JPH11338092A - Silver halide photosensitive material and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the photosensitive material high in sensitivity and free from residual dye stains and superior in storage stability against time lapse and further, improved from stagnation at low temperature and good in manufacture stability by spectrally sensitizing silver halide grains with a combination of specified compounds. SOLUTION: The silver halide grains are spectral-sensitized with a combination of the compound represented by formula I with the compound represented by formula II or III. In formulae I-III, each of R1 -R4 and R11 -R14 is an aliphatic group, and at least one of R2 , R4 , R12 , and R14 is an alkyl group having a sulfa or carboxy group. Each of V1 -V4 is a hydrogen atom or a substituent, at least one of V1 -V4 is an aromatic group, and each of V11 -V14 is a hydrogen atom or a substituent except an aromatic group. Y is an oxygen or sulfur atom or the like, each of R21 and R22 is an alkyl group, each of L21 -L23 is a methine group, each of Z21 and Z22 is a benzene or naphthalene ring, and each of M1 , M11 , and M21 is an ion necessary for neutralizing a molecular charge.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a spectrally sensitized silver halide photographic light-sensitive material, and more particularly, to a silver halide photographic light-sensitive material having high sensitivity, free from dye contamination, and excellent in storage stability and production stability. It relates to the manufacturing method.

[0002]

2. Description of the Related Art In recent years, demands for high sensitivity and rapid processing of silver halide photographic materials have been gradually increasing.
In order to realize rapid processing, it is necessary to shorten the processing time of each processing step such as development, fixing, washing, and drying, and the load of each processing increases.

For example, if the development time is simply shortened, a conventional silver halide photographic material tends to be accompanied by a decrease in density, that is, a decrease in sensitivity and a deterioration in gradation. Further, when the fixing time is shortened, the fixing of the silver halide becomes incomplete and the image quality is liable to deteriorate.

[0004] Further, the shortening of each processing time is caused by the fact that unnecessary dyes from the silver halide photographic light-sensitive material are not sufficiently eluted in the respective processing steps of development, fixing and water washing, so that color contamination due to residual dyes (residual colors) is caused. Remain, and as a result, the image quality tends to deteriorate.

[0005] Therefore, in order to solve such problems, for example, the amount of silver is reduced, the developing speed and the fixing speed are increased, the amount of dye is reduced, and the desorption or decoloration of dye is accelerated. Technology is required.

On the other hand, in recent years, many techniques using tabular silver halide grains have been disclosed as means for achieving high sensitivity of silver halide photographic materials. Tabular silver halide grains have the same volume and a larger surface area than normal crystal grains, so that the amount of photosensitive dye adsorbed on the grain surface can be increased, and spectral sensitivity and image sharpness can be improved. .

However, an increase in the amount of photosensitive dye adsorbed has a problem that the residual color tends to increase in rapid processing.

[0008] As techniques for improving these problems, for example, EP-A-0 506 584 and JP-A-5-88293.
And JP-A-5-93975 disclose techniques using specific benzimidazolocarbocyanines having good decolorization performance as spectral sensitizing dyes.

Japanese Patent Application Laid-Open No. 5-61148 discloses that an oxacarbocyanine compound and a benzoimidazolocarbocyanine compound are combined at a specific ratio with a silver halide emulsion having a silver iodide content of 1 mol% or less. It is disclosed that rapid processing and residual color are improved by performing chemical sensitization with a selenium compound or tellurium compound.

However, although the residual color property and the rapid processing property of development are improved, they are still insufficient, and furthermore, when the silver halide photographic light-sensitive material is stored under high humidity and high temperature for a long time,
There is a problem that the sensitivity is greatly reduced.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic light-sensitive material having high sensitivity, no dye contamination, excellent storage stability with time, improved emulsion low-temperature stagnation, and good production stability. Is to provide.

[0012]

The above objects of the present invention have been attained by the following items 1 to 3.

1. In a silver halide photographic material having at least one photosensitive silver halide emulsion layer on a support, silver halide grains contained in at least one of the silver halide emulsion layers are represented by the following general formula (1). A silver halide photograph characterized by being spectrally sensitized by combining at least one compound selected from the compounds represented by formula (1) and at least one compound selected from compounds represented by formula (2) or (3) below: Photosensitive material.

[0014]

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In the formula, R _{1 to} R ₄ each represent an aliphatic group;
V _{1 to} V ₄ each represent a hydrogen atom or a substituent. However,
At least one of R ₂ and R ₄ represents an alkyl group having a sulfo group or a carboxy group, at least one group of V ₁ ~V ₄ is an aromatic group. M ₁ represents an ion necessary to neutralize an intramolecular charge, and m ₁ represents a number required to neutralize an intramolecular charge.

[0016]

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In the formula, R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each represent an aliphatic group, and at least one of R ₁₂ and R ₁₄ represents an alkyl group having a sulfo group or a carboxy group.
V ₁₁ , V ₁₂ , V ₁₃ and V ₁₄ each represent a hydrogen atom or a substituent other than an aromatic group. M ₁₁ represents an ion necessary to neutralize the intramolecular charge, and m ₁₁ represents a number required to neutralize the intramolecular charge.

[0018]

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In the formula, Y represents an oxygen atom, a sulfur atom or a selenium atom, R ₂₁ and R ₂₂ each represent an alkyl group,
However, at least one represents an alkyl group having a sulfo group or a carboxy group. L ₂₁ , L ₂₂ and L ₂₃ each represent a methine group. Z ₂₁ and Z ₂₂ each represent a benzene ring or a naphthalene ring which may have a substituent, M ₂₁ represents an ion necessary for neutralizing an intramolecular charge, and m ₂₁ represents an intramolecular charge. Represents the number required to neutralize

2. The above-mentioned item 1, wherein at least 70% of the total projected area of the silver halide grains contained in at least one of the photosensitive silver halide emulsion layers is tabular silver halide grains having an average aspect ratio of 2 or more. The silver halide photographic light-sensitive material as described above.

3. It is characterized in that the compound represented by the general formula (1), (2) or (3) is added as an aqueous solution or an aqueous dispersion substantially without using an organic solvent during or after the formation of silver halide grains. Of producing a silver halide photographic light-sensitive material.

Hereinafter, the present invention will be described in detail.

In the above general formulas (1) and (2), R
₁ The aliphatic group represented by to R _4, R ₁₁ to R _14, for example, an alkyl group (e.g., methyl group branched or straight-chain having 1 to 10 carbon atoms, an ethyl group, a propyl group, a butyl group, Pentyl group, iso-pentyl group, 2-ethylhexyl group, octyl group, decyl group, etc.), having 3 to 1 carbon atoms
0 alkenyl group (for example, 2-propenyl group, 3-butenyl group, 1-methyl-3-propenyl group, 3-pentenyl group, 1-methyl-3-butenyl group, 4-hexenyl group, etc.), the number of carbon atoms 7 to 10 aralkyl groups (for example,
Benzyl group, phenethyl group, etc.). These groups further include a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkoxy group (eg, a methoxy group, an ethoxy group, etc.), an aryloxy group (eg, a phenoxy group, a p-tolyloxy group, etc.) ), A cyano group, a carbamoyl group (for example, a carbamoyl group, an N-methylcarbamoyl group, an N, N-tetramethylenecarbamoyl group, etc.), a sulfamoyl group (for example, a sulfamoyl group,
N, N-3-oxapentamethyleneaminosulfonyl group, etc.), haloalkyl group (eg, 2,2,2-trifluoroethyl group, 2,2,3,3-tetrafluoropropyl group, etc.), alkylsulfonyl group (Eg, methanesulfonyl group, ethanesulfonyl group, etc.), alkoxycarbonyl group (eg, ethoxycarbonyl group, butoxycarbonyl group, etc.), aryl group (eg, phenyl group,
Carboxyphenyl group, etc.), acyl group (eg, acetyl group, benzoyl group, etc.), acylamino group (eg, acetylamino group, benzoylamino group, etc.), sulfonamide group (eg, methanesulfonamide group, butanesulfonamide group, etc.) ) May be substituted.

Further, a sulfo group, a carboxy group, a phosphono group, a sulfate group, a hydroxy group, a sulfino group,
Sulfonylaminocarbonyl group (eg, methanesulfonylaminocarbonyl group, ethanesulfonylaminocarbonyl group, etc.), acylaminosulfonyl group (eg, acetamidosulfonyl group, methoxyacetamidosulfonyl group, etc.), acylaminocarbonyl group (eg, acetamidocarbonyl group, Methoxyacetamidocarbonyl group, etc.), sulfinylaminocarbonyl group (for example,
It is preferably substituted with a hydrophilic group such as a methanesulfinylaminocarbonyl group and an ethanesulfinylaminocarbonyl group.

Specific examples of these aliphatic groups substituted with a hydrophilic group include carboxymethyl, carboxyethyl, sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, 5-sulfopentyl, Sulfobutyl group, 3-sulfopentyl group, 6-sulfo-3-oxahexyl group, ω-sulfopropoxycarbonylmethyl group, ω-sulfopropylaminocarbonylmethyl group, 3
-Sulfinobutyl group, 3-phosphonopropyl group, hydroxyethyl group, N-methanesulfonylcarbamoylmethyl group, 4-sulfo-3-butenyl group, 4-carboxybutyl group, 2-carboxy-2-propenyl group, o −
Examples include a sulfobenzyl group, a P-sulfophenethyl group, a p-carboxybenzyl group, and the like.

At least one of R ₂ and R ₄ and R ₁₂ and R ₁₄
Is an alkyl group having a sulfo group, and examples of the alkyl group having a sulfo group include a sulfoethyl group, a sulfopropyl group, a sulfobutyl group, a sulfopentyl group, and a 3-sulfobutyl group.

Examples of the substituent represented by V _{1 to} V ₄ include an alkyl group (methyl group, ethyl group, butyl group, isobutyl group, etc.), an alkenyl group (2-propenyl group, 1-propenyl group, 1- Methyl-3-butenyl group, etc.), aralkyl group (eg, benzyl group, phenethyl group, etc.), thio group (eg, methylthio group, ethylthio group, phenylthio group, etc.), halogen atom (eg, fluorine atom, chlorine atom, bromine Atom, iodine atom, etc.), aryl group (eg, phenyl group, m-chlorophenyl group, p-tolyl group, naphthyl group, etc.), heterocyclic group (eg, pyridyl group, pyrrolyl group, 2-methylpyrrolyl group, indolyl group, Imidazolyl, furyl, thiazolyl, pyrimidinyl, etc.),
Acyl group (eg, acetyl group, benzoyl group, etc.), acyloxy group (eg, acetyloxy group, benzoyloxy group, etc.), cyano group, trifluoromethyl group, sulfonyl group (eg, methanesulfonyl group, benzenesulfonyl group, etc.) Carbamoyl group (eg, carbamoyl group, N, N-dimethylcarbamoyl group, N-morpholinocarbonyl group, etc.), sulfamoyl group (sulfamoyl group, N-phenylsulfamoyl group, morpholinosulfamoyl group, etc.), acylamino group ( For example, acetylamino group, benzoylamino group, etc., sulfonylamino group (eg, methanesulfonylamino group, benzenesulfonylamino group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, trifluoromethoxy Carbonyl group).

However, at least one of V _{1 to} V ₄ is an aromatic group. In the present invention, the aromatic group is
It means an aromatic carbocyclic group and an aromatic heterocyclic group.

Examples of the aromatic carbocyclic group include a benzene ring and a naphthalene ring. The benzene ring and the naphthalene ring may have a substituent.

Examples of the aromatic heterocyclic group include a furan ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxazole ring, a thiazole ring, a 1,2,3-oxadiazole ring, and a 1,2,3-triazole ring. , 1,2,4-triazole ring, 1,3,4-thiadiazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, s-
Examples include a triazine ring, a benzofuran ring, an indole ring, a benzothiophene ring, a benzimidazole ring, a benzothiazole ring, a purine ring, a quinoline ring and an isoquinoline ring.

Further, among the aromatic carbocyclic group and the aromatic heterocyclic group, a benzene ring, a pyrrole ring, a pyridine ring, a thiazole ring, a furan ring, a thiophene ring, an imidazole ring and the like are preferably used.

As the groups represented by V _{1 to} V ₄ , the sum of the Hammett σp values of the substituents is preferably at least 0, more preferably at least 0.4, Particularly preferably, it is 0.6 to 2.4.

The substituents represented by V _{1 to} V ₄ may be further substituted with groups such as a hydroxyl group and a carboxyl group in addition to the above-mentioned groups.

The Hammett σ used in the general formula (1)
The p-value is a substituent constant determined from the electronic effect of the substituent on the hydrolysis of ethyl benzoate by Hammett et al., Journal of Organic Chemistry 23, 420-427 (1958), Laboratory Chemistry Volume 14 (Maruzen Publishing), Physical Organic Chemistry (McGraw Hill Book)
Company: 1940), Drag Design VII (Acad)
emic Press New York: 1976
) And the structure-activity relationship of drugs (Nankodo: 1979).

As the non-aromatic substituents represented by V _{11 to} V ₁₄ , those having the same meanings as the substituents represented by V _{1 to} V ₄ can be used. However, the non-aromatic substituent represented by V _{11 to} V ₁₄ means an aromatic carbocyclic group (for example, benzene ring, naphthalene ring, etc.) or an aromatic heterocyclic group (for example, furan ring, pyrrole ring, Pyrazole ring, imidazole ring, oxazole ring, thiazole ring, 1,2,3-oxadiazole ring, 1,2,3-triazole ring, 1,
2,4-triazole ring, 1,3,4-thiadiazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, s-triazine ring, benzofuran ring, indole ring, benzothiophene ring, benzimidazole ring, benzothiazole ring , A purine ring, a quinoline ring and an isoquinoline ring).

The groups represented by V _{11 to} V ₁₄ include
The sum of the Hammett σp values of the substituents is preferably 0.7 or more, more preferably 1.0 or more, and particularly preferably 1.0 to 2.4.

The ions represented by M ₁ and M ₁₁ include anions and cations. Examples of the anions include chloride, bromine, iodine, thiocyanate, sulfate, perchlorate, and p-toluenesulfonic acid. Examples of the ion include an ion and an ethyl sulfate ion. Examples of the cation include a lithium ion, a sodium ion, a potassium ion, a magnesium ion, a triethylammonium ion, and a diazabicycloundecenium ion.

The spectral sensitizing dyes represented by formulas (1) and (2) used in the present invention are described, for example, in British Patent No. 9
No. 55,961, U.S. Pat. No. 2,739,149, JP-A-43-10251, JP-A-43-10252, and JP-A-43-10252.
4-16589, JP-A-5-88293, 6-2
Nos. 30501, 6-2988731, etc., by Hammer, Cyanine Soybeans Related Compounds (John Wiley & Sons, New York)
k, 1964) and the like.

Next, the above-mentioned general formula (1) used in the present invention
Specific examples of the compound represented by are shown below, but the present invention is not limited thereto.

[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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Next, the above-mentioned general formula (2) used in the present invention
Specific examples of the compound represented by are shown below, but the present invention is not limited thereto.

[0047]

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[0048]

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[0049]

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Next, the above-mentioned general formula (3) used in the present invention
In the dye of formula (I), the alkyl group represented by R ₂₁ and R ₂₂ includes a lower alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group), a hydroxyalkyl group (for example, a 2-hydroxyethyl group) , A 2-hydroxypropyl group, etc.), a carboxyalkyl group (for example, an acyloxyalkyl group such as a 2-acetoxyethyl group, a 3-acetoxybutyl group, a 2-carboxyethyl group, a 3-carboxypropyl group, a 2- (2-carboxy) group. Ethoxy) ethyl group etc.), sulfoalkyl group (for example,
2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, 2-hydroxy-3
-Sulfopropyl group, etc.), alkoxyalkyl group (eg, 2-methoxyethyl group, 3-methoxypropyl group, etc.), phenoxyalkyl group (eg, 2-phenoxyethyl group, 2- (4-carboxyphenyloxy) ethyl group) Carbamoylalkyl group (eg, 1-carbamoylmethyl group, 2-carbamoylethyl group, N-acetylcarbamoylmethyl group, N-methanesulfonylcarbamoylmethyl group, 2-piperazinocarbamoylethyl group, etc.), acylaminoalkyl Group (eg, 2-acetylaminoethyl group, 3-acetylaminopropyl group, etc.), sulfamoylalkyl group (eg, 2-sulfamoylethyl group, 2-N, N-dimethylsulfamoylethyl group, N -Acetylsulfamoylmethyl group, etc.) Le group (e.g., 2,2,
3,3-tetrafluoropropyl group and the like, and aralkyl groups (for example, benzyl group, 2-carboxyphenylmethyl group, 4-carboxyphenylmethyl group, 4-sulfophenylmethylphenethyl group and the like).

However, at least one of R ₂₁ and R ₂₂ is a sulfoalkyl group or a carboxyalkyl group.

Examples of the group to be substituted on the condensed benzene ring or condensed naphtho ring formed by Z ₂₁ and Z ₂₂ include lower alkyl groups (for example, methyl group, ethyl group, propyl group, etc.)
Lower alkoxy groups (eg, methoxy group, ethoxy group, etc.), lower alkylthio groups (eg, methylthio group, ethylthio group, etc.), aryl groups (eg, phenyl group, 4
-Bromophenyl group, 4-ethoxyphenyl group, 3-bromophenyl group, etc.), aryloxy group (for example, phenoxy group, 4-bromophenoxy group, etc.), trifluoromethyl group, halogen atom (for example, fluorine atom, chloro Atom, bromo atom, etc.), carboxy group, hydroxy group,
Alkoxycarbonyl group (for example, ethoxycarbonyl group, methoxycarbonyl group, etc.), 2-hydroxybenzoylamino group, heterocyclic group (for example, 2-furyl group, 1-
Pyrrolyl group, 2-thienyl group, etc.).

Examples of the group substituted on the methine chain represented by L ₂₁ , L ₂₂ and L ₂₃ include a lower alkyl group (for example, a methyl group and an ethyl group) and a lower alkoxy group (for example, a methoxy group and an ethoxy group). , An propoxy group, etc.), an aryloxy group (eg, phenoxy group, 2-fluorophenoxy group, etc.), an aralkyl group (eg, benzyl group, phenethyl group, etc.), a heterocyclic group (eg, thienyl group, furyl group, etc.), Examples thereof include an alkylthio group (for example, a methylthio group, an ethylthio group, and the like).

In the general formula (3), the ion represented by M ₂₁ is the same as the ion defined by M ₁ in the general formula (1).

Next, the above general formula (3) used in the present invention
Specific examples of the compound represented by are shown below, but the present invention is not limited thereto.

[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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As the dye represented by the general formula (3) used in the present invention, other than the above, for example, JP-A-4-9
Compound Examples II-3, II-4, II-6, II described in No. 040
-7, II-8, II-10, II-13, II-14, II-1
6, II-17, II-18, II-20, II-21, II-2
4-II-44 and the like can be similarly used.

The sensitizing dye represented by the general formula (3) used in the present invention is a dye sensitized by F.I. M. Hemmer, Heterocyclic Compounds, Cyanine Soybeans and Relayed Compounds) IV, V, Chapter VI, pp. 89-199,
(John Wiley & Sons, New York
k, London 1964) or D.E. M. Stur
by Mer (Heterocyclic Compounds Special Topics in Heterocyclic Chemistry) Chapter VIII IV. 482-515 (John Wil
eye & Sons, New York, London
1977) and the like.

In the present invention, the above general formula (1)
Both (2) and (3) show only one state of the resonance structure, and even if they are expressed in the extreme state where the + (plus) charge enters the symmetric heterocyclic nitrogen atom, they are the same substance. Represents

The technique of using the spectral sensitizing dyes of the general formulas (1) and (2) or (3) used in the present invention is useful for photosensitive materials requiring sensitivity to green light. In particular, the present invention is remarkably effective in adapting to an X-ray recording light-sensitive material utilizing a phosphor emitting green light in order to increase the recording sensitivity to X-rays, and is particularly effective in X-ray medical photosensitive materials.

When applied to an X-ray recording sensitive material using a phosphor emitting green light, the dye represented by the general formula (1) and the dye represented by the general formula (2) or (3) are used. It is preferable that a dye is combined and adsorbed on silver halide grains so that a J-band is formed in the same wavelength region as green light when its reflection spectrum is measured. That is, it is usually preferable to select and combine spectral sensitizing dyes such that a specific J-band is formed in the 520 nm to 560 nm region.

The amount of the compound represented by the general formula (1) and (2) or (3) in the present invention depends on the kind of the dye and the structure, composition, ripening condition, purpose and purpose of silver halide. Although different, the monolayer coverage of the surface of each photosensitive grain in the silver halide emulsion is 40% or more and 90% or more.
It is preferable to set the following, and further, 50% to 8
0% is particularly preferred.

The appropriate amount per mol of silver halide varies depending on the total surface area of the silver halide grains in the emulsion.
Less than 00 mg is preferred. Further, it is preferably 450 mg or less.

As a solvent for the sensitizing dye, a conventionally used water-miscible organic solvent can be used. For example, alcohols, ketones, alkoxy alcohols and the like can be used. Specific examples include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, 2,2,3,3-tetrafluoropropanol, ethylene glycol, propylene glycol, 1,3-propanediol, acetone, 2-methoxyethanol,
2-ethoxyethanol and the like.

However, in the present invention, the effect is increased by adding the spectral sensitizing dye as an aqueous solution or aqueous dispersion without using an organic solvent. In particular, it is preferable to add at least one kind of spectral sensitizing dye in a solid fine particle dispersion substantially insoluble in water, which is dispersed in an aqueous system substantially free of an organic solvent or a surfactant.

When added as an aqueous solution, the dyes represented by the above general formulas (1), (2) and (3)
By adjusting H, the concentration can be adjusted to an appropriate concentration for addition. A technique for dispersing an organic dye in an aqueous medium is disclosed in, for example, JP-A-3-288842. However, this method is for making the organic dye non-diffusible into the photographic material and is merely a dispersion addition method.

On the other hand, in the dispersion addition method used in the present invention, the above-mentioned spectral sensitizing dye is made to adsorb uniformly and effectively on the surface of silver halide grains. Only the above-mentioned technology has a different purpose and effect.

In the present invention, the aqueous system substantially free of an organic solvent or the above-mentioned surfactant is water containing impurities at a level not adversely affecting the silver halide photographic emulsion, and more preferably ion exchange. Refers to water and distilled water.

The spectral sensitizing dye used in the present invention may be used in combination with another spectral sensitizing dye. Dyes used include cyanine dyes, merocyanine dyes, composite cyanine dyes, composite merocyanine dyes, holoboralar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. These dyes can be applied to any of the nuclei commonly used. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus,
Thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, nucleus and the like fused with an aliphatic hydrocarbon ring to these nuclei, that is, indolenine nucleus, benzindolenin nucleus, indole nucleus, benzoxazole nucleus,
A naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms.

The merocyanine dye or the complex merocyanine dye has pyrazoline- as a nucleus having a ketomethine structure.
5-6 nuclei, thiohydantoin nuclei, 2-thiooxazolidine-2,4-dione nuclei, thiazoline-2,4-dione nuclei, rhodanine nuclei, thiobarbituric acid nuclei, etc.
Member heterocyclic nuclei can be applied.

In addition to these spectral sensitizing dyes, dyes having no spectral sensitizing properties or substances which do not substantially absorb visible light and exhibit supersensitizing action are added to the emulsion layer. You may.

The spectral sensitizing dye used in the present invention can be added at the chemical ripening step, particularly preferably at the start of the chemical ripening step, and can be added from the nucleation step of the silver halide emulsion used in the present invention. By adding it by the end of the desalting step, a high-sensitivity silver halide emulsion having excellent spectral sensitization efficiency can be obtained, but any time after the end of the desalting step, through the chemical ripening step, and immediately before the coating step In addition, the same or different kinds of spectral sensitizing dyes used in the present invention, which are the same as or different from the dyes added in the above step (from the nucleation step to the end of the desalting step), may be additionally added.

The silver halide emulsion used in the present invention can be subjected to chemical sensitization. The chemical sensitization is not particularly limited in the conditions of the process, for example, pH, pAg, temperature, time and the like, and can be performed under the conditions generally used in the art. For chemical sensitization, sulfur sensitization using a compound containing sulfur capable of reacting with silver ions or active gelatin, selenium sensitization using a selenium compound, tellurium sensitization using a tellurium compound, a reducing substance Reduction sensitization method used, gold and other, noble metal sensitization method using noble metal and the like can be used alone or in combination, among them, selenium sensitization method,
Tellurium sensitization, reduction sensitization and the like are preferably used, and selenium sensitization is particularly preferably used.

In the case of selenium sensitization, the selenium sensitizer used comprises a wide variety of selenium compounds. For example, U.S. Patent Nos. 1,574,944, 1,602,592 and 16,234.
No. 99, JP-A-60-150046, JP-A-4-25
No. 832, No. 4-109240, No. 4-147250
And the like. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, etc.), and selenoureas (eg, N, N-dimethylselenourea, N, N, N′-triethylselenourea) , N, N,
N'-trimethyl-N'-heptafluoroselenourea,
N, N, N'-trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N'-trimethyl-N'-4-nitrophenylcarbonylselenourea, etc., selenoketones (for example, selenoacetone, seleno Acetophenone, etc.), selenoamides (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-3-selenobutyrate, etc.), selenophos Phates (eg, tri-
p-triselenophosphate, etc.), selenides (diethyl selenide, diethyl diselenide, etc.) phosphine selenides (triphenylphosphine selenide, pentafluorophenyl-diphenylphosphine selenide, tris (m-chlorophenyl) And phosphine selenide). Particularly preferred selenium sensitizers are selenoureas, selenamides, and phosphine selenides.

The amount of the selenium sensitizer used varies depending on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but is generally from 10 ^-8 mol to 10 mol per mol of silver halide.
^Use about ^-4 moles. Depending on the properties of the selenium compound used, water or methanol, a method of dissolving in a single or mixed solvent of an organic solvent such as ethanol, or a method of premixing with a gelatin solution and adding,
The compound can be added by a method disclosed in JP-A-4-140739, that is, a method of adding a mixed solution with a polymer soluble in an organic solvent in the form of an emulsified dispersion.

The temperature of chemical ripening using a selenium sensitizer is 4
A range from 0 to 90C is preferred. More preferably, it is 45 ° C or more and 80 ° C or less. The pH is 4-9 and the pAg is 6-
A range of 9.5 is preferred.

For tellurium sensitizers and sensitization methods, see US Pat. Nos. 1,623,499 and 3,320,069.
Nos. 3,772,031 and 3,531,289
No. 3,655,394, UK Patent No. 235,21
No. 1, No. 1, 121, 496, No. 1, 295, 462
No. 1,396,696, Canadian Patent No. 800,9
No. 58, JP-A-4-204640, JP-A-4-3330
No. 43 and the like.

Examples of useful tellurium sensitizers include telluroureas (eg, N, N-dimethyltellurourea, tetramethyltellurourea, N-carboxyethyl-N, N'-dimethyltellurourea, N, N'- Dimethyl-N'phenyltellurourea), phosphine tellurides (eg, tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride), telluramides (eg, Telluroacetamide, N, N-dimethyltellurobenzamide), telluro ketones, telluro esters, isotellurocyanates and the like. The technology for using the tellurium sensitizer is based on the technology for using the selenium sensitizer.

By placing the emulsion in an appropriate reducing atmosphere, so-called reduction sensitization can be performed on the grain surface.
Preferred examples of the reducing agent include thiourea dioxide and ascorbic acid and derivatives thereof. Other preferable reducing agents include hydrazine, polyamines such as diethylenetriamine, dimethylamine borane, sulfites and the like.

The amount of the reducing agent added depends on the type of the reduction sensitizer, the particle size of silver halide grains, the composition and crystal habit, the temperature of the reaction system, p
It is preferable to change the value depending on environmental conditions such as H and pAg. For example, in the case of thiourea dioxide, a preferable result can be obtained by using about 0.01 to 2 mg per mol of silver halide. In the case of ascorbic acid, the amount is preferably about 50 mg to 2 g per mol of silver halide.

The conditions for the reduction sensitization are as follows.
0 ° C., time is about 10 to 200 minutes, pH is about 5 to 11, p
Ag is preferably about 1 to 10.

As the water-soluble silver salt, silver nitrate is preferable. By adding a water-soluble silver salt, so-called silver ripening, which is a kind of reduction sensitization technique, is performed. The pAg during silver ripening is suitably from 1 to 6, and preferably from 2 to 4. Conditions such as temperature, pH, and time are preferably in the above-described reduction sensitization condition range. As a stabilizer for a silver halide photographic emulsion containing silver halide grains which have been subjected to reduction sensitization, the following general stabilizers can be used, and examples thereof are disclosed in JP-A-57-82831. Antioxidants and / or V.I. S. Gahle
r's paper [Zeithshift fur wiss
enshaftliche Photographi
e Bd. 63, 133 (1969)] and
Good results are often obtained when thiosulfonic acids described in US Pat. No. -1019 are used in combination. These compounds may be added at any stage of the emulsion production process from the crystal growth to the preparation process immediately before coating.

In the present invention, fine silver iodide may be added to the silver halide emulsion during the process from chemical ripening to coating. Here, the process from chemical ripening to coating includes during chemical ripening and means that fine grain silver iodide is added to the process from coating to coating.

The fine grain silver iodide used in the present invention may be cubic γ-AgI or hexagonal β-AgI.
Or a mixture thereof.

The addition timing of the fine grain silver iodide in the present invention may be any of the steps from the chemical ripening step to immediately before coating, but is preferably the chemical ripening step.

The term "chemical ripening step" as used herein refers to a step of adding a chemical sensitizer from the point of completion of the physical ripening and desalting operations of the emulsion used in the present invention, and then performing an operation for stopping the chemical ripening. Point to the time. The addition of the fine grain silver iodide may be carried out several times at intervals, or another chemically-ripened emulsion may be added after the addition of the fine grain silver iodide. The temperature of the emulsion used in the present invention at the time of adding the fine grain silver iodide is preferably in the range of 30 to 80C, more preferably 40 to 65C.

The silver halide grains of the silver halide emulsion used in the present invention include silver halides such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide and silver chloride. Silver particles can be used arbitrarily. In particular, silver iodochlorobromide, silver chlorobromide or silver chloride having a silver chloride content of 60 mol% or more improves the effect of the present invention.

The silver halide grains used in the present invention include, for example, cubic, octahedral, tetradecahedral, spherical, tabular, and potato-shaped silver halide grains. What is obtained are tabular grains.

Hereinafter, tabular grains will be described as typical examples of the silver halide grains used in the present invention.

The tabular silver halide grains preferably used in the present invention are crystallographically classified as twins. Twins are silver halide crystals having one or more twin planes in one grain, and the classification of twin morphology is based on the report by Klein and Moiser in Photographies Correspondents (Photographisches Korresp).
ondenz), Vol. 99, p. 99, and Vol. 100, p. 57.

The tabular silver halide grains preferably used in the present invention mainly have an even number of parallel twin planes, and these twin planes may or may not be parallel to each other. However, it is particularly preferable to have two twin planes.

The tabular silver halide grains used in the present invention have an average ratio (average aspect ratio) of grain diameter / thickness (aspect ratio) of 2 or more. The average aspect ratio of the tabular silver halide grains used in the present invention is preferably from 2 to 12, and more preferably from 3 to 8.

The outer wall of the crystal of the tabular silver halide grains used in the present invention may be substantially composed of {111} planes or composed of {100} planes. In addition, it may have both the {111} plane and the {100} plane. In this case, 50% or more of the particle surfaces are {111} planes, more preferably 60% to 90%.
% Is {111} plane, particularly preferably 70 to 95%
Is the {111} plane. It is preferable that the plane other than the {111} plane is mainly the {100} plane. This surface ratio utilizes the difference in the adsorption dependency between the {111} plane and the {100} plane in the adsorption of the sensitizing dye [T. Tani, J .; I
imaging Sci. 29,165 (1985)]
Can be obtained by

The tabular silver halide grains used in the present invention may be polydisperse or monodisperse, but are preferably monodisperse. Specifically, when the width of the distribution is defined by the relative standard deviation (coefficient of variation) expressed by (standard deviation of particle size / average particle size) × 100 = width (%) of particle size distribution, 25% The following is preferable, more preferably 20% or less, and particularly preferably 15% or less.
% Or less.

In the present invention, the tabular silver halide grains are preferably hexagonal. Hexagonal tabular grains (hereinafter also referred to as hexagonal tabular grains) are defined as the main plane (｛1
(11 ° plane) is hexagonal, and the maximum adjacency ratio is 1.0 to 2.0. Here, the maximum adjacent side ratio is the ratio of the length of the side having the maximum length to the length of the side having the minimum length forming a hexagon. In the present invention, the hexagonal tabular grains have a maximum adjacent side ratio of 1.0 to 1.0.
If it is 2.0, it is also preferable that the corner is rounded. The length of a side having a rounded corner is represented by the distance between the intersection of the extended straight line portion of the side and the extended straight line portion of the adjacent side. It is also preferred that the tabular grains are further rounded and are substantially circular.

In the present invention, it is preferable that at least one half of each side forming the hexagon of the hexagonal tabular grain is substantially a straight line. In the present invention, the adjacent side ratio is 1.
More preferably, it is 0 to 1.5.

The silver halide grains used in the present invention may have dislocation lines. The dislocation line is described in, for example, F. H
amilton, Photo. Sci. Eng, 57
(1967) and T.W. Shiozawa, J .; So
c. Photo. Sci. Japan, 35, 213 (1
972) can be observed by a direct method using a low-temperature transmission electron microscope at a low temperature. That is, the silver halide grains taken out so as not to apply pressure enough to generate dislocations from the emulsion are placed on a mesh for observation with an electron microscope and damaged by an electron beam (printout, etc.).
Observation is carried out by a transmission method in a state in which the sample is cooled so as to prevent the above. At this time, the thicker the particle, the more difficult it is for the electron beam to penetrate. Therefore, a sharper observation can be obtained by using a high-pressure electron microscope (200 kV or more for a particle having a thickness of 0.25 μm). it can.

From the photographs of the particles obtained by such a method, the position and number of dislocations for each particle can be determined. The dislocation position of the silver halide grains used in the present invention is preferably generated in a region from 0.58 L to 1.0 L from the center of the silver halide grains toward the outer surface, and more preferably 0%. .80L to 0.98L. The direction of the dislocation line is approximately from the center toward the outer surface, but often meanders.

In the present invention, the center of the silver halide grains is defined by dispersing silver halide microcrystals in a methacrylic resin in the same manner as in the method described in the abstract of Inoue et al. Solidified, ultrathin sections with a microtome, with the largest cross-sectional area and 90%
Focusing on the sliced sample having the above cross-sectional area, this is the center of a circle when a circumscribed circle that is the smallest with respect to the cross section is drawn. In the present invention, the distance L from the center to the outer surface is defined as the distance between the point at which the line intersects the outer periphery of the particle when a straight line is drawn outward from the center of the circle and the center of the circle.

Regarding the number of dislocations in the silver halide grains used in the present invention, 50% of the grains containing one or more dislocations
The number (number) is desirably at least (number), and the higher the ratio (number) of the number of tabular grains having dislocation lines, the more preferable.

In the present invention, the particle diameter is a diameter when a projected image of a particle is converted into a circular image having the same area. The projected area of a grain can be determined from the sum of the grain areas. In each case, a silver halide crystal sample distributed on a sample table to such an extent that no grain overlap occurs can be obtained by observing the sample with an electron microscope.

The average projected area diameter of the tabular silver halide grains in the present invention is represented by a circle equivalent diameter of the projected area of the grains, and is preferably 0.30 μm or more, more preferably 0.30 to 5 μm, More preferably 0.40-2μ
m.

The particle size can be obtained by projecting the particles at an enlargement of 10,000 to 70,000 times with an electron microscope and actually measuring the projected area on the print.

Further, the average particle size (φi) is expressed by n
And when the frequency of particles having a particle size φi is ni, it can be obtained by the following equation.

Average particle size (φi) = Σnidi / n (The number of measured particles is indiscriminately 1,000 or more.) The particle thickness is obtained by observing the sample obliquely with an electron microscope. Can be. The preferred thickness of the tabular grains preferably used in the present invention is 0.03 to 1.0.
μm, and more preferably 0.05 to 0.5 μm.

The ratio (b / a) between the longest distance (a) between two or more parallel twin planes of the silver halide grains used in the present invention and the thickness (b) of the grains is 5 or more. It is preferable that the ratio is 50% (number) or more.

The tabular silver halide grains preferably used in the present invention may have a uniform composition, but may contain at least two silver halide grains having substantially different halogen compositions.
Grains having a core / shell structure having a two-layer structure may be contained in the photosensitive silver halide emulsion layer.

The silver halide grains used in the present invention are:
So-called halogen conversion type (conversion type) particles may be used. The halogen conversion amount is 0.1 to silver amount.
It is preferably from 2 mol% to 2.0 mol%, and the conversion may be performed either during physical ripening or after physical ripening. As a method of halogen conversion, an aqueous halogen solution or fine silver halide particles having a smaller solubility product with silver than the halogen composition of the grain surface before the halogen conversion is usually added. The particle size at this time is preferably 0.2 μm or less, more preferably 0.02 to 0.1 μm.

The silver halide grains used in the present invention are:
For example, it is preferable to grow the seed crystal by a method of precipitating silver halide on a seed crystal as described in Examples of JP-A-60-138538.

In the process for producing a silver halide photographic emulsion, a water-soluble silver salt solution and a water-soluble halide solution are supplied to the protective colloid in order to obtain a tabular silver halide emulsion used in the present invention. , (A) silver iodide content 0
A nucleus grain forming step of maintaining the pBr of the mother liquor at 2.5 to -0.7 for a period of at least 1/2 from the beginning of the formation of silver halide precipitates of up to 5 mol%; continue,
A silver halide solvent is added to the mother liquor at a rate of
0 ^-5 mol to 2.0 mol content to or substantially provided seed grain formation step of forming a silver halide seed grains are twinned crystal monodisperse spherical, or subsequent to the nucleic particle generation step, the mother liquor A step of raising the temperature to 40 to 80 ° C. to form seed grains for forming silver halide twin seed grains is provided. (C) Then, a water-soluble silver salt solution and a water-soluble halide solution and / or fine halide particles are added. In addition, a method of providing a growth step for enlarging seed particles is preferably used. Here, the mother liquor is a liquid (including a silver halide emulsion) which is used for preparing a silver halide emulsion up to a completed photographic emulsion.

The silver halide grains formed in the grain forming step are twin grains composed of 0 to 5 mol% of silver iodide.

A water-soluble silver salt may be added for the purpose of adjusting ripening during the seed particle forming step used in the present invention. The seed grain growing step for enlarging the silver halide seed grains is carried out during the precipitation of silver halide and during the Ostwald ripening.
It is achieved by controlling Ag, pH, temperature, concentration of silver halide solvent and silver halide composition, and addition rate of silver salt and halide solution.

In preparing the emulsion used in the present invention, a known silver halide solvent such as ammonia, thioether, thiourea or the like can be present during the step of forming seed grains and growing the seed grains.

In order to obtain tabular silver halide grains for use in the present invention, conditions for enlarging the produced seed grains include, for example, JP-A-51-39027 and JP-A-55-14.
No. 2329, No. 58-113928, No. 54-485
As described in JP-A Nos. 21 and 58-49938, a water-soluble silver salt solution and a water-soluble halide solution were added by a double jet method, and the addition rate was adjusted according to the enlargement of the particles. Alternatively, a method of gradually changing the change within a range in which the occurrence does not occur may be used. As another condition for enlarging the seed grains, a method of adding silver halide fine grains, dissolving and recrystallizing the grains, as shown in Item 88 of the Abstracts of the 58th Annual Meeting of the Photographic Society of Japan, may be used.

For growth, an aqueous silver nitrate solution and an aqueous halide solution can be added by a double jet method, but the iodine can also be supplied into the system as silver iodide.
The addition rate is such that no new nuclei are generated, and the rate at which the size distribution does not spread due to Ostwald ripening,
That is, it is preferable to add in a range of 30 to 100% of the rate at which new nuclei are generated.

In producing the silver halide emulsion used in the present invention, stirring conditions during production are extremely important. As the stirrer, an apparatus disclosed in JP-A-62-160128 in which an additive liquid nozzle is installed in the liquid near the mother liquor suction port of the stirrer is particularly preferably used. In this case,
The rotation speed of the stirring is preferably set to 400 to 1200 rpm.

The silver iodide content and the average silver iodide content of the silver halide grains used in the present invention are determined by the EPMA method (El
electron Probe Micro Analyz
er). According to this method, a sample in which emulsion grains are well dispersed so as not to be in contact with each other is prepared, and elemental analysis of a part smaller than X-ray analysis by electron beam excitation in which an electron beam is irradiated can be performed. By this method, the halogen composition of each grain can be determined by determining the characteristic X-ray intensity of silver and iodine emitted from each grain. If the silver iodide content is determined for at least 100 grains by the EPMA method, the average silver iodide content can be determined from the average thereof.

In the production of the photosensitive silver halide emulsion used in the present invention, the seed emulsion has a total projected area of 50% of the seed grains.
% Or more have two or more parallel twin planes, and both the coefficient of variation of the thickness of the seed grains and the coefficient of variation of the longest distance (at) between the twin planes of the seed grains are 35% or less. It is preferred that

Even if the variation coefficient of only the thickness of the seed grains or only (at) is set to 35% or less, it is not possible to suppress the variation coefficient of the twin plane distance (a) of the grown grains to 35% or less. No, it is necessary that both be established at the same time.

This is probably because twin planes are generally formed at the stage of nucleation, but some are formed during growth.

Further, the silver halide grains used in the present invention may be used in the course of forming and / or growing grains, in the form of cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), rhodium salts. (Including complex salts) and iron salts (including complex salts) by adding at least one kind of metal ion, so that these metal elements can be contained inside the particles and / or in the particle surface layer. By placing in a reducing atmosphere, a reduction sensitizing nucleus can be provided inside the grain and / or on the grain surface.

Further, the action of the reducing agent added at a desired point in time of particle formation is to add an oxidizing agent such as hydrogen peroxide (water) and its adduct, peroxoacid salt, ozone, and I ₂ at a desired point. It is preferable to suppress or stop the reduction.

The time of addition of the oxidizing agent can be arbitrarily selected from the time of silver halide grain formation to the time of chemical sensitization.

In the silver halide emulsion of the silver halide photographic light-sensitive material used in the present invention, unnecessary soluble salts may be removed at the end of the growth of silver halide grains, or may remain contained. When removing the salts, use Research Disclosure (hereinafter abbreviated as RD) N
o. It can be performed based on the method described in 17643 No. II.

The silver halide emulsion layer containing the group of grains in the present invention may contain grains of various shapes as long as the effects of the present invention are not impaired.

Various photographic additives can be used in the silver halide light-sensitive material of the present invention. Known additives include, for example, Research Disclosure (RD) N
o. No. 17643 (December 1978); 187
16 (November 1979) and No. 16 308119
(December 1989). The types of compounds and the locations described in these three RDs are listed below.

[0132]

[Table 1]

The emulsion of the silver halide photographic light-sensitive material used in the present invention may contain a developing agent,
For example, aminophenol, ascorbic acid, pyrocatechol, hydroquinone, phenylenediamine or 3-
It may contain a developing agent such as pyrazolidone.

The support which can be used in the silver halide photographic light-sensitive material of the present invention includes, for example, the aforementioned RD-1
7643 and RD-308119, page 1009. A suitable support is a polyethylene terephthalate film or the like, and the surface of these supports may be provided with an undercoat layer for improving the adhesion of the coating layer, or may be subjected to corona discharge, ultraviolet irradiation, or the like.

Next, the processing method of the silver halide photographic light-sensitive material of the present invention will be described.

The silver halide photographic light-sensitive material of the present invention is preferably a development processing method in which the total processing time is 15 to 90 seconds. In the method for developing a silver halide photographic light-sensitive material of the present invention, the processing from the development to the drying is preferably completed within 90 seconds by an automatic processor. In other words, the time from when the tip of the photosensitive material starts to be immersed in the developing solution to when the tip comes out of the drying zone through the processing step (so-called Dry to Dry time) is within 90 seconds. Preferably, it is within 60 seconds.

Specifically, the development time is preferably from 5 seconds to 45 seconds, more preferably from 8 seconds to 30 seconds. The development temperature is preferably 25C to 50C, more preferably 30C to 40C.

The fixing temperature and time are about 20 ° C. to 50 ° C.
Seconds to 20 seconds are preferable, 30 to 40 degrees C, and 6 to 15 seconds are more preferable. The drying time may be generally 35 to 100 ° C., preferably 40 to 80 ° C., or a drying zone provided with heating means by far-infrared rays may be provided in the automatic developing machine.

The automatic developing machine is provided with a mechanism for applying water or a rinsing solution of an acidic solution having no fixing ability to the photosensitive material during each of the developing, fixing and washing steps (Japanese Patent Laid-Open No.
-264953) may be used. Further, a device capable of adjusting a developing solution and a fixing solution may be incorporated.

As a developing agent used in a preferred developer for developing the silver halide photographic light-sensitive material of the present invention, dihydroxybenzenes described in JP-A-4-15641 and JP-A-4-16841, for example, hydroquinone and paraaminophenol , Such as p-aminophenol, N
Examples of 3-pyrazolidones such as -methyl-p-aminophenol and 2,4-diamiphenol include, for example, 1-
Phenyl-3-pyrazolidones, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 5,5-dimethyl-1-
Phenyl-3-pyrazolidone and the like can be mentioned, and it is preferable to use them in combination.

The preferred amounts of the above-mentioned paraaminophenols and 3-aminopyrazolidones are 0.004 mol / l, more preferably 0.04 to 0.12.
Mol / l.

The total mole number of dihydroxybenzenes, paraaminophenols, and 3-pyrazolidones contained in all the components of the developing solution is preferably 0.1 mol / liter or less.

Preservatives may include sulphites, such as potassium sulphite, sodium sulphite, reductones, such as piperidinohexose reductone, which are preferably 0.2 to 1 mol / l, more preferably Preferably, 0.3 to 0.6 mol / liter is used. Also, the addition of a large amount of ascorbic acids leads to processing stability.

The alkaline agent includes a pH adjuster such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium tertiary phosphate and potassium tertiary phosphate. Further, borate described in JP-A-61-28708, saccharose, acetoxime, 5-sulfosalicylic acid, phosphate described in JP-A-60-93439,
A buffer such as a carbonate may be used. The content of these chemicals should be adjusted to a pH of the developer of 9.0 to 13, preferably pH 1
Choose to be 0-12.5.

Examples of solubilizers include polyethylene glycols and esters thereof. Examples of sensitizers include
For example, a development accelerator, a surfactant and the like such as a quaternary ammonium salt can be contained.

As a silver sludge inhibitor, JP-A-56-1
No. 06244, silver stain inhibitor, JP-A-3-5
The sulfides and disulfide compounds described in Japanese Patent Application No. 1844, and the cysteine derivatives or triazine compounds described in Japanese Patent Application No. 4-92947 are preferably used.

As the organic inhibitor, azole organic antifoggants such as indazole, imidazole, benzimidazole, triazole, benzotriazole, tetrazole and thiadiazole compounds are used.

The inorganic inhibitors include sodium bromide, potassium bromide, potassium iodide and the like. In addition,
L. F. A. Menson, "Photographic Processing Chemistry," Focal Press (19
66), pages 226-229, U.S. Pat.
Nos. 015 and 2,592,364, JP-A-48-64.
933 or the like may be used. Chelating agents for concealing calcium ions mixed in tap water used in the treatment liquid include chelating agents having a chelate stabilization constant of 8 or more with iron described in JP-A-1-193853 as an organic chelating agent. It is preferably used. Examples of the inorganic chelating agent include sodium hexametaphosphate, calcium hexametaphosphate, and polyphosphate.

The replenishment of the processing solution replenishes the processing agent fatigue and the oxidation fatigue. As a replenishment method, Japanese Patent Application Laid-Open No. 55-126
No. 243, replenishment by feeding speed,
Japanese Patent Application Laid-Open No. 1-14991
Area replenishment controlled by the number of continuously processed sheets described in No. 56 may be used, and a preferable replenishment amount is 500 to 150 ml.
/ M ² .

As the fixing solution composition used in the method for processing a silver halide photographic light-sensitive material of the present invention, an ordinary acidic hardening solution can be used.

[0151]

EXAMPLES Example 1 (Preparation of seed emulsion-1) Seed emulsion-1 was prepared as follows.

A1 ossein gelatin 100 g potassium bromide 2.05 g 11.5 l with water B1 ossein gelatin 55 g potassium bromide 65 g potassium iodide 1.8 g 0.2N sulfuric acid 38.5 ml 2.6 l with water C1 ossein gelatin 75g Potassium bromide 950g Potassium iodide 27g Water 3.0l D1 Silver nitrate 95g Water 2.7l E1 Silver nitrate 1410g Water 3.2l A1 solution with reactor temperature kept at 60 ° C, B1 solution and D1
Solution 1 was added by a control double jet method over 30 minutes, and then C1 and E1 solutions were added by a control double jet method over 105 minutes.
The test was performed at 00 rpm.

The flow rate was such that no new nuclei were generated with the growth of the particles, and so-called Ostwald ripening was performed. During the addition of the silver ion solution and the halide ion solution, the pAg was adjusted to 8.3 ± 0.05 using a potassium bromide solution, and the pH was adjusted to 2.0 ± 0.1 using sulfuric acid.

After the addition was completed, the pH was adjusted to 6.0, and in order to remove excess salts, a precipitation desalting treatment was carried out using an aqueous solution of Demol N (manufactured by Kao Atlas Co., Ltd.) and an aqueous solution of magnesium sulfate.

The obtained seed emulsion was observed with an electron microscope. As a result, the seed emulsion was a cubic monodisperse emulsion having an average particle size of 0.27 μm and a particle size distribution of 17% with a slightly rounded corner.

Preparation of Em-1 A monodisperse core / shell emulsion was prepared using the above seed emulsion-1 and the following seven kinds of solutions.

A2 ossein gelatin 10 g ammonia water (28%) 28 ml glacial acetic acid 3 ml seed emulsion-1 0.119 mol equivalent Equivalent to 600 ml with water B2 ossein gelatin 0.8 g potassium bromide 5 g potassium iodide 3 g with water 110 ml C2 Ossein gelatin 2 g Potassium bromide 90 g Finish to 240 ml with water D2 Silver nitrate 9.9 g Ammonia water (28%) 7.0 ml Finish to 110 ml with water E2 Silver nitrate 130 g Ammonia water (28%) 100 ml Finish to 240 ml with water F2 Potassium bromide 94 g Finished to 165 ml with water G2 Silver nitrate 9.9 g Ammonia water (28%) 7.0 ml Finished to 110 ml with water A2 solution was kept at 40 ° C. and stirred at 800 rpm with a stirrer. The pH of solution A2 was adjusted to 9.90 using acetic acid,
Seed emulsion-1 was collected and dispersed and suspended, and then the G2 solution was added at a constant speed over 7 minutes to adjust the pAg to 7.3. Further, B
Solution 2 and solution D2 were added simultaneously over 20 minutes. At this time, the pAg was kept constant at 7.3. The pH was adjusted to 8.83 and pAg using a potassium bromide solution and acetic acid over a further 10 minutes.
Was adjusted to 9.0, and the C2 solution and the E2 solution were simultaneously added over 30 minutes.

At this time, the flow rate ratio at the time of addition and at the end of addition was 1:10, and the flow rate was increased with time.
Further, the pH was lowered from 8.83 to 8.00 in proportion to the flow rate ratio.

When the C2 solution and the E2 solution were added in only 2/3 of the total amount, the F2 solution was additionally injected and added at a constant speed over 8 minutes. At this time, the pAg increased from 9.0 to 11.0. Further, acetic acid was added to adjust the pH to 6.0.

After completion of the addition, precipitation and desalting were carried out in the same manner as in the seed emulsion to remove excess salts, and pAg
An emulsion Em-1 having an average silver iodide content of about 2 mol% at pH 5.85 at 8.5 and 40 ° C. was obtained.

When the obtained emulsion was observed with an electron microscope, it was a rounded tetrahedral monodisperse core / shell type emulsion having an average particle size of 0.55 μm and a particle size distribution of 14%.

(Preparation of Seed Emulsion-2) Seed emulsion-2 was prepared as follows.

A3 Ossein gelatin 24.2 g Water 9657 ml Polypropylene oxy-polyethylene oxy-disuccinate sodium salt (10% aqueous ethanol) 6.78 ml Potassium bromide 10.8 g 10% nitric acid 114 ml B3 2.5 N silver nitrate aqueous solution 2825 ml C3 Potassium bromide 824 g Potassium iodide 23.5 g Finished to 2825 ml with water D3 1.75 N aqueous solution of potassium bromide The following silver potential control amount: 35 ° C, JP-B-58-58288, 58-5828
Using a mixing stirrer described in No. 9, 464.3 ml of each of the solution B3 and the solution C3 was added to the solution A3 by a simultaneous mixing method.
Nucleation was performed by adding over a minute.

After stopping the addition of the solution B3 and the solution C3, it takes 60 minutes to raise the temperature of the solution A3 to 60 ° C., adjust the pH to 5.0 with 3% KOH, and then re-add the solution. B3 and solution C3 were each mixed at a rate of 55.4 by a simultaneous mixing method.
It was added at a flow rate of ml / min for 42 minutes. The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during the temperature rise from 42 ° C. to 60 ° C. and the re-simultaneous mixing with the solutions B3 and C3 was measured using the solution D3.
It was controlled to be 8 mV and +16 mV.

After the addition was completed, the pH was adjusted to 6 with 3% KOH, and immediately, desalting and washing were performed. In this seed emulsion, 90% or more of the total projected area of silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0, and the average thickness of the hexagonal tabular grains is 0.06 μm. It was confirmed with an electron microscope that the diameter (in terms of circular diameter) was 0.59 μm.

Preparation of Em-2 A tabular emulsion Em-2 was prepared using the above seed emulsion-2 and the following three kinds of solutions.

A4 ossein gelatin 5.26 g Polypropylene oxy-polyethylene oxy-disuccinate sodium salt (10% aqueous ethanol solution) 1.4 ml Seed emulsion-2 equivalent to 0.094 mol Equivalent to 569 ml with water B4 ossein gelatin 15 5.5 g Potassium bromide 114 g Potassium iodide 3.19 g Finish up to 658 ml with water C4 Silver nitrate 166 g Finish up to 889 ml with water Add solution B4 and solution C4 to solution A4 vigorously stirred at 60 ° C.
It was added by the double jet method in 7 minutes. During this time, the pH was kept at 5.8 and the pAg was kept at 8.7 throughout. B4 liquid and C4
The addition rate of the liquid was linearly increased so as to be 6.4 times at the beginning and at the end.

After completion of the addition, precipitation and desalting were carried out in the same manner as in Em-1 to remove excess salts.
At pH 5.85 at an average silver iodide content of about 2.0
A mole% emulsion was obtained.

When the obtained emulsion was observed under an electron microscope, 82% of the projected area was tabular silver halide grains having an average grain size of 0.98 μm, a grain size distribution of 18%, and an average aspect ratio of 4.5. there were.

Preparation of Em-3 A tabular emulsion having a core / shell structure was prepared using Seed Emulsion-2 and the following four kinds of solutions.

A5 ossein gelatin 11.7 g Polypropylene oxy-polyethylene oxy-disuccinate sodium salt (10% aqueous solution of ethanol) 1.4 ml Seed emulsion-2 0.10 mol equivalent Equivalent to 550 ml with water B5 ossein gelatin 5 9.9 g Potassium bromide 4.6 g Potassium iodide 3.0 g Finish to 145 ml with water C5 Silver nitrate 10.1 g Finish to 145 ml with water D5 Ossein gelatin 6.1 g Potassium bromide 94 g Finish to 304 ml with water E5 Silver nitrate 137 g with water Finishing to 304 ml To the A5 solution vigorously stirred at 70 ° C., the B5 solution and the C5 solution were added in 58 minutes by a double jet method. Next, D5 solution and E5 solution were added to the same solution by a double jet method for 48 minutes. During this time, the pH was kept at 5.8 and the pAg was kept at 8.7.
After completion of the addition, desalting and precipitation were carried out in the same manner as in the case of emulsion Em-2.
At 0 ° C., an emulsion having a pAg of 8.5 and a pH of 5.85 and an average silver iodide content of about 2.0 mol% was obtained.

Observation of the obtained emulsion with an electron microscope revealed that 81% of the projected area had an average particle size of 0.96 μm, the particle size distribution was 18%, and the average aspect ratio was 4.5. It was silver halide particles.

Next, after the obtained emulsion was heated to 60 ° C.,
After adding a predetermined amount of the spectral sensitizing dye shown in Table 2 as a solid fine particle dispersion, a mixed aqueous solution of the following sensitizer formulation was added,
A further 60 minutes later, a silver iodide fine grain emulsion was added, and ripening was performed for a total of 2 hours. At the end of aging, an appropriate amount of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) was added as a stabilizer.

The additives other than the spectral sensitizing dye and the amounts added are shown below.

Sensitizer formulation Potassium thiocyanate 95 mg Chloroauric acid 2.5 mg Sodium thiosulfate 2.0 mg Pentafluorophenyl-diphenylphosphine selenide 2.0 mg Silver iodide fine particles 850 mg Stabilizer (TAI) 1 g Spectral sensitizing dye Is disclosed in Japanese Patent Application No. 4-9943.
Prepared by a method according to the method described in No. 7. That is, a predetermined amount of the spectral sensitizing dye is added to water whose temperature has been previously adjusted to 27 ° C.
Obtained by stirring for 0-120 minutes.

Next, an additive described below was added to the thus spectrally sensitized emulsion, and Sample No. 1 was prepared as an emulsion coating solution sample. 1-1 to 1-21 were produced. At the same time, a coating solution for the protective layer was prepared.

In order to examine the stagnation property of the above coating liquid samples after preparation, a reference coating liquid left at 40 ° C. for 30 minutes and a coating liquid left at 40 ° C. for 8 hours to prepare aging were prepared.

The obtained coating solution was coated on the support by using two slide hopper type coaters so that the amount of silver per side of the support was 2.0 g / m ² and the amount of gelatin was 3.1 g / m ^2. Was simultaneously coated on both sides and dried to obtain a sample. The support has a thickness of 175 μm, a concentration of glycidyl methacrylate of 50 wt%, a methyl acrylate of 10 wt%, and a butyl methacrylate of 40 wt% on both sides of a polyethylene terephthalate film base for X-ray colored blue at a concentration of 0.15.
% Of the copolymer composed of three kinds of monomers is 10 wt%
The following filter dye (solid dispersion) and gelatin were dispersed in a copolymer aqueous dispersion obtained by diluting so as to obtain an undercoating liquid, and the resultant was used.

The additives added to the emulsion are as follows.
The amount of addition is shown in an amount per mole of silver halide.

1,1-Dimethylol-1-bromo-1-nitromethane 70 mg t-butyl-catechol 400 mg polyvinylpyrrolidone (molecular weight 10,000) 1.0 g styrene-maleic anhydride copolymer 2.5 g nitrophenyl-triphenylphosphonium Chloride 50 mg Ammonium 1,3-dihydroxybenzene-4-sulfonate 2.0 g C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1.0 g 1-phenyl-5-mercaptotetrazole 15 mg

[0181]

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[0182]

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Protective Layer Solution The following was prepared as a protective layer coating solution. The additives are shown in an amount per liter of the coating solution.

Lime-treated inert gelatin 68 g Acid-treated gelatin 2.0 g Sodium-i-amyl-n-decylsulfosuccinate 1.0 g Polymethyl methacrylate (matting agent having an area average particle size of 3.5 μm) 1.1 g Silicon dioxide particles (Mat agent having an area average particle size of 1.2 μm) 0.5 g (CH ₂ ＣＨCHSO ₂ CH ₂ ) ₂ (hardening agent) 500 mg C ₄ F ₉ SO ₃ K 2.0 mg C ₁₂ H ₂₅ CONH (CH ₂ CH) ₂ O) ₅ H 2.0 g

[0185]

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[0186]

[Table 2]

Next, the coating amount sample No. 1-1 to N
o. Each of 1-21 was allowed to stand under the following two conditions, and a storage test was performed as a substitute.

Condition A: Reference sample left at 23 ° C. and 55% RH for 4 days Condition B: Storage test sample left at 40 ° C. and 80% RH for 4 days The evaluation method was as follows. The film was sandwiched between photosensitive paper KO-250 (manufactured by Konica Corporation) and exposed to X-rays at a tube voltage of 80 kVp and a tube current of 100 mA for 0.05 seconds through an aluminum wedge for exposure. Then, using an automatic developing machine SRX-502 (manufactured by Konica Corporation), processing was performed with a developing solution and a fixing solution having the following formulations.

Developer Formulation Part-A (for finishing 12 L) Potassium hydroxide 450 g Potassium sulfite (50% solution) 2280 g Diethylenetriaminepentaacetic acid 120 g Sodium bicarbonate 132 g 5-Methylbenzotriazole 1.2 g 1-Phenyl-5-mercapto Tetrazole 0.2g Hydroquinone 340g Water is added to make up to 5000ml.

Part-B (for finishing 12 L) Glacial acetic acid 170 g Triethylene glycol 185 g 1-Phenyl-3-pyrazolidone 22 g 5-Nitroindazole 0.4 g Starter Glacial acetic acid 120 g Potassium bromide 225 g Add water to make 1.0 L .

Fixer Formulation Part-A (for finishing 18 l) Ammonium thiosulfate (70 wt / vol%) 6000 g sodium sulfite 110 g sodium acetate trihydrate 450 g sodium citrate 50 g gluconic acid 70 g 1- (N, N-dimethylamino) -Ethyl-5-mercaptotetrazole 18 g Part-B 800 g of aluminum sulfate To prepare a developer, add Part A and Part B simultaneously to about 5 l of water, add water while stirring and dissolving, add 12 l to finish, and adjust the pH to 10.40 with glacial acetic acid. It was adjusted. This is used as a developer. 20 m of the above starter is used for 1 liter of the developing solution.
The pH was adjusted to 10.26 by adding 1 / l to make a working solution.

The fixing solution was prepared by adding Part A, P
artB was added at the same time, and water was added while stirring and dissolving.
and the pH was adjusted to 4.4 using sulfuric acid and NaOH. This is used as a fixing replenisher.

The processing temperature and processing time were as follows: development 38 ° C., 15 seconds, fixing 35 ° C., 15 seconds, water washing 20 ° C.,
0 seconds, drying 50 ° C, total processing time is dry to dry
For 45 seconds.

<< Evaluation of Sensitivity >> The treated sample was subjected to PDA-
The developed silver concentration was measured with a K. 65 (manufactured by Konica Corporation), and a characteristic curve was obtained. It was expressed as a relative value with the sensitivity of 1-1 being 100.

[0195] The stagnation of "Evaluation of storage stability and stagnation of" coated from by aging for 30 minutes a coating solution at a temperature 40 ° C. Samples, the sensitivity of the samples stored at the storage conditions A and Si ^A, 40 The sample applied after being aged at 8 ° C. for 8 hours, the sensitivity of the sample stored under the storage condition A described above as SC ^A ,
The value of ΔSp (Si ^A / SC ^A ) was used as a measure of sensitivity fluctuation due to stagnation after preparation of the coating solution.

The sensitivity of the sample stored under the above-mentioned storage condition B was determined by SC
^B , the sensitivity of the sample stored under the storage condition A was SC ^A , and the value of ΔS ^S (SC ^A / SC ^B ) was used as a measure of the sensitivity fluctuation of the storage property. In addition, Δ
F ^S (FC ^A / FC ^B ) was determined and used as a measure of the fog fluctuation of the storage stability. The closer the values of ΔS and ΔF are to 1, the better the production stability (stagnation) and the storage stability with time.

<< Evaluation of Residual Color >> The unexposed sample which was applied after being aged at 40 ° C. for 30 minutes and stored under the storage condition A was processed in the above-mentioned processing step, and the residual color of the obtained sample was measured. It was visually evaluated on a 5-point scale.

Those having no residual color are ranked as the highest rank “5”. Hereinafter, “4”, “3”,
The evaluation was made by sequentially lowering the rank to "2" and "1". "2"
And "1" are levels that are not preferred for practical use.

Table 3 shows the obtained results.

[0200]

[Table 3]

As is clear from Table 3, the sample of the present invention showed little change in sensitivity due to stagnation of the coating solution, and had good storage stability over time of the raw film. Further, it can be seen that the sample of the present invention has little residual color contamination by the dye.

Example 2 << Preparation of Emulsion Em-4 >> A seed emulsion having two parallel twin planes (T-1) was prepared by the following method with reference to the description in JP-A-5-34851. Was prepared.

Solution A 80.0 g of ossein gelatin 47.4 g of potassium bromide HO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) ₁₉ . ₈ (CH ₂ CH ₂ O) _n H (m + n = 9.77) 10% by weight methanol solution 0.48 g 8000 ml with water Solution B 1200 g silver nitrate 1600 ml with water Solution C ossein gelatin 32.2 g potassium bromide 790 g iodide Potassium 70.34 g 1600 ml with water Solution D ammonia water 470 ml Using a stirrer described in JP-A-62-160128, 4
The solution B and the solution C were added to the solution A vigorously stirred at 0 ° C. by the double jet method for 7.7 minutes to generate nuclei. During this time, pBr was kept at 1.60.

Then, the temperature was lowered to 20 ° C. over 35 minutes. Further, the solution D was added for 1 minute, followed by aging for 5 minutes. Potassium bromide concentration during aging is 0.0
3 mol / l and the ammonia concentration was 0.66 mol / l.

After the completion of the ripening, the pH was adjusted to 6.0 and desalting was carried out according to a conventional method. When the seed emulsion particles were observed with an electron microscope, the average grain size was 0.225 μm, and the ratio of two twin planes was 75% by number of all the grains.

Next, two solutions were prepared using the following seven types of solutions.
Monodisperse emulsion Em-4 having a plate shape having two parallel twin planes
Was prepared.

Solution A1 69.0 g of ossein gelatin 3268 ml of distilled water HO (CH ₂ CH ₂ O) _m [CH (CH ₃ ) CH ₂ O] ₁₉ . ₈ (CH ₂ CH ₂ O) _n H (m + n = 9.77) 10% by weight methanol solution 2.50 ml Seed emulsion (T-1) 0.141 mole equivalent Make up to 3500 ml with distilled water.

Solution B1 0.5N silver nitrate aqueous solution 959.0 ml Solution C1 Potassium bromide 52.88 g Ossein gelatin 35.55 g Make up to 959 ml with distilled water.

Solution D1 3.5N aqueous silver nitrate solution 4745.0 ml Solution E1 potassium bromide 1863.8 g ossein gelatin 179.0 g Make up to 4475 ml with distilled water Solution F1 3% by weight gelatin and silver iodide particles (average particle size) Emulsion (preparation method is shown below) * 2492.0 g * To 5000 ml of a 6.0% by weight gelatin solution containing 0.06 mol of potassium iodide, 7.06 mol of silver nitrate and 2,000 ml of an aqueous solution containing 7.06 mol of potassium iodide were added over 10 minutes. The temperature during the formation of the fine particles was controlled at 40 ° C. After the formation of the particles, the pH was adjusted to 6.0 using an aqueous solution of sodium carbonate. The finished weight was 12.53 kg.

Solution G1 1.75N Potassium bromide aqueous solution required amount Solution A1 was added to a reaction vessel, and while vigorously stirring, solutions B1 to F1 were added by a simultaneous mixing method according to the combination shown in Table 1, and seeds were added. The crystals were grown to prepare a core / shell type silver halide emulsion. However, solutions B1 and C
1. At 114.95 minutes after the start of the addition of F1, the pH was adjusted to 7.2 using 10% potassium hydroxide. As a result, reduction sensitization was performed inside the grains.

Here, (1) solution B1, solution C1 and solution F1 addition rates, (2) solution D1, solution E1 and solution F1 addition rates, and (3) solution D1 and solution E1 addition rates are as follows. Appropriate addition is made so that it changes as a function of time according to the critical growth rate of the silver halide grains, so that the generation of small grains other than the growing seed crystal and polydispersion due to Ostwald ripening do not occur. Speed was controlled.

The solution temperature in the reaction vessel was controlled at 75 ° C. and the pAg was controlled at 8.8 over the entire area of crystal growth. Solution p for control of pAg
1 was added.

Table 4 also shows the amount of silver added at that time with respect to the addition time of the reaction solution and the silver iodide content of the silver halide phase forming the surface.

After the grain growth, a desalting treatment was performed in accordance with the method described in JP-A-5-72658, followed by redispersion by adding an aqueous gelatin solution, and adjusting the pH to 5.80 and pAg at 40 ° C.
Was adjusted to 8.06.

The silver halide grains contained in the obtained silver halide emulsion had an average grain size of 1.42 μm (diameter in terms of projected area circle), 85% of grains having an aspect ratio of 3.0 or more, and a grain size distribution of 14.0. % Tabular silver halide grains.

[0216]

[Table 4]

<< Preparation of Emulsion Em-5 >> A monodisperse spherical seed emulsion (T-2) was prepared by the following method.

Solution A2 Ossein gelatin 80 g Potassium bromide 47.4 g 10% methanol solution of polyisopropylene-polyethyleneoxy-disuccinate sodium salt 20 ml Make up to 8000 ml with water.

Solution B2 1200 g of silver nitrate Make up to 1600 ml with water.

Solution C2 32.2 g ossein gelatin 840 g potassium bromide Make up to 1600 ml with water.

Solution D2 470 ml of aqueous ammonia solution B2 and solution C were added to solution A2 which was vigorously stirred at 40 ° C.
2 was added in 11 minutes by the double jet method to generate nuclei. During this time, pBr was kept at 1.60. Thereafter, the temperature was lowered to 30 ° C. over 12 minutes, and ripening was further performed for 18 minutes. Further, the solution D2 was added for 1 minute, and then ripening was performed for 5 minutes. The potassium bromide concentration during aging is 0.07 mol / l, and the ammonia concentration is 0.63
Mol / l.

After the completion of the ripening, the pH was adjusted to 6.0 and desalting was carried out according to a conventional method to obtain a spherical seed emulsion (T-2). When this seed emulsion was observed with an electron microscope, it was a spherical emulsion having two twin planes parallel to each other and an average grain size of 0.318 μm.

Next, Emulsion Em-5 was prepared using the following seven kinds of solutions.

Solution A3 Ossein gelatin 268.2 g Distilled water 4000 ml 10% methanol solution of polyisopropylene-polyethyleneoxy-disuccinate sodium salt 1.5 ml Seed emulsion (T-2) 0.286 mol equivalent 28% by weight Aqueous ammonia solution 528.0 ml 56% by weight aqueous acetic acid solution 795.0 ml 0.001 mol of iodine-containing methanol solution 50.0 ml Distilled water to 5930.0 ml.

Solution B3 3.5N aqueous ammonium nitrate solution (pH adjusted to 9.0 with ammonium nitrate) Solution C3 3.5N aqueous potassium bromide solution containing 4.0% by weight gelatin Solution D3 3% by weight gelatin And a fine grain emulsion comprising silver iodide grains (average grain size: 0.05 μm) (preparation method is shown below *) 0.844 mol * 6.0% by weight gelatin solution containing 0.06 mol of potassium iodide To 5000 ml, 2000 ml each of a solution containing 7.06 mol of silver nitrate and a water solution containing 7.06 mol of potassium iodide were added over 10 minutes. During the formation of the fine particles, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After particle size formation, the pH was adjusted to 6.0 using aqueous sodium carbonate solution.

Solution E3 Silver iodobromide grains containing 1 mol% of silver iodide (average grain diameter 0.04
μm) 2.20 mol of fine particle emulsion (however, the temperature during the formation of fine particles was controlled at 3.0 ° C.) Solution F3 1.75N aqueous potassium bromide solution G3 56% by weight aqueous acetic acid solution 70 ° C. in a reaction vessel After the solution B3, the solution C3 and the solution D3 were added to the kept solution A3 by the simultaneous mixing method over a period of 163 minutes, the solution E3 was independently added at a constant speed for 12 minutes, and the seed crystal was added. Grown to 0.0 μm.

Here, the addition rates of the solution B3 and the solution C3 were changed in a function manner with respect to time so as to match the critical growth rate, and the addition rate was increased due to the generation of small particles other than the growing seed crystal and Ostwald ripening. The addition was performed at an appropriate rate so as not to disperse. The solution D3, ie, the silver iodide fine grain emulsion was supplied by changing the rate ratio (molar ratio) with the aqueous ammonium nitrate solution with respect to the particle size as shown in Table 5.
A core / shell type silver halide emulsion having a multiple structure was prepared.

Also, by using the solution F3 and the solution G3, pAg and pH during the crystal growth were controlled as shown in Table 5. However, at the time of the addition of 82.6 minutes, the pH was adjusted to 8.4 using a 10% aqueous sodium hydroxide solution, whereby reduction sensitization was performed inside the grains. Note that pAg,
The pH was measured using a silver sulfide electrode and a glass electrode according to a conventional method. After the formation of the particles, a desalting treatment was performed according to the method described in JP-A-5-34851, and then gelatin was added and redispersed, and the pH was adjusted to 5.80 and the pAg to 8.06 at 40 ° C.

When the obtained emulsion particles were observed by an electron microscope, it was confirmed that the twin grains were composed of 100% twin grains and had an aspect ratio of 1.2 to 1.6 having two or more parallel twin planes and a twin ratio of 8
It consisted of slightly distorted octahedral twin monodisperse particles having a distribution of 5%, a distribution width of 10% and an average particle size of 1.0 μm.

[0230]

[Table 5]

<< Preparation of Emulsion Em-6 >> In the preparation of Emulsion Em-4, reduction sensitization was performed in the same manner except that potassium hydroxide added 114.95 minutes after the addition of solutions B1, C1 and F1 was not added. Emulsion Em-6 which was not applied was prepared.

<< Preparation of Emulsions A-1 and A-2 >> Emulsion Em
-4 was divided into two parts and dissolved by heating at 55 ° C., the pH was adjusted to 5.80, and then sensitizing dye (sd-1) 1.03 × 10 ⁻⁴ mol / mol per silver halide. l, (sd
-2) 7.1 × 10 ^-5 mol / l, (sd-3) 8.0
× 10 ⁻⁵ mol / l, one of which is a 1: 1 mixture of distilled purified methanol and 2,2,3,3-tetrafluoropropanol.
A 0.5 w / v% concentration dye solution (* I: solution added) of the mixed solvent and a 0.5 w / v% concentration dye dispersion solution (* II: solid dispersion addition) were added to the other. Twenty minutes after the addition of the sensitizing dye, 5 × 10 ^-6 mol of sodium thiosulfate pentahydrate was added per mol of silver halide, followed by 1.42 × 10 ^-6 mol of chloroauric acid and 3.15 ammonium thiocyanate. × 10 ^-4 mol was added and aged for an appropriate time.

At the end of aging, a stabilizer (ST-1) was added.
Emulsion A-1 (* I: solution added) and Emulsion A-2 (* II: solid dispersion added) were obtained by cooling and solidifying, respectively.

* I (solution addition): 1: 1 of D-methanol and 2,2,3,3-tetrafluoropropanol
A predetermined amount of a dye was added to the mixed solution so as to be adjusted to 0.5 w / v%.

* II (addition of solid dispersion): The dye was previously heated at 27 ° C.
, And a predetermined amount of a dispersion aqueous solution obtained by stirring at a high speed with a dissolver was adjusted to a concentration of 0.5 w / v%.

ST-1: 4-hydroxy-6-methyl-
1,3,3a, 7-tetrazaindene

[0237]

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<< Preparation of Emulsions B-1 to U-2 >> Except that growth emulsions and sensitizing dyes shown in Tables 6 and 7 were used,
Emulsion B was prepared in the same manner as in the preparation of emulsions A-1 and A-2.
-1 to N-2 were prepared. However, the amounts of the various additives (sodium thiosulfate, chloroauric acid) were determined in emulsions A-1 and A-1.
The optimum amount is applied to each emulsion in the range of 0.75 to 1.5 times the amount used when preparing No. -2, and the ripening time is also optimum (the best result is obtained in the evaluation of fog sensitivity). It was adjusted to become.

[0239]

[Table 6]

[0240]

[Table 7]

(Preparation of Coating Samples 201 to 242) Emulsions A-1 to U-2 obtained as described above were sequentially coated on a triacetyl cellulose film support which had been subjected to a subbing process according to the following coating formulation. It dried and the application samples 201-242 were produced.

Coating Formulation First Layer: Green-Sensitive Silver Halide Emulsion Layer Emulsion (described in Tables 6 and 7) 2.5 g / m ² magenta coupler (m-1) 0.01 mol / mol Ag Colored magenta coupler (cm -1) 0.005 mol / mol Ag DIR compound (d-1) 0.0002 mol / mol Ag High boiling solvent (TCP) 0.02 g / m ²

[0243]

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Second layer: Yellow filter layer Yellow colloidal silver 0.08 g / m ² Hardener (HI) 10 mg / g gelatin TCP: tricresyl phosphate H-1: 2,4-dichloro-6-hydroxy -S-triazine sodium <Sensitometry evaluation> The coating samples 201 to 242 obtained as described above were subjected to green light for 1/200 second,
After the step wedge exposure of 3.2 CMS, processing is performed in the following processing steps to obtain a characteristic curve, and the relative sensitivity (reciprocal of the exposure amount that gives a density of fog density + 0.10, expressed as a relative value with sample 101 being 100) I asked.

Processing step (38 ° C.) Color development (2 minutes 50 seconds) → Bleaching (6 minutes 30 seconds) → Washing (3 minutes 15 seconds) → Fixing (6 minutes 30 seconds) → Washing (3 minutes 15 seconds)
Sec) → stabilization (1 minute 30 seconds) → drying The composition of the processing solution used in each processing step is as follows.

Color developing solution 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.75 g Sodium sulfite anhydrous 4.25 g Hydroxylamine 1/2 sulfate 2.0 g Anhydrous potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Water is added to make 1 liter, and the pH is adjusted to 10.0.

Bleaching solution Iron ammonium diaminetetraacetic acid tetraacetate 100.0 g Diammonium ethylenediaminetetraacetic acid salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Water was added to make 1 liter, and the pH was adjusted to 6 using ammonia water. Adjust to .0.

Fixing solution 175.0 g of ammonium thiosulfate 8.5 g of anhydrous sodium sulfite 8.5 g 2.3 g of sodium metasulfite Water was added to make 1 liter, and the pH was adjusted to 6.0 with acetic acid.

Stabilizing solution Formalin (37% aqueous solution) 1.5 ml KONIDAX (manufactured by Konica Corporation) 7.5 ml Add water to make 1 liter.

<Evaluation of storage stability>
After forcibly deteriorating at 0% RH for one week, exposure and development were carried out in the same manner as in the sensitometric evaluation. The same day sample used in the sensitometric evaluation was used to measure the concentration fluctuation at the concentration position giving Dmin + 0.3, and the magnitude was determined by the difference | S
Immediate-S time | Therefore, the smaller the value, the better the storage stability.

S Immediately: Same day sample concentration S. Elapsed time: Concentration of forcibly deteriorated sample for one week The results are also shown in Tables 8 and 9.

[0252]

[Table 8]

[0253]

[Table 9]

As is clear from Tables 8 and 9, the samples of the present invention exhibit excellent effects in both sensitivity and storage stability. In comparison, none of the comparative samples shows an effect superior in both sensitivity and storage stability.

Further, it can be seen that there is a large difference in the storage stability of the comparative sample due to the difference in the method of adding the dye.

In Comparative Samples 205 and 206, the storage performance was good, but contamination having a maximum absorption near 550 nm remained. In particular, in a high aspect emulsion having good photographic characteristics, remarkable staining was observed and inferior.

[0257]

According to the present invention, it is possible to provide a silver halide photographic light-sensitive material having good stagnation of coating solution and storage stability of raw film over time and little residual color contamination, and a method for producing the same.

Claims (3)

[Claims] 1. A silver halide photographic material having at least one photosensitive silver halide emulsion layer on a support, wherein silver halide grains contained in at least one of the silver halide emulsion layers are represented by the following general formula: At least one compound selected from the compounds represented by the formula (1) and the following general formula (2)
Or a silver halide photographic material characterized by being spectrally sensitized by combining at least one compound selected from the compounds represented by (3). Embedded image [Wherein, R _{1 to} R ₄ each represent an aliphatic group, and V _{1 to} V ₄ each represent a hydrogen atom or a substituent. However, R ₂ and R ₄
At least one is an alkyl group having a sulfo group or a carboxy group, at least one group of V ₁ ~V ₄ is an aromatic group. M ₁ represents an ion necessary to neutralize an intramolecular charge, and m ₁ represents a number required to neutralize an intramolecular charge. [Chemical formula 2] [Wherein, R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each represent an aliphatic group, and at least one of R ₁₂ and R ₁₄ represents an alkyl group having a sulfo group or a carboxy group. V _11, V _12, V
₁₃ and V ₁₄ each represent a substituent other than a hydrogen atom or an aromatic group. M ₁₁ represents an ion necessary to neutralize the intramolecular charge, and m ₁₁ represents a number required to neutralize the intramolecular charge. [Chemical formula 3] [In the formula, Y represents an oxygen atom, a sulfur atom, or a selenium atom, and R ₂₁ and R ₂₂ each represent an alkyl group, provided that at least one of them represents an alkyl group having a sulfo group or a carboxy group. L ₂₁ , L ₂₂ and L ₂₃ each represent a methine group. Z ₂₁ and Z ₂₂ each represent a benzene ring or a naphthalene ring which may have a substituent, M ₂₁ represents an ion necessary for neutralizing an intramolecular charge, and m ₂₁ represents an intramolecular charge. Represents the number required to neutralize ] 2. The total projected area of the silver halide grains contained in at least one of the photosensitive silver halide emulsion layers is 7
2. The silver halide photographic light-sensitive material according to claim 1, wherein 0% or more is tabular silver halide grains having an average aspect ratio of 2 or more. 3. The general formula (1), (2) or (3)
A method for producing a silver halide photographic light-sensitive material, wherein the compound represented by the formula (1) is added as an aqueous solution or an aqueous dispersion substantially without using an organic solvent during or after the formation of silver halide grains.