JPH11184037A - Silver halide photographic sensitive material, x-ray image forming unit and method, and method for processing silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the silver halide photographic sensitive material high in sensitivity and density and improved in storage stability with the lapse of time. SOLUTION: This sensitive material is provided on a support with hydrophilic colloidal layers including at least one silver halide emulsion layer and at least one of these hydrophilic colloidal layers contains at least cane kind of compound forming a silver complex smaller in solubility product than silver iodide, and a thiocyanate ion in an amount of 1×10<-5> -1×10<-3> , preferably, 1×10<-4> -1×10<-2> mol per 1 mol of the silver halide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide photographic material, and more particularly to an improved X-ray photographic material.

[0002]

2. Description of the Related Art In recent years, with regard to the development processing of silver halide photographic light-sensitive materials, rapid processing and reduction of processing waste liquid have been strongly demanded.

In order to shorten the processing time, it is essential to improve the processing property and drying property of the photosensitive material. It is also important to reduce the amount of replenisher for processing to reduce the amount of processing waste liquid.

However, in the case of rapid processing and low replenishment processing,
Extremely severe for X-ray photosensitive materials requiring high sensitivity and high density, silver halide grains with high covering power are required for that purpose. However, generally high sensitivity,
A silver halide photographic light-sensitive material comprising silver halide grains having a high density has a serious drawback in that the raw preservability of the film is not excellent, and the sensitivity is remarkably reduced along with an increase in fog over time. Conventionally, it is well known that thiocyanate is used as one of the methods for sensitizing silver halide emulsions. However, the use of thiocyanate greatly affects the occurrence of fogging during storage of the film depending on the type, addition conditions, amount and timing of silver halide grains.

It has been desired to develop a technique which can obtain high sensitivity by chemical ripening with an optimum amount of thiocyanate under optimum conditions and suppress generation of fog during storage with time.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material capable of obtaining high sensitivity and high density in rapid processing and having improved storage stability with time, and furthermore, to provide a low replenishment. An object of the present invention is to provide a silver halide photographic light-sensitive material which does not deteriorate in performance (sensitivity) even in processing.

[0007]

The object of the present invention has been attained by the following constitutions.

(1) In a silver halide photographic material having a hydrophilic colloid layer including at least one silver halide emulsion layer on a support, a solubility product is contained in at least one of the hydrophilic colloid layers. Contains at least one compound which forms a silver complex smaller than silver bromide, and has a thiocyanate ion content of 1 × 10 ⁻⁵ mol to 1 mol / mol silver.
A silver halide photographic light-sensitive material characterized in that it contains × 10 ^-3 mol.

(2) It is characterized in that at least one compound forming a silver complex having a solubility product smaller than silver bromide is contained in an amount of 1 × 10 ^-4 mol to 1 × 10 ^-2 mol per mol of silver. The silver halide photographic material as described in (1).

(3) The silver halide grains in the silver halide emulsion layer contain 3 to 15 mol% of silver iodide at any position of 70 to 100% of the volume grain size, and The silver halide photographic light-sensitive material according to (1) or (2), wherein the silver iodide content of the whole silver halide grains is from 0.3 mol% to 5 mol%.

(4) The compound forming a silver complex having a solubility product smaller than that of silver bromide is a compound represented by the following general formula (1) or (2). 3)
6. The silver halide photographic light-sensitive material according to any one of the above.

In the formula (1), R ^1- (S) _n -R ² , wherein R ¹ and R ² may be the same or different and each may be a substituted or unsubstituted aliphatic group, aromatic group or Represents a heterocyclic group, and R ¹ and R ² may combine with each other to form a substituted or unsubstituted ring; n represents an integer of 2 to 6.

In the general formula (2), R ³ -S (M) _{X In the} formula, R ³ is an aliphatic group or an aromatic group substituted with a water-soluble group,
Represents a heterocyclic group or a cycloalkenyl group, and represents S (M) _X
Represents a group that can be adsorbed on silver halide, M represents a hydrogen atom,
X represents 1 or 0, and represents an alkali metal atom or a cation.
And when X is 0, it is represented by R ³ = S.

(5) In the silver halide grains contained in the silver halide emulsion layer, at least one sensitization selected from reduction sensitization, selenium sensitization and tellurium sensitization in any step of emulsion production. (1)-
The silver halide photographic material according to any one of (4) and (4).

(6) The silver halide photographic material described in any one of (1) to (5) above, wherein the surface having the emulsion layer and the fluorescent surface of the fluorescent intensifying screen are brought into close contact with each other. Line image forming unit.

(7) The fluorescent intensifying screen as described in (6) above,
It shows an absorption of 45% or more with respect to X-rays having a line energy of 80 kVp, a phosphor filling rate of 68% or more, and a phosphor thickness of 135 to 200 μm. An X-ray image forming method, comprising performing imagewise exposure by performing irradiation.

(8) The silver halide photographic material according to any one of the above (1) to (5) is processed by an automatic developing machine including a developing step. Material treatment method.

(9) The method for processing a silver halide photographic material as described in (8), wherein the automatic developing machine has a mechanism for supplying a solid processing agent to a processing tank.

(10) When the amount of the replenisher of the developing solution or the fixing solution is
The method for processing a silver halide photographic material according to (8) or (9), which is represented by the following formula:

1 ≦ amount of replenisher / amount taken out by photosensitive material ≦ 7 (11) Processing time required for all processing steps (Dry to
The method for processing a silver halide photographic material according to any one of claims 8 to 10, wherein (Dry) is from 10 seconds to 30 seconds.

Hereinafter, the present invention will be described in detail.

The present invention is also applicable to a low-replenishment rapid processing,
Provided is a silver halide photographic light-sensitive material which has no deterioration in sensitivity and maximum density and has improved storage stability with time. To achieve the object, at least one hydrophilic colloid layer has a solubility product of bromide. It contains at least one compound that forms a silver complex smaller than silver, and contains 1 × 10 ⁻⁵ mol to 1 × 10 ⁻³ mol of thiocyanate ion per mol of silver.

As the thiocyanate ion compound used in the present invention, a metal salt or a water-soluble salt such as NH ₄ SCN can be used. In the case of a metal salt, a metal element which does not adversely affect photographic performance is used. Should. Preferably, KSCN or NaSCN is used.

The amount of the thiocyanate ion to be added is preferably 1 × 10 ⁻⁵ mol to 1 × 10 ⁻³ mol per mol of silver, more preferably 1 × 10 ⁻⁴ mol to 1 × 10 ⁻³ mol per mol of silver. Is preferred.

The timing of adding the thiocyanate ion is not particularly limited, but is preferably during chemical ripening, and is more preferably at the start of chemical ripening.

In the present invention, the compound forming a silver complex having a solubility product smaller than silver bromide and the above-mentioned thiocyanate may be added simultaneously or separately. The addition at the start of ripening is when the silver complex-forming compound is added at the end of chemical ripening.

According to the present invention, the silver halide grains in the silver halide emulsion layer contain 3 to 15 mol% of silver iodide at any position of 70 to 100% of the volume particle size, And the silver iodide content of the whole silver halide grains is from 0.3 mol% to
5 mol%.

Here, the volume particle size of the silver halide grains is 70
Silver iodide grains having a silver iodide content of 0.3 mol% to 5 mol%, preferably at a position of 80 mol% to 100 mol%, preferably 80 mol% to 100 mol%. A silver halide emulsion having a content of 0.5 mol% to 3 mol% is exemplified.

Hereinafter, the general formula (1) will be described in detail.

Formula (1) R ^1- (S) _n -R ^{2 In} formula (1) of the present invention, the aliphatic group represented by R ¹ and R ² has 1 to 30 carbon atoms, preferably 1 to 30 carbon atoms. 20 linear or branched alkyl, alkenyl, alkynyl,
Or a cycloalkyl group. Specifically, methyl, ethyl, propyl, butyl, hexyl, decyl, dodecyl, isopropyl, t-butyl, 2-ethylhexyl, allyl, 2-butenyl, 7-octenyl, propargyl, 2-butynyl, cyclopropyl, cyclopentyl, Cyclohexyl and cyclododecyl. R
Examples of the aromatic group represented by ¹ and R ² include those having 6 to 20 carbon atoms, and specifically include phenyl, naphthyl and anthranyl groups. The heterocyclic group represented by R ¹ and R ² may be a single ring or a condensed ring, and includes a 5- to 6-membered hetero ring having at least one of O, S, and N atoms in the ring. Specifically, pyrrolidine, piperidine, tetrahydrofuran, tetrahydropyran, oxirane,
Morpholine, thiomorpholine, furfuryl, thiopyran, tetrahydrothiophene, pyrrole, pyridine, furan, thiophene, imidazole, pyrazole, oxazole, thiazole, isoxazole, isothiazole, triazole, tetrazole, thiadiazole, oxadiazole and their benzerogues . The ring forming a ring with R ¹ and R ² includes a 4- to 7-membered ring. It is preferably a 5- to 7-membered ring. Preferred groups for R ¹ and R ² are heterocyclic groups, and more preferred are heteroaromatic ring groups. The aliphatic group, aromatic group, or heterocyclic group represented by R ¹ and R ² may be further substituted, and the substituent may be a halogen atom (eg, a chlorine atom or a bromine atom) or an alkyl group (eg, Methyl group, ethyl group, isopropyl group, hydroxyethyl group, methoxymethyl group, trifluoromethyl group, t-butyl group, etc., cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), aralkyl group (eg, benzyl group, Phenethyl group, etc.), aryl group (for example, phenyl group, naphthyl group, p-tolyl group, p-chlorophenyl group, etc.), alkoxy group (for example, methoxy group, ethoxy group, isopropoxy group, n-butoxy group, etc.), aryloxy Group (for example, phenoxy group and the like), cyano group, acylamino group (for example, acetylamino group, propionylamino group and the like), Alkylthio group (eg, methylthio group, ethylthio group, n-butylthio group, etc.), arylthio group (eg, phenylthio group, etc.), sulfonylamino group (eg, methanesulfonylamino group, benzenesulfonylamino group, etc.), ureido group (eg, 3-methyl Ureido group, 3,3-dimethylureido group, 1,3-dimethylureido group, etc., sulfamoylamino group (dimethylsulfamoylamino group, etc.), carbamoyl group (for example, methylcarbamoyl group, ethylcarbamoyl group, dimethylcarbamoyl) Group), a sulfamoyl group (eg, ethylsulfamoyl group, dimethylsulfamoyl group, etc.), an alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.), an aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.) , A sulfonyl group (eg, methanesulfonyl group, butanesulfonyl group, phenylsulfonyl group, etc.), an acyl group (eg, acetyl group, propanoyl group, butyroyl group, etc.), an amino group (methylamino group, ethylamino group, dimethylamino group, etc.) A hydroxy group, a nitro group, a nitroso group, an amine oxide group (for example, a pyridine-oxide group), an imide group (for example, a phthalimide group), a disulfide group (for example, a benzene disulfide group, a benzothiazolyl 2-disulfide group, etc.), a heterocyclic group ( For example, a pyridyl group, a benzimidazolyl group, a benzthiazolyl group, a benzoxazolyl group and the like can be mentioned. R ¹ and R ² may have one or more of these substituents. Further, each substituent may be further substituted with the above substituent. n is an integer of 2 to 6, preferably 2 to 5,
More preferably, n = 2.

Specific examples of the compound represented by the formula (1) used in the present invention are listed below, but the present invention is not limited to these.

[0032]

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[0033]

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[0034]

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[0035]

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The amount of the compound represented by the general formula (1) is from 1 × 10 ^{−8 to} 5 × 10 ⁻² per mol of silver halide.
Molar content is preferred, especially 1 × 10 ⁻⁷ to 2 × 10
^-2 mol is preferred.

The above compounds are described in J. Pharm. Bel
g. , 22 (5-6) 213-219 (1967); U.S. Pat. No. 3,759,932; Org. Chm. ,
Vol10, No. 6, 1170-1172 (196
It can be easily synthesized by the method described in 7).

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

Formula (2) R ³ —S (M) _{X In the} above formula (2), R ³ is an aliphatic group, aromatic group, heterocyclic group or alicyclic group substituted by a water-soluble group. Represents X represents 1 or 0; M represents a hydrogen atom, an alkali metal atom or a cation, and when X is 0, R ³ = S.

As the water-soluble substituent of R ³ , —SO ₃ M ¹ ,
—COOM ¹ , —OH and NHR ⁴ . Among the water-soluble substituents, -COOM ¹ is preferable (however, M ¹ represents a hydrogen atom, an alkali metal atom or a cation), and one or more water-soluble substituents may be substituted. R ⁴ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, -C
OR ⁵ , —COOR ^5, or —SO ₂ R ⁵ , wherein R ⁵ represents a hydrogen atom, an aliphatic group, or an aromatic group. Further, it is particularly preferable to contain an electron-withdrawing group as a substituent of R ³ .

For example, a halogen atom (particularly a fluorine atom,
Chlorine atom), trifluoromethyl, cyano, carboxy, carbamoyl, ethynyl, acetyl, ethoxycarbanyl, trifluoromethoxy, sulfamoyl, methanesulfonyl, benzenesulfonyl, trifluoromethylthio, isothiocyanate, 1-pyrroline, 2-pyridyl and the like Each group is mentioned.

Examples of the aliphatic group represented by R ³ include linear or branched alkyl, alkenyl, alkynyl and cycloalkyl groups having 1 to 30, preferably 1 to 20 carbon atoms. Specifically, for example, methyl, ethyl, propyl, butyl, hexyl, decyl, dodecyl,
Isopropyl, t-butyl, 2-ethylhexyl, allyl, 2-butenyl, 7-octenyl, propargyl, 2
-Butynyl, cyclopropyl, cyclopentyl, cyclohexyl, cyclododecyl and the like.

Examples of the aromatic group represented by R ³ include those having 6 to 20 carbon atoms, and specific examples include phenyl, naphthyl, and anthranyl.

The heterocyclic group represented by R ³ may be a single ring or a condensed ring, and at least one of O, S and N atoms
5- to 6-membered heterocyclic groups having a species in the ring are included.
Specifically, for example, pyrrolidine, piperidine, tetrahydrofuran, tetrahydropyran, oxirane, morpholine, thiomorpholine, thiopyran, tetrahydrothiophene, pyrrole, pyridine, furan, thiophene, imidazole, pyrazole, oxazole, thiazole,
Examples include isoxazole, isothiazole, triazole, tetrazole, thiadiazole, oxadiazole and groups derived therefrom.

The alicyclic group represented by R ³ includes 4 members
To 7 carbon rings. Examples include groups such as cyclopentene, cyclopentadiene, cyclohexane, cyclohexadiene, terpene, and steroid.

The aliphatic group, aromatic group, heterocyclic group or alicyclic group represented by R ³ may be further substituted. Examples of the substituent include a halogen atom (for example, chlorine atom, bromine atom, etc.), Alkyl groups (eg, methyl, ethyl, isopropyl, hydroxyethyl, methoxymethyl, trifluoromethyl, t-butyl, etc.), cycloalkyl groups (eg, cyclopentyl, cyclohexyl, etc.), aralkyl groups (eg, benzyl, Each group such as phenethyl), an aryl group (eg each group such as phenyl, naphthyl, p-tolyl, p-chlorophenyl), an alkoxy group (eg each group such as methoxy, ethoxy, isopropoxy, butoxy), an aryloxy group (Eg phenoxy,
Groups such as 4-methoxyphenoxy), cyano groups, acylamino groups (such as acetylamino and propionylamino), alkylthio groups (such as methylthio, ethylthio and butylthio), arylthio groups (such as phenylthio and p -Methylphenylthio, etc.),
A sulfonylamino group (for example, methanesulfonylamino,
Each group such as benzenesulfonylamino), a ureido group (for example, 3-methylureide, 3,3-dimethylureide,
Each group such as 1,3-dimethylureido), sulfamoylamino group (each group such as dimethylsulfamoylamino, diethylsulfamoylamino), and carbamoyl group (for example, each group such as methylcarbamoyl, tylcarbamoyl, dimethylcarbamoyl) Group), a sulfamoyl group (for example, each group such as ethylsulfamoyl and dimethylsulfamoyl), an alkoxycarbonyl group (for example, each group such as methoxycarbonyl and ethoxycarbonyl), and an aryloxycarbonyl group (for example, phenoxycarbonyl, p-chloro) Phenoxycarbonyl, etc.), sulfonyl group (eg, metasulfonyl, butanesulfonyl, phenylsulfonyl, etc.), acyl group (eg, acetyl, propanoyl, butyroyl, etc.), amino group (eg, methylamino, ethylamido) Each group of dimethylamino, etc.),
Hydroxy group, nitro group, nitroso group, amine oxide group (for example, pyridine-oxide group), imide group (for example, phthalimide group), disulfide (for example, benzene disulfide, benzothiazole-2-disulfide, etc.), heterocycle Groups (eg, pyridyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, etc.). R ³ may have one or more of these substituents. Further, each substituent may be further substituted with the above substituent. m is 2
It is an integer of 6, preferably 2-3. Among them, it is particularly preferable to contain an electron-withdrawing group.

Hereinafter, specific examples of the compound represented by formula (2) of the present invention will be shown, but the present invention is not limited to these.

[0048]

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[0049]

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[0050]

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[0051]

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The amount of the compound represented by the general formula (2) is 1 × 10 ^{−8 to} 5 × 10 ⁻² per mol of silver halide.
Molar content is preferred, especially 1 × 10 ⁻⁷ to 2 × 10
^-2 mol is preferred.

The compound represented by the above general formula (1) or (2) is used by dissolving it in a suitable water-miscible organic solvent, for example, alcohols, ketones, dimethyl sulfoxide, dimethylformamide, methyl cellosolve and the like. Can be. It can also be added as an emulsified dispersion using a known oil. Further, the compound powder can be dispersed in water by a ball mill, a colloid mill, an impeller disperser, or an ultrasonic wave by a method known as a solid dispersion method.

In the present invention, the compound represented by formula (1) or (2) may be present in a silver halide emulsion layer, in a layer adjacent to the emulsion layer, or in another layer via the adjacent layer. it can. Particularly preferred is an emulsion layer and / or a hydrophilic colloid layer adjacent to the emulsion layer, which may be contained in a plurality of different layers. These compounds may be added at any stage during the preparation of the silver halide photographic light-sensitive material. Preferably, the silver halide emulsion is added to the support of the light-sensitive material from 2 hours before the start of chemical sensitization of the silver halide emulsion. It is preferable to add it just before coating.

The compound represented by formula (1) and the compound represented by formula (2) in the present invention are preferably contained in the same silver halide emulsion layer.

In the silver halide emulsion according to the present invention, part or all of the steps during grain formation may be grain forming steps by supplying fine silver halide grains.

The preferred particle size depends on the size and halogen composition of the silver halide grains of the host, since the grain size of the fine particles governs the supply rate of halide ions. Used. It is more preferably 0.1 μm or less. In order for the fine particles to be laminated on the host particles by recrystallization, the size of the fine particles is preferably smaller than the equivalent sphere diameter of the host particles, and more preferably 1/1/3 of the equivalent sphere diameter.
10 or less.

The silver halide emulsion according to the present invention is prepared by removing the soluble salts after completion of the growth of silver halide grains to obtain an Ag ion concentration suitable for chemical sensitization, such as a Nudel washing method or a flocculation sedimentation method. As a preferred washing method, for example, a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in JP-B-35-16086, or a polymer flocculant described in JP-A-2-7037 is used. Desalting methods using exemplified G-3, G-8, etc. can be mentioned. Also, Research Disclosure (RD) Vol. 102, 1972, October issue, It
em10208 and Vol. 131, 1975, March issue, Item 13122, may be used for ultrafiltration.

The silver halide emulsion according to the present invention can be subjected to chemical ripening. The conditions of the chemical ripening step, for example, pH, pAg, temperature, time and the like are not particularly limited, and the steps can be performed under conditions generally performed in the art. For chemical sensitization, sulfur sensitization using a compound containing sulfur capable of reacting with silver ions or active gelatin, selenium sensitization using a selenium compound, tellurium sensitization using a tellurium compound, a reducing substance The reduction sensitization method used, gold and other noble metal sensitization methods using a noble metal and the like can be used alone or in combination. Among them, the selenium sensitization method and the tellurium sensitization method are preferably used.

The silver halide emulsion is preferably subjected to reduction sensitization, selenium sensitization or tellurium sensitization.

Preferred examples of the reducing agent preferably used in the present invention include thiourea dioxide, ascorbic acid and derivatives thereof. Other preferable reducing agents include polyamines such as hydrazine and diethylenetriamine, dimethylamineboranes and sulfites.

The amount of the reducing agent to be added depends on the type of reduction sensitizer, the particle size of silver halide grains, the composition and crystal habit, the temperature of the reaction system, p.
It is preferable to change according to environmental conditions such as H and pAg. For example, in the case of thiourea dioxide, about 0.01 to 2 m per mol of silver halide is generally used as a rough guide.
Preferred results are obtained with g. In the case of ascorbic acid, about 50 mg to 2 g per mole of silver halide
Is preferable.

The conditions for reduction sensitization are as follows:
70 ° C., time is about 10 to 200 minutes, pH is about 5 to 11,
The pAg is preferably in the range of about 1 to 10 (where pAg is used).
The g value is the reciprocal of the Ag ⁺ ion concentration).

As the water-soluble silver salt, silver nitrate is preferred.
By the addition of a water-soluble silver salt, a kind of reduction sensitization technology,
So-called silver ripening is performed. PAg during silver ripening is 1-6
Is suitable, and preferably 2 to 4. Temperature, pH,
Conditions such as time are preferably in the above-described reduction sensitization condition range.

As a stabilizer for a silver halide photographic emulsion containing silver halide grains subjected to reduction sensitization, the following general stabilizers can be used.
2831 and / or V.2831. S. Article by Gehler Zeitshrif
t fur WissenschaftlichePh
autographie Bd. 63, 133 (196
9) and thiosulfonic acids described in JP-A-54-1019 may be used in combination. These compounds may be added at any stage of the emulsion production process from the crystal growth to the preparation process immediately before coating.

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 1,602,592;
JP-A-1623499, JP-A-60-150046, JP-A-4-25832, JP-A-4-109240, JP-A-4-109240
147250.

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'-heptafluoropropylcarbonylseleno Urea, N, N,
N'-trimethyl-N'-4-nitrophenylcarbonylselenourea, etc., selenoketones (eg, selenoacetone, selenoacetophenone, etc.), selenoamides (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.), seleno Carboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-
3-selenobutyrate, etc.), selenophosphates (eg, tri-p-triselenophosphate, etc.),
Selenides (diethyl selenide, diethyl diselenide, etc.). Particularly preferred selenium sensitizers are selenoureas, selenamides, and selenium ketones.

The amount of the selenium sensitizer used depends on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but is generally from 10 ^-8 to 10 ^-4 per mol of silver halide.
Use about moles. Depending on the nature of the selenium compound to be used, the addition method may be a method of adding the compound by dissolving it in water or an organic solvent such as methanol or ethanol, alone or in a mixed solvent, or by adding a mixture with a gelatin solution in advance. The method may also be a method disclosed in JP-A-4-140739, that is, a method of adding the compound in the form of an emulsified dispersion of a mixed solution with an organic solvent-soluble polymer.

The temperature of chemical ripening using a selenium sensitizer is as follows:
A range from 40 to 90C is preferred. More preferably, 45
It is not less than 80 ° C and not less than 80 ° C. The pH is 4-9, pAg
Is preferably in the range of 6 to 9.5.

Regarding tellurium sensitizers and sensitization methods, see US Pat. Nos. 1,623,499, 3,332,069, and 37.
No. 72031, No. 3531289, No. 3655394
Nos., British Patent Nos. 2,352,111 and 1121,496,
Nos. 1295462 and 1396696; Canadian Patent 800958; JP-A-4-204640;
No. 3,330,43.

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

The technique for using the tellurium sensitizer is the same as the technique for using the selenium sensitizer.

In the present invention, reduction sensitization is preferably used in combination. The reduction sensitization is preferably performed during the growth of silver halide grains. As a method of applying during the growth, not only a method of performing reduction sensitization in a state where silver halide grains are growing, but also a method of performing reduction sensitization in a state where growth of silver halide grains is interrupted, and then performing reduction sensitization. It also includes a method of growing the perceived silver halide grains.

The reduction sensitization performed in the present invention is performed during the growth of silver halide grains of the silver halide emulsion, as described below.
It is carried out by adding a reducing agent and / or a water-soluble silver salt to the silver halide emulsion.

The silver halide photographic emulsion used in the light-sensitive material of the present invention can be spectrally sensitized using methine dyes or other spectral sensitizing dyes. The dye used is
Cyanines, merocyanines, complex cyanines, complex merocyanines, holopolar cyanines, hemicyanines, styryl dyes and hemioxonol dyes are included.

Particularly useful dyes are those belonging to cyanines, merocyanines and complex merocyanines. These dyes can be applied to any of the nuclei commonly used.
That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, etc. A renin nucleus, a benzindolenine nucleus, an indole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms.

Merocyanines or complex merocyanines include:
As a nucleus having a ketomethine structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidin-
A 5- to 6-membered heterocyclic nucleus such as a 2,4-dione nucleus, a thiazoline-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus can be applied, and these spectral sensitizing dyes can be used alone. And may be used in combination. Often used in combination with spectral sensitizing dyes. These spectral sensitizing dyes and methods of use are known combinations.

Various photographic additives can be used in the light-sensitive material of the present invention. Examples of the known additives include the aforementioned (RD) 17643 (December, 1978) and the same publication, 18716 (1979). And 308119 (19
(December 1989). The types and locations of the compounds shown in these three (RD) are shown below.

[0079]

[Table 1]

In the present invention, gelatin is particularly preferred as the hydrophilic binder. Examples of hydrophilic binders other than gelatin include cellulose derivatives such as hydroxyethylcellulose, sugar derivatives, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid and polyacrylamide. It may contain a synthetic hydrophilic polymer such as a homopolymer or a copolymer.

From the viewpoint of ultra-rapid and low replenishment treatment, it is preferable to reduce the amount of the hydrophilic binder as much as possible to form a thin film. However, if the film is too thin, the pressure resistance deteriorates, and fogging deteriorates due to pressure.Therefore, a coating amount that satisfies both performances is required.In the present invention, the coating amount per one side of the hydrophilic binder is used. Is 1.5g
/ M ² or more and 2.5 g / m ² or less.

In the present invention, the amount of silver per side is preferably from 1.2 g / m ^{2 to} 1.8 g / m ² .
If it is less than 1.0 g / m ² , it is difficult to obtain an image quality such as sharpness and gradation, which is required for a photosensitive material, particularly for an X-ray photosensitive material. On the other hand, if it is 2.0 g / m ² or more, it is not possible to obtain ultra-rapid and low replenishment suitability.

In the present invention, the X-ray image forming unit is a unit in which the photosensitive material of the present invention is sandwiched from both sides by two fluorescent intensifying screens for imagewise exposing by X-ray irradiation.

When the silver halide photographic light-sensitive material of the present invention is applied to medical X-ray radiography, for example, a fluorescent light mainly composed of a phosphor which generates near-ultraviolet light or visible light upon exposure to penetrating radiation. An intensifying screen is used. This is brought into close contact with both surfaces of a light-sensitive material obtained by coating the emulsion of the present invention on both surfaces and exposed. Here, the penetrating radiation is a high-energy electromagnetic wave and means X-rays and γ-rays. In the present invention, preferable phosphors used for the fluorescent intensifying screen include the following.

Tungstate phosphors (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: T
b, 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 phosphors (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, LaOBr: Tb GdOBr: Tb Gd
OCL: Tb, etc.), thulium-activated rare earth oxyhalide-based phosphors (LaOBr: Tm, LaOCl: Tm)
Etc.), barium sulfate-based phosphor [BaSO ₄ : Pb, Ba
SO4: Eu ²⁺ , (Ba, Sr) SO ₄ : Eu ²⁺ etc.],
Bivalent eurobium-activated alkaline earth metal phosphate phosphor [(Ba ₂ PO ₄ ) ₂ : Eu ²⁺ , (Ba ₂ PO ₄ ) ₂ : Eu
²⁺ etc.] divalent eurobium-activated alkaline earth metal fluorohalide-based phosphor [BaFCl: Eu ²⁺ , BaFB
r: Eu ²⁺ , BaFCl: Eu ²⁺ , Tb, BaFBr:
Eu ²⁺ , Tb, BaF ₂ .BaCl.KCl: Eu ²⁺ ,
(Ba, Mg) F ₂ .BaCl.KCl: Eu ²⁺ etc.],
Iodide phosphors (CsI: Na, CsI: Tl, Na
I, KI: Tl, etc.), sulfide-based phosphors [ZnS: Ag
(Zn, Cd) S: Ag, (Zn, Cd) S: Cu,
(Zn, Cd) S: Cu. Al, etc.), a hafnium phosphate-based phosphor (HfP ₂ O ₇ : Cu, etc.), but the phosphor used in the present invention is not limited to these, and emits light in the visible or near ultraviolet region upon irradiation with radiation. Any phosphor can be used.

It is preferable that the fluorescent intensifying screen used in the present invention is filled with a phosphor in a gradient particle size structure. In particular, it is preferable to apply phosphor particles having a large particle diameter to the surface protective layer side and to apply phosphor particles having a small particle diameter to the support side. Those with a particle size of 10 to 30 μm
Is preferable.

Hereinafter, a preferred method for producing a fluorescent intensifying screen will be described.

Step of forming a phosphor sheet comprising a binder and a phosphor.

It is preferable that the phosphor sheet is mounted on a support, and the phosphor sheet is bonded to the support while being compressed at a temperature not lower than the softening temperature or the melting point of the binder.

The phosphor sheet serving as the phosphor layer of the fluorescent intensifying screen is prepared by applying a coating solution obtained by uniformly dispersing a phosphor in a binder solution onto a temporary support for forming a phosphor sheet, followed by drying. Then, it can be manufactured by peeling off from the temporary support. That is, first, a binder and phosphor particles are added to an appropriate organic solvent, and the mixture is stirred and mixed to prepare a coating solution in which the phosphor is uniformly dispersed in the binder.

The binder has a softening temperature or a melting point of 30.
A thermoplastic elastomer having a temperature of from 150C to 150C is used alone or together with another binder. Since the thermoplastic elastomer has elasticity at room temperature and becomes fluid when overheated, it is possible to prevent the phosphor from being damaged by the pressure at the time of compression. Examples of the thermoplastic elastomer include polystyrene, polyolefin, polyurethane, polyester, polyamide, polybutadiene, ethylene vinyl acetate, polyvinyl chloride, natural rubber, fluorine rubber, polyisoprene, chlorinated polyethylene, styrene-butadiene rubber, and silicon rubber. At least one type of thermoplastic elastomer selected from the group is exemplified. The mixing ratio of the thermoplastic resin in the binder is 10% by weight or more and 100% by weight or more.
The binder may be made up of as much thermoplastic elastomer as possible, in particular 100% by weight.

Examples of the solvent for preparing the coating solution include lower alcohols such as methanol, ethanol, n-propanol and n-butanol, hydrocarbons containing chlorine atoms such as methylene chloride and ethylene chloride, acetone, methyl ethyl ketone and methyl isobutyl ketone. Ketones, esters of lower fatty acids with lower alcohols such as methyl acetate, ethyl acetate and butyl acetate, ethers such as dioxane, ethylene glycol monoethyl ester and ethylene glycol monomethyl ester, and mixtures thereof.

The mixing ratio between the binder and the phosphor in the coating solution varies depending on the characteristics of the intended fluorescent intensifying screen, the kind of the phosphor, and the like. Generally, the mixing ratio between the binder and the phosphor is 1: 1.
It is selected from the range of 1 to 1: 100 (weight ratio), and particularly preferably selected from the range of 1: 8 to 1:40 (weight ratio).

In the coating solution, a dispersant for improving the dispersibility of the phosphor in the coating solution, or a binding agent between the binder and the phosphor in the formed phosphor layer is used. Various additives such as a plasticizer may be mixed.

Examples of dispersants include phthalic acid, stearic acid, caproic acid, lipophilic surfactants and the like.

Examples of the plasticizer include phosphoric esters such as triphenyl phosphate, tricresyl phosphate and diphenyl phosphate, phthalic esters such as diethyl phthalate and dimethoxyethyl phthalate, ethyl phthalylethyl glycolate, and butyl butyl butyl glycolate. And polyesters of polyethylene glycol and aliphatic dibasic acid, such as polyesters of triethylene glycol and adipic acid, polyesters of diethylene glycol and succinic acid, and the like.

The coating solution containing the phosphor and the binder prepared as described above is uniformly applied to the surface of the temporary support for forming a sheet to form a coating film of the coating solution.

[0098] This application can be performed by using, for example, a doctor blade, a roll coater, a knife coater, or the like.

As the temporary support, for example, those made of various materials such as glass, wool, cotton, paper, metal and the like can be used. What can be processed into is preferred. From this point, for example, cellulose acetate film, polyester film, polyethylene terephthalate film, polyamide film, polyimide film, triacetate film, plastic film such as polycarbonate film, metal sheet such as aluminum foil and aluminum alloy foil, general paper and photographic base paper Base paper for printing, such as coated paper or art paper, baryta paper, resin coated paper, paper sized with polysaccharide as described in Belgian Patent No. 784,615, titanium dioxide, etc. Pigmented paper containing pigments, and processed paper such as paper sized with polyvinyl alcohol are particularly preferred.

After a coating solution for forming a phosphor layer is applied on a temporary support and dried, the coating is peeled off from the temporary support to form a phosphor sheet to be a phosphor layer of a fluorescent intensifying screen. Therefore, it is preferable that a release agent is applied to the surface of the temporary support in advance so that the formed phosphor sheet is easily peeled from the temporary support.

A description will now be given. A sheet for setting the phosphor formed as described above is prepared. This support can be arbitrarily selected from the materials listed for the temporary support.

The fluorescent intensifying screen is provided with an undercoat layer for imparting adhesiveness by coating a polymer substance such as gelatin on the surface of the support in order to strengthen the bond between the support and the phosphor layer.
In order to improve image quality (sharpness, granularity), a light reflecting layer made of a light reflecting material such as titanium dioxide or a light absorbing layer made of a light absorbing material such as carbon black may be provided.

The fluorescent intensifying screen used in the present invention can also be provided with these various layers, and the structure thereof can be arbitrarily selected according to the desired purpose and application of the fluorescent intensifying screen.

The phosphor sheet obtained above is placed on a support, and the phosphor sheet is adhered to the support while being compressed at a temperature not lower than the softening temperature or the melting point of the binder.

As described above, by utilizing the method of pressing the fluorescent sheet on the phosphor sheet support without fixing it in advance, the sheet can be spread thinly, and not only can the phosphor be prevented from being damaged, but also the sheet can be fixed. It is possible to obtain a high phosphor filling rate even at the same pressure as compared with the case where the pressure is increased.

Examples of a compression apparatus used for the compression processing include generally known apparatuses such as a calender roll and a hot press. For example, the compression treatment using a calender roll is performed by placing the phosphor sheet obtained on a support and passing the phosphor sheet at a constant speed between rollers heated to a temperature higher than the softening temperature or melting point of the binder. The pressure during compression is 50 kg / cm ²
It is preferable that this is the case.

Usually, the fluorescent intensifying screen is provided with a transparent protective film for physically and chemically protecting the phosphor layer on the surface of the phosphor layer opposite to the side contacting the support. . Such a transparent protective film is preferably provided also for the fluorescent intensifying screen of the present invention. The thickness of the protective film is generally in the range of 0.1 to 20 μ.

The transparent protective layer is made of a cellulose derivative such as cellulose acetate or nitrocellulose, or a synthetic polymer such as polymethyl methacrylate, polyethylene terephthalate, polyvinyl butyral, polyvinyl formal, polycarbonate, polyvinyl acetate, or vinyl chloride / vinyl acetate copolymer. Is dissolved in an appropriate solvent, and a solution prepared by coating the solution on the surface of the phosphor layer can be formed.

Alternatively, a plastic sheet made of polyethylene terephthalate, polyethylene naphthalate, polyethylene, polyvinylidene chloride, polyamide, or the like, or a sheet for forming a protective film such as a transparent glass plate is separately prepared and is appropriately bonded to the surface of the phosphor layer. It can be formed by a method such as bonding using an agent.

In the present invention, as the protective layer used in the fluorescent intensifying screen, a film formed by a coating film containing a fluorine-based resin soluble in an organic solvent is particularly preferable. The fluorine-based resin refers to a polymer of an olefin containing fluorine (fluoroolefin) or a copolymer containing an olefin containing fluorine as a copolymer component. The film formed by the coating film of the fluorine-based resin may be cross-linked. The advantage of a protective film made of a fluorine-based resin is that dirt such as a plasticizer that comes out of a film or the like when coming into contact with another material or an X-ray film hardly penetrates into the protective film, so that the dirt can be easily removed by wiping or the like. There is.

When a fluorine-based resin soluble in an organic solvent was used as the material for forming the protective film, this resin was prepared by dissolving the resin in an appropriate solvent. That is, the protective film is formed by uniformly applying a coating liquid for a protective film forming material containing a fluorine-based resin soluble in an organic solvent to the surface of the phosphor layer using a doctor blade or the like, followed by drying. The formation of this protective film may be performed simultaneously with the formation of the phosphor by simultaneous multilayer coating.

The fluorine-based resin is a polymer of a fluorine-containing olefin (fluoroolefin) or a copolymer containing a fluorine-containing olefin as a copolymer component, such as polytetrafluoroethylene, polychlorotrifluoroethylene, or polyfluoroethylene. Examples include ethylene fluoride, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, and fluoroolein-vinyl ether copolymer.

The fluorine-based resin is generally insoluble in an organic solvent, but a copolymer containing a fluoroolefin as a copolymer component becomes soluble in an organic solvent by a structural unit other than the fluoroolefin to be copolymerized. A protective layer can be easily formed by applying a solution prepared by dissolving in a suitable solvent on the phosphor layer and drying. Examples of such a copolymer include a fluoroolefin-vinyl ether copolymer. Also, polytetrafluoroethylene and its modified products are soluble in a suitable fluorine-based organic solvent such as a perfluoro solvent, and thus are protected by coating in the same manner as the copolymer containing the above-mentioned fluoroolefin as a copolymer component. A film can be formed.

The protective film may contain a resin other than the fluorine-based resin, and may contain a cross-linking agent, a hardening agent, an anti-yellowing agent and the like. However, in order to sufficiently achieve the above object, the content of the fluorine-based resin in the protective film must be 30% by weight.
Or more, more preferably 50% by weight.
The content is most preferably 70% by weight or more.

Examples of the resin other than the fluorine resin contained in the protective film include polyurethane resin, polyacryl resin, cellulose derivative, polymethyl methacrylate, polyester, epoxy resin and the like.

Further, the protective film of the fluorescent intensifying screen used in the present invention may be formed from a coating film containing either a polysiloxane skeleton-containing oligomer or a perfluoroalkyl group-containing oligomer, or both.

The polysiloxane skeleton-containing oligomer has, for example, a dimethylpolysiloxane skeleton.
Preferably, it has at least one functional group, for example, a hydroxyl group, and has a molecular weight of 500 to 100,000.
Is preferably within the range. Especially when the molecular weight is 1000
It is preferably in the range of 100,000, and more preferably in the range of 3,000 to 10,000. Further, the oligomer containing a perfluoroalkyl group, such as a tetrafluoroethylene group, is preferably one containing at least one functional group, for example, a hydroxyl group in the molecule,
The molecular weight is preferably in the range of 500 to 100,000. In particular, the molecular weight is preferably in the range of 1,000 to 100,000, and more preferably in the range of 100 to 100,000.

If an oligomer containing a functional group is used, a crosslinking reaction occurs between the oligomer and the resin for forming the protective layer at the time of forming the protective film, and the oligomer is incorporated into the molecular structure of the film-forming resin. The oligomer is not removed from the protective film by long-term repeated use of the fluorescent intensifying screen or the operation of cleaning the surface of the protective film. Is advantageous. The oligomer is preferably contained in the protective film in an amount of 0.01 to 10% by weight, particularly preferably 0.1 to 2% by weight.

The protective layer may contain a perfluoroolefin resin powder or a silicon resin powder. As the perfluoroolefin resin powder or the silicon resin powder, those having an average particle diameter in the range of 0.1 to 10 μm are preferable, and particularly preferably the average particle diameter is 0.3 to 5 μm.
m. These perfluoroolefin resin powder or silicon resin powder is preferably contained in the protective film in an amount of 0.5 to 30% by weight, more preferably 2 to 20% by weight, based on the weight of the protective film. Preferably, it is most preferably in an amount of from 5 to 15% by weight.

The protective film of the fluorescent intensifying screen is preferably a transparent synthetic resin layer having a thickness of 5 μm or less applied on the phosphor layer. By using such a thin protective layer, the distance from the phosphor of the fluorescent intensifying screen to the silver halide emulsion is reduced, which contributes to the improvement of the sharpness of the obtained X-ray image.

The filling rate of the phosphor in the present invention is determined by peeling off the protective layer of the fluorescent intensifying screen, eluting the phosphor layer with methyl ethyl ketone, filtering, drying and drying using an electric furnace.
When the weight of the phosphor obtained by baking at 1 ° C. for 1 hour to remove the resin on the surface is Og, the thickness of the phosphor layer is Pcm, the screen area Qcm ² used for elution, and the phosphor density is Rg / cm ³ , Filling ratio = [O ÷ (P × Q × R)] × 100.

In the present invention, the intrinsic fluorescence is such that the X-ray energy in an X-ray generator corresponding to 2.2 mm of aluminum has an absorption of 45% or more, more preferably 50% or more, of the X-ray of 80 kVp. It is preferable to use a light-sensitive paper. The X-ray absorption of the fluorescent intensifying screen can be measured by the following method.

X-rays generated from a tungsten target tube operated at 80 kVp with a three-phase
mm through the aluminum plate and reach the fluorescent screen of the sample fixed at a position 200 cm from the tungsten anode of the target tube. Then, the amount of X-rays transmitted through the fluorescent screen is measured by the fluorescent screen. 50cm from the phosphor layer
Measurement is performed at a later position using an ionizing dosimeter to determine the amount of X-ray absorption. Note that, as a reference, the X-ray dose at the above-described measurement position measured without passing through the fluorescent intensifying screen can be used.

It is preferable that the thickness of the phosphor is 135 to 200 μm, and the filling rate of the phosphor at this time is 68% or more.

The silver halide photographic light-sensitive material of the present invention can be prepared, for example, by using RDNo. 17643 XX-XXI, pages 29-30,
Processing with a processing solution as described in 308119, pages XX to XXI, 1011 to 1012 can be performed.

As a developer for black-and-white photographic processing, dihydroxybenzenes (hydroquinone, etc.), 3-pyrazolidones (1-phenyl-3-pyrazolidone, etc.), aminophenols (N-methyl-aminophenol, etc.) and the like can be used. They can be used alone or in combination. In the developer, a preservative, an alkaline agent, a pH buffer, an antifoggant, a hardener, a development accelerator, a surfactant, an antifoaming agent, a color tone, a water softener, a dissolution aid, and a viscosity-imparting agent. Agents and the like can be used as needed.

The fixing solution contains a fixing agent such as thiosulfate and thiocyanate, and may further contain a water-soluble aluminum salt such as aluminum sulfate and potassium alum as a hardening agent. It may contain a regulator, a water softener and the like.

An automatic developing machine having a mechanism for supplying a solid processing agent to a processing tank, which is advantageous for processing the silver halide photographic light-sensitive material of the present invention, will be described. As the processing agent supply means, when the solid processing agent is a tablet,
No. 7783, No. 63-97522, Heihei 1-857
No. 32, etc., and in the case of granules or powders, see Japanese Utility Model Application Laid-Open Nos. 62-81964 and 63-84151.
And Japanese Patent Application Laid-Open Nos. 1-292375 and 63-105159 and 63-195345.
Reference can be made to a screw or a screw method described in the above item, but the present invention is not limited thereto. The place where the solid processing agent is charged is in the processing tank, but it is preferably in communication with the processing section for processing the photosensitive material, where the processing liquid is flowing between the processing section and the processing section. A preferred structure is one in which there is a constant processing solution circulation amount and the dissolved components move to the processing section. Further, it is preferable that the solid processing agent is introduced into a processing liquid whose temperature is controlled.

In the developer used in the processing method of the present invention, reductones are used as developing agents in addition to dihydroxybenzenes, aminophenols and pyrazolidones. As the pyrazolidones, those substituted at the 4-position are preferable since they have little water-soluble property or change with time of the solid processing agent itself.

In processing the silver halide photographic light-sensitive material of the present invention, it is preferable to include a compound represented by the following general formula (A) in the developing step because the processing property is improved.

[0131]

Embedded image

In the above formula (A), R ¹¹ and R ¹²
Each independently represents a hydroxy group, -OM ¹ (M ¹ represents an alkali metal atom or an ammonium group), an amino group (as a substituent, a carbon number of a methyl group, an ethyl group, an n-butyl group, a hydroxyethyl group, etc.) Including those having 1 to 10 alkyl groups), an acylamino group (acetylamino group,
Benzoylamino group, etc.), alkylsulfonylamino group (methanesulfonylamino group, etc.), arylsulfonylamino group (benzenesulfonylamino group, p-toluenesulfonylamino group, etc.), alkoxycarbonylamino group (methoxycarbonylamino group, etc.), mercapto Group,
Represents an alkylthio group (e.g., methylthio group, ethylthio group), preferably a hydroxy group, an amino group, an alkylsulfonylamino group, or an arylsulfonylamino group.
X is ^{-O -, - C (R 13} ) (R 14) -, - C (R 15)
=, - C (= O) -, - N (R 16) -, - N = , etc., preferably a carbon atom, an oxygen atom or a nitrogen atom, R ¹¹
And R ¹² constitute a 5-6 membered ring in cooperation with the two vinyl carbon and carbonyl carbon is substituted. Where R ¹³ -R
^{And 16} each independently has a hydrogen atom and a carbon number of 1 to 10 which may have a substituent (hydroxy group, carboxy group, sulfo group, etc.).
Represents an aryl group having 6 to 15 carbon atoms, a hydroxy group, and a carboxy group which may have a substituent (such as an alkyl group, a halogen atom, a hydroxy group, a carboxy group, and a sulfo group). A saturated or unsaturated condensed ring may be formed on the constituent 5- to 6-membered ring, and a dihydrofuranone ring, dihydropyrone ring, pyranone ring, cyclopentenone ring, cyclohexenone ring, pyrrolinone ring, pyrazolidone ring, pyridone And a azacyclohexenone ring, a uracil ring and the like, and preferably a dihydrofuranone ring, a cyclopentenone ring, a cyclohexenone ring, a pyrazolidone ring, an azacyclohexenone ring and a uracil ring.

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

[0134]

Embedded image

[0135]

Embedded image

[0136]

Embedded image

[0137]

Embedded image

The compound represented by formula (A) is
About 0.005 to 0.5 mol, preferably 0.02 to 0.4 mol per liter is used.

In the developer, an organic reducing agent can be used in addition to a sulfite as a preservative. In addition, a bisulfite adduct of a chelating agent or a hardener can be used. A silver sludge inhibitor, a cyclodextrin compound described in JP-A-1-124852, U.S. Pat. No. 4,269,929.
It is also preferable to add the amine compound described in (1).

It is necessary to use a buffer for the developer.
Sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borate), potassium borate, o-
Sodium hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-sulfo-
Examples thereof include sodium 2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).

Examples of the development accelerator include thioether compounds, p-phenylenediamine compounds, quaternary ammonium salts, p-aminophenols, amine compounds, polyalkylene oxides, other 1-phenyl-3-pyrazolidones, and hydrazine. , A mesoionic compound, an ionic compound, imidazoles and the like can be added as necessary.

As antifoggants, alkali metal halides such as potassium iodide and benzotriazole;
6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole,
Organic antifoggants such as 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine can be used.

Further, methylcellosolve,
Methanol, acetone, dimethylformamide, cyclodextrin compound, JP-B-47-33378, 4
The compounds described in JP-A No. 4-9509 can be used as an organic solvent for increasing the solubility of the developing agent. In addition, a stain inhibitor, an anti-sludge agent, and a multilayer effect promoter can also be used.

Fixing agents include fixing agents, chelating agents, pH
Known compounds such as buffering agents, hardeners, and preservatives can be used. For example, JP-A-4-242246, p.
Those described on pages 2-4 of -116322 can be used.

Prior to the treatment, it is preferable to add a starter, and it is preferable to add the starter after solidifying it. 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 silver halide photographic light-sensitive material of the present invention was prepared by using an automatic developing machine for the total processing time (dry to dry).
The treatment is preferably performed in 10 seconds to 30 seconds,
Even if it is processed in 5 seconds, it is preferably processed.

The time from when the tip of the photosensitive material to be processed is immersed in the developing tank liquid of the automatic developing machine to when it comes into contact with the fixing tank liquid in the next step is referred to as "development time". "Fixing time" refers to the time from contact with the washing tank solution (stabilizing solution) to the "fixing time", "washing time" refers to the time immersed in the washing tank solution, and "drying" refers to the time in the drying zone of the automatic processor. Time, the developing time is 3 to 1
5 seconds (further 2 to 10 seconds), developing temperature 25 to 50 ° C. (further 30 to 40 ° C.), fixing time 2 to 12 seconds (further 1 to 10 seconds)
10 seconds), fixing temperature 20-50 ° C. (further 30-40 ° C.)
℃), water washing (stabilization) time 3-15 seconds (further 4-8
Second), water washing (stabilization) temperature 0 to 50 ° C (further 15 to 4)
0 ° C), a drying time of 3 to 12 seconds (more preferably 2 to 8 seconds), and a drying temperature of 35 to 100 ° C (more preferably 40 to 80 ° C). The silver halide photographic light-sensitive material of the present invention is developed, fixed and washed (or stabilized), dried with a squeeze roller, and then dried.

In processing the silver halide photographic light-sensitive material of the present invention with an automatic developing machine, it is important to employ an automatic developing machine having a transport roller (heat roller) whose outer periphery is heated by a heat source in the drying step. Preferred from the point.
Further, the transport roller preferably has a heat source inside the roller.

In the process of processing the light-sensitive material of the present invention, the developing solution and the fixing solution are respectively replenished, and the replenishing amounts need to satisfy the following formula.

1 ≦ (replenishment amount / carry-out amount by photosensitive material) ≦ 7 If the above (replenishment amount / carry-out amount by photosensitive material) is less than 1, the processing solution in the processing tank continues to decrease. Not practical. Although there is no problem in performance even if it is larger than 5, it is not preferable from the viewpoint of reducing the processing waste liquid. Preferably it is in the range of 2-5.

In the silver halide photographic light-sensitive material of the present invention, the replenishment amounts of the developing solution and the fixing solution are 4 to 21 per m ² of the photographic material.
The processing can be reduced to 6 ml.

[0152]

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

Example 1 (Preparation of Hexagonal Tabular Seed Emulsion Em-1) Pure silver bromide hexagonal tabular seed emulsion Em-1 was prepared by the following method.

Solution A ₁ Ossein gelatin 60.2 g Distilled water 20.0 l HO (CH ₂ CH ₂ O) _n [CH (CH ₃ ) CH ₂ O] ₁₇ (CH ₂ CH ₂ O) _m H (n + m = 5 -7) solution D ₁ 1 to 3500ml with 10% methanol solution _{5.6ml KBr 26.8g 10% H 2 SO} 4 144ml solution B ₁ nitrate 1487.5g solution C ₁ KBr 1050 g of distilled water to 3500ml with distilled water. in 75N KBr aqueous solution following silver potential control amount 35 ° C., using a mixing and stirring machine described in JP-B-58-58288, 2 minutes by double jet precipitation of each 64.1ml of solution B ₁ and solution C ₁ to solution a ₁ And the nuclei were formed.

After stopping the addition of the solution B ₁ and the solution C ₁ ,
By taking 60 minutes to raise the temperature of the solution A ₁ to 60 ° C., by the simultaneous mixing method Solution B ₁ and solution C ₁ again, each 6
It was added at a flow rate of 8.5 ml / min for 50 minutes. During this time the silver potential - was controlled to be + 6 mV using solution D ₁ a (saturated silver measured with a silver ion selection electrode as a comparative electrode silver chloride electrode). After completion of the addition, the pH was adjusted to 6 with 3% KOH, and immediately, desalting and washing were performed to obtain a seed emulsion EM-A. The seed emulsion EM-A thus produced is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0 for 90% or more of the total projected area of the silver halide grains, and the average thickness of the hexagonal tabular grains. 0.07 μm, average diameter (converted to circle diameter) 0.5
μm, the coefficient of variation was found to be 25% by electron microscope observation.

(Preparation of Tabular Pure Silver Bromide Emulsion EM-1) A tabular pure silver bromide emulsion was prepared using the following four types of solutions.

Solution A ₂ ossein gelatin 29.4 g HO (CH ₂ CH ₂ O) _n [CH (CH ₃ ) CH ₂ O] ₁₇ (CH ₂ CH ₂ O) _m H (n + m = 5-7) 10% Methanol solution 1.25 ml Seed emulsion Em-1 2.65 mol equivalent Make up to 3000 ml with distilled water Solution B ₂ 3.50 N AgNO ₃ aqueous solution 1760 ml Solution C ₂ KBr 737 g Make up to 1760 ml with distilled water Solution D ₂ 1.75 N KBr aqueous solution The following silver potential control amount At 60 ° C., the entire amount of solution B ₂ and solution C ₂ was added to solution A ₂ by a simultaneous mixing method (double jet method) using a mixing stirrer described in JP-B-58-58288. Addition growth was performed for 110 minutes so that the flow rate at the end was three times the flow rate at the start of the addition.

[0158] During this time of the silver potential by using the solution D ₂ +40
It controlled so that it might be set to mV.

After completion of the addition, precipitation and desalting were performed using an aqueous solution of Demol N (manufactured by Kao Atlas) and an aqueous solution of magnesium sulfate in order to remove excess salts.

When about 3,000 of the resulting emulsions EM-1 were observed and measured by an electron microscope and analyzed for their shapes, they were hexagonal tabular grains having an average equivalent circle diameter of 0.59 μm and an average thickness of 0.17 μm. The coefficient of variation was 24%.

(Preparation of Tabular Silver Iodobromide Emulsion EM-2) In the above-mentioned method for preparing EM-1, 80% of the volume was adjusted so that the total silver iodide content was 1 mol% simultaneously with D2. Further, the following silver iodide fine particles were dissolved and added.

(Preparation of silver iodide fine particles) A6 ossein gelatin 100 g KI 8.5 g Make up to 2000 ml with distilled water B6 AgNO3 360 g Make up to 605 ml with distilled water C6 KI 352 g Make up with 605 ml with distilled water Solution A6 was placed in a reaction vessel. In addition, while maintaining the temperature at 40 ° C. and stirring, the solution B6 and the solution C6 were added at a constant speed over 30 minutes by the simultaneous mixing method. The pAg during the addition is the normal pAg
It was kept at 13.5 by control means. The formed silver iodide was a mixture of β-AgI and γ-AgI having an average grain size of 0.06 μm.

This emulsion is called a silver iodide fine grain emulsion.

(Preparation of Solid Fine Particle Dispersion of Spectral Sensitizing Dye) The following spectral sensitizing dyes (A) and (B) were added to water previously adjusted to 27 ° C. at a ratio of 100: 1, and a high-speed stirrer (dissolver) was added. ) At 3,500 rpm for 30 to 120 minutes to obtain a solid fine particle dispersion of the spectral sensitizing dye. At this time, the sensitizing dye (A) was adjusted to have a concentration of 2%.

Sensitizing dye (A): 5,5'-di-chloro-
9-ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine-sodium salt anhydride Sensitizing dye (B): 5,5'-di- (butoxycarbonyl) -1,1'-diethyl -3,3'-Di- (4-sulfobutyl) benzimidazolocarbocyanine-sodium salt anhydride (Selenium sensitization) The above emulsions EM-1 and EM-2 were subjected to spectral sensitization and chemical sensitization by the following method. By performing this, chemically sensitized emulsions EM-A and EM-B were obtained.

After the emulsion was heated to 50 ° C., the above solid fine particle dispersion was added so that the sensitizing dye (A) was 460 mg per mol of silver, and ammonium thiocyanate was added to the emulsion at 7.0 mol per silver. × 10 ^-4 mol, and potassium chloroaurate, sodium thiosulfate and triphenylphosphine selenide were added in an amount of 3.0 × 10 ^-6 mol per mol of silver, and the mixture was optimally subjected to chemical ripening. After adding the fine grain emulsion in an amount of 3 × 10 ^-3 mol / Ag mol, 4-hydroxy-
6-methyl-1,3,3a, 7-tetrazaindene (T
AI) stabilized at 3 × 10 ^-2 mol.

(Synthesis example of colloidal tin oxide sol dispersion solution) 65 g of stannic chloride hydrate was dissolved in 2000 ml of an aqueous solution to obtain a homogeneous solution. Then, this was boiled to obtain a coprecipitate. The resulting precipitate is removed by decantation, and the precipitate is washed with distilled water many times. Silver nitrate is dropped into distilled water from which the precipitate has been washed to confirm that there is no reaction of chloride ions. This precipitate is added to 1000 ml of distilled water and dispersed, and the total amount is made 2000 ml. 30% more
When 40 ml of ammonia water is added and heated in a water bath, S
An nO ₂ sol solution is formed. When used as a coating solution, the sol solution is concentrated to about 8% while blowing ammonia into the sol solution. Regarding the volume resistivity of the particles contained in this sol solution, a thin film was formed on silica glass using the sol solution, and the value measured by the four probe method was defined as the volume resistivity of the particles. The measured volume resistivity was 3.4 × 10 ⁴ Ωcm.

(Support) Polyethylene terephthalate film base for X-rays with a thickness of 175 μm and colored blue at a concentration of 0.170 (Preparation of tin oxide sol-subtracted support) A 0.5 kV · A · After performing a corona discharge treatment at a rate of min / m ^2, the undercoat latex liquid shown in the following (L-2) was dried so that the film thickness after drying was 0.2 μm.
-1) was sequentially applied so that the film thickness after drying became 0.053 μm, and dried at 123 ° C. for 2 minutes.

[0169]

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(L-2) n-butyl acrylate 10% by weight, t-butyl acrylate 35% by weight, styrene 2
A copolymer latex solution containing 7% by weight and 28% by weight of 2-hydroxyethyl acrylate (solid content: 30%).

In the lower layer on the other side of the same base, the SnO ₂ sol synthesized in (Synthesis Example), the above (L-2) solution and the following (L-4) solution were mixed at a volume ratio of 35:15:50. The mixed solution was applied to the upper layer (L) so that the film thickness after drying was 0.20 μm and the amount of the sol component applied was 400 mg / m ^2.
-1) and the following (L-3) solution were mixed at a volume ratio of 70:30, and a coating solution was simultaneously applied so as to have a dried film thickness of 0.053 μm, and dried at 120 ° C. for 1 minute. Before coating, a corona discharge treatment of 0.5 kV · A · min / m ² was performed. This support is referred to as support 2.

(L-3) Dimethyl terephthalate 34.0
2 parts by weight, 25.52 parts by weight of dimethyl isophthalate, 5
-Sulfoisophthalic acid dimethyl sodium salt 12.97
Parts by weight, 47.85 parts by weight of ethylene glycol, 1,4
Cyclohexanedimethanol 18.95 parts by weight, calcium acetate monohydrate 0.065 parts by weight, manganese acetate tetrahydrate 0.022 parts by weight under a nitrogen stream 170 to 22 parts
After transesterification while distilling off methanol at 0 ° C., 0.04 parts by weight of trimethyl phosphate, 0.04 parts by weight of antimony trioxide as a polycondensation catalyst and 15.08 parts by weight of 1,4-cyclohexanedicarboxylic acid. Add part, 2
At a reaction temperature of 20 to 235 ° C., almost the theoretical amount of water was distilled off to carry out esterification. Thereafter, the pressure inside the reaction system was further reduced and the temperature was raised over about 1 hour, and finally polycondensation was performed at 280 ° C. and 1 mmHg or less for about 1 hour to obtain a polyester polymer.
(Intrinsic viscosity 0.35) 30 g of styrene, 30 g of butyl methacrylate, 20 g of glycidyl methacrylate, 20 g of acrylamide and 1.0 g of ammonium persulfate were added to 7300 g of an aqueous solution of the obtained polyester polymer, and reacted at 80 ° C. for 5 hours. To adjust the solids content to 10% by weight,
A coating solution was obtained.

(L-4) A copolymer latex liquid containing 40% by weight of n-butyl acrylate, 20% by weight of styrene, and 40% by weight of glycidyl methacrylate.

(Synthesis of Composite Latex FG) 1000 m
A four-necked flask equipped with a stirrer, a thermometer, a dropping funnel, a nitrogen inlet tube, and a reflux condenser, while introducing nitrogen gas for deoxygenation, 360 cc of distilled water and 30 wt% colloidal silica dispersion. Add 126g and the internal temperature is 8
Heated to 0 ° C. 1.3 g of the following surfactant was added, and 0.023 g of ammonium persulfate was used as an initiator.
Was added, and then 8.0 g of vinyl pivalate and 4.6 g of vinyl acetate were added simultaneously, followed by reaction for 4 hours. Thereafter, the mixture was cooled and adjusted to pH 6 with a sodium hydroxide solution to obtain a composite latex FG.

[0175]

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(Preparation of the light-sensitive material of the present invention) The following transverse light blocking layer, emulsion layer coating solution and protective layer coating solution were coated on both sides of the supports 1 and 2 so that the following coating amounts were obtained. Simultaneous multi-layer coating and drying.

First layer (transverse light blocking layer) Gelatin 0.2 g / m ² Solid fine particle dispersion dye (AH) 20 mg / 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) Emulsion EM-A obtained above To -D, the following various additives were added.

Gelatin (including those in emulsions EM-AD) 1.2 g / m ² Compound (G) 0.5 mg / m ² 2,6-bis (hydroxyamino) -4-diethylamino-1,3 5,5-triazine 5 mg / m ² t-butyl-catechol 5 mg / m ² polyvinylpyrrolidone (molecular weight 10,000) 20 mg / m ² styrene-maleic anhydride copolymer 80 mg / m ² sodium polystyrene sulfonate 80 mg / m ² tri Methylol propane 350 mg / m ² Diethylene glycol 50 mg / m ² Nitrophenyl-triphenyl-phosphonium chloride 1 mg / m ² Ammonium 1,3-dihydroxybenzene-4-sulfonate 50 mg / m ² 2-Mercaptobenzimidazole-5-sodium sulfonate 5 mg / m ² compound (H) 0.5 m _{^{/ M 2 n-C 4 H}} 9 OCH 2 CH (OH) CH 2 N (CH 2 COOH) 2 20mg / m 2 Compound (M) 5mg / m ² Compound (N) 5mg / m ² Colloidal silica 0.5 g / m ² latex (L) 0.5 g / m ² Composite latex (FG) 1.0 g / m ² Dextran (molecular weight about 100,000) 0.5 g / m ² Third layer (lower layer of protective layer) Gelatin 0.3 g / m ² dioctyl phthalate 0.2 g / m ² 4th layer (protective layer upper layer) Gelatin 0.3 g / m ² Matting agent composed of polymethyl methacrylate 27 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 latex (L) 0.2g / m ² composite latex (FG) 0.2g / m ² compound (SI) 5 mg / m ² Compound (I) 30mg / m ² Compound (S-1) 7mg / m 2 hardener (B) 2mg / m ² Compound ^{(S-2) 2mg / m} 2

[0179]

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[0180]

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[0181]

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The coating amount of the material was for one side, and the coating amount was adjusted so that the coating amount was 1.5 g / m ² per side. To the second layer of the emulsion layer, the compounds of the present invention were added in the types and amounts shown in Table 2.

(Production of Fluorescent Intensifying Screen 1) Phosphor Gd ₂ O ₂ S: Tb (average particle size: 1.8 μm) 200 g Combined polyurethane thermoplastic elastomer Demolac TPKL-5-262 5 solid content 40% [ Sumitomo Bayer Urethane Co., Ltd.] 20 g Nitrocellulose (digestion degree: 11.5%) 2 g Add a methyl ethyl ketone solvent to the above and disperse it with a propeller type mixer to prepare a coating solution for forming a phosphor layer having a viscosity of 25 ps (25 ° C.). did. (Binder / Phosphor ratio = 1/2)
2) Separately, 90 g of a soft acrylic resin solid content and 50 g of nitrocellulose were added and dispersed and mixed as a coating liquid for forming an undercoat layer with methyl ethyl ketone to obtain a viscosity of 3 to 6 ps (25 g).
C).

A thickness of 250 μm into which titanium dioxide has been kneaded.
Polyethylene terephthalate base (support) was placed horizontally on a glass plate, and the coating solution for forming an undercoat layer was uniformly coated on the support using a doctor blade.
The coating film was dried by gradually raising the temperature from 100 ° C. to 100 ° C. to form an undercoat layer on the support. The thickness of the coating film is 15μ
m.

The above-mentioned coating solution for forming a phosphor layer was uniformly coated thereon with a doctor blade to a thickness of 240 μm and dried, followed by compression. Compression was performed using a calender roll at a pressure of 800 kgw / cm ² and a temperature of 80 ° C. After this compression, Example 1 of JP-A-6-75097 was used.
A transparent protective film having a thickness of 3 μm was formed by the method described above, and a fluorescent intensifying screen 1 was manufactured.

(Production of Fluorescent Intensifying Screen 2) In the production of the fluorescent intensifying screen 1, the same procedure as in the fluorescent intensifying screen 1 was applied except that the thickness of the coating solution for forming the phosphor layer was applied at 150 μm and no compression was performed at all. Thus, a fluorescent intensifying screen 2 comprising a support, an undercoat layer, a phosphor layer, and a transparent protective film was produced.

(Measurement of Characteristics of Fluorescent Intensifying Screen) (1) Measurement of Sensitivity A fluorescent intensifying screen to be measured was placed in front of an X-ray source on an MRE single-sided silver halide photographic material manufactured by Eastman Kodak Company. A photosensitive material and then a fluorescent intensifying screen are placed in contact with each other, and the amount of X-ray exposure is changed by the distance method.
Step exposure was performed with a width of 15 mm. The exposed silver halide photographic light-sensitive material was subjected to development processing by the method described below for the method described in "Measurement of characteristics of silver halide photographic light-sensitive material" to obtain a measurement sample.

For the measurement sample, the concentration was measured with visible light to obtain a characteristic curve. The sensitivity was represented by the reciprocal of the X-ray exposure amount to obtain Dmin + density of 1.0, and was represented by a relative sensitivity with the fluorescent intensifying screen 1 being 100 (reference value). The results are shown in Table 2.

(2) Measurement of X-ray absorption The X-rays generated from a tungsten target tube having a thickness of 2.2 mm corresponding to 2.2 mm of aluminum were subjected to intrinsic filtration operating at 80 kVp with three-phase power supply, and an aluminum plate having a thickness of 3 mm was measured. Through the tungsten anode of the target tube
To reach the sample fluorescent screen fixed at the position of 00 cm,
Then, the X-ray dose transmitted through the intensifying screen was measured at a position 50 cm behind the phosphor layer of the fluorescent intensifying screen using an ionizing dosimeter, and the amount of X-ray absorption was determined. As a reference, X at the above measurement position measured without passing through a fluorescent intensifying screen was used.
Dose was used.

Table 2 shows the measured values of the X-ray absorption of each of the obtained fluorescent intensifying screens.

[0191]

[Table 2]

(Preparation of tablet for development replenishment) A tablet for development replenishment was prepared according to the following operations (A) and (B).

Operation (A) 12,500 g of sodium erythorbate as a developing agent is ground in a commercially available bantam mill until the average particle diameter becomes 10 μm. To this fine powder, 2,000 g of sodium sulfite, 2700 g of dimazone S (1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone), 1250 g of DTPA (pentasodium diethylenetriaminepentaacetate),
-Methylbenzotriazole 12.5 g, 1-phenyl-5-mercaptotetrazole 4 g, N-acetyl-
Add 60 g of D, L-penicillamine, mix in a mill for 30 minutes, and in a commercial stirring granulator at room temperature for about 10 minutes.
After granulation by adding ml of water, the granules are dried in a fluid bed dryer at 40 ° C. for 2 hours to remove almost completely the moisture of the granules. 1670 g of polyethylene glycol # 6000 was added to the granules thus prepared,
After 1670 g of mannitol was uniformly mixed for 10 minutes using a mixer in a room conditioned at 25 ° C. and 40% RH or less, the resulting mixture was converted into a tough press modified by a Kikusui Seisakusho Co., Ltd. Tough Press Collect 1527HU. A tableting machine was used to set the filling amount per tablet to 8.77 g and compression tableting was performed.
Each tablet A for development replenishment was prepared.

Operation (B) 4000 g of potassium carbonate, 2100 g of mannitol, and 2100 g of polyethylene glycol # 6000 are pulverized and granulated in the same manner as in the operation (A). The amount of water added is 30.0
ml, and after granulation, dried at 50 ° C. for 30 minutes to remove almost completely the moisture of the granulated material. The mixture thus obtained was filled with the tableting machine described above in a filling amount per tablet of 3.2.
The tablet was compressed to 8 g and compression tableting was performed to prepare 2500 tablets B for replenishment for development.

(Preparation of Fixing Replenishment Tablet) Next, a fixing replenishment tablet was prepared by the following operation.

Operation (C) Ammonium thiosulfate / sodium thiosulfate (70/3
0 weight ratio) 14000 g, sodium sulfite 1500 g
Is ground in the same manner as in (A), and then uniformly mixed with a commercially available mixer. The amount of water to be added is 500 ml, and after granulation, the granulated material is dried at 60 ° C. for 30 minutes to almost completely remove water from the granulated material. 4 g of sodium N-lauroylalanine was added to the granules thus prepared, and the mixture was added at 25 ° C. and 40%
Mix for 3 minutes using a mixer in a room humidified below RH. Next, the obtained mixture was subjected to compression tableting using the tableting machine described above, with the filling amount per tablet being set to 6.202 g.
500 fixing replenishing tablets C were prepared.

Operation (D) Boric acid 1000 g, aluminum sulfate / 18-hydrate 150
0 g, sodium hydrogen acetate (3,000 g of glacial acetic acid and sodium acetate mixed and dried), tartaric acid 200
g is ground and granulated in the same manner as in the operation (A). The amount of water to be added is 100 ml, and after granulation, it is dried at 50 ° C. for 30 minutes to almost completely remove water from the granulated material. 4 g of sodium N-lauroylalanine was added to the thus-prepared product, and after mixing for 3 minutes, the obtained mixture was compressed to a filling amount of 4.5562 g per tablet using the above-mentioned tableting machine. Tableting was performed to prepare 1250 fixing replenishing tablets D.

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

At the start of the processing of the developing solution (start of running), a solution prepared by adding 330 ml of a starter to 16.5 liters of a developing solution prepared by diluting 434 each of the A agent and the B agent in the tablet for replenishment with dilution water was started. The processing was started by filling the developing tank with the liquid. The pH of the developer to which the starter was added was 10.45.

The fixing tank was filled with 11.0 liters of a fixing solution prepared by diluting a fixing replenishing tablet prepared by diluting water with 298 g of the C agent and 149 g of the D agent with diluting water.

During the running, the photosensitive material was added to the developing solution at 0.1.
62m ² per the A, B agent each four and water 150ml
The addition was performed. When each of the agents A and B was dissolved in 20 ml of water, the pH was 10.70. Four fixing agents, two D agents and 150 ml of water were added to the fixing solution 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.

<Evaluation> The obtained film sample was sandwiched between the fluorescent intensifying screens 1 and irradiated with X-rays through a penetrometer type B (manufactured by Konica Medical Co., Ltd.).
701 (manufactured by Konica Corporation) was equipped with a charging member for the solid processing agent, and the solid processing agent was used for processing.

<Evaluation of Rapid Processing Property> Sensitometry and storage stability over time (raw storage property) were evaluated by treating the entire processing time for 30 seconds as described below. The relationship between the amount of the replenisher of the processing solution / the amount taken out by the photosensitive material was the amount shown in Table 4 for both the developing solution and the fixing solution. The relative sensitivities in the table indicate the sample numbers. This is a relative value when the reciprocal of the X-ray exposure required to obtain a density of 1 + the density of 1.0 + 100 is taken as 100.

<Evaluation of Raw Preservation> Each of the obtained samples was stored under the following conditions, and the same treatment as in the evaluation of sensitometry was performed to evaluate the raw preservability.

The value of (fogging under condition B)-(fogging under condition A) was taken as the evaluation value of storability, and the smaller the value, the better the storability.

Condition A: Stored at 23 ° C. and 55% RH for 4 days Condition B: Stored at 50 ° C. and 55% RH for 4 days Developing time: 8 seconds Fixing time: 6.2 seconds Rinse time: 4 seconds Rinse Drying time (squeeze): 3.2 seconds Drying time: 8.6 seconds Total processing time: 30 seconds The obtained results are shown in Tables 3 and 4 below.

[0207]

[Table 3]

[0208]

[Table 4]

As can be seen from the table, the sample of the present invention has a D
m (maximum density), excellent sensitivity, and little increase in fog even when left for 4 days under severe conditions, indicating that the storage stability with time is excellent.

Table 5 shows the results obtained by using the same film sample and changing the amount of replenisher as shown in Table 5.

However, the processing conditions at this time were as follows.

Development time: 12 seconds Fixing time: 9.3 seconds Washing time: 6 seconds Between washing and drying (squeeze): 4.8 seconds Drying time: 12.9 seconds Total processing time: 45 seconds Similarly, for sample no. The relative values are shown with 1 as 100.

[0213]

[Table 5]

As can be seen from Table 5, the sample of the present invention shows little sensitivity deterioration even in the low replenishment process.

[0215]

According to the present invention, a silver halide photographic light-sensitive material which has little deterioration in sensitivity and maximum density and has excellent storage stability over time can be obtained even when the replenishment process is performed quickly and with low replenishment.

──────────────────────────────────────────────────の Continued on front page (51) Int.Cl. ⁶ Identification code FI G03C 5/26 520 G03C 5/26 520 5/29 5/29 G21K 4/00 G21K 4/00 A

Claims (11)

[Claims] In a silver halide photographic material having a hydrophilic colloid layer including at least one silver halide emulsion layer on a support, a solubility product is contained in at least one of the hydrophilic colloid layers. It contains at least one compound which forms a silver complex smaller than silver bromide, and contains thiocyanate ions in an amount of 1 × 10 ⁻⁵ mol to 1 × 1 per mol of silver.
0 ^-3 mol silver halide photographic material characterized by containing. 2. The method according to claim 1, wherein at least one compound forming a silver complex having a solubility product smaller than silver bromide is added in an amount of 1 × per mole of silver.
2. The silver halide photographic material according to claim 1, wherein the silver halide photographic material is contained in an amount of from 10 ^-4 mol to 1 * 10 ^-2 mol. 3. The method according to claim 1, wherein the silver halide grains in the silver halide emulsion layer are located at any position of 70 to 100% of the volume particle size.
Contains silver iodide of 3 mol% to 15 mol%, and the silver iodide content of the whole silver halide grain is 0.3 mol% to 5 mol%
3. The silver halide photographic light-sensitive material according to claim 1 or 2, wherein 4. The compound according to claim 1, wherein the compound forming a silver complex having a solubility product smaller than that of silver bromide is a compound represented by the following general formula (1) or (2). A silver halide photographic material according to any one of the preceding claims. R ^1- (S) _n -R ^{2 wherein} R ¹ and R ² may be the same or different, and each represents a substituted or unsubstituted aliphatic group, aromatic group, or heterocyclic group. And R ¹ and R ² may combine with each other to form a substituted or unsubstituted ring. n represents an integer of 2 to 6. In the general formula (2) R ³ —S (M) _X , R ³ represents an aliphatic group or an aromatic group substituted with a water-soluble group,
Represents a heterocyclic group or a cycloalkenyl group, and represents S (M) _X
Represents a group that can be adsorbed on silver halide, M represents a hydrogen atom,
X represents 1 or 0, and represents an alkali metal atom or a cation.
And when X is 0, it is represented by R ³ = S. 5. The method according to claim 1, wherein the silver halide grains contained in the silver halide emulsion layer are subjected to at least one sensitization selected from reduction sensitization, selenium sensitization and tellurium sensitization in any step of emulsion production. Claim 1 characterized by being given
5. The silver halide photographic light-sensitive material according to any one of 4. 6. An X-ray image forming unit comprising the silver halide photographic light-sensitive material according to claim 1 and a surface having an emulsion layer and a fluorescent surface of a fluorescent intensifying screen in close contact with each other. . 7. The fluorescent intensifying screen according to claim 6, which has an absorption amount of 45% or more with respect to X-rays having an X-ray energy of 80 kVp, a phosphor filling rate of 68% or more, and a phosphor thickness. Is 135 to 200 μm, and X is measured using the fluorescent intensifying screen.
An X-ray image forming method, wherein imagewise exposure is performed by irradiating a line. 8. A processing method of a silver halide photographic light-sensitive material, wherein the silver halide photographic light-sensitive material according to claim 1 is processed by an automatic developing machine including a developing step. . 9. The method for processing a silver halide photographic material according to claim 8, wherein the automatic developing machine has a mechanism for supplying a solid processing agent to a processing tank. 10. The method for processing a silver halide photographic light-sensitive material according to claim 8, wherein the replenisher amount of the developing solution or the fixing solution is represented by the following formula. 1 ≦ amount of replenisher / amount taken out by photosensitive material ≦ 7 11. A processing time required for all processing steps (Dry
The method for processing a silver halide photographic material according to any one of claims 8 to 10, wherein (to Dry) is 10 seconds to 30 seconds.