JPH1184570A - Silver halide emulsion, silver halide photographic sensitive material, photographing method and processing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide emulsion low in fog and high in sensitivitv and small in residual dye stains and superior in pressure resistance by incorporating at least one of spec-compounds in the silver halide emulsion. SOLUTION: This silver halide emulsion contains at least one of the compounds represented by formulae I and II in which Ar is an aliphatic or aromatic hydrocarbon group; F is an F atom; each of Y and Y' is a group directly or indirectly combined with a -SO3 N, -COOM, or -OM group; M is an H or metal atom or a quaternary ammonium or phosphonium group; each of 5qx and Y' may be same or different; 1<m or m'>9, 1>n or n'>9, m+n or m'+n'<=10; X is an S or Se atom; and (x) is 1 or 2. The silver halide grains to be used for the silver halide emulsion layer can be embodied by silver chloride, silver iodochloride, silver iodobromochloride, silver bromochloride, silver bromide, and silver bromoiodide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide emulsion having high sensitivity, low dye contamination and excellent pressure resistance, and a photographic material using the same. The present invention relates to a processing method and a photographing method.

[0002]

2. Description of the Related Art In recent years, the demand for rapid processing has increased with the increase in processing of silver halide photographic light-sensitive materials (hereinafter, also referred to as light-sensitive materials or light-sensitive materials). For example, medical X
Similar trends are seen in the line film field. X due to the spread of health checkups and the increase in the number of test items for improving diagnostic accuracy
The number of radiographs taken increases. In addition, there is a need to notify the examinee of the diagnosis result earlier, and therefore, there is a strong demand for ultra-rapid development processing after photographing and reduction of processing waste liquid due to environmental problems.

However, in order to speed up processing, development,
Although it is necessary to shorten the processing time of each processing step such as fixing, washing, and drying, the load of each processing increases.
For example, if the development time is simply shortened, with a conventional photosensitive material,
This is accompanied by a decrease in image density, that is, a decrease in sensitivity and a decrease in gradation. On the other hand, when the fixing time is shortened, the fixing of silver halide becomes incomplete and causes deterioration of image quality. Further, shortening the time of each processing step is accompanied by deterioration of image quality due to residual dye (residual color) because the sensitizing dye is not sufficiently eluted in each of the processing of development, fixing and washing. Therefore, in order to solve such a problem, it is necessary to increase the developing speed and the fixing speed, to reduce the amount of the dye, and to accelerate the detachment and / or decoloration of the dye.

On the other hand, in order to reduce development processing waste liquid,
It is necessary to reduce the fatigue of the processing solution and / or the replenishing solution, but this involves the same problems as the above-mentioned speedup.

As techniques for improving these problems, EP0,
506,584, JP-A-5-88293, 5-9
No. 3975 discloses a technique using benzimidazolocarboxycyanines having good decoloring performance as spectral sensitizing dyes. JP-A-5-61148 discloses that oxacarbocyanines and benzimidazolocarbocyanines are used in combination in a specific ratio as a spectral sensitizer in a silver halide emulsion having an iodine content of 1 mol% or less, and selenium is further added. A technique for performing chemical sensitization with a compound and / or a tellurium compound is disclosed.

[0006] However, these disclosed techniques alone improve the residual color property or the speed of development, but are still insufficient to satisfy the recent demand levels for various performances. In particular, they have the disadvantages that they are not sufficient in terms of high sensitivity and safelight resistance, and that when the photosensitive material is stored under high humidity and high temperature, the sensitivity is greatly reduced.

On the other hand, various basic studies have been carried out on the adsorption of silver halide grains and sensitizing dyes for a long time. When adsorbing a sensitizing dye to silver halide grains, studies have been conducted to uniformly and selectively adsorb sensitizing dyes within and between grains. As a method for adding a sensitizing dye, it is also known that chemical sensitization is performed in the presence of a sensitizing dye to control chemical sensitization and reduce intrinsic desensitization. However, these techniques are also inadequate with respect to storage, pressure resistance, safelight resistance and illuminance failure.

For high sensitivity, reduction sensitization attempts have been studied for a long time. U.S. Pat. No. 2,487,850,
Nos. 2,512,925 and 2,518,698
No. 3,930,867, British Patent 789,82.
No. 3 and the like. However, these reduction sensitization methods have not yet reached a practical level.

Meanwhile, in the field of medical X-ray photographic materials, in order to improve patient service and workability, in addition to rapid development processing and reduction of processing waste liquid, simplification of the entire processing work is strongly required. Requested. However, since the liquid processing agent which dilutes the concentrated solution of the developing agent and replenishes it into the processing tank has a large weight and a large volume, it is difficult to improve the work efficiency. As an alternative to this, in recent years, a solid processing agent supplied with a solid component and dilution water to a processing tank of an automatic developing machine has been proposed. As a result, the transportation cost, the storage space, and the working efficiency are reduced, and the amount of packaging material used can be reduced.

However, due to the solubility of the solid components,
In particular, there is a problem that it is difficult to obtain sufficiently stable running performance when the development processing is performed for a very short time.

[0011]

SUMMARY OF THE INVENTION Accordingly, a first object of the present invention is to provide a silver halide emulsion having low fog, high sensitivity, little dye contamination and excellent pressure resistance, and a photographic material using the same. That is. It is a second object of the present invention to provide a method for photographing a silver halide photographic material having the above-mentioned performance and a method for processing the same.

[0012]

The above objects of the present invention are as follows. A silver halide emulsion containing at least one compound represented by the following general formula (1) or (2):

[0013]

Embedded image In the formula, Ar represents an aliphatic hydrocarbon or an aromatic hydrocarbon. F represents a fluorine atom. Y and Y ′ have —SO ₃ M, —COOM, and —OM directly or indirectly, and M represents a hydrogen atom, a metal atom, or a quaternary ammonium group or a phosphonium group. 5qx and Y ′ may be the same or different. In addition, 1 <m or m ′> 9, 1 <n or n ′> 9,
m + n or m '+ n'<= 10, X represents a sulfur, selenium or tellurium atom. x is 1 or 2.

2. 2. a silver halide emulsion containing at least one compound represented by the above general formula (1) and at least one compound represented by the above general formula (2); The contained silver halide grains are subjected to reduction sensitization,
And containing at least one compound represented by the general formula (1) or (2), and sulfur sensitizing in the presence of at least one of the spectral sensitizing dyes represented by the general formula (3) A silver halide emulsion characterized by being subjected to at least one chemical sensitization among selenium sensitization and tellurium sensitization,

[0015]

Embedded image In the formula, R ₁ and R ₃ each represent a substituted or unsubstituted lower alkyl group or alkenyl group, and R ₂ and R ₄
Represents an alkyl group, and at least one of R ₂ and R ₄ represents an alkyl group substituted with a hydrophilic group. Z ₁ , Z ₂ ,
Z ₃ and Z ₄ may be the same or different, and represent a hydrogen atom or a substituent. X represents an ion necessary for neutralizing the charge in the molecule, and n represents 1 or 2. However, when an inner salt is formed, n is 1.

4. 4. The silver halide emulsion according to the above 3, wherein the emulsion contains at least one kind of the compound represented by the general formula (1) and at least one kind of the compound represented by the general formula (2).

5. The silver halide grains contained in the silver halide emulsion have an aspect ratio of 2 to 20, an average iodine content of 0 to 1.0 mol%, and a silver chloride content of 10 to 100 mol%. The silver halide emulsion according to any one of the above 1 to 4, wherein the emulsion contains certain silver halide grains.

6. The halogenation according to any one of 1 to 5 above.
The silver halide emulsion is represented by the following general formula (4) during chemical sensitization.
Phosphine coordinated organic transition metal complexes
Is also characterized by being chemically sensitized in the presence of one kind
Silver halide emulsion represented by the general formula (4) [(R ′) ₃P]_aM [L] _bA In the formula, M is a transition group metal of groups 3 to 7a, group 8 and 1b of the periodic table.
Or a metal of the post-transition group, wherein R 'is any organic ligand
And a is 2 or 3. L represents a substitutable group.
And b is 1 or 2. Formula (4) is preferably 1
It is a complex of 6 electrons.

[7] A silver halide photographic material, comprising the silver halide emulsion according to any one of the above 1 to 6,

8. 7. A method for continuously processing a silver halide photographic material containing a silver halide emulsion according to any one of the above 1 to 6 in a processing step including each step of developing and fixing, wherein each of the processing steps A method for processing a silver halide photographic material, wherein the liquid is a processing liquid obtained from a solid processing agent,

9. A processing method comprising a step of developing, fixing and drying a silver halide photographic light-sensitive material containing the silver halide emulsion according to any one of the above 1 to 6, wherein all processing is performed by an instant self-developing diffusion transfer system. A method for processing a silver halide photographic light-sensitive material,

10. A silver halide photographic material containing the silver halide emulsion according to any one of the above 1 to 6 is sandwiched between intensifying screens having a phosphor filling rate of 68% to 90%, and X-ray photography is performed. Of the silver halide photographic light-sensitive material described above.

[0023]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
As the silver halide grains used in the silver halide emulsion of the present invention, silver chloride, silver iodochloride, silver iodobromochloride, silver bromochloride, silver bromide, silver bromoiodide and the like can be used as silver halide. . Of these, silver chloride, silver iodochloride, silver bromochloride and silver bromide are more preferred. When silver chloride is used as the silver halide grains contained in the silver halide emulsion of the present invention, 10 to 1
The silver chloride content is preferably 00 mol%, particularly preferably 50 mol% of all grains, more preferably 70 mol% or more, more preferably 90 mol% or more.
More preferably, the content is at least mol%. In the case of silver iodochloride, the content of silver iodide is preferably 0.01 mol% or more and 1.0 mol% or less as an average silver iodide content of the whole silver halide grains, and 0.01 mol% or less. % Or more and 0.5 mol% or less.

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. In the present invention, the silver iodide content and the average silver iodide content of each silver halide grain are determined by an EPMA method (Elect).
ron 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 determining the characteristic X-ray intensity of silver and iodine emitted from each grain by this method, the silver halide composition of each grain can be determined. When the silver iodide content of at least 50 grains is determined by the EPMA method, the average silver iodide content is determined from the average thereof.

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

In the present invention, the tabular silver halide grains preferably contain silver iodide, but the silver iodide is preferably contained at least inside. If inside,
More preferably, it exists at least at the center. In this case, the internal composition contains silver iodide in an amount of 0.1 mol% to 5 mol%.
It is preferable to contain the following. Here, the halogen composition distribution inside the silver halide grains can be determined by pre-treating the grains into ultrathin sections, and then observing and analyzing them with a transmission electron microscope while cooling. Specifically, silver halide grains are taken out of the emulsion, embedded in a resin, and cut with a diamond knife to produce a 60-nm-thick section. This section can be obtained by observation and point analysis with a transmission electron microscope equipped with an energy dispersive X-ray analyzer while cooling the section with liquid nitrogen, and by quantitative calculation (Inoue, Nagasawa: Photographic Society of Japan, 1987) Conference Abstracts p. 62).

It is also preferred that silver iodide be present on the outermost surface. In this case, the silver iodide content on the outermost surface is preferably from 1 mol% to 10 mol%. Here, the silver iodide content at the outermost surface of the tabular silver halide grains is XP
S method (X-ray Photoelectron Sp
and a silver iodide content of a portion up to a depth of 50 ° analyzed by X-ray photoelectron spectroscopy.
It can be obtained as follows.

The sample was cooled to −110 ° C. or less in an ultra-high vacuum of 1 × 10 ⁻⁸ torr or less, and MgKα was used as a probe X-ray with an X-ray source voltage of 15 kV and an X-ray source current of 40 mA.
And measure about Ag ₃ d5 / 2, Br ₃ d and I ₃ d3 / 2 electrons. The integrated intensity of the measured peak is corrected by a sensitivity factor, and the halide composition on the outermost surface is determined from these intensity ratios. The purpose of cooling the sample is 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 (particularly iodine)), and to enhance measurement accuracy. By cooling to −110 ° C., sample destruction can be suppressed to a level that does not hinder measurement.

It is also preferred that silver bromide be present on the outermost surface. In this case, the silver bromide content on the outermost surface is preferably from 1 mol% to 10 mol%. The average aspect ratio of the tabular silver halide grains of the present invention is preferably 2 to 20, particularly preferably 8 or less, more preferably less than 7, and most preferably less than 5.

In the present invention, 50% or more of the total projected area of the silver halide grains contained in the emulsion is preferably composed of tabular silver halide grains having a (100) plane as a main plane, and more preferably 70%. % Or more, more preferably 90%
The above is the case of tabular silver halide grains having the (100) plane as the main plane. The fact that the main plane is the (100) plane can be confirmed by an X-ray diffraction method or the like.

In the present invention, the shape of the main plane of the tabular silver halide grains is a right-angled parallelogram or a right-angled parallelogram with no corners or a rounded shape. The adjacent side ratio of the right-angled parallelogram is less than 10, preferably less than 5, and more preferably less than 2. When the corner is missing or rounded, the length of the side is the length of the straight line of the side of the right-angled parallelogram, and the length of the side to the intersection with the line that extends the straight line of the adjacent side. It is represented by

The average particle size of the tabular silver halide grains of the present invention is preferably from 0.15 to 5.0 μm, more preferably from 0.1 to 5.0 μm.
The thickness is more preferably from 4 to 3.0 μm, most preferably from 0.4 to 2.0 μm. The average thickness of the tabular silver halide grains of the present invention is preferably from 0.01 to 1.0 μm, more preferably from 0.02 to 0.40 μm.
m, more preferably 0.02 to 0.30 μm.

The 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 tabular silver halide grains of the present invention are preferably monodisperse grains having a narrow particle size distribution. Specifically, when the width of the distribution is defined by (standard deviation of particle size / average particle size) × 100 = width (%) of particle size distribution, it is 20% or less, preferably 18%. Below, more preferably 15
% Or less.

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

The tabular silver halide grains of the present invention may have dislocations. Dislocations are described in F. Hamilt
on, Photo. Sci. Eng, 57 (1967)
And T. Shiozawa, J .; Soc. Photo. S
ci. Japan, 35, 213 (1972) and can be observed by a direct method using a low-temperature transmission electron microscope. In other words, the silver halide grains taken out so as not to apply enough pressure to cause dislocations in the grains from the emulsion are placed on a mesh for electron microscopic observation, 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,
The thicker the particles, the more difficult it is for the electron beam to pass,
High pressure type (200 kV for 0.25 μm thick particles)
The above can be observed more clearly using an electron microscope.

Next, the compound represented by formula (1) or (2) will be described. In the formula, Ar represents an aliphatic hydrocarbon or an aromatic hydrocarbon. F represents a fluorine atom.
Y and Y ′ are directly or indirectly —SO ₃ M, —COO
It has M and -OM, and M represents a hydrogen atom, a metal atom, or a quaternary ammonium group or a phosphonium group. Y and Y 'may be the same or different. Note that 1 <m> 9, 1 <n
> 9, m + n <= 10, and X represents a sulfur, selenium or tellurium atom. x is 1 or 2.

Method of addition: Before or after chemical sensitization,
It may be an emulsion layer or a non-emulsion layer, or may be in a developer. Addition amount: 1 × 10 ^{−6 to} 5 × 10 ⁻² mol / Ag mol, preferably 1 × 10 ^{−5 to} 5 × 10 ⁻³ mol / A
g mol.

In the course of conducting research to find a method for increasing the photographic sensitivity of a silver halide emulsion, the present inventors have determined that a phosphine-complexed noble metal, such as platinum, and both a reducing function can be combined into one. One class of compounds has been found that have been incorporated into the molecule such that the gelatin colloid cannot complex with the noble metal. As a result, these compounds effectively produce silver halide emulsions, especially when combined with sulfur sensitizers, or with sulfur and gold sensitizers, or with selenium or tellurium sensitizers. Sensitize to Certain combinations have been found to be desirable for various exposure times.

Typical examples of useful compounds that can be used in the present invention are as follows. 4-1 [(CH ₃ ) ₃ P] ₂ PtClH 4-2 [(C ₂ H ₅ ) ₃ P] ₂ PtClH 4-3 [(C ₆ H ₅ ) ₃ P] ₂ PtClH 4-4 [(CH ₃ ) ₃ P] ₂ PtBrH 4-5 [(C ₂ H ₅ ) ₃ P] ₂ PtBrH 4-6 [(C ₆ H ₅ ) ₃ P] ₂ PtBrH 4-7 [(CH ₃ ) ₃ P] ₂ PdClH 4 −8 [(C ₂ H ₅ ) ₃ P] ₂ PdClH 4-9 [(C ₆ H ₅ ) ₃ P] ₂ PdClH 4-10 [(CH ₃ ) ₃ P] ₂ PdBrH 4-11 [(C ₂ H ₅ ) ₃ P] ₂ PdBrH 4-12 [(C ₆ H ₅ ) ₃ P] ₂ PdBrH 4-13 [(CH ₃ ) ₃ P] ₃ IrCl ₂ H 4-14 [(C ₂ H ₅ ) ₃ P] _{3 IrCl 2 H 4-15 [(C} 6 H 5) 3 P] 3 Ir _{l 2 H 4-16 [(CH 3} ) 3 P] 3 IrBr 2 H 4-17 [(C 2 H 5) 3 P] 3 IrBr 2 H 4-18 [(C 6 H 5) 3 P] 3 IrBr _{2 H 4-19 [(CH 3)} 3 P] 3 IrClH 2 4-20 [(C 2 H 5) 3 P] 3 IrClH 2 4-21 [(C 6 H 5) 3 P] 3 IrClH 2 4- 22 [(C ₂ H ₅ ) ₃ P] ₂ NiClH 4-23 [(C ₂ H ₅ ) ₃ P] ₂ Co (NH ₃ ) ₂ ClH 4-24 (dppe) ₂ RiClH 4-25 (dppe) PtClH 4 −26 (dppe) ₂ IrClH where dppe represents Ph ₂ PCH ₂ CH ₂ PPh ₂ .

In the practice of this invention, these novel compounds are added in amounts ranging from about 2-200 .mu.mole per mole of silver halide. It is advantageous to add these compounds in an amount ranging from 5 to 100 .mu.mole per mole of silver halide. These compounds may be added to the emulsion as a dilute solution in an organic hydrating solvent such as methanol or acetone.

Hereinafter, reduction sensitization in the present invention will be described. The production process of a silver halide emulsion is roughly divided into processes such as grain formation, desalting, and chemical sensitization. Particle formation is divided into nucleation, ripening, and growth. These steps are not performed uniformly, but the order of the steps is reversed or the steps are repeatedly performed. Applying reduction sensitization during the production process of a silver halide emulsion basically means that it may be performed in any process. Reduction sensitization may be performed during nucleation, which is the initial stage of grain formation, during physical ripening, or during growth, and may be performed prior to chemical sensitization other than reduction sensitization or after this chemical sensitization. . When performing chemical sensitization in combination with gold sensitization, reduction sensitization is preferably performed prior to chemical sensitization so as not to cause undesirable fog.
Most preferred is a method of reduction sensitization during growth of silver halide grains. Here, "growing" refers to a method of performing reduction sensitization in a state where silver halide grains are growing by physical ripening or addition of a water-soluble silver salt and a water-soluble alkali halide. It is also meant to include a method of further growing after performing reduction sensitization in a state.

The reduction sensitization of the present invention is a method in which a known reducing agent is added to a silver halide emulsion, or a pA called silver ripening.
Either a method of growing in a low pAg atmosphere of g1 to 7 or ripening, a method of growing in an atmosphere of high pH of 8 to 11 called high pH ripening, or a method of ripening can be selected. Also, two or more methods can be used in combination. The method of adding a reduction sensitizer is a preferable method because the level of reduction sensitization can be finely adjusted.

As reduction sensitizers, stannous salts, amine and polyamic acids, hydrazine derivatives, formamidinesulfinic acids, silane compounds, borane compounds and the like are known. In the present invention, these known compounds can be selected for use, and two or more compounds can be used in combination. Stannous chloride, thiourea dioxide as reduction sensitizer,
Dimethylamine borane is a preferred compound. Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount, but 1 × 10 ⁻⁷ per mol of silver halide.
A range of １1 × 10 ⁻³ mol is appropriate.

Ascorbic acid and its derivatives can also be used as the reduction sensitizer of the present invention. Ascorbic acid and its derivatives (hereinafter, “ascorbic acid compound”
That. The following can be mentioned as specific examples of ()). (A-1) L-ascorbic acid (A-2) Sodium L-ascorbate (A-3) Potassium L-ascorbate (A-4) DL-ascorbic acid (A-5) D-sodium ascorbate (A -6) L-ascorbic acid-6-acetate (A-7) L-ascorbic acid-6-palmitate (A-8) L-ascorbic acid-6-benzoate (A-9) L-ascorbic acid-5,6 -Diacetate (A-10) L-ascorbic acid-5,6-O-isopropylidene

It is desirable to use a large amount of the ascorbic acid compound used in the present invention as compared with the amount of the conventional reduction sensitizer which is preferably used. For example,
No. 33572 states that the amount of the reducing agent is usually 0.75 × 10 ⁻² meq (g × 10 ⁻⁴ mol / A / g of silver ion).
gX mol). 0.1 to 10 per kg of silver nitrate
mg amount (1 × 10 ⁻⁷ to 1 × as ascorbic acid)
(10 ⁻⁵ mol / AgX mol) is effective in many cases. Is described. U.S. Pat. No. 2,487,85
No. 0 describes “1 × 10 ^{−7 to} 44 × 10 ⁻⁶ mol as an addition amount in which a tin compound can be used as a reduction sensitizer”.
It is described. Japanese Patent Application Laid-Open No. 57-179835 discloses that the amount of thiourea dioxide added is about 0.01 mg to about 2 mg per mol of silver halide and about 0.0 mg of stannous chloride is used.
It is stated that it is appropriate to use 1 mg to about 3 mg. The ascorbic acid compound used in the present invention includes the grain size of the emulsion, the halogen composition, the temperature for preparing the emulsion, pH, p
Although the preferable addition amount depends on factors such as Ag,
It is desirable to select from the range of 5 × 10 ⁻⁵ to 1 × 10 ⁻¹ mol per mol of silver halide. More preferably, 5
It is preferable to select from the range of × 10 ⁻⁴ to 1 × 10 ⁻² mol. Particularly preferred is 1 × 10 ⁻³ to 1 × 10 ^−2.
Is to choose from a range of moles.

The reduction sensitizer may be water or alcohols,
It can be dissolved in a solvent such as glycols, ketones, esters and amides and added during grain formation, before or after chemical sensitization. The compound may be added during any step of the emulsion production process, but a particularly preferable method is to add the compound during grain growth. It is good to add to the reaction vessel in advance,
It is preferable to add at an appropriate time during the particle formation. Alternatively, a reduction sensitizer may be added to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide in advance, and particles may be formed using these aqueous solutions. It is also a preferred method to add the solution of the reduction sensitizer in several portions as the grains are formed, or to add the solution continuously for a long time.

Spectral sensitizing dyes are those which adsorb to silver halide grains and contribute to sensitization. The spectral sensitizing dye used in the present invention is not particularly limited as long as it has a spectral sensitizing function. When the sensitizing dye according to claim 2 is adsorbed on silver halide emulsion grains and the reflection spectrum is measured, J It is preferable that the maximum absorption wavelength of the cohesive zone is 555 nm or less. In the application to X-ray medical light-sensitive materials utilizing a phosphor emitting green light, the spectral sensitizing dye of the present invention is adsorbed on silver halide emulsion grains, and the fluorescence spectrum is measured when its reflection spectrum is measured. In the same wavelength range as the green light from
It is preferred that a band be formed. That is, the maximum absorption wavelength is preferably 520 nm to 555 nm.
It is preferable to select and combine spectral sensitizing dyes such that a J-band having the maximum absorption is formed in the region (1). More preferably, it is 530-553 nm, most preferably 540-550 nm.

Preferred benzimidazolocarbocyanines spectral sensitizing dyes are represented by the general formula (3). In the general formula (3), R ₁ and R ₃ each represent a substituted or unsubstituted alkyl group or alkenyl group. Examples of the alkyl group include linear or branched groups such as ethyl, propyl, and 3-methylbutyl groups. Examples of the substituted alkyl group include 2-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl, ethoxycarbonylethyl,
Examples include allyl, phenethyl, methanesulfonylethyl, and 3-oxobutyl groups.

The alkyl groups represented by R ₂ and R ₄ include, for example, straight-chain and branched groups such as methyl, ethyl, butyl, and isobutyl groups. , Carboxy, methanesulfonylaminocarbonyl, methanesulfonylaminosulfonyl, acetylaminosulfonyl, sulfoamino, trifluoroacetylaminosulfonyl, acetylaminocarbonyl, N-methylsulfamoyl group and other dissociable groups. Specific examples include 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 5-sulfopentyl, 2-N-ethyl-N-sulfoaminoethyl, carboxymethyl, carboxyethyl, 3-sulfoaminopropyl, 6-sulfo-3-oxahexyl , 10-sulfo-3,6-dioxa Sill, 6-sulfo-3-Chiahekishiru, o- sulfobenzyl, p- carboxybenzyl,
Each group such as a methanesulfonylaminocarbonylmethyl and an acetylaminosulfonylmethyl group is exemplified.

Z ₁ , Z ₂ , Z ₃ and Z ₄ are each the same,
And may be different, including a hydrogen atom, a halogen atom (eg, a fluorine, chlorine, bromine, iodine atom, etc.), an alkyl group (eg, a lower alkyl group such as methyl, ethyl, propyl group), and an alkoxy group (eg, methoxy, ethoxy). , A propoxy group, etc.) and a halogen atom-substituted alkoxy group (for example, fluoromethoxy, trifluoromethyl,
2,2,2-trifluoroethyl group, etc.), aryloxy group (eg, phenoxy, p-bromophenoxy group, etc.), acyl group (eg, acetyl, benzoyl group, etc.),
Acyloxy groups (eg, acetyloxy, propionyloxy groups, etc.), alkylthio groups (eg, methylthio, ethylthio groups, etc.), halogen-substituted alkylthio groups (eg, trifluoromethylthio, difluoromethylthio groups, etc.), and alkoxycarbonyl groups (eg, methoxycarbonylmethyl) , Ethoxycarbonyl group, etc.), carbamoyl group (for example, carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-diethylcarbamoyl, N, N-3-oxa-pentamethylenecarbamoyl, N-phenylcarbamoyl group, etc.) ), Sulfamoyl groups (eg, N-methylsulfamoyl, N, N
-Tetramethylenesulfamoyl, N, N-3-oxapentamethylenesulfamoyl, N-phenylsulfamoyl, N, N-diethylsulfamoyl group, etc.), haloalkyl group (for example, monofluoromethyl, difluoromethyl, Trifluoromethyl, monochloromethyl group, etc.),
A sulfonyl group (eg, methanesulfonyl, ethanesulfonyl, trifluoromethanesulfonyl, fluorosulfonyl, benzenesulfonyl, p-toluenesulfonyl, etc.), an acylamino group (eg, N-acetylamino, N
-Trifluoroacetylamino group, etc.), substituted or unsubstituted aryl groups (eg, phenyl, o-fluorophenyl, p-cyanophenyl, m-chlorophenyl group, etc.),
Examples of the heterocyclic group include substituted or unsubstituted groups (for example, 1-pyrrolyl, 2-furyl, 2-benzoxazolyl group, etc.).

The ion necessary for neutralizing the charge in the dye molecule may be an anion or a cation. Examples of the anion include a halogen ion (an ion such as chloro, bromo and iodine), perchlorate, ethyl There are sulfate, thiocyanate, p-toluenesulfonate, perfluoroborate and the like, and examples of the cation include hydrogen ion, alkali metal ion (lithium,
Examples thereof include ions such as sodium and potassium), alkaline earth metal ions (ions such as magnesium and calcium), ammonium ions, and organic ammonium ions (ions such as triethylammonium, triethanolammonium, and tetramethylammonium).

Next, the general formula (1) according to the present invention,
Specific examples of the spectral sensitizing dyes represented by (2) and (3) will be given below, but the present invention is not limited thereto. Note that N
o. The exemplified compounds 3-1 to 3-35 are represented by making each substituent (atom) correspond to general formula (3).

[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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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, composite cyanine dyes, composite merocyanine dyes, holoboralar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.
These dyes can be applied to any of the nuclei commonly used. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus,
Selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc., these nuclei are fused with an alicyclic hydrocarbon ring, that is, indolenine nucleus, benzindolenine nucleus,
Indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms.

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

Patent techniques relating to these dyes include, for example, German Patent 929,080 and US Pat. No. 2,231,6.
No. 58, No. 2,493,748, No. 2,503,77
No. 6, No. 2, 519, 001, No. 2, 912, 329
Nos. 3,655,394 and 3,656,959
Nos. 3,672,897 and 3,649,217
No., British Patent 1,242,588, JP-B-44-14
030.

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 supersensitization is added to the emulsion layer. Is preferred.

The addition amount of the spectral sensitizing dye in the present invention is
Type of dye and structure, composition, ripening condition of silver halide,
Depending on the purpose and application, the coverage of the monomolecular layer on the surface of each photosensitive particle in the silver halide emulsion is 30% or more and 90% or more.
% Or less, preferably 40% or less.
80% is particularly preferred. In the present invention, the monolayer coverage is relatively determined by defining the saturated adsorption amount when an adsorption isotherm is created at 50 ° C. as an amount corresponding to a coverage of 100%.

The appropriate amount per mol of silver halide varies depending on the total surface area of silver halide grains in the emulsion.
Less than 00 mg is preferred. Further, it is preferably 450 mg or less. In order to further increase the sensitivity and improve the residual color, the ratio of the benzimidazolocarbocyanines spectral sensitizing dye of the present invention is preferably 30% or more of all the dyes in the photographic material.

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,
There are 1,3-propanediol, acetone, acetonitrile, 2-methoxyethanol, 2-ethoxyethanol and the like. Further, a surfactant has been conventionally used as a dispersant for the spectral sensitizing dye. 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 where it is added 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. On the other hand, the present invention is intended to uniformly and effectively adsorb the photographic spectral sensitizing dye on the surface of silver halide grains. It is 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 2 × 10 ⁻⁴ to 4 × 10 ⁻² mol / l, more preferably 1 × 10 ⁻³ to 4 × 10 ⁻² mol / l. It is.

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 m of ion-exchanged water is placed in a 50 ml Erlenmeyer flask.
Then, an amount of the dye that did not completely dissolve 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 with filter paper no. 2 (manufactured by Toyo), the filtrate is filtered using a disposable filter (manufactured by Tosoh), and the filtrate is appropriately diluted.
The absorbance was measured with a 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 = εlcA where D: absorbance, ε: spectral extinction coefficient, l: cell length for absorbance measurement, c: concentration (mol / liter).

The spectral sensitizing dye of the present invention can be added at the chemical ripening step, particularly preferably at the start of the chemical ripening step. In addition, the silver halide emulsion of the present invention is desalted from the nucleation step. 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 invention described in claim 2 of the present invention is characterized in that the silver halide emulsion has been subjected to at least one kind of chemical sensitization among sulfur sensitization, selenium sensitization and tellurium sensitization. .

In the case of selenium sensitization, a wide variety of selenium compounds can be used as the selenium sensitizer, for example, US Pat. Nos. 1,574,944 and 1,602,5.
Nos. 92 and 1,623,499, JP-A-60-150
No. 046, JP-A-4-25832 and JP-A-4-10924.
Compounds described in Nos. 0 and 4-147250 can be used. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg,
Allyl isoselenocyanate, etc.), selenoureas (e.g., N, N-dimethylselenourea, N, N, N'-triethylselenourea, N, N, N'-trimethyl-N'-)
Heptafluoroselenourea, N, N, N'-trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N'-trimethyl-N'-4-nitrophenylcarbonylselenourea, etc., selenoketones (for example, , Selenoacetone, selenoacetophenone, etc.), selenoamides (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-3-selenobutyrate) And the like, selenophosphates (eg, tri-p-triselenophosphate, etc.), and selenides (triphenylphosphine selenide, diethyl selenide, diethyl diselenide, etc.). Particularly preferred selenium sensitizers are selenoureas, selenamides, and selenoketones, selenides.

The amount of the selenium sensitizer used varies depending on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but is generally 10 ^-8 to 10 per mol of silver halide.
^{About -4} mol is used. Depending on the properties of the selenium compound to be used, the addition may be carried out by dissolving in water or an organic solvent such as methanol or ethanol alone or in a mixed solvent. Further, a method in which the mixture is added in advance with a gelatin solution, or a method in which the mixture is added in the form of an emulsified dispersion of a mixed solution with a polymer soluble in an organic solvent by the method disclosed in JP-A-4-140739 may be used.

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

Regarding tellurium sensitizers and sensitization methods, see, for example, US Pat. Nos. 1,623,499 and 3,320,069.
Nos. 3,772,031 and 3,531,289
No. 3,655,394, British Patent 235,211
Nos. 1,121,496 and 1,295,462
No. 1,396,696, Canadian Patent 800,95
No. 8, JP-A-4-204640, JP-A-4-330430
And the like.

Examples of useful tellurium sensitizers include telluroureas (eg, N, N-dimethyltellurourea, tetramethyltellurourea, N-carboxyethyl-N, N'-).
Dimethyltellurourea, N, N'-dimethyl-N'phenyltellurourea), phosphine tellurides (eg, tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride,
Butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride), telluroamides (for example, telluroacetamide, N, N-dimethyltellurobenzamide), telluroketones, telluroesters, and isotellurocyanates.

The silver halide emulsion of the present invention contains selenium and / or
Alternatively, it is also preferable to use a chemical sensitization other than tellurium sensitization in combination. The conditions of the chemical sensitization step, for example, pH, pAg, temperature, time and the like are not particularly limited, and can be performed under conditions generally performed in the art. Preferable chemical sensitization methods when used in combination include a sulfur sensitization method using a compound containing sulfur capable of reacting with silver ions and active gelatin, a reduction sensitization method using a reducing substance, gold and other noble metal sensitization methods using a noble metal. And the like. Among them, a sulfur sensitization method, a gold sensitization method, a reduction sensitization method and the like are preferable.

Examples of the sulfur sensitizer applicable in the present invention include US Pat. Nos. 1,574,944 and 2,410,
No. 689, No. 2,278,947, No. 2,728,6
No. 68, No. 3, 501, 313, No. 3, 656, 95
No. 5, West German Application Publication (OLS) 1,422,869,
Sulfur sensitizers described in JP-A-56-24937 and JP-A-55-45016 can be used.
Specific examples include thiourea derivatives such as 1,3-diphenylthiourea, triethylthiourea, 1-ethyl-3- (2-thiazolyl) thiourea, rhodanine derivatives, dithiacarbamic acids, polysulfide organic compounds, and sulfur alone. And the like are preferred examples. 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.

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

In the present invention, the sulfur sensitizer and the gold sensitizer may be added by dissolving them in water or alcohols or other inorganic or organic solvents and adding them in the form of a solution. Alternatively, it may be added in the form of a dispersion obtained by emulsifying and dispersing using a medium such as gelatin.

In the present invention, selenium and / or tellurium sensitization, sulfur sensitization, and gold sensitization may be performed simultaneously, or separately and stepwise. It is also preferable to perform so-called reduction sensitization on the surface of the grains by placing the grains in an appropriate reducing atmosphere. Preferred examples of the reducing agent include thiourea dioxide and ascorbic acid and derivatives thereof. Other preferable reducing agents include polyamines such as hydrazine and diethylenetriamine, dimethylamineboranes, sulfites and the like.

The dye preferably used in the light-sensitive material of the present invention is substantially insoluble in water at pH 7 or less and pH 8 or more.
And it is substantially water-soluble. The amount added can be varied depending on the sharpness goal. Preferably 0.2m
g / m ^{2 to} 20 mg / m ² , more preferably 0.8 mg
/ M ^{2 to} 15 mg / m ² . The dyes used in the present invention are described in German Patent No. 616,007 and British Patent No. 58.
No. 4,609, No. 1,177,429, No. 26-
No. 7777, No. 39-22069, No. 54-3812
No. 9, JP-A-48-85130 and JP-A-49-99620.
Nos. 49-144420 and 49-129357
No. 50-28827, No. 52-108115,
57-185038, JP-A-2-282244,
No. 4-307539, U.S. Pat. No. 1,878,961
Nos. 1,884,035, 1,912,797
No. 2,098,891 and 2,150,695
No. 2,274,782, 2,298,731
No. 2,409,612, 2,461,484
No. 2,527,583 and 2,533,472
No. 2,865,752, No. 2,956,879
No. 3,094,418, 3,125,448
No. 3,148,187 and 3,177,078
No. 3,247,127, 3,260,601
Nos. 3,282,699 and 3,409,433
No. 3,540,887 and 3,575,704
Nos. 3,653,905 and 3,718,472
Nos. 3,865,817 and 4,070,352
No. 4,071, 312, PB Report 74175
No., PHOTO. ABS. 1, 28 ('21) and the like can be used.

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 No.
No. 17643 (December 1978); 18716
(November 1979) and the same No. 308119 (19
(December 1989). The types of compounds and the locations described in these three research disclosures are listed below.

Additives RD-17643 RD-18716 RD-308119A page classification page classification page classification chemical sensitizer 23 III 648 upper right 996 III sensitizing dye 23 IV 648-649 996-8 IV desensitizing dye 23 IV 998 IVB dye 25 to 26VIII 649 to 650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006 to 7 VI Brightener 24 V 998 V Hardener 26 X 651 Left 1004 to 5 X surfactant 26-7 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 XXI I 1003-4 IX Support 28 XVII 1009 XVII

The silver halide emulsion of the present invention may contain a developing agent such as aminophenol, ascorbic acid, pyrocatechol, hydroquinone, phenylenediamine or 3-pyrazolidone in an emulsion layer or a layer having another layer.

Examples of the support which can be used for the light-sensitive material according to the present invention include, for example, RD-17643-2
8 and RD-308119, page 1009.

A suitable support is a plastic film or the like, and the surface of the support may be provided with an undercoat layer, or subjected to corona discharge, ultraviolet irradiation, etc. in order to improve the adhesion of the coating layer. The undercoat layer preferably contains an antistatic improver such as a colloidal tin oxide sol.

If the photographic light-sensitive material of the present invention is provided with a silver halide emulsion layer and a crossover cut layer on both sides of the support, a light-sensitive material having high sensitivity, high sharpness, and excellent processing properties can be obtained. The amount of gelatin in the silver halide emulsion layer, surface protective layer and other layers is 0.5 to 0.5 in total on one side of the support.
It is preferably in the range of 3.5 g / m ² , especially 1.
A range of 5 to 3.0 g / m ² is preferred.

The latex used in the present invention preferably has no or very little adverse effect on the following points even when used in a silver halide photographic light-sensitive material. That is, the latex surface is photographically inert and has very little interaction with various photographic additives. As an example, dyes and dyes are adsorbed and the photographic element is hardly stained with color. Further, it is difficult to adsorb a development accelerator, a development inhibitor, and the like, which affect the speed of development, and hardly affect sensitivity and fog.

In producing a photographic light-sensitive material, the photographic solution in which the latex of the present invention is dispersed has a low pH dependency and is hardly affected by ionic strength, so that it is hard to aggregate and precipitate.

It is considered that the fact that the latex which can be used in the present invention has the above properties has a great influence on the monomer composition and properties of this latex.

For latex, an index called a glass transition point is often used. The higher the transition point is, the harder it becomes and cannot serve as a buffer. For this reason, considering the photographic characteristics, the selection of the composition and its use amount are not simple. Latexes using monomers such as styrene, butadiene, and vinylidene are well known. Latex refers to a powder processing agent, a solid processing agent such as a tablet, a pill, and a granule, etc., which is subjected to a moisture-proof treatment as required.

In the present invention, the powder refers to an aggregate of fine crystals, and the granule refers to a powder obtained by subjecting a powder to a granulation step and has a particle size of 50 to 5000 μm.
In addition, the tablet in the present invention refers to a tablet obtained by compression-molding a powder or granules into a certain shape. The silver halide photographic material of the present invention is supplied and processed while continuously processing such a solid processing agent.

In order to solidify the processing agent, a concentrated liquid or a fine or granular photographic processing agent and a water-soluble binder are kneaded and molded, or the surface of the temporarily molded processing agent is sprayed with the water-soluble binder. Or any other means such as forming a coating layer. A preferred tablet production method is a method of granulating a powdery solid processing agent and then performing a tableting step to form the tablet.

Compared to a solid processing agent formed by simply mixing a solid processing agent component and forming a tablet, there is an advantage that solubility and storage stability are improved, and as a result, photographic performance is stabilized. As a granulation method for tablet formation, known methods such as tumbling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, fluidized bed granulation, and spray drying granulation can be used. For tablet formation, the average particle size of the obtained granules is 100 to 800 μm, because when mixing the granules and compressing and compressing, the components become non-uniform, so-called segregation hardly occurs. Is preferably used, and more preferably 200 to 750 μm. Further, the particle size distribution is such that 60% or more of the granulated particles are ± 10%.
Those having a deviation of 0 to 150 μm are preferable. Next, when the obtained granules are compressed under pressure, a known compressor such as a hydraulic press, a single-shot tableting machine, a rotary tableting machine and a briquetting machine can be used. The solid processing agent obtained by pressurizing and compression can take an arbitrary shape, but from the viewpoint of productivity, handleability or the problem of dust when used on the user side, a cylindrical type, so-called tablet, is preferable. . Preferably, at the time of granulation, the above effect is further remarkable by separately granulating each component such as an alkali agent, a reducing agent and a preservative.

In the present invention, a solid processing agent is used for a photographic processing agent such as a developer, a fixing agent, and a rinsing agent. The developer which has a large effect of the present invention, particularly, an effect of stabilizing photographic performance is large.

In the present invention, as a supply means for supplying the solid processing agent to the processing tank, for example, when the solid processing agent is a tablet, Japanese Unexamined Utility Model Publication No. 63-137783 and 63-9752.
No. 2, Japanese Utility Model Laid-Open No. 1-85732, etc., but any method may be used as long as the function of supplying tablets to the processing tank is provided at a minimum. When the solid processing agent is in the form of granules or powders, see JP-A-62-81964, 6
3-84151, JP-A-1-292375, and Japanese Utility Model Laid-Open Nos. 63-105159 and 63-105159.
A method using a screw or a screw described in -195345 or the like is known.

The place where the solid processing agent is charged may be in the processing tank, but may be direct or indirect. Preferred is a place where the processing liquid is in communication with the processing section for processing the photosensitive material and the processing liquid is circulating between the processing section and the processing component. Is preferably moved to the processing section. The solid processing agent is preferably introduced into a processing liquid whose temperature is controlled.

The preservative may contain a sulfite such as potassium sulfite, sodium sulfite, and a reductone such as piperidinohexose reductone, preferably 0.2 to 1 mol / l. ,
It is more preferable to use 0.3 to 0.6 mol / l. Also, the addition of a large amount of ascorbic acids leads to processing stability. It is also preferable to add compounds described in JP-A-5-289255 and JP-A-6-308680 (general formulas [4-a] and [4-b]) as silver sludge inhibitors. The addition of a cyclodextrin compound is also preferred, and the compounds described in JP-A-1-124852 are particularly preferred.

An amine compound can be added to the developer of the present invention, and the compounds described in US Pat. No. 4,269,929 are particularly preferred.

It is necessary to use a buffer for the developer used in the present invention. Examples of the buffer include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, and tripotassium phosphate. , Dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (boric acid), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate),
Examples thereof include potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).

Examples of the development accelerator include JP-B-37-160.
Nos. 88, 37-5987, 38-7826, 44-12380, 45-9019, U.S. Pat. No. 3,81,3247, and the like. No. 50-15554
Quaternary ammonium salts represented by JP-A-50-137726, JP-B-44-30074, JP-A-56-156826 and JP-A-52-43429. US Patent 2,61
P-aminophenols described in U.S. Pat. Nos. 0,122 and 4,119,462; U.S. Pat. Nos. 2,494,903, 3,128,182, 4,230,796 and 3,253. No. 919, JP-B-41-11431, U.S. Pat. Nos. 2,482,546, 2,596,926 and 3,582,346, and the like. 42-25201
No. 3,128,183, Japanese Patent Publication No. 411-1143.
Nos. 1 and 42-23883 and U.S. Pat.
No. 501, etc., other 1-phenyl-3-pyrazolidones, hydrozines,
Mesoionic compounds, ionic compounds, imidazoles, and the like can be added as necessary.

As an antifoggant, an alkali metal halide such as potassium iodide and an organic antifoggant can be used. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, Nitrogen-containing heterocyclic compounds such as 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine can be exemplified by 1-phenyl-5-mercaptotetrazole as a typical example.

Further, the developer composition used in the present invention may contain, if necessary, methylcellosolve, methanol,
Acetone, dimethylformamide, cyclodextrin compound, and other JP-B-47-33378, 44-9
No. 509 can be used as an organic solvent for increasing the solubility of a developing agent. Furthermore, various additives such as a stain inhibitor, an anti-sludge agent, and a layering effect promoter can be used.

The fixing agent used in the present invention may contain a compound known as a fixing agent. Fixing agent, chelating agent, p
An H buffer, a hardener, a preservative, and the like can be added. These are described in, for example, JP-A-4-242246 (page 4) and JP-A-5-11.
3632 (pages 2 to 4) can be used.

Prior to the treatment, it is preferable to add a starter, and it is also preferable to add the solidified starter. As the starter, in addition to an organic acid such as a polycarboxylic acid compound, a halide of an alkaline earth metal such as KBr, an organic inhibitor, and a development accelerator are used.

The processing temperature of the development processing of the present invention is preferably from 25 to 50 ° C., more preferably from 30 to 40 ° C. The development time is 3 to 15 seconds, more preferably 4 to 15 seconds.
10 seconds. The total processing time is Dry to Dry, preferably 15 to 90 seconds, more preferably 20 to 60 seconds. The total processing time is a processing time including the steps of developing, fixing and drying the photosensitive material.

When a liquid replenishment type automatic developing machine is used,
The replenishment in the present invention replenishes the treatment agent fatigue and the oxidation fatigue equivalent. The replenishment method is described in Japanese Patent Application Laid-Open No. 55-126243.
Replenishment by width and feed rate described in JP-A-60-10
Area replenishment described in No. 4946 and area replenishment controlled by the number of sheets continuously processed described in JP-A-1-149156 may be used. A preferable replenishment amount is 500 to 150 ml / m ^2.
It is.

In the present invention, the term "fixing solution" refers to a solution in a fixing tank. Preferred fixing solutions can include fixing materials commonly used in the art. The iodine content is preferably 0.3 g / liter or less, more preferably 0.1 g / liter or less. The pH is at least 3.8, preferably 4.2-5.5. The preferred replenishment rate is 50
It is a 0~100ml / ^{m 2.}

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

The fixing solution of the present invention may be one that forms an acidic hardening film. 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.

The fixing solution of the present invention may further contain a preservative such as sulfite or bisulfite, a pH buffer such as acetic acid or boric acid, a mineral acid (sulfuric acid, nitric acid) or an organic acid (citric acid or oxalic acid). ,
Various acids such as malic acid), hydrochloric acid and the like, pH adjusters such as metal hydroxides (potassium hydroxide and sodium), and chelating agents having water softening ability can be contained.

Examples of the fixing accelerator include, for example,
No. 35754, No. 58-122535, No. 58-12
No. 2536, thiourea derivatives, U.S. Pat.
Thioether described in US Pat. No. 6,459.

The silver halide emulsion layer of the present invention preferably has a swelling ratio of 150 to 250% during the development process, and a film thickness after expansion of 70 μm or less. 250% water swelling
If the temperature exceeds the limit, drying failure occurs, and for example, conveyance failure also occurs in automatic developing machine processing, particularly in rapid processing. On the other hand, when the water swelling ratio is less than 150%, uneven development and residual color tend to be deteriorated during development. Here, the water swelling ratio is the difference between the film thickness after swelling in each processing solution and the film thickness before development processing,
This is a value obtained by dividing 100 times the film thickness before processing.

The filling rate of the phosphor in the phosphor layer of the radiation intensifying screen according to the present invention is at least 68%, preferably at least 70%, more preferably at least 72%. In the present invention, the thickness of the phosphor layer is 150 μm or more,
It is 50 μm or less. Here, the thickness of the phosphor layer is 150 μm.
If it is less than m, sharpness sharply deteriorates.

It is preferable that the radiation intensifying screen of the present invention is filled with a phosphor in a gradient particle size structure. In particular, it is preferable to apply phosphor particles having a large particle diameter to the surface protective layer side, and to apply phosphor particles having a small particle diameter to the support side.
5 to 2.0 μm, and those having a large particle diameter preferably have a range of 10 to 30 μm.

The photosensitive material of the present invention is characterized in that an instant type self-developing diffusion transfer processing sheet can be used other than a general liquid replenishment type automatic developing machine.

The silver halide photographic material can be used for forming a dye image through selective formation of a dye in the photographic material. For forming a dye image, the above-described photographic material for forming a silver image can be used by using a developer containing a dye image forming substance such as a color coupler. This is explained in the following patent documents: UK Patent No. 4
No. 78,984, U.S. Pat. No. 3,11 to Yager et al.
No. 3,864, U.S. Pat.
Nos. 2,836, 2,271,238 and 2,
No. 362,598, Schwan et al., US Pat.
50,970, Carroll et al., U.S. Pat.
No. 92,243, Porter et al., U.S. Pat. No. 2,34.
No. 3,703, No. 2,376,380 and No. 2,
369,489, Path, UK Patent 886,7.
No. 23 and U.S. Pat. No. 2,899,306, Tuit
e, U.S. Pat. No. 3,152,896; Mannes et al., U.S. Pat. Nos. 2,115,394;
718 and 2,108,602, and Pil
U.S. Pat. No. 3,547,650 to ato. In this form, the developer contains a color developing agent, such as a primary aromatic amine, which, when in the oxidized state, reacts (couples) with the coupler to form an image dye. It is possible to Further, it is characterized in that an instant type self-developing diffusion transfer processing sheet is used.

Dye-forming couplers can be incorporated into photographic light-sensitive materials as described in the patent documents listed below: Schneider et al., Die
Chemie, Vol. 57, 1994, P113, M
U.S. Patent No. 2,304,940 to Annes et al., Ma.
rtinez US Patent No. 2,269,158, Je
U.S. Pat. No. 2,376,697 to Lley et al., Fie.
No. 2,801,171 to Rke et al., Smit.
U.S. Pat. No. 3,748,141 to Tong, U.S. Pat. No. 2,772,163 to Tong, U.S. Pat. No. 2,835,579 to Thirtle et al., U.S. Pat. No. 2,553,514 to Sawdey et al. U.S. Pat. No. 2,353,745 to Peterson, U.S. Pat. No. 3,409,435 to Seidel, and Research Di
sclosure, Vol. 159, July 1977,
Item 15930. Dye-forming couplers can be incorporated in different amounts to achieve different photographic effects. For example, British Patent No. 923,045 and Ku
Mai et al., U.S. Pat. No. 3,843,369, teaches limiting the concentration of couplers in relation to silver coverage to less than that normally used in fast and moderately sensitive emulsion layers. doing.

Dye-forming couplers are usually chosen to form subtractive primary color (ie, yellow, magenta, and cyan) image dyes, and are non-diffusible, colorless couplers, such as high boiling organic ( Couplers) 2- and 4-equivalent couplers of the open-chain ketomethylene, pyrazolone, pyrazolotriazole, pyrazolobenzimidazole, phenol, and naphthol type that have been hydrophobically stabilized (ballasted) for incorporation into solvents. .

The coupler may be present in a form directly bound by the hydrophilic colloid, or otherwise kept in a high boiling organic solvent and then dispersed in the hydrophilic colloid. May exist as described above. The colloid may be partially or completely cured by any of a variety of known photographic hardeners. Such curing agents include free aldehydes (US Pat. No. 3,23,23).
2,764), aldehyde releasing compounds (U.S. Pat. Nos. 2,870,013 and 3,819,608)
), S-triazines and diazines (U.S. Pat.
25,287 and 3,992,366), aziridine (US Pat. No. 3,217,175), vinyl sulfones (US Pat. No. 3,490,911), and others. Carbimides and the like may be used.

In the fluorescent intensifying screen used in the combination of the present invention, the X-ray absorption of each intensifying screen is 30% per 100 μm of the thickness of the phosphor layer by increasing the filling rate of the phosphor particles. It is preferable that it is above. The amount of X-ray absorption was determined as follows. That is, X-rays generated from a tungsten target operated at 80 kVp from an X-ray generator equivalent to 2.2 mm of aluminum and passed through a 3 mm-thick aluminum plate having a purity of 99% or more are supplied by three-phase power supply. The X-ray absorption amount was measured by using an ionizing dosimeter at a position 50 cm after the phosphor layer of the radiographic intensifying screen, and arriving at a radiographic intensifying screen fixed at 200 cm from the tungsten anode of the target tube. I asked. As a reference, the X-ray dose at the above measurement position measured without passing through the intensifying screen was used.

Preferred binders used in the radiation intensifying screen according to the present invention include thermoplastic elastomers. Specifically, polystyrene, polyolefin, polyurethane, polyester, polyamide, polybutadiene,
At least one type of thermoplastic elastomer selected from the group consisting of ethylene vinyl acetate, polyvinyl chloride, natural rubber, fluororubber, polyisoprene, chlorinated polyethylene, styrene-butadiene rubber and silicone rubber.

The filling rate of the phosphor in the present invention can be determined from the porosity of the phosphor layer formed on the support by the following equation.

[0131]

(Equation 1)

Preferred phosphors for use in the radiation intensifying screen according to the present invention include the following.

A tungstate-based phosphor (CaWO ₄ ,
MgWO ₄ , CaWO ₄ : Pb, etc.), terbium-activated rare earth oxysulfide-based phosphor [Y ₂ O ₂ S: Tb, Gd ₂ O
₂ S: Tb, La ₂ O ₂ S: Tb, (Y, Gd) ₂ O ₂
S: Tb, Tm, etc.], terbium-activated rare earth phosphate-based phosphor (YPO ₄ : Tb, GdPO ₄ : Tb, LaP
O _4: Tb, etc.), terbium activated rare earth oxyhalide phosphor LaOBr: Tb, LaOBr: Tb. T
m, LaOCl: Tb, LaOCl: Tb. TmGdO
Br: Tb, GdOCr: Tb), thulium-activated rare earth oxyhalide-based phosphor (LaOBr: Tm, L
aOCl: Tm, etc.), barium sulfate-based phosphor [BaS
O ₄ : Pb, BaSO ₄ : Eu ²⁺ , (Ba.Sr) S
O 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 fluorohalide-based phosphor [BaFCl: Eu ²⁺ , Ba
FBr: Eu ²⁺ , BaFCl: Eu ²⁺ . Tb, Ba
FBr: Eu ²⁺ . Tb, BaF ₂ . BaCl ₂ . XB
aSO ₄ . KCl: Eu ²⁺ , (Ba.Mg) F ₂ . B
aCl ₂ . KCl: Eu ²⁺ etc.], iodide-based phosphor (C
SI: Na, CSI: Tl, NaI. KI: Tl, etc.) Sulfide-based phosphor [ZnS: Ag, (Zn.Cd) S: A
g, (Zn.Cd) S: Cu, (Zn.Cd) S: C
u. Al, etc.], hafnium phosphate-based phosphor (HfP
₂ O ₇ : Cu, etc.) However, the phosphor used in the present invention is not limited to these, and any phosphor that emits light in the visible or near ultraviolet region upon irradiation with radiation can be used.

[0134]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Example 1 <Preparation of silver iodobromide hexagonal tabular grains> Preparation of Em-1 A1 Ossein gelatin 75.5 g Polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% aqueous ethanol solution) 6.78 ml Potassium bromide 64 0.7 g Finished to 10800 ml with water B1 0.7 N silver nitrate aqueous solution 1340 ml C1 2.0 N silver nitrate aqueous solution 1500 ml D1 1.3 N potassium bromide aqueous solution 410 ml E1 2.0 n potassium bromide aqueous solution The following silver potential control amount F1 ossein gelatin 125 g water 4000 ml H1 Fine grain emulsion composed of 3% by weight of gelatin and silver iodide grains (average grain size: 0.05 μm) Equivalent to 0.008 mol

* Contains 0.06 mol of potassium iodide
To 6.64 liters of a 0% by weight aqueous gelatin solution, 7.0
Two liters each of an aqueous solution containing 6 moles of silver nitrate and 7.06 moles of potassium iodide were added over 10 minutes. During the fine particle formation, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the formation of the particles, the pH was adjusted to 6.0 using an aqueous solution of sodium carbonate.

At 55 ° C, JP-B-58-58288, 5
Solution A using a mixing stirrer described in JP-A-8-58289.
400 ml of the solution B1 and the entire amount of the solution D1 were added to 1 by a simultaneous mixing method over 40 seconds to form nuclei.

After the addition of the solution B1 and the solution D1, the solution F1 is added, and the temperature is raised to 70 ° C. to ripen. After the remaining amount of the solution B1 was further added over 25 minutes, the mixture was aged for 10 minutes using a 28% aqueous ammonia solution, and the pH was adjusted with acetic acid.
To neutral. Simultaneous addition and mixing of solutions C1 and E1 at a rate commensurate with the critical growth rate while maintaining pAg = 7.8,
After the total amount of C1 was added, G1 and H1 were added. After stirring for 5 minutes, soluble salts were desalted and removed by sedimentation. In this emulsion, 90% or more of the total projected area of the silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0,
It was confirmed by an electron microscope that the average thickness of the hexagonal tabular grains was 0.20 μm and the average particle diameter (in terms of circular diameter) was 0.80 μm. The distribution of the circle equivalent diameter was 15%.

Subsequently, the above-mentioned emulsion Em-1 was divided into a predetermined amount, the temperature was set to 55 ° C., and a reduction sensitizer (shown in Table 1)
And then 0.5 mol% of silver iodide fine grains are added,
6,6′-Dithiodinicotinic acid was added at 1 × 10 ⁻⁵ mol. The spectral sensitizing dyes of the present invention and comparative dyes (shown as dye types in Table 1) were added as solid particulate dispersions. Subsequently, a solid particulate dispersion of sodium thiosulfate (10 mg) and triphenylphosphine selenide (2 mg) was added, and ammonium thiocyanate (105 mg) and chloroauric acid (1) were added.
2.5 mg was added. Then, 300 mg of the compounds of the general formulas (1) and (2) were added. Aging was performed for a total of 2 hours. At the end of ripening, 5 mg of 1-phenyl-5-mercaptotetrazole (PMT) and 200 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) were added as stabilizers. The addition amount is Ag
X was added as per mole.

<Preparation of silver iodochloride tabular grains> Preparation of Em-2 Ossein gelatin 75.0 g KI 1.25 g NaCl 33.0 g Finished to 15000 ml with distilled water B2 Silver nitrate 410 g Finished to 684 ml with distilled water C2 1115 g silver nitrate Finish up to 19316 ml with distilled water D2 KI 4 g NaCl 140 g Finish up to 684 ml with distilled water NaCl 3980 g Potassium hexachloroiridate (IV) 8 × 10 ^-6 mol Finish up to 19274 ml with distilled water

At 40 ° C., JP-B-58-58288
No. 58-58289, the entire amount of B2 and D2 was added over 1 minute to the solution A2 in the mixing stirrer. The EAg was adjusted to 149 mV, and after Ostwald ripening for 20 minutes, the total amount of C2 and E2 was added over 320 minutes. Meanwhile, EAg was controlled at 149 mV.

Immediately after the addition was completed, desalting and washing were performed.
Em-2 thus prepared is composed of tabular grains having 65% of the total projected area of the silver halide grains having the (100) plane as the main plane, and has an average thickness of 0.14 μm and an average diameter of 1.0%.
It was found by electron microscope observation that the coefficient of variation was 0 μm and the coefficient of variation was 25%.

Emulsion Em-2 was divided into predetermined amounts, and the temperature was adjusted to 5
After the temperature was raised to 5 ° C. and a reduction sensitizer (shown in Table 1) was added, 0.5 mol% of silver iodide fine particles were added, and 6,6′-dithiodinicotinic acid was added to 1 × 10 ^−5. Mole was added. The spectral sensitizing dye (shown in Table 1) was added as a dispersion in the form of solid fine particles. Subsequently, sodium thiosulfate 15 mg, ammonium thiocyanate 145 mg, chloroauric acid 18.5 m
g and 3 Amg of triphenylphosphine selenide as a solid particulate dispersion. 500 mg of the compounds of the general formulas (1) and (2) (shown in Table 1) were added. Aging was performed for a total of 2 hours. At the end of ripening, 5 mg of 1-phenyl-5-mercaptotetrazole (PMT) and 100 mg of TAI were added as stabilizers. The addition amount was AgX1
Added as per mole.

A solid fine particle dispersion of the 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 is added to water whose temperature has been previously adjusted to 27 ° C., and a high-speed stirrer (dissolver) is used for 3,5.
Obtained by stirring at 00 rpm for 30-120 minutes.

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 the coating solution, the speed per minute 80m using two slide hopper type coater so that the amount of coating is silver amount per one side is 1.6 g / m ^2, gelatin with the amount of the 2.5 g / m ² 2. Simultaneously coat both sides on the support with
After drying for 20 minutes, a sample was obtained. As a support, glycidyl methacrylate 50 wt%, methyl acrylate 10
The copolymer aqueous dispersion obtained by diluting the concentration of the copolymer composed of the three monomers of 10% by weight and 40% by weight of butyl methacrylate was used as a subbing liquid.
A polyethylene terephthalate film base colored blue to a concentration of 0.13 for a μm X-ray film was used.

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

Second Layer (Emulsion Layer) The following various additives were added to each of the emulsions obtained above.

Compound (G) 0.5 mg / m ² 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 5 mg / m ² t-butyl-catechol 130 mg / m ² polyvinylpyrrolidone (Molecular weight 10,000) 35 mg / m ² Styrene-maleic anhydride copolymer 80 mg / m ² Sodium polystyrene sulfonate 80 mg / m ² Trimethylolpropane 350 mg / m ² Diethylene glycol 50 mg / m ² Nitrophenyl-triphenyl-phosphonium chloride 20 mg / m ² Ammonium 1,3-dihydroxybenzene-4-sulfonate 500 mg / m ² 2-Mercaptobenzimidazole-5-sodium sulfonate 5 mg / m ² Compound (H) 0.5 mg / m ² n-C ₄ H ₉ OCH ₂ C H (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 gelatin 1.5 g / m ²

Third layer (protective layer) Gelatin 0.8 g / m ² Matting agent composed of polymethyl methacrylate 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-vinylsulfonyl methyl ether 36 mg / m ² Latex (L) 0.2 g / m ² Polyacrylamide (average molecular weight 10,000) 0.1 g / m ² Polyacryl Sodium acid 30 mg / m ² Polysiloxane (SI) 20 mg / m ² Compound (I) 12 mg / m ² Compound (J) 2 mg / m ² Compound (S-1) 7 mg / m ² Compound (K) 15 mg / m ² Compound (O) 50mg / ^{m 2} compound _{^{(S-2) 5mg / m}} 2 C 9 F 19 -O- (CH 2 CH _{^{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

[0149]

Embedded image

[0150]

Embedded image

[0151]

Embedded image

Each of the obtained samples was subjected to condition A (23 ° C.,
After standing under the conditions (40%, 3 days) and the condition B (55 ° C., 80%, 3 days), the photographic properties were evaluated. First, the sample was sandwiched between two intensifying screens (KO-250, manufactured by Konica Corporation), and a tube voltage of 80 kVp and a tube current of 100 were passed through an aluminum wedge.
Exposure was performed by irradiating X-rays at 0.05 mA for 0.05 seconds. Next, using an automatic developing machine (manufactured by Konica Corporation, SRX-502), processing was performed with a developing solution and a fixing solution having the following formulations.

A tablet for replenishing development was prepared according to the following operations (A, B). Operation (A) 3,000 g of hydroquinone as a developing agent is ground in a commercially available Bandham mill until the average particle size becomes 10 μm. 3000 g of sodium sulfite and 2 parts of potassium sulfite were added to the fine powder.
000 g and 1000 g of Dimaison S were added and mixed in a mill for 30 minutes, and then at room temperature for about 10 minutes in a commercially available stirring granulator.
After granulating by adding 30 ml of water, the granulated material is dried at 40 ° C. for 2 hours in a fluidized bed drier to remove almost completely the moisture of the granulated material. 100 g of polyethylene glycol 6000 was added to the granules thus prepared in 2 parts.
After mixing uniformly for 10 minutes using a mixer in a room conditioned at 5 ° C. and 40% RH or less, the obtained mixture was mixed per tablet with a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. Was compressed and tableted at a filling amount of 3.84 g to prepare 2500 tablets A for development replenishment.

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, and 200 g of N-acetyl-D, L-penicillamine Pulverization and granulation are performed as in (A). The amount of water to be added is 30.0 ml, and after granulation, it is dried at 50 ° C. for 30 minutes to almost completely remove water from the granulated material. The mixture thus obtained was subjected to compression tableting using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho at a filling amount per tablet of 1.73 g, and 2500 tablets B for development replenishment were used. A preparation was made.

Next, tablets for fixing replenishment were prepared by the following operations (C, D). Operation (C) Ammonium thiosulfate / sodium thiosulfate (70/3
0 weight ratio) 14000 g, sodium sulfite 1500 g
Is ground in the same manner as in (A), and then uniformly mixed with a commercially available mixer. Next, in the same manner as in (A), the amount of water added was 500 m
and perform granulation. After the granulation, the granules are dried at 60 ° C. for 30 minutes to almost completely remove the moisture of the granules. 4 g of sodium N-lauroylalanine is added to the granules thus prepared, and mixed for 3 minutes in a room conditioned at 25 ° C. and 40% RH or less using a mixer. Next, the obtained mixture was applied to Tough Presto Collect 15 manufactured by Kikusui Seisakusho Co., Ltd.
27HU was compressed and compressed using a modified tableting machine with a filling amount per tablet of 6.202 g to prepare 2500 fixing supplement refilling tablets C.

Operation (D) Boric acid 1000 g, aluminum sulfate / 18-hydrate 150
0 g, sodium hydrogen acetate (3,000 g of glacial acetic acid and sodium acetate mixed and dried), tartaric acid 200
g is ground and granulated in the same manner as in the operation (A). The amount of water to be added is 100 ml, and after granulation, it is dried at 50 ° C. for 30 minutes to almost completely remove water from the granulated material. 4 g of sodium N-lauroylalanine was added to the thus-prepared product, and after mixing for 3 minutes, the obtained mixture was filled per tablet using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. The amount was 4.562 g, and compression tableting was performed to prepare 1250 fixing replenishing tablets D. Developer Starter Glacial acetic acid 2.98 g KBr 4.0 g Water was added to make up to 1 liter.

When processing of the developing solution is started (starting of running), the developing tank is filled with 16.5 liters of developing solution diluted with diluting water and 330 ml of a starter added to the developing tank as a starting solution to start processing. did. still,
A developer to which a starter has been added (this is designated as D-1)
Had a pH of 10.45.

The photosensitive material prepared above was exposed to light so that the optical density after development processing was 1.0, and the photosensitive material was run. For the running, an automatic developing machine SRX-502 equipped with a charging member for a solid processing agent and modified so as to be able to process at a processing speed of 15 seconds was used.

During the running, the photosensitive material contains 0.6 photosensitive material.
The above-mentioned ^two agents A and B were added per 2 m ^2, and 76 ml of water was added. When each of A and B was dissolved in 38 ml of water, the pH was 10.70. The fixing solution contains 0.
2 pieces of the above C agent, 1 piece of the D agent and 7 pieces of water per 62 m ²
4 ml was added. The rate of addition of water to each processing agent was started almost simultaneously with the addition of the processing agent, and was added at a constant speed for 10 minutes in approximately proportion to the dissolution rate of the processing agent. The photographic performance of each sample was measured. Sample No. The result of No. 1 was shown as a relative value with reference (100).

For evaluation of the residual color, the spectral absorption density at 500 nm of the sample after the development processing was measured by a spectrophotometer. The pressure fog was evaluated by applying a load of 5 g to the unexposed sample using a 0.3-needle scratch hardness tester, performing the same developing treatment as described above, and using a microdensitometer to measure the pressure fog density. Was measured. The samples in Table 1 were evaluated and the results obtained are shown in Table 2.

[0161]

[Table 1]

[0162]

[Table 2]

As is clear from Table 2, the sample of the present invention has high sensitivity, excellent pressure resistance and excellent residual color, and shows little change in performance even after storage under high temperature and high humidity. . It can be seen that when the solid processing agent of the present invention is used, the sensitivity is hardly impaired even in rapid processing such as 15 seconds, and there is no problem at all.

Example 2 Em-1 and Em-2 were each chemically sensitized as in Example 1. However, the reduction sensitizer thiourea dioxide was added to 0.0
2 mg / Ag.mol, spectral sensitizing dye was 3-18 to 450
mg / Ag · mol. Further, the chemical sensitizer and the compounds 1-3 of Chemical formulas 1 and 2 were changed as shown in Table 3. The coating speed was adjusted so that the amount of silver applied per side was 1.5 g / m ² and the amount of gelatin applied was 2.0 g / m ² . Table 3
Sample No. 12-20 were obtained.

The obtained sample was sandwiched between two screens.
Tube voltage 60kVp, tube current 20 via aluminum wedge
It was exposed to X-rays at 0 mA for 0.05 seconds. In Example 2, the above conventional radiation intensifying screen (KO-2.KO-2, manufactured by Konica Corporation) was used.
The following radiographic intensifying screen was used in place of 50) for evaluation.

<Production of High Sensitive Intensifying Screen (S-1)> Phosphor Gd ₂ O ₂ S: Tb (average particle size 1.8 μm) 200 g Binder Polyurethane thermoplastic elastomer (Demolac TPKL-5-2 625) <Solid content 40%> (Sumitomo Bayer Urethane Co., Ltd.) 20 g Nitrocellulose (digestibility: 11.5%) 2 g was added to a methyl ethyl ketone solvent and dispersed with a propeller mixer to form a phosphor layer having a viscosity of 25 PS (25 ° C.). A coating solution was prepared (binder / phosphor ratio = 1/22).

Separately, as a coating solution for forming an undercoat layer, 90 g of soft acrylic resin solids and 50 g of nitrocellulose were used.
Is added to methyl ethyl ketone, dispersed and mixed to obtain a viscosity of 3 to
A 6PS (25 ° C.) dispersion was prepared.

Thickness of 250 μm incorporating titanium dioxide
Of polyethylene terephthalate (support) is placed horizontally on a glass plate, and the above-mentioned coating solution for forming an undercoat layer is uniformly applied on the support using a doctor blade, and then gradually raised from 25 ° C to 100 ° C. The coating film was dried by drying to form an undercoat layer on the support (thickness of the coating film: 15 μm).

The above-mentioned coating solution for forming a phosphor layer was uniformly coated thereon with a doctor blade to a thickness of 240 μm, dried, and then compressed. Compression was performed using a calender roll at a pressure of 300 kgw / cm ² and a temperature of 80 ° C. After this compression, a transparent protective film having a thickness of 3 μm was formed by the method described in Example 1 of JP-A-6-75097. The characteristics of the obtained screen are as follows:
m, the phosphor filling rate was 68%, and the sharpness (CTF) was 48%.

<Production of Comparative Intensifying Intensifying Screen (S-2)>
The coating solution for forming the phosphor layer is uniformly coated to a thickness of 150 μm, and the same process as in S-1 is performed except that no compression is performed. A sensitivity S-2 was produced. The characteristics of the obtained high-sensitivity intensifying screen were that the thickness of the phosphor layer was 105 μm and the filling rate of the phosphor was 65%.

The sample of Example 2 was measured for low illuminance failure characteristics. The evaluation of the low-light failure property was performed by sandwiching the sample between two radiographic intensifying screens so that the amount of explosion was the same as that of the normal exposure, a tube voltage of 60 kVp, and a tube current of 50 m via an aluminum wedge.
A, Exposure was performed by irradiating X-rays for 0.2 seconds. The smaller the difference between the low illuminance exposure sensitivity and the normal exposure sensitivity, the smaller the change and the better the sensitivity. The photographic performance of each sample was measured. Sample No. The results obtained by using 12 intensifying screens (S-2) were shown as relative values with reference (100). Table 4 shows the obtained results.

[0172]

[Table 3]

[0173]

[Table 4]

As is evident from the results in Table 4, the sample of the present invention has high sensitivity, is less affected by low illuminance failure, and is less affected by 15 seconds of treatment using the solid processing agent of the present invention. Exposure and processing using the high-sensitivity intensifying screen of the present invention resulted in higher sensitivity.

Example 3 The sample of Example 2 was replaced with the above-mentioned developer replenishing type automatic developing machine D-
Instead of 1, the processing solution of the present invention was processed in the form of a processing bag using an instant processing, self-developing diffusion transfer processing sheet.

FIG. 1 is a schematic view of an automatic developing machine used for processing, and FIG. 2 is a schematic view showing processing by a processing bag.
Insert the imagewise exposed film. The opening of the processing bag containing the developer (liquid) bag, fixing agent (liquid) bag and the neutralization infiltration layer (containing physical development nuclei and diffusion transfer dyes) is opened, and the film falls naturally into it. I do. The processing bag containing the film is subjected to pressure as it passes between the rolls.
That is, when transported between the rolls, the developer (liquid) in the processing bag
The bag and the fixing agent (liquid) bag are broken, the processing liquid flows out, and is uniformly applied to the film by the uniform pressure of the roll, and the film is developed and fixed. Then, after performing a heat treatment in a heat zone of 36 ° C., it was dried in a drying zone of 50 ° C. The total processing time was 30 seconds.

The sample No. The measured values of the other samples were relatively determined using the result of processing with the 12 comparative developer D-1 as a reference (100). D-2 shows the result of the sample processed by the instant processing.

The evaluation of development unevenness was performed by uniformly exposing each sample of 35 cm × 43 cm to a density of 1.0.
After the development processing described above, the processed film was visually evaluated according to a four-level evaluation level. ◎: No unevenness was observed at all. ○: Some unevenness was observed. Δ: Some unevenness was observed. ×: Unevenness was observed over the entire surface. The obtained results are shown in Table 5 below.

[0179]

[Table 5]

As is clear from Table 5, even when the sample of the present invention is subjected to the instant treatment, the sample of the present invention has high sensitivity and
Moreover, it can be seen that no development unevenness is observed. The sensitivity is high, the pressure resistance and the residual color are excellent, and when a solid processing agent is used, the sensitivity is hardly impaired even in a rapid processing such as 15 seconds, and there is no problem at all.

[0181]

According to the present invention, it is possible to provide a silver halide emulsion having low fog, high sensitivity, little dye contamination and excellent pressure resistance, and a photographic light-sensitive material using the same. According to this, it is possible to provide a method for photographing a silver halide photographic material having the above-described performance and a method for processing the same.

[Brief description of the drawings]

FIG. 1 is a schematic view of an automatic developing machine for a self-developed diffusion transfer processing sheet used in Examples.

FIG. 1 is a schematic diagram showing processing by a processing bag.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] December 25, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Brief description of drawings

[Correction method] Change

[Correction contents]

[Brief description of the drawings]

FIG. 1 is a schematic view of an automatic developing machine for a self-developed diffusion transfer processing sheet used in Examples.

FIG. 2 is a schematic diagram showing processing by a processing bag.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03C 1/08 G03C 1/08 1/09 1/09 1/18 1/18 5/17 5/17 5/26 5/26 520 520 5 / 42 5/42 G21K 4/00 G21K 4/00 B

Claims (10)

[Claims] 1. A silver halide emulsion comprising at least one compound represented by the following general formula (1) or (2). Embedded image In the formula, Ar represents an aliphatic hydrocarbon or an aromatic hydrocarbon. F represents a fluorine atom. Y and Y ′ have —SO ₃ M, —COOM, and —OM directly or indirectly, and M represents a hydrogen atom, a metal atom, or a quaternary ammonium group or a phosphonium group. 5qx and Y ′ may be the same or different. In addition, 1 <m or m ′> 9, 1 <n or n ′> 9,
m + n or m '+ n'<= 10, X represents a sulfur, selenium or tellurium atom. x is 1 or 2. 2. A silver halide emulsion comprising at least one compound represented by the general formula (1) and at least one compound represented by the general formula (2). 3. The silver halide grains contained are subjected to reduction sensitization and contain at least one compound represented by the above general formula (1) or (2). Silver halide characterized in that at least one of sulfur sensitization, selenium sensitization and tellurium sensitization has been subjected to chemical sensitization in the presence of at least one of the represented spectral sensitizing dyes emulsion. Embedded image In the formula, R ₁ and R ₃ each represent a substituted or unsubstituted lower alkyl group or alkenyl group, and R ₂ and R ₄
Represents an alkyl group, and at least one of R ₂ and R ₄ represents an alkyl group substituted with a hydrophilic group. Z ₁ , Z ₂ ,
Z ₃ and Z ₄ may be the same or different, and represent a hydrogen atom or a substituent. X represents an ion necessary for neutralizing the charge in the molecule, and n represents 1 or 2. However, when an inner salt is formed, n is 1. 4. The halogen according to claim 3, comprising at least one kind of the compound represented by the general formula (1) and at least one kind of the compound represented by the general formula (2). Silver halide emulsion. 5. The silver halide grains contained in the silver halide emulsion have an aspect ratio of 2 to 20, an average iodine content of 0 to 1.0 mol%, and a silver chloride content of 10 mol%. ~
The silver halide emulsion according to any one of claims 1 to 4, wherein the emulsion contains 100 mol% of silver halide grains. 6. A halogen according to any one of claims 1 to 5.
The silver halide emulsion is represented by the following general formula (4) during chemical sensitization.
At least phosphine-coordinated organic transition metal complexes
Characterized by being chemically sensitized in the presence of one kind
Silver halide emulsion. General formula (4) [(R ′) ₃P]_aM [L] _bA In the formula, M is a transition group metal of groups 3 to 7a, group 8 and 1b of the periodic table.
Or a metal of the post-transition group, wherein R 'is any organic ligand
And a is 2 or 3. L represents a substitutable group.
And b is 1 or 2. Formula (4) is preferably 1
It is a complex of 6 electrons. 7. A silver halide photographic material comprising the silver halide emulsion according to claim 1. 8. A silver halide photographic light-sensitive material containing the silver halide emulsion according to claim 1;
A method for continuously processing in a processing step including each fixing step, wherein the processing solution in each processing step is a processing solution obtained from a solid processing agent. . 9. Development of a silver halide photographic light-sensitive material containing the silver halide emulsion according to any one of claims 1 to 6,
A method for processing a silver halide photographic material, comprising a fixing and drying step, wherein all the processing is of an instant type self-developing diffusion transfer method. 10. A silver halide photographic light-sensitive material containing the silver halide emulsion according to any one of claims 1 to 6 sandwiched between intensifying screens having a phosphor filling rate of 68% to 90%, and X-rays. A method for photographing a silver halide photographic material, characterized by photographing.