JP2000122201A - Silver halide emulsion and its preparation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide emulsion giving a high gradation image even by high illuminance exposure and less liable to deteriorate the gradation in preservation by adding a functional compound through an ultrafiltration membrane. SOLUTION: The functional compound may be any compound having function to enhance the performance of silver halide grains but a sensitizer, a mercapto heterocyclic compound, a group VIII metal compound or a sensitizing dye is preferably used. The coefficient of variation in the content distribution of the mercapto heterocyclic compound in silver halide grains is <=0.10 and that of the group VIII metal compound is <=0.10. The average silver chloride content of the objective silver halide emulsion is >= 95% and the coefficient of variation in the distribution of a halogen composition except chlorine in the silver halide grains is <=0.10. The coefficient of variation in the distribution of the coating rate of the silver halide grains with a sensitizing dye is <=0.10.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide emulsion which gives an image having a high gradation even under high illuminance exposure and has little gradation deterioration during storage, and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, there has been an increasing demand for performance such as high sensitivity, stable processing and high image quality in color photographic paper. At the same time, there is also a demand for shortening and speeding up a printing process and a developing process. Remarkable. Actually, silver bromide or silver chlorobromide which does not substantially contain silver iodide has been used because of the need to increase the developing speed. It is known that a dramatic increase in speed results.

[0003] However, silver halide emulsions having a high silver chloride content have the drawbacks that they are easily fogged and that it is difficult to obtain high sensitivity by ordinary chemical sensitization. Is disclosed.

JP-A-5-204073 discloses a silver chloride content of 50 mol% or more, a thickness of <0.3 μm, and a principal plane of $ 10.
A silver halide emulsion having a 0 ° plane is disclosed in US Pat.
No. 4,337 describes two main planes which are substantially free of silver iodide and have a silver chloride content of 50 mol% or more and 50% or more of the projected area are parallel with an aspect ratio of <7.5 {100}. Are tabulated in US Pat. No. 5,275,933.
No. 0 has a silver chloride content of 50 mol% or more and a projected area of 30 mol%.
% Or more has an aspect ratio of 8 or more, a thickness of 0.3 μm or less, and two parallel main planes are {100} and a silver chloride content of 75
A silver halide emulsion in which an epitaxy portion of not more than mol% is chemically sensitized is disclosed, and it is disclosed that high sensitivity can be obtained by these. In addition, JP-A-6-30
No. 8648, JP-A-6-337489 and the like also disclose the technique of a tabular silver halide emulsion having a {100} major plane having a high silver chloride content.

Japanese Patent Application Laid-Open No. 6-301131 discloses a tabular silver halide emulsion having a {100} principal plane having a silver chloride content of 50 mol% or more, an adjacent edge ratio of less than 10, and an aspect ratio of 2 or more. There is disclosed a silver halide emulsion containing at least a pair of metal ions of Group 8 and 5 to 6 periods at the cation position on average, and it is described that high sensitivity can be obtained by this. Also, JP-A-6-33
No. 7490 includes Fe, Ru, Re, Os, Rh, and Ir.
Silver chloride content of at least one metal complex of
By adjusting the pH of the coating of a silver halide photographic light-sensitive material containing a tabular silver halide emulsion having a {100} major plane of 0 mol% or more and a mercapto heterocyclic compound to 4.0 to 6.5, It discloses that the problem of fogging and pressure desensitization which occur when a silver halide photographic light-sensitive material stored over time is processed with a developer mixed with a bleach-fixing solution are improved. However, the performance of silver halide emulsions composed of high silver chloride tabular grains has not yet been sufficiently improved, and sensitivity fluctuations occur between exposure and development.
There is a problem that the image quality of the finished image becomes unstable.

On the other hand, various functional compounds have been used in preparing silver halide emulsions with the aim of increasing the sensitivity of silver halide grains. For example, a polyvalent metal compound may be used to control carriers in silver halide grains, as disclosed in Japanese Patent Application Laid-Open Nos. 6-308653 and 7-72569. Further, as disclosed in JP-A-2-68538 and JP-A-6-27564, the dislocation lines formed in the silver halide grains are precisely formed in order to homogenize the halogen composition of the silver halide grains. For control, a halide ion releasing agent may be used during the growth of silver halide grains. When these functional compounds are used, if these compounds are added at a certain stage in the grain formation process, they are non-uniformly adsorbed on the silver halide grains, leading to an increase in fog and a deterioration in storage stability.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an image having a high gradation even under high illuminance exposure, and a halogenation method which causes little gradation deterioration during storage. An object of the present invention is to provide a silver emulsion and a method for producing the same.

[0008]

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

(1) A method for producing a silver halide emulsion, comprising a step of adding a functional compound through an ultrafiltration membrane.

(2) The silver halide as described in (1) above, wherein the functional compound is at least one compound selected from a sensitizer, a mercaptoheterocyclic compound, a Group 8 metal compound and a sensitizing dye. Emulsion manufacturing method.

(3) The above (1) or (2), wherein the silver halide emulsion has an average silver chloride content of 98% or more.
A method for producing a silver halide emulsion as described above.

(4) A silver halide emulsion characterized in that the coefficient of variation of the distribution of the content of the mercaptoheterocyclic compound in the silver halide grains is 0.10 or less.

(5) A silver halide emulsion characterized in that the coefficient of variation of the distribution of the Group 8 metal content of the silver halide grains is 0.10 or less.

(6) A silver halide emulsion characterized in that the average silver chloride content is 95% or more, and the coefficient of variation of the distribution of the halogen composition other than chlorine in the silver halide grains is 0.10 or less.

(7) A silver halide emulsion characterized in that the coefficient of variation of the sensitizing dye coverage distribution of the silver halide grains is 0.10 or less.

(8) The silver halide emulsion as described in any one of (4) to (7) above, wherein the average silver chloride content of the silver halide emulsion is 98% or more.

(9) The silver halide emulsion according to any one of (4) to (8), which is produced by the method for producing a silver halide emulsion according to (1), (2) or (3).

The present invention will be described in more detail. In the present invention, the functional compound may be any compound as long as it has a function of improving the performance of silver halide grains, and in particular, a sensitizer, a mercaptoheterocyclic compound, a Group 8 metal compound, a sensitizing dye, and the like. Is preferred.

The sensitizers preferably used in the present invention include gold compounds, reducing compounds, and chalcogen sensitizers. Examples of the chalcogen sensitizers are a sulfur sensitizer, a selenium sensitizer, and a tellurium sensitizer. Sensitizers and the like. But,
Particularly preferred sensitizers in the present invention include gold compounds, and examples of the gold compound include various gold complexes such as chloroauric acid and gold sulfide. 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 used, the ripening conditions, etc., but usually 1 × 10 ^-4 to 1 × 10 ^-4 per mol of silver halide.
× 10 ⁻⁸ mol, more preferably 1 × 10 ⁻⁸ mol.
It is from × 10 ^-5 to 1 × 10 ^-8 mol.

The mercaptoheterocyclic compound of the present invention is preferably a compound represented by the following formula (I).

[0021]

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In the formula, Z represents an atomic group necessary for forming a 5- or 6-membered heterocyclic ring or a 5- or 6-membered heterocyclic ring condensed with a benzene ring, and M represents a cation.

In the general formula (I), the 5- or 6-membered heterocyclic ring formed by Z or the 5- or 6-membered heterocyclic ring in which a benzene ring is condensed includes, for example, an imidazole ring, a tetrazole ring, Examples thereof include a thiazole ring, an oxazole ring, a benzothiazole ring, a benzotriazole ring, and a benzimidazole ring. Examples of the cation represented by M include cations such as hydrogen, sodium, potassium, and ammonium. The 5- or 6-membered heterocyclic ring formed by Z or a 5- or 6-membered heterocyclic ring in which a benzene ring is condensed may have a substituent. Examples of the substituent include an alkyl group (for example,
Methyl group, ethyl group, propyl group, isopropyl group, t
tert-butyl group, pentyl group, etc.), alkenyl group (eg, vinyl group, allyl group, etc.), alkynyl group (eg, propargyl group, etc.), aryl group (eg, phenyl group, etc.), heterocyclic group (eg, pyridyl group) Group, thiazolyl group, oxazolyl group, imidazolyl group, furyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, sulfolanyl group, piperidinyl group, pyrazolyl group, tetrazolyl group, etc.), halogen atom (for example, chlorine atom) , A bromine atom, an iodine atom, a fluorine atom, etc.), an alkoxy group (eg, methoxy group, ethoxy group, propyloxy group, pentyloxy group, cyclopentyloxy group, hexyloxy group, etc.), an aryloxy group (eg, phenoxy group, etc.) ), An alkoxycarbonyl group (eg, methyloxy Carbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, etc., aryloxycarbonyl group (eg, phenyloxycarbonyl group, etc.), sulfonamide group (eg, methylsulfonylamino group, ethylsulfonylamino group, butylsulfonylamino group, Hexylsulfonylamino group, cyclohexylsulfonylamino group, phenylsulfonylamino group, etc.), sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group) Phenylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), ureido group (for example, methylureido group,
An ethylureido group, a pentylureido group, a cyclohexylureido group, a phenylureido group, a 2-pyridylaminoureido group, and the like; an acyl group (for example, an acetyl group, an ethylcarbonyl group, a propylcarbonyl group, a pentylcarbonyl group, a cyclohexylcarbonyl group, Ethylhexylcarbonyl group, phenylcarbonyl group, pyridylcarbonyl group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, 2- Ethylhexylaminocarbonyl group, phenylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), amide group (for example, methylcarbonylamino group, ethylcarbo group) Amino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, phenylcarbonylamino group, etc., sulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexyl) Sulfonyl group, 2-ethylhexylsulfonyl group, phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc., amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2 -Ethylhexylamino group, anilino group, 2-pyridylamino group, etc.), cyano group, nitro group,
Examples include a carboxyl group and a hydroxyl group. These groups may be further substituted by the above substituents and the like.

Hereinafter, specific examples of the mercaptoheterocyclic compound according to the present invention will be shown, but it should not be construed that the invention is limited thereto.

[0025]

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[0026]

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[0027]

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[0028]

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The amount of the mercaptoheterocyclic compound added to the silver halide emulsion is 1 × per mole of silver halide.
More preferably 10 ^-9 mol or more and 1 × 10 ^-2 mol or less,
In particular, it is preferably from 1 × 10 ⁻⁶ mol to 5 × 10 ⁻³ mol.

As the Group 8 metal compound of the present invention, those represented by the following general formula are preferred.

[MX _m Y _6-m ] ^{n- wherein} M is a metal selected from Group 8 elements of the periodic table, preferably iron, cobalt, ruthenium, rhodium, osmium, nickel, palladium and Iridium, and n ⁻ is 3 or 4.

As the ligands of the above metal complex represented by X and Y, cyanide ions, carbonyl and the like are preferable, and compounds in which some of the ligands are halide ions can also be preferably used.

The amount of the metal complex used in the present invention is preferably from 10 ^-9 to 10 ^-3 mol per mol of silver halide. 1
It is more preferably at least 10 ^-9 mol and at most 1 10 ^-4 mol, and particularly preferably at least 5 10 ^-8 mol and at most 5 10 ^-5 mol. It is preferable that these metal complexes are present in the interior of the particles of 50% or less of the particle volume.

Specific examples of the metal complex that can be used in the present invention include the following, but the present invention is not limited thereto. These compounds are
Since the microwave photoconductivity also changes depending on the amount and method of addition, it is necessary to appropriately adjust the amount and method of addition.

(DI-1) K ₃ [Fe (CN) ₆ ] (DI-2) K ₄ [Fe (CN) ₆ ] (DI-3) K ₄ [Ru (CN) ₆ ] (DI-4) K ₂ [Ir (CN) ₆ ] (DI-5) K ₂ [Fe (CO) ₅ ] (DI-6) K ₃ [Co (CN) ₆ ] (DI-7) K ₂ [Ni (CN) ₄ ] (DI-8) Fe ( C 5 H 5) 2 (DI-9) K 4 [Co (CN) 6] (DI-10) K 4 [Os (CN) 6] Moreover, further advantages of the present invention Among the metal complexes of Group VIII of the Periodic Table, an iridium complex having a halide ion as a ligand or a compound in which at least one of the ligands is a nitrosyl or thionitrosyl ligand is used to increase the particle volume by 50% of the particle volume. It can be contained on the following particle surfaces. Among them, a compound in which at least one of the ligands is a nitrosyl or thionitrosyl ligand is preferable. The compounds that can be used for this purpose are listed below, but the invention is not limited thereto.

(DII-1) Cs ₂ [Os (NO) Cl ₅ ] (DII-2) K ₂ [Ru (NO) Cl ₅ ] (DII-3) K ₂ [Fe (NO) (CN) ₅ ] (DII-4) Cs ₂ [Os (NS) Cl ₅ ] In order to allow these metal complexes to be contained in the silver halide grains, the metal complexes are formed before the formation of the silver halide grains and before the formation of the silver halide grains. Medium and during the physical ripening after the formation of silver halide grains may be added at any place in each step.

As the sensitizing dye, any of the known compounds can be used. Examples of the blue-sensitive sensitizing dye include BS-1 to BS described in JP-A-3-251840, page 28.
-8 can be preferably used alone or in combination. As the green photosensitive sensitizing dye, GS-1 to GS-5 described on page 28 of the same publication are preferable, and as the red photosensitive sensitizing dye, RS-1 to RS-8 described on page 29 of the same publication are preferred.
Is 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. And the dyes IRS-1 to IRS-11 described on pages 6 to 8 are preferably used. Further, these infrared, red, green, and blue photosensitive sensitizing dyes include supersensitizers SS-1 to SS-9 described in JP-A-4-285950, pp. 8-9, and JP-A-5-66515. No. 15-
It is preferable to use compounds S-1 to S-17 described on page 17 in combination.

The amount of the sensitizing dye to be used is not uniform depending on the type of silver halide emulsion, the type of compound used, the ripening conditions, etc., but is usually 1 × 1 per mol of silver halide.
It is preferably from 0 ^-2 to 1 x 10 ^-8 mol, more preferably from 1 x 10 ^-4 to 1 x 10 ^-8 mol. In the present invention, the sensitizing dye coverage is determined by JOURNAL OF IM
AGING SCIENCE Volume 29, N
number 5, September / October
P. 166-P. The coefficient of variation is preferably 0.10 or less when obtained by a method similar to that described in 1701985. Further, the coefficient of variation is preferably 0.05 or less, more preferably 0.03 or less.

The functional compound of the present invention is added through an ultrafiltration membrane in the step of producing a silver halide emulsion. There are no particular restrictions on the ultrafiltration module and circulating pump that can be used when carrying out the addition through the ultrafiltration membrane, but materials and materials that act on the silver halide emulsion and adversely affect photographic performance etc. Preferably, the structure is avoided.
The molecular weight cutoff of the ultrafiltration membrane used in the ultrafiltration module is also arbitrarily selected according to the functional compound.

The silver halide grains contained in the silver halide photographic emulsion of the present invention have a coefficient of variation of the content distribution of the functional compound of 0.10 or less, preferably 0.05 or less.
More preferably, it is 0.03 or less. The variation coefficient is calculated by the same method as the variation coefficient of the particle size distribution described later.

The composition of the silver halide photographic emulsion according to the present invention has an arbitrary halogen composition such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide and silver chloroiodide. However, silver chlorobromide containing 95 mol% or more of silver chloride and containing substantially no silver iodide is preferred. From the viewpoint of rapid processing property and processing stability, a silver halide emulsion containing preferably 97 mol% or more, more preferably 98 to 99.9 mol% of silver chloride is preferable.

In order to obtain the above-mentioned silver halide emulsion, a silver halide emulsion having a portion containing silver bromide at a high concentration is particularly preferably used. In this case, the portion containing silver bromide at a high concentration may be epitaxy-bonded to silver halide emulsion grains, may be a so-called core-shell emulsion, or may be only partially formed without forming a complete layer. May simply have regions with different compositions. The composition may change continuously or may change 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.

Any shape can be used for the silver halide grains. One preferable example is a cube having a (100) plane as a crystal surface. Also, U.S. Pat. Nos. 4,183,756 and 4,225,666, JP-A-55-26589, JP-B-55-42737,
Octahedrons, tetradecahedrons, dodecahedrons, etc., by methods described in documents such as The Journal of Photographic Science (J. Photogr. Sci.) 21, 39 (1973). Can be produced and used. Further, particles having a twin plane may be used.

As the silver halide grains, grains having a single shape are preferably used, and it is particularly preferable to add two or more kinds of monodispersed silver halide emulsions to the same layer.

The grain size of the silver halide grains is not particularly limited, but is preferably 0.1 to 1.2 μm, more preferably 0.2 to 1.2 μm, in consideration of other photographic properties such as rapid processing and sensitivity. The range is 1.0 μm. This particle size can be measured using the projected area or diameter approximation of the particle. If the particles are substantially uniform in shape, the particle size distribution can represent this quite accurately as diameter or projected area.

The particle size distribution of the silver halide grains is preferably a monodispersed silver halide grain having a coefficient of variation of 0.05 to 0.22, more preferably 0.05 to 0.15.
Particularly preferably, two or more monodispersed emulsions of 0.05 to 0.15 are added to the same layer. Where the coefficient of variation is
This is a coefficient indicating the width of the particle size distribution, and is defined by the following equation.

Coefficient of variation = S / R (S is the standard deviation of the particle size distribution, and R is the average particle size.) The particle size referred to here is the diameter of spherical silver halide grains, In the case of particles having a shape other than a cubic or a spherical shape, the diameter represents a diameter when the projected image is converted into a circular image having the same area.

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

The 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 a time, or may be grown after seed particles have been produced. The method for producing the seed particles and the method for growing the seed particles may be the same or different.

The form 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, a combination thereof, and the like, but the 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.

Also, JP-A-57-92523 and JP-A-57-92523.
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. Alternatively, an apparatus or the like for continuously changing the concentration of a water-soluble halide aqueous solution may be used.

For the photographic material, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any of known compounds can be used. In particular, as dyes having absorption in the visible region, dyes of AI-1 to 11 described in JP-A-3-251840, p. The dyes described in JP-A-3770 are preferably used, and as the infrared absorbing dye, compounds represented by the general formulas (I), (II) and (III) described in the lower left column of page 2 of JP-A-1-280750 are preferable. It is preferable because it has spectral characteristics, does not affect the photographic characteristics of the photographic emulsion, and does not 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. For the purpose of improving sharpness, the amount of these dyes added is preferably such that the spectral reflection density at 680 nm of an unprocessed sample of the light-sensitive material is 0.7 to 3.0, and more preferably 0.8 to 3.0. More preferably, it is 3.0.

It is preferable to add a fluorescent whitening agent to the light-sensitive material because the whiteness 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 according to the present invention is used as a color light-sensitive material, it is used in combination with a yellow coupler, a magenta coupler and a cyan coupler in a range of 400 to 900 n.
It has a layer containing a silver halide emulsion spectrally sensitized to a specific region of the m wavelength range. The silver halide emulsion may be of one type or two types.
It contains a combination of two or more sensitizing dyes.

As the coupler used in the light-sensitive material according to the present invention, any compound capable of forming a coupling product having a spectral absorption maximum wavelength in a wavelength range longer than 340 nm by coupling reaction with an oxidized form of a color developing agent is used. Can be used, and particularly typical couplers include a yellow dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, and a wavelength range of 500 to 600.
Examples include a magenta dye-forming coupler having a spectral absorption maximum wavelength in nm, and a cyan dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 600 to 750 nm.

Preferable examples of the cyan coupler which can be preferably used include couplers represented by general formulas [CI] and [C-II] described in the lower left column of JP-A-4-114154, page 5. As a specific compound, the 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.

The magenta dye-forming couplers which can be preferably used include the general formulas (MI) and (M-II) described in the upper right column on page 4 of JP-A-4-114154.
And a coupler represented by the following formula: Specific compounds are listed in the lower left column of page 4 to the upper right column of page 5 in the same publication.
What is described as C-11 can be mentioned. More preferred among the above magenta couplers are couplers represented by the general formula (MI) described in the upper right column on page 4 of the publication, and among them, R _{M of} the general formula (MI) is 3
A coupler which is a lower alkyl group is particularly preferable because of its excellent light resistance. MC-8 to MC- described in the upper column on page 5 of the publication.
No. 11 is preferable because it is excellent in reproducing colors from blue to purple and red, and is also excellent in detail description. Examples of more preferred couplers include exemplified compounds 1 to 64 described on pages 5 to 9 of JP-A-63-253943, and
Exemplified compounds M-1 to M-29 described on pages 5 to 6 of JP-A-100048, and JP-A-7-175186.
Exemplified compounds (1) to (36) described on pages 12 to 12, Exemplified compounds M-1 to M-33 described on pages 14 to 22 of JP-A-7-219170, and JP-A-8-304972. Compounds M-1 to M-1 described on pages 5 to 9 of
6, exemplified compounds M-1 to M-26 described on pages 5 to 10 of JP-A-10-207024, JP-A-10-20
Exemplified compound M- described on page 5 to page 22 of No. 7025
1 to M-36, pages 3 to 6 of U.S. Pat. No. 5,576,150, and exemplified compounds M-1 to M-24, page 3 of U.S. Pat. No. 5,609,996. Exemplified Compounds M-1 to M-48 on pages 9 to 9, US Pat.
Exemplified compound M described on pages 3 to 5 of the specification of Japanese Patent No. 7,952
-1 to M-23, and exemplified compounds M-1 to M-26 described on pages 3 to 6 of U.S. Pat. No. 5,698,386.

As a yellow coupler which can be preferably used, a coupler represented by the general formula [YI] described in the upper right column on page 3 of JP-A-4-114154 can be mentioned. YC on the lower left column of page 3
-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 an oil-in-water emulsification dispersion method is used to add a coupler or other organic compound used in a light-sensitive material, it is usually added to a water-insoluble high-boiling organic solvent having a boiling point of 150 ° C. or higher, if necessary. To dissolve in combination with a low boiling point and / or water-soluble organic solvent, and emulsify and disperse 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 included.

Examples of the high boiling organic solvent which can be used for dissolving and dispersing the coupler include phthalic acid esters such as dioctyl phthalate, di-i-decyl phthalate and dibutyl phthalate, tricresyl phosphate and trioctyl phosphate. And the like 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.

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).

As a compound preferable as a surfactant used for dispersing a photographic additive or adjusting a surface tension at the time of coating, a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or a salt thereof in one molecule are preferable. Containing. 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.

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 in JP-A-2-66541, page 3, and phenols represented by general formula [IIIB] described in JP-A-3-174150. Amine compounds represented by the general formula [A] described in JP-A-64-90445;
General formulas (XII), (XIII) and (XI) described in No. 182741
V] and metal complexes represented by [XV] are particularly preferred for magenta dyes. Also, a compound represented by the general formula [I] described in JP-A-1-19649 and JP-A-5-1141.
The compound represented by the general formula [II] described in No. 7 is particularly preferable for yellow and cyan dyes.

Compounds such as compound d-11 described in the lower left column of page 9 of JP-A-4-114154 and compound A'-1 described in the upper left column of page 10 are used for shifting the absorption wavelength of the coloring dye. 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, a compound which reacts with an oxidized developing agent is added to a layer between the light-sensitive layers to prevent color turbidity, or added to a silver halide emulsion layer to prevent fog or the like. Is preferably improved. As the compound for this, a hydroquinone derivative is preferred, and more preferably
Dialkylhydroquinones such as 5-di-t-octylhydroquinone. Particularly preferred compounds are those represented by the general formula [II] described in JP-A-4-133056, and the compounds II-1 to II-14 described on pages 13 to 14 of the same publication.
Compounds-1 described on pages II-14 and 17 are mentioned.

It is preferable to add an ultraviolet absorber to the light-sensitive material to prevent static fog or to improve the light fastness 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;
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 according to the present invention. If necessary, gelatin derivatives, graft polymers of gelatin and other polymers, proteins other than gelatin, sugar derivatives, cellulose derivatives A hydrophilic colloid such as a synthetic hydrophilic polymer substance such as a single or copolymer can also be used.

As the hardener of these binders, it is preferable to use a vinyl sulfone hardener, a chlorotriazine hardener, and a carboxyl group-active 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.

As the support used for the light-sensitive material, any material may be used, including paper coated with polyethylene or polyethylene terephthalate, paper support made of natural pulp or synthetic pulp, vinyl chloride sheet, and white pigment. For example, polypropylene, polyethylene terephthalate support, baryta paper, etc. 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 a copolymer thereof is preferred.

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, more preferably 15% by weight, in order to improve 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 value of the center surface average roughness (SRa) of the support is 0.15 μm or less, and more preferably 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 is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the surface of the support, if necessary, and then directly or undercoating (adhesion, antistatic property, dimensional stability of the support surface). , One or more undercoating layers for improving friction resistance, hardness, antihalation property, frictional properties and / or other properties).

In coating a 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 photosensitive material according to the present invention, the image recorded on the negative may be optically formed on the photosensitive material to be printed and printed. After the image is once converted to digital information, the image may be formed on a CRT (cathode ray tube), and the image may be formed on a photosensitive material to be printed and printed, or based on the digital information. Printing may be performed by scanning while changing the intensity of the laser beam.

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 which directly forms an image for 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 3 minutes 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, a known developer component compound 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.

After the color development, the light-sensitive material is subjected to a bleaching process and a fixing process. The bleaching process may be performed simultaneously with the fixing process. After the fixing process, a water washing process is usually performed. Further, as an alternative to the washing process, a stabilizing process may be performed.

The developing apparatus used for processing the photosensitive material according to the present invention is a roller transport type in which the photosensitive material is conveyed by sandwiching the photosensitive material between rollers disposed in a processing tank. An endless belt method may be used, in which the processing tank is formed in a slit shape, and a processing liquid is supplied to the processing tank and the photosensitive material is transported, or a spray method in which the processing liquid is sprayed, A web system by contact with a carrier impregnated with a treatment liquid, a system 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. And the method described in JP-A-94-16935 is most preferable.

[0086]

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 A paper support was prepared by laminating high-density polyethylene on both sides of a paper pulp having a basis weight of 180 g / m ² . However, on the side to be coated with the emulsion layer, a molten polyethylene containing a surface-treated anatase-type titanium oxide dispersed in a content of 15% by weight was laminated to produce a reflective support. After the reflective support was subjected to corona discharge treatment, a gelatin undercoat layer was provided thereon, and each layer having the following constitution was further provided thereon to prepare a silver halide photographic light-sensitive material. The coating solution was prepared as follows.

First layer coating solution 23.4 g of yellow coupler (Y-1), 3.34 g of dye image stabilizer (ST-1), 3.34 of (ST-2)
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, and this solution was dissolved in 1 ml containing 7 ml of 20% surfactant (SU-1).
It was emulsified and dispersed in 220 ml of 0% gelatin aqueous solution using an ultrasonic homogenizer to prepare a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive silver halide emulsion prepared under the following conditions to prepare a first layer coating solution.

The coating liquids for the second to seventh layers were prepared in the same manner as the coating liquid for the first layer so that the coating amounts were as shown in Tables 1 and 2.

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

[0091]

[Table 1]

[0092]

[Table 2]

SU-1: sodium tri-i-propylnaphthalenesulfonate SU-2: di (2-ethylhexyl) sodium sulfosuccinate sodium salt SU-3: di (2,2,3,3,4) sulfosuccinate , 4,
5,5-octafluoropentyl) · sodium salt 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 Image Stabilizer A: pt-octylph Enol

[0094]

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[0095]

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[0096]

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[0097]

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(Preparation of Blue-Sensitive Silver Halide Emulsion) 40 ° C.
In a liter of a 2% aqueous gelatin solution kept warm in
Solution) and (solution B) were added simultaneously over 30 minutes while controlling pAg = 7.3 and pH = 3.0, and the following (solution C) and (solution D) were further pAg = 8.0, pH = 5.5 and added simultaneously over 180 minutes. At this time, pAg was controlled by the method described in JP-A-59-45437.
H was controlled using sulfuric acid or an aqueous solution of sodium hydroxide.

(Solution A) 3.42 g of sodium chloride 0.03 g of potassium bromide 200 ml with addition of water (Solution B) 10 g of silver nitrate 200 ml with addition of water (Solution C) 102.7 g of sodium chloride 102.7 g of K ₂ IrCl ₆ 4 × 10 ^-8 mol / mol Ag K ₄ Fe (CN) ₆ 2 × 10 ^-5 mol / mol Ag Potassium bromide 1.0 g Add water 600 ml (Solution D) Silver nitrate 300 g Add water 600 ml after completion of addition, Kao Atlas After desalting using a 5% aqueous solution of Demol N and 20% aqueous solution of magnesium sulfate, the mixture was mixed with an aqueous gelatin solution to give an average particle size of 0.71 μm.
m, coefficient of variation of particle size distribution 0.07, silver chloride content 99.
A 5 mol% monodispersed cubic emulsion EMP-1 was obtained.

Next, EMP was performed except that the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed.
As in the case of -1, the average particle diameter is 0.64 μm, and the coefficient of variation is 0.1.
07, a monodispersed cubic emulsion EMP-1B having a silver chloride content of 99.5 mol% was obtained.

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

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 silver halide emulsion Preparation) (Solution A) and (Solution B)
The average particle diameter was 0.40 μm in the same manner as in EMP-1 except that the addition time of (C) and (C solution) and (D solution) were changed.
m, a coefficient of variation 0.08, and a monodispersed cubic emulsion EMP-2 having a silver chloride content of 99.5%.

Next, a monodispersed cubic emulsion EMP-2B having an average particle size of 0.50 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5% 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 silver halide emulsion) (solution A) and (solution B)
The average particle diameter was 0.40 μm in the same manner as in EMP-1 except that the addition time of (C) and (C solution) and (D solution) were changed.
m, a coefficient of variation 0.08 and a monodisperse cubic emulsion EMP-3 having a silver chloride content of 99.5%. The average particle size is 0.38
A monodisperse cubic emulsion EMP-3B having a particle size of 0.08, a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained.

The above-mentioned 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 amount 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 STAB-1: 1- ( 3-acetamidophenyl) -5-mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole -1 was added in an amount of 2.0 × 10 ^-3 mol per mol of silver halide.

[0108]

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[0109]

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[0110] The sample thus prepared was used as sample 101.
And In the preparation of Sample 101, the liquids A to D
Add the additive solution to the surface liquid level using the double jet method.
Rush was added in minutes. Various additives during chemical sensitization were also rush-added to the surface liquid surface in one minute.

Next, the preparation of the blue-sensitive silver halide emulsion of Sample 101 is shown in Table 3 in the same manner except that chloroauric acid during chemical sensitization was added through an ultrafiltration membrane for 10 to 50 minutes. Such various silver halide emulsions were prepared. Each sample was prepared using these blue-sensitive silver halide emulsions.

Each of these samples was exposed to a blue light laser at a high illuminance of 300 nanoseconds and then developed by the following processing steps. Each sample was subjected to 50 ° C., 40% R.D. H.
, And the above exposure treatment was performed after storage for 5 days.

The reflection densities of 0.3 and 0.
The difference between the gradation calculated from the numerical value of 8 before and after storage was used as a measure of storage stability. Table 3 shows the results.

Processing Step Processing Temperature Time Replenishment Color Development 38.0 ± 0.3 ° C. 45 seconds 80 ml Bleaching and Fixing 35.0 ± 0.5 ° C. 45 seconds 120 ml Stabilization 30-34 ° C. 60 seconds 150 ml Dry Drying 60 to 80 ° C. for 30 seconds The composition of the developing solution is shown below.

<Color developing solution tank solution and replenisher> Tank solution 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 pentaacetate sodium salt 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 Add water to make the total volume 1 liter. pH = 1
Adjust the replenisher to pH = 10.60 to 0.10.

<Bleach-fixing solution tank solution and replenisher> Diethylenetriaminepentaacetic acid ammonium ferric dihydrate 65 g Diethylenetriaminepentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml 2-amino-5-mercapto-1,3,4- Thiadiazole 2.0 g Ammonium sulfite (40% aqueous solution) 27.5 ml 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> o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0 0.02 g Diethylene glycol 1.0 g Optical brightener (Tinopal 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 g Ammonia water (25% aqueous solution of ammonium hydroxide) 2.5 g Nitrilotriacetic acid / trisodium salt 1.5 g Add water to make the total volume 1 liter, and adjust the pH to 7.5 with sulfuric acid or ammonia water. .

[0118]

[Table 3]

Example 2 A sample similar to the sample 101 of Example 1 was prepared, and a sample 20 was prepared.
It was set to 1. Next, in the preparation of a blue-sensitive silver halide emulsion of Sample 201, a mercapto compound (S
TAB-1,2,3) through an ultrafiltration membrane for 10 to 50
Various silver halide emulsions as shown in Table 4 were prepared in the same manner except that the addition was carried out for 1 minute. Each sample was prepared using these blue-sensitive silver halide emulsions and evaluated in the same manner as in Example 1. Table 4 shows the results.

[0120]

[Table 4]

Example 3 A sample similar to the sample 101 of Example 1 was prepared, and a sample 30 was prepared.
It was set to 1. Next, in the preparation of the blue-sensitive silver halide emulsion of Sample 301, solutions A to D were passed through an ultrafiltration membrane for 10 to 5 minutes.
Various silver halide emulsions as shown in Table 5 were prepared in the same manner except that the addition was performed in 0 minute. Each sample was prepared using these blue-sensitive silver halide emulsions and evaluated in the same manner as in Example 1. Table 5 shows the results.

[0122]

[Table 5]

Example 4 In the preparation of the blue-sensitive silver halide emulsion of Sample 101 of Example 1, the same liquids A to D were used except that sodium chloride of liquid A was changed to 3.45 g and potassium bromide was removed. After preparing silver halide grains, 0.03 g of potassium bromide was added to the silver halide grains to make a 200 ml solution, and the solution was rush-added to the emulsion solution surface for 1 minute. Thereafter, the same chemical sensitization as in Sample 101 was performed to prepare a silver halide emulsion. Sample 101 was prepared using this silver halide emulsion.
A sample similar to the above was prepared, and was used as a sample 401. Next, sample 4
In the preparation of the blue-sensitive silver halide emulsion No. 01, various silver halide emulsions as shown in Table 6 were prepared in the same manner except that a potassium bromide solution was added through an ultrafiltration membrane for 10 to 50 minutes. Each sample was prepared using these blue-sensitive silver halide emulsions and evaluated in the same manner as in Example 1.
Table 6 shows the results.

[0124]

[Table 6]

Example 5 A sample similar to the sample 101 of Example 1 was prepared, and a sample 50 was prepared.
It was set to 1. Next, in the preparation of a blue-sensitive silver halide emulsion of Sample 501, a sensitizing dye (BS-1, 2) during chemical sensitization was used.
Was added in the same manner for 10 to 50 minutes through an ultrafiltration membrane to prepare various silver halide emulsions as shown in Table 7. Each sample was prepared using these blue-sensitive silver halide emulsions and evaluated in the same manner as in Example 1. Table 7 shows the results
Shown in

[0126]

[Table 7]

As is clear from Tables 3 to 7, in the sample of the present invention, an image having a high gradation was obtained even with high illuminance exposure. In addition, a sample with little deterioration in gradation during storage was obtained.

[0128]

According to the present invention, it is possible to provide a silver halide emulsion which gives an image having a high gradation even under high illuminance exposure and has little gradation deterioration during storage, and a method for producing the same.

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Claims (9)

[Claims] 1. A method for producing a silver halide emulsion, comprising a step of adding a functional compound through an ultrafiltration membrane. 2. The silver halide according to claim 1, wherein the functional compound is at least one compound selected from a sensitizer, a mercaptoheterocyclic compound, a Group 8 metal compound and a sensitizing dye. Emulsion manufacturing method. 3. The method for producing a silver halide emulsion according to claim 1, wherein the average silver chloride content of the silver halide emulsion is 98% or more. 4. A silver halide emulsion, wherein the coefficient of variation of the distribution of the content of the mercaptoheterocyclic compound in the silver halide grains is 0.10 or less. 5. A silver halide emulsion characterized in that the coefficient of variation of the group 8 metal content distribution of the silver halide grains is 0.10 or less. 6. An average silver chloride content of 95% or more,
A silver halide emulsion characterized in that the variation coefficient of the distribution of the halogen composition other than chlorine in the silver halide grains is 0.10 or less. 7. A silver halide emulsion wherein the coefficient of variation of the distribution of sensitizing dye coverage of silver halide grains is 0.10 or less. 8. The silver halide emulsion according to claim 4, wherein the silver halide emulsion has an average silver chloride content of 98% or more. 9. The silver halide emulsion according to claim 4, which is produced by the method for producing a silver halide emulsion according to claim 1, 2 or 3.