JP2000171932A - Silver halide emulsion and silver halide photographic sensitive material and x-ray photograph forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic emulsion and a silver halide photographic sensitive material low in fog and high in sensitivity and image quality and small in dye stains and superior in storage stability and to form the X-ray photograph high in resolution by incorporating a reduction-sensitized silver halide grains and a specified compound. SOLUTION: This silver halide photographic emulsion contains the reduction- sensitized silver halide grains and the compound represented by the formula R1-R2-Au(I)-R3-R4 in which each of R2 and R3 is a -SO2S-, -(S)m-, -(Se)m-, or -(Te)m- group or the like; (m) is an integer of 1-6; and each of R1 and R4 is, independently, an aliphatic or aromatic hydrocarbon or heterocyclic group. The silver halide grains to be used for the silver halide emulsion may be silver chloride, iodochloride, iodobromochloride, bromochloride, or the like, preferably, silver chloride or iodochloride, and preferably, >=50 mol% silver chloride, further, >=70 mol% chloride, and especially >=95 mol% chloride.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic emulsion excellent in high sensitivity, sharpness and storage stability, a silver halide photographic light-sensitive material which causes less dye contamination of an image, and an X-ray photographing method.

[0002]

2. Description of the Related Art In recent years, demands for rapid processing of silver halide photographic light-sensitive materials (hereinafter, also simply referred to as light-sensitive materials) have been increasing with an increase in the throughput. For example, a similar tendency is seen in the field of medical X-ray photography. The number of images taken has increased remarkably due to the spread of health examinations and the improvement in diagnostic accuracy. In addition, rapid processing of captured images such as intraoperative (surgical) imaging and angiographic imaging is also required. Furthermore, reduction of the processing waste liquid is strongly desired from environmental problems.

However, in order to speed up processing, development,
Although it is necessary to shorten the 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, in 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. Furthermore, the reduction in the time of each processing step is accompanied by deterioration of image quality due to insufficient dye elution of the sensitizing dye in each of the processing of development, fixing, and washing, and residual dye remaining in the dye.

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 spectral sensitizing dye, and to promote the desorption or decolorization of the spectral sensitizing dye. .

On the other hand, in order to reduce development processing waste liquid,
It is necessary to reduce the fatigue of the processing solution or the replenisher,
It has the same problems as the speeding up described above.

As a technique for improving these problems, EP
0,506,584, JP-A-5-88293, 5
No. 93975 discloses a technique using benzimidazolocarbocyanines having good decoloring performance as spectral sensitizing dyes. Also, JP-A-5-61148 describes 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 at least one selenium compound or tellurium compound is selected from selenium compounds and tellurium compounds. A technique for performing chemical sensitization with a compound has been disclosed.

[0007] However, these disclosed techniques alone can improve the residual color property or the speed of development, but they are not sufficient in terms of high sensitivity and safelight resistance, and furthermore, the photosensitive material can be used under high humidity and high temperature. There is a disadvantage that the sensitivity is greatly reduced when stored.

On the other hand, various basic studies have been carried out on the adsorption of silver halide grains and spectral sensitizing dyes for a long time. When adsorbing spectral sensitizing dyes to silver halide grains, studies have been conducted to uniformly and selectively adsorb the spectral sensitizing dyes inside and between grains.

As a method of adding a sensitizing dye, it is also known that chemical sensitization is performed in the presence of a spectral sensitizing dye to control chemical sensitization and reduce intrinsic desensitization. However, these technologies are not
Safelight resistance and reciprocity failure are also inadequate.

Attempts at reduction sensitization for higher sensitivity have been made in US Pat. Nos. 2,487,850 and 2,512,925.
No. 2,518,698, No. 3,930,86
No. 7, British Patent 789,823 and the like. However, these reduction sensitization methods have not yet reached a practical level.

On the other hand, a sensitization method using a gold compound has been proposed for a long time, and a gold compound sensitizer is a gold compound in the oxidized state (I) or (III). However, (III)
Since the oxidized gold compound may cause a side reaction to oxidize gelatin or other components in the emulsion, (I) the oxidized gold compound is preferably used.

Among gold (I) compounds, trisodium gold (I) thiosulfate is generally known as a chemical sensitizer, but this compound is not widely used because it cannot be conveniently provided.

A proposed gold (I) compound is the gold (I) thiolate described in US Pat. No. 3,503,749. However, such a production process of the gold (I) compound involves the use of dangerously explosive gold thunderous acid, which is not practically desirable.

In general, in diagnostic X-ray photography, a diagnostic image is obtained by exposing X-rays through a subject with a silver halide photographic light-sensitive material sandwiched between fluorescent intensifying screens. The sharpness required for diagnosis in bone or mammography requiring high image quality is not obtained.

Therefore, in low replenishment and rapid processing, a silver halide photographic emulsion having low fog, high sensitivity and excellent preservability, a photographic material with less dye contamination of an image, and an X-ray photography method with high sharpness are desired. Was rare.

[0016]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic emulsion having high sensitivity, low fog and excellent storability in low replenishment and rapid processing, and a silver halide having little image dye contamination. Photographic materials and X with high sharpness
It is to provide a radiography method.

[0017]

Means for Solving the Problems The present inventors have proposed an organic gold (I) which has a high sensitization rate to reduction sensitized particles and is not trapped in a gel.
As a result of intensive studies focusing on the fact that the compound selectively forms a photosensitive nucleus such as AgAuS without generating a fog nucleus of AgAu, the above object was achieved by the following constitution.

1. A silver halide photographic emulsion comprising a reduction sensitized silver halide grain and a compound represented by the following general formula (1).

Formula (1) R ₁ -R ₂ -Au (I) -R ₃ -R _{4 In the} formula, R ₂ and R ₃ are each —SO ₂ S—, — (S) _m —, and
(Se) _m- and-(Te) _m- , where m is 1 to 6. R ₁ and R ₄ are substituted or unsubstituted aliphatic hydrocarbon residues,
Represents an aromatic hydrocarbon residue or a heterocyclic group, which may be the same or different.

2. A silver halide photographic emulsion comprising at least one selected from the compounds represented by the general formula (1) and the compounds represented by the following general formulas (2) to (5).

[0021]

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[0022] In the formula, each R ₂₁ and R ₂₃ represents a substituted or unsubstituted lower alkyl or alkenyl group, R ₂₂ and R
₂₄ represents an alkyl group, and at least one of R ₂₂ and R ₂₄ represents an alkyl group substituted with a hydrophilic group. Z ₂₁ , Z ₂₂ , Z
₂₃ and Z ₂₄ may be the same or different and each represents a hydrogen atom or a substituent. X ₂₁ 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.

[0023]

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In the formula, X ₃₁ represents —SO ₃ M ₃₁ , —COOM
Represents an atom group having ₃₁ or -OM ₃₁ directly or indirectly and capable of forming a heterocyclic ring, and M ₃₁ represents a hydrogen atom, a metal atom, a quaternary ammonium group or a phosphonium group. However, compounds partially including the following structures are excluded.

[0025]

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Here, R represents a hydrogen atom or a substituent.

[0027]

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In the formula, (A ₁ ) represents —SO ₃ M ₁ , —COOM ₁
Or -OM ₁ , M ₁ represents a hydrogen atom, a metal atom, a quaternary ammonium group or a phosphonium group, and m is 1 to 10
(A ₂ ) represents an electron-withdrawing group, and n is 1
Is an integer of 10 to 10. (A ₃ ) represents a functional group containing a sulfur atom, a selenium atom or a tellurium atom capable of binding to a silver ion, and r represents 1 or 2. Y represents an aliphatic hydrocarbon residue, an aromatic hydrocarbon residue, or a heterocyclic group.

[0029]

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Where (A ₁ ), (A ₂ ), (A ₃ ), m,
n and r each represent a group having the same meaning as in the above formula (4). (A ₁ ) ′ represents —SO ₃ M ₁ , —COOM _1, or —OM ₁
The stands, M ₁ is representative of the M ₁ group having the same meaning as in the general formula (4). (A ₂ ) 'represents an electron-withdrawing group, and (A ₃ )' represents a functional group containing a sulfur atom, a selenium atom or a tellurium atom, which can bind to a silver ion. (A ₁ ) and (A ₁ ) ′, (A ₂ ) and (A ₂ ) ′, and (A ₃ ) and (A ₃ ) ′ may be the same or different. Y ₁ and Y ₂ represent an aliphatic hydrocarbon residue, an aromatic hydrocarbon residue or a heterocyclic group, and may be the same or different. Z represents a sulfur atom, a selenium atom or a tellurium atom, p is 1 or 2, m + m ′ and n
+ N 'is 1 to 20, respectively.

3. A silver halide photographic light-sensitive material comprising the silver halide emulsion according to 1 or 2 on a support.

An X-ray photographing method characterized in that the silver halide photographic light-sensitive material described in 4.3 is sandwiched by a high-sensitivity intensifying screen having a phosphor filling rate of 68 to 90% to perform X-ray photographing.

Hereinafter, the present invention will be described in detail.

The silver halide grains used in the silver halide photographic emulsion of the present invention include silver chloride, silver iodochloride, silver iodobromochloride,
Silver bromochloride, silver bromide, silver bromoiodide and the like can be used.
Among these, silver chloride and silver iodochloride are more preferred.

The silver halide grains contained in the silver halide photographic emulsion preferably contain at least 50 mol% of silver chloride, more preferably at least 70 mol%,
More preferably, the content is 90 mol% or more. In the case of silver iodochloride, the content of silver iodide is preferably 0.01 to 1.0 mol% as an average silver iodide content in the whole silver halide grains, and 0.01 to 0.5 mol%. Mole% is more preferred.

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

The tabular silver halide grains preferably used are described below.

The silver iodide content and the average silver iodide content of each silver halide grain were 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 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. 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 photographic emulsion 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%.
Hereinafter, it is more preferable that it is 20% or less.

It is preferable that the tabular silver halide grains contain silver iodide, but it is preferable that the tabular silver halide grains be contained at least inside. In the case of the inside, it is more preferable that it exists at least in the center. In this case, the internal composition preferably contains 0.1 to 5 mol% of silver iodide. 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. While cooling this section with liquid nitrogen, observation and point analysis were performed with a transmission electron microscope equipped with an energy dispersive X-ray analyzer,
It can be obtained by quantitative calculation (Inoue, Nagasawa: Abstracts of the 62nd Annual Meeting of the Photographic Society of Japan, 1987 p62).

It is also preferred that silver iodide be present on the outermost surface. In this case, the silver iodide content of the outermost surface is 1 to 10
Preferably it is mol%. Here, the silver iodide content at the outermost surface of the tabular silver halide grains is defined by the XPS method (X-
ray Photoelectron Spectro
(scopie: X-ray photoelectron spectroscopy) means the silver iodide content of a portion up to a depth of 50 °, which can be determined 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 an X-ray for a probe 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 of the outermost surface is 1 to 10
Preferably it is mol%.

The average value (referred to as average aspect ratio) of the grain diameter / thickness (referred to as aspect ratio) of the tabular silver halide grains is preferably 8 or less, more preferably less than 7, and most preferably less than 5. is there.

It is preferable that 20% or more of the total projected area of the silver halide grains contained in the silver halide photographic emulsion is composed of tabular silver halide grains having a (100) plane as a main plane, but preferably 50%. % Or more, more preferably 70%
% Or more are 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.

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 right-angled parallelogram is less than 10, preferably less than 5, and more preferably less than 2. In the case of a shape with missing corners and a rounded shape, the length of the side is the length to the intersection with the line that extends the straight part of the side of the right-angled parallelogram and extends the straight part of the adjacent side. It is represented by

The average grain size of the tabular silver halide grains is 0.3.
It is preferably from 15 to 5.0 μm, more preferably from 0.4 to 3.0 μm, most preferably from 0.4 to 3.0 μm.
2.0 μm.

The average thickness of the tabular silver halide grains is 0.5.
It 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.

The particle size and thickness can be optimized for the best sensitivity and other photographic properties. However, other factors (such as a hydrophilic colloid layer) constituting the photosensitive material which affect the sensitivity and other photographic properties can be used. The optimal particle size and the optimal thickness vary depending on the thickness, hardness, chemical ripening conditions, sensitivity of the photosensitive material, and the amount of silver coating.

The tabular silver halide grains 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 preferably 20% or less, more preferably Is 18% or less, particularly preferably 15% or less.

The tabular silver halide grains preferably have a narrow thickness distribution.

Specifically, when the distribution width is defined by (standard deviation of thickness / average thickness) × 100 = width (%) of thickness distribution, it is preferably 25% or less, more preferably Is not more than 20%, particularly preferably not more than 15%.

The tabular silver halide grains may have dislocation lines. Dislocation lines are described in, for example, F. Hamilto
n, Photo. Sci. Eng, 57 (1967),
T. Shiozawa, J .; Soc. Photo. Sc
i. Japan, 35, 213 (1972), which can be observed by a direct method using a low-temperature transmission electron microscope. That is, the silver halide grains taken out so as not to apply enough pressure to generate dislocation lines from the emulsion are placed on a mesh for electron microscope observation to prevent damage (printout, etc.) by the electron beam. Observation is performed by a transmission method while the sample is cooled. At this time, the thicker the particle, the more difficult it is for the electron beam to penetrate. Therefore, a sharper observation can be obtained by using a high-pressure electron microscope (200 kV or more for a particle having a thickness of 0.25 μm). it can.

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

The process for producing a silver halide photographic emulsion is roughly classified into processes such as grain formation, desalting, and chemical sensitization. Particle formation is divided into nucleation, ripening, growth and the like. These steps are not performed uniformly, but the order of the steps is reversed or the steps are repeatedly performed.

The reduction sensitization may be performed basically in any step. Reduction sensitization may be performed during nucleation, which is the initial stage of grain formation, during physical ripening, during growth, and may be performed prior to chemical sensitization other than reduction sensitization, or performed after chemical sensitization. Good.

When performing chemical sensitization in combination with gold sensitization, reduction sensitization is preferably performed prior to chemical sensitization so as to prevent undesirable fog. Most preferred is a method in which reduction sensitization is performed during the 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;
This means that the method further includes a method of performing reduction sensitization in a state where the growth is temporarily stopped during the growth and then growing the growth.

Reduction sensitization is carried out by adding a known reducing agent to a silver halide emulsion, by growing or ripening in a pAg1-7 low pAg atmosphere called silver ripening,
Either a method of growing in a high pH atmosphere of pH 8-11 called high pH ripening or a method of ripening can be selected. Further, two or more methods can be used in combination.

The method of adding a reduction sensitizer is a preferable method since the level of reduction sensitization can be finely adjusted.

Examples of the reduction sensitizer include stannous salts,
Examples include amines and polyamic acids, hydrazine derivatives, formamidinesulfinic acids, silane compounds, borane compounds, and the like, and these compounds can be used in combination of two or more. Of these compounds, stannous chloride, thiourea dioxide, and dimethylamine borane are preferred compounds. Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is suitably from 10 ^-7 to 10 ^-3 mol per mol of silver halide.

As the reduction sensitizer, ascorbic acid or a derivative thereof can also be used.

Specific examples of ascorbic acid and its derivatives (hereinafter simply referred to as ascorbic acid compounds) include the following.

(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 The ascorbic acid compound is desirably used in an amount larger than the amount of the reduction sensitizer other than the ascorbic acid compound.

The amount of the ascorbic acid compound used in the present invention depends on the grain size of the emulsion, the halogen composition, the temperature for preparing the emulsion, pH, pAg and the like.
The range of 5 × 10 ^-5 to 1 × 10 ^-1 mol per mol is preferable, more preferably 5 × 10 ^-4 to 1 × 10 ^-2 mol, particularly preferably 1 × 10 ^-3 to 1 × 10 ^-2. Is a mole.

The reduction sensitizer is dissolved in water or a solvent such as alcohols, glycols, ketones, esters, amides, etc., during grain formation, before or after chemical sensitization, or in any step of the emulsion production process. Although it may be added, it is particularly preferable to add it 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.

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 grains may be formed using these aqueous solutions. Also, even if the solution of the reduction sensitizer is added in several portions with the formation of grains,
It is also a preferred method to add continuously over a long time.

The organic gold (I) compound represented by the general formula (1) will be described.

In the general formula (1), the aliphatic hydrocarbon residue represented by R ₁ and R ₄ is a linear or branched alkyl, alkenyl or alkynyl having 1 to 30, preferably 1 to 20 carbon atoms. Or each group such as cycloalkyl. Specifically, for example, methyl, ethyl, propyl, butyl, hexyl, decyl, dotesyl, isopropyl, t
-Butyl, 2-ethylhexyl, allyl, 2-butenyl, 7-octenyl, propargyl, 2-butynyl, cyclopropyl, cyclopentyl, cyclohexyl, cyclododecyl and the like.

The substituted and unsubstituted aromatic hydrocarbon residues represented by R ₁ and R ₄ include substituted and unsubstituted aromatic hydrocarbon residues having 6 to 20 carbon atoms. Specific examples include groups such as phenyl, naphthyl, and anthranyl.

The heterocyclic ring of the heterocyclic residue represented by R ₁ and R ₄ may be a single ring or a condensed ring, and may be N, O, S, Se.
And a heterocyclic group having at least one atom of Te in the ring. Specifically, for example, pyrroline, furan, tetrahydrofuran, pyridine, piperidine, morpholine, thiadiazole, thiatriazole, benzothiazole, benzoxazole, benzimidazole,
Examples include benzoselenazole, benzotriazole, indazole, quinoline, quinaldine, pyrrolidine, thiophenyl, oxazole, thiazole, imidazole, selenazole, tellurazole, triazole, tetrazole, and oxadiazole. R ₁ and R ₄ may be the same or different.

The compound represented by the general formula (1) is soluble in water or any of various solvents including an organic solvent such as acetone or methanol, and the most preferred compound is a water-soluble one.

The compound represented by the general formula (1) is preferably dispersed and added as a fine solid so as to exert the effects of the present invention more. The compound represented by the general formula (1) is added during the production process of the silver halide emulsion. The addition conditions are
The conditions of the chemical sensitization step, for example, pH, pAg, temperature, time, etc., are not particularly limited, and the sensitization can be performed under conditions generally performed in the art, and it is preferable to use the sensitization method in combination with another sensitization method. The addition amount of the compound represented by the general formula (1) is preferably from 1 × 10 ⁻⁷ to 1 × 10 ⁻² mol, more preferably from 1 × 10 ⁻⁵ to 1 × 10 ⁻⁴ mol per mol of silver halide. It is.

Specific examples of the compound represented by formula (1) are shown below, but the present invention is not limited thereto.

[0077]

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[0078]

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[0079]

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[0080]

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[0081]

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[0082]

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The spectral sensitizing dye refers to a dye which is adsorbed on silver halide grains and spectrally sensitized.

The spectral sensitizing dye used in the present invention is not particularly limited as long as it has a spectral sensitizing function. In the present invention, silver halide is used in combination with the compound represented by formula (2). A compound having a maximum absorption wavelength of 555 nm or less in the J cohesion band when adsorbed on particles and measuring a reflection spectrum is preferable.

When used in X-ray medical light-sensitive materials utilizing a phosphor that emits green light, a spectral sensitizing dye is adsorbed on silver halide grains, and when its reflection spectrum is measured, the spectral sensitizing dye is removed from the phosphor. Preferably, the J-band is formed in the same wavelength range as the green light.

That is, the maximum absorption wavelength is preferably 520 to
It is preferable to select and combine the compound represented by the general formula (2) of the present invention and a spectral sensitizing dye described below so that a J-band having the maximum absorption in the region of 555 nm is formed. Preferably 530-553 nm
And most preferably 540 to 550 nm.

Next, the compound represented by formula (2) of the present invention will be described.

In the general formula (2), R ₂₁ and R ₂₃ each represent a substituted or unsubstituted alkyl group or alkenyl group. Examples of the alkyl group include ethyl, propyl, 3
Straight-chain and branched groups such as -methylbutyl group; and the substituted alkyl group includes, for example, 2-hydroxyethyl,
Examples of alkenyl groups such as 2-methoxyethyl, 2-ethoxyethyl, ethoxycarbonylethyl, phenethyl, methanesulfonylethyl, and 3-oxobutyl groups include
Each group includes a vinyl group and an allyl group.

Examples of the alkyl group represented by R ₂₂ and R ₂₄ include straight-chain and branched groups such as methyl, ethyl, butyl, and isobutyl groups. For example, dissociative groups such as sulfo, carboxy, methanesulfonylaminocarbonyl, methanesulfonylaminosulfonyl, acetylaminosulfonyl, sulfoamino, trifluoroacetylaminosulfonyl, acetylaminocarbonyl, and N-methylsulfamoyl groups, Specific examples include, for example, 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 5-sulfopentyl, 2-N-ethyl-N-sulfoaminoethyl, carboxymethyl, carboxyethyl, 3-sulfoaminopropyl, 6-sulfoaminopropyl Sulfo-3-oxahexyl, 1
0-sulfo-3,6-dioxadecyl, 6-sulfo-3
-Thiahexyl, o-sulfobenzyl, p-carboxybenzyl, methanesulfonylaminocarbonylmethyl,
Each group includes an acetylaminosulfonylmethyl group.

Z ₂₁ , Z ₂₂ , Z ₂₃ and Z ₂₄ may be the same or different, and each has a hydrogen atom, a halogen atom (for example, fluorine, chlorine, bromine, iodine, etc.) and an alkyl group (for example, Examples of the lower alkyl groups such as methyl, ethyl and propyl), alkoxy groups (such as methoxy, ethoxy, propoxy and the like) and halogen-substituted alkoxy groups (such as fluoromethoxy, trifluoromethyl, 2,2,2 Each atom such as trifluoroethyl), an aryloxy group (for example, each group such as phenoxy, p-bromophenoxy), an acyl group (for example, each group such as acetyl and benzoyl), and an acyloxy group (for example, acetyloxy, propionyloxy and the like) ), Alkylthio groups (for example, methylthio, ethylthio, etc.), halogen-substituted alkyl O group (eg, trifluoromethylthio, difluoromethylthio, etc.), alkoxycarbonyl group (eg, methoxycarbonylmethyl, ethoxycarbonyl, etc.), carbamoyl group (eg, carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl) , N, N-diethylcarbamoyl, N, N
-3-oxa-pentamethylenecarbamoyl, N-phenylcarbamoyl, etc.), sulfamoyl groups (eg, N-methylsulfamoyl, N, N-tetramethylenesulfamoyl, N, N-3-oxapentamethylenesulfur) Famoyl, N-phenylsulfamoyl, N, N-
Groups such as diethylsulfamoyl), haloalkyl groups (such as monofluoromethyl, difluoromethyl, trifluoromethyl, monochloromethyl and the like), sulfonyl groups (such as methanesulfonyl, ethanesulfonyl,
Trifluoromethanesulfonyl, fluorosulfonyl,
Groups such as benzenesulfonyl and p-toluenesulfonyl), an acylamino group (eg, N-acetylamino, N
-Trifluoroacetylamino, etc.), substituted and unsubstituted aryl groups (for example, phenyl, o-fluorophenyl, p-cyanophenyl, m-chlorophenyl, etc.) and heterocyclic groups are substituted and unsubstituted. Each group includes substituted ones (for example, each group such as 1-pyrrolyl, 2-furyl, and 2-benzoxazolyl).

The ion required to neutralize the charge in the molecule of the spectral sensitizing dye may be an anion or a cation. Examples of the anion include a halogen ion (each ion such as chloro, bromo and iodine ions). ), Perchlorate, ethylsulfonate, thiocyanate, p-
There are toluene sulfonate, perfluoroborate, etc.
Examples of the cation include a hydrogen ion, an alkali metal ion (each ion such as lithium, sodium, and potassium), an alkaline earth metal ion (each ion such as magnesium and calcium), an ammonium ion, and an organic ammonium ion (triethylammonium, triethanol). Ammonium, tetramethylammonium, etc.).

Next, specific examples of the compound represented by the above general formula (2) of the present invention will be given, but the present invention is not limited to these.

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[0094]

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[0095]

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Examples of spectral sensitizing dyes (hereinafter, also simply referred to as dyes) which can be used in combination with the compound represented by the general formula (2) of the present invention include cyanine dyes, merocyanine dyes, composite cyanine dyes, composite merocyanine Dyes, horoporacyanine dyes, hemicyanine dyes, styryl dyes or hemioxonol dyes are included. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes or complex merocyanine dyes. The nuclei of these dyes include, for example, 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,
Examples include an indole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, and a quinoline nucleus. 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.
5-6 such as 5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidine-2,4-dione nucleus, thiazoline-2,4-dione nucleus, rhodanine nucleus and thiobarbituric acid nucleus
Member heterocyclic nuclei can be applied.

These specific compounds are described, for example, in German Patent No. 929,080 and US Pat. No. 2,231,658.
No. 2,493,748 and No. 2,503,77
No. 6, No. 2,519,001, No. 2,912,3
No. 29, No. 3,655,394, No. 3,656
No. 959, No. 3,672,897, No. 3,64
9,217, British Patent No. 1,242,588, and JP-B-44-14030.

In addition to the compound represented by the general formula (2) and the spectral sensitizing dye, the compound itself is a dye having no spectral sensitizing property or a substance which does not substantially absorb visible light, It is preferable to add a substance having an effect to the emulsion layer.

The amount of the compound represented by formula (2) and the amount of the spectral sensitizing dye vary depending on the kind of the dye, the structure and composition of silver halide, ripening conditions, purpose and application. It is preferable that the coverage of the monomolecular layer on the surface of each photosensitive particle in the emulsion be 30 to 90%, more preferably 40 to 80%.

In the present invention, the monomolecular layer 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 amount added per mole 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.

To further increase the sensitivity and improve the residual color, the addition ratio of the compound represented by the general formula (2) of the present invention should be 30% or more of the total spectral sensitizing dye in the light-sensitive material. Is preferred.

As the solvent for the compound represented by the formula (2) and the spectral sensitizing dye of the present invention, conventionally used water-miscible organic solvents can be used. For example, alcohols,
Ketones, nitriles, alkoxy alcohols and the like have been used. Specific examples include, for example, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, ethylene glycol, propylene glycol,
1,3-propanediol, acetone, acetonitrile, 2-methoxyethanol, 2-ethoxyethanol and the like.

Further, a surfactant has been conventionally used as a dispersant for the compound represented by the general formula (2) and the spectral sensitizing dye of the present invention. Surfactants include anionic, cationic, nonionic and amphoteric surfactants, and any of these surfactants can be used in the present invention.

However, in the present invention, it is preferable to add the spectral sensitizing dye as a dispersion in the form of solid fine particles, as compared with the case where the spectral sensitizing dye is added as a solution of an organic solvent, in that the effects of the present invention are more exhibited.

In particular, at least one of the compound represented by formula (2) and the spectral sensitizing dye is substantially insoluble in water substantially dispersed in an aqueous system substantially free of an organic solvent or a surfactant. Is preferably added in the form of a solid fine particle dispersion.

On the other hand, the present invention has been made to uniformly and effectively adsorb the compound represented by the general formula (2) and the spectral sensitizing dye on the surface of silver halide grains. The technique of merely adding by means of a different effect.

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

The solubility of the spectral sensitizing dye in the present invention in water is from 2 × 10 ⁻⁴ to 4 × 10 ⁻² mol / l, preferably from 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 a precipitate of the dispersion is formed after the dispersion is completed, or when the dispersion is added to the silver halide emulsion. In some cases, the adsorption process of the dye on 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 general formula (2) and the spectral sensitizing dye in water was measured by the following method.

That is, 30 ml of ion-exchanged water was placed in a 50 ml Erlenmeyer flask, an amount of a 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 a filter paper no. 2 (Toyo Corporation)
The filtrate was filtered with a disposable filter (manufactured by Tosoh Corporation), the filtrate was appropriately diluted, and the absorbance was measured with a spectrophotometer U-3410 (manufactured by Hitachi, Ltd.). Next, based on the measurement results, the solubility was determined according to Lambert-Beer's law, and the solubility was further determined.

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

The compound represented by formula (2) and the spectral sensitizing dye of the present invention can be added at the chemical ripening step, particularly preferably at the start of chemical ripening. By adding the silver emulsion during the nucleation step to the end of the desalting step, a high-sensitivity silver halide emulsion having excellent spectral sensitization efficiency can be obtained. The same or a different kind of the present invention as the compound represented by the general formula (2) and the spectral sensitizing dye added to the above step (from the nucleation step to the end of the desalting step) at any time immediately before the coating step The compound represented by the general formula (2) and a spectral sensitizing dye may be additionally added.

Next, the general formulas (3), (4),
The compound represented by (5) will be described.

In the general formula (3), X ₃₁ represents —SO ₃ M
Examples of the heterocycle of a heterocyclic residue having at least one selected from ₃₁ , -COOM ₃₁ and -OM ₃₁ directly or indirectly include, for example, an oxazole ring, a thiazole ring, an imidazole ring, a selenazole ring, a triazole ring, and a tetrazole ring. , Thiadiazole ring, oxadiazole ring, pentazole ring, pyrimidine ring, thiazine ring, triazine ring,
A thiodiazine ring or a ring linked to another carbon chain or heterocycle,
For example, a benzothiazole ring, a benzotriazole ring, a benzimidazole ring, a benzoxazole ring, a benzoselenazole ring, a naphthoxazole ring, a triazaindolizine ring, a diazaindolizine ring, a tetraazaindolizine ring, and the like, preferably Each heterocyclic ring such as an imidazole ring, a tetrazole ring, a benzimidazole ring, a benzothiazole ring, a benzoxazole ring, and a triazole ring is exemplified.

The compounds represented by the general formula (3) are described in US Pat. Nos. 2,585,388 and 2,541,924;
JP-B-42-21842, JP-A-53-50169
No., British Patent No. 1,275,701; A. Ber
ges et. al. , “Journal of He
terocyclic Chemistry "15,9
81 (1978), "The Chemistry o
f Heterocyclic Chemistry "
Imidazole and Derivatives
part I, p. 336-339, Chemica
l Abstract, 58, 7921 (1963),
p. 394, E.C. Hoggarth "Journal
of Chemical Society ", p.11
60-1167 (1949); R. Saudle
r, W.S. Karo “Organic Functiona”
l Group Preparation "Acade
mic Press, p. 312 to 315 (196
8), M.P. Champdon, et. al. , Bulle
tin de la Society Chimique
ede France, 723 (1954); A.
Shirley, D .; W. Alley, J.M. Amer.
Chem. Soc. 79, 4922 (1954);
Wohl, W.C. Marchwald “Ber.” 22,
p. 568 (1889); Amer. Chem. S
oc. 44, p. 1502-1510, U.S. Pat.
017,270, British Patent No. 940,169, JP-B-49-8334, JP-A-55-59463, "A
advanced in Heterocyclic C
hemistry ", West German Patent No. 2,716,707
No., “The Chemistry of Heter
occyclic Compounds Imidazo
le and Derivatives ", 1, p.3
85, “Org. Synth.” IV. , 569 (196
3), "Ber." 9, 465 (1976), "JA.
mer. Chem. Soc. "45, 2390 (192
3), JP-A-50-89034 and JP-A-53-28426.
No. 55-21007, JP-B-40-28496, and the like.

In the above general formulas (4) and (5), (A
₁₎ and (-SO ₃ M ₁ is represented by A ₁₎ ', -COOM ₁
Alternatively, the metal atom represented by M ₁ of —OM ₁ is preferably a transition metal atom that can bond to sulfur, selenium or tellurium such as alkali metal, silver, gold, and palladium.

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

The functional groups containing a sulfur atom, a selenium atom or a tellurium atom capable of binding to silver ions represented by (A ₃ ) and (A ₃ ) 'include mercapto group, thione group, -SeH
Group, = Se group and the like are preferable.

The aliphatic hydrocarbon residue represented by Y, Y ₁ or Y ₂ is preferably a linear or branched alkyl group, alkenyl group or allyl group having 4 to 20 carbon atoms. As the hydrogen residue, a phenyl group, a naphthyl group and the like are preferable.

The compound represented by formula (4) or (5) 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); Org. Chem. 34, p.
534 (1969), JP-A-60-184057 and JP-A-60-204742. Some are available as commercial products.

The specific examples of the compounds represented by formulas (3), (4) and (5) are shown below, but the invention is not restricted thereto.

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The compound represented by formula (3), (4) or (5) may be added at the time of grain formation, before or after chemical sensitization, or during chemical sensitization. If added before the completion of chemical sensitization, a high fog suppression effect may be obtained. If added separately before and after the completion of the chemical sensitization, a better effect can be obtained. There is also an effect of improving the covering power. The compounds may be used in combination of two or more, or may be used in combination with other inhibitors.

As an addition method, the powder may be added as it is, or as 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. If necessary, a pH adjuster may be used to enhance the solubility. Further, when dispersed and added as fine particulate solids, higher effects may be obtained. In any case,
Before chemical sensitization, usually 1 × 10 5 per mole of silver halide
^-6 to 1 × 10 ^-2 mol, preferably 1 × 10 ^-5 to 1 × 10
^-3 mol, usually 1 × 10 ⁻⁵ to
It is 1 × 10 ⁻¹ mol, preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻² .

In the present invention, the conditions of the step of chemical sensitization,
For example, with respect to PAg, temperature, time and the like, it is preferable to carry out under conditions generally carried out in the art.

The silver halide emulsion of the present invention is preferably subjected to at least one 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 to be used. For example, US Pat. Nos. 1,574,944 and 1,60
No. 2,592, No. 1,623,499;
-150046, JP-A-4-25832, 4-1
Compounds described in JP-A-09240 and JP-A-4-147250 can be used. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, etc.), and selenoureas (eg, 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 (eg, selenoacetone, selenoacetophenone, etc.), selenoamides ( For example, selenoacetamide,
N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-3-selenobutyrate, etc.), selenophosphates (eg, tri-p-triselenophos) And selenides (such as triphenylphosphine selenide, diethyl selenide and diethyl diselenide). Particularly preferred selenium sensitizers are selenoureas, selenamides and selenoketones, selenides.

The amount of the selenium sensitizer varies depending on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but is generally from 10 ^-8 to 10 ^-4 mol per mol of silver halide. Depending on the properties of the selenium compound to be used, the addition method may be a method of dissolving in an organic solvent such as water, methanol or ethanol alone or in a mixed solvent and adding. 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 when a selenium sensitizer is used is preferably from 40 to 90 ° C., more preferably from 45 to 8 ° C.
0 ° C. Further, the pH is preferably 4 to 9, and the pAg is preferably 6 to 9.5.

Regarding tellurium sensitizers and sensitization methods, see, for example, US Pat. Nos. 1,623,499 and 3,320,009.
No. 69, No. 3,772,031, No. 3,531,
No. 289, No. 3,655,394, British Patent No. 23
Nos. 5,211, 1,121,496 and 1,2
Nos. 95,462 and 1,396,696, Canadian Patent 800,958, JP-A-4-204640,
No. 4-330430, and the like.

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

The silver halide emulsion of the present invention is preferably used in combination with a chemical sensitizer other than sensitization by at least one selected from selenium and tellurium. 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. Preferred chemical sensitization methods 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 others, and a noble metal sensitization method using a noble metal. Can be mentioned. Among them, a sulfur sensitization method, a gold sensitization method, a reduction sensitization method and the like are preferable.

Examples of sulfur sensitizers applicable in the present invention include US Pat. Nos. 1,574,944 and 2,41.
No. 0,689, No. 2,278,947, No. 2,7
No. 28,668, No. 3,501, 313, No. 3,
656,955, West German Application Publication (OLS) 1,42
2,869, JP-A-56-24937, and JP-A-55-4937.
Sulfur sensitizers described in, for example, Japanese Patent No. 5016 can be used. Specific examples include 1,3-diphenylthiourea, triethylthiourea, 1-ethyl, 3- (2-
Preferred examples thereof include thiourea derivatives such as thiazolyl) thiourea, rhodanine derivatives, dithiacarbamic acids, polysulfide organic compounds, and sulfur alone.
In addition, as the simple substance of sulfur, α-sulfur belonging to the orthorhombic system is preferable.

Examples of the gold sensitizer other than the organic gold (I) compound represented by the general formula (1) include chloroauric acid, gold thiosulfate, gold thiocyanate and the like, thioureas, rhodanines, and the like. It may be used in combination with a gold complex of other various compounds.

The amount of the sulfur sensitizer used is not uniform depending on the type of silver halide emulsion, the type of compound used, the ripening conditions, etc.
It is preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻⁹ mol. Further, it is preferably 1 × 10 ⁻⁵ 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.

The light-sensitive material of the present invention contains a dye capable of decoloring or flowing out during development in at least one of the layer containing the silver halide emulsion or the layer constituting the light-sensitive material other than the emulsion layer. Thus, a photosensitive material having high sensitivity, high sharpness, and little dye contamination can be obtained. The preferred dye used in the photosensitive material may be appropriately selected from dyes that can improve sharpness by absorbing a desired wavelength and removing the influence of the wavelength, depending on the photosensitive material. I can do it. It is preferable that the dye is decolorized or flows out during the development processing of the light-sensitive material, and that the coloring is not visible when the image is completed.

Preferred dyes for use in the light-sensitive material of the present invention include those which are substantially insoluble in water at pH 7 or less,
8 or more are water-soluble. The amount added can be varied depending on the sharpness goal. Preferably 0.2 to 20
mg / m ^2, more preferably from 0.8~15mg / m ^2.

The dyes preferably used in the present invention are described in West German Patent No. 616,007 and British Patent No. 584,609.
No. 1,177,429, JP-B-26-7777
Nos. 39-22069, 54-38129, JP-A-48-85130, 49-99620, and 4
Nos. 9-114420, 49-129537, 50
-28827, 52-108115, 57-1
85038, JP-A-2-282244, 4-30
No. 7539, U.S. Pat. Nos. 1,878,961, 1,884,035, 1,912,797, 2,098,891, 2,150,695,
No. 2,274,782, No. 2,298,731
No. 2,409,612, No. 2,461,48
No. 4, No. 2,527,583, No. 2,533,4
No. 72, No. 2,865, 752, No. 2,956
No. 879, No. 3,094,418, No. 3,12
No. 5,448, No. 3,148,187, No. 3,1
No. 77,078, No. 3,247,127, No. 3,
No. 260,601, No. 3,282,699, No. 3,409,433, No. 3,540,887, No. 3,575,704, No. 3,653,905,
No. 3,718,472 and No. 3,865,817
No. 4,070,352, 4,071,31
No. 2, PB Report 74175, PHOTO. AB
S. 1, 28 ('21) and the like can be used.

Various photographic additives can be used in the emulsion and light-sensitive material of the present invention. Known additives include, for example, Research Disclosure (RD) No.
No. 17643 (December 1978); 18716
(November 1979) and the same No. 308119 (19
(December 1989). The types and locations of the compounds shown in these three RDs are described below.

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[Table 1]

Examples of the support which can be used in the light-sensitive material of the present invention include those described on page 28 of RD-17643 and page 1009 of RD-308119.

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.

The light-sensitive material of the present invention is preferably provided with a silver halide emulsion layer and a crossover cut layer on both sides of a support, whereby a light-sensitive material having high sensitivity, high sharpness and excellent processability can be obtained. . The total amount of gelatin in the silver halide emulsion layer, surface protective layer and other layers is preferably 0.5 to 3.5 g / m ² , more preferably 1.0 to 3.0 g / m ² on one side of the support. ² is preferred.

The latex preferably used in the present invention does not adversely affect the following points even when used in a silver halide emulsion, or is very little. 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 to prevent color contamination of the photosensitive material. 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. When a silver halide emulsion is produced, the emulsion coating solution in which the latex is dispersed has little pH dependency, and is not easily influenced by ionic strength and hardly aggregates and precipitates.

It is considered that the fact that the latex has the above properties has a great influence on the monomer composition and properties of this latex.

For the latex, an index called a glass transition point is often used. The higher the glass transition point is, the harder it becomes to serve as a buffer, but the lower the glass transition point is, the lower the glass transition point is, generally, it tends to interact with photographic performance and adversely occurs.
Therefore, in consideration of photographic characteristics, it is necessary to consider the selection of the composition and the amount of the composition used. Specifically, latexes using monomers such as styrene, butadiene, and vinylidene are well known. It is said that the introduction of a monomer having a carboxylic acid group such as acrylic acid, itaconic acid or maleic acid at the time of synthesizing the latex reduces the influence on the photographic properties, and such synthesis is often attempted. In addition, a latex obtained by such a combination can be obtained by further incorporating a methacrylate monomer into the latex and appropriately setting the glass transition point according to the light-sensitive material. A specific example is disclosed in
-135335 and JP-A-6-308670, 6
Reference is made to, for example, -308658.

The light-sensitive material of the present invention is preferably processed using a solid processing agent.

The solid processing agent preferably used in the present invention is a solid processing agent such as a powder, a tablet, a pill or a granule, which is subjected to a moisture-proof treatment as required.

The powder-treating agent refers to an aggregate of fine-grained crystals, and the granule-treating agent refers to a product obtained by subjecting a powder to a granulation step and having a particle size of 50 to 5000 μm. In addition, the tablet processing agent refers to one obtained by compression-molding powder or granules into a certain shape.

The light-sensitive material of the present invention is preferably subjected to continuous processing using such a solid processing agent while supplying the solid processing agent and water as replenishing processing agents in accordance with the processing amount.

To solidify the treating agent, a concentrated liquid, fine powder or granular treating agent and a water-soluble binder are kneaded and molded, or the surface of the temporarily molded treating 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 forming the tablet through a tableting step.

There is an advantage that the solubility and storage stability are improved as compared with a solid processing agent formed by simply mixing a solid processing agent component and forming a tablet through a tableting step, and as a result, photographic performance is also stabilized.

Granulation methods for forming tablets include rolling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, and the like.
A known method such as fluidized bed granulation or spray drying granulation can be used.

For tablet formation, the average particle size of the obtained granulated product is preferably 100% because the components are not made uniform, that is, the so-called segregation does not easily occur when the granulated product is mixed and compressed.
It is preferable to use one having a thickness of from 800 to 800 μm, more preferably from 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.
Next, when compressing the obtained granules under pressure, a known compressor,
For example, a hydraulic press, a single-shot tableting machine, a rotary tableting machine, or a briquetting machine can be used.
The solid processing agent obtained by pressurizing and compression can take any shape, but is preferably a cylindrical type, so-called tablet, from the viewpoints of productivity and handleability or generation of dust when used on the user side.

The above-mentioned effect becomes more remarkable by separating and granulating the solid treating agent, for example, an alkali agent, a reducing agent, a preservative, etc. for each component at the time of granulation.

Solid processing agents are used for photographic processing agents such as a developer, a fixing agent and a rinsing agent, but the effect of the present invention, particularly the effect of stabilizing photographic performance, is great for a developer.

As the 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 method described in -85732 or the like, 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 powder, Japanese Utility Model Application Laid-Open Nos. 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 any place in the processing tank, but is preferably a place where the processing liquid is communicated with the processing section for processing the photosensitive material and the processing liquid flows between the processing section and the processing section. Preferably, there is a structure in which there is a certain amount of processing liquid circulation between the processing part and the dissolved components move to the processing part. Further, the solid processing agent is preferably introduced into a processing liquid whose temperature is controlled.

A developer and a solid developer (hereinafter, both referred to as a developer) preferably used in the present invention will be described.

The developing agents preferably used in the present invention may contain the following developing agents in addition to reductones such as ascorbic acids.

1,4-dihydroxybenzenes (for example, hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, methoxyidloquinone, 2,5-dichlorohydroquinone,
3-dibromohydroquinone, 2,5-dimethylhydroquinone, potassium hydroquinone monosulfonate, sodium hydroquinone monosulfonate, etc.).

As the auxiliary drug, 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-
4,4-dimethyl-3-pyrazolidone, 1-phenyl-
4-ethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-phenyl-4-methyl-
4-hydroxymethyl-3-pyrazolidone (dimesone S), 1-phenyl-4,4-dihydroxymethyl-3
-Pyrazolidone, 1-p-tolyl-3-pyrazolidone,
1-phenyl-2-acetyl-4,4-dimethyl-3-
Examples of aminophenols such as pyrazolidone, 1- (2-benzothiazolyl) -3-pyrazolidone, 3-acetoxy-1-phenyl-3-pyrazolidone (for example, o-
Aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, and the like, 1-allyl-3-aminopyrazolines (for example, 1- ( p-hydroxyphenyl) -3-aminopyrazoline, 1- (p-methylaminophenyl) -3-aminopyrazoline, 1- (p
-Amino-m-methylphenyl) -3-aminopyrazoline and the like, and pyrazolones (for example, 4-aminopyrazolone and the like) or a mixture thereof, and preferably 1-phenyl-3-pyrazolidone.

It is preferable to select a developing agent and a developing auxiliary agent which, when combined with the developing agent and the developing auxiliary agent, achieve superchemical conversion in the development theory.

Preferred combinations include the following:
The developing agent is 1-phenyl-3-pyrazolidone / erythorbic acid, 1-phenyl-3-pyrazolidone / hydroquinone, dimezone S / erythorbic acid or hydroquinone, dimezone / erythorbic acid or hydroquinone, more preferably 1-phenyl-3 -Pyrazolidone / erythorbic acid, dimezone S / erythorbic acid.

The ratio of the auxiliary agent / developing agent of the replenisher preferably used in the present invention may be 1.1 times or more with respect to the starting solution, but is preferably 1.1 to 3.0 times. If the ratio exceeds 3.0 times, the effect of the present invention can be obtained, but the fog is increased, which is not preferable.

A developer start solution is separately prepared as a start kit so as to have the ratio of the present invention.

The developer may further include a preservative (eg, sulfites, bisulfite, etc.), a buffer (eg, carbonate, borate, alkanolamine, etc.) and an alkaline agent (eg, carbonate, etc.), if necessary. ), Dissolution aids (eg, polyethylene glycols and esters thereof), pH adjusters (eg, organic acids such as citric acid and tartaric acid), sensitizers (eg, quaternary ammonium salts), development accelerators, Hardening agents (for example, dialdehydes such as glutaraldehyde), surfactants and the like can be contained.

Further, as an antifoggant, an azole organic antifoggant (for example, indazole type, imidazole type, benzimidazole type, triazole type, benzotriazole type, tetrazole type, thiadiazole type, etc.) and calcium ion mixed in tap water (Eg, sodium hexametaphosphate, calcium hexametaphosphate, polyphosphate, etc.) may be added.

As the silver stain inhibitor, for example, the compounds described in JP-A-56-24347 can be used.

The pH of the developer used in the present invention after dissolution and dilution is preferably from 9 to 12, and more preferably 9.5.
１10.0.

As the developer, an amino compound such as an alkanolamine described in JP-A-56-106244 can be used. In addition, L. F. A. Mason, "Photographic Processing Chemistry," Focal Press (1966), pp. 22-229, U.S. Pat. Nos. 2,193,015 and 2,592,36
No. 4 may be used.

It is preferable that the starting developer is supplied by dissolving a solid developer for preservation.

As the replenishment developer, it is preferable to add and supply the developer directly with water.

The fixing solution and the solid fixing agent preferably used in the present invention (hereinafter, both referred to as fixing agent) will be described.

The fixing agent preferably contains a thiosulfate. Thiosulfates are usually used as lithium, potassium, sodium, ammonium salts,
Preferred are sodium thiosulfate and ammonium thiosulfate. Ammonium salts are preferable in that a fixing solution having a high fixing speed can be obtained, and sodium salts are preferable in terms of storage stability and the like.

The concentration of thiosulfate is preferably from 0.1 to 5 mol / l, more preferably from 0.5 to 2 mol / l, even more preferably from 0.7 to 1.8 mol / l.

In addition, iodide, thiocyanate and the like can also be used as fixing agents.

The fixing agent preferably contains a sulfite, and the concentration of the sulfite is 0.2 mol / liter or less when the thiosulfate and the sulfite are dissolved and mixed in an aqueous solvent. As the sulfite, a solid lithium, potassium, sodium, ammonium salt or the like is usually used, and is used together with the above-mentioned solid thiosulfate.

The solid fixing agent may contain a water-soluble chromium salt or a water-soluble aluminum salt. Examples of the water-soluble chromium salt include chromium alum, and examples of the water-soluble aluminum salt include aluminum sulfate, aluminum chloride, and potassium aluminum chloride. The amount of the water-soluble chromium salt or water-soluble aluminum salt to be added is generally 0.2 to 3.0 g per liter of the fixing solution.
Preferably it is 1.2-2.5.

The fixing agent may contain acetic acid, citric acid, isocitric acid, tartaric acid, malic acid, succinic acid, phenylacetic acid or optical isomers thereof. These salts include, for example, potassium citrate, lithium citrate, sodium citrate, ammonium citrate, lithium hydrogen tartrate, potassium hydrogen tartrate, sodium hydrogen tartrate, ammonium hydrogen tartrate, ammonium potassium tartrate, sodium potassium tartrate, sodium malate , Ammonium, malate, sodium succinate, ammonium succinate and the like, lithium, potassium, sodium, ammonium salts and the like are preferred.

Among the above compounds, more preferred are acetic acid, citric acid, isocitric acid, malic acid, phenylacetic acid and salts thereof, and the amount of addition is 0.2 to 0.1.
6 mol / l is preferred.

Examples of the acid include inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid and boric acid, and salts thereof, and organic acids such as propionic acid formic acid, oxalic acid and malic acid, and preferably aminocarboxylic acids boric acid and salts thereof. It is. Particularly preferred aminocarboxylic acids include β-alanine and piperidine acid. The preferable addition amount of the acid is 0.5 to 40.
g / liter.

Examples of the chelating agent include aminopolycarboxylic acids such as nitrilotriacetic acid and ethylenediaminetetraacetic acid, and salts thereof.

Examples of the surfactant include anionic surfactants such as sulfates and sulfonates, ninoon surfactants such as polyethylene glycol and ester, and amphoteric surfactants described in JP-A-57-6840. Is mentioned.

Examples of the lubricant include alkanolamine and alkylene glycol.

Examples of the fixing accelerator include, for example, those described in
No. 35754, No. 58-122535, No. 58-
No. 122,536, thiourea derivatives, alcohols having a triple bond in the molecule, US Pat. No. 4,126,4
No. 59, and the like.

The pH after dissolution and dilution of the fixing agent is usually
It is 3.8 or more, preferably 4.2 to 5.5.

The fixing agent is preferably a solid fixing agent exhibiting acidity after dissolution. This refers to a fixing agent having a pH of less than 7 after dissolving in water and having a fixing ability. When the fixing agent is a tablet, a fixing agent prepared by dividing the tablet into a main fixing agent and an acid agent is also included.

It is preferable to add a starter to the developer before processing, 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 preferable processing temperature of the photographic material of the present invention is 2
The temperature is 5 to 50C, more preferably 30 to 40C. A preferred development time is 3 to 15 seconds, more preferably 4 to 15 seconds.
10 to 10 seconds. Total processing time (Dry to Dry)
Is preferably within 60 seconds, more preferably 1
0 to 45 seconds, particularly preferably 15 to 30 seconds.

Here, the total processing time (Dry to Dr)
y) is the processing time including the steps of developing, fixing, and drying the photosensitive material. From the time when the tip of the photosensitive material starts to be immersed in the developer, the tip is dried through the development, fixing, and washing (stabilizing) processes. Time to get out of the zone.

The replenishment of the processing agent in the processing of the light-sensitive material of the present invention replenishes the amount corresponding to the processing agent fatigue and oxidative fatigue. As the replenishment method, the width described in JP-A-55-126243,
Replenishment by feeding speed, area replenishment described in JP-A-60-104946, or area replenishment controlled by the number of continuously processed sheets described in JP-A-1-149156 may be used.

A preferred processing replenishment rate of the present invention is 20 ml /
The number of cuts is four, and the preferable amount of replenishment for development is 1 to 7 ml /
It is 4 pieces.

In the light-sensitive material of the present invention, the swelling ratio of the silver halide emulsion layer during the development processing is preferably from 150 to 250%, and the film thickness after expansion is more preferably 70 μm or less. When the water swelling ratio exceeds 250%, poor drying 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%, development unevenness and dye residue tend to occur during development.

Here, the water swelling ratio is obtained by calculating the difference between the film thickness after swelling in each processing solution and the film thickness before development processing, dividing the difference by the film thickness before processing, and multiplying it by 100 times. Say what you did.

The filling rate of the phosphor in the phosphor layer of the radiation intensifying screen used in the method for photographing a silver halide photographic light-sensitive material of the present invention is preferably from 68 to 90%, more preferably from 70 to 72%.

The phosphor layer has a thickness of 150 to 250 μm.
m is preferred. Here, if the thickness of the phosphor layer is less than 150 μm, the sharpness sharply deteriorates.

It is preferable that the radiation intensifying screen is filled with a phosphor in a gradient particle size structure. In particular, it is preferable to apply large-sized phosphor particles to the surface protective layer side and to apply small-sized phosphor particles to the support side.
0 μm is preferable, and the particle size of the large particle size is preferably 10 to 30 μm.

The fluorescent intensifying screen used in the X-ray photographing method of the present invention has a high filling rate of the phosphor particles, so that the X-ray of the intensifying screen can be improved.
The linear absorption rate is improved. It is preferably at least 30% per 100 μm thickness of the phosphor layer. The X-ray absorptivity was determined as follows. In other words, with a three-phase power supply, the inherent filtration is 80 mm from an X-ray generator equivalent to 2.2 mm
X-rays generated from a tungsten target operated at kVp are transmitted through a 3 mm thick aluminum plate of at least 99% purity and reach a radiographic intensifying screen fixed at a position 200 cm from the tungsten anode of the target tube. 50c from the phosphor layer of the radiation intensifying screen
This is a value obtained from the ratio to the X-ray dose at the above-mentioned measurement position, which was measured without using an intensifying screen as a reference, by measuring using an ionizing dosimeter at a position after m and measuring the amount of X-ray absorption.

Preferred binders used for the radiographic intensifying screen include thermoplastic elastomers. Specifically, selected from the group consisting of polystyrene, polyolefin, polyurethane, polyester, polyamide, polybutadiene, ethylene, vinyl acetate, polyvinyl chloride, natural rubber, fluororubber, polyisoprene, chlorinated polyethylene, styrene-butadiene rubber or silicon rubber. At least one thermoplastic elastomer.

The phosphor filling ratio of the present invention means that the protective layer of the screen is removed, the entire phosphor layer is peeled or eluted using an organic solvent, filtered, dried, and dried at 600 ° C. using an electric furnace.
When the weight of the phosphor obtained by baking for 1 hour to remove the resin on the surface is Og, the thickness of the phosphor layer before elution is Pcm, the screen area used for elution is Qcm ² , and the specific gravity of the phosphor is Rg / cm ³ , Phosphor filling rate (%) = [O ÷ (P × Q × R)] × 100.

Preferred phosphors for the radiographic intensifying screen used in the X-ray imaging method of 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,
(Y, Gd) O ₂ S: Tb, Tm, etc.], terbium-activated rare earth phosphate-based phosphor (YPO ₄ : Tb, GdPO ₄ : T
b, LaPO ₄ : Tb, etc.), terbium-activated rare earth oxyhalide phosphor (LaOBr: Tb, LaOB)
r: Tb, Tm, LaOCl: Tb, LaOCl: T
b, Tm, GdOBr: Tb, GdOCl: Tb, etc.),
Thulium-activated rare earth oxyhalide phosphor (La
OBr: Tm, LaOCl: Tm, etc.), barium sulfate-based phosphor [BaSO ₄ : Pb, BaSO ₄ : Eu ²⁺ , (B
a. Sr) SO ₄ : Eu ²⁺ etc.] divalent eurobium-activated alkaline earth metal phosphate phosphor [Ba ₃ (P
O ₄ ) ₂ : Eu ²⁺ , (Ba ₃ (PO ₄ ) ₂ : Eu ²⁺ etc.), 2
-Valent eurobium-activated alkaline earth metal fluorohalide-based phosphor [BaFCl: Eu ²⁺ , BaFBr: E
u ²⁺ , BaFCl: Eu ²⁺ , Tb, BaFBr: E
u ²⁺ , Tb, BaF ₂ . BaCl ₂ .KCl: Eu ²⁺ ,
(Ba.Mg) F ₂ . BaCl ₂ .KCl: Eu ²⁺ etc.],
Iodide phosphor (CSI: Na, CSI: Tl, Na
I, KI: Tl, etc.) sulfide-based phosphor [ZnS: Ag,
(Zn.Cd) S: Ag, (Zn.Cd) S: Cu,
(Zn.Cd) S: Cu, Al, etc.], hafnium phosphate-based phosphor (HfP ₂ O ₇ : Cu, etc.), tantalate-based phosphor [YTaO ₄ , YTaO ₄ : Tm, YTaO ₄ : Nb,
(Y, Sr) TaO _4-x : Nb, LuTaO ₄ , LuTa
O ₄ : Nb, (Lu, Sr) TaO _4-x : Nb, GdTa
O ₄ : Tm, Gd ₂ O ₃ .Ta ₂ O ₅ .B ₂ O ₃ : Tb, etc.]. However, the phosphor preferably 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.

[0219]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the embodiments of the present invention are not limited thereto.

[0220] Example 1 (Preparation of silver iodobromide hexagonal tabular grains) <Preparation of Em-1> A ₁ ossein gelatin 75.5g polypropylene oxy - polyethyleneoxy - disuccinate sodium salt (10% aqueous ethanol solution) 6 B ₁ 0.7 N silver nitrate aqueous solution 1340 ml C ₁ 2.0 N silver nitrate aqueous solution 1500 ml D ₁ 1.3 N potassium bromide aqueous solution 410 ml E ₁ 2.0 N aqueous potassium bromide solution following silver finish 10800ml in .78ml potassium bromide 64.7g water a potential control amount F ₁ ossein gelatin 125g water 4000 ml G ₁ 3% by weight of gelatin, fine grain emulsion consisting of silver iodide grains (average grain size 0.05 .mu.m) (*) 0.008 mol equivalent * 0.06 moles of 7.06 mol is added to 6.64 liters of a 5.0% by weight aqueous gelatin solution containing potassium iodide. Of silver nitrate and 2 liters of an aqueous solution containing 7.06 mol 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 particles are formed, p is added using an aqueous sodium carbonate solution.
H was adjusted to 6.0.

[0221] To a solution A ₁ with a mixing and stirring machine shown in Japanese Patent Publication No. 58-58288 at 55 ° C. The solution B ₁ 400 ml
And Solution D ₁ through adding total amount required 40 seconds by double jet precipitation was performed nucleation.

After the addition of the solution B ₁ and the solution D ₁ was completed, the solution F
₁ is added, and the temperature is raised to 70 ° C. for aging. Furthermore it was added over the remaining amount of the solution B ₁ 25 min, subjected to ripening for 10 minutes using a 28% aqueous ammonia solution, returning the pH with acetic acid to neutral. While maintaining the solution C ₁ and E ₁ in pAg = 7.8 and mixed simultaneously added at a rate commensurate with the critical growth rate, C ₁
It was added to the G ₁ and after the addition of the total amount. After stirring for 5 minutes, soluble salts were desalted and removed by the 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. The average thickness of the hexagonal tabular grains is 0.20 μm, and the average grain size is (Circle diameter conversion)
Was confirmed to be 0.80 μm by an electron microscope.
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 adjusted to 50 ° C., and general formulas (3), (4),
The compound represented by (5) is added in the kind and amount as shown in Table 2, and the compound represented by the general formula (2) and the spectral sensitizing dye of the present invention in the form of solid fine particles in the amounts described in Table 2 are added. Added as a dispersion. Then 3.5m sodium thiosulfate
g, 1 mg of ammonium thiocyanate and 3.6 mg of triphenylphosphine selenide were added. Further, the compound represented by the general formula (1) was added in the amounts described in Table 2, and aging was performed for a total of 2 hours.

At the end of aging, 1-phenyl-
5 mg of 5-mercaptotetrazole (PMT) and the compounds represented by formulas (3), (4) and (5) were added in the amounts shown in Table 2. The amount of addition was shown as an amount per mole of silver halide.

[0225] (Preparation of silver iodochloride tabular grain) <Preparation of _Em-2> A 2 ossein gelatin 75.0 g KI 1.25 g NaCl 33.0 g distilled water finish 15000ml with B ₂ 684ml silver nitrate 410g distilled water Finished to 11590 g of C ₂ silver nitrate Finished to 19316 ml with distilled water D ₂ KI 4 g NaCl 140 g Finished to 684 ml with distilled water E ₂ NaCl 3980 g Potassium hexachloroiridium (IV) 8 × 10 ^-6 mol Finished to 19274 ml with distilled water at 40 ° C. The total amount of B ₂ and D ₂ was added to solution A ₂ in a mixing stirrer described in JP-B-58-58288.
It was added over a minute. EAg was adjusted to 149 mV and 2
After Ostwald ripening for 0 minutes, the total amount of C ₂ and E ₂ was reduced to 32
Added over 0 minutes. Meanwhile, EAg was controlled at 149 mV.

Immediately after the addition was completed, desalting and washing were performed.
Em-2 thus produced was composed of tabular grains having 65% of the total projected area of the silver halide grains having the (100) plane as the main plane, with an average thickness of 0.14 μm and an average diameter of 1.
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
The temperature was raised to 5 ° C., 0.05 mg of thiourea dioxide was added, and after 20 minutes, 0.5 mol% of silver iodide fine particles were added. Subsequently, the compounds represented by the general formulas (3), (4) and (5) are added in amounts shown in Table 2, and the solid fine particle dispersion of the compound represented by the general formula (2) and the spectral sensitizing dye of the present invention is added. And 0.4 g of calcium chloride. Subsequently, a solid particulate dispersion containing 4 mg of sodium thiosulfate, 0.5 mg of ammonium thiocyanate, and 4.1 mg of triphenylphosphine selenide was added.

Thereafter, the compound represented by the general formula (1) was added in the amount shown in Table 2, and aging was performed for a total of 2 hours. At the end of ripening, 5 mg of the PMT and the compounds represented by formulas (3), (4) and (5) were added as stabilizers in the amounts shown in Table 2. The amount of addition was shown as an amount per mole of silver halide.

The solid fine particle dispersion of the compound represented by formula (2) and the spectral sensitizing dye of the present invention is disclosed in Japanese Patent Application No. 4-994.
Prepared by a method according to the method described in No. 37. That is, a predetermined amount of the spectral sensitizing dye was added to water previously adjusted to 27 ° C., and the mixture was stirred with a high-speed stirrer (dissolver) at 3,500 rpm for 30 minutes.

[0230] 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 later was prepared. Using both coating solutions, the speed of 80 m / min using two slide hopper type coaters so that the coating amount per side is 1.6 g / m ² and the amount of gelatin is 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, an aqueous dispersion of a copolymer obtained by diluting a copolymer composed of three monomers of glycidyl methacrylate 50 wt%, methyl acrylate 10 wt%, and butyl methacrylate 40 wt% to 10 wt%. Was used as an undercoating liquid, and a polyethylene terephthalate film base colored blue with a concentration of 0.13 for an X-ray film of 175 μm 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) 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) ₂ 350 mg / m ² Compound (M) 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 5 g / m ² Third layer (protective layer) Gelatin 0.8 g / m ² Matt 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-vinylsulfonylmethyl ether 36 mg / m ² latex (L) 0.2 g / m ² polyacrylamide (average molecular weight 10,000) 0.1 g / m ² poly sodium acrylate 30 mg / m ² polysiloxane (SI) 20mg / m ² compound (I) 12mg / m ² compound (J 2 mg / m ² Compound (S-1) 7mg / m 2 Compound (K) 15mg / m ² Compound (N-2) 5mg / m 2 Compound (O-2) 5mg / m 2 Compound (S-2) 5mg / _{^{m 2 C 9 F 19 -O- (}} CH 2 CH 2 O) 11 -H 3mg / m 2 C 8 F 17 SO 2 N- (C 3 H 7) (CH 2 CH 2 O) 15 -H 2mg / m _{^{2 C 8 F 17 SO 2 N-}} (C 3 H 7) (CH 2 CH 2 O) 4 - (CH 2) 4 SO 3 Na 1mg / m 2

[0235]

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[0236]

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[0237]

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(Evaluation of photographic performance) Each of the obtained coated samples was stored for 4 days under the following storage conditions.

A storage condition: 23 ° C., 40% RH B storage condition: 55 ° C., 80% RH For development, a developing tablet and a fixing tablet were prepared and used.

A developing tablet was prepared by the following operations (A, B).

Operation (A) 3,000 g of Na erythorbic acid as a developing agent is pulverized in a commercially available bantam mill until the average particle size becomes 10 μm. To this fine powder, 3000 g of sodium sulfite, 2000 g of potassium sulfite, and 1000 g of Zimezon S were added, and the mixture was added in a mill.
After mixing for 0 minutes and granulating by adding 30 ml of water at room temperature for about 10 minutes in a commercially available stirring granulator, the granulated material is dried at 40 ° C. for 2 hours in a fluidized bed drier. The water in the granulated material is almost completely removed. To the granules thus prepared, polyethylene glycol 6000, 100 g
Was uniformly mixed for 10 minutes using a mixer in a room humidified at 25 ° C. and 40% RH or less, and the obtained mixture was mixed with a tableting machine obtained by modifying Kikusui Seisakusho's Tough Press Collect 1527HU. Compression tableting was performed at a filling amount of 3.84 g per tablet to prepare 2500 developing tablet A agents.

Operation (B) 100 g of diethylenetriaminepentaacetic acid (DTPA), 4000 g of potassium carbonate, 10 g of 5-methylbenzotriazole, 1-phenyl-5-mercaptotetrazole 7
g, 2-mercaptohypoxanthine 5 g, KOH200
g, Manipulate N-acetyl-D, L-penicillamine (A)
Pulverize and granulate in the same manner as described above. 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 filling amount per tablet of the thus obtained mixture was 1.73 g using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd.
And compression tableting was carried out to prepare 2500 tablets B for development.

16.5 L of the obtained developing tablets A and B were mixed and sealed in an aluminum pillow bag for moisture prevention.

Next, fixing tablets 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 pulverized in the same manner as in the operation (A), and then uniformly mixed with a commercially available mixer. Next, in the same manner as in the operation (A), granulation is performed with the addition amount of water being 500 ml. After granulation, the granulated product is
For 30 minutes to remove the moisture of the granules almost completely. 4 g of sodium N-lauroylalanine was added to the granules thus prepared, and the mixture was added at 25 ° C. and 40% RH.
Mix for 3 minutes in a humidified room using a mixer below. Next, 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 set to 6.202 g.
500 fixing tablet C preparations were prepared.

Procedure (D): 1,000 g of boric acid, 3000 g of sodium hydrogen acetate (a mixture obtained by mixing glacial acetic acid and sodium acetate in an equimolar amount and drying),
200 g of tartaric acid are 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, the mixture 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 the mixture was mixed for 3 minutes. Then, the resulting mixture was subjected to tough press collect 1527H manufactured by Kikusui Seisakusho KK
U was converted to a tableting machine with a filling amount of 4.5 per tablet.
Compression tableting was performed at 62 g to prepare 1250 fixing tablet D preparations.

16.5 L of the obtained fixing tablets C and D were mixed and sealed in an aluminum pillow bag for moisture prevention. <Developer starter> Glacial acetic acid 2.98 g KBr 4.0 g Water was added. 1 liter.

<Development / Fixing Initiator> For both development and fixing, open each pillow bag at the solid processing agent inlet of the automatic developing machine, insert the tablets into the built-in chemical mixer, and simultaneously inject warm water at 30 ° C. And stir for 20 minutes
The solution was adjusted to 6.5 liters.

At the start of the processing (running start), the developing tank was filled with a liquid obtained by adding 330 ml of a starter to 16.5 liters of the developing initiator to start the processing. The pH of the developer to which the starter was added was 1
0.45.

<Running> The photosensitive material prepared above was exposed so that the optical density after development processing was 1.0.
Running was performed using the development initiator. In the running, 2,000 pieces of the photosensitive material were cut each day, and this processing was performed for one day. 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 running, the photosensitive material is 0.6
As a development replenisher per 2 m ² , the above-mentioned tablet A for development,
Agent B was prepared by adding two of them and 76 ml of water. The pH when dissolving the agent A and the agent B in 38 ml of water is 10.7.
It was 0. ^Two fixing agents, one D agent and 74 ml of water were added to the fixing agent as fixing replenishers per 0.62 m ² of the photosensitive material. 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.

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. Running using the sample after storage An automatic processor using a processing agent was used to evaluate sensitivity, fog, maximum density, and residual color.

<Sensitivity> Storage condition A of Example 1 (23 ° C.,
40% RH, 4 days), storage condition B (55 ° C., 80% R
The sample stored in H) was placed on two fluorescent intensifying screens KO-250.
(Manufactured by Konica Corporation), a tube voltage of 80 kVp, a tube current of 100 mA, and a penetrometer type B in a conventional manner.
It was irradiated with X-rays for 0.05 seconds, and processed using a processing agent that reached a running equilibrium using an automatic developing machine (SRX-502 manufactured by Konica Corporation).

The sensitivity is represented by the reciprocal of the exposure amount giving a density of fog + 1.0. The relative value was set to 100 with the sensitivity of 1 being 100. Tables 2 and 3 show the obtained results.

<Dye Contamination> Evaluation of dye contamination (residual color) was carried out using a spectrophotometer on a sample after development processing.
The spectral absorption concentration at 0 nm was measured and is shown in Tables 2 and 3.

[0256]

[Table 2]

[0257]

[Table 3]

[0258]

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As is clear from Tables 2 and 3, the sample of the present invention has low fog, high sensitivity, and the highest density (Dma).
x) is high, the color retention is excellent, and when a solid processing agent is used, the sensitivity is hardly impaired even in a quick processing such as 15 seconds and a low replenishment processing, and thus there is no problem at all.

Example 2 (Production of High Sensitive Intensifying Screen (S-1)) <Preparation of Coating Solution for Phosphor Layer Formation> Phosphor Gd ₂ O ₂ S: Tb (average particle size 1.8 μm) 200 g Binding Polyurethane-based thermoplastic elastomer (Demolac TPKL-5-2 625, solid content 40%, manufactured by Sumitomo Bayer Urethane Co., Ltd.) 20 g Nitrocellulose (nitrification degree 11.5%) 2 g Methyl ethyl ketone solvent is added to the above materials, and the mixture is mixed with a propeller mixer. By dispersing, a coating liquid for forming a phosphor layer having a viscosity of 25 PS (25 ° C.) was prepared.

<Preparation of Undercoat Layer Forming Coating Solution> Soft Acrylic Resin Solids 90 g Nitrocellulose 50 g The above materials were added to methyl ethyl ketone, dispersed and mixed to form an undercoat layer forming coating having a viscosity of 3 to 6 PS (25 ° C.). A liquid was prepared.

A thickness of 250 μm into which titanium dioxide has been kneaded.
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 having a thickness of 15 μm on the support.

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 the 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.
60 μm, phosphor filling rate 68%, sharpness (CTF) 48
%Met.

(Production of Comparative Intensifying Intensifying Screen (S-2))
Except that the thickness of the coating solution for forming the phosphor layer is uniformly applied at 150 μm, and no compression is performed, the above-described high-sensitivity intensifying screen (S-
A comparative intensifying screen (S-2) comprising a support, an undercoat layer, a phosphor layer and a transparent protective film was produced in the same manner as in 1).
The characteristics of the comparative high-sensitivity intensifying screen (S-2) obtained were such that the thickness of the phosphor layer was 105 μm and the filling rate of the phosphor was 65%.

(Evaluation of Photographic Performance) The sensitivity and sharpness of each sample were evaluated.

<Sensitivity> Storage condition A of Example 1 (23 ° C.,
The sample stored at 40% RH for 4 days) was sandwiched between fluorescent intensifying screens shown in Table 4 and X-rays were applied through a penetrometer type B using a conventional method at a tube voltage of 60 kVp, a tube current of 200 mA and a current of 0.05 second for 0.05 second. Irradiation was performed, and the sensitivity was measured by performing the same processing as in Example 1.

The sensitivity is represented by the reciprocal of the exposure amount giving a density of fog + 1.0, and is represented by the sample No. using the comparative high-sensitivity intensifying screen (S-2). The relative value was set to 100 with the sensitivity of 1 being 100.

<Sharpness> Storage condition A of Example 1 (23
(C, 40% RH, 4 days) was sandwiched between intensifying screens shown in Table 4, and a funk test chart SM5853 (manufactured by Konica Medical Co., Ltd.) was photographed by an ordinary method. Was done.

The rectangular wave pattern recorded on the processed film was measured using a microdensitometer PDM-5 (manufactured by Konica Corporation) and the measurement slit size was set to 300 μm in the direction parallel to the rectangular wave (height) and in the direction perpendicular to the rectangular wave (width). ) Measured at 25 μm and the resulting MTF value was calculated as spatial frequency 2.0 lines / m
The m-value was compared with the photographing No. using the high-sensitivity intensifying screen (S-2).
The relative values are shown with 1 as 100.

The results are summarized in Table 4.

[0273]

[Table 4]

As is clear from Table 4, it can be seen that an image photographed by the photographing method using the high-sensitivity intensifying screen of the present invention is excellent in sharpness while maintaining high sensitivity.

[0275]

According to the present invention, a silver halide photographic emulsion, a light-sensitive material, and an X-ray photographing method having low fog, high sensitivity, high image quality, little dye contamination, and excellent storage stability can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 5/17 G03C 5/17 G21K 4/00 G21K 4/00

Claims (4)

[Claims] 1. A silver halide photographic emulsion comprising a reduction sensitized silver halide grain and a compound represented by the following general formula (1). General formula (1) R ₁ -R ₂ -Au (I) -R ₃ -R _{4 In the} formula, R ₂ and R ₃ are each -SO ₂ S-,-(S) _m -,-
(Se) _m- and-(Te) _m- , where m is 1 to 6. R ₁ and R ₄ are substituted or unsubstituted aliphatic hydrocarbon residues,
Represents an aromatic hydrocarbon residue or a heterocyclic group, which may be the same or different. 2. A silver halide photograph comprising a compound represented by the general formula (1) and at least one selected from compounds represented by the following general formulas (2) to (5). emulsion. Embedded image In the formula, R ₂₁ and R ₂₃ each represent a substituted or unsubstituted lower alkyl group or alkenyl group, R ₂₂ and R ₂₄ represent an alkyl group, and at least one of R ₂₂ and R ₂₄ represents a hydrophilic group. Represents a substituted alkyl group. Z ₂₁ , Z ₂₂ , Z ₂₃ and Z ₂₄ may be the same or different and each represents a hydrogen atom or a substituent. X ₂₁ 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. Embedded image In the formula, X ₃₁ represents —SO ₃ M ₃₁ , —COOM ₃₁ or —OM
Represents an atom group having ₃₁ directly or indirectly and capable of forming a heterocyclic ring, and M ₃₁ represents a hydrogen atom, a metal atom, 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. Embedded image In the formula, (A ₁ ) represents —SO ₃ M ₁ , —COOM _1, or —OM ₁
M ₁ represents a hydrogen atom, a metal atom, a quaternary ammonium group or a phosphonium group, m is an integer of 1 to 10, (A ₂ ) represents an electron-withdrawing group, and n is 1 to 10 It is an integer. (A ₃ ) is a sulfur atom capable of binding to a silver ion,
Represents a functional group containing a selenium atom or a tellurium atom, and r is 1
Or 2 is represented. Y represents an aliphatic hydrocarbon residue, an aromatic hydrocarbon residue, or a heterocyclic group. Embedded image In the formula, (A ₁ ), (A ₂ ), (A ₃ ), m, n and r each represent a group having the same meaning as in the above formula (4). (A ₁₎ '
Is -SO ₃ M _1, represents -COOM ₁ or -OM _1, M ₁ represents M ₁ group having the same meaning as in the general formula (4). (A ₂ ) 'represents an electron-withdrawing group, and (A ₃ )' represents a functional group containing a sulfur atom, a selenium atom or a tellurium atom, which can bind to a silver ion. (A ₁ ) and (A ₁ ) ′, (A ₂ ) and (A ₂ ) ′,
(A ₃ ) and (A ₃ ) ′ may be the same or different. Y ₁ and Y ₂ represent an aliphatic hydrocarbon residue, an aromatic hydrocarbon residue or a heterocyclic group, and may be the same or different. Z represents a sulfur atom, a selenium atom or a tellurium atom, p is 1 or 2, and m + m 'and n + n' are each 1 to 20. 3. A silver halide photographic light-sensitive material comprising a silver halide emulsion according to claim 1 on a support. 4. An X-ray imaging method, wherein the silver halide photographic light-sensitive material according to claim 3 is sandwiched by a high-sensitivity intensifying screen having a phosphor filling rate of 68 to 90% to perform X-ray imaging.