JPH1184556A - Silver halide emulsion, photosensitive material processing method using the same and photographic method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the photosensitive material superior in photographic characteristics, pressure resistance, storage stability and releasability of residual dyes even in the case of rapid processing and small in an amount of a waste processing solution to be discharged by incorporating silver halide grains subjected to reduction sensitization and a specified compound and subjecting silver halide to specified chemical sensitization in the presence of a specified spectral sensitizing dye. SOLUTION: This silver halide emulsion comprises the silver halide grains subjected to reduction sensitization and the compound represented by formula I and silver halide grains subjected at least to the chemical sensitization selected from sulfur sensitization and selenium sensitization and tellurium sensitization in the presence of the spectral sensitizing dye represented by formula II. In the formulae I and II, X is a group directly or indirectly combined with at least one selected from -So3 and -COOM and -OM groups and capable of forming a hetero ring; M is an H or metal atom or an ammonium group or phosphonium group; each of R1 -R3 is a lower alkyl group or the like; each of R2 and R4 is an alkyl group; each of Z1 -Z4 is an H atom or a substituent; X<-1> is an anion; and (n) is 1 or 2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide emulsion, a method for processing a silver halide photographic light-sensitive material having the emulsion, and a photographing method using the light-sensitive material.

[0002]

2. Description of the Related Art In recent years, there has been an increasing demand for rapid processing with an increase in processing of silver halide photographic light-sensitive materials (hereinafter also referred to as light-sensitive materials). For example, a similar tendency is seen in the field of medical X-ray films. With the spread of health examinations and the increase in examination items for improving the accuracy of diagnosis, the number of X-ray photographs taken increases. In addition, there is a need to notify the examinee of the diagnosis result sooner. 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, the conventional photosensitive material is accompanied by a reduction in image density, that is, a reduction in sensitivity and a deterioration in gradation. On the other hand, if the fixing time is shortened, fixing of the silver halide becomes incomplete and causes deterioration of image quality. Further, shortening the time in 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 problems, it is necessary to increase the developing speed and the fixing speed, to reduce the amount of the dye, and to promote the detachment and / or decoloration of the dye.

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

As techniques for solving these problems, European Patent No. 0,506,584, JP-A-5-88293 and JP-A-5-93975 disclose benzoimidazolocarboxycyanines having good decolorizing performance as spectral sensitizing dyes. A technique using a class is disclosed. JP-A-5-61148 discloses that oxacarbocyanines and benzimidazolocarbocyanines are used in a specific ratio as a spectral sensitizer in a silver halide emulsion having an iodine content of 1 mol% or less. A technique for performing chemical sensitization with a selenium compound and / or a tellurium compound is disclosed.

[0006] However, these techniques alone, although improving the residual color property or the speed of development, are still insufficient to satisfy the recent demand level 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. 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.

Further, attempts for reduction sensitization for high sensitivity have been studied for a long time, and are disclosed in US Pat. No. 2,487,850.
No. 2,512,925, No. 2,518,69
No. 8, No. 3,930,867, British Patent 789,8
No. 23, etc. However, these reduction sensitization methods have not yet reached practical levels.

Incidentally, 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 operation 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 can be reduced, and the amount of packaging material used can be reduced, which is favorable for the environment.

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

[0011]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object to provide photographic characteristics, pressure resistance and storage stability even when processing is carried out continuously in a system with rapid processing and a low waste liquid amount. It is to provide a photosensitive material which is excellent in bleeding and has good dye removal.

[0012]

The object of the present invention is to provide a reduction sensitized silver halide grain and a compound represented by formula (1), (2) or (3). ,
In the presence of the spectral sensitizing dye represented by the general formula (4),
A silver halide emulsion which has been subjected to at least one kind of chemical sensitization selected from sulfur sensitization, selenium sensitization and tellurium sensitization, wherein said chemical sensitization is further carried out in the presence of a compound represented by formula (5) , The aspect ratio of the contained silver halide grains is from 2 to 20, and the average iodine content is from 0 to
1.0 mol% and a silver chloride content of 10 to 100 mol%, and a photographic light-sensitive material having these silver halide emulsions is continuously processed in processing steps including development and fixing steps. A method for processing a silver halide photographic light-sensitive material which is processed while supplying a solid processing agent to a processing solution in each processing step; and a method for processing a photographic light-sensitive material having these silver halide emulsions, wherein the filling rate of a phosphor is 68%. This is achieved by a method for photographing a silver halide photographic light-sensitive material which is sandwiched between intensifying screens of up to 90% and X-ray photographed.

Hereinafter, the present invention will be described in detail.

As the silver halide of the silver halide grains of 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. However, silver chloride, silver iodochloride, silver bromochloride and silver bromide are preferred. When the silver halide grains of the silver halide emulsion of the present invention contain silver chloride, the silver chloride content is preferably at least 10 mol%, more preferably at least 50 mol%,
90 mol% or more is more preferable. In the case of silver iodochloride, the average silver iodide content is preferably from 0.01 mol% to 1.0 mol%, more preferably from 0.01 mol% to 0.5 mol%.

The shape of the silver halide grains used in the present invention may be any of cubic, octahedral, tetradecahedral, spherical, tabular, potato-like and the like, but tabular grains are particularly preferred. .

The silver iodide content and the average silver iodide content of each silver halide grain are determined by the EPMA method (Electron).
Probe Micro Analyzer method). According to this method, a sample in which emulsion grains are well dispersed so as not to be in contact with each other is prepared, an electron beam is irradiated, and X-ray analysis is performed by electron beam excitation. 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. EPM for at least 50 particles
If the silver iodide content is determined by the method A, 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 uniform iodine content between grains. When the distribution of iodine content between grains is measured by the EPMA method, the relative standard deviation is preferably 35% or less, more preferably 20% or less.

In the present invention, the tabular silver halide grains preferably contain silver iodide, preferably at least 0.1 mol% to 5 mol%. In the case of the inside, it is more preferable that it exists at least in the center. 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 irradiated with MgKα as a probe X-ray at an X-ray source voltage of 15 kV and an X-ray source current of 40 mA. 2, measured for Br3d and I3d3 / 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 increase 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 used in the present invention is preferably from 2 to 20, 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%. As described above, more preferably 90% or more is composed of tabular silver halide grains having a (100) plane as a 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 this case, the shape of the main plane of the tabular silver halide grains is a right-angled parallelogram or a shape of a right-angled parallelogram with no corners or a rounded shape. The adjacent side ratio of the rectangular parallelogram is less than 10, preferably less than 5, and more preferably less than 2. If the corner is missing or rounded, the length of the side is the length of the straight line of the right-angled parallelogram extending to the intersection with the line that extends the straight line of the adjacent side. It is represented by

The average grain size of the tabular silver halide grains is 0.1.
It is preferably from 15 to 5.0 μm, and from 0.4 to 3.0 μm.
More preferably, it is 0 μm, most preferably 0.1 μm.
4 to 2.0 μm. The average thickness of the tabular silver halide grains is preferably from 0.01 to 1.0 μm, more preferably from 0.02 to 0.40 μm, even more preferably from 0.02 to 0.30 μm. Particle size and thickness can be optimized to optimize sensitivity and other photographic properties. Sensitivity and other factors that make up the photosensitive material that affect photographic properties (thickness of hydrophilic colloid layer, hardness,
The optimal particle size and the optimal thickness vary depending on the conditions of chemical ripening, the sensitivity of the photosensitive material, the amount of silver, etc.).

The tabular silver halide grains used in the present invention are preferably monodisperse grains having a narrow grain size distribution. Specifically, (standard deviation of grain size / average grain size) × 100 = width of grain size distribution ( %), It is 20% or less, preferably 18% or less, more preferably 15% or less.

It is preferable that the thickness distribution of the tabular silver halide grains is narrow. Specifically, when the width of the distribution is defined by (standard deviation of thickness / average thickness) × 100 = width (%) of thickness distribution, it is 25% or less;
It is more preferably at most 20%, particularly preferably at most 15%.

The tabular silver halide grains may have dislocations. Dislocations are described in F. Hamilton, P
hot. Sci. Eng., 57 (1967); S
hiozawa, J .; Soc. Photo. Sci. Ja
Pan, 35, 213 (1972), which 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 particle, the more difficult it is for an electron beam to pass through. Therefore, a high-pressure type (200 kV or more for a particle having a thickness of 0.25 μm)
Can be observed more clearly using an electron microscope.

The reduction sensitization applied to the silver halide grains of the silver halide emulsion of the present invention will be described.

The process for producing 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. In the present invention, reduction sensitization may be basically performed in any step. 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 according to the present invention is carried out by adding a known reducing agent to a silver halide emulsion, called p ripening.
Either a method of growing in a low pAg atmosphere of Ag1 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 acid, 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. However, the addition amount is 10 ^-7 to 10 ^-7 per mol of silver halide.
A range of ^-3 moles is suitable.

Ascorbic acid and its derivatives can also be used as the reduction sensitizer of the present invention.

Ascorbic acid and its derivatives (hereinafter referred to as
It is called "ascorbic acid compound". 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-ascorbic acid Sodium (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 ascorbic acid compound should be used in a large amount as compared with the amount in which a reduction sensitizer is conventionally preferably used. Is desirable. For example, Japanese Patent Publication No. 57-33572 states that the amount of a reducing agent usually does not exceed 0.75 × 10 ⁻² meq (8 × 10 ⁻⁴ mol / AgX mol) per gram of silver ion.
An amount of 0.1 to 10 mg / kg (10 ^-7 to 10 ^-5 mol / AgX mol ascorbic acid) is often effective. Is described. US Patent No. 2,48
No. 7,850 describes "1.times.10.sup.- ^{7 to} 44.times.10.sup.- ⁶ mol as an addition amount in which a tin compound can be used as a reduction sensitizer". In JP-A-57-179835, it is appropriate to use about 0.01 mg to about 2 mg of thiourea dioxide per mole of silver halide and about 0.01 mg to about 3 mg of stannous chloride. It is described. The ascorbic acid compound used in the present invention has a grain size of an emulsion, a halogen composition, a temperature for preparing an emulsion,
The preferred amount of addition depends on factors such as pH and pAg, but is from 5 × 10 ^-5 to 1 × 10 ^-1 per mol of silver halide.
It is desirable to select from the molar range. It is more preferably selected from the range of 5 × 10 ^-4 to 1 × 10 ^-2 mol, and particularly preferably selected from the range of 1 × 10 ^-3 to 1 × 10 ^-2 mol.

The reduction sensitizer can be dissolved in water or a solvent such as alcohols, 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. Although it may be added to the reaction vessel in advance, it is preferable to add it at an appropriate time during the formation of particles. Alternatively, a reduction sensitizer may be added in advance to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide, 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.

Next, the compound represented by formula (1) will be described.

In the general formula (1), X represents —SO ₃ M,
A heterocyclic residue directly or indirectly having at least one selected from -COOM and -OM, for example, an oxazole ring, a thiazole ring, an imidazole ring, a selenazole ring,
Triazole ring, tetrazole ring, thiadiazole ring,
Oxadiazole ring, pentazole ring, pyrimidine ring,
A thiazine ring, a triazine ring, a thiodiazine ring or a ring bonded to another carbon chain or a heterocyclic ring, such as a benzothiazole ring, a benzotriazole ring, a benzimidazole ring, a benzoxazole ring, a benzoselenazole ring, a naphthoxazole ring, and triazaindole. It is a lysine ring, a diazaindolizine ring, a tetraazaindolizine ring or the like, and preferably an imidazole ring, a tetrazole ring, a benzimidazole ring, a benzothiazole ring, a benzoxazole ring, and a triazole ring.

Specific examples of the compound represented by the formula (1) are shown below, but it should not be construed that the invention is limited thereto.

[0042]

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[0043]

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These compounds are disclosed in US Pat. No. 2,582.
5,388, 2,541,924, Tokiko 42
No. 21842, JP-A-53-50169, British Patent No. 1,275,701; A. Berges et.
al. , “Journal of Heterocyc
like Chemistry " 15 , 981 (197
8), "The Chemistry of Hete
rocyclic Chemistry "Imidaz
ole and Derivatives part
I, p. 336-339, Chemical Abst
ract, 58 , 7921 (1963), p. 394,
E. FIG. Hoggarth "Journal of Che
medical Society ", p.116-116.
7 (1949); R. Saudler, W.C. Kar
o “Organic Functional Group”
p Preparation "Academic Pr
ess, p. 312-315 (1968); Cha
mdon, et. al. , Bulletin del
a Society Chimique de Fra
nce, 723 (1954); A. Shirle
y, D. W. Alley, J.M. Amer. Chem. S
oc. 79 , 4922 (1954); Wohl,
W. Marchwald “Ber.” 22 , p. 568
(1889); Amer. Chem. Soc. 4
4 , p. 1502-1510; U.S. Pat.
No. 270, UK Patent No. 940,169, JP-B-49-
No. 8334, JP-A-55-59463, "Advan.
ced in HeterocyclicChemis
try ", West German Patent No. 2,716,707," The
Chemistry of Heterocyclic
c Compounds Imidazole and
Derivatives ", 1 , p. 385," Or
g. Synth. "IV., 569 (1963)," Be
r. 9 , 465 (1976); Amer. Ch
em. Soc. 45 , 2390 (1923), JP-A-50-89034, JP-A-53-28426, and JP-A-55-28426.
No. 21007, JP-B-40-28496, and the like.

Next, the compound represented by formula (2) or (3) will be described.

In the general formulas (2) and (3), (A ₁ )
And -SO ₃ M, -COOM or-represented by (A ₁ ) '
The metal atom represented by M in OM is preferably an alkali metal, silver such as silver, gold, or palladium, or a transition metal capable of binding to selenium or tellurium.

The electron-withdrawing groups represented by (A ₂ ) and (A ₂ ) ′ include a fluorine atom, a trifluoromethyl group, a cyano group, a nitro group, a —SOCF ₃ group, a —SO ₂ NH ₂ group,
—SO ₂ CH ₃ groups and the like are preferred.

The functional group containing a sulfur atom, a selenium atom or a tellurium atom which can bind to a silver ion represented by (A ₃ ) and (A ₃ ) 'includes mercapto group, thione group, -SeH
Group, = Se group and the like are preferable.

The aliphatic hydrocarbon represented by Y is preferably one having 4 to 20 carbon atoms, and the aromatic hydrocarbon is preferably a benzene ring, a naphthalene ring or the like.

The compound represented by the general formula (2) or (3) further includes a halogen atom other than fluorine, a hydroxyl group, an amino group, an acylamino group, an alkylamino group, an alkyl group, an alkenyl group, a cycloalkyl group, Aryl group, alkoxy group, aryloxy group, alkylthio group, alkoxycarbonyl group, carbamoyl group, alkoxyalkyl group, aminoalkyl group, acylaminoalkyl group, hydroxyalkyl group, carboxyalkyl group, sulfoalkyl group, alkylsulfonamide group, etc. May have a substituent.

These compounds are described in "J. Chem. So
c. Sect. C "p.626 (1965) & p.13
47 (1971), "J. Org. Chem." 34 ,
p. 534 (1969), JP-A-60-184057.
And No. 60-204742. Some are available as commercial products.

Specific examples of the compound represented by formula (2) or (3) are shown below, but are not limited thereto.

[0053]

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[0054]

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[0055]

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[0056]

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The compound represented by formula (1), (2) or (3) may be added before, after or during chemical sensitization. When added before the completion of chemical sensitization, a high effect may be obtained, and when added separately before and after the end of the chemical sensitization, a better effect may be obtained in some cases. The compounds may be used in combination of two or more, or may be used in combination with other inhibitors.

As a method of addition, powder may be added as it is, or a solution dissolved in a low-boiling organic solvent such as methanol, ethanol or ethyl acetate, water, or a mixed solvent of a low-boiling organic solvent and water may be used. It may be added. If necessary, a pH adjuster may be used to enhance the solubility. or,
When dispersed and added as finely divided solids, higher effects may be obtained. In each case, the amount of silver added was 1
0.01 to 0.5 g per mole, preferably 0.02 to
0.2 g.

The silver halide emulsion of the present invention has the general formula (4)
Is subjected to at least one chemical sensitization selected from sulfur sensitization, selenium sensitization and tellurium sensitization in the presence of the spectral sensitizing dye represented by

The spectral sensitizing dye is adsorbed on silver halide grains and contributes to sensitization. In the present invention, when the sensitizing dye represented by the general formula (4) is adsorbed on silver halide emulsion grains and the reflection spectrum is measured, the maximum absorption wavelength of the J aggregation band is preferably 555 nm or less. . In the application to X-ray medical light-sensitive materials utilizing a phosphor emitting green light, the spectral sensitizing dye according to the present invention is adsorbed on silver halide emulsion grains, and the fluorescence is measured when its reflection spectrum is measured. Preferably, the J-band is formed in the same wavelength range as the green light from the body. 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 in the region is formed. More preferably, it is 530-553 nm, most preferably 540-550 nm.

In the general formula (4), examples of the alkyl group represented by R ₁ and R ₃ include a linear or branched group such as an ethyl group, a propyl group and a 3-methylbutyl group. Each group includes a 2-hydroxyethyl group, a 2-methoxyethyl group, a 2-ethoxyethyl group, an ethoxycarbonylethyl group, an allyl group, a phenethyl group, a methanesulfonylethyl group, and a 3-oxobutyl group.

Examples of the alkyl group represented by R ₂ and R ₄ include straight-chain and branched groups such as a methyl group, an ethyl group, a butyl group, and an isobutyl group. For example, dissociation such as a sulfo group, a carboxy group, a methanesulfonylaminocarbonyl group, a methanesulfonylaminosulfonyl group, an acetylaminosulfonyl group, a sulfoamino group, a trifluoroacetylaminosulfonyl group, an acetylaminocarbonyl group, and an N-methylsulfamoyl group And specific examples thereof include a 2-sulfoethyl group, a 3-sulfopropyl group, a 3-sulfobutyl group and a 5-sulfoethyl group.
A sulfopentyl group, a 2-N-ethyl-N-sulfaminoaminoethyl group, a carboxymethyl group, a carboxyethyl group,
3-sulfoaminopropyl group, 6-sulfo-3-oxahexyl group, 10-sulfo-3,6-dioxadecyl group, 6-sulfo-3-thiahexyl group, o-sulfobenzyl group, p-carboxybenzyl group, methane Each group includes a sulfonylaminocarbonylmethyl group and an acetylaminosulfonylmethyl group.

As Z ₁ , Z ₂ , Z ₃ and Z ₄ , a hydrogen atom, a halogen atom, an alkyl group (for example, a lower alkyl group such as a methyl group, an ethyl group and a propyl group), an alkoxy group (a methoxy group and an ethoxy group) , A propoxy group, etc.), an alkoxy group substituted with a halogen atom (fluoromethoxy group, trifluoromethyl group, 2,2,2-trifluoroethyl group, etc.), an aryloxy group (phenoxy group, p-
Bromophenoxy group, etc.), acyl group (eg, acetyl group, benzoyl group, etc.), acyloxy group (acetyloxy group, propionyloxy group, etc.), alkylthio group (methylthio group, ethylthio group, etc.), alkylthio group substituted by halogen atom (Trifluoromethylthio group, difluoromethylthio group, etc.), alkoxycarbonyl group (methoxycarbonylmethyl group, ethoxycarbonyl group, etc.), carbamoyl group (carbamoyl group, N-methylcarbamoyl group, N, N-dimethylcarbamoyl group, N,
N-diethylcarbamoyl group, N, N-3-oxa-pentamethylenecarbamoyl group, N-phenylcarbamoyl group, etc.), sulfamoyl group (N-methylsulfamoyl group, N, N-tetramethylenesulfamoyl group, N ,
N-3-oxapentamethylenesulfamoyl group, N-
Phenylsulfamoyl group, N, N-diethylsulfamoyl group, etc., haloalkyl group (monofluoromethyl group, difluoromethyl group, trifluoromethyl group, monochloromethyl group, etc.), sulfonyl group (methanesulfonyl group, ethanesulfonyl) Group, trifluoromethanesulfonyl group, fluorosulfonyl group, benzenesulfonyl group,
p-toluenesulfonyl group), acylamino group (N-
Acetylamino group, N-trifluoroacetylamino group, etc.), substituted or unsubstituted aryl group (phenyl group, o-
Examples include a fluorophenyl group, a p-cyanophenyl group, an m-chlorophenyl group, and the like, and a heterocyclic group (1-pyrrolyl group, 2-furyl group, 2-benzooxazolyl group, and the like).

[0064] X ₁ ^- an anion as ion necessary to neutralize the charge in the dye molecule represented, may be any cation, the anion halogen ion, perchlorate, ethyl sulfate, thiocyanate ,
There are p-toluenesulfonate, perfluoroborate and the like, and as cations, hydrogen ion, alkali metal ion (ion of lithium, sodium, potassium, etc.), alkaline earth metal ion (ion of magnesium, calcium, etc.), ammonium ion, And organic ammonium ions (ions such as triethylammonium, triethanolammonium, and tetramethylammonium).

Next, specific examples of the spectral sensitizing dye represented by the general formula (4) will be described, but the present invention is not limited thereto.

[0066]

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[0067]

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[0068]

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These spectral sensitizing dyes may be used in combination with other spectral sensitizing dyes. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex 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, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, etc. Indolenine nucleus, benzindolenin nucleus, indole 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 includes pyrazoline- as a nucleus having a ketomethine structure.
A 5- to 6-membered heterocyclic nucleus such as a 5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, a thiazoline-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus is applied. can do.

These dyes are described in German Patent No. 929,0
No. 80, U.S. Pat. Nos. 2,231,658 and 2,491
3,748, 2,503,776, 2,51
9,001, 2,912,329 and 3,65
5,394, 3,656,959 and 3,67
2,897 and 3,649,217, British Patent No. 1,242,588, JP-B-44-14030, and the like.

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.
%, Preferably 40% to 8%.
0% is particularly preferred.

In the present invention, the monolayer coverage is 5%.
The saturated adsorption amount when the adsorption isotherm is created at 0 ° C. is relatively determined 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 improve the sensitivity and the residual color, the ratio of the dye represented by the general formula (4) is preferably 30% or more of all the dyes.

As a solvent for the sensitizing dye, a conventionally used water-miscible organic solvent can be used. Examples of the solvent include alcohols, ketones, nitriles, and alkoxy alcohols. Examples include propyl alcohol, isopropyl alcohol, ethylene glycol, propylene glycol, 1,3-propanediol, acetone, acetonitrile, 2-methoxyethanol, and 2-ethoxyethanol.

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

In the present invention, however, the effect is increased by adding the spectral sensitizing dye as a dispersion in the form of solid fine particles, as compared with the case of adding it as a solution of an organic solvent.
In particular, at least one of the spectral sensitizing dyes is added in the form of a solid fine particle dispersion substantially insoluble in water dispersed in an aqueous system substantially free of an organic solvent and / or a surfactant. Is preferred because the spectral sensitizing dye is uniformly and effectively adsorbed on the surface of the silver halide grains. here,
The aqueous system substantially free of an organic solvent and / or a surfactant is water containing impurities at a level not to adversely affect the silver halide photographic emulsion, more preferably ion-exchanged water and distilled water. .

[0079] solubility in water of a spectral sensitizing dye for use in the present invention is 2 × 10 ^-4 ~4 × 10 ^-2 mol / l approximately, more 1 × 10 ^-3 ~4 × 10 ^-2 mol / l is preferred . If the solubility is lower than this range, the dispersion particle size is extremely large and non-uniform, so that after the dispersion is completed, a precipitate of the dispersion is formed, or when the dispersion is added to the silver halide emulsion, May hinder the adsorption process of silver halide to silver halide. On the other hand, if the solubility is higher than the above range,
The viscosity of the dispersion is unnecessarily increased, and air bubbles are involved, disturbing the dispersion, and dispersing becomes impossible at a higher solubility. The solubility of the spectral sensitizing dye in water is measured by the following method.

That is, 30 ml of ion-exchanged water was placed in a 50 ml Erlenmeyer flask, an amount of the dye which was not completely dissolved visually was added thereto, the temperature was maintained at 27 ° C. in a thermostat, and the mixture was stirred with a magnetic stirrer for 10 minutes. The suspension was filtered with filter paper no. 2
(Toyo Corp.), the filtrate was filtered with a disposable filter (Tosoh Corp.), the filtrate was appropriately diluted, and a spectrophotometer U-3410 (Hitachi Corp.) was used.
The absorbance was measured with. Next, based on the measurement results, the solubility was determined in accordance with Lambert-Beer's law, and the solubility was further determined.

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

The spectral sensitizing dye of the present invention can be added at the time of the chemical sensitization step, particularly preferably at the start of the chemical sensitization. By adding it by the end of the process, a high-sensitivity silver halide emulsion having excellent spectral sensitization efficiency can be obtained.

Examples of the sulfur sensitizer applicable to the present invention include:
U.S. Pat. Nos. 1,574,944 and 2,410,68
No. 9, 2,278,947 and 2,728,668
Nos. 3,501,313, 3,656,955
And sulfur sensitizers described in West German Application (OLS) 1,422,869, JP-A-56-24937 and JP-A-55-45016. Specifically, thiourea derivatives such as 1,3-diphenylthiourea, triethylthiourea, 1-ethyl, 3- (2-thiazolyl) thiourea, rhodanine derivatives, dithiacarbamic acids, polysulfide organic compounds, sulfur alone And the like are preferred examples. In addition, as the elemental sulfur, α-sulfur belonging to the orthorhombic system is preferable.

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

As the selenium sensitizer used in the present invention, a wide variety of selenium compounds can be used. For example, US Pat. Nos. 1,574,944 and 1,602,591.
No. 2, No. 1,623,499, JP-A-60-1500
No. 46, JP-A-4-25832, JP-A-4-109240
And compounds described in JP-A No. 4-147250 and the like can be used. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (such as allyl isoselenocyanate), selenoureas (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, selenoketones (selenoacetone, selenoacetophenone, etc.), selenoamides (selenoacetamide, N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (2-selenopropionic acid, methyl -3-selenobutyrate, etc.), selenophosphates (tri-p-triselenophosphate, etc.), selenides (triphenylphosphine selenide, diethyl selenide, diethyl diselenide, etc.)
Is mentioned. Particularly preferred selenium sensitizers are selenoureas, selenamides, and selenoketones, selenides.

The amount of the selenium sensitizer used depends on the selenium compound used, silver halide grains, chemical sensitization conditions and the like, but generally about 10 ^-8 to 10 ^-4 mol per mol of silver halide is used. The temperature of chemical sensitization using a selenium sensitizer is preferably in the range of 40 to 90 ° C, more preferably 45 to 90 ° C.
The temperature is not less than 80 ° C and not less than 80 ° C. The pH is 4-9, pAg
Is preferably in the range of 6 to 9.5.

For tellurium sensitizers and sensitization methods, see, for example, US Pat. Nos. 1,623,499 and 3,320,06.
Nos. 9, 3,772,031, 3,531,289
No. 3,655,394, UK Patent No. 235,21
No. 1, No. 1, 121, 496, No. 1, 295, 462
No. 1,396,696, Canadian Patent No. 800,9
No. 58, JP-A-4-204640, JP-A-4-33304
No. 3 and the like.

Examples of useful tellurium sensitizers include telluroureas (N, N-dimethyltellurourea, tetramethyltellurourea, N-carboxyethyl-N, N'-dimethyltellurourea, N, N'- Dimethyl-N'phenyltellurourea), phosphine tellurides (tributylphosphine telluride, tricyclohexylphosphine telluride,
Triisopropylphosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride, etc., telluramides (telluroacetamide, N, N-dimethyltellurobenzamide, etc.), telluroketones, telluroesters, isotellurocyanates, etc. No.

In the present invention, it is preferable to use chemical sensitization other than sulfur sensitization, selenium sensitization, and 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. Examples of the chemical sensitization method preferably used in combination include a reduction sensitization method using a reducing substance, gold and other noble metal sensitization methods using a noble metal, and a gold sensitization method and a reduction sensitization method are preferable.

Examples of the gold sensitizer include chloroauric acid, gold thiosulfate, gold thiocyanate, and gold complexes of thioureas, rhodanines, and other various compounds.
The amount of the gold sensitizer used is the same as that of the aforementioned sulfur sensitizer.

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

In the present invention, each sensitization may be applied 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, ascorbic acid and its derivatives, hydrazine, polyamines such as diethylenetriamine, dimethylamine borane, and sulfite.

The silver halide emulsion of the present invention is preferably subjected to chemical sensitization in the presence of the compound represented by formula (5).

In the general formula (5), ₅ represented by Z 5
Non-metallic atoms required to complete a 6- or 6-membered nitrogen-containing heterocycle include thiazoliums (thiazolium,
Methylthiazolium, benzothiazolium, 5-methylbenzothiazolium, 5-chlorobenzothiazolium,
5-methoxybenzothiazolium, 6-methylbenzothiazolium, 6-methoxybenzothiazolium, naphtho [1,2-d] thiazolium, naphtho [2,1-d] thiazolium and the like, oxazolium (oxazolium) ,
4-methyloxazolium, benzoxazolium, 5
-Chlorobenzoxazolium, 5-phenylbenzoxazolium, 5-methylbenzoxazolium, naphtho [1,2-d] oxazolium and the like, imidazolium (1-methylbenzimidazolium, 1-propyl-)
5-chlorobenzimidazolium, 1-ethyl-5,6
-Dichlorobenzimidazolium, 1-allyl-5-trichloromethyl-6-chloro-benzimidazolium, etc.), selenazolium (benzoselenazolium, 5-
Chlorobenzoselenazolium, 5-methylbenzoselenazolium, 5-methoxybenzoselenazolium, naphtho [1,2-d] selenazolium and the like), preferably thiazoliums, especially benzothiazolium And naphthothiazolium are preferred.

Specific examples of the compound represented by formula (5) are shown below, but it should not be construed that the invention is limited thereto.

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These compounds are used in an amount of about 10 mg to 5 g per mol of silver halide, and may be directly dispersed in the emulsion or an appropriate solvent (water, methyl alcohol, ethyl alcohol, propanol, methyl cellosolve, acetone, etc.). ) Can be added to the emulsion. Further, it can be added by a method according to the method of adding a sensitizing dye.

The dye used in the light-sensitive material of the present invention is preferably substantially insoluble in water at a pH of 7 or less and substantially water-soluble at a pH of 8 or more. The addition amount can be changed according to the sharpness target, but is preferably 0.2%.
To 20 mg / m ^2, more preferably 0.8～15Mg /
m ² . Specifically, West German Patent No. 616,007
Nos. 584,609 and 1,177,429.
No., Japanese Patent Publication No. 26-7777, No. 39-22069,
JP-A-54-38129, JP-A-48-85130, JP-A-49-99620, JP-A-49-114420, and JP-A-49-114420
No.-129537, No.50-28827, No.52-1
08115, 57-185038, JP-A-2-2-2
Nos. 82244, 4-307538, U.S. Pat.
Nos. 878,961, 1,884,035, 1,91
2,797, 2,098,891, 2,150,6
No. 95, 2,274,782, 2,298,731
Nos. 2,409,612, 2,461,484, 2,527,583, 2,533,472, 2,8
Nos. 65,752, 2,956,879, 3,094,
No. 418, No. 3,125,448, No. 3,148,187
No. 3,177,078, No. 3,247,127, No. 3,260,601, No. 3,282,699, No. 3,4
09,433, 3,540,887, 3,575,
No. 704, No. 3,653,905, No. 3,718,472
No. 3,865,817, No. 4,070,352, No. 4,071,312, PB Report No. 74175, PH
OTO. ABS. 1, 28 ('21) and the like can be used.

Various photographic additives can be used in the light-sensitive material according to the present invention. Known additives include, for example, Research Disclosure No. 17643
No. (December 1978). 18716 (1979
No.) and the same No. 308119 (December 1989
Month).

The light-sensitive material according to the present invention may contain a developing agent such as aminophenol, ascorbic acid, pyrocatechol, hydroquinone, phenylenediamine, 3-pyrazolidone or the like in the emulsion layer or other layers.

As the support which can be used in the light-sensitive material according to the present invention, for example, the above-mentioned RD-17643-2
8 and RD-308119, page 1009. The surface of these supports may be provided with an undercoat layer, or subjected to corona discharge, ultraviolet irradiation, or the like 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.

When the light-sensitive material according to the present invention is used for X-ray photography, a silver halide emulsion layer and a crossover cut layer may be provided on both surfaces of the support to provide high sensitivity, high sharpness, and excellent processability. Can be obtained. The amount of gelatin in the silver halide emulsion layer, surface protective layer, and other layers is preferably in the range of 0.5 to 3.5 g / m ² , particularly 1.5 to 3 g / m ² , on one side of the support. A range of 0 g / m ² is preferred.

The latex used has a latex surface which is photographically inactive and has very little interaction with various photographic additives. That is, for example, the latex used may adsorb a dye or a dye and contaminate the photosensitive material. It is preferable that they do not adsorb a development accelerator, a development inhibitor, and the like that have no influence on the development speed, and do not affect sensitivity and fog.

The light-sensitive material according to the present invention can be processed using a powder processing agent or a solid processing agent such as tablets, pills and granules. Powder is an aggregate of fine-grained crystals, and granules are obtained by adding a granulation process to powder, and have a particle size of 50 to 5000 μm.
Means a granular material. In addition, a tablet means a powder or granule obtained by compression molding into a certain shape.

In order to solidify the processing agent, a concentrated solution or fine powder or granular photographic processing agent and a water-soluble binder are kneaded and molded, or the water-soluble binder is sprayed on the surface of the temporarily molded processing agent. 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 tableting. Granulation method is rolling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation,
Known methods such as fluidized bed granulation and spray drying granulation can be used.

For tablet formation, the average particle size of the obtained granules is from 100 to 100 in that, when the granules are mixed and compressed under pressure, nonuniformity of components, that is, so-called segregation hardly occurs.
It is preferable to use one having a thickness of 800 μm, more preferably 200 to 750 μm. Further, the particle size distribution is preferably such that 60% or more of the granulated particles have a deviation of ± 100 to 150 μm.

For compressing the granules under pressure, known compressors 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 any shape, but from the viewpoint of productivity, handling, or 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, a preservative and the like.

As the solid processing agent, a developer, a fixing agent, a rinsing agent and the like are used, but the developer has a great effect of stabilizing the photographic performance.

As a supply means for supplying the solid processing agent to the processing tank, for example, when the solid processing agent is a tablet,
3-137793, 63-97522, Kaikai 1
There is a known method such as -85732, 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, Japanese Utility Model Application Laid-Open No. 62-81964 and 63-84151.
No., gravity drop method described in JP-A-1-292375,
63-105159 and 63-195345
Nos. 2, 3 and 4. A method using a screw or a screw described in Japanese Patent Application Laid-Open No. H10-214, 1993 is known. The place where the solid processing agent is charged may be in the processing tank, but is preferably in communication with the processing section for processing the photosensitive material,
It is preferable that the processing liquid circulates between the processing unit and the processing unit, and that the processing component has a constant circulation amount between the processing unit and the dissolved components move to the processing unit. The solid processing agent is preferably introduced into a processing liquid whose temperature is controlled.

When the silver halide emulsion of the present invention is used as a light-sensitive material for X-ray photography and an intensifying screen having a phosphor filling rate of 68 to 90% is used, the effects of the present invention can be fully exhibited.

[0113]

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

Example 1 << Preparation of Emulsion Em-1 >> (Solution A1) 56.6 g of ossein gelatin 0.36 ml of a 10% aqueous ethanol solution of the following compound (A) 48.2 g of potassium bromide Finished to 8083 ml with water (solution B1) 1791 ml of 2.0 N aqueous silver nitrate solution (solution C1) 11505 ml of 3.5 N aqueous silver nitrate solution (solution D1) 10962 ml of 4.0 N aqueous potassium bromide solution (solution E1) 2.0 N aqueous potassium bromide solution The following silver potential control amount (solution F1) Ossein gelatin 245 g 10% aqueous solution of compound (A) in ethanol 14.12 ml Water 2264 ml (solution G1) 1.556 g thiosulfonic acid Finished to 156 ml with water (solution H1) 3% by weight of gelatin and silver iodide particles (average) Fine particle emulsion (*) 0.088 Le corresponds (solution I1) finish 170ml with thiourea dioxide 0.171g water (solution J1) 2,2'-dithiobis (pyridine) N- oxide compound finish 156ml with 1.556g solution (A): HO (CH _{2 CH 2 O) n - [CH} (CH 3) CH 2 O] -
(CH ₂ CH ₂ O) _m H m + n = 5 to 7 Fine particle emulsion (*): 7.06 to 6.64 l of a 5.0% by weight aqueous gelatin solution containing 0.06 mol of potassium iodide
An aqueous solution containing 2 moles of silver nitrate and 7.06 moles of potassium iodide, 2 l each, was 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.

The total amount of (solution B1) and 895 ml of (solution D1) were added to (solution A1) at 55 ° C. for 3 minutes using a mixing stirrer described in JP-B-58-58288 for 3 minutes.
Addition took a few seconds to effect nucleation.

After the addition of (Solution B1) and (Solution D1), (Solution F1) was added, and the temperature was raised to 70 ° C. for 30 minutes to ripen. Subsequently (solution C1) 907 m
was added over 11 minutes, a 28% aqueous ammonia solution was added, the mixture was aged at pH = 8.2 for 10 minutes, and then the pH was returned to 6.0 with 56% acetic acid (solution I1).
Was added in its entirety. (Resolution C1) and (Resolution D)
While keeping the pAg at 7.8, 1) was simultaneously added and mixed over 134 minutes while gradually increasing the addition rate so that the initial flow rate of (solution C1) was 23 ml / min and the final flow rate was 154 ml / min. On the way, when the remaining amount of (Solution C1) becomes 6360 ml, a 56% acetic acid aqueous solution is added to adjust the pH to 4.4.
Was adjusted. At 122 minutes after the start of (solution C1), the addition of (solution H1) was started, and the entire amount of (solution H1) was added over 12 minutes. The addition of (solution H1) was completed at the same time as the addition of (solution C1).

After stirring for 10 minutes, at 50 ° C. (solution J
1) was added in its entirety. The temperature was lowered to 40 ° C., and soluble salts were desalted and removed by a sedimentation method.

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, and the average thickness of the hexagonal tabular grains is 0.18.
It was confirmed by an electron microscope that the average particle diameter was 0.81 μm and the average aspect ratio was 4.5 μm. The distribution of the circle equivalent diameter was 15%.

<< Preparation of Comparative Emulsion Em-2 >> (Solution I1)
And Em-2 was prepared in the same manner as in the preparation of Em-1, except that and (solution J1) were not added.

<< Chemical Sensitization >> Subsequently, the emulsion Em-
1, Em-2 were each divided into predetermined amounts, and the temperature was 55 ° C.
Then, 0.5 mol% of silver iodide fine particles were added, and a compound represented by the general formula (1), (2) or (3) was added as shown in Table 1. Further, the spectral sensitizing dye of the present invention and a comparative dye (shown as dye types in Table 1) were added as solid fine particle dispersion. Subsequently, a solid particulate dispersion of 10 mg of sodium thiosulfate and 2 mg of triphenylphosphine selenide was added, and 105 mg of ammonium thiocyanate was added.
12.5 mg of chloroauric acid 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 A
It was added as per gX mol.

<Preparation of silver iodochloride tabular grains><< Preparation of emulsion Em-3 >> (Solution A2) Ossein gelatin 75.0 g KI 1.25 g NaCl 33.0 g Finished with distilled water to 15000 ml (Solution B2) finish 684ml with 410g of distilled water (solution C2) Silver nitrate 11590g distilled water finish 19316Ml (solution D2) KI 4g NaCl 140g finish 684ml with distilled water (solution E2) NaCl 3980g of potassium hexachloroiridate (IV) 8 × 10 ^- Finishing to 19274 ml with ⁶ mol distilled water At 40 ° C, (Solution B2) and (Solution D) were added to (Solution A2) in a mixing stirrer described in JP-B-58-58288.
The whole amount of 2) was added over 1 minute. EAg is 149m
V, and after Ostwald ripening for 20 minutes, the total amount of (Solution C2) and (Solution E2) was added over 320 minutes. Meanwhile, EAg was controlled at 149 mV.

Immediately after the addition was completed, desalting and washing were performed.
Emulsion Em-3 prepared in this manner was composed of tabular grains having a (100) plane as a main plane for 65% of the total projected area of silver halide grains, and had an average thickness of 0.14 μm and an average diameter of 1 mm. It was found by observation with an electron microscope that the dispersion coefficient was 0.0 μm and the coefficient of variation was 25%.

<< Chemical Sensitization >> Emulsion Em-3 was divided into predetermined amounts, the temperature was raised to 55 ° C., and 4.25 mg of a reduction sensitizer thiourea dioxide was added. 0.5 mol% of silver iodide fine particles were added. 25.3 mg of 2,2′dithiobis (pyridine) N-oxide was added. The spectral sensitizing dye (shown in Table 1) was added as a solid particulate dispersion. Subsequently, a solid particulate dispersion of 15 mg of sodium thiosulfate and 3 mg of triphenylphosphine selenide was added. 145 mg of ammonium thiocyanate, 18.5 of chloroauric acid
mg, a compound represented by the general formula (1), (2) or (3) was added as shown in Table 1. Aging was performed for a total of 2 hours. At the end of aging 5mg PMT and TAI as stabilizer
100 mg was added. The addition amount was per mol of AgX.

A solid particulate dispersion of the spectral sensitizing dye was prepared as follows according to the method described in JP-A-5-297496. That is, a predetermined amount of the spectral sensitizing dye is added to water whose temperature has been previously adjusted to 27 ° C., and 3,500
Obtained by stirring at rpm for 30-120 minutes.

<< Preparation of Photosensitive Material Sample >> 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 coaters so as the coating amount of silver amount per one side is 1.6 g / m ^2, gelatin with the amount of the 2.5 g / m ² Was applied simultaneously on both sides of the support, and dried for 2 minutes and 20 seconds to obtain a sample. As a support, glycidyl methacrylate 50 wt%, methyl acrylate 10 wt%, butyl methacrylate 40
When the concentration of the copolymer composed of three kinds of wt% is 10 w
A concentration of 0.1% for a 175 μm X-ray film was obtained by using an aqueous dispersion of the copolymer obtained by diluting the solution to be t% as a subbing liquid.
A blue-colored polyethylene terephthalate film base was used for No. 3.

The additives used in the emulsion are as follows.

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) Various additives were added.

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 ( 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 1,3 ammonium dihydroxybenzene-4-sulfonic acid 500 mg / m ² 2-mercaptobenzimidazole-5-sulfonate sodium 5 mg / m ² compound ^{(H) 0.5mg / m 2 n} -C 4 H 9 _{OCH 2 CH (OH) CH 2} N _{CH 2 COOH) 2 350mg / 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 0.2 g / m ² gelatin 1.5 g / m ² Compound (1) (2) (3) Third layer (protective layer) shown in Table 1 Gelatin 0.8 g / m ² Matting agent composed of polymethyl methacrylate (area average) 50 mg / m ² formaldehyde 20 mg / m ² 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 10 mg / m ² bis-vinylsulfonylmethyl ether 36 mg / m ² latex (particle size 7.0 μm) L) 0.2 g / m ² polyacrylamide (average molecular weight 10,000) 0.1 g / m ² sodium polyacrylate 30 mg / m ² polysiloxa (SI) 20 mg / m ² Compound (I) 12 mg / m ² Compound (J) 2 mg / m ² Compound (S-1) 7 mg / m ² Compound (K) 15 mg / m ² Compound (O) 50 mg / m ² compound (S-2) 5mg / m 2 C 9 F 19 -O- (CH 2 CH 2O) 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

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<< Evaluation >> Each of the obtained samples was left under the condition A (23 ° C., 40%, 3 days) and the condition B (55 ° C., 80%, 3 days), and then the photographic characteristics were evaluated. First, the sample was sandwiched between two intensifying screens (KO-250, manufactured by Konica Corporation), a tube voltage of 80 kVp, a tube current of 100 mA, and an aluminum wedge.
It was exposed to X-rays for 0.05 seconds.

Separately, a solid developer was prepared in a quantity of 100 liters as a developer by the following operation.

[Granulated product (A)] 3000 g of hydroquinone as a developing agent, phenidone 40
0 g, boric acid 1000 g, N-acetyl-D, L-penicillamine 10 g, glutaraldehyde bisulfite Na salt 5
In a commercially available bantam mill.
Grind to μm. To this fine powder, 700 g of sodium sulfite and 200 g of a binder D-sorbite were added and mixed in a mill for 30 minutes. After granulating by adding 30 ml of water for about 5 minutes at room temperature in a commercially available stirring granulator, the granulated product is dried at 40 ° C. for 2 hours in a fluidized bed drier to obtain a granulated product. Water was almost completely removed.

[Preparation of Solid Developer A] The granulated product (A) thus obtained was mixed with 100 g of sodium 1-octanesulfonate in a room conditioned at 25 ° C. and 40% RH or less using a mixer. After the mixture was uniformly mixed for 10 minutes, the obtained mixture was subjected to compression tableting using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd., with the filling amount per tablet being 10 g, and a diameter of 30 g.
Thus, a hydroquinone-based developed tablet was prepared so as to have a cylindrical shape of mm.

[Granulated product (B)] Potassium carbonate was added in such an amount that the buffer capacity became 0.16. Here, the buffer capacity indicates a range of pH fluctuation when 0.1 mol / Lwp of acetic acid is added to the developer adjusted to pH 10.0. Add sodium bicarbonate 1000
g and KBr are crushed in a commercially available bantam mill until the average particle size becomes 10 μm. L for each fine powder
200 g of iOH · H ₂ O, DTPA · 5H 250
g, 1-phenyl-5-mercaptotetrazole 5 g,
4000 g of sodium sulfite, compound (M) 4 described above
0 g, compound (N) 8 g and binder mannitol 1000
g for 30 minutes in a mill and granulated by adding 30 ml of water for about 15 minutes at room temperature in a commercial stirring granulator. And dried for 2 hours to remove the moisture of the granules almost completely.

[Preparation of Solid Developer B] A granulator (B) obtained as described above was mixed with 200 g of sodium 1-octanesulfonate in a room conditioned at 25 ° C. and 40% RH or less using a mixer. After the mixture was uniformly mixed for 10 minutes, the obtained mixture was compressed and compressed into tablets at a filling amount of 10 g per tablet using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. Produced. Both developers A and B were sealed and packaged in 4.0 liter quantities in a pillow bag containing aluminum for moisture protection.

The following procedure was used to prepare a solid fixing agent in an amount of 100 liters as a fixing solution.

[Granulated Material (C)] Ammonium thiosulfate / sodium thiosulfate (90/1
15000 g) in a commercially available bantam mill until the average particle size is 10 μm. 500 g of sodium sulfite, 750 g of Na ₂ S ₂ O _{5, and} 1300 g of binder pine flow were added to this fine powder, and the amount of water added was adjusted to 50 ml to carry out stirring granulation. The granulated product was dried at 40 ° C. with a fluid bed dryer. Almost completely removes water.

[Granulated Material (D)] 400 g of boric acid, 1200 g of aluminum sulfate octahydrate, 1200 g of succinic acid, and 300 g of tartaric acid are ground in a commercially available bantam mill until the average particle diameter becomes 10 μm. D
-Mannit 250g, D-Sorbit 120g, PE
G # 400160g is added and the amount of water added is 30 ml, and the mixture is stirred and granulated, and the granulated product is dried at 40 ° C. with a fluidized bed drier to completely remove water.

[Solid Fixing Agent] β-alanine 3 was added to the granulated product (C) thus obtained.
000 g, sodium acetate 4330 g and sodium 1-octanesulfonate were added to 1.5% of the total weight, and 750 g of sodium metabisulfite and sodium 1-octanesulfonate were further added to the granulated product (D). It is added so that it becomes 1.0% of the total weight,
After mixing uniformly for 10 minutes using a mixer in a room humidified to less than% RH, the resulting mixture is mixed with Kikusui Seisakusho Co., Ltd.
Using a tableting machine modified from Tough Press Collect 1527HU, the filling amount per tablet (C) was 10.2 g, (D)
Was compressed to 11.2 g to produce a cylindrical fixing tablet having a diameter of 30 mm. Each of these was sealed in a pillow bag containing aluminum for moisture proofing in a quantity of 40 liters.

<Treatment Method> SRX-201 (manufactured by Konica Corporation) was modified and used as the automatic processing machine. The developer in the developing tank at the start is prepared by mixing the solid developers A and B, and then diluting and dissolving with a dilution water using a modified chemical mixer. The tablets were completely dissolved, and no precipitate was observed. 7.8 liters of this developing solution
RX-201, a starter described later was added thereto, and the processing was started by filling the developing tank as a starting solution. The starter addition amount was 33 cc / liter. The fixing agent is prepared by diluting the solid fixing agents (C) and (D) with dilution water using a chemical mixer. The tablets were completely dissolved, and no precipitate was observed. 5.6 liters of the adjusted fixing solution was put into an SRX-201 fixing processing tank to be used as a start solution.

Starter formulation KBr 5.5 g HO (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH) ₂ OH 0.05 g N-acetyl-D, L-penicillamine 0.10 g Sodium metabisulfite Starting solution pH In addition, a modified chemical mixer input port was provided so that each solid agent could be charged for both development and fixing of the SRX-201, and the built-in chemical mixer for dissolving the solid agent was modified.

In each of the developing and fixing steps, the packaging bag opened by hand is set at the inlet of each solid agent, and the tablets are dropped into the built-in chemical mixer.
(0 ° C.) and dissolve with stirring to dissolve in 25 minutes.
Adjust to 0 liters. This was used as a developing and fixing replenisher. The replenisher thus prepared is supplied to a developing tank and a fixing tank to satisfy the above-mentioned amount.

The pH at the time of dissolving the development was finely adjusted with acetic acid and potassium hydroxide so as to become 10.55. The pH of the dissolution replenisher for the fixer was 4.80.

The built-in chemical mixer is divided into a liquid preparation tank and a spare tank tank. The capacity of the liquid preparation tank is 3.0 liters and the capacity of the spare tank is 3.0 liters. Even if the replenisher runs out,
A spare tank was provided so that the replenisher was supplied so as not to be in a non-replenished state during the stirring and dissolving time (about 25 minutes). The pH of the developer when the starter was added was 10.45.

The sample prepared above was exposed to light so that the optical density after development processing was 1.0, and the sample was run. During the running in developer and the photosensitive material 1 m ² per developer replenisher was added 90 ml. 1m of photosensitive material in fixer
90 ml of the fixing replenisher was added per ^two .

Processing Conditions Development 39 ° C. 5.0 sec. Fixing 36 ° C. 3.5 sec. Washing 35 ° C. 2.5 sec. Squeeze 1.5 sec. Drying 50 ° C. 2.5 sec. Total 15 sec. An evaluation was performed.

The photographic performance of each sample was measured, and the spectral absorption density at 500 nm of the sample after the development processing was measured with a spectrophotometer to evaluate the residual color. After a load of 5 g was applied to the unexposed sample with a 0.3-needle scratch hardness tester, the same developing treatment as above was performed, and the density of pressure fogging was measured with a microdensitometer.

The obtained results are shown in Sample Nos. Table 2 shows relative values when the measured value of 1 is set to 100.

[0151]

[Table 1]

[0152]

[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 when stored under high temperature and high humidity. In addition, it can be seen that the sensitivity is hardly impaired even if rapid processing such as 15 seconds is performed using a solid processing agent, and there is no problem at all.

Example 2 Except that after adding the spectral sensitizing dye, the compound represented by the general formula (5) was added to Em-1 in the same manner as in Example 1 except that the compound represented by Table 3 was added. Sensitization was applied. Coating was performed in the same manner as in Example 1 except that the compound represented by the general formula (1), (2) or (3) shown in Table 3 was added to the coating solution of the emulsion layer in an amount of 300 mg per mol of silver. Photosensitive material samples were used.

A sample using Em-2 was prepared in the same manner as in Example 1.

The sample using Em-3 was coated with the compound represented by the general formula (1), (2) or (3) shown in Table 3 in an amount of 350 mg per mol of silver to the emulsion layer coating solution. Others were prepared similarly to Example 1.

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. The following screen was used.

<Production of High Sensitive Screen (S-1)> Phosphor Gd ₂ O ₂ S: Tb (average particle size: 1.8 μm) 200 g Binder Polyurethane thermoplastic elastomer 20 g (manufactured by Sumitomo Bayer Urethane Co., Ltd.) Demolac TPKL-5-2625 to 40% solids) Nitrocellulose (digestibility: 11.5%) To a composition consisting of 2 g, add a methyl ethyl ketone solvent, disperse with a propeller mixer, and phosphor layer having a viscosity of 25 PS (25 ° C.). A coating solution for formation was prepared (binder / phosphor ratio = 1).
/ 22).

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

Thickness of 250 μm incorporating titanium dioxide
The polyethylene terephthalate support is placed horizontally on a glass plate, and the above-mentioned coating solution for forming an undercoat layer is uniformly applied using a doctor blade. Was performed to form an undercoat layer having a thickness of 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 and dried, and then dried at 300 kgw / calender using a calender roll.
Compression was performed at 80 ° C. and cm ² . After compression, see JP-A-6-7
A transparent protective film having a thickness of 3 μm was formed by the method described in Example 1 of No. 5097.

The screen obtained had a phosphor thickness of 160 μm.
m, the phosphor filling rate was 68%, and the sharpness (CTF) was 48%.

<Manufacture of Comparative Screen (S-2)> The support was formed in the same manner as in S-1 except that the coating liquid for forming the phosphor layer was uniformly coated to a thickness of 150 μm and no compression was performed. , An undercoat layer, a phosphor layer and a transparent protective film
2 was produced. The resulting screen has a phosphor layer thickness of 1
05 μm, and the packing ratio of the phosphor was 65%.

The photographic performance of each sample was measured. Further, the portion where the optical density of the developed sample was 1.0 was measured with an aperture of 30 μm × 500 μm, and the MTF value at a spatial frequency of 1.0 cycle / mm was defined as sharpness.

The obtained results are shown in Sample Nos. 12 S-2
Table 4 shows a relative value when the measured value exposed by using is 100.

[0166]

[Table 3]

[0167]

[Table 4]

As is clear from the results shown in Table 4, the sensitivity of the sample of the present invention was high even in the 15-second treatment using the solid processing agent, and a higher sensitivity was obtained by exposure using a high-sensitivity intensifying screen. And excellent sharpness.

[0169]

According to the present invention, a silver halide photographic material suitable for rapid processing and low replenishment can be obtained.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03C 5/38 G03C 5/38

Claims (5)

[Claims] Claims: 1. A composition comprising a reduction-sensitized silver halide grain and a compound represented by the following general formula (1), (2) or (3), and represented by the following general formula (4) A silver halide emulsion characterized by being subjected to at least one kind of chemical sensitization selected from sulfur sensitization, selenium sensitization and tellurium sensitization in the presence of a spectral sensitizing dye. Embedded image [Wherein X represents, directly or indirectly, at least one selected from —SO ₃ M, —COOM, and —OM, and an atom group capable of forming a heterocyclic ring, and M represents a hydrogen atom, a metal atom or Represents a quaternary ammonium group or a phosphonium group. However, compounds partially including the following structures are excluded. Embedded image Here, R represents a hydrogen atom or a substituent. [Chemical formula 3] [Wherein (A ₁ ) and (A ₁ ) ′ are each —SO ₃ M,
Represents COOM or -OM, M represents a hydrogen atom, a metal atom, or a quaternary ammonium group or a phosphonium group, and m is an integer of 1 to 10. (A ₂ ) and (A ₂ ) ′ each represent an electron-withdrawing group, and n is an integer of 1 to 10.
(A ₃ ) and (A ₃ ) ′ each represent a functional group containing a sulfur atom, a selenium atom or a tellurium atom capable of binding to a silver ion;
r represents 1 or 2. Y represents an aliphatic hydrocarbon, an aromatic hydrocarbon or a heterocyclic ring, Z represents a sulfur atom, a selenium atom or a tellurium atom, and p is 1 or 2. [Formula 4] [Wherein, R ₁ and R ₃ each represent a substituted or unsubstituted lower alkyl group or an alkenyl group, R ₂ and R ₄ each represent an alkyl group, at least one of which is an alkyl substituted with a hydrophilic group. Group. Z ₁ , Z ₂ , Z ₃ and Z ₄ each represent a hydrogen atom or a substituent. X ₁ ^- represents an ion necessary to neutralize the molecular charge, n represents 1 or 2. However, when an inner salt is formed, n is 1. ] 2. The silver halide emulsion according to claim 1, wherein said chemical sensitization is further performed in the presence of a compound represented by the following general formula (5). Embedded image Wherein, Z ₅ represents a non-metallic atomic group necessary for forming a nitrogen-containing heterocyclic 5- or 6-membered, R ₅ represents a hydrogen atom, an alkyl group or an alkenyl group. R ₆ represents a hydrogen atom or a lower alkyl group, and X ⁻ represents an acid anion. ] 3. The silver halide grains contained 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 claim 1 or 2, wherein 4. When the photographic light-sensitive material having the silver halide emulsion according to claim 1 is continuously processed in processing steps including development and fixing steps, a solid solution is added to the processing solution in each processing step. A method for processing a silver halide photographic light-sensitive material, wherein the processing is performed while supplying a processing agent. 5. A photographic light-sensitive material having the silver halide emulsion according to claim 1, wherein the filling rate of the phosphor is 68% to 9%.
A method for photographing a silver halide photographic light-sensitive material, characterized in that the film is sandwiched between 0% intensifying screens and photographed by X-rays.