JPH09258355A - Photosensitive silver halide emulsion and silver halide photographic sensitive material using the same and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the photosensitive silver halide emulsion high in sensitivity and rapid processing aptitude and capable of reproducing stably superior gradation against change of exposure conditions and the silver halide photographic sensitive material using it and its image forming method. SOLUTION: The silver halide emulsion is prepared by using, as seed crystals, silver halide grains having been desilvered and comprising silver halide grains having an aspect ratio of >=2.0 and principal (100) faces but not twin faces and occupying >=50% of the projection areas of the total projection areas, and the obtained silver halide grains comprises flat silver halide grains having an average silver chloride content of >=50mol%, an aspect ratio of >=3.0, a grain thickness of <=0.3μm, and principal (100) faces, occupying >=50% of the projection areas of the total silver halide grains. The silver halide photographic sensitive material using this emulsion undergoes redox amplification development processing.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive silver halide emulsion which is highly sensitive and has excellent rapid processability, and is capable of stable and excellent gradation reproduction with respect to changes in exposure conditions. The present invention relates to a silver halide photographic light-sensitive material and an image forming method, and more specifically, to a light-sensitive silver halide emulsion capable of reproducing stable gradation even under high illuminance and short-time exposure, and halogenation using the same. The present invention relates to a silver photographic light-sensitive material and an image forming method.

[0002]

2. Description of the Related Art Silver halide photographic light-sensitive materials are very popular today because they have very high characteristics, such as high sensitivity and excellent gradation, as compared with other light-sensitive materials. It is used for Among them, a light-sensitive material using silver halide grains having a high silver chloride content is preferred from the viewpoint of processing speed.

In such silver halide grains having a high silver chloride content, tabular silver halide grains have been recently used with the aim of further increasing sensitivity, sharpening, improving graininess, and speeding up processing. Research on particles is active. As tabular silver halide grains having a high silver chloride content, grains having a (111) main plane and grains having a (100) main plane are known.

Among these, as a method for forming tabular grains having a (111) plane as a main plane, the grains are formed in the presence of a crystal habit controlling agent such as aminoazaindene, pyrimidine, aminoazine, thiourea, or xanthoidoid. Methods are known. However, in general, a silver halide grain having a high silver chloride content has a stable (100) plane, and when the salts generated during the formation of the silver halide grain are removed, these crystal habit controlling agents are removed. There is also a phenomenon that the shape of particles changes when they are separated,
It was difficult to stably obtain tabular grains having a (111) main plane. Further, such a crystal habit controlling agent is
Many are known as so-called inhibitors, and there has been a problem that chemical sensitization cannot be performed well in the presence of these compounds.

On the other hand, a method for forming tabular grains having a (100) plane as a main plane is disclosed in JP-A-5-204073, US Pat. Nos. 5,264,337, 5,275,930, and JP-A-6- 301131, 6-308648, 6
-337489, 6-337490, 6-33
No. 7507 and the like. These tabular silver halide grains having the (100) plane as the main plane are (111)
Compared with tabular silver halide grains having a plane as the main plane, the shape is more stable and there is an advantage that spectral chemical sensitization can be easily performed because a crystal habit controlling agent is not particularly required.

However, tabular silver halide grains having a high silver chloride content and having the (100) plane as the principal plane have insufficient stability against changes in exposure conditions when compared with cubic silver halide grains. It has been found that there is a problem that gradations are difficult to be stably reproduced, especially when exposure is performed at high illuminance and for a short time.

The technique of using a seed emulsion in the production of tabular silver halide grains is disclosed in, for example, JP-A-6-301127, 6-308639, and 5-34851, but all of them are disclosed. The present invention relates to the production of a silver iodochlorobromide emulsion using a silver halide grain having a twin plane as a seed emulsion for the purpose of improving production stability, improving sensitivity / graininess relation, and improving pressure resistance. As described above, the tabular silver halide grains having a high silver chloride content and having the (100) plane as the main plane have insufficient gradation reproduction stability with respect to changes in exposure conditions. It does not mention the problem that gradations on exposure are difficult to reproduce stably.

Further, Japanese Patent Application Nos. 6-78827 and 7-89.
No. 522, No. 7-60656 and the like describe that a seed emulsion can be used for preparing tabular silver halide grains having a high silver chloride content.
There is no description about the problem that the tabular silver halide grains having the (100) plane as the main plane are inferior in the gradation reproducibility with respect to the change of the above-mentioned exposure conditions, and there is no suggestion about the solution.

On the other hand, a method of forming an image by subjecting a light-sensitive material to a redox amplification development process has been known for a long time as a preferable means in that the amount of silver halide in the light-sensitive material is small and effective utilization of resources is carried out. For example British Patents 1, 2
68,126, 1,399,481, 1,40
3,418, International Patents 9013059, 9301
No. 524, US Pat. Nos. 4,371,609 and 5,41.
1,848, JP-A-3-111844, 4-23
No. 3535 discloses the processing method.

However, in such a redox amplification development process, the lack of stable reproducibility of gradation with respect to changes in exposure conditions becomes more remarkable as compared with the normal process in which redox amplification development is not performed, and particularly in high illuminance. -When short-time exposure was performed, stable reproduction of gradation in the highlight portion tended to become more difficult. The cause of this decrease has not been clarified yet, but the oxidant used for redox amplification development not only oxidizes the developing agent, but also against latent images and relatively small developed silver nuclei produced by exposure. It is thought that this is because it works as an oxidizing agent, and it was difficult to reproduce gradation stably, especially when tabular silver halide grains having a high silver chloride content and having the (100) plane as the main plane were used.

A method of redox amplification developing a photosensitive material using tabular silver halide grains having a high silver chloride content (100) plane as a main plane is disclosed in, for example, JP-A-6-3011.
No. 28, etc., the above-mentioned problem of insufficient gradation reproducibility with respect to changes in exposure conditions is not mentioned, and no improvement method thereof is suggested.

[0012]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photosensitive silver halide emulsion which is highly sensitive and excellent in rapid processability and which can stably reproduce excellent gradation even when the exposure conditions are changed. And a silver halide photographic light-sensitive material using the same and an image forming method, and more specifically, a light-sensitive silver halide emulsion capable of reproducing stable gradation even under high-illuminance and short-time exposure, and the same. To provide a silver halide photographic light-sensitive material and a method for forming an image.

[0013]

The above object of the present invention has been attained by the following constitutions.

(1) A silver halide grain that has been desalted, has an aspect ratio of 2.0 or more, and has a (100) plane as a main plane and no twin planes is a projected area of all silver halide grains. Of which the average silver chloride content is 50%.
Mol% or more, aspect ratio 3.0 or more, particle thickness 0.
The tabular silver halide grains having a principal plane of (100) plane of 3 μm or less have a projected area of 5 of all silver halide grains.
Light-sensitive silver halide emulsion accounting for 0% or more.

(2) The photosensitive silver halide emulsion according to (1), wherein the seed emulsion is desalted by at least one of electrodialysis and ultrafiltration.

(3) A silver halide photographic light-sensitive material having a light-sensitive silver halide emulsion layer containing at least one layer of blue-light-sensitive silver halide grains and a dye-providing substance on a support. A silver halide photographic light-sensitive material containing the light-sensitive silver halide emulsion according to (1) or (2) in a silver halide emulsion layer.

(4) A silver halide photographic light-sensitive material having, on a support, at least two layers of light-sensitive silver halide grains having different color sensitivities and a light-sensitive silver halide emulsion layer containing a dye-donor substance. In the blue light-sensitive silver halide emulsion layer contains the light-sensitive silver halide emulsion described in (1) or (2), and each of the remaining light-sensitive silver halide emulsion layers contains 50% of projected area
The above is a silver halide photographic light-sensitive material comprising silver halide grains having an average silver chloride content of 50 mol% or more and an aspect ratio of 2.0 or less.

(5) Silver halide having at least one layer of the photosensitive silver halide emulsion described in (1) or (2) and a photosensitive silver halide emulsion layer containing a dye-providing substance on a support. An image forming method in which a photographic light-sensitive material is subjected to redox amplification development processing.

Hereinafter, the present invention will be described in detail.

In the light-sensitive silver halide emulsion of the present invention, the silver halide grains having an aspect ratio of 2.0 or more and having a (100) plane as a main plane and having no twin plane are 50 of all silver halide grains. % Of the silver halide emulsion is formed and then desalted, and the seed emulsion is used to have an aspect ratio of 3.0 or more, a grain thickness of 0.3 μm or less, and a silver chloride content. Desalting after forming a silver halide emulsion in which tabular silver halide grains having a ratio of 50 mol% or more and having a (100) plane as a main plane occupy 50% or more of all silver halide grains. It is prepared by a grain growth process.

Aspect ratio is 2.0 or more and (100)
The production process of the seed emulsion in which the silver halide grains having the main plane as the main plane and having no twin plane occupy 50% or more of all the silver halide grains includes a process of forming nuclei of silver halide crystals and a process of forming nuclei of silver halide crystals. It can be divided into a physical ripening process, a grain growth process and a desalination process.

The step of forming nuclei of silver halide crystals is carried out by adding and mixing an aqueous silver salt solution and an aqueous halide solution with stirring in a dispersion medium such as an aqueous gelatin solution. At this time, due to the difference in crystal lattice size between silver chloride and silver iodide or silver bromide in the presence of a method of adding a (100) face formation promoter such as imidazole or 3,5-diaminotriazole. A method is known in which strain is generated in the wire and a screw transition is introduced. When the spiral transition is introduced, the formation of the two-dimensional nuclei on that surface is not rate-determining, so crystallization on this surface proceeds, and two (10
When introduced into the (0) plane, tabular grains are formed.

The pCl during nucleation is preferably 1.5 to 2.5, the temperature is preferably 90 ° C. or lower, and more preferably 40 to 80 ° C. The amount of protective colloid such as gelatin used for nucleation is preferably 0.1 to 5%, more preferably 0.2 to 3%. As the gelatin, a low methionine gelatin which is weakly adsorbed on silver halide grains is preferably used.

The content of silver iodide used for nucleation is preferably 0.5 mol% or less as an average value of the whole.
0.1 mol% or less is more preferable. The local concentration of the portion containing silver iodide is preferably 2 mol% or less, more preferably 1 mol% or less. When the amount of silver iodide is too large, phenomena such as inhibition of bleach-fixing become remarkable, and there are problems such as spread of grain shape distribution in the ripening step subsequent to the nucleation step. It is better to decide experimentally according to.

The method described in JP-A-6-337489 can be used as a method for introducing a screw transition using silver bromide during nucleation.
After forming 3-5% of the total silver chloride in silver, 1% of the total
A gap surface having a halogen composition can be formed by forming ˜5% of silver bromide and further forming silver chloride in an amount of 20 to 30% of the total to complete the nucleation process.

As with the crystal habit controlling agent used for preparing the tabular grains having the (111) plane as the main plane,
Since the influence on the photographic performance of the (100) plane formation accelerator cannot be ignored, a method utilizing a halogen composition gap plane by silver iodide or silver bromide is preferably used.

It is difficult to prepare only silver halide grains having a screw transition in the nucleation process, and the difference in growth rate between the grains having the screw transition and the grains not having the screw transition is used to cause the screw transition. To eliminate the missing particles,
Physical ripening is performed following the nucleation process. The physical ripening temperature is preferably set higher than the nucleation temperature.
The temperature is preferably 0 to 90 ° C, more preferably 60 to 80 ° C. The aging speed is different depending on conditions such as pCl. Excessive aging is not preferred because the particle size distribution is widened.

The tabular grain nuclei remaining in the ripening process may be used as they are as a seed emulsion, or may be grown as necessary. For the growth of nuclei, a method such as a commonly used simultaneous mixing method can be preferably used, but if the supply rate of the silver salt is too fast, the anisotropy of growth becomes small,
As a result, the aspect ratio becomes smaller. Further, if the supply rate of the silver salt is too slow, the tabular grains have a large specific surface area, which causes phenomena such as unclear edges and a small aspect ratio. The problem of deterioration occurs. Appropriate addition conditions can be determined experimentally, but it is advantageous to use a method of supplying a silver salt by using a fine grain silver halide emulsion because it is easy to maintain proper addition conditions.

In order to keep the aspect ratio high, it is preferable to set the temperature during the crystal growth to a high temperature, 60 to 80 ° C.
Furthermore, the range of 65 to 75 ° C. is preferably used.

The halogen composition of the seed emulsion grains is arbitrary,
Any of silver bromide, silver iodobromide, silver chloride, silver chlorobromide, silver iodochlorobromide and silver iodochloride may be used.
It is preferably at least mol%.

In the seed emulsion of the present invention, grains having an aspect ratio of 2.0 or more occupy 50% or more of the projected area of all grains, and the grain size is not particularly limited, but the average diameter is not limited. 0.3 to 0.6 μm is preferable. 0.
If it is less than 3 μm, the seed emulsion particles are likely to be unstable, while
If it exceeds 0.6 μm, it becomes difficult to obtain the effects of the present invention.

The average thickness of the seed emulsion grains is preferably 0.2 μm or less, more preferably 0.15 μm or less.

Unwanted soluble salts are removed from the seed emulsion by a desalting process. Known methods can be used for the desalting method, for example, a method in which the emulsion is cooled and set, and then finely or noodle-shaped and washed with water, a combination of a precipitant and a polyvalent metal ion, modified gelatin, and synthetic. Examples thereof include a flocculation-precipitation method in which the supernatant is removed by decantation after flocculation using a polymer flocculant or the like, or a membrane separation method such as electrodialysis and ultrafiltration. Above all, it is preferable to use a desalting method that does not use an aggregating agent, because the effect of the present invention that gradations can be stably reproduced with respect to changes in exposure conditions becomes more remarkable. In particular, the electrodialysis method and the ultrafiltration method do not increase the volume of the emulsion due to water absorption and are preferably used.

The seed emulsion desalted by the above method may be supplemented with a protective colloid such as gelatin, if necessary.

The seed emulsion after desalting may be adjusted to pH or p as necessary.
Cl can be adjusted. In particular, when storing by cooling and setting, in order to avoid unnecessary ripening of the particles at the time of re-dissolving, the pH at 40 ° C. is adjusted to pH 6.0 or lower and pC
It is preferable to set l to 1.2 or more.

In the present invention, the seed emulsion may be used in the grain growth process immediately after desalting, or after being cooled and set,
If necessary, it can be used after re-dissolving.

Next, using the above seed emulsion, the aspect ratio is 3.0 or more, the grain thickness is 0.3 μm or less, the average silver chloride content is 50 mol% or more, and the (100) plane is the main plane. A method for preparing a silver halide emulsion in which tabular silver halide grains occupy 50% or more of the projected area of all silver halide grains will be described.

The amount of the seed emulsion used in this process is arbitrary and is appropriately determined according to the desired final grain size, but it is 1 / molar to the total amount of the silver salt supplied for grain growth. It is preferable to use a seed emulsion in an amount corresponding to a silver amount of 15 or less, more preferably 1/25 or less, and particularly preferably 1/30 or less.

As the apparatus and method for preparing a silver halide emulsion, various methods known in the art can be used.

Regarding the growth of silver halide grains in the presence of a seed emulsion, an acidic method and a neutral method are preferably used.

The method of reacting the soluble silver salt with the soluble halide may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, and a combination thereof, but a method obtained by the simultaneous mixing method is preferable. . Further, as one form of the simultaneous mixing method, pA described in JP-A-54-48521 and the like are described.
g The controlled double jet method can also be used.

In addition, JP-A-57-92523 and 57-57
No. 92524, etc., a device for supplying a water-soluble silver salt and a water-soluble halide aqueous solution from an addition device arranged in a reaction mother liquor, and a water-soluble silver salt described in DE 2,921,164. And an apparatus for continuously adding an aqueous solution of a water-soluble halide while changing its concentration, Japanese Patent Publication No. 56-5017.
No. 76, etc., a reaction mother liquor may be taken out of the reactor and concentrated by an ultrafiltration method to form grains while keeping the distance between silver halide grains constant.

If necessary, a silver halide solvent such as thioether may be used. Also, triazole, 3-
A compound having a crystal habit controlling agent such as amino-1H-1,2,4-triazole, 3,5-diamino-1H-1,2,4triazole, and imidazole, a compound having a mercapto group, or a compound such as a sensitizing dye, It may be added at the time of forming the silver halide grains.

The grain size of the silver halide grain according to the present invention is not particularly limited, but it is preferably 3.0 μm or less in consideration of rapid processing property and photographic performance such as sensitivity.
It is more preferably 2.0 μm or less. The grain size of the silver halide grains can be measured by various methods generally used in this technical field. A typical method is Loveland's “particle size analysis method”.
(A.S.T.M. Symposium on Right Microscopy, 94-122, 1955) or "The Theory of Photographic Process, 3rd Edition" (co-authored by Mies and James, Chapter 2, published by Macmillan, Inc.). 1966).

In the present invention, the particle size is expressed by using the diameter of a circle having the same projected area as that of the particles. Aspect ratio is defined as the grain size divided by the grain thickness.

The photosensitive silver halide emulsion according to the present invention comprises
After growing the particles to the desired size, unwanted soluble salts are removed during the desalting process. In the desalting process, a conventionally known method as described in the preparation of seed emulsion can be used.

The silver halide emulsion according to the present invention is a flat plate having an aspect ratio of 3.0 or more, a grain thickness of 0.3 μm or less, an average silver chloride content of 50 mol% or more, and a (100) plane as a main plane. -Shaped silver halide grains occupy 50% or more of the projected area of all silver halide grains, preferably the tabular silver halide grains are 70% or more of all silver halide grains, more preferably all halogens. 80 of silver halide grains
% Or more.

The composition of the silver halide photographic emulsion according to the present invention may be any halogen composition such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide and silver chloroiodide. Although it may be contained, silver chloride is contained in an amount of 50 mol% or more, preferably 8 from the viewpoint of rapid processability and process stability.
A silver halide emulsion containing 0 mol% or more, and more preferably 95 mol% of silver chloride is preferable. In the present invention, a silver halide emulsion having a portion containing a high concentration of silver bromide is particularly preferably used.

To obtain the silver halide emulsion of the present invention, it is advantageous to contain heavy metal ions. Examples of heavy metal ions that can be used for such purposes include Group 8 to 10 metals such as iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, and cobalt; and twelfth metals such as cadmium, zinc, and mercury. Group transition metals, and ions of lead, rhenium, molybdenum, tungsten, gallium, chromium, and the like. Among them, metal ions of iron, iridium, platinum, ruthenium, gallium and osmium are preferred.

These metal ions can be added to the silver halide emulsion in the form of salt or complex salt.

When the heavy metal ion forms a complex,
Examples of the ligand or ion include cyanide ion, thiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, nitrate ion, carbonyl, and ammonia. Among them, cyanide ion, thiocyanate ion, isothiocyanate ion,
Chloride ions, bromide ions and the like are preferred.

In order to contain a heavy metal ion in the silver halide emulsion, the heavy metal compound is added before the formation of silver halide grains, during the formation of silver halide grains, and during the physical ripening after the formation of silver halide grains. It may be added at any place in the process. In order to obtain a silver halide emulsion satisfying the above-mentioned conditions, a method of dissolving a heavy metal compound together with a halide salt and continuously adding it over the whole or a part of the grain forming step is preferably used.

The amount of heavy metal ions added to the silver halide emulsion is 1 × 10 ^-9 to 1 × 1 per mol of silver halide.
It is preferably from 0 to ² mol, and particularly preferably from 1 × 10 ^{−8 to} 5 × 10 ⁻⁵ mol.

The silver halide emulsion of the present invention can be used in combination with a sensitizing method using a gold compound and a sensitizing method using a chalcogen sensitizer.

As the chalcogen sensitizer applied to the silver halide emulsion, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer and the like can be used, but the sulfur sensitizer is preferable.

Examples of the sulfur sensitizer include thiosulfate, allylthiocarbamide, thiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, rhodanine and inorganic sulfur.

The addition amount of the sulfur sensitizer is preferably changed depending on the kind of silver halide emulsion to be applied and the magnitude of expected effect, but 5 × per mol of silver halide.
10 ^{-10 to} 5 × 10 ^-5 mol, preferably 5 × 10 ^{-8 to} 3
A range of ^10-5 mol is desirable.

As the gold sensitizer, various gold complexes other than chloroauric acid, gold sulfide and the like can be added. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, mercaptotriazole and the like. The amount of the gold compound used is not uniform depending on the type of silver halide emulsion, the type of compound to be used, the ripening conditions, etc., but usually 1 × 10 ^-4 to 1 × 10 ^-8 mol per mol of silver halide. Is preferably
More preferably, it is 1 × 10 ⁻⁵ to 1 × 10 ⁻⁸ mol.

The chemical sensitization method for silver halide emulsions is as follows:
A reduction sensitization method may be used.

The silver halide emulsion contains a known antifoggant for the purpose of preventing fog occurring during the process of preparing a light-sensitive material, reducing performance fluctuations during storage, and preventing fog occurring during development. Agents can be used. Preferred examples of the compound used for such purpose include a compound represented by the general formula [II] described in the lower column on page 7 of JP-A-2-14636, and more preferred specific compounds include II described on page 8 of the publication
a-1 to IIa-8, IIb-1 to IIb-7, 1
Compounds such as-(3-methoxyphenyl) -5-mercaptotetrazole and 1- (4-ethoxyphenyl) -5-mercaptotetrazole can be mentioned.

These compounds are added in steps such as the step of preparing silver halide emulsion grains, the step of chemical sensitization, the end of the chemical sensitization step and the step of preparing a coating solution, depending on the purpose. When chemical sensitization is performed in the presence of these compounds, 1 × 10 ^{−5 to} 5 × 10 ⁻⁴ per mol of silver halide is used.
It is preferably used in a molar amount. When added at the end of chemical sensitization, 1 × 10
^-6 to 1 × 10 ^-2 mol is preferable, and 1 × 10 ^-5 to
5 × 10 ⁻³ mol is more preferred. When added to the silver halide emulsion layer in the coating solution preparation step, the amount is preferably about 1 × 10 ⁻⁶ to 1 × 10 ⁻¹ mol per mol of silver halide, and 1 × 10 ⁻⁵ to × 10 ^{−. 2} mol is more preferred.
Further, when added to a layer other than the silver halide emulsion layer,
The amount in the coating film is 1 × 10 ⁻⁹ to 1 × 10 ⁻³ per m ^2.
Amounts on the order of moles are preferred.

For the light-sensitive material, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any of the known compounds can be used. Particularly, as the dye having absorption in the visible region, the dyes of AI-1 to 11 described in JP-A-3-251840, p. The dyes described in No. 3770 are preferably used, and as the infrared absorbing dye, the compounds represented by the general formulas (I), (II) and (III) described in JP-A 1-280750, page 2, lower left column are preferable. It is preferable because it has a spectral characteristic, has no influence on the photographic characteristics of the photographic emulsion, and has no stain due to residual color. Specific examples of preferred compounds include the exemplified compounds (1) to (45) listed in the lower left column of page 3 to the lower left column of page 5 of the same publication.

The amount of these dyes added is 680 n of an untreated sample of a light-sensitive material for the purpose of improving sharpness.
The amount of the spectral reflection density at m is preferably 0.7 to 3.0, and more preferably 0.8 to 3.0.

It is preferable to add a fluorescent whitening agent to the light-sensitive material because the white background can be improved. The compound preferably used is a compound represented by the general formula [I] described in JP-A-2-232652.
I].

When the light-sensitive material of the present invention is used as a color light-sensitive material, it is combined with a yellow dye-donor substance, a magenta dye-donor substance, and a cyan dye-donor substance to give 400 to 400 parts by weight.
It has a layer containing a silver halide emulsion spectrally sensitized in a specific region of a wavelength range of 900 nm. The silver halide emulsion is 1
Or a combination of two or more sensitizing dyes.

The silver halide emulsion of the present invention, particularly when used in the blue-sensitive layer, has a great effect of reproducing a stable gradation with respect to changes in exposure conditions. It is preferred that 80% or more of the projected area of the silver halide emulsion contained in the blue-sensitive layer is the silver halide emulsion of the present invention, more preferably 90% or more, still more preferably 95% or more of the projected area. This is an embodiment comprising the silver halide emulsion of the present invention.

When the silver halide emulsion of the present invention is used in the blue-sensitive layer, the remaining silver halide emulsion layers have a silver chloride content of 50% or more of the projected area of each silver halide emulsion. 50 mol% or more and an aspect ratio of 2.
It is preferable that each layer is composed of silver halide grains of 0 or less from the viewpoint that each layer is well balanced with respect to changes in exposure conditions and that gradation can be reproduced stably. More preferably,
The remaining silver halide emulsion layers have a silver chloride content of 50% or more in 80% or more of the projected area of each silver halide emulsion.
1 with mol% or more and (100) face ratio of 70% or more
In this embodiment, the photosensitive silver halide grains are tetrahedral or cubic.

Any known compound can be used as the spectral sensitizing dye used in the present invention. As the blue-sensitive sensitizing dye, BS-1 to BS-1 described in JP-A-3-251840, page 28 can be used. BS-8 can be preferably used alone or in combination. Green photosensitive sensitizing dyes include:
GS-1 to GS-5 described on page 28 of the publication are preferable,
Further, as the red-sensitive sensitizing dye, RS-1 to RS-8 described on page 29 of the same publication are preferably used. When performing image exposure with infrared light using a semiconductor laser or the like, it is necessary to use an infrared-sensitive sensitizing dye,
As the infrared-sensitive sensitizing dye, JP-A-4-285950
And the dyes IRS-1 to IRS-11 described on pages 6 to 8 are preferably used. These infrared, red, green, and blue light-sensitive sensitizing dyes include supersensitizers SS-1 to SS-9 and JP-A-5-6 described in JP-A-4-285950, pp. 8-9.
No. 6515, pages 15 to 17, compounds S-1 to S-
It is preferable to use 17 in combination.

The sensitizing dye may be added at any time from the formation of silver halide grains to the end of chemical sensitization.

The sensitizing dye may be added as a solution by dissolving it in a water-miscible organic solvent such as methanol, ethanol, fluorinated alcohol, acetone, dimethylformamide or water, or as a solid dispersion. You may add.

As the dye-donor substance used in the light-sensitive material of the present invention, a coupler capable of forming a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm by a coupling reaction with an oxidized product of a color developing agent. Alternatively, a compound that releases a pre-incorporated image dye corresponding to silver development or inversely corresponding thereto can be used, but a typical example thereof is a yellow dye having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm. Forming coupler, wavelength range 500-
Examples include magenta dye-forming couplers having a spectral absorption maximum wavelength at 600 nm, and cyan dye-forming couplers having a spectral absorption maximum wavelength in a wavelength range of 600 to 750 nm.

Examples of cyan couplers that can be preferably used include couplers represented by the general formulas [C-I] and [C-II] described in JP-A-4-114154, page 5, lower left column, As a specific compound, the same publication 5
There can be mentioned those described as CC-1 to CC-9 in the lower right column of page 6 to the lower left column of page 6.

Examples of magenta couplers that can be preferably used include couplers represented by the general formulas [MI] and [M-II] described in JP-A-4-114154, page 4, upper right column, Specific compounds include those described as MC-1 to MC-11 in the same publication, page 4, lower left column to page 5, upper right column. Among the above magenta couplers, more preferred are those represented by the general formula [MI]
A coupler represented by the general formula [M-
The coupler of the formula (I) wherein R _M is a tertiary alkyl group is particularly preferred because of its excellent light resistance. M described in the upper column of page 5 of the same publication
C-8 to MC-11 are preferable because they are excellent in reproduction of colors ranging from blue to purple and red, and are also excellent in detail description.

Examples of yellow couplers that can be preferably used include couplers represented by the general formula [Y-I] described in JP-A-4-114154, page 3, upper right column, and specific compounds are the same. YC on page 3, lower left column
-1 to YC-9. Among them, a coupler of the formula [Y-I] in which R _Y1 is an alkoxy group or a coupler represented by the formula [I] described in JP-A-6-67388 is preferable because it can reproduce yellow having a preferable color tone. Of these, YC-8 and YC-9 and JP-A-6-673881 described in the upper left column of page 4 of JP-A-4-114154 are particularly preferred.
Compounds represented by Nos. (1) to (47) on pages 3 to 14 can be exemplified. The most preferred compound is a compound represented by the general formula [Y-1] described in JP-A-4-81847, pages 1 and 11-17.

When the oil-in-water type emulsion dispersion method is used to add the dye-donor substance or other organic compound used in the light-sensitive material, it is usually necessary to use a water-insoluble high-boiling point organic solvent having a boiling point of 150 ° C. or higher. According to the above, a low boiling point and / or a water-soluble organic solvent is also used in combination to dissolve, and a surfactant is emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution. As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser, or the like can be used. After or simultaneously with the dispersion, a step of removing the low-boiling organic solvent may be included.

As the high boiling point organic solvent which can be used to dissolve and disperse the dye-providing substance, phthalic acid esters such as dioctyl phthalate, di-i-decyl phthalate and dibutyl phthalate, tricresyl phosphate and trisyl phthalate. Phosphate esters such as octyl phosphate are preferably used. The high-boiling organic solvent preferably has a dielectric constant of 3.5 to 7.0. Further, two or more kinds of high-boiling organic solvents can be used in combination.

Further, instead of the method using a high-boiling point organic solvent, or in combination with a high-boiling point organic solvent, a water-insoluble and organic solvent-soluble polymer compound is added, if necessary, to a low-boiling point and / or water-soluble organic solvent. It is also possible to employ a method in which the surfactant is dissolved in a hydrophilic binder such as an aqueous gelatin solution and various emulsion means are used for emulsion dispersion. Examples of the water-insoluble and organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).

Preferred compounds as the surfactant used for dispersing the photographic additives and adjusting the surface tension during coating include a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or a salt thereof in one molecule. The thing contained is mentioned. Specifically, A-1 to A-1 described in JP-A-64-26854.
1 is mentioned. Further, a surfactant in which a fluorine atom is substituted for an alkyl group is also preferably used. These dispersions are
Usually, it is added to a coating solution containing a silver halide emulsion, but it is better that the time until the addition to the coating solution after dispersion and the time from the addition to the coating solution to the coating are shorter, each being preferably within 10 hours. More preferably, within 3 hours and within 20 minutes.

An anti-fading agent is preferably used in combination with each of the above dye-providing substances in order to prevent fading of the formed dye image due to light, heat, humidity and the like. Particularly preferred compounds include phenyl ether compounds represented by formulas [I] and [II] described in JP-A-2-66541, page 3, and general formula [IIIB] described in JP-A-3-174150.
A phenolic compound represented by
No. 5, an amine compound represented by the general formula [A], and general formulas [XII] and [XII] described in JP-A-62-182741.
The metal complexes represented by I], [XIV] and [XV] are particularly preferable for the magenta dye. Also, Japanese Patent Laid-Open No. 1-196049
And a compound represented by formula [I]
The compound represented by the general formula [II] described in No. 11417 is particularly preferable for yellow and cyan dyes.

For the purpose of shifting the absorption wavelength of the coloring dye, compounds d-11 described in JP-A-4-114154, page 9, lower left column, and compound A'-1, described in page 10, upper left column are used. be able to. In addition, the fluorescent dye releasing compounds described in U.S. Pat. No. 4,774,187 can also be used.

In the light-sensitive material of the present invention, a compound which reacts with an oxidized product of a developing agent is added to the layer between the light-sensitive layers to prevent color turbidity, or is added to the silver halide emulsion layer. It is preferable to improve fog and the like. The compound for this purpose is preferably a hydroquinone derivative, more preferably a dialkylhydroquinone such as 2,5-di-t-octylhydroquinone. Particularly preferred compounds are the compounds represented by the general formula [II] described in JP-A No. 4-133056, and the compounds described on pages 13 to 14 of the same.
II-1 to II-14 and Compound-1 described on page 17 can be mentioned.

It is preferable to add an ultraviolet absorber to the light-sensitive material to prevent static fog or improve the light resistance of the dye image. Preferable ultraviolet absorbers include benzotriazoles, and particularly preferable compounds are those represented by the general formula [III-] described in JP-A-1-250944.
3], a compound represented by the general formula [III] described in JP-A-64-66646, and a compound represented by JP-A-63-18
No. 7240, UV-1L to UV-27L;
Examples thereof include compounds represented by the general formula [I] described in JP-A-1633 and compounds represented by the general formulas (I) and (II) described in JP-A-5-165144.

It is advantageous to use gelatin as a binder in the light-sensitive material of the present invention, but if necessary, a gelatin derivative, a graft polymer of gelatin and another polymer, a protein other than gelatin, a sugar derivative, a cellulose derivative, Hydrophilic colloids such as synthetic hydrophilic polymeric substances such as homopolymers or copolymers can also be used.

As the hardener for these binders, it is preferable to use a vinyl sulfone type hardener, a chlorotriazine type hardener, or a carboxyl group active type hardener alone or in combination. JP-A-61-249054, 61-
It is preferable to use the compounds described in US Pat. Further, in order to prevent the growth of molds and bacteria which adversely affect the photographic performance and image storability, JP-A-3-15764 is incorporated in the colloid layer.
It is preferable to add a preservative and an antifungal agent as described in No. 6. In order to improve the physical properties of the surface of the light-sensitive material or the processed sample, it is preferable to add a slipping agent or a matting agent described in JP-A-6-118543 or JP-A-2-73250 to the protective layer.

The support used for the light-sensitive material may be made of any material, including paper coated with polyethylene or polyethylene terephthalate, paper support made of natural pulp or synthetic pulp, vinyl chloride sheet, and white pigment. Alternatively, polypropylene, polyethylene terephthalate support, baryta paper or the like may be used. Among them, a support having a water-resistant resin coating layer on both sides of the base paper is preferable.

As the water resistant resin, polyethylene, polyethylene terephthalate or their copolymers are preferable.

As the white pigment used for the support, inorganic and / or organic white pigments can be used, and preferably inorganic white pigments are used. For example, sulfates of alkaline earth metals such as barium sulfate, carbonates of alkaline earth metals such as calcium carbonate, silicas such as fine silica powder, synthetic silicates, calcium silicate, alumina, alumina hydrate, titanium oxide, oxide Zinc, talc, clay and the like can be mentioned. The white pigment is preferably barium sulfate or titanium oxide.

The amount of the white pigment contained in the water resistant resin layer on the surface of the support is preferably 13% by weight or more, and more preferably 15% by weight in order to improve the sharpness.

The degree of dispersion of the white pigment in the water resistant resin layer of the paper support can be measured by the method described in JP-A-2-28640. When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, more preferably 0.15 or less, as the variation coefficient described in the publication.

Further, it is more preferable that the center surface average roughness (SRa) of the support is 0.15 μm or less, and further 0.12 μm or less because the effect of good gloss can be obtained.
Also, in the white pigment-containing water-resistant resin of the reflective support or in the applied hydrophilic colloid layer, to improve the whiteness by adjusting the spectral reflection density balance of the white background after treatment, ultramarine blue, oil-soluble dyes, etc. It is preferable to add a small amount of a bluing agent or a reddish agent.

The photosensitive material may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the surface of the support, if necessary, and then directly or undercoat layer (adhesiveness, antistatic property, dimensional stability of the support surface). , One or more undercoating layers for improving abrasion resistance, hardness, antihalation property, frictional properties and / or other properties).

When coating a light-sensitive material using a silver halide emulsion, a thickener may be used in order to improve coatability. Extrusion coating and curtain coating, in which two or more layers can be applied simultaneously, are particularly useful as a coating method.

In order to form a photographic image using the photosensitive material of the present invention, the image recorded on the negative may be optically formed on the photosensitive material to be printed and printed. Is once converted into digital information, the image is formed on a CRT (cathode ray tube), and this image may be formed on a photosensitive material to be printed and printed, or a laser based on the digital information may be used. Printing may be performed by scanning while changing the light intensity.

The present invention is preferably applied to a light-sensitive material in which a developing agent is not incorporated in the light-sensitive material, and particularly preferably applied to a light-sensitive material for forming an image for direct viewing. For example, color paper, color reversal paper, photosensitive material for forming a positive image, photosensitive material for display,
A light-sensitive material for color proof can be used. In particular, it is preferably applied to a photosensitive material having a reflective support.

As the aromatic primary amine developing agent used in the present invention, known compounds can be used. The following compounds can be mentioned as examples of these compounds.

CD-1: N, N-diethyl-p-phenylenediamine CD-2: 2-amino-5-diethylaminotoluene CD-3: 2-amino-5- (N-ethyl-N-lauryl) aminotoluene CD-4: 4- (N-ethyl-N-β-hydroxyethyl) aminoaniline CD-5: 2-methyl-4- (N-ethyl-N-β-hydroxyethyl) amino) aniline CD-6: 4 -Amino-3-methyl-N-ethyl-N-
(Β-methanesulfonamido) ethylaniline CD-7: 4-amino-3-β-methanesulfonamidoethyl-N, N-diethylaniline CD-8: N, N-dimethyl-p-phenylenediamine CD-9: 4-amino-3-methyl-N-ethyl-N-
Methoxyethylaniline CD-10: 4-amino-3-methyl-N-ethyl-N
-(Β-ethoxyethyl) aniline CD-11: 4-amino-3-methyl-N-ethyl-N
-(Γ-hydroxypropyl) ethylaniline In the present invention, the above color developer can be used in an arbitrary pH range, but from the viewpoint of rapid processing, the pH is 9.5 to 13.0.
And more preferably pH 9.8-1.
It is used in the range of 2.0.

The processing temperature for color development in the present invention is 3
5-70 ° C is preferred. The higher the temperature, the shorter the processing time is possible, which is preferable. However, it is preferable that the temperature is not too high from the viewpoint of the stability of the processing solution.

Conventionally, the color development time is generally 30 minutes.
Although it is performed in about seconds, in the present invention, it is preferably performed within 40 seconds, and more preferably within 25 seconds.

To the color developing solution, known developer component compounds can be added in addition to the above color developing agent. Usually, an alkali agent having a pH buffering action, a development inhibitor such as chloride ion and benzotriazole, a preservative, a chelating agent and the like are used.

The photographic material is subjected to bleaching processing and fixing processing after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process, a water washing process is usually performed. Further, as a substitute for the washing treatment, a stabilizing treatment may be performed.

As the development processing apparatus used for processing the light-sensitive material of the present invention, even if it is a roller transport type in which the light-sensitive material is sandwiched between rollers arranged in a processing tank and conveyed, the light-sensitive material is fixed to a belt. Although it may be an endless belt method of transporting by a process, a processing tank is formed in a slit shape, a processing solution is supplied to the processing tank and a photosensitive material is transported, and a spray method of spraying the processing solution, A web method by contact with a carrier impregnated with a treatment liquid, a method by a viscous treatment liquid, etc. can also be used.
When processing in large quantities, it is normal to run using an automatic developing machine, but in this case, the replenishment amount of the replenisher is preferably as small as possible. And the method described in JP-A-94-16935 is most preferable.

When the silver halide emulsion of the present invention is used in an image forming method in which a light-sensitive material is subjected to redox amplification development after exposure, it is possible to obtain stable and excellent gradation reproduction with respect to changes in exposure conditions. The effect of the present invention is remarkable.

In the present invention, the redox amplification development treatment is to develop a latent image formed by exposure of a color light-sensitive material with a color or black and white developer to form a developed silver nucleus, and a redox using the developed silver nucleus as a catalyst. It is defined as a method of forming or releasing an image dye by a reaction.For example, an image dye is formed by a coupling reaction between an oxidized product of a developing agent and a coupler produced by a redox reaction of a developing agent and an oxidizing agent using a developed silver nucleus as a catalyst. Methods and the like.

Examples of the oxidizing agent include peroxy compounds such as hydrogen peroxide, compounds that give hydrogen peroxide such as addition compounds of hydrogen peroxide, cobalt (III) complexes such as cobalt hexaammine complex, and chlorous acid. Halogenous acids,
Periodic acid or the like can be used. Among them, the method using hydrogen peroxide is advantageous because the amplification effect is high and the load on the environment is reduced.

In the redox amplification developing process of the present invention, a combination of an aromatic primary amine developing agent and hydrogen peroxide is preferably used, and as the aromatic primary amine developing agent, a known compound as described above is used. You can

The redox amplification developing method used in the present invention is described in, for example, JP-A Nos. 52-13335 and 55.
No. 127555, No. 61-77851, etc., a developing agent and an oxidizing agent are present in the same processing bath (development / amplification solution), and development silver nuclei serving as a catalyst and subsequent redox amplification are produced. As described in JP-A-5-216192, JP-A-5-346647 and the like, a developing bath containing a developing agent and an amplifying bath containing an oxidizing agent are separated from each other, and the developing bath is used. A method of forming developed silver nuclei and carrying a developing agent into an amplification bath for redox amplification development,
Alternatively, JP-A-61-88259 and JP-A-7-0777.
As described in No. 88, etc., there may be mentioned a method of performing redox amplification development processing in a processing bath containing a developing agent and an oxidizing agent after processing in a developing bath containing a developing agent to form developed silver nuclei. Further, as described in JP-A-61-80150, a method of spraying a developing solution and / or an amplifying solution onto a photosensitive material in a mist state can be used.

The amount of the developing agent in the developing solution is 0.2 to 10 g /
It is preferably 1 liter, and particularly preferably 1 to 5 g / liter. The preferred amount of developing agent in the developer / amplifier is 0.
5 to 15 g / liter, more preferably 1 to 7 g / liter, and the amount of hydrogen peroxide (30% solution) is 0.1 to
30 ml / liter is preferable, and more preferably 1 to 5
ml / liter. Hydrogen peroxide in amplification solution (30%
The amount of (solution) is 0.1 to 100 ml / liter.

In the color light-sensitive material to be subjected to such redox amplification development processing, the silver halide grains may be present in an amount necessary to generate a catalytic amount of developed silver nuclei, for example, coupling with a coupler. The amount of coated silver can be greatly reduced as compared with a conventional color color developing method in which an oxidized product of a color developing agent necessary for the above is produced by a redox reaction between a silver halide and the developing agent. In this case, the coated silver amount is preferably 0.5 g / m ² or less in terms of silver amount per silver halide emulsion layer, and more preferably 0.1 g / m ^2.
g / m ² or less.

[0109]

EXAMPLES The present invention will be described below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 <Preparation of blue-sensitive silver halide emulsion> (Preparation of cubic silver halide emulsion using no seed emulsion) 4
In 1 liter of a 2% aqueous gelatin solution kept at 0 ° C., the following (solution A1) and (solution B1) were pAg = 7.3, pH =
Simultaneously added over 30 minutes while controlling to 3.0, the following (C1 solution) and (D1 solution) were further added to pAg = 8.0, pH =
Simultaneous addition was carried out over 180 minutes while controlling at 5.5. At this time, pAg was controlled by the method described in JP-A-59-45437, and pH was controlled by using a sulfuric acid or sodium hydroxide aqueous solution.

(A1 solution) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to 200 ml (B1 solution) Silver nitrate 10 g Water was added to 200 ml (C1 solution) Sodium chloride 102.7 g Potassium hexachloroiridium (IV) acid salt 4 × 10 ^-8 mol Potassium hexacyanoferrate (II) 2 × 10 ^-5 mol Potassium bromide 1.0 g Water added 600 ml (D1 solution) Silver nitrate 300 g Water added 600 ml After the addition is complete, Kao Atlas Demol Desalination was performed using a 5% aqueous solution of N and a 20% aqueous solution of magnesium sulfate, and then mixed with a gelatin aqueous solution to obtain an average particle size of 0.71 μm.
m, monodispersed cubic emulsion E having a silver chloride content of 99.5 mol%
MP-11 was obtained.

Next, except that the addition time of (A1 solution) and (B1 solution) and the addition time of (C1 solution) and (D1 solution) were changed, the average particle size was 0.64 μm and chloride was obtained in the same manner as EMP-11. Monodisperse cubic emulsion EMP-1 having a silver content of 99.5 mol%.
2 was obtained.

The EMP-11 was optimally chemically sensitized at 60 ° C. using the following compounds. Also, EMP-1
Similarly, for No. 2, after chemically sensitizing optimally, the sensitized EMP-11 and EMP-12 were mixed in a silver ratio of 1: 1 to obtain a blue-sensitive silver halide emulsion (Em-B101). Got

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stable Agent STAB-3 3 × 10 ^-4 mol / mol AgX sensitizing dye BS-1 4 × 10 ^-4 mol / mol AgX sensitizing dye BS-2 1 × 10 ^-4 mol / mol AgX STAB-1: 1- ( 3-acetamidophenyl) -5-mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole

[0115]

Embedded image

(Preparation of Cubic Emulsion Using Seed Emulsion) 40
The following (solution A2) and (solution B2) were added to 3 liters of a 2% gelatin aqueous solution kept at a temperature of 370 ° C., with pAg = 7.3 and pH =
Simultaneous addition was performed at an equal flow rate while controlling to 3.0.

(A2 solution) Sodium chloride 10.26 g Potassium bromide 0.09 g Water was added to 600 ml (B2 solution) Silver nitrate 30 g Water was added to 600 ml After the addition was completed, the mixture was cooled to 40 ° C. and manufactured by Kao Atlas demol N. 5% aqueous solution of magnesium sulfate and a 20% aqueous solution of magnesium sulfate were added to cause aggregation, and the mixture was allowed to stand, and the supernatant was removed by decantation. After that, ion-exchanged water heated to 40 ° C. was added and redispersed, then a 20% aqueous solution of magnesium sulfate was added again and the mixture was allowed to stand, and the supernatant was removed by decantation. Furthermore, after mixing with an aqueous gelatin solution and performing redispersion, pH = 5 at 40 ° C.
5. Adjusted to pCl = 1.8. Thus, the average particle size is 0.
A 23 μm seed emulsion (EmS-C1) was obtained.

The above (C1) was added to 2 liters of a 3.5% gelatin aqueous solution containing a seed emulsion (EmS-C1), the amount of which was appropriately adjusted so that the finished grain size was about 0.71 μm, and kept at 40 ° C. Solution) and (D1 solution) were pAg = 8.
While maintaining 0 and pH = 5.5, simultaneous addition was carried out over 180 minutes to grow particles.

After the addition is completed, Demol N manufactured by Kao Atlas Co., Ltd.
Was desalted using a 5% aqueous solution of the above and a 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution to perform redispersion. Thus, a monodisperse cubic emulsion EMP-13 having an average grain size of 0.71 μm and a silver chloride content of 99.5 mol% was obtained. Next, the amount of seed emulsion (EmS-C1) added and (C1
EM except that the addition time of (solution) and (D1 solution) was appropriately changed
A monodisperse cubic emulsion EMP-14 having an average particle size of 0.64 μm and a silver chloride content of 99.5 mol% in the same manner as in P-13.
I got

The above-mentioned EMP-13 was optimally chemically sensitized at 60 ° C. in the same manner as in EMP-11 using the above compound. Similarly, after optimally chemically sensitizing EMP-14, the sensitized EMP-13 and EMP-14 were mixed at a silver ratio of 1: 1 to prepare a blue-sensitive silver halide emulsion ( Em-B102) was obtained.

(Preparation of (111) tabular silver halide emulsion without seed emulsion) pH = 5.8, 2 kept at 40 ° C.
% Gelatin solution (containing 7.8 g of sodium chloride and 0.186 g of adenine sulfate) in 500 ml of the following (A3
Solution) and (B3 solution) while controlling pCl to 1.0
Added over minutes.

(Solution A3) Sodium chloride 57.2 g Potassium hexachloroiridium (IV) ate 2.2 × 10 ⁻⁸ mol Potassium hexacyanoferrate (II) 1.1 × 10 ⁻⁵ mol Water 250 ml (solution B3) ) Silver nitrate 169.9 g Water was added and 250 ml was added, and then desalting was performed using a 5% aqueous solution of Demol N manufactured by Kao Atlas and a 20% aqueous solution of magnesium sulfate, followed by redispersion by mixing with an aqueous gelatin solution. went. The obtained silver halide grains have a (111) plane as a main plane, an average grain size of 1.5 μm, an average thickness of 0.21 μm (average aspect ratio of 7.1), and an aspect ratio of 3.0 or more. It was a tabular silver halide emulsion EMP-15 in which the grains accounted for 70% of the projected area.

Next, the above-mentioned EMP-15 was optimally chemically sensitized at 60 ° C. using the above-mentioned compound at 60 ° C. to obtain a blue-sensitive silver halide emulsion (Em-B103).
I got

(Preparation of (111) tabular silver halide emulsion using seed emulsion) 2% of pH = 5.8 kept at 40 ° C.
The following (A4) was added to 2 liters of a gelatin solution (containing 31.2 g of sodium chloride and 0.744 g of adenine sulfate).
Solution) and (B4 solution) were added while controlling pCl = 1.0.

(Liquid A4) Sodium chloride 11.4 g Water was added to 50 ml (Liquid B4) Silver nitrate 34.0 g Water was added 50 ml After the addition was completed, the mixture was cooled to 40 ° C., and a 5% aqueous solution of Demol N manufactured by Kao Atlas Co., Ltd. A 20% aqueous solution of magnesium sulfate was added to cause aggregation, and the mixture was allowed to stand, and the supernatant was removed by decantation. Thereafter, ion-exchanged water heated to 40 ° C. was added for re-dispersion, then a 20% aqueous solution of magnesium sulfate was added again, and the mixture was allowed to stand, and the supernatant was removed by decantation. After further mixing with an aqueous gelatin solution and redispersion, pH = 5.5 at 40 ° C.,
The pCl was adjusted to 1.8. Thus the average particle size is 0.23
A μm seed emulsion (EmS-T1) was obtained.

A seed emulsion (EmS-T1), the amount of which was appropriately adjusted so that the finished grain size was about 1.5 μm,
The above-mentioned (A3 solution) and (B3 solution) were simultaneously added to 2 liters of a 3.5% gelatin aqueous solution kept at 40 ° C. while keeping pCl = 1.0 to grow grains.

After the addition is completed, Demol N manufactured by Kao Atlas Co., Ltd.
Was desalted using a 5% aqueous solution of the above and a 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution to perform redispersion. The silver halide grains thus obtained are (11
1) having a surface as a main plane, having an average particle diameter of 1.5 μm and an average thickness of 0.21 μm (average aspect ratio 7.1),
It was a tabular silver halide emulsion EMP-16 in which grains having an aspect ratio of 3.0 or more occupied 72% of the projected area.

Next, the above-mentioned EMP-16 was optimally chemically sensitized at 60 ° C. using the above compounds in the same manner as in EMP-11 to obtain a blue-sensitive silver halide emulsion (Em-B104).
I got

(Preparation of (100) tabular silver halide emulsion without seed emulsion) In 2 liter of 3.5% gelatin aqueous solution (containing 0.654 g of sodium chloride and 0.050 g of potassium iodide) kept at 40 ° C. The following (A5 solution) and (B5 solution) were simultaneously added for 30 seconds, and after aging for 10 minutes, the following (C5 solution) and (D5 solution) were further added with pCl = 2.
While controlling at 32, simultaneous addition was carried out over 170 minutes.

(Solution A5) Sodium chloride 3.49 g Potassium iodide 0.05 g Water added 30 ml (Solution B5) Silver nitrate 10.2 g Water added 30 ml (Solution C5) Sodium chloride 54.9 g Hexachloroiridium (IV) Potassium acid salt 2.2 × 10 ^-8 mol Potassium hexacyanoferrate (II) acid 1.1 × 10 ^-5 mol Water added 1880 ml (D5 solution) Silver nitrate 159.7 g Water added 1880 ml Kao Atlas After desalting was performed using a 5% aqueous solution of DEMOL N and a 20% aqueous solution of magnesium sulfate, the mixture was mixed with an aqueous gelatin solution for redispersion. Thus, the average particle size is 1.53 μm and the average thickness is 0.11 μm
A silver chloroiodide emulsion EMP-1 having a (100) plane with an average aspect ratio of 13.9 as a main plane and containing 75% of a projected area of silver halide grains having an aspect ratio of 3.0 or more.
7 was obtained.

Then, the above-mentioned EMP-17 was subjected to optimum chemical sensitization at 60 ° C. using the above-mentioned compounds at a temperature of 60 ° C. to obtain a blue-sensitive silver halide emulsion (Em-B105).
I got

(Preparation of seed emulsion EmS-1) 3.5% aqueous gelatin solution (sodium chloride 5.0 g
Further, the following (A6 solution) and (B6 solution) were simultaneously added in 6 liters of 6 liters (containing 0.40 g of potassium iodide), the temperature was raised to 65 ° C., and the mixture was aged for 15 minutes.

(Solution A6) Sodium chloride 27.92 g Potassium iodide 0.40 g Water was added to 240 ml (Solution B6) Silver nitrate 81.6 g Water was added to 240 ml After aging, the mixture was cooled to 40 ° C. and manufactured by Kao Atlas demol. A 5% aqueous solution of N and a 20% aqueous solution of magnesium sulfate were added to cause coagulation and allowed to stand, and the supernatant was removed by decantation. Thereafter, ion-exchanged water heated to 40 ° C. was added for re-dispersion, then a 20% aqueous solution of magnesium sulfate was added again, and the mixture was allowed to stand, and the supernatant was removed by decantation. After further mixing with an aqueous gelatin solution and redispersion, pH = 5.5 at 40 ° C.,
The pCl was adjusted to 1.8. Thus, the average particle size 0.4
A seed emulsion (EmS-1) having (m) and (100) faces as main planes and containing 75% of silver halide grains having an aspect ratio of 2.0 or more in a projected area was obtained.

(Preparation of seed emulsion EmS-2) Seed emulsion (Em Em-2)
In the preparation of S-1), cooling to 40 ° C. after completion of aging,
A 10% aqueous solution of modified gelatin in which 90% of the amino groups of gelatin were replaced by phenylcarbamoyl groups was added, and the pH was adjusted to 3.0 with sulfuric acid, and the mixture was allowed to stand and then decanted. After that, ion-exchanged water and an aqueous sodium hydroxide solution were added to re-disperse the solution to pH 5.5,
The pH was lowered again with sulfuric acid and the mixture was allowed to stand and the supernatant was removed by decantation. After further mixing with an aqueous gelatin solution and redispersion, pH = 5.5 at 40 ° C.,
A seed emulsion (EmS-2) was prepared in the same manner except that pCl was adjusted to 1.8.

(Preparation of seed emulsion EmS-3) Seed emulsion (Em Em-3)
In the preparation of S-1), cooling to 40 ° C. after completion of aging,
A seed emulsion (EmS-3) was prepared in the same manner except that the desalting treatment was performed by an ultrafiltration treatment using a semipermeable membrane having an NMWL (nominal molecular weight limit) of 100,000.

(Preparation of (100) Tabular Silver Halide Emulsion Using Seed Emulsion) The amount of seed emulsion (EmS-1) was appropriately adjusted so that the finished grain size was about 1.53 μm, and the temperature was 40 ° C.
The following (C6 solution) and (D6 solution) were simultaneously added to 2 liters of a 3.5% gelatin aqueous solution kept warm at 170 ° C. for 170 minutes to grow grains.

(C6 Solution) Sodium Chloride 54.9 g Potassium Hexachloroiridium (IV) ate 2.2 × 10 ⁻⁸ mol Potassium Hexacyanoferrate (II) 1.1 × 10 ⁻⁵ mol Water 1880 ml (D6 Solution) ) Silver nitrate 159.7 g Water was added and 1880 ml was added, and then desalting was performed using a 5% aqueous solution of Demol N manufactured by Kao Atlas and a 20% aqueous solution of magnesium sulfate, followed by mixing with a gelatin aqueous solution for redispersion. went. Thus, the average particle size is 1.54 μm and the average thickness is 0.11 μm.
A silver chloroiodide emulsion EMP-1 having a (100) plane of (average aspect ratio 14.0) as a main plane and containing 75% of a projected area of silver halide grains having an aspect ratio of 3.0 or more.
8 was obtained.

In the preparation of emulsion EMP-18, (EmS-2) and (EmS-2) were used instead of seed emulsion (EmS-1).
-3), except that silver chloroiodide emulsion EMP was used.
-19 and EMP-20 were obtained.

Emulsion EMP-19 had an average grain size of 1.54 μm.
m, average thickness 0.11 μm (average aspect ratio 14.
No. 0) has a (100) plane as a main plane and contains 72% of a silver halide grain having an aspect ratio of 3.0 or more in a projected area. Emulsion EMP-20 has an average grain size of 1.54 μm.
m, average thickness 0.11 μm (average aspect ratio 15.
It was an emulsion having the (100) plane of 4) as the main plane and containing 80% of the projected area of silver halide grains having an aspect ratio of 3.0 or more.

Then, the above EMP-18 to EMP-20 were optimally chemically sensitized at 60 ° C. in the same manner as in EMP-11 using the above compounds to obtain a blue-sensitive silver halide emulsion (E
m-B106) to (Em-B108) were obtained.

<Preparation of Photosensitive Material> High density polyethylene was laminated on both sides of paper pulp having a basis weight of 180 g / m ² .
A paper support was prepared. However, on the side where the emulsion layer is applied,
15% by weight of surface-treated anatase-type titanium oxide
A molten support was laminated by laminating with a content of 1 to prepare a reflective support. After subjecting this reflective support to corona discharge treatment, a gelatin subbing layer was provided, and then each layer having the constitution shown below was coated to prepare a monochromatic color light-sensitive material 101. The coating liquid was prepared as follows.

First Layer Coating Liquid Yellow coupler (Y-1) 23.4 g, dye image stabilizer (ST-1) 3.34 g, (ST-2) 3.34.
g, (ST-5) 3.34 g, a stain inhibitor (HQ-
1) 0.34 g, 5.0 g of image stabilizer A, 3.33 g of high-boiling organic solvent (DBP) and high-boiling organic solvent (DNP)
To 1.67 g, 60 ml of ethyl acetate was added and dissolved.
A yellow coupler dispersion was prepared by emulsifying and dispersing 220 ml of 0% gelatin aqueous solution using an ultrasonic homogenizer. This dispersion was mixed with the blue-sensitive silver halide emulsion prepared under the above conditions to prepare a first layer coating solution.

The coating liquid for the second layer was also prepared so as to have the coating amount shown in Table 1.

Further, as a hardening agent (H-1), (H-2)
Was added. Surfactants (SU-
2) and (SU-3) were added to adjust the surface tension.
In addition, the total amount of antifungal agent (F-1) is 0.04 g / m ² in each layer.
Was added so that

[0145]

[Table 1]

SU-1: Sodium tri-i-propylnaphthalene sulfonate SU-2: Di (2-ethylhexyl) sulfosuccinate sodium salt SU-3: Di (2,3,3,4) sulfosuccinate , 4,
5,5-octafluoropentyl) sodium salt DBP: dibutyl phthalate DNP: dinonyl phthalate H-1: tetrakis (vinylsulfonylmethyl) methane H-2: 2,4-dichloro-6-hydroxy-s-triazine sodium HQ-1: 2,5-di t-octyl hydroquinone Image stabilizer A: p-t-octyl phenol

[0147]

Embedded image

Photosensitive materials 102 to 108 were prepared in the same manner as in Table 2 except that the silver halide emulsion was changed as shown in Table 2.
Was prepared.

The photosensitive materials 101 to 101 thus prepared
108, blue light 0.5 seconds, 0.02 seconds,
After light wedge exposure for 10 ⁻³ seconds and color development processing in the following development processing steps, the reflection density by blue light was measured using a densitometer PDA-65 (manufactured by Konica).

The gradations are 0.75 for reflection density and 1.
It is defined as an average gradient between 75, and in each light-sensitive material, the gradation when exposed for 0.5 seconds is used as a reference,
Gradation reproduction stability was evaluated by the difference from the gradation when exposed for 0.02 seconds and 10 ⁻³ seconds. Table 2 shows the results.

Treatment Process Treatment Temperature Time Replenishment Amount Color development 38.0 ± 0.3 ° C. 45 seconds 80 ml Bleach-fix 35.0 ± 0.5 ° C. 45 seconds 120 ml Stabilization 30-34 ° C. 60 seconds 150 ml Dry 60 to 80 ° C. 30 seconds The composition of the development processing solution is shown below.

Color developer tank solution and replenisher tank solution Replenisher solution Pure water 800 ml 800 ml Triethylenediamine 2 g 3 g Diethylene glycol 10 g 10 g Potassium bromide 0.01 g-Potassium chloride 3.5 g-Potassium sulfite 0.25 g 0.5 g N-ethyl -N- (β methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 6.0 g 10.0 g N, N-diethylhydroxylamine 6.8 g 6.0 g triethanolamine 10.0 g 10.0 g diethylenetriamine penta Sodium acetate salt 2.0 g 2.0 g Fluorescent brightener (4,4′-diaminostilbene disulfonic acid derivative) 2.0 g 2.5 g Potassium carbonate 30 g 30 g Water was added to make the total volume 1 liter, and the tank liquid had pH = 1
Adjust the replenisher to pH = 10.60 to 0.10.

Bleach-fixing solution tank solution and replenishing solution Diethylenetriamine pentaacetic acid ammonium ferric dihydrate 65 g Diethylenetriamine pentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml 2-Amino-5-mercapto-1,3,4-thiadiazole 2 0.0 g Ammonium sulfite (40% aqueous solution) 27.5 ml Water is added to bring the total volume to 1 liter, and the pH is adjusted to 5.0 with potassium carbonate or glacial acetic acid. The replenisher used has the same composition as the tank solution.

Stabilizing solution tank solution and replenishing solution o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g Diethylene glycol 1.0 g Optical brightener (Tinopearl SFP) 2.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.8 g Bismuth chloride (45% aqueous solution) 0.65 g Magnesium sulfate heptahydrate 0.2 g PVP 1 0.0 g Ammonia water (ammonium hydroxide 25% aqueous solution) 2.5 g Nitrilotriacetic acid trisodium salt 1.5 g Water is added to bring the total volume to 1 liter, and pH is adjusted to 7.5 with sulfuric acid or ammonia water. The replenisher used has the same composition as the tank solution.

[0155]

[Table 2]

From the results shown in Table 2, the silver halide emulsion prepared by growing the desalted seed emulsion was remarkably improved in the drawback that it was softened by high-intensity short-time exposure. It can be seen that the gradation variation is reduced. As is clear from the comparison of the results of the photosensitive materials 101 and 105,
This variation in gradation is a drawback of tabular grains and has been desired to be improved. A comparison of the light-sensitive materials 108 and 106, 107 shows that the effect of this improvement is particularly great when the seed emulsion is prepared by desalting by ultrafiltration.

Example 2 <Preparation of green-sensitive silver halide emulsion> (A1 solution) and (B1)
Solution) and the addition time of (C1 solution) and (D1 solution) are changed, the same as EMP-11, except that the average particle size is 0.40 μm and the silver chloride content is 99.5 mol%. A cubic emulsion EMP-21 was obtained. Next, average particle size 0.5
A monodisperse cubic emulsion EMP-22 having 0 μm and a silver chloride content of 99.5 mol% was obtained.

The above-mentioned EMP-21 was optimally chemically sensitized at 55 ° C. using the following compounds. Also, EMP-2
Similarly, after optimally chemically sensitizing No. 2 with each other, the sensitized EMP-21 and EMP-22 were mixed in a silver ratio of 1: 1 to prepare a green-sensitive silver halide emulsion (Em-G101). Got

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stable Agent STAB-3 3 × 10 ⁻⁴ mol / mol AgX Sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX E except for changing the addition time of (A5 solution) and (B5 solution)
In the same manner as MP-20, an average particle size of 1.05 μm and an average thickness of 0.09 μm (aspect ratio 11.7) (10
A silver chloroiodide emulsion EMP-23 having a 0) plane as a main plane and containing 80% of a silver halide grain having an aspect ratio of 3.0 or more in a projected area was obtained.

Next, the above-mentioned EMP-23 was optimally chemically sensitized at 60 ° C. using the above-mentioned compound in the same manner as in EMP-21, and a green light-sensitive silver halide emulsion (Em-G108) was obtained.
I got

<Preparation of Red-Sensitive Silver Halide Emulsion> (A1
Solution) and (B1 solution) addition time and (C1 solution) and (D1
The same as EMP-11 except that the addition time of the solution was changed, the average particle size was 0.40 μm, and the silver chloride content was 99.5.
A mol% monodisperse cubic emulsion EMP-31 was obtained. Further, a monodisperse cubic emulsion EMP-32 having an average particle size of 0.38 μm and a silver chloride content of 99.5 mol% was obtained.

The above EMP-31 was optimally chemically sensitized at 60 ° C. using the following compounds. Also, EMP-3
In the same manner as in No. 1, the same chemical sensitization was performed, and then the sensitized EMP-31 and EMP-32 were mixed in a silver ratio of 1: 1 to obtain a red-sensitive silver halide emulsion (Em-R101). Obtained.

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stable Agent STAB-3 3 × 10 ^-4 mol / mol AgX sensitizing dye RS-1 1 × 10 ^-4 mol / mol AgX sensitizing dye RS-2 1 × 10 ^-4 mol / mol AgX Supersensitizer SS- 12 × 10 ^-3 mol / mol AgX

[0164]

Embedded image

An average particle size of 1.0 was obtained in the same manner as EMP-20 except that the addition time of (A5 solution) and (B5 solution) was changed.
0 μm, average thickness 0.08 μm (aspect ratio 12.
A silver chloroiodide emulsion EMP-33 having (100) plane of 5) as a main plane and containing 80% of silver halide grains having an aspect ratio of 3.0 or more in a projected area was obtained.

Then, the above compound was subjected to optimum chemical sensitization at 60 ° C. to EMP-33 in the same manner as in EMP-31 to obtain a red-sensitive silver halide emulsion (Em-R10).
8) was obtained.

<Preparation of Photosensitive Material> After the reflective support described in Example 1 was subjected to corona discharge treatment, a gelatin subbing layer was provided, and each layer having the constitution shown below was coated to prepare a multilayer color photosensitive material. did.

The coating solutions were prepared in the same manner as in Example 1 so that the coating amounts were as shown in Tables 3 and 4.

Further, as a hardening agent (H-1), (H-2)
Was added. Surfactants (SU-
2) and (SU-3) were added to adjust the surface tension.
Further, (F-1) was added to each layer so that the total amount was 0.04 g / m ² .

The types of silver halide emulsions used are shown in Table 5.

[0171]

[Table 3]

[0172]

[Table 4]

DOP: Dioctylphthalate DIDP: Di-i-decylphthalate PVP: Polyvinylpyrrolidone HQ-2: 2,5-di-sec-dodecylhydroquinone HQ-3: 2,5-di-sec-tetradecylhydroquinone HQ- 4: 2-sec-dodecyl-5-sec-tetradecylhydroquinone HQ-5: 2,5-di [(1,1-dimethyl-4-hexyloxycarbonyl) butyl] hydroquinone

[0174]

Embedded image

[0175]

Embedded image

[0176]

[Chemical 6]

The photosensitive materials 201 to 201 thus produced
205 with white light, 0.5 seconds, 0.02 respectively
Optical wedge exposure for 10 seconds to 10 ^-3 seconds, and after performing the same processing as in Example 1, using a densitometer PDA-65 (described above), B,
The G and R reflection densities were measured.

Gradation is defined in the same manner as in Example 1, and when each light-sensitive material is exposed for 0.5 seconds, the gradation of each color image is used as a reference, and when exposed for 0.02 seconds and 10 ^-3 seconds. The stability with respect to changes in the exposure conditions was evaluated based on the difference from the gradation.

The results are shown in Table 5.

[0180]

[Table 5]

From the results shown in Table 5, the effect of the present invention is remarkable, particularly when the emulsion of the present invention is used in the blue photosensitive layer, and the halogenation of cubic grains is used in the photosensitive layers other than the blue photosensitive layer. It is understood that the use of the silver emulsion is preferable because the gradation variation between the emulsion layers is balanced.

Example 3 In the preparation of the light-sensitive materials 101 to 108 of Example 1, the coating amount of the silver halide emulsion in the blue light-sensitive layer was 0.05 g / m 2.
Except for using ² were similarly prepared photosensitive material 301-308.

The photosensitive materials 301 to 301 thus produced
The same exposure as in Example 1 was performed on 308, and after redox amplification development processing was performed by the following development processing step,
The reflection density by blue light was measured using a densitometer PDA-65 (described above).

For the gradation, the average gradient between the reflection densities of 0.75 and 1.75 is the shoulder gradation, and the reflection densities of 0.3 and 0.7.
The average gradient between 5 is defined as the leg gradation, and in each light-sensitive material, the gradation when exposed for 0.5 seconds is used as a reference, and the gradation when exposed for 0.02 seconds and 10 ^-3 seconds. The stability of gradation reproduction was evaluated by the difference between the gradation and the gradation.

The results are shown in Table 6.

Processing Step Treatment Temperature Time Amplified Development 35.0 ± 0.3 ° C. 45 seconds Bleaching Fixing 35.0 ± 0.5 ° C. 20 seconds Stabilization 30 to 34 ° C. 30 seconds Dry 60 to 80 ° C. 30 The composition of the second developing solution is shown below.

Redox amplification developer tank liquid Pure water 800 ml Potassium bromide 0.001 g Potassium chloride 0.35 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 4.0 g N, N-diethylhydroxylamine 4.7 g Diethylenetriaminepentaacetic acid sodium salt 2.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 0.35 g Optical brightener (4,4′-diaminostilbenedisulfonic acid derivative) 2. 0 g Potassium carbonate 10 g Hydrogen peroxide solution (30%) 5.0 g Water is added to bring the total volume to 1 liter, and the pH is adjusted to 10.0.

Bleach-fixing solution tank solution and replenisher solution Same as Example 1 Stabilizing solution tank solution and replenisher solution Same as Example 1

[0189]

[Table 6]

From the results shown in Table 6, the silver halide emulsion prepared by growing a desalted seed emulsion has a soft shoulder when exposed to high illuminance and for a short time when used in a light-sensitive material for amplification development processing. It is understood that the disadvantage that the legs become harder is greatly improved, and the fluctuation of the gradation due to the change of the exposure condition is reduced.

As is clear from the comparison of the results of the light-sensitive materials 301 and 305, this gradation variation is a drawback of tabular grains and has been desired to be improved. A comparison between the light-sensitive materials 308 and 306, 307 shows that the effect of this improvement is particularly large when the seed emulsion is prepared by desalting by ultrafiltration.

Example 4 In the preparation of the light-sensitive materials 201 to 205 of Example 2, the coating amount of the silver halide emulsion in the blue light-sensitive layer was 0.05 g / m.
² , the coating amount of silver halide emulsion in the green photosensitive layer is 0.03
g / m ^2, except that the coating amount of silver halide emulsion of the red-sensitive layer and 0.04 g / m ² in the same manner, the light-sensitive material 4
01 to 405 were produced, each light-sensitive material was exposed to light in the same manner as in Example 2, and was subjected to the same redox amplification development process as in Example 3.

As a result, even when the silver halide emulsion of the present invention was applied to a full-color light-sensitive material and subjected to redox amplification development processing, variations in shoulder gradation and leg gradation were small with respect to changes in exposure time. It was confirmed.

[0194]

According to the silver halide emulsion of the present invention and the silver halide photographic light-sensitive material using the same, the sensitivity is high and the processability is excellent, and even when the exposure condition is changed, especially when the redox amplification development process is performed, it is high. Images can be formed with little change in gradation due to illuminance and short-time exposure.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G03C 7/00 520 G03C 7/00 520 7/407 501 501 7/407 501

Claims (5)

[Claims] 1. A silver halide grain which has been desalted, has an aspect ratio of 2.0 or more, and has a (100) plane as a main plane and has no twin planes, has a projected area of all silver halide grains. An emulsion prepared by using a silver halide emulsion occupying 50% or more as a seed emulsion, having an average silver chloride content of 50 mol% or more, an aspect ratio of 3.0 or more, and a grain thickness of 0.3.
The tabular silver halide grains having a main plane of (100) plane or less are 50 μm or less of the projected area of all silver halide grains.
% Of the photosensitive silver halide emulsion. 2. The photosensitive silver halide emulsion according to claim 1, wherein the seed emulsion is desalted by at least one of an electrodialysis method and an ultrafiltration method. 3. A silver halide photographic light-sensitive material having a light-sensitive silver halide emulsion layer containing at least one layer of blue-light-sensitive silver halide grains and a dye-providing substance on a support, wherein the blue-light-sensitive halogen is used. A silver halide photographic light-sensitive material comprising a silver halide emulsion layer containing the light-sensitive silver halide emulsion according to claim 1 or 2. 4. A silver halide photographic light-sensitive material having, on a support, at least two layers of light-sensitive silver halide grains having different color sensitivities and a light-sensitive silver halide emulsion layer containing a dye-donor substance. A blue light-sensitive silver halide emulsion layer contains the light-sensitive silver halide emulsion according to claim 1 or 2, and each of the remaining light-sensitive silver halide emulsion layers contains 50 times the projected area of the silver halide emulsion. % Or more, the silver halide photographic light-sensitive material is characterized by comprising silver halide grains having an average silver chloride content of 50 mol% or more and an aspect ratio of 2.0 or less. 5. The method according to claim 1, wherein at least one layer is provided on the support.
Alternatively, a method for forming an image, which comprises subjecting a silver halide photographic light-sensitive material having a light-sensitive silver halide emulsion layer containing the light-sensitive silver halide emulsion and the dye-providing substance described in 2 to redox amplification development.