JP3248034B2 - Silver halide photographic material and processing method thereof - Google Patents

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, low dye contamination, and excellent storage stability and pressure resistance, and more particularly to a silver halide photographic light-sensitive material for X-ray medical care and its processing. It is about the method.

[0002]

2. Description of the Related Art High sensitivity of silver halide photographic materials,
Although high image quality is an eternal theme in the industry, in recent years, a technique of achieving high sensitivity and high image quality using tabular silver halide grains has been disclosed, for example, Japanese Patent Application Laid-Open No. 58-11193.
No. 5, No. 58-111936, No. 58-111937, No. 58-113927,
No. 59-99433.

JP-A-63-92942 discloses a technique of providing a core having a high silver iodide content in tabular silver halide grains, and JP-A-63-151618 discloses a hexagonal tabular silver halide grain. Is disclosed, and it is disclosed that high sensitivity can be obtained.

[0004] In addition, JP-A-63-106746 and JP-A-1-1
No. 83644, JP-A-1-279237, etc. disclose techniques relating to the composition distribution of tabular silver halide grains. With respect to the crystal structure of the tabular silver halide grains, several techniques regarding the shape of the grains and parallel twin planes have been disclosed.For example, Japanese Patent Application Laid-Open No. 1-131541 discloses the use of circular tabular grains and sensitivity. A technique for improving graininess has been disclosed.

Japanese Patent Application Laid-Open No. 63-163451 discloses a ratio of the distance between twin planes (a) and the thickness (b) of tabular silver halide grains having two or more twin planes in parallel. A technique using particles having b / a) of 5 or more is disclosed, and the effects of increasing sensitivity and improving graininess are shown. Here, a technique for improving the uniformity between twin plane distances between grains, and thereby a high sensitivity and an improvement in graininess are described.

[0006] WO 91/18320 discloses that the distance between twin planes is 0.01.
A technique using tabular silver halide grains having a size of less than 2 μm is disclosed, and it is stated that high sensitivity can be achieved.

Further, in EP 515894A1, (particle size) / (thickness) ²
The tabularity represented by (1) achieves high sensitivity by making the (111) plane ratio of the edge faces of 25 or more tabular silver halide grains less than 75%.

On the other hand, many techniques have been disclosed for improving the defects of tabular silver halide grains. For example,
No. 39 discloses an emulsion having a (particle size) / (thickness) ratio, that is, an emulsion in which tabular grains having an aspect ratio of 3 or more and having (111) and (100) planes account for 50% or more of the projected area. Techniques for improving the storability under moisture have been disclosed.

These tabular silver halide grains are hexahedral,
Compared with octahedral and other so-called normal crystal silver halide grains, the surface area is large in the same volume, so that the amount of sensitizing dye adsorbed on the grain surface can be increased, resulting in higher sensitivity and scattered light. It is considered that there is an advantage that the sharpness can be improved by reducing the density.

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 cannot be increased as much as expected. Dye contamination, image quality deterioration, and the like due to the residual dye have become apparent as problems.

In particular, in recent years, the processing time of silver halide photographic light-sensitive materials has been increasing in response to the needs of users as the consumption of the light-sensitive materials has increased, and medical light-sensitive materials have been no exception.

In the medical field, the spread of regular medical examinations, medical checkups, etc., and the number of examinations including diagnosis in general medical treatment have increased sharply. As a result, the number of images to be taken has increased and the demand for ultra-rapid development processing after image taking has been increasing. It is rare.

However, increasing the processing speed shortens the processing time of each of the development, fixing, washing, and drying processes, thereby increasing the load of each processing. For example, in development, it is necessary to increase the development speed because the development time is short, but there are problems such as graininess and fog increase. If the fixing time is short, the fixing speed of the unexposed (undeveloped) silver halide must be increased, and poor fixing causes discoloration of the image. In particular, residual color contamination (a phenomenon in which a dye remains in a finished image and deteriorates image quality) is a serious problem in rapid processing because the sensitizing dye is not sufficiently eluted in each of development, fixing, and water washing processes.

As a solution to this, for example, EP0506584,
JP-A-5-88293 and JP-A-5-93975 disclose techniques using a dye having good decolorization performance. However, this technique alone is not always sufficient for the recent demand for high sensitivity, and furthermore, the sensitivity decreases during storage of the photosensitive material, especially when stored under high humidity and high temperature. This was a major obstacle from a practical point of view.

When various water-insoluble photographic additives are introduced into a silver halide emulsion, a method of dissolving the photographic additive in an organic solvent such as methanol and adding the resulting solution to the silver halide emulsion is generally employed. Was widely practiced.

In place of such a conventional method, an additive is used without using an organic solvent in the presence of a wetting agent or a dispersing agent.
Attempts have been made to disperse and prepare an aqueous solution, and to add an aqueous dispersion of the resulting additive to a silver halide emulsion. That is, JP-A-52-110012 discloses that a sensitizer is pulverized in an aqueous phase in the presence of a dispersant (surfactant) that gives a constant surface tension, and water is removed from the obtained aqueous dispersion. A method is described in which after drying, it is added as it is to a silver halide emulsion, or it is dispersed in water or an aqueous gelatin solution and then added to a silver halide emulsion.

JP-A-53-102733 discloses a homogeneous mixture (paste admixture) comprising a photographic fine particle additive, a dispersant such as sorbitol, and a protective colloid such as gelatin, and noodles the mixture. Air-dry to form granules. A method of adding the obtained granules to an aqueous photographic colloid coating composition is described.

Further, US Pat. No. 4,006,025 discloses that a spectral sensitizing dye is mixed with water to form a slurry, and the temperature is raised to 40 to 50 ° C. in the presence of a surfactant to homogenize or mill to homogenize in water. It discloses a method of dispersing and adding a dispersion of the obtained spectral sensitizing dye to a silver halide emulsion.

However, any of these adding methods is a method of adding a photographic additive such as a sensitizing dye in an aqueous system without using an organic solvent, but has the following problems in practical use. Was. That is, since the aqueous dispersion is powderized by freeze-drying or the like, the time required for adsorbing sensitizing dyes or the like to silver halide grains becomes longer, so that within a short period of time, the desired photographic sensitivity cannot be obtained due to insufficient adsorption. Further, when such a silver halide emulsion is coated, a coating failure due to a precipitate or the like is likely to occur.

Further, since a wetting agent or a dispersing agent is used for dispersing the additive, the emulsion present in the silver halide emulsion may be destroyed, or a coating failure may occur when the emulsion is coated at a high speed. The photographic light-sensitive materials obtained were not excellent in film formation and often had problems in terms of quality.

On the other hand, it is known that a disadvantage of tabular silver halide grains is poor pressure resistance. As is well known, there are two types of so-called pressure fog, in which unexposed portions are developed when pressure is applied to a silver halide photographic light-sensitive material, and pressure desensitization, in which sensitivity is reduced by pressure. If the pressure resistance is poor, the silver halide photographic material becomes a serious defective product.

Generally, silver halide grains are sensitive to pressure, and as the sensitivity is increased, they become more and more sensitive to pressure. Is remarkable. This is because, when compared with the same volume, even if the materials have the same mechanical strength, the tabular grains are thinner than the spherical grains, so a larger moment is more likely to be applied, and the mechanical strength of the whole grains is higher. It is interpreted as weak.

The pressure resistance varies depending on not only the shape of the silver halide grains but also the halogen composition distribution in the silver halide grains and the conditions of chemical sensitization. Generally insufficient degree of chemical sensitization
In the case of (insufficient chemical ripening), pressure desensitization is poor. If the degree of chemical sensitization is excessive, pressure desensitization decreases but pressure fog increases. When a high iodine portion is present inside the silver halide grains, pressure fog is improved, but pressure desensitization tends to increase.

Many proposals have been made for such a method for improving the pressure resistance. For example, JP-A-59-99433, JP-A-59-99433,
-301937, 63-149641, 63-106746, 63-1516
No. 18, 63-220238, JP-A-1-31541, JP-A-2-193
No. 138, No. 3-72836, and No. 3-231739 are disclosed, but these conventional techniques have not been able to obtain a sufficient improvement effect.

Among the above, JP-A-63-163451, JP-A-1-131541, WO91 / 18320 and EP515894A1 disclose the distance between twin planes, the coefficient of variation thereof, the storage stability with time, the pressure resistance and the like. There is no description suggesting the relationship and improvement.

[0026]

SUMMARY OF THE INVENTION Accordingly, a first object of the present invention is to provide a photosensitive halide comprising tabular silver halide grains having high sensitivity, little residual color, and excellent storage stability and pressure resistance over time. An object of the present invention is to provide a silver halide photographic material containing a silver emulsion.

A second object of the present invention is to provide a medical silver halide photographic light-sensitive material containing a light-sensitive silver halide emulsion comprising tabular silver halide grains having the above-mentioned properties, and a processing method therefor. It is. Other objects will be apparent from the following description.

[0028]

The above problems have been solved by the present invention described below. That is, (1) in a photosensitive silver halide emulsion layer, at least one kind of spectral sensitizing dye represented by the following general formula (I);
A silver halide photographic material comprising a combination of at least one of the spectral sensitizing dyes represented by (II).

[0029]

Embedded image

[0030] In the formula, each R ₁ and R ₃ represents a substituted or unsubstituted alkyl group, at least one of the one group of R ₁ and R ₃ are groups other than ethyl group, R ₂ and R ₄ represents a lower alkyl group, and 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 each represent a hydrogen atom or a displaceable group in which the sum of the added Hammett σp values is smaller than 1.7, and V ₁ , V ₂ , V ₃ and V ₄ simultaneously represent a hydrogen atom or It cannot be a chloro atom.

X ₁ represents an ion necessary for neutralizing the charge in the molecule, and n represents 1 or 2. However, when an internal salt is formed, n is one.

[0032]

Embedded image

In the formula, R ₅ and R ₆ each represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or 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 non-metallic atomic group necessary for completing 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 an internal salt is formed, m is 1.

(2) At least 70% of the total projected area of the silver halide grains contained in the photosensitive silver halide emulsion contains tabular silver halide grains having an aspect ratio of 2 or more. (1) The silver halide photographic material as described in (1) above.

(3) The photosensitive silver halide emulsion contains a silver halide emulsion in which the average iodine content of the silver halide grains is at least 0.01 mol% and at most 2 mol%. The silver halide photographic light-sensitive material according to the above 1) or 2).

(4) 50% of the above tabular silver halide grains
(Number) has two or more twin planes which are parallel or more, and the average value of the maximum distance (a) of the distance between two or more twin planes which the tabular grains have is 0.008 μm or more The silver halide photographic light-sensitive material as described in (2), wherein the silver halide grains contain (a) a coefficient of variation of 35% or less.

(5) 50 in the above-mentioned photosensitive silver halide emulsion
% Or more (number) of grains having a core-shell type structure are described in (1), (2), (3) and (4).

(6) The photosensitive silver halide emulsion described in (1) above
A silver halide photographic light-sensitive material for medical use comprising at least one of the items (2), (3), (4) and (5).

(7) The medical halogen according to item (6), wherein the processing is carried out in a processing step containing a developer containing substantially no hardener and the total processing time is from 15 seconds to 90 seconds. Processing method of silver halide photographic light-sensitive material.

(8) containing at least one kind of spectral sensitizing dye represented by the above general formula (I) and at least one kind of spectral sensitizing dye represented by the above general formula (II), And at least one of the spectral sensitizing dyes is added as a substantially water-insoluble solid fine particle dispersion dispersed in an aqueous system substantially free of an organic solvent and / or a surfactant; When the spectrum is measured, the characteristic J-
A silver halide photographic material characterized in that the spectral sensitizing dye is adsorbed on silver halide grains so that a band is formed.

(9) At least 70% of the total projected area of the silver halide grains contained in the photosensitive silver halide emulsion is tabular silver halide grains having an aspect ratio of 2 or more ( 8) The silver halide photographic light-sensitive material according to the above.

(10) A medical silver halide photographic material, characterized in that the photosensitive silver halide emulsion has at least one of the above items (8) and (9).

(11) The silver halide photographic light-sensitive material described in the above item (10) is processed in a processing step containing a developing solution containing substantially no hardener in a total processing time of 15 to 90 seconds. A method for processing a silver halide photographic light-sensitive material for medical use, comprising:

Has been achieved. Hereinafter, the present invention will be described in detail.

The above-mentioned spectral sensitizing dye in the present invention refers to a dye which contributes to the sensitivity of silver halide grains, and does not include an organic dye which 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. For example, lower alkyl groups such as methyl, ethyl, propyl, butyl and the like can be mentioned.

Examples of the lower alkyl group represented by R ₂ and R ₄ include groups such as methyl, ethyl, butyl, and trifluoroethyl. 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,
groups such as o-sulfobenzyl and p-carboxybenzyl.

As the substituent represented by V ₁ , V ₂ , V ₃ and V ₄ , when the Hammett σp value of the substituent is added,
Any group having a total sum not exceeding 1.7 may be used, for example, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), an alkyl group (a group such as methyl, ethyl, t-butyl, etc.), an alkoxy group ( Methoxy group), alkylthio group (methylthio group), trifluoromethyl group, 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.), acetylamino group, acetyloxy group and the like. .

The ion necessary for neutralizing the charge in the molecule represented by X ₁ may be either an anion or a cation.
(Ions of chlor, brom, iodine, etc.), perchlorate,
Ethyl sulfate, thiocyanate, p-toluenesulfonate, perfluoroborate and the like, examples of cations include hydrogen ions, alkali metal ions (ions of lithium, sodium, potassium, etc.), and alkaline earth metal ions (magnesium, calcium, etc.) ), Ammonium ions, and organic ammonium ions (ions such as triethylammonium, triethanolammonium, and tetramethylammonium).

Among the substituents represented by V ₁ , V ₂ , V ₃ and V ₄ , those which give an S value less than 1.0 derived from the following [Formula-A] are preferred.

S = L / {(B ₁ + B ₂ + B ₃ + B ₄ ) / 2} [Formula-A] In the formula, L, B ₁ , B ₂ , B ₃ and B ₄ represent STERIMOL parameters.

Specifically, methyl (S = 0.815), ethyl (S
= 0.992), t-butyl (S = 0.728), methoxy (S = 0.99
3), methylthio (S = 0.982), trifluoromethyl (S =
0.697), acetyl (S = 0.893), methanesulfonyl (S =
0.825), carboxy (S = 0.877), carbamoyl (S = 0.
93), sulfamoyl (S = 0.726), etc., fluorine atom
(S = 0.981), chlorine atom (S = 0.978), bromine atom (S = 0.9
82).

The Hammett σ used in the general formula (I)
The p-value is a substituent constant determined by Hammett et al. from the electronic effect of the substituent on the hydrolysis of ethyl benzoate, and the STERIMOL parameter is the length determined from a projection on the bond axis with the benzene nucleus. Defined value, Journal of Organic Chemistry 23
Vol. 420-427 (1958), Experimental Chemistry Course 14 (Maruzen Publishing), Physical Organic Chemistry (Mc G)
Raw Hill Book: 1940), Drug Design VII (Academic Press New York: 1976), Structure-activity relationship of drugs (Nankodo: 1979), etc.

Next, the above general formula (I) used in the present invention
Specific examples of the spectral sensitizing dye represented by are shown below.

[0056]

[Table 1]

[0057]

[Table 2]

The dyes represented by the general formula (I) of the present invention include, in addition to the specific examples described above, examples of the compounds II-3 and II described in JP-A No. 4-9040. -4, II-
6, II-7, II-8, II-10, II-13, II-14, II-16, II-1
7, II-18, II-20, II-21, II-24 to II-44 and the like can be used in the same manner.

The spectral sensitizing dyes represented by formula (I) according to the present invention include, for example, British Patent Nos. 521,165 and 745,546.
No., Belgian Patent 615,549, Soviet Patent 412,218
Nos. 432,166, JP-B-38-7828, 42
-27165, 42-27166, 43-13823, 43-14497
Nos., 44-2530, 45-27676, 45-32740, etc., according to the method described in Hammer's Cyanine Soy Reated Compounds (Jhon Wiley & Sons, New York, 1964). Can be synthesized.

Next, in the spectral sensitizing dye represented by 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 group. Wherein 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 group of non-metallic atoms necessary to complete a benzene ring or naphtho ring which may have a substituent, and X ₂ represents an ion required to neutralize intramolecular charge. m represents 1 or 2, and when forming an internal 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 to be substituted on R ₅ and R ₆ include 2-hydroxyethyl and 4-hydroxybutyl groups as a hydroxyalkyl group, and 2-acetoxyethyl and 3-acetoxybutyl groups as an acetoxyalkyl group.
2-carboxyethyl, 3-carboxypropyl, 2- (2-carboxyethoxy) ethyl and the like as carboxyalkyl groups, and 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl and 2-hydroxy as sulfoalkyl groups -3-sulfopropyl group and the like. Examples of the alkenyl group represented by R ₅ and R ₆ include an allyl, butynyl, octenyl and oleyl group. Further, examples of the aryl group represented by R ₅ and R ₆ include a phenyl and carboxyphenyl group.

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

The ion represented by X ₂ in the general formula (II) includes, for example, chloride ion, bromine ion, iodine ion, thiocyanate ion, sulfate ion, perchlorate ion, p-toluenesulfonic acid ion, Examples thereof include ethyl sulfate ion, sodium ion, potassium ion, magnesium ion, and triethylammonium ion.

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

Z ₁ and Z ₂ represent a group of nonmetallic atoms necessary for completing a substituted or unsubstituted benzene ring. m represents 1 or 2 and m is 1 when an inner salt is formed. Next, specific examples of the spectral sensitizing dye represented by the general formula (II) used in the present invention will be described.

[0067]

Embedded image

[0068]

Embedded image

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

It should be noted that each of the above general formulas (I) and (II) merely shows one state of the resonance structure, and can be expressed in an extreme state in which + charge enters a symmetric heterocyclic nitrogen atom. It means the same substance.

The technique of using two kinds of spectral sensitizing dyes according to the present invention is useful for a photographic material requiring sensitivity to green light. In particular, it is remarkably effective in adapting to an X-ray recording material using a phosphor emitting green light in order to increase the recording sensitivity to X-rays, and is particularly effective in X-ray medical photosensitive materials.

For application to X-ray medical light-sensitive materials using a phosphor emitting green light, a spectral sensitizing dye represented by the general formula (I) and a spectral sensitizing dye represented by the general formula (II) are used. In combination, it is preferable that a J-band is formed in the same wavelength region as the green light from the phosphor when its reflection spectrum is measured and its reflection spectrum is measured. That is, the J specific to the 520 nm to 560 nm region
It is preferred to select and combine spectral sensitizing dyes such that a band is formed.

The amount of the spectral sensitizing dyes represented by formulas (I) and (II) in the present invention varies depending on the kind of the dye and the structure, composition, ripening conditions, purpose and application of the silver halide. It is preferable that the coverage of the monomolecular layer on the surface of each photosensitive particle in the silver emulsion be 40% or more and 90% or less, more preferably 50% to 80%.

In the present invention, the monolayer coverage is 50%.
Coverage is the saturated adsorption amount when the adsorption isotherm is created at ℃
It will be decided relatively as an amount equivalent to 100%.

The appropriate amount per mole of silver halide varies depending on the total surface area of the silver halide grains in the emulsion.
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 and the like have been used. Specific examples include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, ethylene glycol, propylene glycol,
3-propanediol, acetone, acetonitrile, 2-methoxyethanol, 2-ethoxyethanol and the like.

As a dispersant for the spectral sensitizing dye, a surfactant has been conventionally used. Surfactants include anionic, cationic, nonionic and amphoteric surfactants, and any of these surfactants can be used in the present invention.

In the present invention, however, the effect is increased by adding the spectral sensitizing dye as a dispersion in the form of solid fine particles, as compared with the case of adding it as a solution of an organic solvent.
In particular, at least one of the spectral sensitizing dyes is added in the form of a solid fine particle dispersion substantially insoluble in water dispersed in an aqueous system substantially free of an organic solvent and / or a surfactant. Is preferred.

A technique for mechanically dispersing an organic dye in an aqueous medium is disclosed in, for example, JP-A-3-288842. However, this method is for making the organic dye diffusion-resistant in the photographic light-sensitive material, and is merely a dispersion addition method.

On the other hand, the present invention is intended to uniformly and effectively adsorb photographic photosensitizing dyes on the surface of silver halide grains. The purpose and effect are different.

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

The solubility of the spectral sensitizing dye in the present invention in water is from 2 × 10 ^-4 to 4 × 10 ^-2 mol / l.
More preferably, it is 1 × 10 ⁻³ to 4 × 10 ⁻² mol / l.

If the solubility is lower than this range, the dispersion particle size is very large and non-uniform, so that after the dispersion is completed, a precipitate of the dispersion is formed or the dispersion is added to the silver halide emulsion. Occasionally, the process of adsorbing the dye onto silver halide may be hindered.

On the other hand, when the solubility is higher than the above range, the viscosity of the dispersion increases more than necessary and bubbles are involved, which hinders the dispersion, and the dispersion becomes impossible at a higher solubility. This has become 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 the dye which was not completely dissolved visually was added thereto.
The mixture was kept at 27 ° C. in a thermostat and stirred with a magnetic stirrer for 10 minutes. The suspension was filtered using filter paper No. 2 (manufactured by Toyo Corporation).
The filtrate was filtered with a disposable filter (manufactured by Tosoh Corporation), the filtrate was appropriately diluted, and the absorbance was measured with a spectrophotometer U-3410 (manufactured by Hitachi, Ltd.). Next, based on the measurement results, the solubility was determined in accordance with Lambert-Beer's law, and the solubility was further determined.

D = εlc where D: absorbance, ε: spectral extinction coefficient, 1: cell length for absorbance measurement, c: concentration (mol / liter).

The spectral sensitizing dye of the present invention can be added at the time of the chemical ripening step, particularly preferably at the start of the chemical ripening. By adding it by the end of the process, a high-sensitivity silver halide emulsion having excellent spectral sensitizing efficiency can be obtained. (From the nucleation step to the end of the desalting step), the same or a different kind of spectral sensitizing dye of the present invention may be additionally added.

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

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

These patents are described, for example, in German Patent 929,08.
No. 0, U.S. Pat.Nos. 2,231,658, 2,493,748, 2,503,7
No. 76, No. 2,519,001, No. 2,912,329, No. 3,655,394
Nos. 3,656,959, 3,672,897, 3,649,217,
This is described in British Patent 1,242,588 and Japanese Patent Publication No. 44-14030.

In addition to these spectral sensitizing dyes, a dye having no spectral sensitization or a substance which does not substantially absorb visible light and exhibits supersensitizing effect is added to the emulsion layer. You may.

In the present invention, a noble metal salt such as a sulfur compound or a gold salt can be further sensitized with a selenium compound or a tellurium compound. Further, reduction sensitization can be performed, or sensitization can be performed by combining these methods.

Examples of the sulfur sensitizer applicable to the present invention include:
U.S. Patent Nos. 1,574,944, 2,410,689, 2,278,947
No. 2,728,668, 3,501,313, 3,656,955,
West German Application Publication (OLS) 1,422,869, JP-A-56-24937,
Sulfur sensitizers described in JP-A-55-45016 can be used. Specific examples include 1,3-diphenylthiourea, triethylthiourea, 1-ethyl, 3- (2-thiazolyl)
Preferred examples include thiourea derivatives such as thiourea, rhodanine derivatives, dithiacarbamic acids, polysulfide organic compounds, and sulfur alone. In addition, as the elemental sulfur, α-sulfur belonging to the orthorhombic system is preferable.

Examples of the gold sensitizer include chloroauric acid, gold thiosulfate, gold thiocyanate, and gold complexes of thioureas, rhodanines, and other various compounds.

In the present invention, fine silver iodide may be added to the silver halide emulsion during the process from chemical ripening to coating. Here, the process from chemical ripening to coating includes during chemical ripening and means that fine grain silver iodide is added to the process from coating to coating. Further, the fine grain silver iodide used in the present invention may be either cubic γ-AgI or hexagonal β-AgI, may have a crystal structure thereof, or may be a mixture thereof. .

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

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

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

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

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

The tabular silver halide grains used in the present invention are crystallographically classified as twins. Twins are silver halide crystals that have one or more twin planes in one grain, and the twin morphology is classified by Klein and Moiser.
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. These twin planes 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 average aspect ratio of the tabular silver halide grains used in the present invention is preferably from 2 to 12, and more preferably from 3 to 8.

The outer wall of the crystal of the tabular silver halide grains according to the present invention may be substantially composed of {111} planes or substantially {100} planes. Further, the surface may have both the {111} plane and the {100} plane. In this case, 50% or more of the particle surface is a {111} plane, more preferably 60% to 90% is a {111} plane, and particularly preferably 70 to 95% is a {111} plane. It is preferable that the plane other than the {111} plane is mainly the {100} plane. This surface ratio is determined by the {111} face and {100} in sensitizing dye adsorption.
T.Tani, J.Imaging
Sci. 29,165 (1985)].

The tabular silver halide grains according to the present invention include:
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 breadth of the distribution is defined by the relative standard deviation (coefficient of variation) 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 the distribution is defined by (%), it is preferably 25% or less, more preferably 20% or less, and particularly preferably 15% or less.

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

In the present invention, the tabular silver halide grains are preferably hexagonal. Hexagonal tabular grains
(Hereinafter also referred to as hexagonal tabular grains) is defined as the principal plane ({111}
Surface) is hexagonal, and the maximum adjacent ratio is 1.0 to 2.
Say 0. Here, the maximum adjacent side ratio is the ratio of the length of the side having the maximum length to the length of the side having the minimum length forming a hexagon. In the present invention, the hexagonal tabular grains preferably have rounded corners if the maximum adjacent side ratio is 1.0 to 2.0. The length of a side having a rounded corner is represented by the distance between the intersection of the extended straight line portion of the side and the extended straight line portion of the adjacent side. It is also preferred that the tabular grains are further rounded and are substantially circular.

In the present invention, it is preferable that at least one half of each side forming the hexagon of the hexagonal tabular grain is substantially a straight line. In the present invention, the adjacent side ratio is 1.0
More preferably, it is 1.5.

The halogenated grains according to the present invention may have dislocations. The dislocation is, for example, JF Hamilton, Phot. Sc
i.Eng, 57 (1967), T.Shiozawa, J.Soc.Phot.Sci.Japa
n, 35, 213 (1972) can be observed by a direct method using a transmission electron microscope at low temperature. That is, silver halide grains taken out so as not to apply enough pressure to generate dislocations from the emulsion are placed on a mesh for observation with an electron microscope, and the sample is prepared so as to prevent damage (printout, etc.) by electron beams. Observation is performed by a transmission method in a state of cooling. At this time, since the electron beam becomes harder to penetrate as the thickness of the particles becomes thicker, it is possible to more clearly observe using an electron microscope of a high-pressure type (200 KV or more for particles having a thickness of 0.25 μm). .

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

In the present invention, the center of the silver halide grains is defined by dispersing silver halide microcrystals in a methacrylic resin in the same manner as in the method described in the abstract of Inoue et al. When the circumscribed circle that minimizes the cross section is drawn by focusing on the sample with the maximum cross-sectional area and the sample with the cross-sectional area of 90% or more than that, 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 point at which the line intersects the outer periphery of the particle when a straight line is drawn outward from the center of the circle and the center of the circle.

Regarding the number of dislocations in the silver halide grains according to the present invention, it is desirable that at least 50% (number) of grains containing one or more dislocations exist, and the ratio of the number of tabular grains having dislocation lines (number) ) Is more preferable. In the present invention, the particle size is a diameter when a projected image of a particle is converted into a circular image having the same area. The projected area of a grain can be determined from the sum of the grain areas. In each case, a silver halide crystal sample distributed on a sample table to such an extent that no grain overlap occurs can be obtained by observing the sample with an electron microscope.

The average projected area diameter of the tabular silver halide grains in the present invention is represented by a circle-equivalent diameter of the projected area of the grains, and is preferably at least 0.30 μm, 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 projecting the particles at a magnification of 10,000 to 70,000 times with an electron microscope and measuring the projected area on the print.

The average particle diameter (φi) can be obtained 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) = Σnidi / n (The number of measured particles is indiscriminately 1.000 or more.) The particle thickness can be obtained by obliquely observing the sample with an electron microscope. . The preferred thickness of the tabular grains of the present invention is 0.03 to 1.0 μm, more preferably
It is 0.05 to 0.5 μm.

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

The distance between twin planes (a) can be determined as follows. That is, the section was observed using the above-mentioned transmission electron microscope, and arbitrarily selected 100 or more tabular silver halide grains showing a cross section cut almost perpendicularly to the main plane. a) is measured, and it can be determined by the averaging thereof.

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

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

Further, in the present invention, the tabularity represented by the following equation is taken into account by taking into account the factors of the aspect ratio and the thickness of the particles: A
= ECD / b ² is preferably 20 or more.

Where ECD is the average projected diameter of tabular grains.
(μm) and (b) is the thickness of the particles. Here, the average projected diameter represents the number average of the diameter of a circle having an area equal to the projected area of the tabular grains. The tabular silver halide grains used in the present invention may have a uniform composition, but have a core / shell type structure having at least two layer structures having substantially different halogen compositions in the silver halide grains. More than 50%, 100% by number of grains in the photosensitive silver halide emulsion layer
It is preferred to contain.

The core / shell type grains may have a halogen composition region different from that of the core at the grain center. In such a case, the halogen composition of the seed grains 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 2 mol% or less, more preferably.
It is 0.01 to 1.5 mol%. Of the grains having a layer structure with a different halogen composition, grains having a high silver iodide layer inside the grains and a low silver iodide layer or a silver bromide layer on the outermost layer are preferred. At this time, the silver iodide ratio of the inner layer (core) having the highest silver iodide content is preferably 2.5 mol% or more, more preferably 5 mol% or more. The silver content is 0 to 5 mol%, preferably 0 to 3 mol%, and the silver iodide content of the core is preferably at least 3 mol% or more than the silver iodide content of the shell.

The silver iodide distribution of the core is usually uniform, but may have a distribution. For example, as the concentration goes from the center to the outside, the concentration may become higher, or the intermediate region may have a maximum or minimum concentration.

The silver halide grains usable in the present invention include:
So-called halogen conversion type (conversion type) particles may be used. The halogen conversion amount is preferably from 0.2 mol% to 2.0 mol% with respect to the silver amount, and the conversion may be carried out during physical ripening or after physical ripening. As a method of halogen conversion, an aqueous halogen solution or fine silver halide particles having a smaller solubility product with silver than the halogen composition of the grain surface before the halogen conversion is usually added. The particle size at this time is preferably 0.2 μm or less, more preferably 0.02 to 0.1
μm. The silver halide grains of the present invention are preferably grown by, for example, a method of depositing silver halide on a seed crystal as described in Examples of JP-A-60-138538.

In the method for producing a silver halide photographic emulsion according to the present invention, in which a water-soluble silver salt solution and a water-soluble halide solution are supplied to the protective colloid in order to obtain a tabular silver halide emulsion, B) a step of forming nucleus grains for maintaining the pBr of the mother liquor at 2.5 to -0.7 during a period of 1/2 or more from the beginning of the formation of a silver halide precipitate having a silver iodide content of 0 to 5 mol%;
(B) Subsequent to the nucleus grain forming step, the mother liquor contains a silver halide solvent in an amount of 10 ^-5 mol to 2.0 mol per mol of silver halide and substantially monodisperse spherical twin grains. Or a seed grain forming step of forming a silver halide twin seed grain by increasing the temperature of the mother liquor to 40 to 80 ° C. following the core grain forming step. (C) Next, a method is preferably used in which a growth step of enlarging seed particles by adding a water-soluble silver salt solution and a water-soluble halide solution and / or halogenated fine particles is preferably used. Here, the mother liquor is a liquid (including a silver halide emulsion) which is used for preparing a silver halide emulsion up to a completed photographic emulsion.

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

A water-soluble silver salt may be added for the purpose of adjusting ripening during the seed particle forming step of the present invention.

The seed grain growing step for enlarging the silver halide seed grains includes pAg, pH, temperature, silver halide solvent concentration and silver halide composition, silver halide and silver salt during silver halide precipitation and Ostwald ripening. This can be achieved by controlling the rate of addition of the chloride solution.

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

In order to obtain tabular silver halide grains according to the present invention, conditions for enlarging the produced seed grains include, for example, JP-A-51-39027, JP-A-55-142329, and JP-A-58-113928.
As described in Nos. 54-48521 and 58-49938, a water-soluble silver salt solution and a water-soluble halide solution were added by the double jet method, and the addition rate was changed according to the enlargement of the particles. A method of gradually changing the temperature within a range in which Ostwald ripening does not occur may be used. As another condition for enlarging the seed grains, a method of adding silver halide fine grains, dissolving and recrystallizing the grains, as shown in Item 88 of the Abstracts of the 58th Annual Meeting of the Photographic Society of Japan, may be used.

For growth, an aqueous silver nitrate solution and an aqueous halide solution can be added by a double jet method, but the iodine can also be supplied into the system as silver iodide.
The addition rate is such that no new nuclei are generated, and the rate at which the size distribution does not spread due to Ostwald ripening,
That is, it is preferable to add in 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 stirrer, a device disclosed in JP-A-62-160128 in which an additive liquid nozzle is installed in the liquid near the mother liquor suction port of the stirrer is particularly preferably used. At this time, the stirring rotation speed is 400 to 120.
Preferably, it is 0 rpm.

The silver iodide content and the average silver iodide content of the silver halide grains of the present invention were determined by an EPMA method (Electron Probe).
Micro Analyzer). According to this method, a sample in which emulsion grains are well dispersed so as not to be in contact with each other is prepared, and element analysis of a minimum portion can be performed by X-ray analysis by electron beam irradiation for irradiating an electron beam. By this method, the halogen composition of each grain can be determined by determining the characteristic X-ray intensity of silver and iodine emitted from each grain. When the silver iodide content is determined for at least 100 grains by the EPMA method, the average silver iodide content is determined from the average thereof.

In the preparation of the photosensitive 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. Preferably, the coefficient of variation and the coefficient of variation of the longest distance (at) between twin planes of the seed grains are both 35% or less.

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

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

Further, the silver halide grains according to the present invention can be used in the step of forming and / or growing grains, in the course of cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), rhodium salts (including complex salts). At least one metal ion selected from the group consisting of a complex salt and an iron salt (including a complex salt) so that these metal elements can be contained inside the particles and / or in the particle surface layer. By placing the particles in a suitable atmosphere, reduction sensitization nuclei can be provided inside the grains and / or on the surface of the grains.

The effect of the reducing agent added at a desired point in time of particle formation is to add an oxidizing agent such as hydrogen peroxide (water) and its adduct, peroxoacid salt, ozone, and I ₂ at a desired point in time. It is preferable to deactivate 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 time of chemical sensitization.

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 remain contained. When removing the salts, use Lisa
H. Disclosure (hereinafter abbreviated as RD) No. 17643 II
It can be performed based on the method described in the section.

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

The silver halide light-sensitive material according to the present invention includes:
Various photographic additives can be used. Known additives include, for example, Research Disclosure (RD)
No. 17643 (December 1978), No. 18716 (November 1979) and
No. 308119 (December 1989). The types of compounds and the locations described in these three RDs are listed below.

Additive RD-17643 RD-18716 RD-308119 page classification page page classification Chemical sensitizer 23 III 648 upper right 996 III sensitizing dye 23 IV 648-649 996-8 IV A desensitizing dye 23 IV 998 IV B Dye 25-26 VIII 649-650 1003 VIII Development accelerator 29 XXI 648 Upper right Fog inhibitor / stabilizer 24 IV 649 Upper right 1006-7 VI Brightener 24 V 998 V Surfactant 26-27 XI 650 Right 1005-6 XI Antistatic agent 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 emulsion of the silver halide photographic light-sensitive material according to the invention,
The emulsion layer or other layers may contain a developing agent such as an aminophenol, ascorbic acid, pyrocatechol, hydroquinone, phenylenediamine or 3-pyrazolidone.

The support which can be used in the light-sensitive material according to the present invention includes, for example, the aforementioned RD-17643, page 28 and RD-17643.
-308119 at page 1009.

A suitable support is a polyethylene terephthalate film or the like. The surface of these supports may be provided with an undercoat layer to improve the adhesion of the coating layer, or may be subjected to corona discharge, ultraviolet irradiation, or the like.

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

The present invention relates to an X-ray processing method in which the silver halide photographic light-sensitive material of the present invention is processed in a processing step containing a developing solution substantially free of a hardener, with a total processing time of 15 to 90 seconds. An object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material for medical use.

The term "developer substantially free of a hardener" as used in the present invention means that a developer before processing a silver halide photographic light-sensitive material, a replenishment developer, or a starter solution containing no hardener. Say Therefore, if unreacted hardener contained in the photosensitive material elutes into the developing solution, it is out of the scope of the present invention.

Preferred developers for developing the light-sensitive material of the present invention include, as developing agents, JP-A-4-15641,
-16841, such as hydroquinone, paraaminophenols such as p-aminophenol, N-methyl-p-aminophenol, 2,4-diamiphenol, and the like, and 3-pyrazolidones such as 1 -Phenyl-3-pyrazolidones, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-
It is preferable to use pyrazolidone, 5,5-dimethyl-1-phenyl-3-pyrazolidone or the like, or to use them in combination.

The preferred amount of the above-mentioned para-aminophenols and 3-aminopyrazolidones is 0.004 mol / l, more preferably 0.04 to 0.12 mol / l.

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

The preservatives may include sulfites such as potassium sulfite, sodium sulfite and reductones such as piperidinohexose reductone.
These are preferably used in an amount of 0.2 to 1 mol / l, more preferably 0.3 to 0.6 mol / l. Also, addition of a large amount of ascorbic acids leads to processing stability.

As the alkaline agent, sodium hydroxide,
PH adjusters such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium tertiary phosphate, potassium tertiary phosphate. Furthermore, a buffer such as borate described in JP-A-61-28708, saccharose, acetoxime, 5-sulfosalicylic acid, phosphate and carbonate described in JP-A-60-93439 can be used. Good. The content of these agents is
H is selected to be 9.0 to 13, preferably pH 10 to 12.5.

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

The silver sludge inhibitor is disclosed in JP-A-56-106.
No. 244, a silver stain inhibitor, a sulfide described in JP-A-3-51844, a disulfide compound, and Japanese Patent Application No. 4-92.
A cysteine derivative or a triazine compound described in Japanese Patent No. 947 is preferably used.

As organic inhibitors, azole organic antifoggants such as indazole, imidazole, benzimidazole, triazole, benzotriazo, tetrazole and thiadiazole compounds are used.

The inorganic inhibitors include sodium bromide, potassium bromide, potassium iodide and the like. In addition, L.
FA Menson, "Photographic Processing Chemistry," Focal Press (1966), 22
Those described in pages 6 to 229, U.S. Pat. Nos. 2,193,015 and 2,592,364 and JP-A-48-64933 may be used.
Chelating agents for concealing calcium ions mixed in tap water used in the treatment solution include chelating agents having a chelate stabilization constant of 8 or more with iron described in JP-A-1-93853 as an organic chelating agent. It is preferably used. Examples of the inorganic chelating agent include sodium hexametaphosphate, calcium hexametaphosphate, and polyphosphate. The development temperature is preferably 25 to 50 ° C, more preferably 30 to 40 ° C.
° C. The development time is 5 to 90 seconds, more preferably 8 to 60 seconds. Processing time is preferably 20 for Dryto Dry.
210210 seconds, more preferably 30 to 90 seconds.

The replenishment of the processing liquid replenishes the amount corresponding to the processing agent fatigue and oxidative fatigue. As the replenishment method, width described in JP-A-55-126243, replenishment by feed rate, area replenishment described in JP-A-60-104946, area controlled by the number of continuously processed sheets described in JP-A-1-149156 Replenishment may be performed, and a preferable replenishment amount is 500 to 150 cc / m ² .

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

The swelling ratio of the emulsion layer of the silver halide photographic light-sensitive material according to the present invention is preferably 150 to 250% during the development processing, and the film thickness after expansion is preferably 70 μm or less. When the water swelling ratio exceeds 250%, poor drying occurs, and, for example, poor conveyance also occurs in, for example, automatic developing machine processing, particularly rapid processing. Further, if the water swelling ratio is less than 150%, uneven development may occur upon development.
The residual color tends to deteriorate. Here, the water swelling ratio is obtained by calculating the difference between the film thickness after swelling in each processing solution and the film thickness before development processing, dividing this by the film thickness before processing and multiplying by 100. .

[0165]

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

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

A1 ossein gelatin 100 g potassium bromide 2.05 g 11.5 l in water B1 ossein gelatin 55 g potassium bromide 65 g potassium iodide 1.8 g 0.2 N sulfuric acid 38.5 ml 2.6 l in water C1 ossein gelatin 75 g potassium bromide 950 g iodine Potassium chloride 27g 3.0l with water D1 Silver nitrate 95g 2.7l with water E1 Silver nitrate 1410g 3.2l with water The A1 solution which kept the temperature of the reactor at 60 ° C, B1 solution and D1
The solution was added by the control double jet method over 30 minutes, and then the C1 and E1 solutions were added by the control double jet method over 105 minutes, and stirring was performed at 500 rpm.

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

After the addition, the pH was adjusted to 6.0, and then Demol N (Kao Atlas Co., Ltd.) was added to remove excess salts.
) Aqueous solution and an aqueous solution of magnesium sulfate.

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

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

A2 Ossein gelatin 10 g Ammonia water (28%) 28 ml Glacial acetic acid 3 ml Seed emulsion-1 0.119 mol equivalent Finished to 600 ml with water B2 Ossein gelatin 0.8 g Potassium bromide 5 g Potassium iodide 3 g Finished to 110 ml with water C2 Ossein gelatin 2g Potassium bromide 90g Finish to 240ml with water D2 Silver nitrate 9.9g Ammonia water (28%) 7.0ml Finish to 110ml with water E2 Silver nitrate 130g Ammonia water (28%) 100ml Finish to 240ml with water F2 Potassium bromide 94g Finish with water to 165 ml G2 Silver nitrate 9.9 g Ammonia water (28%) 7.0 ml Finish with water to 110 ml A2 solution was kept warm at 40 ° C and stirred with a stirrer at 800 rpm.
The pH of Solution A2 was adjusted to 9.90 with acetic acid, and Seed Emulsion-1 was collected and dispersed and suspended. Then, Solution G2 was added at a constant speed over 7 minutes to adjust the pAg to 7.3. Furthermore, B2 solution and D2 solution are simultaneously
Added over 20 minutes. The pAg at this time was kept constant at 7.3. Using potassium bromide solution and acetic acid for another 10 minutes
After adjusting H = 8.83 and pAg = 9.0, solution C2 and solution E2 were simultaneously added over 30 minutes.

At this time, the flow ratio between the addition speed and the end of the addition was 1:10, and the flow rate was increased with time. or,
The pH was reduced from 8.83 to 8.00 in proportion to the flow ratio.

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

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

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

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

A3 Ossein gelatin 24.2 g Water 9657 ml Polypropylene oxy-polyethylene oxy-disuccinate sodium salt (10% 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 824 g 23.5 g of potassium iodide Finish to 2825 ml with water D3 1.75 N aqueous solution of potassium bromide Solution B3 was added to solution A3 using a mixing stirrer described in JP-B-58-58288 and JP-B-58-58289 at the following silver potential control amount at 42 ° C 464.3m each of solution C3
l was added by a double jet method over 1.5 minutes to perform nucleation.

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

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

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

A4 ossein gelatin 5.26 g Polypropylene oxy-polyethylene oxy-disuccinate sodium salt (10% aqueous ethanol solution) 1.4 ml seed emulsion-2 0.094 mol equivalent Equivalent to 569 ml with water B4 ossein gelatin 15.5 g potassium bromide 114 g Potassium iodide 3.19 g Make up to 658 ml with water C4 Silver nitrate 166 g Make up to 889 ml with water To solution A4 which was vigorously stirred at 60 ° C., solution B4 and solution C4 were added by the double jet method in 107 minutes. During this time, the pH was 5.8
In addition, pAg was kept at 8.7 throughout. The addition rates of the B4 solution and the C4 solution were linearly increased so that the initial and final addition rates were 6.4 times.

After completion of the addition, precipitation and desalting were carried out in the same manner as in Em-1 to remove excess salts. At 40 ° C. and pAg 8.5, the average silver iodide content at pH 5.85 was about 2.0 mol%. An emulsion was obtained.

When the obtained emulsion was observed with an electron microscope, tabular silver halide grains having an average grain size of 0.98 μm, a grain size distribution of 18%, and an average aspect ratio of 4.5 were found to account for 82% of the projected area. The average twin plane distance (a) was 0.006 μm, and the coefficient of variation of a was 42%.

Preparation of Em-3 Em-3 was prepared in exactly the same manner as Em-2 except that the mixing temperature in the nucleation of seed emulsion-2 was changed from 42 ° C. to 35 ° C. Observation of the obtained emulsion under an electron microscope revealed that 84% of the projected area was tabular silver halide grains having an average grain size of 0.98 μm, a grain size distribution of 17%, and an average aspect ratio of 4.5. The average of the twin plane distance (a) is 0.006 μm.
Had a coefficient of variation of 30%.

Preparation of Em-4 Em-4 was prepared in exactly the same manner as Em-2 except that the mixing time in the nucleation of Seed Emulsion-2 was changed from 1.5 minutes to 2.0 minutes.

When the obtained emulsion was observed with an electron microscope, 84% of the projected area was tabular silver halide grains having an average grain size of 0.98 μm, a grain size distribution of 18%, and an average aspect ratio of 4.5. The average of the twin plane distance (a) was 0.020 μm, and the variation coefficient of a was 42%.

Preparation of Em-5 Em-5 was prepared in exactly the same manner as Em-2 except that the mixing temperature in nucleation of seed emulsion-2 was changed from 42 ° C. to 35 ° C., and the mixing time was changed from 1.5 minutes to 2.0 minutes. Was prepared.

Observation of the obtained emulsion under an electron microscope revealed that 86% of the projected area was tabular silver halide grains having an average grain size of 0.98 μm, a grain size distribution of 16%, and an average aspect ratio of 4.5. The average of the twin plane distance (a) was 0.020 μm, and the variation coefficient of a was 30%. The coefficient of variation of the thickness of the seed emulsion was 32%, and the coefficient of variation of the distance between twin planes was 29%.

Preparation of Em-6 to 8 The amount of KBr of A3 in the nucleation of seed emulsion-2, the mixing temperature, the mixing time, and the pAg at the time of preparation of Em-2, except for Em-
Em-6 to 8 were prepared in exactly the same manner as in 2.

Preparation of Em-9 A tabular emulsion having a core / shell structure was prepared using Seed Emulsion-2 and the following four solutions.

A5 Ossein gelatin 11.7 g Polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% aqueous solution of ethanol) 1.4 ml Seed emulsion-2 0.10 mol equivalent Equivalent to 550 ml with water B5 Oscein gelatin 5.9 g Potassium bromide 4.6 g Potassium iodide 3.0 g Finished to 145 ml with water C5 Silver nitrate 10.1 g Finished to 145 ml with water D5 Ossein gelatin 6.1 g Potassium bromide 94 g Finished to 304 ml with water E5 137 g silver nitrate Finished to 304 ml with water A5 stirred vigorously at 70 ° C The B5 solution and the C5 solution were added to the solution by the double jet method in 58 minutes. Then D5 in the same liquid
Liquid and E5 liquid were added by a double jet method for 48 minutes. During this time, the pH was kept at 5.8 and the pAg at 8.7.

After completion of the addition, desalting was carried out in the same manner as in the case of emulsion Em-2.
Precipitation was performed to obtain an emulsion having an average silver iodide content of about 2.0 mol% at pAg 8.5 and pH 5.85 at 40 ° C.

When the obtained emulsion was observed with an electron microscope, tabular silver halide grains having an average grain size of 0.96 μm, a grain size distribution of 18%, and an average aspect ratio of 4.5 were obtained at 81% of the projected area. Met. The average of the twin plane distance (a) is 0.00
The coefficient of variation of a was 45%.

Preparation of Em-10 to Em -24 Amount of KBr in Solution A3 of Seed Emulsion-2 of Em-9, Solution B
3. Addition time of C3, addition temperature, amount of seed emulsion-2 in solution A4 in preparation of Em-2, amount of potassium bromide and amount of potassium iodide in solution B5, pAg at the time of addition, addition rate Em-10 to 24 were prepared in the same manner as Em-3 except that the addition time, the addition temperature and the like were changed.

The shapes, iodine compositions, structures, average particle diameters, average aspect ratios (AR) of the obtained emulsions Em-1 to Em-24,
Table 3 below shows the average value and the variation coefficient of (a).

[0197]

[Table 3]

First, 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) using the above emulsion (Em-12) will be described. Examined.

That is, after the emulsion was heated to 60 ° C., a predetermined amount of the spectral sensitizing dye shown in Table 2 was added as a dispersion in the form of solid fine particles, and then a mixed aqueous solution of ammonium thiocyanate, chloroauric acid and sodium thiosulfate was added. In addition, a silver iodide fine grain emulsion was further added 60 minutes later, and ripening was performed for a total of 2 hours. 4-hydroxy-6-methyl-1,3,3a, 7 as stabilizer at the end of aging
-An appropriate amount of tetrazaindene (TAI) was added.

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

Potassium thiocyanate 95 mg Chloroauric acid 25 mg Sodium thiosulfate 25 mg Silver iodide fine particles 850 mg Stabilizer (TAI) 1 g The solid fine particle dispersion of the spectral sensitizing dye is according to the method described in Japanese Patent Application No. 4-99437. Prepared by the following method.

That is, a predetermined amount of the spectral sensitizing dye was added to water previously adjusted to 27 ° C., and stirred by a high-speed stirrer (dissolver) at 3.500 rpm for 30 to 120 minutes.

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

Coating was performed on both sides of the support simultaneously using two slide hopper type coaters so that the amount of silver per side was 2.0 g / m ² and the amount of gelatin was 3.1 g / m ² per side. It dried and the sample No. 1-No. 15 were obtained. The support consists of a copolymer consisting of three monomers of 50 wt% glycidyl methacrylate, 10 wt% methyl acrylate, and 40 wt% butyl methacrylate on both sides of a polyethylene terephthalate film base for X-rays with a thickness of 175 μm and a blue color of 0.15. The following filter dye and gelatin were dispersed in an aqueous copolymer dispersion obtained by diluting so as to have a concentration of 10% by weight, and the resultant was applied as a subbing liquid.

Filter dye (solid dispersion)

[0206]

Embedded image

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

1,1-dimethylol-1-bromo-1-nitromethane 70 mg t-butyl-catechol 400 mg polyvinylpyrrolidone (molecular weight 10.000) 1.0 g styrene-maleic anhydride copolymer 2.5 g nitrophenyl-triphenylphosphonium chloride 50 mg 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 m
g

[0209]

Embedded image

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

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

[0212]

Embedded image

[0213]

[Table 4]

Next, each of the obtained samples No. 1 to No. 13 was subjected to two kinds of conditions (condition A: 23 ° C., 55% RH, condition B: 40
(C, 80% RH) for 4 days, and the photographic properties were evaluated.

The evaluation method was as follows. First, a sample was placed on two intensifying screens KO-2.
The film was sandwiched between 50 (manufactured by Konica Corporation) and exposed to X-rays at a tube voltage of 80 kvp and a tube current of 100 mA for 0.05 seconds through an aluminum wedge for exposure. Then, using an automatic developing machine SRX-502 (manufactured by Konica Corporation), processing was performed with a developing solution and a fixing solution having the following formulations.

Developer Formulation Part-A (for 12 liter finishing) Potassium hydroxide 450 g Potassium sulfite (50% solution) 2280 g Diethylenetetraamine pentaacetic acid 120 g Sodium bicarbonate 132 g 5-Methylbenzotriazole 1.2 g 1-Phenyl-5- Mercaptotetrazole 0.2 g Hydroquinone 340 g Add water to make 5000 ml.

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

Fixer Formulation Part-A (for 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 about 5L of water at the same time, add water while stirring and dissolving, and make up to 12L.
H was adjusted to 10.40. This is used as a developer.

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

The fixer was prepared by adding Part A and Part B to about 5 liters of water.
Was added at the same time, water was added while stirring and dissolving to make up to 18 l, and the pH was adjusted to 4.4 with sulfuric acid and NaOH. This is used as a fixing replenisher.

The processing temperature was 35 ° C. for development, and
33 ° C, water washing 20 ° C, drying 50 ° C, processing time is dry to dry 45
Seconds.

After the treatment, the sensitivity was measured. The sensitivity is expressed as the reciprocal of the exposure amount that gives a density of fog +0.5.
The relative sensitivity was defined assuming that the sensitivity of 13 (storage condition A) was 100. The results obtained are shown in Table 5 below.

[0223]

[Table 5]

As is clear from Table 5, the sample sensitized by the combined use of the two spectral sensitizing dyes according to the method of the present invention was more sensitive than the comparative sample sensitized by only one spectral sensitizing dye. It can be seen that the sensitivity and fog change were excellent even when stored under high temperature and high humidity.

The same result was obtained when the spectral sensitizing dye was added as a methanol solution instead of as a solid fine particle dispersion. However, the latter method requires almost the same performance as the former. Approximately 20-30% extra loading was required. Therefore, in the latter method, the amount of the spectral sensitizing dye remaining after the development processing is increased, and the image quality is significantly deteriorated due to coloring contamination.

Next, the various emulsions thus prepared were sensitized using the following two sensitizing formulations, and the features of the combined use technique of the spectral sensitizing dye of the present invention were evaluated. The evaluation method and results are described below.

Sensitizing Formulation (P) After the silver halide emulsion was heated to 60 ° C., an exemplary spectral sensitizing dye was prepared.
After adding (I-16) and (II-2) as dispersions in the form of solid fine particles, a mixed aqueous solution of ammonium thiocyanate, chloroauric acid and sodium thiosulfate was added. In addition, aging was performed for a total of 2 hours. At the end of aging, an appropriate amount of (TAI) was added as a stabilizer.

The amounts of the above-mentioned various additives are shown in the case of the emulsion (Em-12) as a typical example. For other emulsions, a correction amount proportional to the surface area of the silver halide grains was added.

Spectral sensitizing dye (I-16) 140 mg Spectral sensitizing dye (II-2) 140 mg Potassium thiocyanate 95 mg Chloroauric acid 25 mg Sodium thiosulfate 25 mg Silver iodide fine particles 850 mg Stabilizer (TAI) 1 g Sensitizing formulation ( Q) In the above formulation (P), (I-16)
Same conditions except that only was added.

Next, various additives were added to the emulsion sensitized by the above two sensitizing formulations in the same manner as described above, and coating samples Nos. 14 to 3 were coated.
7 was produced and evaluated.

Photographic Performance The relative sensitivities in the table are relative sensitivities when the sensitivity of sample No. 14 sensitized with the above sensitizing formula Q and stored under storage conditions A was defined as 100. The storage resistance of each sample was determined based on the sensitivity difference between storage conditions A and B for each sample.
The relative value is shown with the sensitivity difference of 4 being 100. The smaller the value, the smaller the change and the better.

Pressure resistance The pressure resistance was evaluated as follows. The needle head 0.3 mm was added to the unexposed sample Nos. 14 to 37 stored under the storage condition A described above.
After applying a load of 5 g with a needle hardness meter, the same developing treatment as described above was performed, and the pressure fogging density was measured with a microdensitometer. The degree of fog was shown as a relative value when the fog increase value of Sample No. 14 (sensitizing formulation Q) was set to 100. The results obtained are shown below.

[0233]

[Table 6]

As is clear from Table 6, the sensitivity, storage resistance, and pressure of the sample according to the present invention (sensitizing formulation P) containing two types of spectral sensitizing dyes were higher than that of the sample containing one type of spectral sensitizing dye (sensitizing formulation Q). It can be seen that the resistance is excellent regardless of the type of silver halide emulsion. Further, when compared from the viewpoint of the structure of silver halide grains, tabular crystals are better than normal crystals, grains having a core / shell structure than grains having a uniform distribution of iodine, and the iodine content is 2 mol% or less. It is understood that the requirement for achieving the effects of the present invention more remarkably is that the particles have a relative variation coefficient of the twin plane distance of 30% or less.

Example 2 The sensitizing effect obtained by combining the spectral sensitizing dye represented by the general formula (I) and the spectral sensitizing dye represented by the general formula (II) in the emulsion Em-24 prepared in Example 1 is as follows. I checked it.

That is, after the emulsion was heated to 60 ° C., a predetermined amount of the spectral sensitizing dye shown in Table 2 was added as a dispersion of solid fine particles, and then ammonium thiocyanate, chloroauric acid and
A mixed aqueous solution of sodium thiosulfate and a methanol solution of N, N'-dimethylselenourea were added, and after 60 minutes, a silver iodide fine grain emulsion was added, followed by ripening for a total of 2 hours. At the end of ripening, an appropriate amount of (TAI) was added as a stabilizer.

The additives other than the spectral sensitizing dyes and the amounts thereof are as follows.

Potassium thiocyanate 95mg Chloroauric acid 25mg Sodium thiosulfate 20mg N, N'-dimethylselenourea 4mg Silver iodide fine particles 850mg Stabilizer (TAI) 1g The obtained emulsion was added with additives in the same manner as in Example 1. An emulsion layer coating solution was obtained. A protective layer coating solution was prepared in exactly the same manner as in Example 1, and both the coating solutions were used to apply and dry in the same manner as in Example 1.
Sample Nos. 38 to 50 were obtained.

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

However, the processing time was adjusted by the automatic developing machine,
Seconds and 45 seconds. The evaluation method was the same as in Example 1. The results obtained are shown in Table 7 below.

[0241]

[Table 7]

As is clear from Table 7, the processing time was 30 minutes.
It can be seen that the sample of the present invention has higher sensitivity and less change due to the processing time than the comparative sample even when shortened to seconds.

[0243]

According to the present invention, a silver halide photographic light-sensitive material having high sensitivity, excellent pressure resistance and excellent storage stability with time can be obtained. Further, according to the present invention, a silver halide photographic light-sensitive material having little residual color contamination due to the residual dye after the development processing was obtained.

Further, the silver halide photographic light-sensitive material of the present invention can obtain the above-mentioned features even if it is processed in a processing step containing a developing solution containing no hardener, and its effect can be obtained even in a more rapid processing. It was even more pronounced.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI G03C 1/06 502 G03C 1/06 502 1/18 1/18 5/26 5/26 (56) References JP-A-7- 36150 (JP, A) JP-A-5-61148 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03C 1/29 G03C 1/035 G03C 1/18 G03C 1/06 502

Claims (6)

(57) [Claims] To 1. A light-sensitive silver halide emulsion layer, silver
70% or more of the total projected area of silver halide grains has an aspect ratio of 2 or less
Upper tabular silver halide grains, wherein said tabular silver halide grains are
Two or more twin planes in which 50% (number) or more of silver halide grains are parallel
And two or more parallel twins of the tabular grains
The average value of the maximum distance (a) among the distances between surfaces is 0.00
8 μm or more, and the variation coefficient of (a) is 35% or less.
And at least one spectral sensitizing dye represented by the following general formula (I) containing silver halide grains represented by the following general formula (I):
A silver halide photographic material comprising a combination of at least one of the spectral sensitizing dyes represented by I). Embedded image In the formula, R ₁ and R ₃ each represent a substituted or unsubstituted alkyl group, at least one of R ₁ and R ₃ is a group other than an ethyl group, and R ₂ and R ₄ are lower groups. Represents an alkyl group, and 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:
Each represents a hydrogen atom or a displaceable group whose sum of the added Hammett σp values is less than 1.7, V ₁ , V ₂ ,
V ₃ and V ₄ are not simultaneously a hydrogen atom or a chloro atom. X ₁ represents an ion necessary for neutralizing an intramolecular charge, and n represents 1 or 2. However, when an internal salt is formed, n is one. Embedded image In the formula, R ₅ and R ₆ each represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group, and at least one of R ₅ and R ₆ is a sulfoalkyl Or a carboxyalkyl group. R ₇ represents a hydrogen atom, an alkyl group, or an aryl group.
Z ₁ and Z ₂ are each a benzene ring which may have a substituent <br/> or represents a non-metallic atomic group necessary for forming a naphtho ring. X ₂ represents an ion necessary for neutralizing the charge in the molecule, and m represents 1 or 2. However, when an internal salt is formed, m is 1. 2. A photosensitive silver halide emulsion comprising a silver halide emulsion wherein the average iodine content of the silver halide grains is 0.01 mol% or more and 2 mol% or less. A silver halide photographic material according to claim 1 . (3) 50% of the above-mentioned photosensitive silver halide emulsion;
3. The silver halide photographic light-sensitive material according to claim 1, wherein said (number) is a core-shell type grain. 4. The method according to claim 1, wherein the photosensitive silver halide emulsion is
4. A silver halide photographic light-sensitive material for medical use, comprising at least one of the items 2 and 3 . 5. The medical silver halide according to claim 4 , wherein the total processing time is from 15 seconds to 90 seconds in the processing step including a developer containing substantially no hardener. Processing method of photographic photosensitive material. 6. A photosensitive silver halide emulsion layer comprising a halogen atom.
70% or more of the total projected area of silver halide grains has an aspect ratio of 2 or less
A tabular silver halide grains of the above, the flat-halogeno
Two or more twin planes in which 50% (number) or more of silver halide grains are parallel
And two or more parallel twins of the tabular grains
The average value of the maximum distance (a) among the distances between surfaces is 0.00
8 μm or more, and the variation coefficient of (a) is 35% or less.
At least one kind of the spectral sensitizing dye represented by the above general formula (I) and at least one kind of the spectral sensitizing dye represented by the above general formula (II) At least one of the spectral sensitizing dyes is added as a substantially water-insoluble solid fine particle dispersion dispersed in an aqueous system substantially free of an organic solvent and / or a surfactant. , And when the reflection spectrum is measured, 52
A silver halide photographic material, wherein the spectral sensitizing dye is adsorbed on the silver halide grains so that a characteristic J-band at 0 to 560 nm is formed.