JPH095908A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To obtain provide a silver halide photographic sensitive material high in sensitivity and low in fog and high in contrast and superior in storage stability even in the case of rapid processing with low replenishment by forming a layer containing a specified chemically sensitized silver halide emulsion. CONSTITUTION: The emulsion layer contains flat silver halide grains in >=50% of the projection areas of the total silver halide grains and these flat grains have principal faces comprising (100) faces each having an ajacent side ratio of <10 and an average aspect ratio of >=2 and a high silver chloride content, and the emulsion is chemically sensitized in the presence of a dye by at least one compound selected from a selenium compound represented by formula I and a tellurium compound represented by formula II and in formulae I and II, each of Z1 -Z6 is an aliphatic or aromatic or heterocyclic group or a -OR1 , -N(R2 )(R3 ), -SR4 , or -SeR5 group or an H or halogen atom; each of R1 , R4 , and R5 is an aliphatic, aromatic, or heterocyclic group or an H atom or a cation; and each of R2 and R3 is an aliphatic, aromatic, or heterocyclic group or an H atom.

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 fog, high contrast and excellent storage stability, and particularly to a silver halide photographic light-sensitive material suitable for X-ray medical treatment. It is a thing.

[0002]

2. Description of the Related Art A silver halide photographic light-sensitive material (hereinafter, also referred to as a light-sensitive material) has a high sensitivity and is excellent in gradation, and is therefore widely used at present. Particularly in the case of a photographic light-sensitive material, silver iodobromide mainly containing silver bromide is mainly used as a silver halide mainly for high sensitivity.

Further, in recent years, there has been an increasing demand from the market for improvement in quick and low replenishment treatment.
For products used in markets where strong demands are being made for large quantities of prints, such as color photographic paper photosensitive materials, the silver halide used is silver chlorobromide or chloride, which does not substantially contain silver iodide. Silver is used. This is because silver halide grains having a low silver iodide ratio and a high silver chloride ratio are more advantageous in accelerating development and fixing.

However, silver halide emulsions having a high silver chloride content have the drawbacks of low sensitivity and difficulty in obtaining a hard gradation, and the crystal growth of high chloride silver halide grains is usually high. Fogging tends to be high because it is performed in a concentrated atmosphere.

Therefore, various ideas have been disclosed from the viewpoint of modifying the sensitizer and the high chloride silver halide grains. As a method for obtaining a highly sensitive silver halide photographic light-sensitive material, a method of sensitizing using selenium sensitization or tellurium sensitization has been disclosed. Regarding selenium sensitization technology,
In JP-A-4-335338, 80 mol% or more is composed of silver chloride.
Selenium sensitization of a silver halide emulsion having a localized phase of which mol% or more is silver bromide is disclosed in JP-A-4-335339, in which a selenium-sensitized halogen consisting of 90 mol% or more of silver chloride is used. It is known that a silver halide emulsion may contain a reducing agent.
JP-A-6-308652 discloses a technique for containing a selenium-sensitized silver halide emulsion containing 80 mol% or more of silver chloride and adjusting the pH of a film of a light-sensitive material to 4.0 to 6.5.
No. 95 mol% containing a specific gold compound inside the particle
The above has disclosed a technique for sensitizing a silver halide emulsion, which is silver chloride, with selenium. Descriptions of the tellurium sensitization technique are described in JP-A-5-11387 and JP-A-6-308652.

However, in any case, (10
When it is used as a tabular grain having the (0) plane as the main plane, the sensitizing effect is still insufficient, and the fog is high, and the rise of fog during storage cannot be suppressed.

On the other hand, technical studies using silver halide grains include, for example, JP-A-58-108533 and JP-A-60-222845,
JP-A-3-188435, JP-A-3-188436 and the like describe a method of localizing a phase composed of silver bromide on the surface of high chloride silver halide grains. In addition, Japanese Examined Japanese Patent Publication Nos. 50-36978 and 58-24077
Multi-phase structure particles such as core / shell double structure particles or junction structure particles obtained by adding bromine ions or simultaneous addition of bromine ions and silver ions to the high chloride silver halide particles described in No. 2 etc. Are known to make. Further, JP-A No. 64-26837 describes a high chloride silver halide grain having a silver bromide rich region near the apex of the grain.

However, in each case, the sensitizing effect and the contrast enhancement are insufficient, and rapid processing, low fog, high sensitivity and contrast silver halide photographic light-sensitive material of a level still satisfying the market demands. Has not been realized.

[0009]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to provide high sensitivity and low fog even when rapid processing is performed with a low replenishment, a high contrast and a good storage stability. An object is to provide an excellent silver halide photographic light-sensitive material.

[0010]

DISCLOSURE OF THE INVENTION The inventors of the present invention have made extensive studies on a silver halide photographic light-sensitive material using a high chloride silver halide emulsion, and the above-mentioned object of the present invention is to contain silver halide grains. 50% or more of the total projected area of the tabular tabular high chloride silver halide grains having an average aspect ratio of 2 or more, whose main planes are (100) planes with adjacent side ratios of less than 10, and A layer containing a silver halide emulsion chemically sensitized with at least one selected from the selenium compound represented by the general formula (1) and the tellurium compound represented by the general formula (2) in the presence thereof. It has been found that the silver halide photographic light-sensitive material has a silver bromide-rich region in the vicinity of at least one apex or surface of the silver halide grains.

The present invention will be described in detail below.

In the present invention, the silver halide grains contained in the emulsion layer are tabular silver halide grains. The tabular silver halide grain in the present invention is a grain having two parallel main planes facing each other, and has an average ratio of grain size to grain thickness (hereinafter, referred to as aspect ratio) of 2 or more. Is. Here, the grain size refers to the average projected area diameter, and is shown by the diameter of a circle having the same projected area as the projected area of silver halide grains, and the thickness is the thickness of two parallel main grains forming tabular silver halide grains. The distance between planes.

The tabular silver halide grain of the present invention has an average aspect ratio of 2 or more, preferably 2 or more and less than 15.0. It is particularly preferably 4 or more and less than 8.

At least 50% of the total projected area of the silver halide grains contained in the silver halide emulsion of the present invention consists of tabular silver halide grains having the (100) plane as the principal plane, but preferably 70 % Or more, more preferably 90% or more.

The shape of the principal plane of the tabular silver halide grain of the present invention is a right-angled parallelogram or a right-angled parallelogram with rounded corners. The ratio of adjacent sides of the right-angled parallelogram is less than 10, preferably less than 5, more preferably less than 2. When the corners are rounded, the side length is
It is represented by the distance between the intersection of the straight line portion of the side and the straight line portion of the adjacent side.

The average grain size of the tabular silver halide grains of the present invention is about 0.15 to 5.0 μm, preferably 0.4 to 3.0 μm, more preferably 0.4 to 2.0 μm. Average thickness 0.01-1.0μ
m, preferably 0.02 to 0.40 μm, more preferably 0.02
~ 0.30 μm.

Particle size and thickness can be optimized to optimize sensitivity and other photographic properties. Optimum particle size and optimum depending on other factors constituting the photosensitive material (sensitivity of hydrophilic colloid layer, hardness, chemical ripening conditions, sensitivity of photosensitive material, amount of silver coating, etc.) that affect sensitivity and other photographic characteristics The thickness is different.

The grain size distribution of the tabular silver halide grains of the present invention is preferably monodisperse. Specifically, the breadth (%) of the grain size distribution is defined as (standard deviation of grain size / average grain size). ) × 100, 25% or less is preferable, and further 20
% Or less, particularly preferably 15% or less.

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

In the tabular silver halide grains of the present invention, silver chloride, silver chlorobromide, silver iodochloride and silver chloroiodobromide can be used as the silver halide, and the content of silver iodide is halogenated. The average silver iodide content in the entire silver grains is preferably 1.0 mol% or less, more preferably 0.5 mol% or less.

In the present invention, the halogen content and average halogen content of individual silver halide grains can be determined by using the EPMA method (Electron Probe Micro Analyzer method). 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, an electron beam is irradiated, and X-ray analysis by electron beam excitation is performed. By this method,
The silver halide composition of individual grains can be determined. If the halogen content is obtained by the EPMA method for at least 50 particles, the halogen content can be obtained from the average thereof.

The tabular silver halide grains contained in the silver halide emulsion of the present invention preferably have a more uniform halogen content between grains. When the halogen content distribution between particles is measured by the EPMA method, the relative standard deviation is preferably 35% or less, more preferably 20% or less.

In the present invention, when tabular silver halide grains contain silver iodide, the position of the silver iodide is preferably inside, more preferably at the center. Further, it is also preferable that it is present on the outermost surface in addition to the inside.

In the present invention, the halogen composition distribution inside the silver halide grain is obtained by slicing the grain into ultrathin sections and observing and analyzing with a transmission electron microscope while cooling. Specifically, after taking out the silver halide grains from the emulsion, embedded in resin, by cutting this with a diamond knife, to make a slice of thickness 60nm,
It is determined by observing and spot analysis with a transmission electron microscope equipped with an energy dispersive X-ray analyzer while cooling this section with liquid nitrogen, and performing quantitative calculation. (See Inoue and Nagasawa: Abstracts of the Annual Meeting of the Photographic Society of 1987, p. 62) In the present invention, the silver iodide content on the outermost surface of tabular silver halide grains is determined by the XPS method (X-ray Photoelectron
Spectroscopy: X-ray photoelectron spectroscopy) refers to the silver iodide content in a portion up to a depth of 50 Å, and is determined as follows.

The sample is placed in an ultrahigh vacuum of 1 × 10 ^-8 torr or less
Cool down to 110 ° C or below and use MgKα as X-ray for the probe.
Irradiate with a source voltage of 15KV and an X-ray source current of 40mA, Ag3d5 / 2, Br3
d, Measure for I3d3 / 2 electrons. The integrated intensity of the measured peak is corrected by a sensitivity factor (Sensivity Factor), and the halide composition of the outermost surface is obtained from the intensity ratio of these. The sample is cooled to eliminate measurement errors caused by destruction of the sample by X-ray irradiation at room temperature (decomposition of silver halide and diffusion of halide (especially iodine)) and increase the measurement accuracy. If cooled, sample destruction can be suppressed to a level that does not hinder measurement.

The tabular silver halide grains of the present invention preferably contain silver chloride in an amount of 50 mol% or more, more preferably 70 mol% or more.

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

The tabular silver halide grains of the present invention can be prepared by the method described in US Pat. No. 5,320,938. That is, it is preferable to nucleate with low pCl in the presence of iodide ions under the condition that the (100) plane is easily formed. After nucleation, Ostwald ripening and / or growth can be performed to obtain tabular silver halide grains having a desired grain size and distribution.

For example, first, a silver salt solution, a halide solution containing iodide ions, and a protective colloid solution are added to the first container to form nuclei, and after the nucleation, the mixed solution is transferred to the second container. The method of growing there is preferably used.

At this time, the growth may be temporarily stopped on the way and seed grains may be used to deposit silver halide on the seed grains.

Specifically, an aqueous solution containing a protective colloid and seed particles may be present in advance in a reaction vessel, and silver ions, halogen ions or silver halide fine particles may be supplied as necessary to grow the seed particles. .

To prepare the tabular silver halide grains of the present invention, pCl of the protective colloid solution is about 0.5 to 3.5, preferably 1.0 to 3.0, more preferably 1.5 to 2.5.

In the preparation of the tabular silver halide grains of the present invention, nucleation is started at the time when the silver salt solution is added to the protective colloid solution, and the iodine ion is added simultaneously with the silver salt solution or the silver salt solution. It is preferred that it is added prior to the salt solution, especially preferred that before the silver salt solution. It is possible to introduce iodine up to the solid solution limit of silver iodide and silver chloride, but the iodine ion concentration in the protective colloid solution at the start of nucleation is preferably 10 mol% or less, more preferably 0.01 mol%. % Or more and 10 mol% or less, and most preferably 0.05 mol% or more and 10 mol% or less.

In the preparation of the tabular silver halide grains of the present invention, the addition time of the silver salt solution during nucleation is preferably 5 seconds or more and less than 1 minute. Further, it is preferable that both a silver salt solution and a halide solution (particularly iodine ion) are added at the time of nucleation. The bromine ion in the protective colloid solution during nucleation may be present as long as the chlorine ion is present in an amount of 50 mol% or more.

In the present invention, the silver chloride content of the nucleus is 50 mol% or more, preferably 70 mol% or more, and further 90 mol% or more. The pH during nucleation is preferably 2-8 and the temperature is 30
The temperature is preferably up to 90 ° C, more preferably 35 to 70 ° C. The amount of silver added during nucleation is preferably 0.1 to 10 mol% of the total amount of silver.

In the preparation of the silver halide grains of the present invention, a known silver halide solvent such as ammonia, thioether or thiourea can be present.

In the preparation of the tabular silver halide grains of the present invention, a silver salt solution and a halide solution are added at the time of growth by the double jet method, and the rate of addition depends on the growth of grains and no new nucleation occurs, In addition, particles having a desired particle size and distribution can be obtained by a method in which the size distribution does not spread due to Ostwald ripening, that is, a method of gradually changing it within a range of 30 to 100% of the speed at which new nuclei are generated.
As another condition for further growth, a method in which silver halide fine particles are added and dissolved and recrystallized to grow, as shown in page 88 of the Annual Meeting of the Photographic Society of Japan, 1988, is also preferably used. In particular, silver iodide fine grains, silver bromide fine grains, silver iodobromide fine grains, and silver chloride fine grains are preferably used.

The tabular silver halide grains of the present invention may be so-called halogen conversion type grains. The timing of halogen conversion may be physical ripening or after physical ripening. Examples of the halogen conversion include a method of adding an aqueous halogen solution or silver halide fine particles having a smaller solubility product with silver than the halogen composition on the surface of the grain before the halogen conversion. At this time, the particle size is preferably 0.2 μm or less, more preferably 0.02 to 0.1 μm.

When silver bromide is contained on the outermost surface of the tabular silver halide grains of the present invention, the method is to add a silver nitrate solution and a solution containing bromide ion to the emulsion containing the tabular grains as the base. A method of simultaneously adding, a method of adding fine particles of silver bromide and the like can be applied, but the latter is preferable. At this time, iodine and / or chlorine may be contained if necessary. Particularly in the case of iodine, an organic compound that releases iodine ions may be used.

The silver halide grain of the present invention contains at least 1
It is preferred to have a silver bromide rich region near one vertex or near the surface. The vicinity of the surface mentioned here means a position within 1/5 of the particle size as measured from the outermost surface of the particle, and preferably within 1/7. As the halogen composition, the content of silver bromide localized near the surface is preferably 20 mol% or more, more preferably 50 mol% or more. At this time, the content of silver bromide in the whole grain is preferably 5 mol% or less, more preferably 1 mol% or less. Similarly, the silver iodide content in the localized phase containing silver iodobromide or silver iodochlorobromide is preferably 1 mol% or less, and the total amount of grains is 1 mol% or less, more preferably 0.5 mol%. The following are preferred.

The apex of the silver halide grain referred to in the present invention means a portion which is judged to be substantially apex in crystallography.
The vicinity of the apex means within 1/4 of the length of the shortest side of the principal plane of the tabular grain from the apex. In the case of a tabular grain whose side is not a straight line, the position corresponding to the apex is estimated from the curvature of the curve and similarly determined. As a method of forming a desired localized phase in the vicinity of the apex, a method of adsorbing a compound that selectively adsorbs on the (100) plane to the surface of the grain to control or prevent the initiation of halogen substitution can be preferably used. As such a compound, a cyanine dye,
Examples thereof include merocyanine dyes, mercaptoazoles and purines. The silver bromide content of the localized phase thus formed is preferably 20 mol% or more, more preferably 50 mol% or more. The silver iodide content is preferably 1 mol% or less. At this time, silver bromide may be contained in the vicinity of the surface as long as the localization effect is not impaired, but it must be at least 20 mol% or less. Especially when a localized phase is formed near the apex, pressure desensitization tends to occur, but this is not recognized in the present invention. It is considered to be peculiar to tabular grains having the (100) plane as the principal plane, but this was not easily expected at first.

The time for adjusting the silver iodide content on the outermost surface is from the final step of the silver halide crystal production step to the chemical ripening step, and further from the completion of the solution preparation step immediately before the coating of the silver halide emulsion. Although it can be selected as appropriate, it is preferable to adjust it by the end of the chemical ripening step. The chemical ripening step referred to here is a point in time when physical ripening and desalting of the silver halide emulsion of the present invention are completed, when a chemical sensitizer is added, and thereafter, an operation for stopping chemical ripening is performed. Up to. Further, the addition of silver halide fine particles may be carried out in several times with a time interval, and after the addition of the fine particles,
Further chemically ripened emulsions may be added.

The temperature of the emulsion of the present invention when the silver halide fine grains are added is preferably in the range of 30 to 80 ° C., and further,
A 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 lost 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.

In producing the tabular silver halide grains of the present invention, the stirring conditions during production are extremely important. As the stirring device, a device in which the additive liquid nozzle disclosed in JP-A-62-160128 is installed in the liquid near the mother liquid suction port of the stirrer is particularly preferably used. The stirring speed at this time is 100
It is preferably set to ~ 1200 rpm.

In the tabular silver halide grain of the present invention, the cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (including complex salt), rhodium salt ( It is preferable to add a metal ion by using at least one selected from the group consisting of complex salts) and iron salt so that these metal elements are contained inside and / or on the surface of the particles.

In the present invention, it is also preferable to add a silver halide solvent before the desalting step in order to accelerate the developing rate. For example, it is preferable to add a thiocyanate compound (potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate, etc.) in an amount of 1 × 10 ^{−3 to} 3 × 10 ⁻² mol per mol of silver.

In the present invention, it is preferable to use gelatin as the dispersion medium for the protective colloid of silver halide grains. As the gelatin, alkali-treated gelatin, acid-treated gelatin, low molecular weight gelatin (molecular weight of 20,000 to 100,000),
Modified gelatin such as phthalated gelatin is used. or,
Other hydrophilic colloids can also be used. Specifically, Research Disclosure
Hereinafter, it is abbreviated as RD. ) Volume 176 No.17643 (December 1978)
Months) are listed.

In the production of the tabular silver halide grains of the present invention, unnecessary soluble salts may be removed during the growth of the silver halide grains, or they may be contained therein.
The removal of the salts can be carried out according to the method described in Item II of RD Vol. 176, No. 17643.

The selenium sensitizer and tellurium sensitizer used in the present invention are compounds represented by the general formulas (1) and (2), respectively. In these general formulas, Z _{1 (4)} ,
The aliphatic group represented by Z _{2 (5)} , Z _{3 (6)} , R ₁ , R ₂ , R ₃ , R ₄ and R ₅ is a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group, Aralkyl group (for example, methyl group, ethyl group, n-propyl group, isopropyl group, t-butyl group, n-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopentyl group, cyclohexyl group, Allyl group, 2-butenyl group, 3-pentenyl group, propargyl group, 3-pentynyl group, benzyl group, phenethyl group). The aromatic group represented by Z _{1 (4)} , Z _{2 (5)} , Z _{3 (6)} , R ₁ , R ₂ , R ₃ , R ₄ and R ₅ is a monocyclic or condensed ring aryl group (for example, , Phenyl group, pentafluorophenyl group, 4-
Chlorophenyl group, 3-sulfophenyl group, α-naphthyl group, 4-methylphenyl group). Z _{1 (4)} , Z _{2 (5)} , Z
_The heterocycle represented by _{3 (6)} , R ₁ , R ₂ , R ₃ , R ₄ and R ₅ is a saturated 3- to 10-membered ring containing at least one of a nitrogen atom, an oxygen atom or a sulfur atom. Alternatively, it represents an unsaturated heterocyclic group (for example, a pyridyl group, a thienyl group, a furyl group, a thiazolyl group, an imidazolyl group, a benzimidazolyl group). The cation represented by R ₁ , R ₄ and R ₅ represents an alkali metal atom or ammonium, and the halogen atom represented by X represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Z _{1 (4)} , Z _{2 (5)} and Z _{3 (6)} are preferably an aliphatic group, an aromatic group or —OR ₁ , and R ₁ is an aliphatic group or an aromatic group. More preferably, it is a trialkylphosphine selenide (telluride), a triarylphosphine selenide (telluride), a trialkylseleno (tellino) phosphate or a triarylseleno (tellino) phosphate.

The present inventors have investigated selenium sensitizers and tellurium sensitizers, which are known to have sensitizing effects, and
It was found that the sensitizer represented by formula (1) or (2) is effective for sensitizing the tabular silver halide grains of the present invention and suppressing fog. The amount of the selenium sensitizer used is about 10 ^-8 to 10 ^-4 mol per mol of the silver halide. The addition method is water or an organic solvent such as methanol or ethyl acetate, or a solvent mixed in a mixed solvent and added. Although it may be added as an emulsified dispersion, it is preferably added as an emulsified dispersion. In the present invention. The selenium sensitizer is added in the presence of the dye, which is preferably added during chemical ripening. The chemical ripening temperature using the selenium sensitizer in the present invention is preferably 40 ° C or higher and 90 ° C or lower, and more preferably 45 ° C or higher and 80 ° C or lower. Also, p
It is preferable that H is 4 or more and 9 or less and pAg is 6 or more and 9.5 or less. When the tellurium sensitizer is used, the selenium sensitizer and the tellurium sensitizer may be appropriately used in accordance with this.

In the present invention, a sulfur sensitizer may be used in combination, and US Pat. Nos. 1,574,944, 2,410,689 and 2,410,689 may be used in combination.
278,947, 2,728,668, 3,501,313, 3,656,9
55, West German Application Publication (OLS) No. 1,422,869, JP-A-5
Nos. 6-24937 and 55-45016 can be used, for example, 1,3-diphenylthiourea, triethylthiourea, 1-ethyl-3- (2-thiazolyl) thiourea, etc. Preferred examples include thiourea derivatives, rhodanine derivatives, dithiacarbamic acids, polysulfide organic compounds, elemental sulfur, and inorganic compounds such as sodium thiosulfate. Particularly preferable sulfur sensitizers are thiourea derivatives represented by the following general formula (3) and α-sulfur simple substance belonging to the orthorhombic system.

[0052]

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[In the formula, R ₆ represents a heterocyclic residue containing a nitrogen atom and / or a sulfur atom, R ₇ represents a hydrogen atom, a lower alkyl group, an allyl group or an aryl group, and R ₈ represents R ₆ or R
₇ in the above formula, R ₇ and R ₈ may form a heterocyclic ring bonded to each other. Here, R ₆ represents a heterocyclic residue, and examples of the heterocycle include a pyrroline ring, a pyridine ring, a quinoline ring, an indole ring, an oxazole ring, a benzoxazole ring, a naphthoxazole ring, an imidazole ring,
Benzimidazole ring, thiazoline ring, thiazole ring,
Examples thereof include a benzothiazole ring, a naphthothiazole ring, a selenazole ring, a benzoselenazole ring, and a naphthoselenazole ring. These heterocycles may be substituted with an alkyl group such as a methyl group or an ethyl group; an alkoxy group such as a methoxy group or an ethoxy group; an aryl group such as a phenyl group; a halogen atom or the like.

The lower alkyl group for R ₇ has 6 carbon atoms.
Up to unsubstituted alkyl groups (eg, methyl group, ethyl group, n-propyl group, isobutyl group, isoamyl group), hydroxyalkyl groups (eg, hydroxyethyl group),
Examples thereof include a cyanoalkyl group (for example, cyanoethyl group) and an aminoalkyl group (for example, dimethylaminoethyl group). As the aryl group, a phenyl group,
Examples thereof include naphthyl group, p-tolyl group and p-chlorophenyl group.

Examples of the hetero ring formed by combining R ₇ and R ₈ include a morpholine ring, a piperidine ring, a piperazine ring and a pyrrolidine ring.

Specific examples of the compound represented by formula (3) will be given below.

[0057]

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[0058]

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[0059]

[Chemical 6]

[0060]

[Chemical 7]

[0061]

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Examples of gold sensitizers that can be used in combination include chloroauric acid, gold thiosulfate, gold thiocyanate and the like, as well as gold complexes of thioureas, rhodanins and other various compounds. You can

The amounts of the sulfur sensitizer and the gold sensitizer used are not uniform depending on the type of silver halide emulsion, the type of compound used, the ripening conditions, etc. 1 × 10 ⁻⁴ to 1 × 10 ⁻⁹ mol, preferably 1
It is ^{x10 -5} to 1 x 10 ^-8 mol. The sulfur sensitizer and the gold sensitizer may be added by dissolving them in water or alcohols, an inorganic or organic solvent and adding them in the form of a solution. Insoluble in water or using a medium such as gelatin. Then, it may be added in the form of a dispersion obtained by emulsifying and dispersing. Sulfur sensitization and gold sensitization may be performed simultaneously or separately and stepwise. In the latter case, favorable results may be obtained by performing gold sensitization after or during the appropriate sulfur sensitization.

It is also preferable to carry out so-called reduction sensitization inside the grains by placing in an appropriate reducing atmosphere. As the reducing agent, thiourea dioxide and ascorbic acid and their derivatives, hydrazine, polyamines such as diethylenetriamine, dimethylamine boranes, sulfites and the like are preferable, and the addition amount is the type of reduction sensitizer, silver halide grain Particle size, composition and crystal habit, reaction system temperature, p
Although it varies depending on the environmental conditions such as H and pAg, for example, in the case of thiourea dioxide, a preferable result is obtained by using about 0.01 to 2 mg per mol of silver halide as a rough guide. In the case of ascorbic acid, it is preferably in the range of about 50 mg to 2 g per mol of silver halide. The conditions for reduction sensitization are as follows: temperature is about 40-70 ℃, time is about 10-200 minutes,
Is preferably about 5 to 11, and pAg is preferably about 1 to 10.

Further, so-called silver ripening, which is a kind of reduction sensitization technique, is carried out by adding a water-soluble silver salt. PA during silver aging
1-6 is suitable for g, Preferably it is 2-4. Conditions such as temperature, pH and time are in accordance with the above-mentioned reduction sensitization conditions, and silver nitrate is preferable as the water-soluble silver salt. As a stabilizer for a silver halide photographic emulsion containing reduction-sensitized silver halide grains, the following general stabilizers can be used, but the antioxidant described in JP-A-57-82831 is used. Agent and / or VS Gahler, "Zeit shrift fur wissenschaftliche P
Hotographie Bd. 63, 133 (1969) "and the thiosulfonic acids described in JP-A-54-1019 are often used in combination with good results. These compounds may be added at any stage of the emulsion production process from the crystal growth to the preparation process immediately before coating.

The tabular silver halide grains of the present invention may be spectrally sensitized with methine dyes and the like. As the dye used, a cyanine dye, a merocyanine dye,
Examples thereof include complex cyanine dyes, complex merocyanine dyes, horoboler cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes, and particularly useful dyes are cyanine dyes, merocyanine dyes, and complex merocyanine dyes. These dyes are ordinary, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus,
Oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, fused with an aliphatic hydrocarbon ring, indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus,
Any of a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, and the like can be applied, and the carbon atom may have a substituent.

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 sensitizing dyes may be used alone or in combination, and the combination is often used for the purpose of supersensitization. Further, together with the sensitizing dye, a dye having no spectral sensitizing property by itself or a substance which does not substantially absorb visible light and exhibits a supersensitizing effect may be contained in the emulsion layer. For example, a substituted aminostilbene compound having a nitrogen-containing heterocyclic nucleus group (for example, US Pat.
2,933,390, 3,635,721), aromatic organic acid formaldehyde condensate (for example, US Pat. No. 3,743,
No. 510), cadmium salt, azaindene compound and the like.

US Pat. Nos. 3,615,613 and 3,615,641,
The combinations described in Nos. 3,617,295 and 3,635,721 are particularly useful. The sensitizing dye is present in the selenium sensitization and tellurium sensitization of the present invention, in addition to nucleation, growth, desalting,
It may be added either during or after each step of chemical sensitization or after chemical sensitization.

In the present invention, the following cyanine or carbocyanine dyes can be used.

[0071]

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[0072]

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[0073]

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[0074]

[Chemical 12]

[0075]

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[0076]

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[0077]

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When at least one of the silver halide emulsion layer of the present invention or any of constituent layers other than the emulsion layer contains a dye capable of decoloring and / or flowing out during development processing, high sensitivity and high sharpness can be obtained. It is possible to obtain a light-sensitive material which is suitable for rapid processing. The dye used in the photosensitive material may be appropriately selected from dyes capable of improving sharpness by absorbing a desired wavelength and removing the influence of the wavelength, depending on the photosensitive material. it can. It is preferable that the dye is decolorized or flows out during the development processing of the light-sensitive material, and the color is not visually recognized when the image is completed.

Such a dye is a dye which is substantially insoluble in water at a pH of 7 or less and water-soluble at a pH of 8 or more, and is specifically represented by the following general formula.

[0080]

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[In the formula, A and A'each represent an acidic nucleus,
B is a basic nucleus, Q is an aryl group or a heterocyclic group, Q '
Is a heterocyclic group, X and Y are electron withdrawing groups, L
₁ , L ₂ and L ₃ each represent a methine group. m represents 0 or 1, n represents 0, 1 or 2, and p represents 0 or 1. However, the dye represented by these general formulas has at least one group selected from a carboxy group, a sulfonamide group and a sulfamoyl group in the molecule. The acidic nucleus represented by A and A ′ is preferably 5-pyrazolone, barbituric acid, thiobarbituric acid, rhodanine, hydantoin, thiohydantoin, oxazolone, isoxazolone, indandione, pyrazolidinedione, oxazolidine. Dione, hydroxypyridone,
Examples include pyrazolopyridone.

Examples of the basic nucleus represented by B include pyridine, quinoline, oxazole, benzoxazole, naphthoxazole, thiazole, benzthiazole, naphthothiazole, indolenine, pyrrole and indole.

Examples of the aryl group represented by Q include a phenyl group, a naphthyl group and a julolidyl group.
Examples of the heterocyclic group represented by Q and Q'include a pyridyl group, a quinolyl group, an isoquinolyl group, a pyrrolyl group, a pyrazolyl group, an imidazolyl group, an indolyl group, a furyl group and a thienyl group. These aryl groups and heterocyclic groups may have a substituent, and are alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, halogen atoms, alkoxycarbonyl groups, aryloxycarbonyl groups, carboxy groups, cyano groups, hydroxy groups. , A mercapto group,
Examples of the substituent include an amino group, an alkoxy group, an aryloxy group, an acyl group, a carbamoyl group, an acylamino group, a ureido group, a sulfonamide group and a sulfamoyl group. Preferred substituents are alkyl groups having 1 to 8 carbon atoms (eg, methyl group, ethyl group, t-butyl group, n-octyl group, 2-hydroxyethyl group, 2-methoxyethyl group), hydroxy group, cyano group. , A halogen atom, an alkoxy group having 1 to 6 carbon atoms (eg, methoxy group, ethoxy group, 2-hydroxyethoxy group, methylenedioxy group, n-
Butoxy group), substituted amino group (eg, dimethylamino group, diethylamino group, di (n-butyl) amino group, N-ethyl-N-hydroxyethylamino group, N-ethyl-N-methanesulfonamidoethylamino group, morpholino Group, piperidino group, pyrrolidino group), carboxy group, sulfonamide group (eg methanesulfonamide group, benzenesulfonamide group), sulfamoyl group (eg sulfamoyl group, methylsulfamoyl group, phenylsulfamoyl group). .

The electron-withdrawing groups represented by X and Y may be the same or different, and the substituent constant Hammett's σ _p value (edited by Toshio Fujita: “Chemical Region Special Issue No. 122: Structure-Activity Relationship of Drugs”). 96-103 (1979) Nankodo, etc.) is preferably a group of 0.3 or more, for example, a cyano group, an alkoxycarbonyl group (eg, a methoxycarbonyl group,
Ethoxycarbonyl group, butoxycarbonyl group, octyloxycarbonyl group, etc., aryloxycarbonyl group (eg phenoxycarbonyl group, 4-hydroxyphenoxycarbonyl group), carbamoyl group (eg carbamoyl group, methylcarbamoyl group, ethylcarbamoyl group, butylcarbamoyl group) Group, dimethylcarbamoyl group,
Phenylcarbamoyl group, 4-carboxyphenylcarbamoyl group), acyl group (eg, methylcarbonyl group, ethylcarbonyl group, butylcarbonyl group, phenylcarbonyl group, 4-ethylsulfonamidophenylcarbonyl group), alkylsulfonyl group (eg, methylsulfonyl group) , An ethylsulfonyl group, a butylsulfonyl group, an octylsulfonyl group) and an arylsulfonyl group (eg, a phenylsulfonyl group, a 4-chlorosulfonyl group).

The methine group represented by L ₁ , L ₂ and L ₃ is
It may have a substituent, for example, an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, hexyl group), aryl group (eg, phenyl group, tolyl group, 4-hydroxyphenyl group), aralkyl group ( For example, benzyl group, phenethyl group), heterocyclic group (eg pyridyl group, furyl group, thienyl group), substituted amino group (eg dimethylamino group, diethylamino group, anilino group), alkylthio group (eg methylthio group), etc. As.

In the present invention, among the dyes represented by the above general formula, those having at least one carboxy group in the molecule are preferable, and more preferably those represented by the general formula [I] having a carboxy group. And a dye in which Q is a furyl group.

Specific examples of these dyes and synthesizing methods are described in JP-A Nos. 52-92716, 55-120030, 55-155350 and 55-1.
55351, 56-12639, 63-197943, JP-A-2-1838
No. 2-1839, World Patent 88/04794, US Patent No. 4,86
No. 1,700, No. 4,950,586, and European Patent No. 489,973.

When the dye used in the present invention is a solid fine particle dispersion, it is disclosed in JP-A-52-92716, JP-A-55-155350 and JP-A-55-155350.
The methods described in 155351, 63-197943, Japanese Patent Laid-Open No. 3-182743, World Patent 88/04794 and the like can be used. Specific examples include the use of a surfactant, for example, a ball mill,
It is prepared using a fine dispersion machine such as a vibration mill, a planetary mill, a sand mill, a roller mill, a jet mill, a disc impeller mill and the like. Also, after dissolving the dye in a weak alkaline aqueous solution, the pH is lowered to make it weakly acidic to precipitate fine particle solids, or a weak alkaline solution of the dye and an acidic aqueous solution are simultaneously mixed while adjusting the pH. A dispersion of dyes can also be obtained by the method of producing a particulate solid.

When dispersed in the form of solid fine particles, it is preferable to disperse the dye fine particles so that the average particle diameter thereof is 0.01 to 5 μm, more preferably 0.01 to 1 μm, and particularly 0.01 to 0.5 μm.
It is. When the coefficient of variation of particle size distribution is (standard deviation of particle size / average value of particle size) × 100, it is preferably 50% or less, more preferably 40% or less, and particularly 30% It is the following.

In the light-sensitive material of the present invention, any of anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants is used as the surfactant used for forming the fine particle dispersion of the dye. Alkyl sulfonate, alkyl benzene sulfonate, alkyl naphthalene sulfonate, alkyl sulfates, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers,
Anionic surfactants such as N-acyl-N-alkyltaurines; nonionic surfactants such as saponins, alkylene oxide derivatives, and alkyl esters of sugars.

The amount of the anionic surfactant and / or the nonionic surfactant used is not uniform depending on the kind of the surfactant or the conditions of the dispersion liquid of the dye, but it is usually about 0.1 to 2000 mg per 1 g of the dye. , Preferably 0.5-1000 mg,
Furthermore, it is 1 to 500 mg. The concentration of the surfactant in the dye dispersion is about 0.01 to 10% by weight, preferably 0.1 to 5% by weight. The timing of adding the surfactant is preferably before the dispersion of the dye is started, and if necessary, it may be further added after the dispersion is completed.

In the present invention, a hydrophilic colloid used as a binder for a photographic constituent layer can be added to the dye dispersion at the start of dispersion or at the end of dispersion. As the hydrophilic colloid, it is advantageous to use gelatin, but in addition, gelatin derivatives such as phenylcarbamylated gelatin, acylated gelatin, phthalated gelatin and the like; Graft polymers; carboxymethyl cellulose, hydroxymethyl cellulose, cellulose derivatives such as cellulose sulfate; polyvinyl alcohol, partially oxidized polyvinyl acetate, polyacrylamide, poly-N, N-dimethylacrylamide, poly-N-vinylpyrrolidone, polymethacrylic acid Synthetic hydrophilic polymers such as; agar; gum arabic; alginic acid; albumin; casein and the like can be used. You may use these in combination of 2 or more types. The amount of hydrophilic colloid added to the dye dispersion is about 0.1 to 12% by weight, preferably 0.5.
８8% by weight.

In the present invention, the constituent layer to which the dye is added is preferably a silver halide emulsion layer or a layer closer to the support or both, and more preferably a coating layer adjacent to the support. It is effective to add it inside. The dye preferably has a high concentration on the side close to the support. The amount of the dye added is about 0.2 to 20 mg / m ² , preferably 0.8 to 15 mg / m ² .

Mordant agents can be used in order to fix the dye concentration at a high concentration on the side close to the support. For example, as a non-diffusible agent for binding with the above-mentioned dye, West German Patent No. 2,263,031 can be used. , British Patent No. 1,221,131,
1,221,195, JP-A-50-47624, 50-71332, JP-B-51-1418, U.S. Pat.No. 2,548,564, 2,675,316
No., No. 2,795,519, No. 2,839,401, No. 2,882,156,
3,048,487, 3,184,309, 3,444,138, 3,4
45,231, 3,706,563, 3,709,690, 3,788,85
The compounds described in No. 5 and the like can be preferably used. Although various methods can be adopted for binding the non-diffusible moldant and the dye, the method of binding in a gelatin binder is preferable. Also, combine them in an appropriate binder,
You may disperse | distribute in a gelatin aqueous solution using an ultrasonic wave etc. The binding ratio is not uniform depending on the compound, but it is usually 0.1 to 10 parts of the non-diffusible moldant with respect to 1 part of the water-soluble dye. In this case, the added amount of the dye can be larger than that of the dye alone.

In the surface layer of the light-sensitive material of the present invention, as a slip agent, in addition to the silicon compounds described in US Pat. Nos. 3,489,576 and 4,047,958, colloidal silica described in JP-B-56-23139, paraffin wax. , Higher fatty acid esters, starch derivatives and the like can be used.

Further, polyols such as trimethylolpropane, pentanediol, butanediol, ethylene glycol and glycerin can be added as a plasticizer to the light-sensitive material of the present invention.

Further, the light-sensitive material of the present invention may contain a polymer latex for improving pressure resistance, and may be a homopolymer of an alkyl ester of acrylic acid or a copolymer with acrylic acid, styrene, etc., a styrene-butadiene copolymer, or an active material. A polymer or copolymer composed of a monomer having a methylene group, a water-soluble group or a crosslinkable group with gelatin can be preferably used. In particular, a copolymer with an alkyl ester of acrylic acid, a water-soluble group containing a hydrophobic monomer such as styrene as a main component or a monomer having a crosslinkable group with gelatin in order to enhance affinity with gelatin as a binder is most preferable. Preferred examples of the monomer having a water-soluble group are acrylic acid, methacrylic acid, maleic acid, 2-acrylamido-2-methylpropanesulfonic acid and styrenesulfonic acid, and preferred examples of the monomer having crosslinkability with gelatin are , Glycidyl acrylate, glycidyl methacrylate, N-methylol acrylamide and the like.

Examples of matting agents include US Pat. No. 2,992,101
No. 2, No. 2,702,245, No. 4,142,894, No. 4,396,706 homopolymers of polymethylmethacrylate or polymers of methylmethacrylate and methacrylic acid, organic compounds such as starch, silica, titanium dioxide, strontium sulfate, barium sulfate, etc. Fine particles of inorganic compounds can be used, and the particle size is 0.6 to 10 μm, especially 1 to 5 μm.
Are preferred. In addition, it is possible to use organic aggregate particles in which primary particles of about 0.05 to 0.50 μm are aggregated into particles of about 1.0 to 20 μm, and the shape thereof may be spherical or amorphous. The organic component is an alkyl methacrylate, an alkyl acrylate or a methacrylate in which an alkyl group is substituted with fluorine or silicon, an acrylate and a styrene, and may be a homopolymer or a copolymer, but polymethyl methacrylate is preferable, and Soken Chemical GR-5 and GR-5P manufactured by K.K. The effective addition amount is 10 to 200 mg / m ² without deteriorating the haze.

Further, for the purpose of improving the pressure resistance, the silver halide emulsion layer may contain inorganic fine particles, the main components of which are silicon, aluminum, titanium, indium, yttrium, tin, antimony, zinc, nickel, copper, Oxides selected from iron, cobalt, manganese, molybdenum, niobium, zirconium, vanadium, alkali metals, alkaline earth metals and the like can be mentioned. Among them, silicon oxide (colloidal silica) and aluminum oxide are preferred in terms of transparency and hardness. , Tin oxide, vanadium oxide, and yttrium oxide are preferable. When these inorganic oxides are dispersed in water to form a sol, the surface may be treated with alumina, yttrium, cerium or the like in order to enhance the water dispersion stability of itself. Further, in order to improve the affinity with gelatin, it may be shelled with pre-crosslinked gelatin. The amount of the inorganic fine particles added is about 0.05 to 1.0 by dry weight ratio to the binder gelatin of the layer to be added, preferably 0.1 to 0.
7 The preferred particle size of the inorganic fine particles is 1 to 300 nm
It is.

The light-sensitive material of the present invention preferably contains a water-soluble polymer, and polyacrylamides such as polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, etc. described in US Pat. No. 3,271,158, and polysaccharides such as dextrin, dextran, sucrose, pullulan are effective. Among them, polyacrylamide, dextran and dextrin are preferable, and dextrin is particularly preferable. The average molecular weight of these substances is preferably 20,000 or less, more preferably 10,000 or less.

In the present invention, the amount of the hydrophilic binder and the amount of silver of the silver halide emulsion layer are 3.0 g / m ² or less per one side of the support when the emulsion layers are on both sides of the support, respectively.
It is preferably from 1.8 g / m ^2, and more respectively 2.0 g / m ² or less and 0.5 to 1.5 g / m ^2. When the emulsion layer is on only one side of the support, it is preferably 6.0 g / m ² or less and 3.6 g / m ² or less, and further 4.0 g / m ² or less and 1.0 g, respectively.
/ M ^{2 to} 3.0 g / m ² .

The silver halide photographic light-sensitive material of the present invention is a black-and-white silver halide photographic light-sensitive material such as a medical light-sensitive material, a printing light-sensitive material, a negative light-sensitive material for general photography; a color negative light-sensitive material, a color reversal light-sensitive material, a color material. It can be used as a color photographic light-sensitive material such as a printing light-sensitive material; a diffusion transfer light-sensitive material; a heat-development light-sensitive material; and the like, but a black-and-white silver halide photographic light-sensitive material is preferable, and a medical light-sensitive material is particularly preferable.

The light-sensitive material of the present invention has a total processing time of 15
Suitable for processing with an automatic processor in ~ 45 seconds. The light-sensitive material of the present invention includes aminophenol, ascorbic acid,
A developing agent such as pyrocatechol, hydroquinone, phenylenediamine or 3-pyrazolidone may be incorporated.

The light-sensitive material of the present invention includes, 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.), mucohalogen acids (mucochloric acid, mucophenoxycycloric acid, etc.), isoxazoles, 2-chloro-6-hydroxytriazinylated gelatin It is preferable that the amount of water swelling in the treatment is optimized so as to be suitable for rapid treatment by containing a hardening agent such as. Preferred compounds include JP-A Nos. 53-41221, 53-57257, 59-162456, and 60-80.
Active vinyl compounds and US Pat.
The active halogen compounds described in 5,287 are preferred. or,
Polymeric hardeners can also be used effectively. Polymers having aldehyde groups such as dialdehyde starch, polyacrolein, acrolein copolymers described in US Pat. No. 3,396,029, polymers having epoxy groups described in US Pat. No. 3,623,878, US Pat. No. 3,362,827, RD -1733
3 (1978) etc., a polymer having a dichlorotriazine group, active vinyl groups described in JP-A Nos. 54-65033 and 56-142524, US Pat. No. 4,161,407, RD-16725 (1978) or the like. Polymers having a precursor group, and the like are preferable. Among them, as described in JP-A-56-142524, an active vinyl group or a precursor group thereof is bonded to a polymer main chain by a long spacer. Polymers are particularly preferred.

The swelling ratio of the light-sensitive material of the present invention in the development processing is preferably 150 to 250%, and the film thickness after expansion is preferably 70 μm or less. When the water swelling rate exceeds 250%, poor drying occurs, and, for example, poor transport is also caused in processing by an automatic processor, especially in rapid processing. Also, the water swelling rate is 15
If it is less than 0%, uneven development or residual color may increase during development. The water swelling ratio here means the difference between the film thickness after swelling in each processing solution and the film thickness before development processing, and this is divided by the film thickness before processing and multiplied by 100.

Further, the following can be referred to for various techniques which can be adopted for the light-sensitive material of the present invention.

RD-17643 RD-18716 RD-308119 Page classification Page classification Page classification Chemical sensitizer 23 III 648 Upper right 996 III Desensitizing dye 23 IV 998 IVA Development accelerator 29 XXI 648 Upper right Fog inhibitor / stabilizer 24 IV 649 Top right 1006 to 1007 VI Whitening agent 24 V 998 V Antistatic agent 27 XII 650 Right 1006 to 1007 XIII Support 28 XVII 1009 XVII Preferred developing agents for the developer used in the light-sensitive material of the present invention are JP-A No. -15641, 4-16841, etc., dihydroxybenzene (hydroquinone, etc.), para-aminophenols (p-aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc.), 3-pyrazolidone Class (1-phenyl-3-pyrazolidone, 1-phenyl-
4-methyl-4-hydroxymethyl-3-pyrazolidone, 5,5-dimethyl-1-phenyl-3-pyrazolidone, etc., and the preferable amount of paraaminophenols and 3-pyrazolidones used is 0.004 mol / l or more. , And 0.04 to 0.12 mol / l
It is. Further, the total amount of dihydroxybenzenes, paraaminophenols and 3-pyrazolidones contained in the developing solution is preferably 0.1 mol / l or less.

As the preservative, sulfites (potassium sulfite, sodium sulfite, etc.) and reductones (piperidinohexose reductone, etc.) may be contained, and these are preferably 0.2 to 1 mol / l, more preferably 0.3. Used at ~ 0.6 mol / l. In addition, adding a large amount of ascorbic acid also leads to processing stability.

The alkaline agent includes a pH adjusting agent such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium triphosphate and potassium triphosphate.

Further, a borate described in JP-A-61-28708 and a buffer such as saccharose, acetoxime, 5-sulfosalicylic acid, phosphate and carbonate described in JP-A-60-93439 are used. Good. The content of these agents is
It is selected to be 9.0 to 13, preferably 10 to 12.5.

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

Examples of the silver sludge inhibitor include those disclosed in JP-A-56.
-106244 silver stain inhibitor, sulfide and disulfide compounds described in JP-A-3-51844, Japanese Patent Application No. 4-92947
The cysteine derivative or the triazine compound described in JP-A No. 1994-110 is preferably used.

As the organic inhibitor, an azole type organic antifoggant, for example, an indazole type, an imidazole type, a benzimidazole type, a triazole type, a benztriazole type, a tetrazole type or a thiadiazole type compound is used.

As the inorganic inhibitor, sodium bromide, potassium bromide, potassium iodide and the like are contained. Besides this, LF
A. Menson "Photographic Processing
Chemistry "Focal Press, Inc. (1966), 226
~ 229, U.S. Pat. Nos. 2,193,015, 2,592,364, and JP-A-48-64933 may be used.

The chelating agent for concealing calcium ions mixed in tap water used in the treatment liquid is a chelating agent having a chelate stabilization constant of 8 or more with iron described in JP-A 1-193853 as an organic chelating agent. 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 light-sensitive material in advance rather than in the developing step.

The processing temperature of the developer is preferably 25 to 50 ° C.
And more preferably 30 to 40 ° C.

The developing time is preferably 3 to 45 seconds, more preferably 5 to 30 seconds. Processing time is Dry to Dry 15 to 45
Seconds are preferred, but more preferably 15-30 seconds.

The processing solution is replenished by replenishing the processing agent fatigue and oxidative fatigue. The replenishment method was controlled by the width and feed rate replenishment described in JP-A-55-126243, the area replenishment described in JP-A-60-104946, and the continuous processing number described in JP-A-1-149156. Area replenishment may be used, and the preferable replenishment rate is 500 to 150 cc / m ² .

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

The fixing agent is a thiosulfate such as ammonium thiosulfate and sodium thiosulfate, and ammonium thiosulfate is particularly preferable from the viewpoint of the fixing speed. The concentration of the ammonium thiosulfate is preferably in the range of 0.1 to 5 mol / l, more preferably 0.8 to 3 mol / l. The fixing solution may be one that forms an acidic hardening. In this case, aluminum ions are preferably used as the hardener. For example, it is preferable to add in the form of aluminum sulfate, aluminum chloride, potassium alum and the like. Other fixers include preservatives such as sulfite and bisulfite, pH buffers such as acetic acid and boric acid, mineral acids (sulfuric acid, nitric acid) and organic acids (citric acid, oxalic acid, malic acid, etc.), hydrochloric acid, if desired. PH adjusting agents such as various acids and metal hydroxides (potassium hydroxide, sodium hydroxide) and chelating agents having a water softening ability. Examples of fixing accelerators include Japanese Patent Publication Nos. 45-35754 and 58-122535.
No. 58-122536 and the like, and thioethers and the like described in US Pat. No. 4,126,459.

It is also possible to use a powder processing agent or a solid processing agent such as tablets, pills, granules, etc., which has been subjected to a moisture-proof treatment, if necessary. Here, the powder refers to an aggregate of fine crystals, the granule refers to a granular material having a particle size of 50 to 5000 μm obtained by subjecting the powder to a granulation step, and the tablet refers to a powder or granule compression-molded into a certain shape. .

The filling rate of the phosphor in the phosphor layer of the radiation intensifying screen used for photographing when the light-sensitive material of the present invention is used for medical purposes is preferably 68% or more, more preferably 70% or more. Is over 72%. Further, the thickness of the phosphor layer is preferably 150 μm or more and 250 μm or less, and when the thickness of the phosphor layer is less than 150 μm, sharpness is rapidly deteriorated. Further, the radiation intensifying screen is preferably filled with the phosphor in a gradient grain size structure. In particular, it is preferable to apply large-diameter phosphor particles to the surface protective layer side, and to apply small-diameter phosphor particles to the support side.
The size of 2.0 μm and the large particle size is preferably in the range of 10 to 30 μm.

The fluorescent intensifying screen used in the light-sensitive material of the present invention has an X-ray absorptivity of 30% or more per 100 μm of the phosphor layer of each intensifying screen by increasing the filling rate of the phosphor particles. Preferably. The X-ray absorption amount is obtained as follows. That is, the X-ray generated from the tungsten target operated at 80KVP from the X-ray generator of aluminum 2.2mm equivalent in the three-phase power supply is transmitted through the aluminum plate with the thickness of 3mm and the purity of 99% or more. The target tube is made to arrive at a radiographic intensifying screen fixed at a position 200 cm from the tungsten anode, and then the radiographic intensifying screen is measured at a position 50 cm after the phosphor layer using an ionization dosimeter. As a reference, the X-ray dose at the above measurement position measured without passing through the intensifying screen is used.

As a preferable binder used in the radiation intensifying screen, a thermoplastic elastomer, specifically, polystyrene, polyolefin, polyurethane, polyester, polyamide, polybutadiene, ethylene vinyl acetate, polyvinyl chloride, natural rubber, fluororubber, poly is used. At least one selected from the group consisting of isoprene, chlorinated polyethylene, styrene-butadiene rubber and silicone rubber can be mentioned.

The filling rate of the phosphor described herein can be obtained from the following equation from the porosity of the phosphor layer formed on the support.

[0127]

[Equation 1]

Further, preferable phosphors used for the radiation intensifying screen include those shown below.

Tungstate phosphor (CaWO ₄ , MgW
O ₄ , CaWO _4, Pb, etc.), terbium-activated rare earth oxysulfide phosphors (Y ₂ O ₂ S: Tb, Gd ₂ O ₂ S: Tb, La ₂ O ₂ S: Tb, (Y, G
d) ₂ O ₂ S: Tb, Tm, etc.], terbium activated rare earth phosphate phosphor (YPO ₄ : Tb, GdPO ₄ : Tb, LaPO ₄ : Tb, etc.), terbium activated rare earth oxyhalide phosphor LaOBr : Tb, L
aOBr: Tb.Tm, LaOCl: Tb, LaOCl: Tb. TmGdOBr: Tb, Gd
OCr: Tb, etc.), thulium-activated rare earth oxyhalide-based phosphor (LaOBr: Tm, LaOCl: Tm, etc.), barium sulfate-based phosphor [BaSO ₄ : Pb, BaSO ₄ : Eu ²⁺ , (Ba.Sr) SO ₄ : Eu
²⁺ etc.] Divalent eurobium-activated alkaline earth metal phosphate phosphor [Ba ₃ (PO ₄ ) ₂ : Eu ²⁺ , (Ba, Sr) ₃ , (PO ₄ ) ₂ : Eu
^2+, etc.] Divalent eurobium activated alkaline earth metal fluoride halide phosphor [BaFCl: Eu ²⁺ , BaFBr: Eu ²⁺ , Ba
FCl: Eu ²⁺ .Tb, BaFBr: Eu ²⁺ .Tb, BaF ² .BaCl ₂ .XBaSO ₄ .KC
l: Eu ²⁺ , (Ba.Mg) F ₂ .BaCl ₂ .KCl: Eu ^2+, etc.), iodide type phosphors (CSI: Na, CSI: Tl, NaI.KI: Tl, etc.) sulfide type fluorescence Body (ZnS: Ag, (Zn.Cd) S: Ag, (Zn.Cd) S: Cu, (Zn.Cd)
S: Cu.Al, etc.], hafnium phosphate-based phosphor (HfP2O7: Cu
Etc.), but not limited to these, and a phosphor that emits light in the visible or near-ultraviolet region upon irradiation with radiation can be used.

[0130]

The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 << Preparation of Em-1 >> A tabular silver iodochlorobromide emulsion Em-1 was prepared using the following 6 kinds of solutions.

A1 Low methionine gelatin 35.53g Sodium chloride 1.324g Finish with water 2030ml B1 Sodium chloride 0.869g Finish with water 15ml B12 Sodium chloride 0.869g Potassium iodide 24.90mg Finish with water 15ml C1 Silver nitrate 5.096g Water 30ml D1 Sodium chloride 46.80 g Water to 800 ml E1 Silver nitrate 135.90 g Water to 800 ml Stir vigorously while keeping solution A1 at 40 ° C in the reaction vessel. 30 ml
Of the solution B12 and 15 ml of the solution C1 at a flow rate of 30 ml / min.
It was added by the simultaneous mixing method over a second. During this time, pCl was kept at 1.95 throughout. The obtained core particles contained 2 mol% of iodine. Next, this mixed solution was kept at 40 ° C. for 10 minutes, and then the total amount of the solution D1 and the solution E1 was added by the simultaneous mixing method at a flow rate of 2 ml per minute over 40 minutes. During this time, pCl was kept at 1.95 throughout. Immediately after the addition was completed, desalting and washing with water were performed.

When the obtained silver halide emulsion was observed by an electron microscope, 50% or more of the total projected area had an adjacent edge ratio of 1 or more.
It consists of right-angled parallelogrammatic tabular grains having a (100) plane less than 0 as the main plane, and the right-angled parallelogrammatic tabular grains have an average particle diameter (circular diameter conversion) of 0.84 μm and an average thickness of 0.037.
μm, average aspect ratio 15, width of particle size distribution 17.2
% Tabular silver halide grains.

<< Preparation of Em-2 >> A cubic silver chlorobromide emulsion Em-2 was prepared as follows.

With reference to the method for producing the emulsion (EMP-11) of the example described in Japanese Patent Application No. 4-1053133, average grains having an average silver bromide content of about 10 mol% on the surface are obtained. Diameter 0.60
A silver halide emulsion consisting of cubic silver chlorobromide cubic grains was prepared.

Subsequently, each of the above-mentioned emulsions Em-1 and Em-2 was divided into predetermined amounts and heated to 55 ° C., and then predetermined amounts of the following spectral sensitizing dyes D-2 and D-17 were added in the form of solid fine particles. After addition as a dispersion, ammonium thiocyanate, an aqueous solution of chloroauric acid, an aqueous solution of the following sulfur sensitizer or a methanol solution and / or triphenylphosphine selenide and / or
Alternatively, a fine particle dispersion of triphenylphosphine telluride was added, and the mixture was aged for a total of 2 hours to obtain Em-1 to Em-8.
Was prepared. At the end of aging, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) was added as a stabilizer.

The additives and their addition amounts (per 1 mol of AgX) were as follows.

Spectral sensitizing dye D-2 300 mg Spectral sensitizing dye D-17 375 mg Ammonium thiocyanate 145 mg Chloroauric acid 18.5 mg Sodium thiosulfate (pentahydrate) (sulfur sensitizer-1) 15.0 mg Triethylthiourea ( Sulfur sensitizer-2) 3.0 mg 1-Ethyl, 3- (2-thiazolyl) thiourea (sulfur sensitizer-3) 3.8 mg Triphenylphosphine selenide (selenium sensitizer-1) 3.0 mg Triphenylphosphine Telluride (tellurium sensitizer-1) 3.0 mg Stabilizer (TAI) 1000 mg A solid fine particle dispersion of a spectral sensitizing dye was prepared by a method 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 had been adjusted to 27 ° C. in advance, and the mixture was stirred by a high-speed stirrer (dissolver) at 3,500 rpm for 30 to 120 minutes.

EmNO. Particle NO. Sulfur sensitizer Selenium sensitizer Tellurium sensitizer Em-A Em-1 1 None None Em-B Em-1 1 Yes Yes No Em-C Em-1 2 Yes No Em-D Em-1 3 Yes No Em-E Em-1 1 No Yes Em-F Em-21 1 No Yes No Em-G Em-21 1 Yes No Em-H Em-2 2 Yes No Em-I Em-2 3 Yes None Em-J Em-21 No None Yes The following additives were added to the obtained emulsion to prepare an emulsion layer coating solution. At the same time, a coating solution for a protective layer described below was prepared. Using both coating solutions, support at a speed of 80 m / min using two slide hopper type coaters so that the coating amount on one side is 1.6 g / m ² and the amount with gelatin is 2.7 g / m ^2. Simultaneous coating on both sides on the body, drying in 2 minutes 20 seconds, sample No. 1
Got ~ 10. Glycidimethacrylate 50 as a support
The concentration of the copolymer composed of three kinds of monomers of 10% by weight, 10% by weight of methyl acrylate and 40% by weight of butyl methacrylate is 10% by weight.
A polyethylene terephthalate film base colored blue with a concentration of 0.15 for an X-ray film of 175 μm was used as an undercoating solution of the copolymer aqueous dispersion obtained by diluting the resulting copolymer to a concentration of 0.1%.

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

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 500mg / m ² 2-Mercaptobenzimidazole-5-sodium sulfonate 5mg / m ² Compound (H) 0.5mg / 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, as gelatin 1.0 g / m ² Adjusted to be m ² .

Third layer (protective layer) Gelatin 0.8 g / m ² 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 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 10,000) 0.1 g / m ² sodium polyacrylate 30 mg / m ² polysiloxane (S1) 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- (C ₃ H ₇ ) _{(CH 2 CH 2 O) 4} - (CH 2) 4 SO 3 Na 1mg / m 2

[0145]

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[0146]

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[0147]

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Here, the emulsion of each sample was as follows.

Sample NO EmNO Inside / Outside of Invention Sample NO EmNO Inside / Outside of Invention 1 A Outside 6 F Outside 2 B Inside 7 G Outside 3 C Inside 8 H Outside 4 D Inside 9 I Outside 5 E Inside 10 J Outside Sample No. Photographic properties were evaluated after storage under the following two conditions using .1-10.

<Condition-1> 23 ° C. to 55% RH to 7 days <Condition-2> 40 ° C. to 80% RH to 7 days First, a sample was prepared with two screens (Konica [KO-25] .KO-25.
It was sandwiched between 0) and irradiated with 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.

Next, an automatic processor (manufactured by Konica Corporation. SR
X-502) was used to treat the developer and fixer of <Formulation-1> below.

<Prescription-1> A development supplement tablet was prepared according to the following procedure (A, B).

Operation (A) 3000 g of hydroquinone as a developing agent is pulverized in a commercially available bandam mill until the average particle size becomes 10 μm. To this fine powder,
Add 3000g of sodium sulfite, 2000g of potassium sulfite, 1000g of dimezone S and mix for 30 minutes in a mill and granulate by adding 30ml of water in a commercial stirred granulator at room temperature for about 10 minutes, then granulate. The product is dried in a fluidized bed dryer at 40 ° C. for 2 hours to almost completely remove the water content of the granulated product. In this way, polyethylene glycol 60
00 was mixed uniformly for 100 minutes in a room where the humidity was controlled to 100 g at 25 ° C and 40% RH or less, and the obtained mixture was used as a tablet press with a modified Tuffpress Collect 1527HU manufactured by Kikusui Seisakusho. Thus, the tablet was compressed into tablets with a filling amount of 3.84 g per tablet to prepare 2500 replenishment tablet A agents.

Operation (B) 100 g of DTPA, 4000 g of potassium carbonate, 10 g of 5-methylbenzotriazole, 7 g of 1-phenyl-5-mercaptotetrazole, 5 g of 2-mercaptohypoxanthine, 200 g of KOH,
N-acetyl-D, L-penicillamine is pulverized and granulated in the same manner as in the operation (A). The amount of water added is 30.0 ml, and after granulation, 50 ℃
Dry for 30 minutes to remove almost completely the water content of the granulated product.
The mixture thus obtained was compressed into tablets with a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd., so that the filling amount per tablet was 1.73 g, and 2500 developing replenishing tablets were prepared. The agent B was prepared.

Next, fixing replenishing tablets were prepared by the following operations (C, D).

Operation (C) 14000 g of ammonium thiosulfate / sodium thiosulfate (70/30 weight ratio) and 1500 g of sodium sulfite were pulverized in the same manner as in (A), and then uniformly mixed with a commercially available mixer. Then, in the same manner as in (A), the amount of water added is adjusted to 500 ml and granulation is performed. After the granulation, the granulated product is dried at 60 ° C for 30 minutes to almost completely remove the water content of the granulated product. In this way, 4 g of sodium N-lauroylalanine was added to the thus-prepared granulated product, and mixed for 3 minutes using a mixer in a room where the humidity was controlled to 25 ° C. and 40% RH or less. Next, the resulting mixture is used by Kikusui Seisakusho.
Tuffpresto Correct 1527HU manufactured by Co., Ltd. was recompressed with a tableting machine having a modified filling amount of 6.202 g to prepare 2500 tablets of fixing replenishing tablet C.

Operation (D) 1000 g of boric acid, 1500 g of aluminum sulfate · 18-hydrate, 3000 g of sodium hydrogen acetate (dried by mixing equimolar amounts of glacial acetic acid and sodium acetate), and 200 g of tartaric acid were pulverized in the same manner as in the operation (A). Granulate. The amount of water added is 100 ml, and after granulation, the granules are dried for 30 minutes to almost completely remove the water content. In this way, 4 g of sodium N-lauroylalanine was added to the thus prepared product, and the mixture was mixed for 3 minutes.
The obtained mixture was compressed into tablets using a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. with a filling amount of 4.562 g to make 1250 fixing replenishing tablet D agents. did.

<< Developer Starter >> Glacial acetic acid 2.98 g KBr 4.0 g Water was added to make 1 liter.

At the start of processing of the developing solution (starting of running), the developing tank was filled with a solution prepared by adding 330 ml of starter to 16.5 l of the developing solution prepared by diluting the developing tablet with diluting water to start the processing. The pH of the developer containing the starter was 10.45.

The light-sensitive material prepared above was exposed to light so that the optical density after development was 1.0, and running was carried out. For running, an automatic processor SRX-502 (manufactured by Konica Co., Ltd.) was equipped with a solid processing agent charging member,
The one modified so that it can be processed in 25 seconds was used.

During running, the developing solution contained 0.62 m ² of light-sensitive material.
For each test, two A and B agents and 76 ml of water were added. The pH when each of A and B was dissolved in 38 ml of water was 10.70. For the fixer, ² parts of the above C agent per 0.62 m ² of light-sensitive material
And 1 part of D agent and 74 ml of water were added. The rate of water addition to each treatment agent was started almost at the same time as the addition of the treatment agent, and was added at a constant rate for 10 minutes in proportion to the dissolution rate of the treatment agent.

<Processing conditions> Development 35 ° C 8.2 seconds Fixing 33 ° C 5 seconds Water washing 4.5 seconds Squeeze 1.6 seconds Dry 40 ° C 5.7 seconds Total 25 seconds << Development starter composition >> Per 1000 ml of water Potassium carbonate 40g Hydroquinone 30g Dimezone S 10g Diethylenetriamine Pentaacetic acid-5Na (DTPA) 1g Potassium bromide 2g 5-Methylbenzotriazole 0.1g 1-Phenyl-5-mercaptotetrazole 0.07g 2-Mercaptohypoxanthine 0.05g Sodium sulfite 30.00g Potassium sulfite 25g KOH 2g Diethylene glycol 50g N -Acetyl-D, L-penicillamine 0.1g << Fixing starter composition >> Sodium thiosulfate 42.0g Potassium thiosulfate 98.0g Sodium sulfite 15.0g Boric acid 10.0g Sodium hydrogen acetate 30.0g Glacial acetic acid 17.3g Sodium acetate 12.7g Tartaric acid 2.0g Dissolve these in 400 ml of water and finally add pure water to 500 ml Finished

The results are shown below.

Condition-1 Condition-2 Sample number Relative sensitivity Relative fog Gradation (γ) Relative fog Inner and outer of invention 1 120 90 90 110 + 20% Outer 2 160 90 90 110 + 20% Outer 3 185 85 115 115 + 15% Outer 4 185 85 115 + 15% Outer 5 195 100 100 110 + 25% Outer 6 100 100 100 100 + 30% Outer 7 125 120 120 95 + 50% Outer 8 145 115 100 Outer + 40% Outer 9 140 115 115 100 + 40% Outer 10 150 160 160 85 + 90% Outer here , Relative to the sample No. 6 as a reference. Sensitivity is + as photographic optical density from fog
The comparison was made with the logarithm of the exposure amount of 1.0. The gradation was obtained as a photographic optical density from the slope of +0.5 to +2.0, and compared.

As is clear from this, the tabular grains of the present invention are more advantageous than the normal crystal grains, and more preferable results in selenium sensitization and tellurium sensitization are obtained regardless of the type of sulfur sensitizer. was gotten. It can be clearly seen that the present invention is excellent in terms of photographic performance and raw storability. Furthermore, it is sufficiently suitable for ultra-rapid treatment using a solid treatment agent.

Example 2 Further, using the sample numbers 2, 5, 7 and 10 prepared in Example 1, a developing / fixing process was carried out according to the following <formulation-2> to suppress fluctuations in photographic performance of the present invention. I saw the effect.

<Formulation-2> << Developer formulation >> Part-A (for 12 l 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 0.2g Hydroquinone 340g Add water to make up to 5000ml.

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

<< Fixing Solution Formulation >> Part-A (for 18l Finishing) Ammonium Thiosulfate (70wt / vol%) 6000g Sodium Sulfite 110g Sodium Acetate Trihydrate 450g Sodium Citrate 50g Gluconic Acid 70g 1- (N, N-Dimethyl) Amino) -ethyl-5-mercaptotetrazole 18g Part-B (for 18l finishing) Aluminum sulphate 800g To prepare the developer, add Part A and Part B simultaneously to about 5l of water, add water while stirring and dissolve, and add 12l to finish glacial acetic acid. At p
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 about 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 used as a 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.

The fluctuation range of the photographic performance between processing-1 and processing-2 is shown below.

[0174] As is clear from this, since the sample in the present invention has a very small variation due to the processing conditions, and stable performance is obtained,
It turns out that it is very advantageous.

Example 3 The sample prepared in Example 1 was evaluated using the following radiation intensifying screen.

<< Production of Screen 1 >> Phosphor: Gd ₂ O ₂ S: Tb (average particle size 1.8 μm) 200 g Binder: Polyurethane thermoplastic elastomer 20 g (Sumitomo Bayer Urethane Co., Ltd .; Demolac TPKL-5- 2625 <solid content 40%>) 2 g of nitrocellulose (nitrification degree: 11.5%) was added to a methyl ethyl ketone solvent and dispersed with a propeller mixer to prepare a coating liquid for forming a phosphor layer having a viscosity of 25 PS (25 ° C). (Binder / phosphor ratio = 1/22) Separately, 90 g of soft acrylic resin solids and 50 g of nitrocellulose were added to methyl ethyl ketone as a coating liquid for forming an undercoat layer, dispersed and mixed to give a viscosity of 3 to 6 PS (25 C) dispersion was prepared.

A 250 μm-thick polyethylene terephthalate (support) in which titanium dioxide was kneaded was placed horizontally on a glass plate, and the above coating solution for forming the undercoat layer was uniformly applied on the support using a doctor blade. After 25 to 100 ℃
The coating film was dried by gradually increasing it to form an undercoat layer on the support. (Thickness of coating film: 15 μm) The above coating liquid for forming a phosphor layer was uniformly applied thereon by a doctor blade to a thickness of 240 μm, dried, and then compressed. The compression was performed using a calender roll at a pressure of 300 kgw / cm ² and a temperature of 80 ° C. After this compression, JP-A-6-7509
A transparent protective film having a thickness of 3 μm was formed by the method described in Example 1 of No. 7.

The characteristics of the obtained screen are the phosphor layer thickness.
It was 160 μm, the phosphor filling rate was 68%, and the sharpness (CTF) was 48%.

Here, the sharpness is the medical imaging film SR-IC (manufactured by Konica Corporation) (manufacturing number 837).
9. Using single-sided photosensitive material of expiration date December 12, 1995, single-pack method (using fluorescent intensifying screen only on the side opposite to the X-ray emitting side, and sticking the emulsion surface of SR-IC to the fluorescent intensifying screen) It was obtained by performing the following measurements according to the method of photographing).

<< Measurement of Modulation Transfer Function (CTF) >> An MRE single-sided photosensitive material manufactured by Eastman Kodak Co. was placed in contact with an intensifying screen to be measured, and a rectangular chart for MTF measurement (made of molybdenum, thickness: 80 μm, Spatial frequency:
0 line / mm to 10 lines / mm) was taken. The chart was placed at a position 2 m from the X-ray tube, a photosensitive material was placed in front of the X-ray source, and then an intensifying screen was placed. The X-ray tube used was a DRX-3724HD (manufactured by Toshiba Corporation) with a tungsten target and a focal spot size.
It is 0.6 mm × 0.6 mm, and X-rays are generated through a 3 mm aluminum equivalent material including the diaphragm.

A voltage of 80 KVP was applied to the three phases with a pulse generator, and X-rays that passed through a filter of 7 cm of water having absorption almost equivalent to the human body were used as a light source. For the light-sensitive material after photographing, a measurement sample was prepared under the development processing conditions described below.

The exposure amount at the time of X-ray photography was adjusted so that the average value of the maximum density and the minimum density after the development processing was 1.0. Next, the measurement sample was operated with a microdensitometer. At this time, the aperture direction is 30
The concentration profile was measured at a sampling interval of 30 μm using a slit of μm and a vertical direction of 500 μm.

This operation was repeated 20 times to calculate an average value, which was used as a concentration profile on which CTF was calculated. Thereafter, the density contrast for each frequency of this density profile was calculated. The above values are spatial frequency 3 lines / mm
Is the value measured for.

Using the screen 1, the photographic characteristics of the sample numbers 1, 2, 5, 6, 7, and 10 prepared in Example 1 were evaluated. The evaluation was performed in exactly the same manner as in Example 1 except that the screen in Example 1 was changed to screen 1. Further, the sharpness (CTF) was evaluated as follows.

That is, the portion where the optical density after development is 1.0 is 3
Measured with an aperture of 0 μm × 500 μm, the spatial frequency is 1.
Measure the CTF value at 0 cycles / mm and set the value of sample No. 6 to 1
It is shown as a relative value when 00 is set. The results are shown below.

Sample No. Sharpness Inner / outer initial of invention After running 1 102 98 Outer 2 107 107 Outer 5 5 105 104 Outer 6 100 93 Outer 7 93 88 Outer 10 89 85 Outer It turns out that it is small and excellent. This result was completely unexpected at first. Furthermore, probably because the mottle of the intensifying screen was reduced, the graininess of the developed film which was apparent in the visual evaluation was improved.

[0187]

INDUSTRIAL APPLICABILITY The silver halide photographic light-sensitive material according to the present invention, the processing method thereof and the photographic material have high sensitivity, high image quality, rapid processing suitability, and excellent storage stability.

Claims (2)

[Claims] 1. A tabular high chloride having an average aspect ratio of 2 or more in which 50% or more of the total projected area of silver halide grains contained is a (100) plane whose main plane has an adjacent side ratio of less than 10. The silver halide grains are chemically sensitized with at least one selected from the selenium compound represented by the general formula (1) and the tellurium compound represented by the general formula (2) in the presence of a dye. And a silver halide photographic light-sensitive material having a layer containing a silver halide emulsion. Embedded image [In the formula, Z ₁ , Z ₂ and Z ₃ are each an aliphatic group, an aromatic group, a heterocyclic group, —OR ₁ , —NR ₂ (R ₃ ), —SR ₄ , —SeR ₅ , X or hydrogen. Represents an atom, R ₁ , R ₄ and R ₅ are each an aliphatic group,
Represents an aromatic group, a heterocyclic group, a hydrogen atom or a cation, R
₂ and R ₃ each represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, and X represents a halogen atom. ] [Chemical 2] [In the formula, Z ₄ , Z ₅ and Z ₆ have the same meanings as Z ₁ , Z ₂ and Z _{3 in} formula (1). ] 2. The silver halide photographic light-sensitive material according to claim 1, which has a silver bromide-rich region in the vicinity of at least one vertex or surface of the silver halide grains.