JPH07281334A - Silver halide photographic emulsion, silver halide photographic sensitive material and its processing method - Google Patents

Abstract

PURPOSE:To enhance sensitivity and storage stability against the lapse of time and to reduce residual dye stuff stains by specifying the total iodine content of platelike silver halide grains. CONSTITUTION:The silver halide emulsion layer contains the platelike silver halide grains occupying >=70% of the projection areas of the total silver halide grains and having an average aspect ratio of >=2 and an average total iodine content of <=1.5mol%, and an average iodine content of <=10mol% in the uppermost layer of each grain, and the emulsion layer contains at least one of spectrally sensitizing dyes stuff represented by formula I and at least one of spectrally sensitizing dyes stuff represented by formula II and at least one of azaindene compounds in an amount of <=4.7X10<-3>mol per mol of silver. In formulae I and II, each of R1 and R3 is alkyl; each of R2 and R4 is lower alkyl; each of V1-V4 is H, halogen or the like; each of R5 and R6 is alkyl, alkenyl, or the like; R7 is H, alkenyl, or the like; each of Z1 and Z2 is a nonmetallic atomic group necessary to form a benzene ring or the like; and X2 is an ion.

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, little dye contamination, and excellent storage stability, and more particularly to a silver halide photographic light-sensitive material for X-ray medical treatment and its processing method. Is.

[0002]

BACKGROUND OF THE INVENTION In recent years, with respect to the development processing of silver halide photographic light-sensitive materials, it has been more and more desired to shorten the processing time and reduce the processing waste liquid. For example, in the medical field, regular health checkups, medical checkups, and the like have spread, The number of examinations including diagnoses in general medical care has rapidly increased, so that the number of X-ray photographs taken has increased, and there has been an increasing demand for ultra-fast development processing after photography and reduction of processing waste liquid.

However, in order to speed up the processing, it is necessary to shorten the processing time of each processing step such as developing, fixing, washing with water, and drying, but the load of each processing increases. For example, if the developing time is simply shortened, in the conventional light-sensitive material, the image density is lowered, that is, the sensitivity is lowered and the gradation is deteriorated. Further, if the fixing time is shortened, the fixing of silver halide becomes incomplete, which causes deterioration of image quality. Further, shortening the time of each processing step causes deterioration of image quality due to residual dye (residual color) because elution of the sensitizing dye in each processing of development, fixing and washing is not sufficient. Therefore, in order to solve such problems,
It is necessary to accelerate the developing speed and fixing speed, reduce the amount of dye, and accelerate the desorption and / or decolorization of the dye.

On the other hand, in order to reduce the waste liquid of the development processing, it is necessary to reduce the fatigue of the processing liquid and the replenishing liquid, but this is accompanied by the common problems with the speeding up.

Techniques for improving these problems include, for example, EP05.
No. 06584, JP-A-5-88293, JP-A-5-93975 and the like disclose techniques using benzimidazolocarbocyanines having good decolorization performance as spectral sensitizing dyes. In addition, JP-A-5-6
No. 1148 uses a silver halide emulsion having an iodine content of 1 mol% or less in combination with oxacarbocyanine and benzimidazolocarbocyanine as a spectral sensitizing dye at a specific ratio, and further uses a selenium compound and / or tellurium compound A technique for sensitizing is disclosed.

[0006] Although these disclosed techniques improve the color retention, they are still insufficient to meet the recent demand levels for various performances. In particular, it has a drawback in that it is not sufficiently high in sensitivity, and that the sensitivity is greatly reduced when the light-sensitive material is stored under high humidity and high temperature.

On the other hand, in order to shorten the development time, it is preferable to reduce the iodine content of the silver halide grains, especially the iodine content of the surface, but when the iodine content of the surface of the silver halide grains is reduced. It is known that the adsorptivity of the spectral sensitizing dye deteriorates, causing a problem that the sensitivity decreases during the production or storage of the light-sensitive material. On the contrary, increasing the iodine content on the surface has the advantage of increasing the adsorption of the spectral sensitizing dye, but it slows down the development speed and deteriorates the sensitivity and gradation at the development processing within a certain time, and leaves It is known that chromaticity deteriorates.

It is also known that pressure resistance is improved as a merit by increasing the iodine content on the surface of silver halide grains.

As described above, it is known that iodine contained in silver halide grains affects various photographic performances, and many techniques relating to iodine composition distribution have been disclosed in patents and scientific literatures. There is. For example, Japanese Patent Laid-Open No. 4-1074
No. 42 and the patents cited therein. However, the technologies disclosed so far cannot satisfy the recent demands for higher sensitivity, higher image quality, and ultra-fast development processing.

By the way, in recent years, an extremely large number of techniques for improving sensitivity and image quality using tabular silver halide grains have been disclosed, for example, JP-A Nos. 58-111935 and 58-111936,
No. 58-111937, No. 58-113927, No. 59-99433 and the like. Further, JP-A-63-92942 discloses a technique of providing a core having a high silver iodide content inside a tabular silver halide grain, and JP-A-63-151618 discloses a hexagonal tabular halide. The technique of using silver particles is disclosed and the effect of increasing the sensitivity is shown.

In addition to these, JP-A-63-106746, JP-A-1-183644, JP-A-1-279237 and the like disclose techniques relating to the composition distribution of tabular silver halide grains.

Regarding the crystal structure of tabular silver halide grains, some techniques regarding the shape of grains and parallel twin planes have been disclosed. For example, JP-A 1-131541 discloses the use of circular tabular grains. Techniques for improving sensitivity and graininess are disclosed.

Further, in Japanese Patent Laid-Open No. 63-163451, parallel 2
The ratio (b /) between the distance between twin planes (a) and the thickness (b) of a tabular silver halide grain having three or more twin planes.
A technique using particles in which a) is 5 or more is disclosed, and effects of increasing sensitivity and improving graininess are shown. Here, a technique for increasing the uniformity of the distance between twin planes among grains, as well as high sensitivity and improvement of graininess by the technique are described.

In WO91 / 18320, the distance between twin planes is 0.0.
A technique using tabular silver halide grains having a size of less than 12 μm is disclosed, and it is stated that high sensitivity can be achieved.

In EP515894A1, (particle size) / (thickness) 2
The tabularity represented by (3) achieves high sensitivity by setting the (111) plane ratio of the edge planes of tabular silver halide grains of 25 or more to less than 75%.

On the other hand, many techniques for improving the drawbacks of tabular silver halide grains have been disclosed. For example, Japanese Patent Laid-Open No. 3-1424
No. 39 discloses an emulsion in which tabular grains having an aspect ratio of 3 or more and having (111) faces and (100) faces occupy 50% or more of the projected area, and a technique for improving the storability at high humidity is disclosed. ing.

These tabular silver halide grains are hexahedral,
Compared with so-called normal crystal silver halide grains such as octahedron, it is possible to increase the adsorption amount of the spectral sensitizing dye on the grain surface because of the large surface area in the same volume, which results 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 sensitivity is not as high as expected, and as a drawback, the residual amount is increased as the developing process is accelerated. Contamination due to dyes, deterioration of image quality, etc. have become apparent as problems.

By the way, when various poorly water-soluble spectral sensitizing dyes are introduced into a silver halide emulsion, the spectral sensitizing dyes are dissolved in an organic solvent such as methanol and the solution is added to the silver halide emulsion. The method was generally widespread.
Further, instead of such a conventional method, the additive is dispersed and prepared as an aqueous solution system in the presence of a wetting agent or a dispersant without using an organic solvent, and the aqueous dispersion of the obtained additive is subjected to halogenation. A method of adding to a silver halide emulsion has been attempted.
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. After removing and drying, add it to the silver halide emulsion as it is, or
Alternatively, a method in which it is dispersed in water or an aqueous gelatin solution and then added to a silver halide emulsion is described.

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 it is made into noodles and dried with warm air 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 sensitizer is mixed with water to form a slurry, which is then homogenized or milled by raising the temperature to 40 to 50 ° C. in the presence of a surfactant to obtain a spectral spectrum. A method in which a sensitizing dye is uniformly dispersed in water and the resulting dispersion is added to a silver halide emulsion is described.

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 practical problems. .

That is, since the aqueous dispersion is pulverized by freeze-drying or the like, the time required for adsorption of additives such as a spectral sensitizer to the silver halide grains becomes long, so that the desired photographic sensitivity can be obtained within a short time. If the silver halide emulsion is not applied, coating failure due to precipitates and the like is likely to occur when the silver halide emulsion is applied. 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 silver halide emulsion, or a film may not be formed. There was also a problem in terms of product quality due to a failure that deteriorates the product.

[0024]

SUMMARY OF THE INVENTION Therefore, the first object of the present invention is to provide a light-sensitive tabular silver halide emulsion having high sensitivity, little residual color, and excellent storability, and a halogen using the same. A silver halide photographic light-sensitive material is provided.

The second object of the present invention is to provide a medical silver halide photographic light-sensitive material containing a light-sensitive silver halide emulsion composed of tabular silver halide grains having the above-mentioned properties and a processing method thereof. Is.

[0026]

The above problems have been solved by the present invention described below. That is, (1) at least 70% of the total projected area of silver halide grains contained in the silver halide emulsion layer has an average aspect ratio of 2
The above tabular silver halide grains having an average total iodine content of the tabular silver halide grains of 1.5 mol%
The average iodine content of the outermost layer of the grains is 10 mol% or less, and is represented by at least one spectral sensitizing dye represented by the following general formula (I) and the following general formula (II). It contains at least one spectral sensitizing dye and is 4.7 per mol of silver.
A silver halide photographic emulsion characterized by containing at least one azaindene compound in an amount of × 10 ^-3 mol or less.

[0027]

[Chemical 3]

(In the formula, R ₁ and R ₃ each represent a substituted or unsubstituted alkyl group, R ₂ and R ₄ represent a lower alkyl group. At least one of R ₂ and R ₄ is a hydrophilic group. V ₁ , V ₂ , V ₃ and V ₄ represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, a trifluoromethyl group, a cyano group, a carboxy group, an alkoxycarbonyl group, It represents an acyl group, a sulfonyl group, a carbamoyl group, a sulfamoyl group, an acetylamino group or an acetyloxy group, and is V ₁ , V ₂ , V _{3 or} V _4.
Do not become hydrogen atoms at the same time. X ₁ represents an ion necessary for neutralizing the charge in the molecule, and n represents 1 or 2. However, n is 1 when forming an intramolecular salt. )

[0029]

[Chemical 4]

(Wherein 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. Z ₁ and Z ₂ each represent a nonmetallic atom group necessary for completing a benzene ring or a naphtho ring which may have a substituent. X ₂ represents an ion necessary for neutralizing the charge in the molecule, and m represents 1 or 2. However, m is 1 when forming an intramolecular salt. (2) At least one of the spectral sensitizing dyes represented by the above general formulas (I) and (II) is dispersed in a water system in which an organic solvent or a surfactant does not substantially exist, and is substantially dispersed. The silver halide photographic emulsion according to item (1), which is added as a dispersion of solid fine particles hardly soluble in water. (3) The average iodine content of the outermost layer of tabular silver halide grains having an average aspect ratio of 2 or more is 2 mol% or more and 8 mol% or more.
A silver halide photographic light-sensitive material comprising the silver halide photographic emulsion described in the items (1) and (2) below.

(4) The iodine in the outermost layer of tabular silver halide grains having an average aspect ratio of 2 or more is imparted during the chemical ripening step in the presence of a chemical sensitizer (1) to
A silver halide photographic emulsion as described in the item (3).

(5) The tabular silver halide grains having an average aspect ratio of 2 or more contain at least one of the spectral sensitizing dyes represented by the general formula (I) and the spectral sensitization represented by the general formula (II). The silver halide photographic emulsion as described in (1) to (4), which is chemically sensitized in the presence of at least one dye.

(6) Dispersing at least one of the spectral sensitizing dyes represented by the above general formulas (I) and (II) in an aqueous system in which substantially no organic solvent or surfactant is present. The spectral sensitizing dye is added to the silver halide grains so that it is added as a solid fine particle dispersion which is substantially insoluble in water, and a J-band characteristic at 520 to 560 nm is formed when the reflection spectrum is measured. Is adsorbed (2) ~
A silver halide photographic emulsion as described in the item (5). (7) The silver halide photographic emulsion as described in (2) to (6), wherein the tabular silver halide grains having an average aspect ratio of 2 or more have an average total iodine content of 0.5 mol% or less.

(8) At least one kind of azaindene compound contained in the silver halide emulsion layer and / or the non-photosensitive layer is 1.7 × 10 ^-4 mol / m ² or less per one side of the photosensitive material. A silver halide photographic light-sensitive material containing the silver halide photographic emulsion according to (2) to (7).

(9) The method for processing a silver halide photographic light-sensitive material according to the item (8), wherein the total processing time by the automatic processor is 15 to 45 seconds.

The present invention will be described in detail below.

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 R ₁ and R ₃ of the general formula (I),
Examples of the substituted alkyl group include groups such as hydroxymethyl, ethoxycarbonylethyl, ethoxycarbonylmethyl, allyl, benzyl, phenethyl, methoxyethyl, methanesulfonylaminoethyl and 3-oxobutyl, and the unsubstituted alkyl group, Examples thereof include lower alkyl groups such as methyl, ethyl, propyl and butyl. It is preferable that at least one of R ₁ and R ₃ has a group other than an ethyl group.

Examples of the lower alkyl group represented by R ₂ and R ₄ include groups such as methyl, ethyl, butyl and trifluoroethyl, and examples of the alkyl group substituted with a hydrophilic group include carboxymethyl and carboxyethyl. ,
Methanesulfonylaminoethyl, sulfobutyl, sulfoethyl, sulfopropyl, sulfopentyl, 6-sulfo-3
-Oxahexyl, 4-sulfo-3-oxapentyl, 10-sulfo-3,6-dioxadecyl, 6-sulfo-3-thiahexyl,
Examples thereof include groups such as o-sulfobenzyl and p-carboxybenzyl.

The substituent represented by V ₁ , V ₂ , V ₃ and V ₄ is, for example, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), an alkyl group (methyl, ethyl, t-). Groups such as butyl), alkoxy groups (methoxy groups), alkylthio groups (methylthio groups), trifluoromethyl groups,
Cyano group, carboxy group, alkoxycarbonyl group (methoxycarbonyl, ethoxycarbonyl group, etc.), acyl group (acetyl group), sulfonyl group (methanesulfonyl group),
Carbamoyl group (carbamoyl, N, N-dimethylcarbamoyl, N-morpholinocarbonyl group, etc.), sulfamoyl group
(Sulfamoyl, N, N-dimethylsulfamoyl group, etc.),
Examples thereof include acetylamino group and acetyloxy group.

The ion necessary for neutralizing the charge in the molecule represented by X ₁ may be either an anion or a cation, and the anion is, for example, a halogen ion.
(Ions such as chlorine, bromine, iodine), perchlorate,
There are ethylsulfate, thiocyanate, p-toluenesulfonate, perfluoroborate and the like, and as the cation, for example, hydrogen ion, alkali metal ion (ion such as lithium, sodium and potassium), alkaline earth metal ion (magnesium, calcium etc.). Ion), ammonium ion, organic ammonium ion (ion such as triethylammonium, triethanolammonium, and tetramethylammonium).

Next, the above-mentioned general formula (I) used in the present invention is used.
Specific examples of the spectral sensitizing dye represented by

[0044]

[Table 1]

[0045]

[Table 2]

As the dye represented by the general formula (I) of the present invention, in addition to the above specific examples, for example, the compound examples II-3 and II-4 described in JP-A No. 4-9040 can be used. , II-6, II-
7, II-8, II-10, II-13, II-14, II-16, II-17, II-1
8, II-20, II-21, II-24 to II-44 and the like can be similarly used.

The spectral sensitizing dye represented by the above general formula (I) according to the present invention includes, for example, British Patents 521,165 and 745,546.
No., Belgium Patent 615,549, Soviet Patent 412,218
No. 432,166, etc., Japanese Patent Publication No. 38-7828, No. 42
-27165, 42-27166, 43-13823, 43-14497
No., No. 44-2530, No. 45-27676, No. 45-32740, etc., according to the method described in Harmer's Cyanine Dried Related Compounds (Jhon Wiley & Sons, New York, 1964), etc. Can be synthesized.

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, a substituted or unsubstituted Of the 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. Z ₁ and Z ₂ each represent a non-metal 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 when forming an intramolecular salt, m
Is 1.

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. Furthermore, examples of the aryl group represented by R ₅ and R ₆ include phenyl and carboxyphenyl groups.

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

Examples of the ion represented by X ₂ in the general formula (II) include chlorine ion, bromine ion, iodine ion, thiocyanate ion, sulfate ion, perchlorate ion, p-toluenesulfonate ion, Examples thereof include ethylsulfate ion, sodium ion, potassium ion, magnesium ion and triethylammonium ion.

R ₇ represents a hydrogen atom, a lower alkyl group or an aryl group, and examples of the lower alkyl group include groups such as methyl, ethyl, propyl and butyl. Examples of the aryl group include a phenyl group.

Z ₁ and Z ₂ represent a group of non-metal atoms necessary for completing a substituted or unsubstituted benzene ring. 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

[0056]

[Chemical 5]

[0057]

[Chemical 6]

The sensitizing dye represented by the above general formula (II) used in the present invention is "Heterocycrlic compoun" by FM Hamer.
ds Cyaninedyes and related compounds ”(Heterocyclic Compounds-Cyanine Dyes and Relayed Compounds) IV.V.VI, Chapter 89-199
Wiley & Sons (New York, London) 1964, or D.
M. Sturmer “Heterocycrlic compounds special topi
cs in Heterocycrlicchemistry ”(Heterocyclic Compounds-Special Topics in Heterocyclic Chemistry) Chapter VIII IV.482-515 John W
It can be easily synthesized based on the method described in iley & Sons (New York, London), 1977, etc.

It should be noted that each of the above general formulas (I) and (II) merely shows one state of the resonance structure, and even if it is expressed in the limit state where the + charge enters the symmetrical heterocyclic nitrogen atom. It means the same substance.

The combined use technique of 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 the application to an X-ray recording material using a phosphor that emits green light in order to increase the recording sensitivity to X-rays, and is particularly effective in a light-sensitive material for X-ray medical treatment.

When applied to an X-ray medical light-sensitive material using a fluorescent substance that 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, J that is usually peculiar to 520 nm to 560 nm region
-It is preferable to select and combine the spectral sensitizing dyes so that a band is formed.

The amount of the spectral sensitizing dyes of the general formulas (I) and (II) in the present invention to be added varies depending on the kind of the dye and the structure, composition, ripening condition, purpose, use of the silver halide, The surface coverage of each photosensitive particle in the silver emulsion is preferably 40% or more and 100% or less, and more preferably 50% to 80%.

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 appropriate 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 a 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,
Examples include 3-propanediol, acetone, acetonitrile, 2-methoxyethanol and 2-ethoxyethanol.

Surfactants have conventionally been 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 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 spectral sensitizing dye is added in the form of a solid fine particle dispersion that is substantially water-insoluble and is dispersed in a water 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 is made to uniformly and effectively adsorb the photographic photosensitizing dye to 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, substantially organic solvent and / or
Alternatively, the aqueous system in which no surfactant is present is water containing impurities at a level that does not adversely affect the silver halide photographic emulsion, and more preferably ion-exchanged water and 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.

If the solubility is lower than this range, the dispersion particle size becomes very large and non-uniform, so that a precipitate of the dispersion may be formed after the dispersion is completed, or when the dispersion is added to the silver halide emulsion. It may interfere with the adsorption process of the dye to the 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 entrained 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, 30 ml of ion-exchanged water was placed in a 50 ml Erlenmeyer flask, and an amount of dye which was not completely dissolved by visual observation was added to it.
The temperature was maintained at 27 ° C in a constant temperature bath, and stirring was performed for 10 minutes with a magnetic stirrer. The suspension is filter paper No. 2 (manufactured by Toyo Corporation)
Filter with a disposable filter (Tosoh
(Manufactured by Hitachi, Ltd.), the filtrate was diluted appropriately, and the absorbance was measured by a spectrophotometer U-3410 (manufactured by Hitachi Ltd.). Next, based on this measurement result, the dissolved concentration was determined according to the Lambert-Beer law, and the solubility was further 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 addition of the spectral sensitizing dye according to the present invention can be carried out during the chemical ripening step, particularly preferably at the start of the chemical ripening step, and the desalting can be carried out from the nucleation step of the silver halide emulsion according to the present invention. A high-sensitivity silver halide emulsion excellent in spectral sensitization efficiency can be obtained by adding it by the end of the process, and the above-mentioned process can be carried out at any time after the completion of the desalting process, through the chemical ripening process, and immediately before the coating process. The spectral sensitizing dye according to the present invention, which is the same as or different from the dye added in the step (from the nucleation step to the end of the desalting step), 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 cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar 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 aliphatic hydrocarbon ring is fused to these nuclei, that is, India. A renin nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms.

The merocyanine dye or the complex merocyanine dye has pyrazoline-5 as a nucleus having a ketomethine structure.
-One nucleus, thiohydantoin nucleus, 2-thiooxazolidine-
A 5- or 6-membered heterocyclic nucleus such as a 2,4-dione nucleus, a thiazoline-2,4-dione nucleus, a rhodanine nucleus or a 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 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.

The selenium sensitizers used in the chemical sensitization of the present invention include a wide variety of selenium compounds. For example, in this regard, U.S. Patents 1,574,944, 1,602,592, 1,
623,499, JP-A-60-150046, JP-A-4-25832, and JP-A-4-5832
-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 '
-Heptafluoropropylcarbonyl selenourea, N, N,
N'-trimethyl-N'-4-nitrophenylcarbonyl selenoureas, 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, triphenylphosphine selenide, etc.). Particularly preferred selenium sensitizers are selenoureas, selenoamides, and selenium ketones.

Specific examples of the technique of using these selenium sensitizers are disclosed in the following patent specifications. That is, US Patent 1,
574,944, 1,602,592, 1,623,499, 3,297,4
No. 46, No. 3,297,447, No. 3,320,069, No. 3,408,196
No. 3,408,197, 3,442,653, 3,420,670,
No. 3,591,385, French Patent No. 2693038, No. 2093209
No. 52-34491, 52-34492, 53-295, 53-295
57-22090, JP-A-59-180536, 59-185330, 59
-181337, 59-187338, 59-192241, 60-1500
46, 60-151637, 61-246738, JP 3-4221
No. 3, No. 3-24537, No. 3-111838, No. 3-116132, No. 3-1
48648, 3-237450, 4-16838, 4-25832,
4-32831, 4-96059, 4-109240, 4-140738
No. 4-140739, 4-147250, 4-149437, 4-
184331, 4-190225, 4-191729, 4-195035
No., British Patent Nos. 255846 and 861984. HE Spence
r et al., Journal of Photographic Science, 31, 158
~ 169 (1983) and other scientific literatures.

The amount of the selenium sensitizer used varies depending on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but generally about 10 ^-8 mol to 10 ^-4 mol per mol of silver halide is used. In addition, the addition method may be a method of adding it by dissolving it in water or an organic solvent such as methanol, ethanol, and ethyl acetate alone or in a mixed solvent depending on the properties of the selenium compound to be used, or by previously mixing with a gelatin solution. Or the method 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.

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 80
It is below ℃. The pH is preferably in the range of 4 to 9 and the pAg is preferably in the range of 6 to 9.5.

Regarding the tellurium sensitizers and sensitization methods used in the chemical sensitization of the present invention, US Pat.
Issue 3,320,069, Issue 3,772,031, Issue 3,531,289,
No. 3,655,394, British Patent No. 235,211, No. 1,121,496
No. 1,295,462, No. 1,396,696, Canadian Patent No. 800,
No. 958, JP-A-4-204640, and JP-A-4-333043. Examples of useful tellurium sensitizers include telluroureas (e.g., N, N-dimethyl tellurourea, tetramethyl tellurourea, N-carboxyethyl-N, N'-dimethyl tellurourea, N, N'-dimethyl. -N'phenyl tellurourea), phosphine tellurides (eg, tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride), telluroamides (eg, , Telluroacetamide, N, N-dimethyl tellurobenzamide), telluroketones, telluroesters, isotellocyanates, and the like.

The technique for using the tellurium sensitizer is in accordance with the technique for using the selenium sensitizer.

In the present invention, it is also preferable to use reduction sensitization together. The reduction sensitization is preferably performed during the growth of silver halide grains. As a method of applying during the growth, not only a method of performing reduction sensitization while the silver halide grains are growing, but also a method of performing reduction sensitization while the growth of the silver halide grains is interrupted and then performing the reduction sensitization Also included are methods of growing the perceived silver halide grains.

In the present invention, the sensitization can be carried out 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 2,278,
947, 2,728,668, 3,501,313, 3,656,955
No. 1, West German Application Publication (OLS) 1,422,869, JP-A-56-24937
The sulfur sensitizers described in JP-A No. 55-45016 and the like can be used. Specific examples thereof include thiourea derivatives such as 1,3-diphenylthiourea, triethylthiourea, 1-ethyl, 3- (2-thiazolyl) thiourea, rhodanine derivatives, dithiacarbamic acids, polysulfide organic compounds, and 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.

Examples of gold sensitizers include chloroauric acid, gold thiosulfate, and gold thiocyanate, as well as gold complexes of thioureas, rhodanines, and various other compounds.

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

In the present invention, 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. Using a medium like gelatin,
You may add in the form of the dispersion obtained by emulsifying and dispersing.

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, after the sulfur sensitization is appropriately applied,
Alternatively, gold sensitization may be performed in the middle to obtain preferable results.

The reduction sensitization carried out in the present invention is carried out during the growth of silver halide grains of a silver halide emulsion.
It is carried out by adding a reducing agent and / or a water-soluble silver salt to the silver halide emulsion.

Preferred examples of the reducing agent include thiourea dioxide and ascorbic acid and their derivatives. Another preferred reducing agent is hydrazine,
Examples thereof include polyamines such as diethylenetriamine, dimethylamineboranes, and sulfites.

The amount of the reducing agent added 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,
Although it is preferable to change the pH depending on the environmental conditions such as pH 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 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.

Silver nitrate is preferred 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 to 6, preferably 2 to 4. The conditions such as temperature, pH and time are preferably within the above-mentioned reduction sensitization condition range. As the stabilizer of the silver halide photographic emulsion containing the silver halide grains subjected to the reduction sensitization method according to the present invention, a general stabilizer described below can be used, but it is described in JP-A-57-82831. Disclosed antioxidants and / or VS Gahler's article “Zeitshrift fur wissenschaftliche Photographie B
d.63, 133 (1969) ”and the thiosulfonic acids described in JP-A-54-1019 are often used in combination, and good results are often obtained. It may be added at any step in the emulsion manufacturing process up to the immediately preceding step.

As the silver halide grains of the silver halide emulsion used in the present invention, silver halide grains such as silver iodobromide, silver iodochloride, silver chloroiodobromide and the like can be optionally used. Silver halide and silver chloroiodobromide are preferred.

The silver halide grains contained in the silver halide emulsion of the present invention may have any shape. However, at least one emulsion is an emulsion mainly containing tabular grains having an average aspect ratio of 2.0 or more.

Tabular grains will be described below as typical examples of the silver halide grains preferably used in the present invention.

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 have an average aspect ratio of preferably 2 or more and 12 or less, and more preferably 3 to 8.

The outer wall of the crystal of the tabular silver halide grain according to the present invention may be substantially composed of {111} planes or {100} planes. 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. It is preferable that the planes other than the {111} plane are mainly the {100} plane. This plane ratio is {111} plane and {100} plane in the adsorption of sensitizing dye.
Utilizing the difference in adsorption dependence with the surface [T. Tani, J. Imaging
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 = width of particle size distribution
When the width of the distribution is defined by the relative standard deviation (coefficient of variation) that can be expressed by (%), it is preferably 25% or less, more preferably 20% or less, and particularly preferably 15% or less.

The tabular silver halide grains of the present invention preferably have a small thickness distribution. Specifically, (standard deviation of thickness / average thickness) x 100 = width of thickness distribution
When the breadth of distribution is defined by (%), it is preferably 25% or less, more preferably 20% or less, and particularly preferably 15% or less.

Further, it is preferable that the distribution of the halogen content of each grain in the tabular silver halide grain emulsion of the present invention is also small. Specifically, (standard deviation of halogen content / average halogen content) x 10
0 = 25% or less is preferable when the breadth of the halogen content is defined by the breadth (%) of the halogen content, more preferably 20% or less, and particularly preferably 15% or less.

In the present invention, the tabular silver halide grains are preferably hexagonal. Hexagonal tabular grains
(Hereinafter also referred to as hexagonal tabular grains) means its main plane ({111}
The shape of (face) is hexagonal, and the maximum adjacency ratio is 1.0 to 2.
Say it is 0. Here, the maximum adjacent side ratio is the ratio of the length of the side having the maximum length to the length of the side having the minimum length forming a hexagon. In the present invention, it is also preferable that the hexagonal tabular grains have rounded corners if the maximum adjacent side ratio is 1.0 to 2.0. The length of a side when the corner is rounded is represented by the distance between the straight line portion of the side and the intersection with the line obtained by extending the straight line portion of the adjacent side. Further, it is also preferable that the tabular grains are more rounded and have a substantially circular shape.

In the present invention, each side forming the hexagon of the hexagonal tabular grain preferably has at least ½ thereof substantially a straight line. In the present invention, the ratio of adjacent sides is 1.0
More preferably, it is ˜1.5.

The silver halide grain according to the present invention may have dislocations. The rearrangement is, for example, JF Hamilton, Phot.S.
ci.Eng, 57 (1967), T.Shiozawa, J.Soc.Phot.Sci.Jap
It can be observed by a direct method using a transmission electron microscope at low temperature described in an, 35, 213 (1972). That is, the silver halide grains, which were taken out carefully so as not to apply pressure enough to cause dislocation to the grains from the emulsion, were placed on the mesh for electron microscope observation, and the sample was taken to prevent damage (printout etc.) due to electron beams. In the cooled state, observation is performed by the transmission method. At this time, the thicker the particles, the more difficult it is for the electron beam to penetrate, so it is possible to observe more clearly by using a high-pressure electron microscope (200 KV or more for particles having a thickness of 0.25 μm). .

The position and number of dislocations in each grain can be determined from the photograph of the grain obtained by such a method. The dislocation position of the silver halide grain according to the present invention is 0.58 L from the center of the silver halide grain toward the outer surface.
It is desirable that it occurs in the area up to 1.0L,
More preferably, it is generated in the region of 0.80L to 0.98L. The direction of the dislocation line is approximately from the center to the outer surface, but it often meanders.

In the present invention, the center of a silver halide grain means that silver halide microcrystals are dispersed in a methacrylic resin in the same manner as the method described in the summary of Inoue et al. When solidified and made into an ultrathin section with a microtome, and focusing on the section sample with the maximum cross-sectional area and the cross-sectional area of 90% or more than that, when drawing the minimum circumscribed circle to the cross section Is the center of the circle. In the present invention, the distance L from the center to the outer surface is defined as the distance between the center of the circle and the point intersecting the outer circumference of the particle when a straight line is drawn outward from the center of the circle.

With respect to the number of dislocations in the silver halide grains according to the present invention, it is desirable that 50% (number) or more of grains containing one or more dislocations are present, and the ratio of the number of tabular grains having dislocation lines (number) ) Is higher, the more preferable.

In the present invention, the particle size is the diameter when the projected image of the particles is converted into a circular image having the same area. The projected area of a grain can be calculated from the sum of the grain areas. All of them can be obtained by observing, with an electron microscope, a silver halide crystal sample distributed on the sample stage to the extent that grains do not overlap.

The average projected area diameter of the tabular silver halide grains in the present invention is represented by the diameter corresponding to the circle of the projected area of the grains, and is preferably 0.30 μm or more, more preferably
It is 0.30 μm to 5 μm, more preferably 0.40 μm to 2 μm.

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

The average particle diameter (φi) can be calculated by the following equation, where n is the number of measured particle diameters and ni is the frequency of particles having the particle diameter φi.

Average particle diameter (φi) = Σn idi / n (The number of measured particles is indiscriminately 1,000 or more.) The particle thickness can be obtained by observing the sample obliquely with an electron microscope. . The preferred thickness of the tabular grains of the present invention is 0.03-1.0 μm, more preferably
It is 0.05 to 0.5 μm.

The longest distance (a) between two or more parallel twin planes of the silver halide grain of the present invention and the grain thickness (b).
The ratio (b / a) is preferably 5 or more, and the ratio is preferably 50% (number) or more.

The twin plane distance (a) can be obtained as follows. That is, observation of the section using the above transmission electron microscope, with respect to the main plane, arbitrarily select 100 or more tabular silver halide grains showing a cross section cut substantially perpendicularly, for each grain ( It can be obtained by measuring a) and averaging them.

In the present invention, the average value of (a) is 0.008 μm.
Or more, but more preferably 0.010 μm or more,
It is 0.05 μm or less.

Further, in the present invention, it is necessary that (a) is within the above value range, and at the same time, its variation coefficient is 35% or less, preferably 30% or less.

Further, in the present invention, tabularity expressed by the following equation: A in consideration of factors of aspect ratio and grain thickness: A
= ECD / b ² is preferably 20 or more.

Here, ECD is the average projected diameter of tabular grains.
(b) is the thickness of the particles. Here, the average projected diameter represents the number average of diameters of circles having an area equal to the projected area of tabular grains.

Among the silver halide emulsions used in the light-sensitive material of the present invention, the average iodine of the whole grains including tabular silver halide grains having an average aspect ratio of 2.0 or more including the outermost surface of the grains. The content must be 1.5 mol% or less, preferably 1.0% or less, and more preferably 0.5 mol% or less.

The average iodine content of the outermost surface of the emulsion of tabular silver halide grains having an average aspect ratio of 2.0 or more according to the present invention is 10 mol% or less, preferably 2 mol% or more 8 It is not more than mol%. The iodine content of the outermost surface is preferably higher than that of the layer inside the outermost surface. Further, it is preferable that the distribution of the iodine content on the outermost surface of each particle is narrow, and the variation coefficient of the distribution is preferably 25% or less, particularly 20% or less.

As a method of adjusting the iodine content of the outermost surface of the tabular silver halide grains, a method of simultaneously adding a silver nitrate solution and a solution containing iodine ions to an emulsion containing tabular grains as a base, Method of adding fine silver halide grains such as silver iodide, silver iodobromide or silver chloroiodobromide, method of adding potassium iodide or a mixture of potassium iodide and potassium bromide, 2-iodoethanol, p- Sodium iodoacetamide benzene sulfonate etc.
The iodo ion releasing agent disclosed in Japanese Patent No. 782 can be applied. Among these, a preferred method is a method of adding fine silver halide grains and the above-mentioned iodine ion-releasing organic compound. Especially preferred is the addition of fine silver iodide grains.

The time for adjusting the iodine content on the outermost surface is between the final step of the silver halide crystal production step, the chemical ripening step, and the end of the solution preparation step immediately before the coating of the silver halide emulsion. It can be selected, but it is preferable to adjust it by the end of the chemical ripening step. The term "chemical ripening step" as used herein refers to a point from the time when physical ripening and desalting operations of the silver halide emulsion of the present invention are completed, to the time when a chemical sensitizer is added and then the operation for stopping the chemical ripening is performed. Up to. Further, the addition of silver halide fine grains may be carried out several times with a time interval, or another chemically ripened emulsion may be added after the addition of the fine grains. The temperature of the emulsion of the present invention when adding silver halide fine grains is
The range of 30 to 80 ° C is preferable, and the range of 40 to 65 ° C is particularly preferable. Further, the present invention is preferably carried out under the condition that the silver halide fine particles to be added are partially or wholly disappeared after the addition and immediately before coating. More preferable condition is that of the added silver halide fine particles. 20% or more has disappeared just before coating.

The iodine content on the outermost surface of the tabular silver halide grains according to the present invention was determined as follows.

In the emulsion, 0.1% of proteolytic enzyme (pronase) was added.
A 05 wt% aqueous solution was added, and the mixture was stirred at 45 ° C for 30 minutes to decompose gelatin. This is centrifuged to settle the emulsion particles,
Remove the supernatant. Next, distilled water is added to disperse the emulsion particles in distilled water, and the mixture is centrifuged to remove the supernatant. Further, the emulsion particles are redispersed in water and thinly coated on a mirror-polished silicon wafer to obtain a measurement sample. Surface silver iodide measurement by XPS was performed using the sample thus prepared.

In order to prevent the destruction of the sample due to X-ray irradiation, the sample was cooled to -110 to -120 ° C in the XPS measurement chamber. MgKα as X-ray for probe, X-ray source voltage 15kV,
It was irradiated with an X-ray source current of 40 mA and measured for Ag3d5 / 2, Br3d, and I3d3 / 2 electrons. The integrated intensity of the measured peak was corrected by a sensitivity factor (Sensitivity Factor), and the halide composition of the outermost surface was determined from the intensity ratio of these.

The iodine content of each particle is EPMA (El
ectron-Probe Micro Analyzer) method. The coefficient of variation of the iodine content of each particle is determined in the same manner as the coefficient of variation of the various characteristic values described above. That is, the iodine content of at least 100 particles is measured by the EPMA method, and the value obtained by dividing the standard deviation by the average iodine content is multiplied by 100.

The tabular silver halide grain used in the present invention may have a uniform composition in the portion other than the outermost surface of the grain, but at least two grains having substantially different halogen compositions are contained in the silver halide grain. Grains having a core / shell structure having a layered structure are contained in the photosensitive silver halide emulsion layer in number.
It is preferable to contain 50% or more.

The core / shell type structured particles may have a halogen composition region different from that of the core in the center part of the particles. 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 silver iodide content of the silver halide emulsion according to the present invention is preferably 1.5 mol% or less, more preferably 0.01 to 1.0 mol%. In the grains having a layer structure having different halogen compositions, a high silver iodide layer is formed inside the grain.
Grains having a low silver iodide layer or a silver bromide layer in the surface layer (shell layer) are preferable. At this time, the silver iodide content of the inner layer (core) having the highest silver iodide content is preferably 2.5 mol% or more, more preferably 5 mol% or more, and the iodide of the surface layer (shell layer) is The silver content is 0 to 5 mol%, preferably 0.
It is preferable that the silver iodide content of the core is at least 3 mol% or more than the silver iodide content of the shell.

The silver iodide distribution in 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
So-called halogen conversion type particles may be used. The amount of halogen conversion is preferably 0.2 mol% to 2.0 mol% with respect to the amount of silver, and the conversion time may be physical ripening or after physical ripening.

As a method of converting halogen, an aqueous solution of halogen or silver halide fine particles having a solubility product with silver smaller than the halogen composition on the surface of the grain before halogen conversion is usually added. The fine particle size at this time is preferably 0.2 μm or less, more preferably 0.02 to 0.1 μm. The silver halide grains of the present invention are preferably grown by a method of precipitating silver halide on a seed crystal such as the method described in Examples of JP-A-60-138538. A water-soluble silver salt may be added for the purpose of controlling ripening during the seed grain forming step according to the present invention. The seed grain growing process for enlarging the silver halide seed grains is carried out during the precipitation of silver halide.
It is achieved by controlling the pAg, pH, temperature, concentration of silver halide solvent and silver halide composition, addition rate of silver salt and halide solutions during Ostwald ripening. 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, a water-soluble silver salt solution and a water-soluble halide solution are added by the double jet method, and the addition rate is adjusted according to the enlargement of particles to form new nuclei. You may use the method of changing gradually in the range which does not occur and 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 iodine can also be supplied to the system as silver iodide. The addition rate is preferably such that new nuclei are not generated, and there is no spread of the size distribution due to Ostwald ripening, that is, in the range of 30 to 100% of the rate at which new nuclei are generated.

In producing the silver halide emulsion of the present invention, 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 400 to 120.
It is preferably 0 rpm.

The silver iodide content and average silver iodide content of the silver halide grains of the present invention are measured by the EPMA method (Electron Probe
It can be obtained by using Micro Analyzer). 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 iodine 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 to each other, 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 thickness of the seed grains or only of (at) is 35% or less, it is possible to suppress the variation coefficient of the twin plane distance (a) of the grown grains to 35% or less. It is not possible, and it is necessary for both to be established 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, in the process of forming and / or growing the grain, cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (including complex salt), 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 inside the particles and / or in the surface layer of the particles. The reduction sensitizing nuclei can be imparted 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 grain 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 adding 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 of the silver halide photographic light-sensitive material according to the present invention, unnecessary soluble salts may be removed at the end of the growth of silver halide grains, or may be left contained. The salts can be removed by the method described in Research Disclosure (hereinafter abbreviated as RD) No. 17643 No. II.

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

As the azaindenes used in the present invention, for example, hydroxytriazaindene, hydroxytetraazaindene, hydroxypentaazaindene and the like are preferable. The heterocycle of azaindenes may have a substituent other than a hydroxy group. For example, an alkyl group,
Substituted alkyl group, alkylthio group, amino group, hydroxyamino group, alkylamino group, dialkylamino group,
It may have an arylamino group, a carboxy group, an alkoxycarbonyl group, a mercapto group, a cyano group, a halogen atom and the like.

Specific examples are listed below, but the present invention is not limited to these.

(1) 2,4-dihydroxy-6-methyl-1,3a, 7-
Triazaindene (2) 2,5-Dimethyl-7-hydroxy-1,4,7a-triazaindene (3) 5-Amino-7-hydroxy-2-methyl-1,4,7a-triazaindene ( 4) 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (5) 4-hydroxy-1,3,3a, 7-tetrazaindene (6) 4-hydroxy-6-phenyl 1 , 3,3a, 7-Tetrazaindene (7) 4-methyl-6-hydroxy-1,3,3a, 7-tetrazaindene (8) 2,6-dimethyl-4-hydroxy-1,3,3a , 7-Tetrazaindene (9) 4-hydroxy-5-ethyl-6-methyl-1,3,3a, 7-tetrazaindene (10) 2,6-dimethyl-4-hydroxy-5-ethyl 1, 3,3a, 7-Tetrazaindene (11) 4-hydroxy-5,6-dimethyl-1,3,3a, 7-tetrazaindene (12) 2,5,6-trimethyl-4-hydroxy-6- Phenyl-1,3,3
a, 7-Tetrazaindene (13) 2-Methyl-4-hydroxy-6-phenyl-1,3,3a, 7-tetrazaindene (14) 4,6-Dihydroxy-5-amino, iminomethylthio-1 ,
3,3a, 7-Tetrazaindene (15) 4-hydroxy-6-methyl-1,2,3a, 7-tetrazaindene (16) 4-hydroxy-6-ethyl-1,2,3a, 7- Tetrazaindene (17) 4-Hydroxy-6-phenyl-1,2,3a, 7-tetrazaindene (18) 4-Hydroxy-1,2,3a, 7-tetrazaindene (19) 4-methyl- 6-Hydroxy-1,2,3a, 7-tetrazaindene (20) 7-hydroxy-5-methyl-1,2,3,4,6-pentazaindene (21) 5-hydroxy-7-methyl- 1,2,3,4,6-Pentazaindene (22) 5,7-dihydroxy-1,2,3,4,6-pentazaindene (23) 7-hydroxy-5-methyl-2-phenyl- 1,2,3,4,6-pentazaindene (24) 5-dimethylamino-7-hydroxy-2-phenyl-1,2,
3,4,6-Pentazaindene The amount of azaindenes contained in the silver halide emulsion of the present invention is 4.7 × 10 ⁻³ mol or less, preferably 1.5 × 10 ⁻⁴ mol or more, per mol of silver. , 3.0 × 10 ⁻³ mol or less, more preferably 3.0 × 10 ⁻⁴ mol or more and 2.3 × 10 ⁻³ mol or less. In the silver halide photographic light-sensitive material of the present invention, the amount of the azaindene added may be 1.7 × 10 ⁻⁴ mol / m ² or less per side of the light-sensitive material depending on the amount of the compound added and the coating conditions. adjust. It is preferably 1.2 × 10 ⁻⁴ mol / m ² or less.

The azaindene can be added to the emulsion as a solution by dissolving it in a suitable solvent (for example, water or an aqueous alkali solution) that does not adversely affect the photographic emulsion. Further, it can be added in the form of solid fine particles.

When the azaindenes are added to the silver halide emulsion, they may be added before starting the chemical sensitization step.
Although it may be performed at any time during or after the completion, a preferable performance is often obtained by adding a part of it as a control agent for the chemical sensitization step before adding the chemical sensitizer after adding the spectral sensitizer. Further, the timing of addition of the balance is preferably at the end of the chemical sensitization step or immediately before the coating step. It is preferable that a part of azaindene is contained in a non-photosensitive layer of a photographic light-sensitive material, for example, a protective layer.

The effect of the present invention is that the amount of azaindenes contained in the light-sensitive material of the present invention is 1.7 × 1 per mol of silver.
It is preferably expressed when it is 0 ^-4 mol / m ² or less.

In addition to the above-mentioned azaindenes, JP-A-5-
The light-sensitive material of the present invention may contain a polymer compound containing a repeating unit having a residue of azaindenes disclosed in Japanese Patent No. 333465.

Latex can be used in the silver halide photographic light-sensitive material of the present invention. The latex is preferably one which has no or very little adverse effect in the following points even when used in a silver halide photographic element. That is, it is preferable that the latex surface is photographically inactive and has little interaction with various photographic additives.

As an example thereof, a material which is less likely to contaminate a photographic element by adsorbing a dye or a dye, or a material which is less likely to adsorb a development accelerator, a development inhibitor or the like which affects the developing speed and which is less likely to affect sensitivity or fog. Further, when producing a photographic element, it is characterized in that it has a low pH dependency in a photographic solution in which a latex is dispersed, or is less susceptible to ionic strength, and is less likely to aggregate and precipitate. The above-mentioned properties of the latex are greatly influenced by the monomer composition and properties of the latex. An index called a glass transition point is often used for 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. or,
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. Further, 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 a specific example, for example,
Japanese Patent Application No. 5-13 by the same applicant as the present invention
9113, 5-119114, etc. will be helpful.

At least one layer selected from the layer containing the light-sensitive silver halide emulsion of the present invention and the constituent layers other than the emulsion layer contains a dye capable of decoloring and / or flowing out during development processing. Thus, a light-sensitive material having high sensitivity, high sharpness and less dye stain can be obtained.

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

Specific examples of dyes that can be used include West German Patent 616,007, British Patent 584,609 and 1,
177,429, Japanese Patent Publication No. 26-7777, 39-22069, 54-381
29, JP-A-48-85130, 49-99620, 49-114420
No. 49, No. 49-129537, No. 50-28827, No. 52-108115, No.
57-185038, U.S. Patents 1,878,961, 1,884,035,
1,912,797, 2,098,891, 2,150,695, 2,2
74,782, 2,298,731, 2,409,612, 2,461,4
No. 84, No. 2,527,583, No. 2,533,472, No. 2,865,752
No., No. 2,956,879, No. 3,094,418, No. 3,125,448,
3,148,187, 3,177,078, 3,247,127, 3,2
60,601, 3,282,699, 3,409,433, 3,540,88
No. 7, No. 3,575,704, No. 3,653,905, No. 3,718,472, No. 3,865,817, No. 4,070,352, No. 4,071,312, PB
It is described in Report 74175, PHOTO.ABS.1, 28 ('21), etc.

In the present invention, the layer in which the dye is added may be any photographic constituent layer of the light-sensitive material. That is, at least one layer such as a light-sensitive emulsion layer constituting the light-sensitive material and another hydrophilic colloid layer on the emulsion layer coating surface side (for example, a non-light-sensitive layer such as an intermediate layer, a protective layer or an undercoat layer). It may be contained in the inside. It is preferably in a silver halide emulsion layer or a layer closer to the support or both, and more preferably in a coating layer adjacent to the transparent support. The dye preferably has a high concentration on the side close to the support.

In the present invention, the amount of the above dye added can be changed according to the sharpness target. Preferably 0.2 m
a ^{g / m 2 ~20mg / m 2} , more preferably 0.8 mg / m ² to 15
It is mg / m ² .

In the present invention, the above dye can be introduced into the hydrophilic colloid layer by a conventional method. That is, the dye can be introduced as an aqueous solution having an appropriate concentration or as a solid fine particle dispersion.

[0166] Specifically, JP-A 1-158430 and 2-
115830, 4-251838, etc. can be referred to.

In the light-sensitive material of the present invention, when the silver halide emulsion layer is colored, these solutions are added to the support before they are added to the silver halide emulsion solution before coating or to the aqueous solution of the hydrophilic colloid. It may be applied to the surface directly or through another hydrophilic colloid layer by various methods.

As described above, it is preferable that the dye has a high concentration on the side closer to the support, but a moldant can be used to fix the dye on the side closer to the support. For example at least one of the dyes mentioned above
A non-diffusible moldant can be used as the substance to be combined with the seed, and examples thereof include West German Patent No. 2,263,031, British Patent No. 1,221,131, and No. 1,221,19.
5, JP-A-50-47624, JP-A-50-71332, JP-B-51-1418
U.S. Pat.Nos. 2,548,564, 2,675,316, 2,795,
No. 519, No. 2,839,401, No. 2,882,156, No. 3,048,487
Issue 3,184,309, Issue 3,444,138, Issue 3,445,231,
The compounds described in No. 3,706,563, No. 3,709,690, No. 3,788,855 and the like can be preferably used.

In carrying out the present invention, the method of binding the non-diffusible moldant to the dye may be carried out by various methods known in the art, and the method of binding in a gelatin binder is preferably applied. It In addition, it is also possible to apply a method in which a suitable binder is combined and dispersed in an aqueous gelatin solution by ultrasonic waves or the like.

The binding ratio is not uniform depending on the compound, but usually 0.1 part to 10 parts of the non-diffusible moldant is bonded to 1 part of the water-soluble dye. Since the amount of the water-soluble dye added is combined with the non-diffusible moldant, the dye can be used in a larger amount than when used alone.

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 a transparent support. It is effective to use it as a coating layer adjacent to.

The silver halide photosensitive material according to the present invention comprises
Various photographic additives can be used. Known additives include, for example, Research Disclosure (RD) N
o.17643 (December 1978), No.18716 (November 1979) and N.
o.308119 (December 1989). The types of compounds and the places where they are described in these three Research Disclosures are listed below.

Additives 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 IVA Desensitizing dye 23 IV 998 IVB 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 Surfactant 26 ~ 27 XI 650 Right 1005 ~ 6 XI Charge Inhibitor 27 XII 650 Right 1006-7 XIII Plasticizer 27 XII 650 Right 1006 XII Sliding agent 27 XII Matting agent 28 XVI 650 Right 1008-9 XVI Binder 26 XXII 1009-4 XXII Support 28 XVII 1009 XVII The silver halide emulsion may contain a developing agent such as aminophenol, ascorbic acid, pyrocatechol, hydroquinone, phenylenediamine or 3-pyrazolidone in the emulsion layer or other layers.

The silver halide emulsion layer and the non-photosensitive hydrophilic colloid layer of the light-sensitive material of the present invention preferably contain an inorganic or organic hardener. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.) , Active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis (β- (vinylsulfonyl) propionamide)
Etc., active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogenates (mucochloric acid, mucophenoxycyclolate, etc.), isoxazoles, 2-chloro-6-hydroxytriazinyl Gelatinized gelatin and the like can be used alone or in combination.

Among them, JP-A-53-41221 and JP-A-53-57257
Nos. 59-162456, 60-80846 and the like, and active halogen compounds described in US Pat. No. 3,325,287 are preferred.

As the hardener, a polymer hardener can be effectively used. For example, dialdehyde starch, polyacrolein,
Polymers having aldehyde groups, such as the acrolein copolymers described in U.S. Pat.No. 3,396,029, U.S. Pat.
Polymer having an epoxy group described in US Pat. No. 3,36,36
No. 2,827 or Research Disclosure No 17333 (1
978), a polymer having a dichlorotriazine group, a polymer having an active ester group described in JP-A-56-66841, JP-A-56-142524, U.S. Pat. -65033, a polymer having an active vinyl group described in Research Disclosure No 16725 (1978), or a group serving as a precursor thereof, and the like are preferable, and among them, as described in JP-A-56-142524. Particularly preferred are polymers in which the active vinyl group or its precursor group is attached to the polymer backbone by long spacers. The photographic light-sensitive material of the present invention is prepared by adding an appropriate amount of a hardening agent in advance in the step of applying the light-sensitive material so as to be suitable for rapid processing, and adjusting the water swelling rate in the developing-fixing-water washing step. It is preferable to reduce the water content in the light-sensitive material before the start of drying.

The silver halide light-sensitive material 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. Also, the water swelling rate is 150%
If it is less than the range, uneven development and residual color tend to be deteriorated upon 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. .

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 plastic 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.

Next, preferable development processing of the light-sensitive material of the present invention will be described. As a preferred developing solution for developing the light-sensitive material of the present invention, as a developing agent, dihydroxybenzenes such as those described in JP-A-4-15641 and JP-A-4-16841, such as hydroquinone and para-aminophenols, for example,
p-aminophenol, N-methyl-p-aminophenol,
Examples of 3-pyrazolidones such as 2,4-diammiphenol include 1-phenyl-3-pyrazolidones and 1-phenyl-
4-Methyl-4-hydroxymethyl-3-pyrazolidone, 5,5-dimethyl-1-phenyl-3-pyrazolidone and the like are preferably used in combination. Further, the preferable amount of the above-mentioned para-aminophenols and 3-aminopyrazolidones used is
0.004 mol / l, more preferably 0.04 to 0.1
It is 2 mol / liter.

Further, dihydroxybenzenes, para-aminophenols, 3- and 3-aminophenols contained in these developing solution constituents.
The total number of moles of pyrazolidones is preferably 0.1 mol / liter or less.

Preservatives may include sulfites such as potassium sulfite, sodium sulfite, reductones such as piperidinohexose reductone,
These are preferably used in an amount of 0.2 to 1 mol / liter, more preferably 0.3 to 0.6 mol / liter. In addition, adding a large amount of ascorbic acid also leads to processing stability.

As the alkaline agent, sodium hydroxide,
Includes pH regulators such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium triphosphate, potassium triphosphate. Further, it is possible to use a borate described in JP-A-61-28708, a buffer such as saccharose, acetoxime, 5-sulfosalicylic acid, a phosphate and a carbonate described in JP-A-60-93439. Good. The contents of these agents are
H is chosen to be 9.0 to 13, preferably pH 10 to 12.5.

As the solubilizing agent, polyethylene glycols and their esters can be contained, and as the sensitizing agent, for example, a quaternary ammonium salt, a development accelerator, a surfactant and the like can be contained.

As a silver sludge preventive agent, 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 are preferably used.

As the organic inhibitor, an azole organic antifoggant, for example, an indazole compound, an imidazole compound, a benzimidazole compound, a triazole compound, a benztriazo compound, a tetrazole compound, a thiadiazole compound, or the like is used. Inorganic inhibitors include sodium bromide, potassium bromide, potassium iodide and the like. Besides this, LFA
Menson's "Photographic Processing Chemistry" published by Focal Press (1966), 226-2
Page 29, U.S. Pat.Nos. 2,193,015 and 2,592,364, JP-A-48
-64933 etc. may be used.

The chelating agent for concealing calcium ions mixed in tap water used in the treatment liquid is an organic chelating agent having a chelate stabilization constant of 8 or more with iron described in JP-A 1-193853. Chelating agents 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. However, for rapid processing, it is preferable that the hardener is allowed to act in the coating step of the photosensitive material in advance as described above, rather than the hardener is allowed to act in the development processing step.

The processing temperature of the developer of the present invention is preferably
The temperature is 25 to 50 ° C, more preferably 30 to 40 ° C. The development time is 5 to 45 seconds, more preferably 5 to 15 seconds. The processing time is Dry to Dry, preferably 15 to 90 seconds, more preferably 15 to 90 seconds.
~ 45 seconds. The replenishment in the present invention replenishes the treatment agent fatigue and oxidative fatigue. As a replenishment method, JP-A-55-1
Replenishment according to the width and feeding speed described in 26243, JP-A-60-10
Area replenishment described in 4946 and area replenishment controlled by the number of continuously processed sheets described in JP-A-1-149156 may be used, and a preferable replenishment rate is 150 to 500 cc / m ² .

Preferred fixing solutions can include fixing materials commonly used in the art. Of fixer
The pH is 3.8 or more, preferably 4.2 to 5.5.

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 / l, more preferably 0.8 to 3 mol / l.

The fixer may be one which performs acidic hardening, and in this case, aluminum ions are preferably used as a hardening agent. For example, it is preferably added in the form of aluminum sulfate, aluminum chloride, potassium alum, or the like.

If desired, the fixer may include preservatives such as sulfite and bisulfite, pH buffers such as acetic acid and boric acid, mineral acids (sulfuric acid and 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.
No. 54, No. 58-122535, No. 58-122536, and the thioethers described in US Pat. No. 4,126,459.

[0195]

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) 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 2825ml C1 Potassium bromide 824g Potassium iodide 23.5g Finish to 2825ml with water D1 1.75N Potassium bromide aqueous solution At the following silver potential control amount 35 ° C, as described in JP-B-58-58288 and 58-58289 464.3 m each of solution B1 and solution C1 in solution A1 using a mixing stirrer
1 was added by the double-sided mixing method over 1.5 minutes to perform nucleation.

After stopping the addition of solution B1 and solution C1, it took 60 minutes to raise the temperature of solution A1 to 60 ° C., adjust the pH to 5.0 with 3% KOH, and then add solution B1 again. Solution C1 was mixed by the simultaneous mixing method at a flow rate of 55.4 ml / min.
Added for 2 minutes. This temperature rise from 35 ° C to 60 ° C and solution B
The silver potentials (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during re-simultaneous mixing by 1 and C1 were controlled to +8 mv and +16 mv, respectively, using the solution D1.

After completion of the addition, the pH was adjusted to 6 with 3% KOH, and desalting and washing with water were immediately performed. 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 variation coefficient of thickness is 40
%, And the coefficient of variation in the distance between twin planes was 42%.

Preparation of Em-1 A tabular emulsion having a core / shell structure was prepared using the above seed emulsion-1 and the following four kinds of solutions.

A2 ossein gelatin 11.7 g polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% aqueous ethanol solution) 1.4 ml seed emulsion-1 0.10 mol equivalent Equal to 550 ml of water B2 ossein gelatin 5.9 g potassium bromide 6.2 g Potassium iodide 0.8g Finished to 145ml with water C2 Silver nitrate 10.1g Finished to 145ml with water D2 Ocein gelatin 6.1g Potassium bromide 94g Finished to 304ml with water E2 Silver nitrate 137g Finished to 304ml with water A2 vigorously stirred A2 Solution B2 and solution C2 were added to the solution by the double jet method in 58 minutes. Next, in the same liquid, D2
Solution and E2 solution were added by the double jet method for 48 minutes. During this period, pH was kept at 5.8 and pAg was kept at 8.7.

After completion of the addition, desalting and precipitation were carried out in the same manner as in the seed emulsion-1, and an emulsion having an average silver iodide content of pAg 8.5 and pH 5.85 of about 0.5 mol% was obtained at 40 ° C.

Observation of the obtained emulsion with an electron microscope revealed that tabular silver halide grains having an average grain size of 0.96 μm in 81% of the projected area and a grain size distribution of 19% and an average aspect ratio of 4.5. Met. The average distance between twin planes (a) is 0.01.
It was 9 μm, and the coefficient of variation of (a) was 28%.

Preparation of Em-2 and Em-3 Amount of KBr in Solution A1 of Seed Emulsion-1, Solutions B1 and C1
Addition time, addition temperature, solution A in the preparation of Em-1
Same as Em-1 except that the amount of seed emulsion-1 in 2, the amount of potassium bromide in solution B2, the amount of potassium iodide, pAg at the time of addition, addition rate, addition time, addition temperature, etc. are changed. And the average iodine contents are 1.5 mol% and 2.5 mol%, respectively.
Of the core-shell type (the core portion has a higher iodine content than the shell portion) Em-2 and Em-3 were prepared.
Each emulsion is a tabular grain having an average aspect ratio of about 4.5, and the other shape characteristics are that the average grain size is
1.02μm, 0.98μm, particle size dispersion coefficient is 21%, 22
% The average twin plane distance (a) was 0.24 μm and 0.018 μm, and the variation coefficient of (a) was 30% and 33%.

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

A3 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 B3 2.5N silver nitrate aqueous solution 2825 ml C3 potassium bromide 841 g 2825 ml of D3 1.75N potassium bromide aqueous solution with water At the following silver potential control amount of 42 ° C., each of solution B3 and solution C3 was added to solution A3 using the mixing stirrer shown in JP-B-58-58288 and 58-58289.
Nucleation was performed by adding 464.3 ml by the double-sided mixing method over 1.5 minutes.

After stopping the addition of the solutions B3 and C3, it took 60 minutes to raise the temperature of the solution A3 to 60 ° C., adjust the pH to 5.0 with 3% KOH, and then add the solution B3 again. Solution C3 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 B3 and C3 was +8 mv each using the solution D3. And +16 mv.

After completion of the addition, the pH was adjusted to 6 with 3% KOH, and desalting and washing with water were immediately performed. 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 0.064 μm and an average grain size (circle diameter conversion) of 0.595 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-4 Tabular pure silver bromide emulsion Em-4 was prepared using seed emulsion-2 and the following three kinds of solutions.

A4 ossein gelatin 34.03 g Polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% ethanol aqueous solution) 2.25 ml Seed emulsion-1 1.218 mol equivalent Equivalent to 3150 ml of water B4 Potassium bromide 1747 g Water to 3669 ml C4 Silver nitrate 2493 g Finished with water to 4193 ml Solution A4 was vigorously stirred in a reaction vessel while keeping it at 60 ° C., and the total amount of solution B4 and solution C4 was added thereto by the simultaneous mixing method over 100 minutes. During this period, pH was kept at 5.8 and pAg was kept at 8.8. Here, the addition rates of the solution B4 and the solution C4 were changed in a function-like manner with respect to time so as to be commensurate with 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.

After completion of the addition, this emulsion was cooled to 40 ° C., and an aqueous solution of 13.8% (by weight) modified gelatin modified with phenylcarbamoyl groups as a flocculating polymer agent (substitution rate 90%) 18
00 ml was added and stirred for 3 minutes. Then, a 56% (weight) acetic acid aqueous 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. After that, 9.0 l of distilled water at 40 ° C was added and the mixture was left to stir, then the supernatant was drained and 11.25 l of distilled water was added,
After standing with stirring, the supernatant liquid was drained. Then add a gelatin aqueous solution and a 10% (weight) aqueous solution of sodium carbonate to adjust the pH.
Was adjusted to 5.80, and the mixture was stirred at 50 ° C. for 30 minutes and redispersed.

After redispersion, pH was adjusted to 5.80 and pAg was adjusted to 8.06 at 40 ° C. When the obtained silver halide emulsion was observed with an electron microscope, it was a tabular silver halide grain having an average grain size of 1.11 μm, an average thickness of 0.25 μm, an average aspect ratio of about 4.5, and a grain size distribution width of 18.1%. .

The average twin plane distance (a) is 0.020 μm.
The coefficient of variation of m and (a) was 32%.

Next, using the above emulsion (Em-1), the sensitizing effect of the combination of the spectral sensitizing dye represented by the general formula (I) and the spectral sensitizing dye represented by the general formula (II) was as follows. I looked it up.

That is, after the emulsion was heated to 60 ° C., a predetermined amount of the spectral sensitizing dye shown in Table 3 was added as a solid fine particle dispersion, and then adenine, ammonium thiocyanate, chloroauric acid and sodium thiosulfate were mixed. An aqueous solution and a solution obtained by dissolving triphenylphosphine selenide in a mixed solvent of ethyl acetate and methanol were added, and after 60 minutes, a silver iodide fine grain emulsion was added, and a total of 2 hours of chemical ripening was performed.

At the end of the chemical ripening, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) Exemplified (4) as a stabilizer was added in a predetermined amount shown in Table 3.

Additives other than the spectral sensitizing dye and the addition amount (per 1 mol of AgX) are shown below.

Adenine 15 mg Potassium thiocyanate 95 mg Chloroauric acid 2.5 mg Sodium thiosulfate 2.0 mg Triphenylphosphine selenide 0.4 mg Silver iodide fine particles 280 mg The solid fine particle dispersion of the spectral sensitizing dye is the same applicant as the present invention. Was prepared according to the method described in Japanese Patent Application No. 4-99437. That is, a predetermined amount of the spectral sensitizing dye was added to water whose temperature was previously adjusted to 27 ° C. and a high-speed stirrer (dissolver) was operated at 3,500 rpm at 30 rpm.
Obtained by stirring for ~ 120 minutes.

The average iodine content on the outermost surface of the silver halide grains in the silver halide emulsion (Em-1) was about 4 mol% by the addition of the above silver iodide fine grains.

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 is 2.
Samples No. 1 to No. 15 were obtained by simultaneous coating on both sides using two slide hopper type coaters so that the amount of gelatin attached at 0 g / m ² was 3.1 g / m ² and drying. .

The support has a thickness of 175 μm and a density of 0.15 and is blue-colored. A polyethylene terephthalate film base for X-rays is coated on both sides with 50% by weight of glycidyl methacrylate, 10% by weight of methyl acrylate and 40% by weight of butyl methacrylate.
The following copolymer dye consisting of three monomers was diluted to a concentration of 10 wt% and the resulting aqueous copolymer dispersion was dispersed with the following filter dye and gelatin and applied as an undercoating liquid. .

Filter dye (solid dispersion)

[0222]

[Chemical 7]

Additives added to the emulsion are as follows.
The addition amount is indicated by the amount per mol 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

[0225]

[Chemical 8]

Protective Layer Solution Next, the following was prepared as a protective layer coating solution. The additive is shown in the amount per liter of coating liquid.

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 C1 ₂ H _25CO NH (CH ₂ CH ₂ O) ₅ H 2.0 g

[0228]

[Chemical 9]

Each of the obtained samples No. 1 to No. 14 was subjected to two kinds of conditions (condition A: 23 ° C., 55% RH, condition B: 40).
Photographic properties were evaluated after storage at 4 ° C. and 80% RH for 4 days.

The evaluation method is as follows. First, two samples of intensifying screen KO-2 are used.
It was sandwiched between 50 (manufactured by Konica Corp.) and exposed to X-rays through an aluminum wedge for 80 seconds at a tube voltage of 80 kvp and a tube current of 100 mA for 0.05 seconds. Then, using an automatic processor SRX-502 (manufactured by Konica Corp.), processing was carried out with a developing solution and a fixing solution having the following formulations.

Developer Formulation Part-A (for finishing 12 liters) 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 Water is added to a final volume of 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 temperature is 35 ° C. for development and fixing, respectively.
33 ℃, 20 ℃ water wash, 50 ℃ dry, treatment time is dry to dry 45
Seconds.

After the treatment, the sensitivity was measured. Sensitivity is expressed as the reciprocal of the exposure dose that gives a density of fog + 0.5, and is the sample No.
The relative sensitivity is shown when the sensitivity of 1 (storage condition A) is 100. Further, regarding the residual color property, the spectral absorption density at 510 nm was measured, and the relative density was represented by setting the density of Sample No. 1 to 100. The results obtained are shown in Table 3 below.

[0238]

[Table 3]

As is clear from Table 3, the comparative sample sensitized with only one spectral sensitizing dye was sensitized by the combined use of two spectral sensitizing dyes according to the method of the present invention, and TAI was added. High sensitivity is obtained for samples with an amount of 600 mg / mol AgX or less,
Further, it can be seen that even when stored under high temperature and high humidity, sensitivity and fog do not fluctuate and are excellent.

Although the same result was obtained by adding the spectral sensitizing dye as a methanol solution instead of adding it as a solid fine particle dispersion, the latter method was used to obtain almost the same performance as the former method. About 20-30% extra loading was required. Therefore, in the latter method, a large amount of the spectral sensitizing dye remains after the development processing, and the deterioration of the image quality due to the coloring stain is remarkable.

Further, as a result of measuring the reflection spectrum of the silver halide photographic light-sensitive material in which the two kinds of spectral sensitizing dyes according to the present invention were used in combination, a J aggregate having an absorption maximum at around 545 nm was formed. . Illustrative example of spectral sensitizing dye I-
FIG. 1 shows the absorption curve of the reflection spectrum of a silver halide photographic light-sensitive material in which 12 (60 mg) and II-2 (60 mg) were used in combination.

The sample for reflection spectrum measurement did not contain the above filter dye.

Example 2 The following experiment was conducted to examine the influence of the average iodine content of silver halide emulsion grains and the iodine content of the outermost surface of the grains.

Silver halide emulsion Em prepared in Example 1
-1 to Em-4 were divided into equal parts, each of them was heated to 60 ° C., and a predetermined amount of the spectral sensitizing dye shown below was added as a solid fine particle dispersion, followed by adenine, ammonium thiocyanate, and gold chloride. A mixed aqueous solution of acid and sodium thiosulfate and a solution obtained by dissolving triphenylphosphine selenide in a mixed solvent of ethyl acetate and methanol were added, and after 60 minutes, a predetermined amount of silver iodide fine grain emulsion shown in Table 5 was added. In addition, aging was performed for a total of 2 hours. At the end of aging, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) was added as a stabilizer.

Additives other than the silver iodide fine particles and their addition amounts (per 1 mol of AgX) are shown below. Spectral sensitizing dye (I-28) 60 mg Spectral sensitizing dye (II-2) 60 mg Adenine 15 mg Potassium thiocyanate 95 mg Chloroauric acid 2.5 mg Sodium thiosulfate 2.0 mg Triphenylphosphine selenide 0.4 mg Stabilizer (TAI) 300 mg Additives were added to the obtained emulsion in the same manner as in Example 1 to prepare an emulsion layer coating solution. Further, a protective layer coating solution was prepared in exactly the same manner as in Example 1, and both coating solutions were applied and dried in the same manner as in Example 1,
Sample Nos. 15 to 30 were obtained.

Next, these samples were exposed and developed in the same manner as in Example 1.

However, the processing time was set to 25 seconds and 45 seconds by adjusting the pH of the developing solution and the automatic developing machine. The evaluation method was the same as in Example 1. The results obtained are shown in Table 4 below.

[0248]

[Table 4]

As is clear from Table 4, the sensitivity of the sample obtained by the emulsion containing iodine on the outermost surface of the silver halide grain is high. However, when the iodine content on the outermost surface is around 12 mol%, the residual dye after the treatment is too large to be practically ignored. This tendency becomes stronger as the average iodine content of silver halide grains in the silver halide emulsion increases.

If the processing time is reduced to 25 seconds,
Furthermore, the tendency becomes remarkable. It can be seen that the sample of the present invention has higher sensitivity than the comparative sample, less residual color, and less change with processing time.

Example 3 After the emulsion (Em-1) used in Example 1 was heated to 60 ° C., a predetermined amount of the spectral sensitizing dye was added as a dispersion in the form of solid fine particles, and then adenine, ammonium thiocyanate, A mixed aqueous solution of chloroauric acid and sodium thiosulfate and a solution obtained by dissolving triphenylphosphine selenide in a mixed solvent of ethyl acetate and methanol were added, and after 60 minutes, silver iodide fine grain emulsion was added for a total of 2 hours. Aged. 4-hydroxy-6-methyl-1,3,3a, 7 as a stabilizer at the end of aging
-A predetermined amount of tetrazaindene (TAI) was added.

The above-mentioned additives and their addition amounts (per mol of AgX) are shown below.

Spectral sensitizing dye (Ex. I-56) 2.0 mg Spectral sensitizing dye (Ex. II-2) 120 mg Adenine 15 mg Potassium thiocyanate 95 mg Chloroauric acid 2.5 mg Sodium thiosulfate 2.0 mg Triphenylphosphine selenide 0.4 mg Silver iodide fine particles 280 mg 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) 50 mg A solid fine particle dispersion of a spectral sensitizing dye is disclosed in Japanese Patent Application No. 4-99437.
It was prepared according to the method described in No. That is, a predetermined amount of the spectral sensitizing dye was added to water whose temperature was 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 to obtain the dye.

The average iodine content on the outermost surface of the silver halide grains contained in the silver halide emulsion (Em-4) by the addition of the above silver iodide fine grains was about 4 mol%.

The following additives were added to the emulsion thus sensitized to prepare an emulsion layer coating solution, and at the same time, a protective layer coating solution was prepared.

Next, a polyethylene terephthalate film base for X-rays having a density of 0.15 and having a blue color (thickness of 175 μm
m), the following dye layers were pre-coated on both sides of the support, and the emulsion layer coating solution and the protective layer coating solution were applied simultaneously on the both sides in the following predetermined coating amounts and dried. .

To the protective layer coating solution, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) and the azaindene derivative of Example (15) were added in various amounts. As shown, samples having different coating amounts per unit area were prepared.

First layer (dye layer) Solid fine particle dispersion dye (AH) 180 mg / m ² Gelatin 0.2 g / m ² Sodium dodecylbenzenesulfonate 5 mg / m ² Compound (I) 5 mg / m ² 2,4-dichloro -6-Hydroxy-1,3,5-triazine sodium salt 5 mg / m ² colloidal silica (average particle size 0.014 μm) 10 mg / m ² 2nd layer (emulsion layer) The following additions to each emulsion obtained above. The agent was added.

Compound (G) 0.5 mg / m ² 2,6-bis (hydroxyamino) -4-diethylamino-5 mg / m ² 1,3,5-triazine t-butyl-catechol 130 mg / m ² polyvinylpyrrolidone (molecular weight 10,000) 35 mg / m ² Styrene-maleic anhydride copolymer 80 mg / m ² Sodium polystyrene sulfonate 80 mg / m ² Trimethylolpropane 350 mg / m ² Diethylene glycol 50 mg / m ² Nitrophenyl-triphenyl-phosphonium chloride 20 mg / m ² Ammonium 1,3-dihydroxybenzene-4-sulfonate 500 mg / m ² 2-Mercaptobenzimidazole-5-sodium sulfonate 5 mg / m ² Compound (H) 0.5 mg / m ² nC ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 350 mg / m ² compound (M) 5 mg / m ² compound (N) 5 mg / m ² colloidal silica 0.5 g / m ² latex (L) 0.2 g / m ² dextrin (average molecular weight 1000 ) 0.2 g / m ² However, adjust so that gelatin becomes 1.0 g / m ^2. Arranged

Third layer (protective layer) Gelatin 0.8 g / m ² 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene Amount shown in Table 3 Matting agent consisting of polymethylmethacrylate 50 mg / m ² (Area average particle size 7.0 μm) Formaldehyde 20 mg / m ² 2,4-Dichloro-6-hydroxy-1,3,5-triazine sodium salt 10 mg / m ² Bis-vinylsulfonylmethyl ether 36 mg / m ² latex (L ) 0.2 g / m ² polyacrylamide (average molecular weight 10000) 0.1 g / m ² sodium polyacrylate 30 mg / m ² polysiloxane (SI) 20 mg / m ² compound (I) 12 mg / m ² compound (J) 2 mg / m ² compound (S-1) 7 mg / m ² compound (K) 15 mg / m ² compound (O) 50 mg / m ² compound (S-2) 5 mg / m ² C ₉ F ₁₉ -O- (CH ₂ CH ₂ O ) ₁₁ -H 3mg / m ² C ₈ F ₁₇ SO ₂ N- (C ₃ H ₇ ) (CH ₂ CH ₂ O) ₁₅ -H 2mg / m ² C ₈ F ₁₇ SO ₂ N- (C3H7) (CH _{2 CH 2 O) 4 - (CH} 2) 4 SO 3 Na 1mg / m 2

[0261]

[Chemical 10]

[0262]

[Chemical 11]

[0263]

[Chemical 12]

The amount of additive added was for one side, and the coated silver amount was adjusted to be 1.6 g / m ² for one side.

[0265] Sample Nos. 31 to 38 thus obtained
Was stored under the same storage conditions A and B as in Example 1, and the desensitization range under the latter condition with respect to the former condition was evaluated. That is, the sensitivity difference between the storage conditions A and B was determined for each sample, and shown as a relative value when the sensitivity difference of sample No. 34 and the sensitivity difference of No. 38 were set to 100. The smaller the value, the smaller the fluctuation and the better. The development processing conditions for evaluation were the same as in Example 2 with a total dry to dry time of 25 seconds.

The results obtained are shown in Table 5 below. As is clear from Table 5, the sample according to the present invention has a small desensitization width under high temperature and high humidity (storage condition B) and is excellent.

[0267]

[Table 5]

[0268]

According to the present invention, a silver halide photographic light-sensitive material having high sensitivity and excellent storage stability over time can be obtained. Further, according to the present invention, a silver halide photographic light-sensitive material having less residual color contamination due to residual dye after development processing can be obtained. Further, the silver halide photographic light-sensitive material of the present invention can obtain the above-mentioned characteristics even when processed with a developer containing no hardener, and its effect is more remarkable in rapid processing.

[Brief description of drawings]

FIG. 1 is an absorption curve of a reflection spectrum.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location G03C 1/34 5/26

Claims (9)

[Claims] 1. A tabular silver halide grain having an average aspect ratio of 2 or more in at least 70% of the total projected area of silver halide grains contained in a silver halide emulsion layer, and said tabular halogenated grain. The average of all iodine contents of silver particles is
When it is 1.5 mol% or less, the average iodine content of the outermost layer of the particles is 1
0 mol% or less, and contains at least one spectral sensitizing dye represented by the following general formula (I) and at least one spectral sensitizing dye represented by the following general formula (II), and A silver halide photographic emulsion containing at least one azaindene compound in an amount of 4.7 × 10 ^-3 mol or less per mol of silver. [Chemical 1] (In the formula, R ₁ and R ₃ each represent a substituted or unsubstituted alkyl group, and R ₂ and R ₄ represent a lower alkyl group.
At least one of R ₂ and R ₄ represents an alkyl group substituted with a hydrophilic group. V ₁ , V ₂ , V ₃ and V ₄ are a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group,
Represents a trifluoromethyl group, a cyano group, a carboxy group, an alkoxycarbonyl group, an acyl group, a sulfonyl group, a carbamoyl group, a sulfamoyl group, an acetylamino group and an acetyloxy group, and V ₁ , V ₂ , V ₃ and V ₄ are simultaneously hydrogen. It never becomes an atom. X ₁ represents an ion necessary for neutralizing the charge in the molecule, and n represents 1 or 2. However, n is 1 when forming an intramolecular salt. ) [Chemical 2] (In the formula, R ₅ and R ₆ each represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, 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, Z ₁ and Z ₂ are each required to complete a benzene ring or naphtho ring which may have a substituent. X ₂ represents an ion necessary for neutralizing the charge in the molecule, and m represents 1 or 2. However, when forming an inner salt, m is 1. ) 2. At least one of the spectral sensitizing dyes represented by the general formula (I) and the general formula (II) is dispersed in an aqueous system in which an organic solvent or a surfactant does not substantially exist. 2. The silver halide photographic emulsion according to claim 1, wherein the silver halide photographic emulsion is added as a solid fine particle dispersion which is hardly soluble in water. 3. The silver halide photograph according to claim 1 or 2, wherein the average iodine content of the outermost layer of tabular silver halide grains having an average aspect ratio of 2 or more is 2 mol% or more and 8 mol% or less. A silver halide photographic light-sensitive material containing an emulsion. 4. Iodine in the outermost layer of tabular silver halide grains having an average aspect ratio of 2 or more is imparted during the chemical ripening step in the presence of a chemical sensitizer. The silver halide photographic emulsion according to claim 2 or claim 3. 5. A tabular silver halide grain having an average aspect ratio of 2 or more comprises at least one of the spectral sensitizing dyes represented by the general formula (I) and the spectral sensitization represented by the general formula (II). Chemical sensitization is carried out in the presence of at least one kind of dye.
Alternatively, the silver halide photographic emulsion according to claim 4. 6. At least one of the spectral sensitizing dyes represented by the general formula (I) and the general formula (II) is dispersed in an aqueous system in which an organic solvent or a surfactant is substantially absent. The spectral sensitizing dye is added to the silver halide grains so that it is added as a solid fine particle dispersion that is sparingly soluble in water and a characteristic J-band is formed at 520 to 560 nm when the reflection spectrum is measured. The silver halide photographic emulsion according to claim 2, 3 or 4 or 5, which is adsorbed. 7. The tabular silver halide grains having an average aspect ratio of 2 or more have an average total iodine content of 0.5 mol% or less, claim 2, claim 3 or claim 4,
The silver halide photographic emulsion according to claim 5 or 6. 8. A silver halide emulsion layer and / or at least one kind of azaindene compound contained in the non-photosensitive layer is 1.7 × 10 ⁻⁴ mol / m ² or less per one side of the photosensitive material. A silver halide photographic light-sensitive material containing the silver halide photographic emulsion according to claim 2, claim 3, claim 4, claim 5, claim 6, or claim 7. 9. The total processing time by the automatic processor from 15 seconds
9. The method for processing a silver halide photographic light-sensitive material according to claim 8, wherein the processing is performed for 45 seconds.