JPH08146545A - Silver halide compound photosensitive material and its processing method - Google Patents

Abstract

PURPOSE: To provide a photosensitive material of high sensitivity and excellent pressure resistance, little coloring matter pollution, and excellent sharpness, by containing a specific spectral sensitization coloring matter in halide silver compound particles in emulsion. CONSTITUTION: Over 70% of the full projected area of halide silver compound particles in an emulsion layer are the particles of aspect ratio over 2 and mean iodine content under 1.0mol%, and containing at least one sort under 0.02g/m selected from spectral coloring matters shown by the formula I or II. In the formula I, R1 , R3 are methyl group or ethyl group, R2 , R4 are substituted or non-substituted alkyl group of carbon number 1-6, Z1 -Z4 are hydrogen atom, methyl group, or the like, and X1 shows ion necessary for neutralizing intramolecular electric charge. (n) shows 1 or 2. In the formula II, R5 , R6 are substituted or non-substituted alkyl group of carbon number 1-6, R7 is alkyl group of carbon number 1-4, V1 , V2 are benzene group capable of having respective substituents, and X2 shows ion necessary for neutralizing intramolecular electric charge. (m) shows 1 or 2, and (m)=1 in the case of forming intramolecular salt.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material having high sensitivity, less dye stain and excellent sharpness, and more particularly to an X-ray medical silver halide photographic light-sensitive material and a processing method thereof.

[0002]

2. Description of the Related Art In recent years, the demand for rapid processing of silver halide photographic light-sensitive materials has increased more and more as the processing amount has increased.
For example, in the field of medical X-ray films, the number of X-ray photographs taken is increasing due to the popularization of medical examinations and the increase in inspection items for improving diagnostic accuracy. Further, it is necessary to inform the examinee of the diagnosis result sooner, and it is strongly desired that the development process after photographing is super-rapid.

However, for rapid processing, it is necessary to shorten the processing time of each processing step such as developing, fixing, washing with water and drying. However, shortening the processing time causes various problems. For example, if the developing time is simply shortened, the image density is lowered, that is, the sensitivity is lowered and the gradation is deteriorated, when a conventional photosensitive material is used. Further, if the fixing time is shortened, the fixing of silver halide becomes incomplete, which causes deterioration of image quality. Further, when the time of each processing step is shortened, the elution of the sensitizing dye in each processing becomes insufficient, and as a result, the residual dye stains the residual image, resulting in deterioration of the image quality.

Therefore, in order to solve such a problem, the developing speed and the fixing speed are increased or the dye amount is reduced.
In addition, it is necessary to accelerate desorption and decolorization of the dye.

On the other hand, in recent years, reduction and detoxification of industrial waste have been promoted from the viewpoint of environmental protection, and in the photographic industry, reduction of the amount of processing waste liquid has been demanded.

In order to reduce the development processing waste liquid, a method of reducing the degree of fatigue of the processing liquid and reducing the amount of replenisher can be mentioned. However, similar to the rapid processing described above, photographic performance and residual color It causes problems.

As an improved technique corresponding to these, for example, EP
No. 0-506584, JP-A-5-88293, JP-A-5-93975 and the like disclose techniques using benzimidazolocarbocyanines having good decolorizing performance as spectral sensitizing dyes. Further, in JP-A-5-61148, oxacarbocyanines and benzimidazolocarbocyanines are used in combination at a specific ratio as a spectral sensitizing dye in a silver halide emulsion having an iodine content of 1 mol% or less, and selenium. Techniques for chemical sensitization with compounds and / or tellurium compounds are disclosed.

However, although these disclosed techniques improve the residual color property and the rapid developing property, they are still insufficient for satisfying the required level for other performances. In particular, it has a drawback that the sensitivity is not sufficient, and that the sensitivity is greatly reduced when the light-sensitive material is stored under high humidity and high temperature.

By the way, in the X-ray photographic light-sensitive material, while crossover light is cut to achieve high sharpness,
In addition, various researches and developments have been carried out for increasing the sensitivity of silver halide emulsions in order to maintain the high sensitivity. For example, many techniques for achieving high sensitivity and high image quality by using tabular silver halide grains have been disclosed, and as examples thereof, JP-A Nos. 58-111935, 58-111936 and 58-111936 have been disclosed. 111937, 5
No. 8-113927 and No. 59-99433 are disclosed. Further, JP-A-63-92942 proposes a technique for providing a core having a high silver iodide content inside a tabular silver halide grain.
Further, Japanese Patent Application Laid-Open No. 63-151618 discloses a technique using hexagonal tabular silver halide grains and shows the effect of increasing the sensitivity.

In addition to these, for example, JP-A-63-106746
JP-A No. 1-183644 and JP-A No. 1-279237 disclose techniques relating to the composition distribution of tabular silver halide grains.

On the other hand, as a technique for improving the drawbacks of tabular silver halide grains, for example, in Japanese Patent Laid-Open No. 3-124439, tabular grains having an aspect ratio of 3 or more and having (111) faces and (100) faces are projected areas. A technique for improving the storability at high humidity in an emulsion that accounts for 50% or more of the above is disclosed.

These tabular silver halide grains are hexahedral,
Compared with so-called normal crystal silver halide grains such as octahedron, the surface area is large in the same volume, so it is possible to increase the adsorption amount of the sensitizing dye on the grain surface, resulting in higher sensitivity and scattering. It is considered that there is an advantage that the sharpness can be improved by reducing the light.

However, in practice, even if the amount of the sensitizing dye is increased in accordance with the surface area of the tabular grains, the high sensitivity cannot be obtained as expected, and as a drawback, the residual sensitization is accompanied by the rapid development process. Contamination of residual color and deterioration of image quality due to pigments have become apparent as problems.

In order to enable rapid processing, it is very important to reduce the thickness of the photosensitive material. For example, many proposals have been made in order to obtain a low silver content and a low binder content to improve the developing speed, fixing / washing efficiency, and drying speed. As examples of these, JP-A 1-158434 and JP-A
1-158436, JP-A Nos. 2-068537, 5-61148, etc. are disclosed. However, the reduction of the binder amount deteriorates the pressure resistance of the light-sensitive material, which easily causes pressure fog and pressure desensitization. Further, since lowering the silver content of the emulsion significantly deteriorates photographic performance, it is necessary to further increase the sensitivity and the covering power of the emulsion.

When various water-insoluble photographic additives are added to a silver halide emulsion, a method of dissolving the additives in an organic solvent such as methanol and adding the solution to the silver halide emulsion is generally widely used. It is being appreciated.

On the other hand, recently, instead of the conventional method, an additive is dispersed and prepared as an aqueous solution in the presence of a wetting agent or a dispersant without using an organic solvent, and an aqueous solution of the obtained additive is prepared. Attempts have been made to add the dispersion to a silver halide emulsion. That is, in JP-A-52-110012, a spectral sensitizing dye is ground in an aqueous phase in the presence of a dispersant (surfactant) which gives a constant surface tension, and water is removed from the resulting aqueous dispersion. A method is disclosed in which, after removal and drying, the silver halide emulsion is added as it is or dispersed in water or an aqueous gelatin solution and then added to the silver halide emulsion.

Further, in JP-A-53-102733, a homogeneous mixture (paste mixture) comprising a fine grain additive for photography, a dispersant such as sorbitol, and a protective colloid such as gelatin is prepared, and the mixture is made into noodles and heated. Wind-dried to give granules. The resulting granules are added to a photographic aqueous colloid coating composition.

Further, in US Pat. No. 4,006,025, a spectral sensitizing dye is mixed with water to form a slurry, and the temperature is raised to 40 to 50 ° C. in the presence of a surfactant to homogenize or mill to spectrally sensitize. A method is described in which the agent is uniformly dispersed in water and the resulting dispersion is added to a silver halide emulsion.

However, all of these addition methods are methods of adding a photographic additive such as a spectral sensitizing dye in an aqueous system without using an organic solvent, but have the following problems in practical use. It was That is, since the aqueous dispersion is pulverized by freeze-drying or the like, the time required for adsorption of additives such as spectral sensitizing dyes to silver halide grains becomes long, and therefore desired photographic sensitivity cannot be obtained within a short time. Furthermore, when such a silver halide emulsion is coated, coating failure due to precipitates or the like is likely to occur. In addition, since a wetting agent or a dispersant is used to disperse the additives, the emulsion present in the silver halide emulsion may be destroyed, coating failure may occur during high-speed coating of the emulsion, and further the coating of the emulsion layer may occur. There were many problems in terms of product quality such as deterioration.

[0020]

SUMMARY OF THE INVENTION Accordingly, the first object of the present invention is to provide a silver halide photographic light-sensitive material having high sensitivity, excellent pressure resistance, less dye contamination and excellent sharpness. .

A second object of the present invention is to provide an X-ray medical silver halide photographic light-sensitive material having the above-mentioned properties and a processing method thereof.

[0022]

The above problems have been solved by the present invention described below. (1) In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, 70% or more of the total projected area of silver halide grains in the emulsion layer has an aspect ratio of 2 or more. And a silver halide grain having an average iodine content of 1.0 mol% or less and having the following general formula [I] or [II]
At least one selected from the spectral sensitizing dyes represented by
Silver halide photographic light-sensitive material characterized by containing 0.02 g / m ² or less

[0023]

Embedded image

In the formula, R ₁ and R ₃ represent a methyl group or an ethyl group, and at least one of R ₁ and R ₃ represents a methyl group. R
₂ and R ₄ represent a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. However, both R ₂ and R ₄ are not methyl groups at the same time.

Z ₁ , Z ₂ , Z ₃ and Z ₄ represent a hydrogen atom, a methyl group, a methylthio group, a trifluoromethyl group and a sulfamoyl group, and Z ₁ , Z ₂ , Z ₃ and Z ₄ simultaneously represent a hydrogen atom. It never happens. X ₁ represents an ion necessary for neutralizing the charge in the molecule, and n is 1 or 2 and n is 1 when forming an intramolecular salt.

[0026]

[Chemical 6]

In the formula, R ₅ and R ₆ represent a substituted or unsubstituted alkyl group or alkenyl group having 1 to 6 carbon atoms, and R 5
_At least one of ₅ and R ₆ represents a sulfoalkyl group or a carboxyalkyl group. R ₇ represents an alkyl group having 1 to 4 carbon atoms. V ₁ and V ₂ each represent a non-metal atom group necessary for completing a benzene ring or a naphthalene ring which may have a substituent. X ₂ represents an ion necessary for neutralizing the charge in the molecule, and m is 1 or 2 and when forming an intramolecular salt, m is 1.

(2) At least one selected from the spectral sensitizing dyes represented by the above-mentioned general formula [I] or [II] is dispersed in an aqueous system in which an organic solvent or a surfactant does not exist and is substantially dispersed. to be added to the emulsion as a solid particle dispersion of the sparingly soluble in water and contains a silver halide solvent is 0.05 g / m ² or more, and the emulsion layer of silver per support one side at 2.0 g / m ^2, The total amount of gelatin in the hydrophilic layer including the protective layer is 1.5g to 3.5g.
The silver halide photographic light-sensitive material as described in the item (1), wherein the silver halide photographic light-sensitive material is coated in the range of / m ² .

(3) The silver halide photographic light-sensitive material as described in the item (1) or (2), which contains at least one compound represented by the following general formula [III].

[0030]

[Chemical 7]

In the formula, R ₈ is —0H group, —SO ₃ M ¹ group, —COOM ²
It represents an aliphatic group or an aromatic group in which at least one of the groups is substituted, and M ¹ , M ² and M ³ represent a hydrogen atom or an alkali metal atom.

(4) Item (1), which contains at least one compound represented by the following general formula (IV):
A silver halide photographic light-sensitive material according to the item (2).

[0033]

Embedded image

In the formula, Y represents a hydrogen atom, a lower alkyl group, a halogen atom or a SO ₃ M group, M represents a hydrogen atom, an alkali metal atom or an ammonium group, and n represents 0 or 1 to 1
Represents 2.

(5) The silver halide photographic light-sensitive material is a medical silver halide photographic light-sensitive material
The silver halide photographic light-sensitive material according to any one of items (1) to (4).

(6) The method for processing a silver halide photographic light-sensitive material according to item (5), wherein the total processing time is 30 seconds or less.

(7) The method of processing a silver halide photographic light-sensitive material according to item (6), wherein the iodide content in the fixing solution is 0.2 g / liter or less.

(8) The replenishing amount of the fixing solution is 1 m ^{2 of the} light-sensitive material.
The method for processing a silver halide photographic light-sensitive material according to the item (7), wherein the fixing time is 0.2 liter or less and the fixing time is 7 seconds or less.

Was achieved by Hereinafter, the present invention will be described in detail.

The above-mentioned spectral sensitizing dye in the present invention refers to one that contributes to the sensitization of silver halide grains, and does not include an organic dye that functions as a filter.

In the above formula [I], R ₁ and R ₃ are methyl or ethyl, and at least one of R ₁ and R ₃ is methyl. R ₂ and R ₄ are defined as a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. R ₂ and R ₄
Examples of are lower alkyl groups such as methyl, ethyl, propyl, butyl, pentyl and hexyl. Examples of substituents are one or more sulfo, sulfato, carboxyl, fluoro, amides, esters,
Examples include cyano, substituted or unsubstituted aryl groups and other substituents commonly used in spectral sensitizing dyes. Examples of R ₂ and R ₄ as the substituted alkyl group include sulfopropyl, sulfobutyl, trifluoroethyl, allyl, 2-butynyl, N, N-dimethylcarbamoylmethyl, methylsulfonylcarbamoylmethyl, cyanomethyl, cyanoethyl, ethoxycarbonylmethyl and the like. Is mentioned.

Z _{1 to} Z ₄ are each methyl, methylthio, fluoro-substituted methylthio, or hydrogen. Fluoromethyl, difluoromethyl, trifluoromethyl, fluoromethylthio, difluoromethyltyl and trifluoromethylthio.

Depending on the substituents R ₂ and R ₄ , the counterion X ₁ may be necessary to neutralize the charge on the dye molecule. For example, if the dye molecule is substituted with two anionic substituents (eg sulfo groups) then X ₁ will be a cation. If the dye molecule is replaced with only one anionic substituent, the counterion X ₁ will be absent and the dye molecule will become an anionic substituent. Such counterions are well known in the art and examples include cations such as sodium,
Potassium, triethylammonium and the like, and examples of the anions include chloride, bromide, iodide, p-toluenesulfonate, methanesulfonate, methylsulfate, ethylsulfate, perchlorate and fluoroborate.

Next, the above-mentioned general formula [I] used in the present invention is used.
Specific examples of the spectral sensitizing dye represented by are shown below, but the present invention is not limited thereto.

[0045]

[Chemical 9]

As the spectral sensitizing dye represented by the above general formula [I] of the present invention, in addition to the above-mentioned specific examples, for example, Table 1 of Japanese Patent Application No. 5-261264 filed by the same applicant as the present invention. Also, the compounds described in Table 2 or the compounds described in Table 1 of JP-A-5-88293 can be similarly used.

Next, in the spectral sensitizing dye represented by the general formula [II] according to the present invention, R ₅ and R ₆ are each a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group,
It represents a substituted or unsubstituted aryl group, and at least one of R ₅ and R ₆ is a sulfoalkyl group or a carboxyalkyl group. R ₇ represents a hydrogen atom, an alkyl group or an aryl group. V ₁ and V ₂ each represent a nonmetallic atom group necessary for completing a benzene ring or a naphtho ring which may have a substituent, and X ₂ represents an ion necessary for neutralizing the intramolecular charge. m represents 1 or 2, and m is 1 when forming an intramolecular salt.

Specific examples of the substituted or unsubstituted alkyl group represented by R ₅ and R ₆ include lower alkyl groups such as methyl, ethyl, propyl and butyl.

Examples of the substituted alkyl group substituted for R ₅ and R ₆ include 2-hydroxyethyl and 4-hydroxybutyl groups as hydroxyalkyl groups, 2-acetoxyethyl and 3-acetoxybutyl groups as acetoxyalkyl groups, and the like.
2-carboxyethyl, 3-carboxypropyl, 2- (2-carboxyethoxy) ethyl group etc. as carboxyalkyl group, 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2-hydroxy as sulfoalkyl group Examples thereof include a 3-sulfopropyl group. Examples of the alkenyl group represented by R ₅ and R ₆ include allyl, butynyl, octenyl and oleyl groups. Further, examples of the aryl group represented by R ₅ and R ₆ include phenyl,
A carboxyphenyl group etc. are mentioned.

However, at least one of R ₅ and R ₆ is a sulfoalkyl group or a carboxyalkyl group.

The ion represented by X ₂ in the general formula [II] is, for example, chlorine ion, bromine ion, iodine ion, thiocyanate ion, sulfate ion, perchlorate ion, p-toluenesulfonate ion. , Ethylsulfate ion, sodium ion, potassium ion, magnesium ion, triethylammonium ion and the like.

R ₇ represents a hydrogen atom, a lower alkyl group or an aryl group, and examples of the lower alkyl group include methyl, ethyl, propyl and butyl groups. Examples of the aryl group include a phenyl group. m represents 1 or 2, and when forming an intramolecular salt, m is 1.

Next, the above general formula [II] used in the present invention
Specific examples of the spectral sensitizing dye represented by are shown below, but the present invention is not limited thereto.

[0054]

[Chemical 10]

[0055]

[Chemical 11]

The above-mentioned spectral sensitizing dyes according to the present invention include, for example, British Patent Nos. 521,165 and 745,546, and Belgian Patent 615,
549, Soviet patents 412,218, 432,166, etc., each specification, Japanese Patent Publication No. 38-7828, 42-27165, 42-27166
No. 43, No. 43823, No. 43-14497, No. 44-2530, No. 45-
No. 27676, No. 45-32740, etc., Harmer's cyanine soybean-related compounds (Jhon Wiley &
Sons, New York, 1964) and the like.

The combined use technique of at least two kinds of spectral sensitizing dyes according to the present invention is useful in a light-sensitive material which requires sensitivity to green light. In particular, it is remarkably effective in application to an X-ray recording material that uses a phosphor that emits green light in order to enhance recording sensitivity to X-rays.
It is particularly effective in a line medical light-sensitive material.

When applied to an X-ray medical light-sensitive material using a fluorescent substance which emits green light, the spectral sensitizing dye represented by the general formula [I] and the spectral sensitizing dye represented by the general formula [II] are used. It is preferable to combine them so that they are adsorbed on silver halide emulsion grains and a J-band is formed in the same wavelength range as the green light from the phosphor when the reflection spectrum thereof is measured. That is, it is preferable to select and combine the spectral sensitizing dyes so that the J-band having the maximum absorption is usually formed in the 520 nm to 560 nm region.

The addition amount of the spectral sensitizing dye of the general formula [I] or [II] in the present invention varies depending on the kind of the dye and the structure, composition, ripening condition, purpose and use of the silver halide. The coverage of the monolayer on the surface of the silver halide grain is
It may be 40% or more and 90% or less, and particularly preferably 50% to 80%. 0.02 per 1 m ^{2 on} both sides or one side of photosensitive material support
It may be g to 0.002 g, preferably 0.015 to 0.01 g.

In the present invention, the monolayer coverage is 50.
Saturated adsorption amount when the adsorption isotherm was created at ℃
The amount corresponding to 100% will be decided relatively.

The suitable amount per mol of silver halide varies depending on the total surface area of silver halide grains in the emulsion, but 60
Less than 0 mg is preferred. Further, it is preferably 450 mg or less.

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

Surfactants have been conventionally used as dispersants for spectral sensitizing dyes. The surfactant includes anionic, cationic, nonionic and amphoteric surfactants, and any of these surfactants can be used in the present invention.

However, in the present invention, the effect is increased by adding the spectral sensitizing dye as a dispersion in the form of solid fine particles, as compared with the case of adding it as a solution of an organic solvent. In particular, at least one of spectral sensitizing dyes is added in the state of a substantially water-insoluble solid fine particle dispersion dispersed in an aqueous system in which substantially no organic solvent and / or surfactant is present. Is preferred.

A technique for mechanically dispersing an organic dye in an aqueous medium is disclosed in, for example, Japanese Patent Laid-Open No. 3-288842. However, this method is for making the organic dye resistant to diffusion in the photographic light-sensitive material and is merely a dispersion addition method.

On the other hand, the present invention was made to uniformly and effectively adsorb the photographic photosensitizing dye onto the surface of the silver halide grain, and the above-mentioned technique for merely adding in a dispersed manner is , The purpose and effect are different.

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

The solubility of the spectral sensitizing dye in the present invention in water is 2 × 10 ⁻⁴ to 4 × 10 ⁻² mol / liter,
It is more preferably 1 × 10 ⁻³ to 4 × 10 ⁻² mol / liter.

When the solubility is lower than this range, the dispersion particle size becomes very large and the dispersion becomes non-uniform, so that a precipitate of the dispersion is formed after the dispersion is completed, or when the dispersion is added to the silver halide emulsion. In some cases, this may interfere with the adsorption process of the dye onto silver halide.

On the other hand, when the solubility is higher than the above range, the viscosity of the dispersion is increased more than necessary, air bubbles are entrapped and the dispersion is hindered, and further higher solubility makes dispersion impossible. It became clear from the study of the present inventors.

In the present invention, the solubility of the spectral sensitizing dye in water was measured by the following method.
That is, put 30 ml of ion-exchanged water in a 50 ml Erlenmeyer flask,
To this, add an amount of dye that does not completely dissolve it visually and in a constant temperature bath at 27 ° C.
The temperature was maintained at 10 ° C. and stirred for 10 minutes with a magnetic stirrer. The suspension was filtered with filter paper No. 2 (manufactured by Toyo [stock]), the filtrate was filtered by a disposable filter (manufactured by Tosoh [stock]), the filtrate was diluted appropriately, and a spectrophotometer U-3410 (Hitachi) was used. (Manufactured by [stock]) was used to measure absorbance. Next, based on this measurement result, determine the dissolved concentration according to Lambert-Beer's law,
Further solubility was determined.

D = εlc Here, D is the absorbance, ε is the spectral extinction coefficient, l is the cell length for measuring absorbance, and c is the concentration (mol / liter).

The spectral sensitizing dye according to the present invention can be added during the chemical ripening step, particularly preferably at the start of the chemical ripening step, and the desalting can be performed from the nucleation step of the silver halide emulsion according to the present invention. By adding by the end of the process, a high-sensitivity silver halide emulsion having excellent spectral sensitization efficiency can be obtained.

Further, after the completion of the desalting step, through the chemical aging step and immediately before the coating step, the same or different kind of dye as the dye added to the above step (from the nucleation step to the end of the desalting step) The spectral sensitizing dye according to the invention may be additionally added.

The spectral sensitizing dye of the present invention may be used in combination with other spectral sensitizing dyes. The dyes used include known cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holobola 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 commonly used nuclei. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, etc., a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei, that is, Indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, 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-5 as a nucleus having a ketomethine structure.
-One nucleus, thiohydantoin nucleus, 2-thiooxazolidine-
A 5- to 6-membered heterocyclic nucleus such as 2,4-dione nucleus, thiazoline-2,4-dione nucleus, rhodanine nucleus, and thiobarbituric acid nucleus can be applied.

These patents are, for example, German Patent 929,08.
0, U.S. Patents 2,231,658, 2,493,748, 2,503,7
No. 76, No. 2,519,001, No. 2,912,329, No. 3,655,394
No. 3,65,959, 3,672,897, 3,649,217,
It is described in British Patent No. 1,242,588 and Japanese Patent Publication No. 44-14030.

Along with these spectral sensitizing dyes, a dye having no spectral sensitizing property or a substance which does not substantially absorb visible light and exhibits a supersensitizing effect is added to the emulsion layer. May be.

Next, in the nitrogen-containing heterocyclic compound represented by the general formula [III] according to the present invention, the aliphatic group represented by R ₈ is specifically a straight chain having 1 to 20 carbon atoms. Or, it is a branched alkyl group such as methyl, propyl, hexyl, dodecyl or isopropyl group. Specific examples of the aromatic group include aryl groups having 6 to 20 carbon atoms, such as phenyl and naphthyl groups. Further, the heterocyclic group is specifically a 5- or 6-membered or 7-membered heterocyclic ring containing one or more nitrogen, oxygen or sulfur atoms, and further forms a condensed ring at an appropriate position. Such as pyridine ring, quinoline ring, pyrimidine ring, isoquinoline ring and the like. Also,
The above linear or branched alkyl group, cycloalkyl group, aryl group and heterocyclic group are -COOM ² or -SO ₃ M ¹
In addition to, it may have other substituents. Specific examples of the substituent include a halogen atom, an alkyl group, an aryl group,
Alkoxy group, aryloxy group, sulfonyl group, sulfonamide group, sulfamoyl group, carbamoyl group, amide group, ureido group, alkoxycarbonylamino group,
Examples thereof include an aryloxycarbonylamino group, an aryloxycarbonyl group, cyano, hydroxy, carboxy, sulfo, nitro, an amino group, an alkylsulfinyl group, an arylsulfinyl group, and an alkylthio group. These substituents may be substituted by two or more. May be. Further, the substituents may be the same or different. M ¹ , M ² , M ³
Is a hydrogen atom or an alkali metal atom such as Na or K.

[0080]

[Chemical 12]

[0081]

[Chemical 13]

Specific examples of the polyhydroxybenzenes having a water-soluble group represented by the general formula (IV) according to the present invention include the following compounds.

[0083]

Embedded image

When the compounds of the above general formulas [III] and [IV] are used in the present invention, they are dissolved in water or a hydrophilic organic solvent such as methanol or ethanol and added to the emulsion. The addition amount is preferably 50 to 1350 mol / mol Ag, and more preferably 100 to 600 mol / mol Ag.

The time of addition may be any time during the ripening of the spectral sensitizing dyes of the general formulas [I] and [II], but it is preferable before the addition of the chemical sensitizer. Then, the compounds of the general formulas [III] and [IV] are added at the end of the chemical ripening to prepare a silver halide photographic light-sensitive material.

The silver halide photographic light-sensitive material according to the present invention may be chemically sensitized by a known method. The selenium sensitizers used for chemical sensitization include a wide variety of selenium compounds. For example, in this regard, U.S. Pat.
2592, 1623499, JP-A-60-150046, JP-A-4-25
832, 4-109240, 4-147250, etc. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, etc.), selenoureas (eg, N, N-dimethylselenourea, N, N, N′-triethylselenoate). Urea, N, N,
N'-trimethyl-N'-heptafluoroselenourea, N, N,
N'-trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N'-trimethyl-N'-4-nitrophenylcarbonylselenourea, etc.), selenoketones (eg, selenoacetone, selenoacetophenone, etc.), Selenoamides (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-3-selenobutylate, etc.), selenophosphates (eg, , Tri-p-triselenophosphate, etc.) and selenides (diethyl selenide, diethyl diselenide, etc.). Particularly preferred selenium sensitizers are selenoureas, selenoamides, and selenium ketones.

Specific examples of the technique of using these selenium sensitizers are, for example, US Pat. Nos. 1,574,944, 1,602,592 and 1,
623,499, 3,297,446, 3,297,447, 3,320,0
No. 69, No. 3,408,196, No. 3,408,197, No. 3,442,653
, 3,420,670, 3,591,385, French Patent 2,69
No. 3,038, No. 2,093,209, Japanese Patent Publication No. 52-34491, No. 52-344
No. 92, No. 53-295, No. 57-22090, JP-A-59-180536
No. 59-185330, 59-181337, 59-187338,
59-192241, 60-150046, 60-151637, 61-
246738, JP 3-4221 A, 3-24537 A, 3-111838 A
No. 3, No. 3-116132, No. 3-148648, No. 3-237450, No. 4-
No. 16838, No. 4-25832, No. 4-32831, No. 4-96059, No.
4-109240, 4-140738, 4-140739, 4-147250
No. 4, No. 4-149437, No. 4-184331, No. 4-190225, No. 4-
191729, 4-195035, British Patent 255846, 861984
Issue, HE Spencer et al., Journal of Photographic Scien
Ce magazine, Vol. 31, p. 158-169 (1983).

The amount of the selenium sensitizer used varies depending on the selenium compound used, silver halide grains, chemical ripening conditions, etc., but generally it is about 10 ^-8 to 10 ^-4 mol per mol of silver halide. The addition method is, depending on the properties of the selenium compound used, a method of adding it by dissolving it in water or an organic solvent such as methanol, ethanol, ethyl acetate or a mixed solvent, or by adding it in advance with a Latin solution. As the method, any of the methods disclosed in JP-A-4-140739, that is, the method of adding in the form of an emulsion dispersion of a mixed solution with a polymer soluble in an organic solvent may be used.

The temperature of the chemical ripening using the selenium sensitizer is
The range of 40 to 90 ° C is preferable. More preferably 45 ° C or higher
It is below 80 ℃. The pH is preferably in the range of 4 to 9 and the pAg is preferably in the range of 6 to 9.5.

Tellurium sensitization may be carried out in the chemical sensitization of the present invention. Regarding the tellurium sensitization method, for example, US Pat.
3,499, 3,320,069, 3,772,031, 3,531,289
No. 3,655,394, British Patent 235,211 and 1,121,496
No. 1,295,462, No. 1,396,696, Canadian Patent 800,9
No. 58, JP-A-4-204640, and JP-A-4-333043. Examples of useful tellurium sensitizers include telluroureas (eg, N, N-dimethyl tellurourea, tetramethyl tellurourea, N-carboxyethyl-N, N'-dimethyl tellurourea, N, N'-dimethyl-N ′ Phenyltellureas), phosphine tellurides (eg tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride), telluroamides (eg telluroacetamide) ,
N, N-dimethyl tellurobenzamide), telluroketones,
Examples thereof include telluroesters and isotellurocyanates. The technique for using the tellurium sensitizer is similar to that for the selenium sensitizer.

The silver halide emulsion layer of the present invention may be combined with reduction sensitization. The reduction sensitization is preferably performed during the growth of silver halide grains. Not only the method of performing reduction sensitization while the silver halide grains are growing, but also the method of performing reduction sensitization while the growth of silver halide grains is interrupted, and then the reduction sensitization is performed. A method of growing the formed silver halide grains.

In the present invention, the sensitization can be performed with a selenium compound or a tellurium compound, but further with a noble metal salt such as a sulfur compound or a gold salt. Further, reduction sensitization can be performed, and these methods can be combined to perform sensitization.

Examples of the sulfur sensitizer applicable in the present invention include US Pat. Nos. 1,574,944, 2,410,689 and 2,410,689.
278,947, 2,728,668, 3,501,313, 3,656,9
No. 55, West German Application Publication (OLS) 1,422,869, JP-A-56-249
The sulfur sensitizers described in No. 37, No. 55-45016, etc. can be used. Specific examples thereof include thiourea derivatives such as 1,3-diphenylthiourea, triethylthiourea, and 1-ethyl-3- (2-thiazolyl) -thiourea, rhodanine derivatives, dithiacarbamic acids, polysulfide organic compounds, sulfur simple substance. And the like are preferred examples. still,
As the simple substance of sulfur, α-sulfur belonging to the orthorhombic system is preferable.

As the gold sensitizer, chloroauric acid, gold thiosulfate,
In addition to gold thiocyanate, thioureas, rhodanines,
Other examples include gold complexes of various compounds.

The amount of sulfur sensitizer and gold sensitizer used is not uniform depending on the type of silver halide emulsion, the type of compound used, the ripening conditions, etc., but is usually 1 × 10 6 per mol of silver halide. It is preferably ⁻⁴ mol to 1 × 10 ⁻⁹ mol. More preferably, it is 1 × 10 ⁻⁵ mol to 1 × 10 ⁻⁸ mol.

The sulfur sensitizer and the gold sensitizer may be added by dissolving them in water or alcohols, other inorganic or organic solvents, and adding them in the form of a solution, such as a solvent insoluble in water or gelatin. It may be added in the form of a dispersion obtained by emulsification and dispersion using a medium.

In the present invention, both sulfur sensitization and gold sensitization may be performed simultaneously, or may be performed separately and stepwise. In the latter case, preferable results may be obtained by performing gold sensitization after or during the appropriate sulfur sensitization.

Reduction sensitization is carried out by adding a reducing agent and / or a water-soluble silver salt to the silver halide emulsion, as is carried out during the growth of silver halide grains of the silver halide emulsion. Preferred examples of reducing agents include thiourea dioxide and ascorbic acid and their derivatives. Other preferred reducing agents include hydrazine, polyamines such as diethylenetriamine, dimethylamineboranes, sulfites and the like.

The addition amount of the reducing agent depends on the type of reduction sensitizer, the grain size of silver halide grains, the composition and crystal habit, the temperature of the reaction system, p
Although it is preferable to change it depending on environmental conditions such as H and pAg, for example, in the case of thiourea dioxide, a preferable result is obtained by using about 0.01 to 2 mg per mol of silver halide as a rough guide. In the case of ascorbic acid, it is preferably in the range of about 50 mg to 2 g per mol of silver halide.

As the conditions for reduction sensitization, the temperature is about 40 to 70.
C, time about 10-200 minutes, pH about 5-11, pAg about 1-1
A range of 0 is preferred (where the pAg value is the reciprocal of the Ag ⁺ ion concentration).

Silver nitrate is preferable as the water-soluble silver salt. 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 1-6, preferably 2-4. The conditions such as temperature, pH and time are preferably within the above-mentioned reduction sensitization condition range. As a stabilizer of a silver halide photographic emulsion containing reduction-sensitized silver halide grains, a general stabilizer described below can be used, but it is disclosed in, for example, JP-A-57-82831. Antioxidants, Paper by VS Gahler [Zeitshrift fur wi
ssenschaftliche Photographie Bd. 63, 133 (1969)] and Japanese Patent Laid-Open No. 54-1019 are used in combination with thiosulfonic acids to often obtain good results. The addition of these compounds may be carried out at any stage of the emulsion production process from crystal growth to the preparation process immediately before coating.

In the present invention, as a chemical sensitization aid, thiocyanates such as potassium thiocyanate and ammonium thiocyanate, thioethers, silver halide solvents such as tetramethylthiourea and its derivatives having a hydrophilic group are chemically sensitized. Can be added at any time. The addition amount is preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻¹ mol per mol of silver halide. More preferably, it is 1 × 10 ⁻⁴ to 1 × 10 ⁻² mol.

In the present invention, it is preferable that a silver halide emulsion is constituted by adding fine grain silver iodide in the process from chemical ripening to coating. Here, "in the process from chemical ripening to coating" means that fine grain silver iodide is added during the process of chemical ripening and thereafter in the process of coating a light-sensitive material. Further, the fine grain silver iodide which can be used in the present invention will be described.

For silver iodide, generally cubic γ-AgI is used.
And hexagonal β-AgI are known, and the fine grain silver iodide used in the present invention may have any crystal structure or a mixture thereof. The fine grain silver iodide may be added in any step from the chemical ripening step to immediately before coating, but it is preferably added in the chemical ripening step. The term "chemical ripening step" as used herein means a period from the time when the physical ripening and desalting operations of the emulsion of the present invention are completed to the time when an operation for adding a chemical sensitizer and then stopping the chemical ripening is performed. Point to. Further, the addition of fine grain silver iodide may be carried out in several times with a time interval, or another chemically ripened emulsion may be added after the addition of fine grain silver iodide. The temperature of the emulsion of the present invention when the fine grain silver iodide is added is preferably in the range of 30 to 80 ° C, more preferably 40 to 65 ° C. Further, it is preferable to carry out under the condition that part or all of the fine grain silver iodide to be added disappears immediately before coating, and more preferable condition is that 20% or more of the fine grain silver halide added is coated. It has disappeared just before. The amount of disappearance is quantified by centrifuging the emulsion or coating solution after addition of fine grain silver iodide under appropriate conditions and then measuring the absorption spectrum of the supernatant to determine the absorption of fine grain silver iodide solution of known concentration. This can be done by comparing with the spectrum. In the present invention, the addition amount of fine grain silver iodide is preferably such that the outermost surface iodine content is 8.0 mol% or less, more preferably 5.0 mol% or less.

The silver halide grains of the emulsion used in the present invention have a silver halide composition such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide and silver chloride. Although silver halide grains can be optionally used, silver bromide, silver iodobromide and silver chloroiodobromide are particularly preferable.

The silver halide grains used in the present invention may have any shape. For example, the shape may be a cube, an octahedron, a tetradecahedron, a sphere, a plate, a potato, or the like. Particularly preferred are tabular grains.

Hereinafter, the aspect ratio 2 used in the present invention is 2
The tabular grains having an average iodine content of 1.0 mol% or less will be described above.

The tabular silver halide grains used in the present invention are crystallographically classified as twin crystals. Twins are silver halide crystals that have one or more twin planes in one grain.The morphology of twins is classified by Klein and Moiser in the article Photographie Correspondents (Photogr
aphisches Korrespondenz) 99, 99, 100, 57.

The tabular silver halide grains used in the present invention mainly have an even number of parallel twin planes, which may or may not be parallel to each other. Particularly preferably, it has two twin planes.

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

The outer wall of the crystal of the tabular silver halide grains according to the present invention may be substantially composed of (111) faces or (100) faces. Further, it may have both a (111) plane and a (100) plane. In this case, 50% or more of the grain surface is the (111) plane, more preferably 60% to 90% is the (111) plane, and particularly preferably 70 to 95% is the (111) plane. The planes other than the (111) plane are preferably mainly the (100) plane. This plane ratio is (111) plane and (100) plane in the adsorption of sensitizing dye.
"T. Tani, J. Imagin
g Sci. 29, 165 (1985) ”.

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

In the present invention, each side forming the hexagon of the hexagonal tabular grain preferably has a half or more of a substantially straight line. More preferably, the ratio of adjacent sides is 1.0 to 1.5.

The tabular silver halide grains used in the present invention may have a uniform composition, but a core / shell structure having at least two layer structures having substantially different halogen compositions within the silver halide grains. 50% or more, or 100% may be contained in the photosensitive silver halide emulsion layer.

The core / shell type structure grain may have a halogen composition region different from that of the core in the center portion of the grain. The halogen composition of the seed grains in such a case may be any combination of silver bromide, silver iodobromide, silver chloroiodobromide, silver chlorobromide, silver chloride and the like.

The average iodide content of the silver halide emulsion according to the present invention is preferably 2 mol% or less, more preferably 0.
It is from 01 to 1.5 mol%. More preferably, it is 1 mol% or less.

Among the grains having a layer structure having different halogen compositions, grains having a high silver iodide layer inside the grain and a low silver iodide layer or a silver bromide layer at the outermost surface layer are preferable. At this time, the silver iodide ratio of the inner layer (core) having the highest silver iodide content is 2.5.
It is preferably at least mol%, more preferably 5 mol%
As described above, the content is 40 mol% or less, and the silver iodide content of the outermost surface layer (shell) is 0 to 10 mol%, preferably 0 to 8 mol%, and more preferably 0 to 5 mol%. Regarding the low silver iodide grains in the outermost surface layer, 4-hydroxy-6-methyl-1,3,3a, 7 which is a stabilizer added at the end of ripening of the silver halide emulsion is used.
-It is preferable to reduce the amount of tetrazaindene (TAI) added. The surface iodide is 5 mol% or less, and the addition amount of TAI is preferably 200 mg or less, and more preferably 60 mg or less, per mol of silver halide.

The silver iodide distribution of the core is usually uniform, but it may have a distribution. For example, the concentration may increase from the center toward the outside, or may have a maximum or minimum concentration in the intermediate region.

The silver halide grains used in the present invention are:
It may be so-called halogen conversion type (conversion type) particles. Halogen conversion is 0.2 mol% with respect to silver
˜2.0 mol% is preferable, and the conversion may be carried out during physical aging or after completion of physical aging. As a method of converting halogen, an aqueous solution of halogen or silver halide fine particles having a smaller solubility product with silver than the halogen composition on the surface of the grain before halogen conversion is usually added. The particle size at this time is 0.
It is preferably 2 μm or less, and more preferably 0.02 to 0.1 μm. The silver halide grain of the present invention is, for example, disclosed in JP-A-60-1
It is preferable to grow by a method of precipitating silver halide on a seed crystal like the method described in the Example of 38538.

In order to obtain the tabular silver halide emulsion of the present invention, a method for producing a silver halide photographic emulsion comprising supplying a water-soluble silver salt solution and a water-soluble halide solution to the presence of a protective colloid, (A) A nucleus particle forming step of maintaining the pBr of the mother liquor at 2.5 to -0.7 for a period of 1/2 or more from the initial stage of silver halide precipitation formation having a silver iodide content of 0 to 5 mol% is provided. Subsequent to the grain formation step, seed grains containing a silver halide solvent in the mother liquor in an amount of 10 ^{−5 to} 2.0 mol per mol of silver halide to form substantially monodisperse spherical twin crystal silver halide seed grains A forming step is provided, or, following the core particle forming step, the temperature of the mother liquor is raised to 40 to 80 ° C., and a seed grain forming step of forming a silver halide twin seed grain is provided, (C)
Then, a water-soluble silver salt solution and a water-soluble halide solution and / or
Alternatively, a method of providing a growth step of adding halogenated fine particles to enlarge seed particles is preferably used.

Here, the mother liquor is a liquid (including a silver halide emulsion) which is used for the preparation of silver halide emulsions up to the completed photographic emulsion.

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

A water-soluble silver salt may be added for the purpose of controlling ripening during the seed grain forming step of the present invention. The seed grain growing step for enlarging the silver halide seed grains includes pAg, pH, temperature, silver halide solvent concentration and silver halide composition, silver halide composition and silver salt and halide solution concentration during silver halide precipitation and Ostwald ripening. This is achieved by controlling the rate of addition. In the preparation of the emulsion according to the present invention, a known silver halide solvent such as ammonia, thioether or thiourea can be present during the seed grain forming step and the seed grain growth.

Conditions for enlarging the produced seed grains in order to obtain the tabular silver halide grains according to the present invention include, for example, JP-A Nos. 51-39027, 55-142329, and 58-113928.
No. 54-48521 and No. 58-49938, etc., a water-soluble silver salt solution and a water-soluble halide solution were added by the double jet method, and the addition rate was changed according to the enlargement of particles to form new nuclei. May be used, and a method of gradually changing it may be used within a range in which Ostwald ripening does not occur. As another condition for enlarging the seed grains, a method for enlarging by adding silver halide fine particles and dissolving and recrystallizing can be used as shown in Section 88 of the 1983 Annual Meeting of the Photographic Society of Japan.

For growth, an aqueous solution of silver nitrate and an aqueous solution of halide can be added by the double jet method, but iodide can be supplied to the system as silver iodide.
The rate of addition is such that no new nuclei are generated, and there is no spread of the size distribution 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 the production of silver halide emulsion, the stirring conditions during production are extremely important. As the stirring device, the device shown in JP-A-62-160128, in which the additive liquid nozzle is installed in the liquid near the mother liquor suction port of the stirrer, is particularly preferably used. At this time, the stirring rotation speed is preferably 400 to 1200 rpm.

The silver iodide content and the average silver iodide content of the silver halide grains of the present invention are determined by the EPMA method (Electron Probe Micr
o Analyzer) can be used.

According to this method, a sample in which emulsion grains are well dispersed so that they do not come into contact with each other is prepared, and elemental analysis of a smaller portion than X-ray analysis by electron beam excitation with electron beam irradiation can be performed. By this method, the halogen composition of each grain can be determined by obtaining the characteristic X-ray intensities of silver and iodide emitted from each grain. If the silver iodide content of at least 100 grains is determined by the EPMA method, the average silver iodide content can be determined from the average thereof.

In the production of the light-sensitive silver halide emulsion of the present invention, the seed emulsion has two or more twin planes in which 50% or more of the total projected area of the seed grains are parallel, and Both the variation coefficient and the variation coefficient of the longest distance (at) between twin planes of the seed grains are preferably 35% or less. Even if the variation coefficient of only the seed grain thickness or only (at) is 35% or less, the variation coefficient of the twin plane distance (a) of the grown grain cannot be suppressed to 35% or less, It is necessary for both to hold at the same time.

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

Further, the silver halide grain according to the present invention is such that a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt (including a complex salt), a rhodium salt ( It is possible to add at least one metal ion selected from the group consisting of complex salts) and iron salt (including complex salts) to make these metal elements contained in the inside of the particles and / or the surface layer of the particles, and to carry out appropriate reduction. It is possible to impart a reduction sensitizing nucleus to the inside of the grain and / or the surface of the grain by exposing the grain to a selective atmosphere.

Further, the action of the reducing agent added at a desired time of particle formation is to add an oxidizing agent such as hydrogen peroxide (water) and its adduct, peroxo acid salt, ozone, and I ₂ at a desired time. It is preferable to deactivate the reducing agent and suppress or stop the reducing agent. The timing of addition of the oxidizing agent can be arbitrarily selected from the time of silver halide grain formation to the chemical sensitization step.

In the silver halide emulsion, unnecessary water-soluble salts may be removed at the end of the growth of silver halide grains, or may be contained. For example, Research Disclosure (hereinafter abbreviated as RD) No.17643 is used to remove salts.
It can be performed based on the method described in Section II.

A polymer latex can be used in the silver halide photographic light-sensitive material of the present invention. Preferred latexes are those which have no or very little adverse effect when used in silver halide photographic elements. That is, it is preferable that the latex surface is photographically inactive and the interaction with various photographic additives is extremely small.

An index called a glass transition point is often used for the latex. The higher the transition point, the harder it becomes so that it cannot serve as a buffering agent. However, if it is low, the transition point is generally likely to interact with the photographic performance, resulting in adverse effects. Therefore, considering the photographic characteristics, the selection of the composition and the amount used are not simple. Latex using monomers such as styrene, butadiene and vinylidene is well known. Further, it is said that introduction of a monomer having a carboxylic acid group such as acrylic acid, itaconic acid, maleic acid or the like during the synthesis of a latex reduces the influence on photographic properties, and such a synthesis is often attempted. Also, the glass transition point may be appropriately set according to the photosensitive material by including a methacrylate unit in the latex obtained by such a combination. As specific examples, JP-A-2-135335 and Japanese Patent Application No. 5-119113, filed by the same applicant as the present invention, 5-
119114 etc. will be helpful.

When a dye capable of being decolorized or discharged during the development processing is contained in at least one layer selected from the layers containing the light-sensitive silver halide emulsion of the present invention or the layers other than the emulsion layer, high sensitivity can be obtained. A light-sensitive material having high sharpness and less dye stain can be obtained.

The dye to be used can be appropriately selected from dyes capable of improving sharpness by absorbing a desired wavelength and eliminating the influence of the wavelength depending on the light-sensitive material. . It is preferable that the dye be decolorized or flowed out during the development processing of the light-sensitive material, and the coloring is not visible when the image is completed.

Specific examples of the dye used in the light-sensitive material include West German Patent 616,007, British Patent 584,609 and the same.
1,177,429, Japanese Patent Publication No. 26-7777, 39-22069, 54-3
8129, JP-A-48-85130, 49-99620, 49-11442
No. 0, 49-129537, 50-28827, 52-108115,
57-185038, U.S. Patents 1,878,961 and 1,884,035
No. 1, No. 1,912,797, No. 2,098,891, No. 2,150,695,
2,274,782, 2,298,731, 2,409,612, 2,
No. 461,484, No. 2,527,583, No. 2,533,472, No. 2,865,7
52, 2,956,879, 3,094,418, 3,125,448
No. 3,148,187, 3,177,078, 3,247,127,
3,260,601, 3,282,699, 3,409,433, 3,5
40,887, 3,575,704, 3,653,905, 3,718,47
No. 2, No. 3,865,817, No. 4,070,352, No. 4,071,312
No., PB Report 74175, PHOTO. ABS.1, 28 ('21), etc.

Examples of the dye that can be used in the present invention include dyes that are substantially insoluble in water at pH 7 or less and substantially water-soluble at pH 8 or more. Specifically, the following general formula [V ] To [X] are selected from the dyes.

[0140]

[Chemical 15]

(In the formula, A and A ′ may be the same or different and each represents an acidic nucleus, B represents a basic nucleus, Q represents an aryl group or a heterocyclic group, and Q ′ represents a heterocyclic group. Group, X and Y, which may be the same or different, each represent an electron-withdrawing group, and are L ₁ , L ₂ and L _3.
Each represents a methine group. m represents 0 or 1, and n
Represents 0, 1 or 2, and p represents 0 or 1. However, the dyes represented by the general formulas [V] to [X] have at least one group selected from a carboxy group, a sulfonamide group and a sulfamoyl group in the molecule. The acid nuclei represented by A and A'in the general formulas [V], [VI] and [VII] are preferably 5-pyrazolone, barbituric acid, thiobarbituric acid, rhodanine, hydantoin, thiohydantoin and oxazolone. , Isoxazolone, indandione, pyrazolidinedione, oxazolidinedione, hydroxypyridone, and pyrazolopyridone.

The basic nucleus represented by B in the general formulas [VII] and [IX] is preferably pyridine, quinoline,
Examples include oxazole, benzoxazole, naphthoxazole, thiazole, benzthiazole, naphthothiazole, indolenine, pyrrole and indole.

Examples of the aryl group represented by Q in the general formulas [V] and [X] include a phenyl group, a naphthyl group,
Examples thereof include julolidyl group. In addition, the general formula [V],
Examples of the heterocyclic group represented by Q and Q'of [VIII] and [X] include a pyridyl group, a quinolyl group, an isoquinolyl group, a pyrrolyl group, a pyrazolyl group, an imidazolyl group,
Examples thereof include an indolyl group, a furyl group and a thienyl group.
The aryl group and the heterocyclic group include those having a substituent, and examples of the substituent include an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group,
Carboxy group, cyano group, hydroxy group, mercapto group, amino group, alkoxy group, aryloxy group, acyl group, carbamoyl group, acylamino group, ureido group,
Examples thereof include a sulfonamide group and a sulfamoyl group, and these substituents may have two or more kinds in combination. Preferred substituents are alkyl groups having 1 to 8 carbon atoms (eg methyl group, ethyl group, t-butyl group, n-octyl group, 2-hydroxyethyl group, 2-methoxyethyl group, etc.), hydroxy group, cyano Group, halogen atom (eg, fluorine atom, chlorine atom, etc.), alkoxy group having 1 to 6 carbon atoms (eg, methoxy group, ethoxy group, 2-hydroxyethoxy group, methylenedioxy group, n-butoxy group, etc.), substituted amino Groups (eg dimethylamino group, diethylamino group, di (n-butyl) amino group, N-ethyl-N-hydroxyethylamino group, N-ethyl-N-methanesulfonamidoethylamino group, morpholino group, piperidino group, pyrrolidino group Base etc.),
A carboxy group, a sulfonamide group (for example, a methanesulfonamide group, a benzenesulfonamide group, etc.), a sulfamoyl group (for example, a sulfamoyl group, a methylsulfamoyl group, a phenylsulfamoyl group, etc.), and by combining these substituents Good.

X and Y in the general formulas [VIII] and [IX]
The electron-withdrawing groups represented by may be the same or different, and the substituent constant Hammett's σp value (edited by Toshio Fujita, “Chemical Region Special Issue No. 122. Structure-activity Relationship of Drugs”, pp. 96-103 ( 197
9) It is listed in Nankodo. ) Is 0.3 or more, for example, a cyano group, an alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, octyloxycarbonyl group, etc.), an aryloxycarbonyl group (eg, phenoxycarbonyl group, 4-hydroxy group). Phenoxycarbonyl group), carbamoyl group (eg carbamoyl group, methylcarbamoyl group, ethylcarbamoyl group, butylcarbamoyl group, dimethylcarbamoyl group, phenylcarbamoyl group, 4-carboxyphenylcarbamoyl group, etc.), acyl group (eg methylcarbonyl group, ethyl Carbonyl group, butylcarbonyl group, phenylcarbonyl group, 4-ethylsulfonamidophenylcarbonyl group, etc.), alkylsulfonyl group (eg, methylsulfonyl group, ethylsulfonyl group) Group, butylsulfonyl group, octylsulfonyl group, etc.) and arylsulfonyl group (eg, phenylsulfonyl group, 4-chlorosulfonyl group, etc.).

L ₁ , L ₂ and L of the general formulas [V] to [IX]
_The methine group represented by ₃ includes those having a substituent,
Examples of the substituent include an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, hexyl group, etc.), aryl group (eg, phenyl group, tolyl group, 4-hydroxyphenyl group, etc.), aralkyl group (eg, Benzyl group, phenethyl group, etc.), heterocyclic group (eg pyridyl group, furyl group,
And a substituted amino group (eg, dimethylamino group, diethylamino group, anilino group, etc.), and alkylthio group (eg, methylthio group, etc.).

In the present invention, among the dyes represented by the general formulas [V] to [X], a dye having at least one carboxy group in the molecule is preferably used, and more preferably the general formula [V]. A dye represented by the formula, and particularly preferably a dye in which Q is a furyl group in the general formula [V].

When it is contained in the light-sensitive material, a constituent layer containing a combination of a dye and a non-diffusible moldant may be newly provided as a constituent layer, and its position can be arbitrarily selected, but it is preferably transparent support. Effectively used as a coating layer adjacent to the body.

The emulsion used in the silver halide photographic light-sensitive material of the present invention can use various photographic additives in the steps before and after physical ripening or chemical ripening. Examples of the compound used in such a process include Research Disclosure (RD) No. 17643 (December 1978), No. 18716 (197).
Various compounds described in No. 308119 (December 1989) and No. 308119 can be used. These three (RD)
The types of compounds and their locations described in are listed below.

Additive RD-17643 RD-18716 RD-308119 Page Classification Page Page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IV A Desensitizing dye 23 IV 998 IV B Dye 25-26 VIII 649-650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006-7 VI Whitening agent 24 V
998 V Hardener 26 X 651 Left
1004-5 X Surfactant 26-27 XI 650 Right 1005-6 XI Plasticizer 27 XII 650 Right 1006 XII Sliding Agent 27 XII Matting Agent 28 XVI 650 Right 1008-9 XVI Binder 26 XXII 1003-4 IX Support 28 XVII 1009 XVII Incidentally, the silver halide emulsion of the present invention may contain a developing agent such as aminophenol, ascorbic acid, pyrocatechol, hydroquinone, phenylenediamine or 3-pyrazolidone in the emulsion layer or a layer having other layers.

Examples of the support that can be used in the light-sensitive material of the present invention include the above-mentioned RD-17643, page 28 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, corona discharge, or ultraviolet irradiation in order to improve the adhesion of the coating layer.

The amount of gelatin in the emulsion layer, surface protective layer and other layers of the photographic light-sensitive material of the present invention is 1.
It should be in the range of 5 to 3.5 g / m ² . Especially 2.0
The range of up to 3.0 g / m ² is preferred.

Next, preferable development processing of the light-sensitive material of the present invention will be described.

Preferred developers for developing the light-sensitive material of the present invention include, as developing agents, JP-A-4-15641 and JP-A-4.
-16841 and the like dihydroxybenzene, such as hydroquinone, para-aminophenols, such as p-aminophenol, N-methyl-p-aminophenol, 2,4-diamiphenol, 3-pyrazolidones, 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, and it is preferable to use them in combination.

The amount of the para-aminophenols and 3-aminopyrazolidones used is preferably 0.004 mol / liter, more preferably 0.04-0.12 mol / liter. Further, the total number of moles of dihydroxybenzenes, para-aminophenols and 3-pyrazolidones contained in these components of all developing solutions is preferably 0.1 mol / liter or less.

The preservative may include sulfites such as potassium sulfite, sodium sulfite, reductones such as piperidinohexose reductone, and these are preferably 0.2 to 1 mol / liter, more preferably It is recommended to use 0.3 to 0.6 mol / liter. Also,
Adding a large amount of ascorbic acid also leads to process stability. Examples of the alkaline agent include pH adjusting agents such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium triphosphate and potassium triphosphate.
Further, borate described in JP-A-61-28708, JP-A-60-
-93439 described saccharose, acetoxime,
A buffering agent such as 5-sulfosalicylic acid, phosphate or carbonate may be used. The content of these agents is such that the pH of the developer is 9.0.
~ 13, preferably pH10 ~ 12.5. As a solubilizing agent, polyethylene glycols and their esters can be contained, and as a sensitizing agent, for example, a quaternary ammonium salt, a development accelerator, a surfactant and the like can be contained.

As a silver sludge inhibitor, JP-A-56-10624
The silver stain preventing agent described in No. 4, the sulfide or disulfide compound described in JP-A-3-51844, the cysteine derivative or the triazine compound described in Japanese Patent Application No. 4-92947 by the same applicant as the present invention are preferably used.

As the organic inhibitor, an azole type organic antifoggant, for example, an indazole type, an imidazole type, a benzimidazole type, a triazole type, a benztriazo type, a tetrazole type or a thiadiazole type compound is used. Inorganic inhibitors include sodium bromide, potassium bromide, potassium iodide and the like. In addition, LFA Menson's "Photographic Processing Chemistry" published by Focal Press (1966), 226-229.
Page, U.S. Pat.Nos. 2,193,015 and 2,592,364, JP-A-48-6
You may use what is described in No. 4933 etc. As a chelating agent for concealing calcium ions mixed in tap water used as a treatment liquid, as an organic chelating agent, JP-A-1-
Chelating agents having a chelate stabilization constant of 8 or more with iron described in 193853 are preferably used. Examples of the inorganic chelating agent include sodium hexametaphosphate, calcium hexametaphosphate, and polyphosphate.

As the development hardening agent, a dialdehyde compound may be used. In this case, glutaraldehyde is preferably used.

In the method for developing a silver halide photographic light-sensitive material according to the present invention, it is preferable that the processing is carried out by an automatic developing machine and the steps from development to drying are completed within 30 seconds. That is, the time from the time when the tip of the photosensitive material starts to be immersed in the developing solution to the time when the tip comes out of the drying zone after the processing step (so-called Dry to Dry time) is within 30 seconds, and more preferably Within 25 seconds.

The development processing temperature is preferably 25 to 50 ° C.,
More preferably, it is 30 to 40 ° C. The developing time is 5 to 15 seconds, more preferably 5 to 10 seconds.

The fixing temperature and time are about 20 ° C to 50 ° C for 3 seconds to
20 seconds is preferable, and 30 to 40 ° C. is more preferably 3 to 15 seconds. The drying time is usually 35 to 100 ° C., preferably 40 to 80 ° C., or a drying zone provided with a heating means by far infrared rays may be installed in the automatic processor.

In the present invention, the method for replenishing the treatment liquid is to replenish the treatment agent fatigue and the amount equivalent to oxidation fatigue. As the replenishment method, for example, the replenishment according to the width and the feeding speed described in JP-A-55-126243, Area replenishment described in Sho 60-104946, JP-A-1
Area replenishment controlled by the number of continuously processed sheets described in No. 149156 may be used. The preferred replenishment rate is 500-150 ml / m ²
Is.

In the present invention, the fixing liquid means the liquid in the fixing tank. Preferred fixing solutions can include fixing materials commonly used in the art. The iodine content in the liquid is preferably 0.3 g / liter or less, more preferably 0.1
It is not more than g / liter.

The pH is 3.8 or higher, preferably 4.2 to 5.5. The preferable replenishing amount is 0.2 liter or less per 1 m ^{2 of the} silver halide photographic light-sensitive material.

As a fixing agent, ammonium thiosulfate,
It is a thiosulfate such as sodium thiosulfate, and ammonium thiosulfate is particularly preferable in terms of fixing speed. The concentration of ammonium thiosulfate is preferably in the range of 0.1 to 5 mol / liter, more preferably 0.8 to 3 mol / liter.

The fixing solution of the present invention may be one which performs acidic hardening. In this case, aluminum ions are preferably used as the hardener. For example, it is preferably added in the form of aluminum sulfate, aluminum chloride, potassium alum, or the like.

Others In the fixing solution of the present invention, if desired, preservatives such as sulfite and bisulfite, pH buffers such as acetic acid and boric acid, mineral acids (sulfuric acid, nitric acid) and organic acids (citric acid, oxalic acid). , Malic acid, etc.), various acids such as hydrochloric acid, pH adjusting agents such as metal hydroxides (potassium hydroxide, sodium hydroxide) and chelating agents having a water softening ability.

As the fixing accelerator, for example, JP-B-45-357 is used.
No. 54, No. 58-122535, No. 58-122536, and the thioethers described in US Pat. No. 4,126,459.

The silver halide emulsion layer of the present invention preferably has a swelling ratio during development of 150 to 250% and a film thickness after expansion of 70 μm or less. If the water swelling rate exceeds 250%, poor drying occurs, and, for example, poor handling occurs in automatic processor processing, especially rapid processing. Further, if the water swelling ratio is less than 150%, uneven development and residual color tend to be deteriorated during development. Here, the water swelling rate means the difference between the film thickness after swelling in each processing solution and the film thickness before the development processing, which is divided by the film thickness before processing and multiplied by 100. .

[0171]

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

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

A1 ossein gelatin 24.2 g water 9657 ml polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% ethanol aqueous solution) 6.78 ml potassium bromide 10.8 g 10% nitric acid 114 ml B1 2.5N silver nitrate aqueous solution 2825 ml C1 potassium bromide 824 g Potassium iodide 23.5 g Water 2825 ml D1 1.75N Potassium bromide aqueous solution At the following silver potential control amount 42 ° C., use solution A1 and solution B1 using a mixing stirrer as shown in JP-B-58-58288 and 58-58289. Each of solution C1
Nucleation was performed by adding 464.3 ml by the double-sided mixing method over 1.5 minutes.

After stopping the addition of the solution B1 and the solution C1, it took 60 minutes to raise the temperature of the solution A1 to 60 ° C., adjust the pH to 5.0 with 3% KOH, and then add the solution B1 again. Solution C1 was added by the double jet method at a flow rate of 55.4 ml / min each 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 this temperature increase from 42 ° C. to 60 ° C. and re-simultaneous mixing with the solutions B1 and C1 was +8 mv using the solution D1. And +16 mv.

After the completion of the addition, the pH was adjusted to 6 with 3% KOH, and the mixture was immediately desalted and washed with water. This seed emulsion has a maximum adjacent side ratio of 1.0 to 90% of the total projected area of silver halide grains.
It was confirmed by an electron microscope that the hexagonal tabular grains of 2.0 had an average thickness of 0.06 μm and an average grain size (converted to a circle diameter) of 0.59 μm. The coefficient of variation of thickness is 40
%, And the coefficient of variation in the distance between twin planes was 42%.

(Preparation of Em-1) A tabular silver halide emulsion Em-1 having an average silver iodide content of 1.0 mol% was prepared using seed emulsion-1 and the following four kinds of solutions.

A2 ossein gelatin 34.03 g polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% ethanol aqueous solution) 2.25 ml seed emulsion-1 1.218 mol equivalent Water to make 3150 ml B2 potassium bromide 1967 g to make water 4151 ml C2 Silver nitrate 2468 g Finish with water to 4151 ml D2 3% by weight of gelatin and silver iodide grains (average grain size 0.05 μm) Fine grain emulsion (*) Equivalent to 0.145 mol * 0.06 mol of potassium iodide 5.0% by weight To 6.64 liters of a gelatin aqueous solution, 2 liters of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide were added over 10 minutes. Nitric acid is used for pH during the formation of fine particles.
The temperature was controlled to 2.0 and the temperature was controlled to 40 ° C. After particle formation, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution.

Solution A1 was vigorously stirred in the reaction vessel while maintaining the temperature at 60 ° C., and part of solution B2, part of solution C2 and solution D2 were added thereto by the simultaneous mixing method over 46 minutes, After that, the remaining amounts of the solution B2 and the solution C2 were continuously added over 24 minutes by the simultaneous mixing method. During this time, pH was 5.8 and pA
g kept at 9.0 all the time. Here, the addition rates of solution B2 and solution C2 were changed in a function-like manner with respect to time so as to match the critical growth rate. That is, the addition was performed at an appropriate addition rate so that small particles were not generated other than the growing seed particles and polydispersion did not occur due to Ostwald ripening. Solution D
Regarding the addition rate of 2, the rate ratio (molar ratio) with the solution C2 was kept at 0.11.

After completion of the addition, this emulsion was cooled to 40 ° C., and a 13.8% (by weight) aqueous solution of modified gelatin modified with phenylcarbamoyl groups as a flocculating polymer (substitution rate 90%) 1800
ml was added and stirred for 3 minutes. Then, a 56% (weight) aqueous acetic acid solution was added to adjust the pH of the emulsion to 4.6, the mixture was stirred for 3 minutes, allowed to stand for 20 minutes, and the supernatant was drained by decantation. Then, 9.0 l of distilled water at 40 ° C was added, the mixture was left to stir and the supernatant was drained, and 11.25 l of distilled water was added.
Was added and the mixture was allowed to stand with stirring, and the supernatant was drained. Subsequently, a gelatin aqueous solution and a 10% (weight) aqueous sodium carbonate solution were added to adjust the pH to 5.80, and the mixture was stirred at 50 ° C. for 30 minutes and redispersed. After redispersion at 40 ℃ pH is 5.80, pAg
Adjusted to 8.06.

The obtained silver halide emulsion having an average iodine of 1.0 mol% was observed by an electron microscope to find that the average grain size was 0.98 μm.
m, average thickness 0.22 μm, average aspect ratio (AR) about 4.5, AR
The ratio of particles with> = 2 is 93%, the ratio of particles with b / a> = 5 is 79%, the ratio of (111) faces is 85%, and the size of the particle size distribution is 20.9%. It was a silver particle. Also,
The average distance between twin planes was 0.018 μm. Incidentally, grains having a thickness / twin plane distance ratio of 10 or more contain 50% or more of all grains.

(Preparation of Em-2) In the same manner as the method for preparing Em-1, the seed 1 and the solution D2 were not used, and the amount of potassium bromide in the solution B2 was changed to prepare pure silver bromide. Tabular grains were prepared and designated as Em-2. When the obtained silver halide emulsion was observed with an electron microscope, the average grain size was 0.97μ.
m, average aspect ratio (AR) about 4.7, the ratio of particles with AR> = 2 is 94%, the ratio of particles with b / a> = 5 is 83%, the ratio of (111) faces is 84%, It was a tabular silver halide grain having a width distribution of 20.5%.

Next, the effect of the present invention was examined by using the silver halide emulsion thus obtained.

First, in order to evaluate the effects of the method of adding a spectral sensitizing dye as a methanol solution and the method of adding it as a solid fine particle dispersion, emulsion Em-1 was subjected to the following spectral sensitization and chemical sensitization. Seed formulation was applied.

(Formulation A) After the emulsion was heated to 60 ° C., a methanol solution was added to a predetermined amount of the spectral sensitizing dye, and then a mixed aqueous solution of ammonium thiocyanate, chloroauric acid and sodium thiosulfate, a silver iodide fine grain emulsion. Was added and the mixture was aged for 2 hours. At the end of aging, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) was added as a stabilizer.

(Formulation B) In Formula A, the difference is that the spectral sensitizing dye is added as a dispersion in the form of solid fine particles instead of being added as a methanol solution. The dispersion was prepared by a method according to Japanese Patent Application No. 4-99437. That is, a predetermined amount of the spectral sensitizing dye was added to water whose temperature had been adjusted to 27 ° C. in advance, and the mixture was stirred by a high speed stirrer (dissolver) at 3,500 rpm for 30 to 120 minutes.

The amounts of the above additives (per mol of AgX) are shown below.

Ammonium thiocyanate 95 mg Chloroauric acid 2.5 mg Sodium thiosulfate 2.5 mg Fine silver iodide 220 mg Stabilizer (TAI) 350 mg For Formula B, addition when adding a spectral sensitizing dye as a solid fine particle dispersion The amount varied.

Next, the following additives were added to the emulsion thus sensitized to prepare an emulsion layer coating solution. At the same time, a protective layer coating solution was also prepared.

The coating amount was 2.0 g / m ² on one side and the amount with gelatin was 3.1 g / m ² using two slide hopper type coaters, and both sides were coated simultaneously on the support. A sample was obtained after drying. The support is a 175 μm thick, 0.15 concentration blue-colored polyethylene terephthalate film base for X-rays, and a copolymer consisting of three types of monomers of 50 wt% glycidyl methacrylate, 10 wt% methyl acrylate, and 40 wt% butyl methacrylate on both sides. The concentration of
The following copolymer dyes were dispersed in an aqueous copolymer dispersion obtained by diluting to 10 wt% and applied as an undercoating liquid.

Filter dye (solid dispersion)

[0191]

Embedded image

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 1, Ammonium 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

[0194]

[Chemical 17]

Protective Layer Solution Next, 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 Polymethylmethacrylate (matting agent having an area average particle size of 3.5 μm) 1.1 g Silicon dioxide particles (area average particles Matting agent with a diameter of 1.2 μm) 0.5 g (CH ₂ = CHSO ₂ CH ₂ ) ₂ (hardener) 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

[0197]

Embedded image

The photographic characteristics of Sample Nos. 1 to 3 thus obtained were evaluated. The evaluation method was as follows. First, the sample was sandwiched between two intensifying screens KO-250 (manufactured by Konica Corporation) and exposed through an aluminum wedge to an X-ray of a tube voltage of 80 kvp, a tube current of 100 mA, and a time of 0.05 seconds for exposure. Then, using an automatic processor 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 12 liter finish) Potassium hydroxide 450 g Potassium sulfite (50% solution) 2280 g Diethylenetetraamine-5-acetic acid 120 g Sodium bicarbonate 132 g 5-Methylbenzotriazole 1.2 g 1-phenyl-5- Mercaptotetrazole 0.2g Hydroquinone 340g Add water to make 5000ml.

Part-B (for finishing 12 liters) 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 18-liter finishing) 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 18g Part-B Aluminum sulfate 800g To prepare a developer, add Part A and Part B to approximately 5 liters of water at the same time, add water while stirring and dissolve, and add 12 liters with glacial acetic acid.
The H was adjusted to 10.40. This is used as a developing solution.

20 ml / l of the above-mentioned starter was added to 1 liter of this developing solution to adjust the pH to 10.26 to prepare a working solution.

The fixing solution was prepared by adding Part A and Part B to approximately 5 liters of water.
Was simultaneously added, water was added while stirring and dissolving to make 18 l, and the pH was adjusted to 4.4 using sulfuric acid and NaOH. This is the fixing replenisher.

The processing temperatures are 35 ° C. for development and fixing, respectively.
33 ℃, 20 ℃ water wash, 50 ℃ dry, processing time is dry to dry 30
Seconds.

After the treatment, the sensitivity was measured. Sensitivity is expressed as the reciprocal of the amount of light exposure that gives a density of fog + 0.5, and the relative sensitivity when the sensitivity of emulsion coating sample No. 1 with a sensitizing formulation in which a spectral sensitizing dye is added as a methanol solution is 100. I asked. Regarding the evaluation of the residual color, the spectral absorption density at 510 nm of the sample after the development treatment was measured with a spectrophotometer and compared. Taking the measured value of the residual color density of sample No. 1 as 100, the measured values of other samples were relatively determined. The results thus obtained are shown in Table 1 below.

[0206]

[Table 1]

As can be seen from Table 1, the spectral sensitizing dye according to the method of the present invention is excellent in high sensitivity and little residual color even though the addition amount is small.

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

A3 ossein gelatin 100 g Potassium bromide 2.05 g Water 11.5 l B3 ossein gelatin 55 g Potassium bromide 65 g Potassium iodide 1.8 g 0.2 N sulfuric acid 38.5 ml Water 2.6 l C3 ossein gelatin 75 g Potassium bromide 950 g Iodine Potassium iodide 27g Water 3.0l D3 silver nitrate 95g Water 2.7l E3 Silver nitrate 1410g Water 3.2l To solution A3 kept at 60 ° C in a reaction kettle, add solution B3 and D3 by control double jet method over 30 minutes. Then, the C3 solution and the E3 solution were added by the control double jet method over 105 minutes. Agitation was performed at 500 rpm. With respect to the flow rate, new nuclei were not generated with the growth of particles, and so-called Ostwald ripening was caused, so that the particle size distribution was not widened. When the silver ionic liquid and the halide ionic liquid were added, the pAg was adjusted to 8.3 ± 0.05 using potassium bromide liquid, and the pH was adjusted to 2.0 ± 0.1 using sulfuric acid.

After completion of the addition, the pH was adjusted to 6.0, and then desalting treatment was carried out by the method described in JP-B-35-16086 in order to remove excess salts. When the seed emulsion was observed with an electron microscope, it was a cubic tetradecahedral monodisperse emulsion having an average grain size of 0.27 μm and a slightly wide angle of 17%.

Preparation of Em-3 A monodisperse core / shell type emulsion was prepared using the above seed emulsion-2 and the following seven kinds of solutions.

A4 Ocein gelatin 100 g Ammonia water (28%) 8 ml Glacial acetic acid 3 ml Seed emulsion-2 0.119 mol equivalent Equivalent to 600 ml with water B4 Ocein gelatin 0.8 g Potassium bromide 5 g Potassium iodide 3 g Water to 110 ml C4 Ocein gelatin 2g Potassium bromide 90g Finish to 240ml with water D4 Silver nitrate 9.9g Ammonia water (28%) 7.0ml Finish to 110ml with water E4 Silver nitrate 130g Ammonia water (28%) Finish to 240ml with water F4 Potassium bromide 94g Finish with water to 165 ml G4 Silver nitrate 9.9 g Ammonia water (28%) 7.0 ml Finish with water to 110 ml Solution A4 was kept at 40 ° C and stirred at 800 rpm with a stirrer.
The pH of the A4 solution was adjusted to 9.90 with acetic acid, and the seed emulsion-1 was collected and dispersed and suspended. Then, the G4 solution was added at a constant rate over 7 minutes to adjust the pH to 7.3. Furthermore, B4 solution and D4 solution are simultaneously
Added over 20 minutes. At this time, pAg was kept constant at 7.3. Add potassium bromide solution and acetic acid for 10 min.
After adjusting H = 8.83 and pAg = 9.0, the C4 solution and the E4 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.
The pH was decreased from 8.83 to 8.00 in proportion to the flow rate ratio.

Further, when the C4 solution and the E4 solution were added by ⅔ of the total amount, the F4 solution was additionally injected and added at a constant rate over 8 minutes. At this time, 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 desalting was carried out in the same manner as in the above seed emulsion to remove excess salts, and pAg8.5,
The average silver iodide content at pH 5.85 at 40 ° C is about 2 mol%.
Emulsion Em-3 was obtained.

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

In emulsions Em-2 and Em-3, in the sensitizing formulation (B) used in Example 1, N, N-dimethylselenourea (of sodium thiosulfate) was used as a chemical sensitizer in addition to the above compounds. Aging was performed in the same manner as in Example 1 except that 1/5 mol of the added amount) was added.

Next, the silver halide emulsion prepared as described above was coated in the same manner as in Example 1 to obtain a sample.

Each of the obtained samples No. 6 to No. 9 was subjected to two kinds of conditions (condition A: 23 ° C., 55% RH, condition B: 40 ° C., 80
% RH) for 4 days before being evaluated for photographic properties.

The samples were exposed and developed in the same manner as in Example 1 and evaluated for photographic performance. Regarding sharpness (MTF), the optical density of the sample after development processing is 1.0
Was measured with an aperture of 30 μm × 500 μm, and the MTF value with a spatial frequency of 1.0 cycle / mm was measured. Sample N
The results of condition A of O.6 were used as the standard (100), and shown in relative values.

[0221]

[Table 2]

As is clear from Table 2, the sample sensitized by the combined use of the two spectral sensitizing dyes according to the method of the present invention is higher than that sensitized by only one spectral sensitizing dye. It can be seen that the sensitivity and the sharpness are excellent, and the sensitivity and the sharpness change little even when stored under high temperature and high humidity.

Example 3 Emulsions Em-1 and Em-2 prepared as described above were added to the sensitizing formulations (A) and (B) described in Example 1 in the same manner as in Example 2 except that chemical sensitizers were used. As the sensitizing compound, N, N-dimethylselenourea (corresponding to 1/5 mol of the added amount of sodium thiosulfate) was added for sensitization. However, at the end of the chemical ripening, a compound represented by the general formula [III] was added to obtain samples NO.10 to NO.17. Further, these samples were exposed and developed in the same manner as in Example 2 to evaluate the photographic performance. The relative values are shown in Table 3 using the sample No. 10 containing no compound represented by the general formula [III] as the reference (100).

[0224]

[Table 3]

As is clear from Table 3, the sample prepared by the method of the present invention has low fog, high sensitivity, and excellent storage stability.

Example 4 Sample No. 3 of Example 3 in which the emulsion Em-2 prepared as described above was combined with the spectral sensitizing dye represented by the general formula [I] and the spectral sensitizing dye represented by the general formula [II]. The samples were sensitized by the same sensitization method as in Example 13 to obtain Sample Nos. 18 to 22. Also, sample N of Example 3
The samples were sensitized by the same sensitization method as that of O.17 to obtain Sample Nos. 23-27. However, at the end of the chemical ripening of samples No. 18 to No. 27, 8 g of the compound represented by the general formula [IV] was added per 1 mol of silver,
The coating amount of the emulsion layers of Sample Nos. 18 to 27 was changed so that the amount of silver was 1.5 g / m ² per side and the amount of gelatin was 2.0 g / m ² .

The sample thus obtained was evaluated for photographs in the same manner as in Example 3. Regarding the evaluation of the pressure fog, after applying a load of 5 g to the unexposed sample with a scratch hardness meter of a needle having a needle head of 0.3 mm, the same development processing as described above was performed, and the density of pressure fog generation was measured with a microdensitometer. . Sample No.1
Relative values are shown in Table 4 with 8 as the standard (100).

[0228]

[Table 4]

As is clear from Table 4, the sample of the present invention has better sensitivity and pressure fog than the comparative sample, and there is no problem in practical use. Further, it can be seen that the medical silver halide photographic light-sensitive material of the present invention has the above effect even in rapid processing.

Example 5 Sample of the above-mentioned Example-4 in which the emulsion Em-2 prepared as described above was combined with the spectral sensitizing dye represented by the general formula [I] and the spectral sensitizing dye represented by the general formula [II]. It was sensitized by the same sensitization method as NO.27. However, the addition amount of AgI fine particles of Samples No. 28 to No. 31 was changed. These samples were photographically evaluated in the same manner as in Example 1. Further, the fixing time was measured while changing the iodide content in the fixing running solution. Sample N
Relative values are shown in Table 5 with O.28 as the standard (100).

[0231]

[Table 5]

As is apparent from Table 5, the sample having the iodine content of the outermost surface of 8 mol% or less is superior to the comparative sample in that it has a shorter fixing time and less residual color. Further, it can be seen that the sample having an iodide content of 5 mol% or less on the outermost surface has a shorter fixing time and is excellent in residual color.

Next, these samples were exposed and developed in the same manner as in Example 5. However, the processing time was adjusted to 25 seconds and 45 seconds by adjusting the automatic processor. The evaluation method is Example 5
It carried out similarly to. The results obtained are shown in Table 6 below.

[0234]

[Table 6]

As is clear from Table 6, even when the replenishing amount of the fixing solution is reduced and the processing time is shortened to 25 seconds, the sample of the present invention has high sensitivity as compared with the comparative sample and the change due to the processing time is small. It turns out that there are few.

[0236]

According to the present invention, a silver halide photographic light-sensitive material having high sensitivity, low fog and high sharpness can be obtained. Furthermore, according to the light-sensitive material of the present invention, it has excellent pressure resistance and has good storage stability over time.

Further, according to the present invention, a silver halide photographic light-sensitive material having less residual color contamination can be obtained even in the case of ultra-rapid development processing. Further, in the silver halide photographic light-sensitive material of the present invention, the iodide content in the fixing solution is reduced, and the fixability is not deteriorated even if the replenishing amount of the fixing solution is 0.2 liter or less per 1 m ² of the light-sensitive material. A method of processing a photographic light-sensitive material was obtained.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical indication location G03C 5/38 5/395 (72) Inventor Nobuaki Tsuji No. 1 Sakuramachi, Hino City, Tokyo Konica Stock Association In-house

Claims (8)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
70% or more of the total projected area of silver halide grains in the emulsion layer are silver halide grains having an aspect ratio of 2 or more and an average iodine content of 1.0 mol% or less, and have the following general formula [I].
Or a silver halide photographic light-sensitive material containing at least one selected from the spectral sensitizing dyes represented by [II] in an amount of 0.02 g / m ² or less. In the formula, R ₁ and R ₃ represent a methyl group or an ethyl group, and at least one of R ₁ and R ₃ represents a methyl group. R ₂ and R ₄ represent a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. However, both R ₂ and R ₄ are not methyl groups at the same time. Z ₁ , Z ₂ , Z ₃ and Z ₄ are a hydrogen atom, a methyl group,
It represents a methylthio group, a trifluoromethyl group or a sulfamoyl group, and Z ₁ , Z ₂ , Z ₃ and Z ₄ are not hydrogen atoms at the same time. X ₁ represents an ion necessary for neutralizing the charge in the molecule, and n is 1 or 2 and n is 1 when forming an intramolecular salt. Embedded image In the formula, R ₅ and R ₆ are substituted or unsubstituted C 1 to C 6
Of R ₅ and R ₆ and at least one of R ₅ and R ₆ represents a sulfoalkyl group or a carboxyalkyl group. R ₇ represents an alkyl group having 1 to 4 carbon atoms. V ₁ and V ₂ each represent a non-metal atom group necessary for completing a benzene ring or a naphthalene ring which may have a substituent. X ₂ represents an ion necessary for neutralizing the charge in the molecule, and m is 1 or 2 and when forming an intramolecular salt, m is 1. 2. At least one selected from the spectral sensitizing dyes represented by the above general formula [I] or [II] is dispersed in an aqueous solvent in which an organic solvent or a surfactant does not exist, and is substantially dispersed. water is added to the emulsion as a solid particle dispersion of the poorly soluble, and contains silver halide solvent is 0.05 g / m ² or more, and the emulsion layer of silver per support one side at 2.0 g / m ^2, the protective The total amount of gelatin in the hydrophilic layer including the layer is 1.5g to 3.5g
^2. The coating composition is applied in a range of / m ^2.
The described silver halide photographic light-sensitive material. 3. The silver halide photographic light-sensitive material according to claim 1 or 2, which contains at least one compound represented by the following general formula [III]. Embedded image In the formula, R ₈ represents an aliphatic group or an aromatic group in which at least one of —0H group, —SO ₃ M ¹ group, and —COOM ² group is substituted, and M ¹ ,
M ² and M ³ represent a hydrogen atom or an alkali metal atom. 4. The silver halide photographic light-sensitive material according to claim 1 or 2, which contains at least one compound represented by the following general formula [IV]. [Chemical 4] In the formula, Y represents a hydrogen atom, a lower alkyl group, a halogen atom or a SO ₃ M group, M represents a hydrogen atom, an alkali metal atom or an ammonium group, and n represents 0 or 1-2. 5. The silver halide photographic light-sensitive material is a medical silver halide photographic light-sensitive material.
5. The silver halide photographic light-sensitive material according to any one of items 1 to 4. 6. The method for processing a silver halide photographic light-sensitive material according to claim 5, wherein the total processing time is 30 seconds or less. 7. The method of processing a silver halide photographic light-sensitive material according to claim 6, wherein the iodide content in the fixing solution is 0.2 g / liter or less. 8. The replenishing amount of the fixing solution is 0 per 1 m ^{2 of the} light-sensitive material.
8. The processing method for a silver halide photographic light-sensitive material according to claim 7, wherein the processing time is 2 liters or less and the fixing time is 7 seconds or less.