was added, and the emulsion was redispersed to pH 6.0 and pCl 2.0. Then, the emulsion was collected, and an electron microscope photograph image (TEM image) of the grain replica was observed. According to the report, 98% of the projected area meter of all AgX grains is tabular grains having a {100} major plane, with an average grain size of 1.60 μm and an average grain thickness of 0.26 μm.
m, the average aspect ratio was 6.5, and the change factor was 16.1%.

[0038]

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Example 2 A reaction vessel was charged with [1200 cc of H ₂ O, 25 g of gelatin, 1 g of NaCl,
Including 4.5 cc of HNO ₃ 1N solution and pH 4.5), keep the temperature at 40 ° C, and simultaneously mix Ag-1 solution (AgNO ₃ 0.2 g / cc) and X-1 while stirring.
The solution (NaCl 0.069 g / cc) was added at 48 cc / min for 12 seconds. Three minutes later, solution X-2 (mixture of KI 0.010 g / cc and NaCl 0.0035 g / cc) was added at 62 cc / min for 22 seconds. Fine grain emulsion-2 prepared in advance was added in an amount of AgX of 1.35 × 10 ⁻³ mol. After 3 minutes, the temperature was raised to 75 ° C. in 12 minutes, and simultaneously the Ag-1 solution (AgNO ₃
0.2g / cc) and X-1 solution (NaCl 0.069g / cc) at 48cc / min for 2 minutes
Simultaneous addition was performed for 30 seconds. One minute later, an aqueous gelatin solution (120 cc of H ₂ O, 10 g of gelatin, and 7 cc of a NaOH 1N solution) was added. After 4 minutes, the temperature was raised to 75 ° C. for 12 minutes, and after aging for 25 minutes, Ag-1 solution (AgNO ₃ 0.2 g / cc) and X-
One solution (NaCl 0.069 g / cc) was added simultaneously for 36 minutes while linearly increasing the flow rate from 7 cc / min to 8.8 cc / min while keeping pCl 2.36 constant. Then Cl as the second ripening ^- with pCl 1.21
After aging for 20 minutes, 50% of non-tabular grains in the projected area meter of all AgX grains disappeared, and the tabularization rate was improved. Then, the emulsion is collected, and an electron micrograph image of the grain replica is taken.
(TEM image) was observed. Collect the emulsion and make a replica of the grain.
The TEM image was observed. According to the report, 95.2% of the total projected area of all AgX grains are tabular grains having a {100} major plane, with an average grain size of 2.35 μm and an average grain thickness of 0.22 μm.
The average aspect ratio was 11.1 and the coefficient of variation was 20%.

Comparative Example 1 In Example 1, an Ag-2 solution (AgNO ₃ 0.02 g / c) was used instead of the X-2 solution.
c) and X-21 solution (KBr 0.014 g / cc) at 62 cc / min for 22 seconds,
Simultaneous addition was performed. Others were the same as Example 1. Similarly, Ag-1 solution (AgNO ₃ 0.2 g / cc) and X-1 solution (N
aCl (0.069 g / cc) was added simultaneously for 36 minutes while linearly increasing the flow rate from 7 cc / min to 8.8 cc / min while maintaining pCl at 2.36. Additive-1 was added, the temperature was lowered to 35 ° C, and the precipitate was washed by settling. An aqueous gelatin solution was added, and the emulsion was redispersed.
6.0 and pCl 2.0. Then, the emulsion was collected, and an electron microscope photograph image (TEM image) of the grain replica was observed. According to the report, 90% of the projected area meter of all AgX particles has a principal plane of ｛10
0-plane tabular grains, the average grain size of which is 1.2 μm,
The average grain thickness was 0.22 μm, the average aspect ratio was 5.5, and the change factor was 23%.

The emulsions of Example 1 and Comparative Example 2 were each subjected to the following chemical sensitization. Chemical sensitization The particles prepared as described above were subjected to chemical sensitization while being kept at 56 ° C. while stirring. First, a thiosulfonic acid compound
1 × 10 ^-4 mol per mol of silver halide, and then AgBr fine particles having an average grain diameter of 0.10 μm are added at 1.0 mol% with respect to the total silver amount. After 5 minutes, a 1% by weight KI solution is added. Was added at 1 × 10 ^-3 mol per mol of silver halide, and 3
One minute later, 1 × 10 ⁻³ mol / mol Ag of thiourea dioxide was added, and the mixture was kept as it was for 22 minutes to perform reduction sensitization. Next, 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene was added to 3 × 10 ^-4 mol / mol Ag and a sensitizing dye.
1, 2, and 3 were added, respectively. Further, 1 × 10 ⁻³ mol / mol Ag of calcium chloride was added. Furthermore, chloroauric acid 1
× 10 ^-6 mol / mol Ag and potassium thiocyanate 3.0
× 10 ^-3 mol / mol Ag, followed by sodium thiosulfate (6 × 10 ^-6 mol / mol Ag) and selenium compound-
1 (4 × 10 ⁻⁶ mol / mol Ag) was added. After a further 3 minutes, the nucleic acid (0.5 g / mol Ag) was added. After 40 minutes, water-soluble mercapto compound-1 was added, and the mixture was cooled to 35 ° C. Thus, the preparation of the emulsion (chemical ripening) was completed.

[0042]

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(Preparation of Coating Solution for Emulsion Layer) The following chemicals were added per mole of silver halide to the emulsions of Example 1 and Comparative Example 1 which had been subjected to chemical sensitization to prepare an emulsion coating solution. -Gelatin (including gelatin in the emulsion) 50.0 g-Dextran (average molecular weight 39,000) 10.0 g-Sodium polyacrylate (average molecular weight 400,000) 5.1 g-Sodium polystyrene sulfonate (average molecular weight 60) 10,000 g) 1.2 g potassium iodide 78 mg hardener 1,2-bis (vinylsulfonylacetamido) ethane Addition amount is adjusted so that the swelling ratio becomes 90%. Compound A-1 42.1 mg. Compound A-2 10.3 g Compound A-3 0.11 g Compound A-4 8.5 mg Compound A-5 0.43 g Compound A-6 0.04 g Compound A-7 70 g

[0044]

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Dye emulsion a (as dye solid content) 0.50 g

(Preparation of Dye Emulsion a) 60 g of Dye-1
62.8 g of 2,4-diamylphenol, 62.8 g of dicyclohexyl phthalate and ethyl acetate 3
33 g were melted at 60 ° C. Next, 65 ml of a 5% by weight aqueous solution of sodium dodecylbenzenesulfonate, 94 g of gelatin and 581 ml of water were added, and a dissolver was used at 60 ° C.
For 30 minutes. Next, 2 g of methyl p-hydroxybenzoate and 6 liters of water were added, and the temperature was lowered to 40 ° C. Next, Asahi Kasei ultrafiltration lab module ACP
Using 1050, concentrate to a total volume of 2 kg, p
-Dye emulsion a by adding 1 g of methyl hydroxybenzoate
And

[0047]

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30 mg of Dye Emulsion m (as Dye Solids) (Preparation of Dye Emulsion m) 10 g of Dye-2 was weighed and dissolved in a solvent composed of 10 ml of tricresyl phosphate and 20 ml of ethyl acetate. , Anionic surfactant-17
Dye emulsion m was prepared by emulsifying and dispersing in 100 ml of a 15% by weight aqueous gelatin solution containing 50 mg.

[0049]

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(Adjustment to pH 6.1 with NaOH) (Preparation of Dye Layer Coating Solution) A coating solution was prepared so that each component of the dye layer had the following coating amount.・ Gelatin 0.25 g / m ²・ Compound A-8 1.4 mg / m ²

[0051]

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• Sodium polystyrene sulfonate (average molecular weight: 600,000) 5.9 mg / m ² • Dye dispersion i (as dye solids) 20 mg / m ²

(Preparation of Dye Dispersion i) Dye-3 was handled as a wet cake without drying, and weighed to a dry solid content of 6.3 g. The dispersing aid V was treated as a 25% by weight aqueous solution, and was added so that the dry solid content was 30% by weight based on the solid content of the dye. Add water and add 6
3.3 g, and mixed well to form a slurry. 100 ml of zirconia beads having an average diameter of 0.5 mm is prepared, placed in a vessel together with the slurry, and dispersed for 6 hours with a dispersing machine (1 / 16G sand grinder mill: manufactured by Imex Co., Ltd.) to give a dye concentration of 8 wt. % To obtain a dye dispersion. The resulting dispersion has a dye solids content of 5
% By weight, and photographic gelatin were mixed so as to be equal to the dye solid content by weight. Distilled water was added as an antiseptic so that Additive D was 2,000 ppm based on the gelatin, followed by refrigeration.
Stored in jelly form. In this way, a dye-like dye dispersion i was obtained as a non-elutable solid fine particle dispersion dye having a light absorption maximum at 915 nm. The average particle diameter of the solid fine particles of the dye dispersion i was 0.4 μm.

[0054]

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[0055]

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(Preparation of Coating Solution for Surface Protective Layer) A coating solution for surface protective layer was prepared such that each component had the following coating amount.・ Gelatin 0.780 g / m ²・ Sodium polyacrylate (average molecular weight: 400,000) 0.025 g / m ²・ Sodium polystyrene sulfonate (average molecular weight: 600,000) 0.0012 g / m ²・ Mat agent-1 (average particle size: 3. 7 μm) 0.072 g / m ² · Mat agent-2 (average particle size 0.7 μm) 0.010 g / m ²

[0057]

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[0058] - Compound ^{A-9 0.018 g / m 2} · Compound ^{A-10 0.037 g / m 2} · Compound A-11 0.0068g / m ² · Compound A-12 0.0032g / m ² · Compound A-13 0.0012 g / m ² · compound A-14 0.0022 g / m ² · compound A-15 0.030 g / m ² · proxel (manufactured by ICI) 0.0010 g / m ² (adjusted to pH 6.8 with NaOH)

[0059]

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(Preparation of Support) (1) Preparation of Dye Dispersion B for Undercoat Layer The following Dye-4 was ball-milled by the method described in JP-A-63-197943.

[0061]

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434 ml of water and Triton X200
(Registered trademark) surfactant (TX-200 (registered trademark))
791 ml of a 6.7% aqueous solution was placed in a 2 liter ball mill. 20 g of Dye-4 were added to this solution. 400 ml of zirconium oxide (ZrO ₂ ) beads (2 m
m diameter) and the contents were ground for 4 days. After this, 1
160 g of 2.5% gelatin was added. After defoaming, the ZrO ₂ beads were removed by filtration. Observation of the obtained dye dispersion showed that the particle size of the pulverized dye was 0.0
It had a wide distribution from 5 to 1.15 μm, and the average particle size was 0.37 μm. Furthermore, dye particles having a size of 0.9 μm or more were removed by centrifugation. Thus, a dye dispersion B was obtained.

(2) Preparation of Support A corona discharge was performed on a biaxially stretched polyethylene terephthalate film having a thickness of 175 μm, and a first undercoating solution having the following composition was applied to a coating amount of 4.9 ml / m ^2. And dried at 185 ° C. for 1 minute. Next, a first undercoat layer was similarly provided on the opposite surface. The used polyethylene terephthalate contained Dye-1 at 0.04% by weight. (First undercoat liquid)-Butadiene-styrene copolymer latex solution (solid content: 40%; butadiene / styrene weight ratio = 31/69) 158 ml-2,4-dichloro-6-hydroxy-s-triazine sodium salt 4 weight % Solution 41 ml ・ Distilled water 801 ml * In the latex solution, compound A-
Contains 16 wt% of 16 based on the solid content of latex

[0064]

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(3) Coating of undercoat layer A second undercoat layer having the following composition was applied on the first undercoat layers on both sides so that the application amount would be as described below.
Apply to both sides by wire bar coder method, 15
Dried at 5 ° C. Gelatin 80 mg / m ² Dye dispersion B (as dye solids) 50 mg / m ² Compound A-17 1.8 g / m ² Compound A-18 0.27 g / m ² Matting agent Average particle size 2 2.5 μm polymethyl methacrylate 2.5 g / m ²

[0066]

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(Preparation of photographic material) The above dye layer, emulsion layer and surface protective layer were combined and coated on both sides by a simultaneous extrusion method on the support prepared as described above, and dried. The amount of silver coated on one side was 1.4 g / m ² , and the total amount of gelatin applied on one side was 1.8 g / m ² .

(Measurement of swelling ratio)
It is aged for 7 days at 0 ° C. and 60% RH. Next, this photosensitive material is immersed in distilled water at 21 ° C. for 3 minutes, and this state is frozen and fixed with liquid nitrogen. This photosensitive material is cut by a microtome so as to be perpendicular to the surface of the photosensitive material, and then freeze-dried at -90 ° C. The swelled film thickness Tw is determined by observing the processed product under a scanning electron microscope. On the other hand, the film thickness Td in a dry state is also obtained by cross-sectional observation using a scanning electron microscope. The difference between Tw and Td thus obtained is divided by Td to obtain 100.
The multiplied value was defined as a swelling ratio (unit%). {(Tw−Td) / Td} × 100 = Swelling rate (%) In this photographic material, Tw = 3.5 μm, Tw =
6.65 μm, and the swelling ratio was 90% as described above.

(Preparation of Developing Solution) A developing solution having the following formulation and using sodium erythorbate as a developing agent was prepared.

Diethylenetriaminepentaacetic acid 8.0 g Sodium sulfite 20.0 g Sodium carbonate monohydrate 52.0 g Potassium carbonate 55.0 g Sodium erythorbate 60.0 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 13.2 g 3,3'-diphenyl-3,3'dithiopropionic acid 1.44 g diethylene glycol 50.0 g

[0071]

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Add 2 liters of water. Adjust to pH 10.1 with sodium hydroxide.

(Preparation of developer replenisher) The above developer was used as it was as a developer replenisher.

(Preparation of developing mother liquor) 2 liters of the above developing solution was taken, and a starter solution having the following composition was added to 55 ml per liter of the developing solution, and a developing solution having a pH of 9.5 was used as a developing mother liquor. (Preparation of starter solution) Potassium bromide 11.1 g Acetic acid 10.8 g Water was added to make up to 55 ml.

(Preparation of concentrated fixing solution) A concentrated fixing solution having the following formulation was prepared. Water 0.5 L Ethylenediaminetetraacetic acid dihydrate 0.05 g Sodium thiosulfate 200 g Sodium bisulfite 98.0 g Sodium hydroxide 2.9 g Adjust the pH to 5.2 with NaOH, and add water to make 1 L.

(Preparation of Fixing Replenisher) The concentrated fixing solution was diluted by a factor of two with the first washing water waste solution and used as a fixing replenisher.

(Preparation of Fixing Mother Solution) 2 L of the above concentrated fixing solution was diluted with water to make 4 L. pH was 5.4.

(Washing water replenisher) Glutaraldehyde 0.3 g Diethylene-triamine-penta-acetic-acid 0.5 g Diluted with distilled water and adjusted to pH 4.5 with NaOH to obtain 1 liter of the finished solution. Was.

(Processing of photographic material) CEPROS-S manufactured by Fuji Photo Film Co., Ltd. was modified and the second washing layer was supplemented with washing water with a two-stage countercurrent washing. Also,
The opening ratios of the developing tank and the fixing tank were improved to 0.02. The capacity of each washing tank is 6 liters. For drying, a heat roller method (roller surface temperature: 85 ° C.) was used. The developing mother liquor and fixing the mother liquor, using a washing water replenisher, the developer replenisher and the fixing replenisher, both the washing water replenisher was performed while replenishing 65ml per photosensitive material 1 m ^2.

Process temperature Processing time Current image 35 ° C 8 seconds Fixed 35 ° C 7 seconds Rinse 1st 30 ° C 5 seconds Rinse 2nd 25 ° C 5 seconds Dry 3 seconds Total 28 seconds

(Evaluation of photographic performance) A photographic material prepared using the emulsions of Example 1 and Comparative Example 1 was subjected to 0.05 seconds from both sides using an X-ray orthoscreen HGM manufactured by Fuji Photo Film Co., Ltd. Exposure. As a result of the photographic characteristics, when the coating sample B (Comparative Example 1) was set to 100 in the (sensitivity value / granularity) ratio, the coating sample A was 110, confirming the superiority of the particles of the invention. The sensitivity value was represented by the reciprocal of the ratio of the exposure amount giving a density of 1.0 in addition to fog. The granularity is determined by adding a sample to fog, exposing the sample to light at a light amount giving a density of 1.0, performing a development process in advance, and then using Macmillan's "Theory of the Photographic Process", p. The measurement was carried out using a G filter in the manner described in (1).

[0082]

The AgX emulsion of the present invention has a better tabularization rate than the conventional AgX emulsion containing tabular grains having {100} major planes, and the photographic sensitivity using the AgX emulsion of the present invention. The material is excellent in (sensitivity / granularity).

[Brief description of the drawings]

FIG. 1 is a replica TEM image showing the crystal structure of silver halide grains obtained in Example 1. Magnification is about 3500 times.

Claims (1)

[Claims] 1. The sum of the projected areas of all silver halide grains.
50 to 100% are tabular grains having a principal plane of {100} planes and an aspect ratio (diameter / thickness) of 2.0 to 50.
^- a method of manufacturing a silver halide emulsion content: is 30 to 99.99 mol%, the production method is at least as seed crystals formed, the first ripening step, the steps of the growth process and the second ripening step, And a method for producing a silver halide emulsion having the following characteristics a), b) and c). a) the seed crystal forming process forms first fine particles (AgX ₁ ), and then a halide salt solution (Xc) or a silver salt solution with Xc is added;
A halogen conversion reaction is caused to the fine particles, and a silver salt (Ag
X ₂ ) layer, and a step of forming a halogen composition gap plane of (AgX ₁ | AgX ₂ ), and [(moles of Ag ^{+ in} the added silver salt solution) / (the Xc The number of moles of halogen ions) = 0 to 0.8, and the [(number of moles of Cl ⁻ ) / (total number of moles of Br ⁻ and I ⁻ )] in the Xc is 0.05 to 10 ⁴ . b) At the end of the first ripening, 5.0 to 70% of the total projected area of all silver halide grains are nontabular grains having an aspect ratio of 1.5 or less. c) Cl in 1.5 to 300 times the growth year in the second ripening process ^-
By increasing the concentration and aging, 40 to 100% of the non-tabular grains present in the total non-tabular grains having an aspect ratio of 1.5 or less disappear.