JPH1031278A - Seed emulsion for forming tabular silver halide, production of tabular silver halide photographic emulsion, and silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a seed emulsion for forming tabular silver halide having high sensitivity and rapid processing property, a process for producing a tabular silver halide photographic emulsion and a silver halide photographic sensitive material. SOLUTION: Particles of cubic normal crystals composed of (100) faces are used as the seed crystals forming the tabular silver halide particles consisting essentially of silver chloride. This process for producing the tabular silver halide photographic emulsion of >=50% in the average silver chloride content of the silver halide particles produces the tabular silver halide photographic emulsion formed of the seed emulsion for forming the tabular silver halide which is the cubic normal crystals formed by growing the cubic normal crystal silver halide particles as the seed crystals to the tabular particles and constituting the seed particles of the (000) faces and contains these seed particles in such a manner that the tabular silver halide particles having an aspect ratio of >=3.0, a particle thickness of <=0.3μm and having the (100) faces as main planes occupy >=50% of the projection area of the entire silver halide particle.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a seed emulsion for forming tabular silver halide, a method for producing a tabular silver halide photographic emulsion, and a method for producing a silver halide photographic emulsion. About the material.

[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, recently, higher sensitivity, higher sharpness, improved graininess,
For the purpose of speeding up processing and the like, studies on tabular silver halide grains (hereinafter, also simply referred to as tabular grains, tabular grains) have been actively conducted.

As such tabular silver halide grains having a high silver chloride content, grains having a (111) major plane and grains having a (100) major 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, the (100) plane is stable in silver halide grains having a high silver chloride content, and these crystal habit controlling agents are desorbed when salts formed during the formation of silver halide grains are removed. The shape of the particles changes (1)
11) It has been found difficult to stably obtain tabular grains having a main plane.

Further, it has been found that many of such crystal habit control agents are known as so-called inhibitors, and there is a problem that chemical sensitization cannot be performed well in the presence of these compounds.

On the other hand, tabular grains having a (100) plane as a main plane are disclosed in JP-A-5-204073, US Pat. Nos. 5,264,337, 5,275,930 and JP-A-6-275930. No. 301131, No. 6-308648, No. 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 to tabular silver halide grains having a major surface as a plane, the shape is more stable, and there is an advantage that spectral chemical sensitization is easily performed since no crystal habit controlling agent is particularly required.

However, such tabular silver halide grains having a high silver chloride content and having the (100) plane as the main plane form non-tabular grains, particularly polygonal grains having twin planes at the same time during the formation process. This causes a reduction in the projected area ratio of the tabular grains to the entire grains (hereinafter referred to as a tabular ratio).

Further, JP-A-7-287332, JP-A-7-89522 and JP-A-7-60656 disclose the preparation of tabular silver halide grains having a high silver chloride content.
Although there is a description that a seed emulsion can be used, there is no mention of improving the tabular ratio as a seed grain, and further there is no description of the effect of using a normal crystal.

Further, in the method using tabular grains as seeds for forming tabular grains, the shape, grain size, and the like between grains are varied at the stage of forming the tabular grains, and the variation is caused in the grown grains. It turned out that there was a problem that it had a significant effect. Further, it has been found that this variation has an adverse effect on the sensitization process, storage, and further development processes after grain formation.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a seed emulsion for tabular silver halide formation, a method for producing a tabular silver halide photographic emulsion, and a silver halide photographic light-sensitive material having excellent sensitivity and rapid processing. Is to provide.

[0011]

The above object of the present invention is achieved by the following constitution.

[0012] As seed grains for forming tabular silver halide grains containing silver chloride as a main component, grains of cubic normal crystals composed of (100) planes are used. The seed emulsion is used as the seed emulsion or in the emulsion manufacturing vessel, and is consciously and temporarily used to form an excellent silver halide photographic light-sensitive material. Tabular silver halide grains containing silver chloride as a main component that can be provided are preferred and can be advantageously formed.

Further, the present invention relates to a method for producing a tabular silver halide photographic emulsion wherein the average silver chloride content of the silver halide grains is 50 mol% or more, wherein the tabular grains are grown using cubic normal crystal silver halide grains as seed grains. And the seed particles are (100)
A tabular silver halide photographic emulsion formed from a tabular silver halide forming seed emulsion containing the seed grains and having a normal aspect ratio of 3.0 or more and a grain thickness of 0 3. A method for producing a tabular silver halide photographic emulsion, wherein tabular silver halide grains having a size of not more than 3 .mu.m and having a (100) plane as a main plane occupy 50% or more of the projected area of all silver halide grains. Is preferable, and a tabular silver halide grain capable of providing an excellent silver halide photographic light-sensitive material is preferable and can be advantageously produced.

The total number of seed particles of the cubic normal crystals is 6
If the particle size of 0% or more is 0.20 μm or less, it can be more preferably produced.

The tabular silver halide forming seed emulsion containing the seed grains is more preferably desalted by electrodialysis and / or ultrafiltration to produce a tabular silver halide emulsion more preferably.

A silver halide photographic material having at least one silver halide emulsion layer on a support, wherein the tabular silver halide emulsion of the present invention is produced on at least one silver halide emulsion layer. A silver halide photographic light-sensitive material containing a tabular silver halide emulsion produced by the above method has an unprecedented excellent sensitivity and maximum density.

The light-sensitive silver halide emulsion of the present invention has a grain growth method comprising the steps of producing a seed emulsion and forming a tabular silver halide emulsion having a (100) plane in the main plane using the seed emulsion. And a step of introducing anisotropic growth into the grains for growing normal crystals into tabular grains between the seed emulsion producing step and the grain growing step (hereinafter referred to as an anisotropic growth introducing step). You. The present invention is characterized in that the seed production process and the anisotropic growth introducing process are separated.

In the conventional method for forming (100) silver chloride tabular grains, many nontabular grains having twins are formed at the same time, and as a result, there is a technical need to be improved in that the ratio of tabular grains is reduced. Was. The present invention has been surprisingly made based on the experimental fact that, when a cubic normal crystal composed of (100) planes is used as seed grains, the non-tabular grains are significantly reduced. Although the reason for this is not clear, for the purpose of growing tabular silver halide grains, the crystal is grown with a strain at an early stage of the crystal growth. The particle itself interacts with the intrinsic factors such as distortion,
At the same time, many non-tabular grains are formed in order to form twin planes on the surface of the silver halide grains or to create favorable conditions for forming them. On the other hand, normal crystals having a cubic shape are the seed grains themselves. It is presumed that there are few factors such as distortion inherent therein.

For example, a cubic normal crystal can be preferably used as a seed emulsion known as a grain formation technique.
The seed particles preferably have a monodisperse particle size distribution, and the particle size distribution preferably has a coefficient of variation of 15% or less, more preferably 10% or less. Here, the coefficient of variation is a coefficient representing the width of the particle size distribution, and is defined by the following equation.

Coefficient of variation = S / R × 100 (where, S represents the standard deviation of the grain size distribution, and R represents the average grain size. Here, the grain size means the volume of the silver halide grains in terms of cube. Here, it is preferable to use a monodisperse seed crystal in the case where grains are usually formed from a silver salt and a halogen salt. Further, variation between lots occurs. However, by using monodispersed species, monodisperse particles can be obtained with good reproducibility even when the scale is increased, and stable production becomes possible.

The seed particles are preferably composed of the (100) plane, and the phrase "constituted by the (100) plane" means that they only need to be composed substantially of the (100) plane. Is also good. Preferably, 60% or more should be constituted by the (100) plane.

The halogen composition of the seed emulsion grains is optional.
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 subsequent process of introducing anisotropic growth, it is difficult to make all the seed particles have anisotropic growth. Therefore, the difference in growth rate between particles having anisotropic growth and particles having no anisotropic growth is determined. In order to eliminate particles without anisotropy by using,
Preferably, 60% or more of the total number of the seed particles is 0.20 μm or less, and more preferably 0.10 μm or less.

In the present invention, the seed emulsion is preferably subjected to a desalting process to remove unnecessary soluble salts. Known techniques can be used for the desalting method.For example, a method in which the emulsion is cooled and set, cut into fine or noodle shapes and washed with water, a combination of a precipitant and a polyvalent metal ion, modified gelatin, synthetic gelatin, A coagulation sedimentation method in which the supernatant is removed by decantation after coagulation using a polymer coagulant or the like, or a separation method using a membrane such as electrodialysis and / or ultrafiltration is exemplified. In particular, when a desalting method without using a flocculant is used, gradation can be stably reproduced with respect to changes in exposure conditions, which is preferable. In particular, the electrodialysis method and the ultrafiltration method are preferably used without increasing the volume of the emulsion due to water absorption. When tabular grains are grown using the seed emulsion subjected to ultrafiltration, a photographic light-sensitive material having surprisingly good performance such as sensitivity and maximum density can be obtained. When the ultrafiltration treatment is applied to the seed emulsion, the particles having a small particle diameter are unstable, so that the particle diameter is required to be a certain level or more, and specifically, 0.08 μm or more is preferable.

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

The seed emulsion after desalting may be adjusted to pH or p
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 that l be 1.2 or more.

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

As a method for introducing anisotropic growth into grains for growing normal crystals into tabular grains, imidazole,
A method of adding a (100) plane formation accelerator such as 3,5-diaminotriazole, and a method of forming a gap in a halogen composition or causing a strain (dislocation) in a crystal plane under conditions such as high temperature and high pressure. There is a method of causing growth anisotropy. As a typical example, there is known a method in which silver iodide and silver bromide are present to cause dislocations in nuclei due to the difference in crystal lattice size from silver chloride, thereby introducing dislocations. This dislocation is considered to be a screw dislocation, an edge dislocation, or a mixed dislocation in which both are superposed. In any case, these dislocations cause a step on a specific surface of the cube, and the growth of the surface Is promoted, so that anisotropic growth is thought to occur.

As with the crystal habit controlling agent used for preparing the above-mentioned 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.

Regarding the content of silver iodide used to introduce anisotropic growth with respect to the total silver amount, if the amount of silver iodide is too large, there is a problem that phenomena such as inhibition of bleach-fix become remarkable. It is better to determine experimentally according to various conditions.

Physical ripening is performed following the anisotropic growth introducing process. The aging temperature is preferably 50 to 90 ° C, and 60 to 90 ° C.
80 ° C. is preferred. The aging speed is different depending on conditions such as pCl. Excessive aging is not preferred because the particle size distribution is widened.

Next, there is described a method for producing a tabular silver halide photographic emulsion wherein the average silver chloride content of the silver halide grains is 50 mol% or more. Growing the seed particles (100)
A tabular silver halide photographic emulsion formed from a tabular silver halide forming seed emulsion containing the seed grains and having a normal aspect ratio of 3.0 or more and a grain thickness of 0 3. A method for producing a tabular silver halide photographic emulsion, wherein tabular silver halide grains having a size of not more than 3 .mu.m and having a (100) plane as a main plane occupy 50% or more of the projected area of all silver halide grains. Will be described.

The amount of the seed emulsion used in the preparation process for obtaining the tabular silver halide grains is optional, and is appropriately determined according to the desired final grain size. It is preferable to use a seed emulsion in an amount corresponding to a silver amount of 1/15 or less with respect to the total amount of the salt, more preferably 1/25 or less, particularly preferably 1/30 or less.

The composition of the tabular silver halide grains is Ag
Cl, AgClBr, AgClI, AgClBrI, etc. can be used arbitrarily, but it is preferable that AgCl is contained in an amount of 50 mol% or more, and it is more preferable that AgCl is a high silver chloride particle in which the AgCl is 90 mol% or more. More preferably A
Ag in which gCl is 95 mol% or more and AgI is 1 mol% or less
Cl, AgClBr, AgClI or AgClBrI. From the viewpoint of rapid processing property and processing stability, AgCl
A silver halide emulsion containing at least mol% is more preferable,
A in which AgCl is 98 mol% or more and AgI is 1 mol% or less
gCl, AgClBr, AgClI or AgClBrI
Is particularly preferred.

In the tabular grains, silver halide having a different composition can be epitaxially grown or shelled on a specific surface portion. In order to control the photosensitive nucleus, dislocation lines may be provided on the surface or inside of the tabular grains.

In the silver halide emulsion produced by the method for producing a tabular silver halide photographic emulsion of the present invention, 50% or more of the total projected area of all silver halide grains has a thickness of 0 or more with an aspect ratio of 3.0 or more. .3 μm or less tabular grains.
Particularly, as the proportion of tabular grains increases to 70% and further to 80%, more favorable results are obtained. The aspect ratio here indicates the ratio of the diameter of a circle having the same area as the projected area of a tabular grain to the distance between two parallel planes. In the present invention, the average aspect ratio is preferably 3.0 or more, more preferably 3 or more and less than 20, and particularly preferably 4 or more and less than 16.

The average thickness (the distance between the main planes) is equal to 0.
Preferably it is 3 μm or less. In addition, the distribution of tabular grains having a (100) plane having an aspect ratio of 3.0 or more and a thickness of 0.3 μm or less as a main plane is often used as a coefficient of variation (distribution of a diameter of a circle when the projected area is approximated by a circle). Is 100 times the value of S / D, which is the standard deviation S of
0% or less is preferable.

In order to control the growth of the grains at the time of forming tabular grains, for example, ammonia, a thioether compound, a thione compound or the like can be used as a silver halide solvent. In addition, metal salts such as zinc, lead, thallium, iridium, and rhodium can coexist during physical ripening or chemical ripening.

In the tabular silver halide grains according to the present invention, the parallel principal plane is preferably the (100) plane. The principal plane referred to here is a set of parallel planes having the largest area among the crystal surfaces forming substantially rectangular parallelepiped emulsion grains. The average particle diameter of the main plane can be obtained by, for example, photographing the particle with an electron microscope at a magnification of 10,000 to 50,000 times and actually measuring the projected area of the particle on the print.
(The number of measured particles is assumed to be 1000 or more indiscriminately.) The particle thickness can also be obtained by actually measuring an electron micrograph.

The fact that the main plane is the (100) plane can be determined by an electron diffraction method or an X-ray diffraction method. According to electron micrograph observation, particles having a (100) principal plane have an orthogonal square (square or rectangular).
It can be checked because it is a surface.

In the grain growth process, a double jet method is preferably used. One type of the double jet method is a method of maintaining a constant pAg in a liquid phase in which silver halide is formed, that is, a so-called controlled double method. The jet method can also be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

In the tabular silver halide emulsion of the present invention, a part or all of the steps during grain formation may be a grain forming step by supplying fine silver halide grains.

Since the particle size of the fine particles supports the supply rate of halide ions, the preferred particle size varies depending on the size and halogen composition of the silver halide grains of the host, but those having an average equivalent sphere diameter of 0.3 μm or less are preferred. It is preferably used. More preferably, it is 0.1 μm or less. In order for the fine particles to be laminated on the host particles by recrystallization, the size of the fine particles is desirably smaller than the equivalent sphere diameter of the host particles, and more preferably 1/5 or less.

The silver halide emulsion used in the practice of the present invention is prepared by removing the soluble salts after completion of the growth of silver halide grains to obtain a pAg ion concentration suitable for chemical sensitization. A sedimentation method or the like may be used, and a preferred water washing method is, for example, a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in JP-B-35-16086, or a method disclosed in
Illustrative G-3, G-, which is a polymer flocculant described in No. 7037
8 and the like. Also, Research Disclosure (RD) Vol. 102,
1972, October issue, Item 10208 and Vo
l. 131, 1975, March issue, Item 13122, may be used for ultrafiltration.

In the silver halide color photographic light-sensitive material according to the present invention, silver halide grains other than tabular grains can be used in combination. One preferable example is a cube having a (100) plane as a crystal surface. Also, U.S. Pat.
Nos. 3,756, 4,225,666;
No. 26589, JP-B-55-42737, and The Journal of Photographic Science (J.
Photogr. Sci. ), Octahedron, tetrahedron, etc. by methods described in documents such as 21, 39 (1973).
Particles having a shape such as a dodecahedron can be produced and used. Further, particles having a twin plane may be used.

The composition of the silver halide grains other than the tabular grains is not particularly limited, and the preferred range is the same as the above-mentioned tabular grains. The particle size is not particularly limited, but is preferably 0.1 to 1.2 μm, more preferably 0.1 to 1.2 μm, in consideration of other photographic properties such as rapid processing property and sensitivity.
It is in the range of 2 to 1.0 μm. Here, the particle size is represented by the length of one side of a cube when the silver halide grains are converted into a cube having the same volume.

The particle size distribution of the non-tabular silver halide grains is preferably monodisperse silver halide grains having a variation coefficient of 22% or less, more preferably 15% or less. Here, the coefficient of variation is a coefficient representing the width of the particle size distribution, and is defined by the following equation.

Coefficient of variation = S / R × 100 (where, S represents the standard deviation of the grain size distribution, and R represents the average grain size.) The apparatus and method for preparing a silver halide emulsion other than tabular are as follows. Various methods known in the art can be used.

The non-tabular silver halide emulsion may be obtained by any of an acidic method, a neutral method, and an ammonia method. The particles may be grown at one time or may be grown after seed particles have been made. The method of producing the seed particles and the method of growing them may be the same or different.

The form in which the soluble silver salt and the soluble halide salt are reacted may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like. Is preferred. Further, as one type of the double jet method, a pAg controlled double jet method described in JP-A-54-48521 can be used.

Also, JP-A-57-92523 and JP-A-57-92523.
No.-92524, etc., a device for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition device disposed in a reaction mother liquor, and a water-soluble silver described in DE-A-2,921,164. A device for continuously adding a salt and an aqueous solution of a water-soluble halide salt while changing the concentration,
No. 501776, etc., a reaction mother liquor may be taken out of a 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. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye may be added at the time of forming silver halide grains or after the completion of grain formation.

In the present invention, regardless of whether the silver halide grains are tabular or not, when high silver chloride AgBrCl or AgBrClI grains are used, the silver halide grains having a portion containing a high concentration of silver bromide are used. Silver particles are particularly preferably used. In this case, the portion containing a high concentration of silver bromide may be epitaxy-bonded to silver halide emulsion grains, a so-called core-shell emulsion, or may be formed only partially without forming a complete layer. May simply have regions with different compositions. Further, the composition may change continuously or discontinuously. It is particularly preferable that the portion where silver bromide exists at a high concentration is the top of crystal grains on the surface of silver halide grains.

It is advantageous that silver halide grains contain heavy metal ions. Heavy metal ions that can be used for such purposes include iron, iridium, platinum,
Group 8-10 metals such as palladium, nickel, rhodium, osmium, ruthenium, cobalt and cadmium,
Group 12 transition metals such as zinc and mercury, lead, rhenium,
Examples include molybdenum, tungsten, gallium, and chromium ions. 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 a salt or a complex salt.

When the heavy metal ion forms a complex, the ligand may be a cyanide ion, thiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, nitrate ion, carbonyl, ammonia And the like. Among them, cyanide ion, thiocyanate ion, chloride ion, bromide ion and the like are preferable.

In order to allow the silver halide grains to contain heavy metal ions, the heavy metal compound is added during the physical ripening 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 heavy metal compound can be dissolved together with a halide salt and added continuously over the whole or a part of the grain forming step.

The amount of the heavy metal ions to be added is at least 1 × 10 ⁻⁹ mol per mol of silver halide and 1 × 10 ⁻² mol or more.
Mol or less, more preferably 1 × 10 ⁻⁸ mol or more and 5 × or less.
It is preferably at most 10 ^-5 mol.

In the silver halide emulsion layer of the silver halide photographic light-sensitive material according to the present invention, a silver halide emulsion composed of single-shaped grains is preferably used, and two types of monodisperse silver halide emulsions are used. These may be added to the same layer.

The silver halide photographic emulsion can be used in combination with a sensitization method using a gold compound and a sensitization method using a chalcogen sensitizer.

As a chalcogen sensitizer applied to a silver halide photographic emulsion, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer, and the like can be used, and a sulfur sensitizer is preferable. As a sulfur sensitizer, thiosulfate, allyl thiocarbamide thiourea, allyl isothiocyanate, cystine, p-toluene thiosulfonate, rhodanine,
Inorganic sulfur and the like.

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

As the gold sensitizer, various gold complexes such as chloroauric acid and gold sulfide can be added. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, and mercaptotriazole. The amount of the gold compound used is not uniform depending on the type of the silver halide emulsion, the type of the compound used, the ripening conditions and the like.
It is preferably from 1 × 10 ⁻⁴ to 1 × 10 ⁻⁸ mol per mol. More preferably, it is 1 × 10 ⁻⁵ to 1 × 10 ⁻⁸ mol. As a chemical sensitization method for a silver halide emulsion, a reduction sensitization method may be used.

In the silver halide photographic light-sensitive material according to the present invention, 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. In particular, dyes having absorption in the visible region include AI described in JP-A-3-251840, page 308.
The dyes of Nos. -1 to 11 and the dyes described in JP-A-6-3770 are preferably used. Examples of the infrared-absorbing dye include general formulas (I) and (I) described in the lower left column of page 2 of JP-A-1-280750. The compounds represented by II) and (III) have preferable spectral characteristics, do not affect the photographic characteristics of the silver halide photographic emulsion, and are preferable without contamination by residual color. As specific examples of preferred compounds, exemplified compounds (1) to (3) on the lower left column of page 3 to the lower left column of page 5 of the same publication
(45).

In order to improve the sharpness, the amount of these dyes added is 680 nm for an unprocessed sample of a light-sensitive material.
Is more preferably 0.7 or more, and even more preferably 0.8 or more.

It is preferable to add a fluorescent whitening agent to the light-sensitive material according to the present invention since the white background can be improved. Preferred examples of the compound include a compound represented by the general formula II described in JP-A-2-232652.

In order to use the present invention in a silver halide color photographic light-sensitive material, a yellow coupler, a magenta coupler,
It has a layer containing a silver halide emulsion spectrally sensitized to a specific region in an arbitrary wavelength region in combination with a cyan coupler.
The silver halide emulsion preferably contains one kind or a combination of two or more kinds of sensitizing dyes.

As the spectral sensitizing dye used in the silver halide emulsion according to the present invention, any of the known compounds can be used.
BS-1 to 8 described in page 28 of JP 51840 can be preferably used alone or in combination. Examples of the green photosensitive sensitizing dye include G
S-1 to S-5 are preferably used. RS-1 to 8 described on page 29 of the same publication are preferably used as red-sensitive sensitizing dyes. Also, supersensitizers SS-1 to SS-9 described on pages 8 to 9 of JP-A-4-285950 and 15 to 17 of JP-A-5-66515 are used as red, green and blue photosensitive sensitizing dyes. It is preferable to use compounds S-1 to S-17 described on the page 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 by dissolving it in a water-miscible organic solvent such as methanol, ethanol, fluorinated alcohol, acetone, dimethylformamide or the like or water, or adding it as a solid dispersion. It may be added, but is preferably added as a solid dispersion.

As the coupler used in the silver halide photographic light-sensitive material according to the present invention, a coupling reaction with an oxidized form of a color developing agent is carried out to form a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm. Any compound that can be used can be used, and particularly typical examples include a yellow dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a wavelength range of 500.
Typical examples are magenta dye-forming couplers having a spectral absorption maximum wavelength in the range of -600 nm and cyan dye-forming couplers having a spectral absorption maximum wavelength in the wavelength range of 600 to 750 nm.

Cyan couplers that can be preferably used in the silver halide photographic light-sensitive material according to the present invention include:
Couplers represented by general formulas (C-I) and (C-II) described in the lower left column of page 5 of JP-A-4-114154 can be exemplified. Specific compounds include those described as CC-1 to CC-9 in page 5, lower right column to page 6, lower left column in the same publication.

The magenta couplers which can be preferably used in the silver halide photographic light-sensitive material according to the present invention include those represented by 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 lower left column of page 4 to the upper right column of page 5 of the publication. Preferred from among the magenta couplers is a coupler represented by the general formula described in the publication 4 pages, right upper column (M-I), of which, R _M of the formula (M-I) is 3
A coupler which is a lower alkyl group is particularly preferable because of its excellent light resistance. MC-8 to M described in the upper column on page 5 of the publication
C-11 is preferable because it is excellent in reproducing colors from blue to purple and red, and is also excellent in detail description.

In the silver halide photographic light-sensitive material according to the present invention, known yellow couplers such as a pivaloylacetanilide type yellow coupler and a benzoylacetanilide type yellow coupler can be used.

The silver halide photographic light-sensitive material according to the present invention may further comprise, in addition to the above-mentioned yellow coupler, JP-A-4-14-1.
No. 14,154, the general formula (Y-
The couplers represented by I) can be used. Specific compounds are described in YC-1 to YC-1 in the lower left column on page 3 of the publication.
What is described as YC-9 can be mentioned. Also, couplers represented by the general formula [I] described in JP-A-6-67388 can be used, and specifically, YC-8 described in the lower left column of page 4 of JP-A-4-114154 can be used. , YC-9, and JP-A-6-6
No. 1 (7) described on pages 13 to 14 of No. 7388
The compound represented by (47) can be mentioned. Further, the compounds represented by the general formula [Y-1] described in JP-A-4-81847, page 1 and 11 to 17 can also be used.

When an oil-in-water emulsion dispersion method is used to add the couplers and other organic compounds used in the silver halide photographic light-sensitive material according to the present invention, the water-insoluble emulsion usually has a boiling point of 150 ° C. or higher. In the boiling point organic solvent, if necessary, dissolve in combination with a low boiling point and / or water-soluble organic solvent,
It is emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant.

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 added. Examples of high boiling organic solvents that can be used to dissolve and disperse the coupler include dioctyl phthalate, diisodecyl phthalate, phthalic acid esters such as dibutyl phthalate, tricresyl phosphate, and phosphoric acid esters such as trioctyl phthalate; Is preferably used. The high-boiling organic solvent has a dielectric constant of 3.5 to 7.0.
It is preferably 0. Further, two or more kinds of high-boiling organic solvents can be used in combination.

In place of the method using a high-boiling organic solvent or in combination with a high-boiling organic solvent, a water-insoluble and organic solvent-soluble polymer compound may be added, if necessary, to a low-boiling and / or water-soluble organic solvent. In a hydrophilic binder such as an aqueous gelatin solution by using a surfactant and emulsifying and dispersing by various dispersing means. Examples of the water-insoluble and organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).

Preferred examples of the compound used as a surfactant for dispersing a photographic additive or 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. Containing. Specifically, A-1 to A- described in JP-A-64-26854.
11 are mentioned. Also, a surfactant in which a fluorine atom is substituted for an alkyl group is preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion, and the time until the addition to the coating solution after the dispersion and the time from the addition to the coating solution after the addition are preferably 10 hours each. Preferably within 3 hours, more preferably within 20 minutes.

It is preferable to use an anti-fading agent in combination with each of the above couplers 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 general formulas I and II described on page 3 of JP-A-2-66541, phenolic compounds represented by general formula IIIB described in JP-A-3-174150, and An amine compound represented by the general formula A described in Japanese Unexamined Patent Publication (Kokai) No. 64-90445;
The metal complexes represented by the general formulas XII, XIII, XIV and XV described in JP 182741 are particularly preferred for magenta dyes. Further, compounds represented by the general formula I 'described in JP-A-1-19649 and compounds represented by the general formula II described in JP-A-5-11417 are particularly preferred for yellow and cyan dyes.

For the purpose of shifting the absorption wavelength of the coloring dye, compound (d-11) described in the lower left column of page 9 of JP-A-4-114154 and compound (A'-) described in the lower left column of page 10 of the same publication are disclosed. Compounds such as 1) can be used. In addition to this, U.S. Pat.
Can be used.

In the silver halide light-sensitive material according to the present invention, a compound which reacts with an oxidized developing agent is added to a layer between the light-sensitive layers to prevent color turbidity. 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 those represented by the general formula II described in JP-A-4-133,056.
Compounds II-1 to II-14 and 17 described on pages 3 to 14
Compound 1 described on the page.

It is preferable to add an ultraviolet absorber to the light-sensitive material according to the present invention to prevent static fog or to improve the light fastness of a dye image. Preferred examples of the ultraviolet absorber include benzotriazoles. Particularly preferred compounds are those represented by the formula III-3 described in JP-A-1-250944 and JP-A-64-666.
No. 46, a compound represented by the general formula III, and JP-A-63-187240, UV-1L to UV-2.
7L, compounds represented by the general formula I described in JP-A-4-1633, and compounds represented by the general formulas (I) and (II) described in JP-A-5-165144.

As the hardener of the binder used in the silver halide photographic light-sensitive material of the present invention, it is preferable to use a vinyl sulfone hardener or a chlorotriazine hardener alone or in combination. It is preferable to use the compounds described in JP-A-61-249054 and JP-A-61-245153. Further, in order to prevent the growth of molds and bacteria which adversely affect the photographic performance and image storability, JP-A-3-15.
It is preferable to add a preservative and an antifungal agent as described in JP-A-7646. In order to improve the physical properties of the surface of the light-sensitive material or the sample after processing, a protective layer is disclosed in
It is preferable to add a slip agent or a matting agent described in JP-A No. 3 or JP-A-2-73250.

As the support used for the silver halide photographic light-sensitive material according to the present invention, any material may be used, such as paper coated with polyethylene or polyethylene terephthalate, paper support made of natural pulp or synthetic pulp, A vinyl chloride sheet, a polypropylene which may contain a white pigment, a polyethylene terephthalate support, cellulose triacetate, baryta paper and the like can 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 a copolymer thereof is 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, alkaline earth metal sulfates such as barium sulfate, alkaline earth metal carbonates such as calcium carbonate, finely divided silica, silica such as synthetic silicate, calcium silicate, alumina, alumina hydrate, oxidation Examples include titanium, zinc oxide, talc, and clay. 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 was 13% by weight for improving sharpness.
The above is preferred, and more preferably 15% by weight.

The degree of dispersion of the white pigment in the water-resistant resin layer of the paper support according to the present invention 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 coefficient of variation described in the above publication.

It is more preferable that the value of the center plane average roughness (SRa) of the support is 0.15 μm or less, more preferably 0.12 μm or less, since the effect of good gloss can be obtained.
In addition, trace amounts of ultramarine, oil-soluble dyes, etc. to adjust the spectral reflection density balance of the white background after treatment in the white pigment-containing water-resistant resin of the reflective support or in the applied hydrophilic colloid layer to improve whiteness It is preferable to add a bluing agent or a reddish agent.

The silver halide photographic light-sensitive material according to the present invention may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the support surface, if necessary, and then directly or undercoat layer (adhesion of the support surface, (1 or 2 or more subbing layers for improving antistatic properties, dimensional stability, friction resistance, hardness, antihalation properties, friction properties and / or other properties). Good.

In coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used 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 silver halide photographic light-sensitive material according to the present invention, an image recorded on a negative is optically formed on a silver halide photographic light-sensitive material to be printed. The image may be printed and printed, or once the image is converted into digital information, the image is formed on a CRT (cathode ray tube), and this image is formed on a silver halide photographic material to be printed. Alternatively, the image may be printed by scanning while changing the intensity of the laser beam based on digital information.

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 to a light-sensitive material which directly forms an image for viewing. For example, color paper, color reversal paper, a photosensitive material for forming a positive image, a photosensitive material for a display, and a photosensitive material for a color proof can be used. It is particularly preferable to apply the invention to a photosensitive material having a reflective support.

As the aromatic primary amine developing agent preferably 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-laurylamino) toluene CD-4) 4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline CD-5) 2-Methyl-4- (N-ethyl-N- (β-
Hydroxyethyl) amino) aniline CD-6) 4-amino-3-methyl-N-ethyl-N-
(Β- (methanesulfonamido) ethyl) -aniline CD-7) N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide 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) aniline In the present invention, the above color developing solution 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 according to the present invention is preferably 35 ° C. or more and 70 ° C. or less. The higher the temperature, the shorter the processing time is possible, which is preferable. However, from the viewpoint of the stability of the processing solution, the higher the temperature, the more preferable.

The color development time is preferably within 90 seconds, more preferably within 60 seconds. Recently, processing conditions for performing color development within 45 seconds, and even within 25 seconds, are also used.

To the color developing solution, a known developer component compound can be added in addition to the above color developing agent. Usually, alkaline agents having a pH buffering action, chloride ions, development inhibitors such as benzotriazoles, preservatives,
A chelating agent or the like is used. The silver halide photographic light-sensitive material of the present invention is preferably subjected to bleaching and fixing or bleach-fixing after color development.
It is particularly preferable to perform a bleach-fixing process. The processing temperature of the bleaching and bleach-fixing is preferably 30 ° C. or higher,
Particularly, the temperature is preferably 35 ° C. or higher. After the bleach-fixing process or the fixing process, a washing process is usually performed. Further, as an alternative to the water washing treatment, a stabilization treatment may be performed. The developing apparatus used for developing the silver halide photographic light-sensitive material of the present invention is a roller transport type in which the light-sensitive material is conveyed across rollers arranged in a processing tank. An endless belt system that transports fixedly may be used, but a processing tank is formed in a slit shape, and a processing liquid is supplied to this processing tank and a photosensitive material is transported. A method, a web method by contact with a carrier impregnated with a treatment liquid, a method using a viscous treatment liquid, and the like can also be used.
When processing in large quantities, it is usual to perform a running process using an automatic developing machine. At this time, the replenishment amount of the replenisher is preferably as small as possible. The most preferred method is to add a treating agent in the form of the method described in JP-A-94-16935.

[0099]

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 tabular grain emulsion EM-1 without using seed emulsion> Solution A1 39.0 g of ossein gelatin Make up to 2295 ml with distilled water.

Solution B1 2210 cc of 4N silver nitrate Solution C1 2210 cc of 4N NaCl solution D1 KI 1.31 g Make up to 986 ml with distilled water.

At 35 ° C., Japanese Patent Publication No. 58-58288
No. 58-58289, 40 ml of the solution B1 and the same amount of the solution C1 were simultaneously added to the solution A1 in the mixing and stirring apparatus over 1.6 minutes, the EAg was adjusted to 173 mV, and the solution D1 was added. Added. After stirring for 5 minutes, solution B
1. Add 740 ml of solution C1 in 70 minutes. The temperature is raised to 65 ° C. for 20 minutes with the addition, and adjusted to 159 mV. After aging for 20 minutes, each of solution B1 and solution C1
30 ml was added over 45 minutes. Meanwhile, EAg is 15
It was controlled at 9 mV.

Then, after aging at a temperature of 65 ° C. for 20 minutes, the temperature was raised to 40 ° C., and a precipitation desalting was performed to remove excess salts. A gelatin solution was added and dispersed to obtain EM-1.

<Preparation of Seed Emulsion EMT-1> Solution A1 Ossein gelatin 75.14 g NaCl 1.2 g Make up to 4000 ml with distilled water.

Solution B1 3786 g of silver nitrate Make up to 5680 ml with distilled water.

Solution C1 1300 g of NaCl Make up to 5680 ml with distilled water.

At 40 ° C., JP-B-58-58288
After adjusting the solution A1 to a pH of 2.0 and an EAg of 190 mV using a mixing and stirring device described in JP-A Nos. 58-58289, all of the solution B1 and the solution C1 were simultaneously added over 95 minutes. After ripening, a 5% aqueous solution of Demol N and 20% aqueous solution of magnesium sulfate manufactured by Kao Atlas Co., Ltd. were added to cause aggregation and allowed to stand, and then 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. Further, after redispersion by mixing with an aqueous gelatin solution, pH = 5.5, pCl = 1.8.
Was adjusted. In this way, a seed emulsion EMT-1 having cubic normal crystal silver halide grains having an average grain size of 0.22 μm and a variation coefficient of 9% was obtained. The number of grains having a grain size of 0.20 μm or less was 60% or less of the total number of grains.

<Seed Emulsion EMT-2, EMT-3, EMT
-4, Preparation of EMT-5 and EMT-6> Emulsion EMT
-1, the solution B1 and the solution C1 were 54.8%, 16%, 9.5%, 4.8% and 1.2% of the added amount of EMT-1.
The average particle size was 0.18 μm, 0.12 μm, 0.10 μm, 0.08 μm
μm and 0.05 μm, each of which is a cubic normal-crystal silver halide grain having a coefficient of variation of 10% or less, EMT-
2, EMT-3, EMT-4, EMT-5, EMT-6
I got The number of grains having a grain size of 0.20 μm or less was 60% or more of the total number of grains. In each case, the (100) plane was 80% or more.

<Preparation of seed emulsion EMT-7> Seed emulsion EMT
In the preparation of -4, after the addition was completed, the average particle diameter was 0.10 μm in the same manner except that the desalting treatment was performed by ultrafiltration using a semipermeable membrane having NMWL (nominal molecular weight limit) of 100,000. A seed emulsion EMT-7 having a cubic normal crystal silver halide grain having a coefficient of variation of 10% or less was prepared. The number of particles having a particle size of 0.2 μm or less was 60% or more of the total number of particles, and the (100) plane was 80% or more.

<Preparation of Emulsion EM-2 Using Seed Emulsion> Solution A1 39.0 g of ossein gelatin Make up to 2295 ml with distilled water.

Solution B1 2170 cc of 4N silver nitrate solution C1 2170 cc of 4N NaCl solution D1 KI 1.31 g Make up to 986 ml with distilled water.

At 35 ° C., JP-B-58-58288
No. 58-58289, EMT-1 equivalent to 0.16 mol was previously added to the solution A1 in the mixing stirrer and stirred, the EAg was adjusted to 173 mV, and the solution D1 was added. After stirring for 5 minutes, 740 ml of each of the solution B1 and the solution C1 is added in 70 minutes. 65 ° C for 20 minutes with addition
To 159 mV. After aging for 20 minutes, 1430 ml each of solution B1 and solution C1 were added over 45 minutes. During that time, the EAg was controlled at 159 mV.

Then, after aging at a temperature of 65 ° C. for 20 minutes, the temperature was raised to 40 ° C., and a precipitation desalting was performed to remove excess salts. A gelatin solution was added and dispersed to obtain EM-2.

<Preparation of Emulsions EM-3, EM-4 and EM-5> In the emulsion EM-2, the solution A
EMT-2, EMT- in place of EMT-1
3, EMT-4, EMT-5, EMT-6, EMT-7
EM-3, EM-4, EM-
5, EM-6, EM-7 and EM-8 were obtained.

About 3000 each of the obtained emulsions EM-1 to EM-8 were observed and measured by an electron microscope, and the shape was analyzed. The results are shown in Tables 1 and 2. In addition, it was confirmed that the main surface of the tabular grains was an orthogonal rectangular plane and a (100) plane. The small grains referred to in Table 1 are non-tabular grains including cubic grains and have a distribution peak on the smaller grain size side than the grain size distribution of the grown grains in the emulsion. In addition, single twin particles, double twin particles, and triple twin particles refer to FIGS.
Refers to the particles shown in FIG.

[0116]

[Table 1]

[0117]

[Table 2]

It can be seen that the silver halide photographic emulsion of the present invention reduces nontabular grains having twins and has a better grain size distribution than the comparative silver halide photographic emulsion. In addition, it can be seen that the use of the small grain size species significantly reduces the small grains remaining in the silver halide photographic emulsion after growth and significantly improves the lithographic ratio.

<Preparation of Blue-Sensitive Silver Halide Emulsion>
For M-1 to 8, sodium thiosulfate, chloroauric acid, stabilizer STAB-1, stabilizer STAB-2, stabilizer STA
Optimum chemical sensitization was performed using B-3, sensitizing dye BS-1, and sensitizing dye BS-2, and EM-1B, EM-2B, and EM-
3B, EM-4B, EM-5B, EM-6B, EM-7
B, EM-8B was prepared.

(Preparation of Cubic Silver Halide Emulsion) <Preparation of Blue-Sensitive Cubic Silver Halide Emulsion> The following (solution A) and (solution B) were pAg = 7 in 1 liter of 2% gelatin aqueous solution kept at 40 ° C. And pH = 3.0 while simultaneously adding over 30 minutes and further adding the following (solution C) and (D
Liquid) at pAg = 8.0 and pH = 5.5 while controlling
Co-added over 0 minutes. At this time, the pAg was controlled by the method described in JP-A-59-45437, and the pH was controlled using sulfuric acid or an aqueous sodium hydroxide solution.

(Solution A) 3.42 g of sodium chloride 0.03 g of potassium bromide Water is added to make up to 200 ml.

(Solution B) Silver nitrate 10 g Water was added to make up to 200 ml.

(Solution C) Sodium chloride 102.7 g Potassium bromide 1.0 g Water was added to make up to 600 ml.

(D solution) 300 g of silver nitrate was added to 600 ml of water. After the addition was completed, 5% of Demol N manufactured by Kao Atlas Co., Ltd. was added.
After desalting was performed using an aqueous solution and a 20% aqueous solution of magnesium sulfate, the resultant was mixed with an aqueous gelatin solution to obtain an average particle size of 0.7.
1 μm, coefficient of variation of particle size distribution 7%, silver chloride content 99.
A 5 mol% monodispersed cubic emulsion EMP-1 was obtained. Next, the addition time of (Solution A) and (Solution B) and (Solution C) and (Solution D)
Monodispersed cubic emulsion EMP-1B having an average particle size of 0.64 μm, a variation coefficient of particle size distribution of 7%, and a silver chloride content of 99.5 mol% in the same manner as in EMP-1 except that the addition time was changed.
I got

After optimally chemical sensitizing EMP-1 and EMP-1B using the following compounds, the sensitized EM
P-1 and EMP-1B were mixed at a silver ratio of 1: 1;
A blue-sensitive silver halide emulsion (Em-B) was obtained.

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 stability 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 <green-sensitive cubic silver halide Preparation of Emulsion> The average particle size of the emulsion was adjusted in the same manner as in EMP-1 except that the addition time of (solution A) and (solution B) and the addition time of (solution C) and (solution D) were changed.
40 μm, coefficient of variation 8%, silver chloride content 99.5 mol%
To obtain a monodispersed cubic emulsion EMP-2. Next, a monodisperse cubic emulsion EMP-2B having an average particle size of 0.50 μm, a coefficient of variation of 8%, and a silver chloride content of 99.5 mol% was obtained.

The above-mentioned EMP-2 was optimally subjected to chemical sensitization at 55 ° C. using the following compounds. Also EMP-2B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-2 and EMP-2B were mixed at a silver amount of 1: 1 to obtain a green-sensitive silver halide emulsion (Em-G).

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 stability Agent STAB-3 3 × 10 ^-4 mol / mol AgX Sensitizing dye GS-1 4 × 10 ^-4 mol / mol AgX <Preparation of red-sensitive cubic silver halide emulsion> Addition of (solution A) and (solution B) Time and the addition time of (Solution C) and (Solution D) were changed in the same manner as in EMP-1 except that the average particle size was 0.1.
A monodispersed cubic emulsion EMP-3 having a particle size of 40 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5 mol% was obtained. The average particle size is 0.38 μm, the coefficient of variation is 0.08, and the silver chloride content is 9
A 9.5 mol% monodispersed cubic emulsion EMP-3B was obtained.

The above EMP-3 was optimally subjected to chemical sensitization at 60 ° C. using the following compounds. Also EMP-3B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-3 and EMP-3B were mixed at a silver ratio of 1: 1 to obtain a red-sensitive silver halide emulsion (Em-R).

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 stability 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 The following SS-1 was added in an amount of 2.0 × 10 ^-3 per mol of silver halide. Here, the sensitizing dyes RS-1 and RS-2 were added by an additive solution in which the sensitizing dye obtained by the method described on page 51 of JP-A-6-308656 was present as solid fine particles.

STAB-1: 1- (3-acetamidophenyl) -5-mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole

[0132]

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[0133]

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High-density polyethylene was laminated on both sides of a paper pulp having a basis weight of 180 g / m ² to prepare a paper support. However, on the side to be coated with the emulsion layer, a molten polyethylene containing surface-treated anatase-type titanium oxide dispersed at a content of 15% by weight was laminated to produce a reflective support. After the reflective support was subjected to a corona discharge treatment, a gelatin undercoat layer was provided thereon, and further, each layer having the composition shown in Table 3 below was provided thereon, whereby a silver halide color photographic light-sensitive material 101 was produced. (H-1) and (H-2) were added as hardeners.

[0135]

[Table 3]

* Em-B, Em-G and Em-R were added in the amounts of silver contained in each.

Image stabilizer A: Pt-octylphenol DBP: dibutyl phthalate DNP: dinonyl phthalate DOP: dioctyl phthalate DIDP: di-i-decyl phthalate PVP: polyvinylpyrrolidone H-1: tetrakis (vinylsulfonylmethyl) methane H -2: 2,4-dichloro-6-hydroxy-s-triazine sodium HQ-1: 2,5-di-t-octylhydroquinone 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

[0138]

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[0139]

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[0140]

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[0141]

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[0142]

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[0143]

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In the preparation of Sample 101, Samples 102 to 110 were prepared in the same manner as in Table 4 below except that the blue-sensitive silver halide emulsion of the first layer and the amount thereof were changed. Each of the samples was exposed to white wedge light with a light exposure time of 0.5 seconds by a conventional method, and then subjected to a development process by the following rapid development process.

[Reference conditions] Processing step Processing temperature Time Replenishment amount Color development 38.0 ± 0.3 ° C 45 seconds 80cc Bleaching and fixing 36.0 ± 0.5 ° C 45 seconds 120cc Stabilization 30-34 ° C 60 seconds 150cc Drying 60 to 80 ° C. for 30 seconds (the replenishing amount is a value per 1 m ^{2 of the} silver halide color photographic light-sensitive material) The composition of the developing solution is shown below.

Color developer tank liquid and replenisher tank liquid Replenisher 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 Sodium pentaacetate 2.0 g 2.0 g Optical 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. = 1
Adjust the replenisher to pH = 10.60 to 0.10.

Bleach-fix solution and replenisher Ferric ammonium diethylenetriaminepentaacetate dihydrate 65 g Diethylenetriaminepentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml 2-amino-5-mercapto-1,3,4-thiadiazole 2 0.0g ammonium sulfite (40% aqueous solution) 27.5ml Water is added to make up to 1 liter, and the pH is adjusted to 5.0 with potassium carbonate or glacial acetic acid.

Stabilizing solution tank solution and replenisher 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 Fluorescent whitening agent (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 (25% aqueous solution of ammonium hydroxide) 2.5 g nitrilotriacetic acid / trisodium salt 1.5 g Water was added to make the total volume 1 liter, and the pH was adjusted to 7.5 with sulfuric acid or ammonia water.

[Test Method] {Relative sensitivity} The obtained sample was measured for a characteristic curve of blue density using a PDA-65 densitometer (manufactured by Konica Corporation).
The highest concentration and sensitivity were obtained. The sensitivity was defined based on the reciprocal of the exposure amount giving a density of 0.75, and was expressed as a relative value with the sensitivity of 101 as a standard sample as 100.

[0150]

[Table 4]

As can be seen from the results shown in Table 4, the samples of the present invention have high sensitivity, are excellent in rapid processing property, and have high maximum density even when the amount of silver halide applied is small. It can also be seen that the effect increases as the grain size of the seed emulsion decreases. Further, by performing ultrafiltration on the seed emulsion, an effect equivalent to or higher than that obtained by using a seed emulsion having a smaller particle size can be obtained, showing the advantages of the present invention.

[0152]

The seed emulsion for forming a tabular silver halide, the method for producing a tabular silver halide photographic emulsion and the silver halide photographic light-sensitive material according to the present invention have high sensitivity and excellent maximum density.

[Brief description of the drawings]

FIG. 1 is a perspective view showing an example of single twin particles.

FIG. 2 is a perspective view showing an example of twin twin particles.

FIG. 3 is a perspective view showing an example of triple twin particles.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kazuyoshi Ichikawa Konica Corporation, 1 Sakuracho, Hino-shi, Tokyo

Claims (5)

[Claims] 1. Tabular silver halide grains characterized by using, as seed grains for forming tabular silver halide grains containing silver chloride as a main component, grains of cubic normal crystals composed of (100) planes. Seed emulsion for formation. 2. A method for producing a tabular silver halide photographic emulsion wherein the average silver chloride content of the silver halide grains is 50 mol% or more, wherein the tabular grains are grown using cubic normal-crystal silver halide grains as seed grains. The tabular silver halide photographic emulsion formed from the tabular silver halide-forming seed emulsion containing the seed grains is a normal cubic crystal having the (100) plane, and the aspect ratio is 3 A tabular silver halide grain having a grain size of at least 0.0, a grain thickness of at most 0.3 μm, and a (100) plane as a main plane, occupying 50% or more of the projected area of all silver halide grains. For producing a silver halide photographic emulsion. 3. The tabular silver halide photographic emulsion according to claim 2, wherein a grain size of 60% or more of the total number of the cubic normal crystal seed grains is 0.20 μm or less. Method. 4. The tabular silver halide forming seed emulsion containing the seed grains is desalted by electrodialysis and / or ultrafiltration. A method for producing the tabular silver halide photographic emulsion described above. 5. A silver halide photographic material having at least one silver halide emulsion layer on a support, wherein at least one silver halide emulsion layer is provided on at least one silver halide emulsion layer. A silver halide photographic light-sensitive material comprising a silver halide photographic emulsion produced by the method for producing a silver halide photographic emulsion described in (1).