JPH1138549A - Silver halide photographic sensitive material, x-ray image forming unit, x-ray image forming method and processing method for silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive material capable of rapid processing, giving a silver image excellent in color tone and less liable to contaminate a fluorescent intensifying paper and a developing soln. and to provide an image forming method using the photosensitive material and an image forming unit. SOLUTION: The silver halide photographic sensitive material has a silver halide emulsion layer and a hydrophilic colloidal layer on the substrate and contains a sulfur-contg. compd. having a water-soluble group in the silver halide emulsion layer and a leuco compd. forming a blue dye by reaction with the oxidized body of a developing agent in at least one of the hydrophilic colloidal layer and the silver halide emulsion layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel leuco dye, a silver halide photographic material (hereinafter, also simply referred to as a "photosensitive material"), an image forming unit, an image forming method and a processing method. The present invention relates to a black-and-white light-sensitive material having excellent storage stability over time and a cool black tone of a silver image, an image forming unit, an image forming method and a processing method thereof.

[0002]

2. Description of the Related Art In recent years, in the development of photosensitive materials, it has been required to reduce the processing time and the amount of waste liquid accompanying the processing.

In order to shorten the processing time, it is considered to be advantageous to use a silver chlorobromide or silver chloride emulsion having higher solubility than a silver iodobromide emulsion and to make silver halide grains finer and flatter. ing.

In order to reduce the amount of processing waste liquid, it is necessary to improve the developability. Therefore, silver halide grains having a high covering power and capable of obtaining a high density with a small amount of silver are desirable. It is known that tabular grains are suitable from the viewpoint of sharpness, color sensitization efficiency and the like.

However, when the grain size and grain thickness of the silver halide grains are reduced, the light scattering of the blue light component by the silver formed by the development processing is increased and the light becomes strongly yellowish, so that the silver image becomes yellowish. Result.

This phenomenon occurs when a fine grain emulsion (for example, an average grain size of 0.4 μm or less) or a tabular grain having a small grain thickness (for example, a grain thickness of 0.4 μm or less) is used as a silver halide emulsion. In particular, it is known that when the content of silver iodide is reduced, or when the content of silver chloride is increased, a yellowish tint is likely to occur.

Conventionally, many studies have been reported on techniques for improving the color tone of silver images from the light-sensitive material and developing solution side. For example, a specific mercapto compound is well known as a typical color tone agent. . More recently, there has been proposed a technique disclosed in, for example, JP-A-5-165147, in which a specific dye is dissolved in a water-insoluble high-boiling organic solvent, dispersed in a fine size in a water solvent, and contained in a photosensitive material. However, depending on the storage conditions before exposure, the sensitivity fluctuated. Particularly, in the case of a medical X-ray photosensitive material, there is a problem that the fluorescent intensifying screen which is brought into contact with the photosensitive material at the time of exposure is stained. In addition, this technique also has a disadvantage that the fog density increases because the same amount of dye is contained in the unexposed portion as in the exposed portion. In order to solve this drawback, Japanese Patent Application Laid-Open No. 3-157645 proposes a technique in which a dye image corresponding to silver development is formed by a diffusion-resistant compound which releases a diffusible dye by the action of silver ions while forming a silver image. However, the effect of improving the blackness of the silver image and the effect of reducing fog were insufficient. Further, JP-A-3-153
No. 234 proposes a technique using a leuco dye which gives a blue image corresponding to a silver image. Although the contamination of the developer and the occurrence of stains are suppressed by this technique, the blue dye formed from the leuco dye described in the patent has a long wavelength and a greenish tint, so that the silver image is black. The effect of the degree improvement was insufficient. Further, the leuco dye remaining in the unexposed area of the processed photographic material is liable to develop color with the passage of time, and has a drawback that fog is increased.

On the other hand, when the leuco compound is added to the light-sensitive material, the leuco compound develops color during storage before the development processing, causing a problem that the fog density increases.
Up to now, no effective means for improving this has been reported.

[0009]

SUMMARY OF THE INVENTION Accordingly, a first object of the present invention is to provide a novel leuco dye. A second object of the present invention is to provide a photosensitive material which can be rapidly processed and has a neutral black or cool black color tone of a silver image, an image forming method thereof, and a processing method thereof. A third object of the present invention is to provide a photosensitive material which does not easily contaminate a fluorescent intensifying screen and a developing solution, an image forming method thereof and a processing method thereof. A fourth object of the present invention is to provide a light-sensitive material in which photographic performance does not fluctuate with time, an image forming method thereof, and a processing method thereof.

[0010]

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

1. A silver halide photographic light-sensitive material having a silver halide emulsion layer and a hydrophilic colloid layer on a support, wherein the silver halide emulsion layer contains a sulfur-containing compound having a water-soluble group, and the hydrophilic colloid layer and And / or a silver halide photographic material characterized in that at least one layer selected from the silver halide emulsion layers contains a leuco compound which reacts with an oxidized form of a developing agent to form a blue dye.

2. The sulfur compound having a water-soluble group,
2. The silver halide photographic material as described in 1, wherein the material is a compound represented by the following general formula (1) or (2). In the formula (1), R ^1- (S) _n -R ² , wherein R ¹ and R ² each represent a substituted or unsubstituted aliphatic group, aromatic group or heterocyclic group, and R ¹ and R ² represent They may combine with each other to form a substituted or unsubstituted ring, and R ¹ and R ² may be the same or different, and n represents an integer of 2 or more and 6 or less.

Formula (2) R ³ —S (M) _{x In the} formula, 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,
Represents an alkali metal atom or a cationic group, and x is 1 or 0
When x is 0, the general formula (2) is R ³ = S.

3. 2. The silver halide photographic material according to 1, wherein the leuco compound is a compound represented by the following general formulas (3) to (6).

[0015]

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Wherein W is -NR ₁ R ₂ , -OH or-
Represents OZ, R ₁ and R ₂ represent an alkyl group or an aryl group, respectively, and Z represents an alkali metal ion or a quaternary ammonium ion. R ₃ represents a hydrogen atom, a halogen atom or a monovalent substituent, and n represents an integer of 1 to 3. Z ₁ and Z ₂ are each a nitrogen atom or ＣC (R
₃ ) represents-. X represents an atomic group necessary for forming a 5- to 6-membered aromatic heterocycle together with Z ₁ , Z ₂ and carbon atoms adjacent thereto. R ₄ represents a hydrogen atom, an acyl group, a sulfonyl group, a carbamoyl group, a sulfo group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. R represents an aliphatic group or an aromatic group. p
Represents an integer of 1 to 2. CP1 represents the following groups. ]

[0017]

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[0018]

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[Wherein, R _{5 to} R ₈ each represent a hydrogen atom, a halogen atom or a substituent capable of substituting on a benzene ring. R ₅ and R ₆ and R ₇ and R ₈ are bonded to each other to form 5 to 7;
A member ring may be formed. R ₉ has the same meaning as R ₄ . R ₁₀
And R ₁₁ each represents an alkyl group, an aryl group or a heterocyclic group. R ₁₂ has the same meaning as R ₄ . R ₁₃ and R ₁₄ have the same meaning as R ₁₀ and R ₁₁ . R ₁₅ has the same meaning as R ₁₂ . R ₁₆ represents an alkyl group, an aryl group, a sulfonyl group, a trifluoromethyl group, a carboxy group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group or a cyano group. R ₁₇ has the same meaning as R ₄ . R ₁₈ has the same meaning as R ₃ , and m represents an integer of 1 to 3. Y1 represents an atomic group necessary for constructing a 5- or 6-membered monocyclic or condensed nitrogen-containing heterocyclic ring together with two nitrogen atoms. R ₁₉ and R ₂₀ represent an alkyl group or an aryl group. R ₂₁ has the same meaning as R ₄ . R ₂₂ and R ₂₃ are R
It is synonymous with ₁₉ and R _20. R ₂₄ has the same meaning as R ₂₁ .
R ₂₅ , R ₂₇ and R ₂₈ represent a hydrogen atom or a substituent.
R ₂₆ has the same meaning as R ₄ . R ₂₉ , R ₃₁ and R ₃₂ have the same meanings as R ₂₅ , R ₂₇ and R ₂₈ . R ₃₀ has the same meaning as R ₂₆ . R ₃₄ , R ₃₅ and R ₃₆ are R ₂₅ , R ₂₇ and R ₂₈
Is synonymous with R ₃₃ has the same meaning as R ₂₆ . R ₃₈ , R ₃₉ and R ₄₀ have the same meaning as R ₂₅ , R ₂₇ and R ₂₈ . R ₃₇ has the same meaning as R ₂₆ . R ₄₁ , R ₄₂ and R ₄₃ are R ₂₅ , R ₂₇
And R ₂₈ have the same meanings. R ₄₄ has the same meaning as R ₂₆ . ★
Represents a bonding point between CP1 and another partial structure in the general formula (3). ]

[0020]

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[Wherein R ₁ , R ₂ , R ₃ , R ₄ , CP 1,
n, R and p represent R ₁ , R ₂ ,
It has the same meaning as R ₃ , R ₄ , CP 1, n, R and p. ]

[0022]

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Wherein R ₃ , n, R ₄ , W, X, Z ₁ ,
Z ₂ and CP1 represent R ₃ , n, R in the general formula (3).
₄ , synonymous with W, X, Z ₁ , Z ₂ and CP1. ]

[0024]

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[Wherein R ₁ , R ₂ , R ₃ , R ₄ , CP 1 and n represent R ₁ , R ₂ , R ₃ , R ₄ , CP in the general formula (3)
Synonymous with 1 and n. ] 4. The silver halide grains contained in the silver halide emulsion layer are tabular grains having a main plane composed of two parallel (100) planes, and have a silver chloride content of 10 mol% or more. 4. The silver halide photographic light-sensitive material as described in any one of 1 to 3 above.

[5] Silver halide grains contained in the silver halide emulsion layer, reduction sensitization in any step of emulsion production,
5. The silver halide photographic material as described in any one of items 1 to 4, which has been subjected to at least one sensitization selected from selenium sensitization and tellurium sensitization.

6. 6. The silver halide photographic light-sensitive material according to any one of 1 to 5, wherein the support is polyethylene naphthalate.

7. The silver halide photographic light-sensitive material according to any one of claims 1 to 6, wherein the polyethylene naphthalate support has a thickness of 70 µm to 170 µm.

An X-ray image forming unit comprising a surface of the silver halide photographic material according to any one of items 1 to 7 having an emulsion layer and a fluorescent surface of a fluorescent intensifying screen in close contact with each other.

The fluorescent intensifying screen described in 9.8 shows an absorption of 45% or more with respect to X-rays having an X-ray energy of 80 kVp, a filling rate of the phosphor of 68% or more, and An X-ray image forming method having a thickness of 135 to 200 μm and performing imagewise exposure by irradiating X-rays.

10. Item 8. A method for processing a silver halide photographic light-sensitive material, wherein the silver halide photographic light-sensitive material according to any one of Items 1 to 7 is processed in a processing step of an automatic developing machine including a developing step.

11. The method for processing a silver halide photographic light-sensitive material, wherein the automatic processor according to 11.10 has a mechanism for supplying a solid processing agent to a processing tank.

12. The amount of the replenisher replenished in the developing step and / or the fixing step is represented by the following formula:
12. The method for processing a silver halide photographic light-sensitive material according to 0 or 11.

1 ml / m ² ≦ replenishing solution amount / amount taken out by photosensitive material ≦ 7 ml / m ² 13. Processing time (Dry to D) required for all processing steps
ry) is not more than 30 seconds, 11 or 1
3. The method for processing a silver halide photographic light-sensitive material according to item 2.

Hereinafter, the present invention will be described in detail.

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 general formula (1) used in the present invention are listed below, but the present invention is not limited to these.

[0039]

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[0040]

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[0041]

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[0042]

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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} formula (2), R ³ represents an aliphatic group, aromatic group, heterocyclic group or alicyclic group substituted by a water-soluble group. Represent. x
Represents 1 or 0, M represents a hydrogen atom, an alkali metal atom or a cation, and when x is 0, the general formula (2) is represented by 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
Represents 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.

The aromatic group represented by R ³ includes 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, tetrahydripyran, oxirane, formolin, thiomorpholine, thiopyran, tetrahydrothiophene, pyrrole, pyridine, furan, thiophene, imidazole, pyrazole, oxazole, thiazole, isoxazole, isothiazole , Triazole, tetrazole, thiadiazole, oxadiazole, and each group derived from these benzerogues.

The alicyclic group represented by R ³ includes 4 members
To 7 carbon rings.

For example, cyclopentene, cyclopentadiene, cyclohexane, cyclohexadiene, terpene,
Examples include groups such as steroids.

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, etc., imide group (for example, phthalimide group, etc.), disulfide (for example, benzene disulfide, benzothiazole-2-disulfide, etc.), heterocyclic group (Eg, each group such as pyridyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, etc.) R ³ can have one or more of these substituents, and each substituent is further substituted as described above. M may be 2 to 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 given, but the present invention is not limited thereto.

[0056]

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[0057]

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[0058]

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[0059]

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

Next, the leuco compounds represented by the general formulas (3) to (6) will be described.

In the general formulas (3) to (6), the alkyl group represented by R ₁ and R ₂ preferably includes a methyl group, an ethyl group, a propyl group and a butyl group.
These may be further substituted, and preferred substituents include a hydroxy group and a sulfonamide group.

The aryl group represented by R ₁ and R ₂ is preferably a phenyl group.

Examples of the monovalent substituent represented by R ₃ include an alkyl group (eg, a methyl group, an ethyl group, an isopropyl group, a hydroxyethyl group, a methoxymethyl group, a trifluoromethyl group, a t-butyl group, etc.), a cycloalkyl group and the like. Group (eg, cyclopentyl group, cyclohexyl group, etc.), aralkyl group (eg, benzyl group, 2-phenethyl group, etc.), aryl group (eg, phenyl group, naphthyl group, p
-Tolyl group, p-chlorophenyl group, etc.), alkoxyl group (eg, methoxy group, ethoxy group, isopropoxy group, n-butoxy group, etc.), aryloxy group (eg, phenoxy group, etc.), cyano group, acylamino group (eg, acetyl group) Amino group, propionylamino group, etc., 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 groups (eg, 3-methylureido group, 3,3-dimethylureido group, 1,3-dimethylureido group, etc.), sulfamoylamino groups (dimethylsulfamoylamino group, etc.),
Carbamoyl group (eg, methylcarbamoyl group, ethylcarbamoyl group, dimethylcarbamoyl group, etc.), sulfamoyl group (eg, ethylsulfamoyl group, dimethylsulfamoyl group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.) ,
Aryloxycarbonyl group (for example, phenoxycarbonyl group, etc.), sulfonyl group (for example, methanesulfonyl group, butanesulfonyl group, phenylsulfonyl group, etc.),
Acyl group (for example, acetyl group, propanoyl group, butyroyl group, etc.), amino group (methylamino group, ethylamino group, dimethylamino group, etc.), hydroxy group, nitro group,
Examples include an imide group (for example, a phthalimido group) and a heterocyclic group (for example, a pyridyl group, a benzimidazolyl group, a benzothiazolyl group, a benzoxazolyl group, and the like).

The acyl group represented by R ₄ is preferably an acetyl group, a trifluoroacetyl group or a benzoyl group. Preferred examples of the sulfonyl group include a methanesulfonyl group and a benzenesulfonyl group. Preferable examples of the carbamoyl group include a diethylcarbamoyl group and a phenylcarbamoyl group. Preferred examples of the sulfamoyl group include a diethylsulfamoyl group. The alkoxycarbonyl group preferably includes a methoxycarbonyloxy group and an ethoxycarbonyloxy group. Preferable examples of the aryloxycarbonyl group include a phenoxycarbonyloxy group.

The alkali metal represented by Z includes sodium, potassium and the like. Examples of the quaternary ammonium include ammonium having a total carbon number of 8 or more, such as trimethylbenzylammonium, tetrabutylammonium, and tetradecylammonium.

Examples of the 5- or 6-membered aromatic hetero ring composed of X, Z ₁ , Z ₂ and carbon atoms adjacent thereto include a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a triazine ring, a tetrazine ring and a pyrrole ring. Ring, furan ring, thiophene ring, thiazole ring, oxazole ring, imidazole ring, thiadiazole ring, oxadiazole ring and the like. Preferably it is a pyridine ring.

Examples of the substituent capable of substituting on the benzene ring represented by R _{5 to} R ₈ include groups having the same meaning as the above-mentioned monovalent substituent represented by R ₃ . Preferred are an alkyl group and an acylamino group.

Examples of the 5- to 7-membered ring formed by combining R ₅ and R ₆ and R ₇ and R ₈ include an aromatic carbon ring and a heterocyclic ring, preferably a benzene ring. it can.

Examples of the alkyl group represented by R ₁₀ and R ₁₁ include a methyl, ethyl, propyl and butyl group.
Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the heterocyclic group include a 5- to 6-membered aromatic heterocycle having at least one of O, S, and N atoms in the ring (for example, pyridine, pyrazine , A 6-membered ring azine such as a pyrimidine ring and the like, and their benzerogues: pyrrole, thiophene, furan and their benzerogues: imidazole, pyrazole,
5-membered ring azoles such as triazole, tetrazole, thiazole, oxazole, thiadiazole, and oxadiazole, and benzerogue, etc.). R ₁₀ and R ₁₁ preferably include a phenyl group, a pyrazolyl group, a pyridyl group and the like.

Examples of the alkyl group represented by R ₁₆ include a methyl group, an isopropyl group, a pentyl group and a t-butyl group. Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the sulfonyl group include a methine sulfonyl group and a benzenesulfonyl group. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group. Examples of the alkoxycarbonyl group include an ethoxycarbonyl group. Examples of the carbamoyl group include a diethylaminocarbamoyl group.

Examples of the nitrogen-containing hetero ring represented by Y1 include each of imidazole, triazole, tetrazole and the like, and benzo-fused rings thereof.

Examples of the alkyl group represented by R ₁₉ and R ₂₀ include a methyl group, a pentyl group and a t-butyl group. Examples of the aryl group include a phenyl group and a naphthyl group.

Examples of the substituent represented by R ₂₅ , R ₂₇ and R ₂₈ include a phenyl group, a methyl group, a benzoyl group, a phenoxy group and an ethoxy group.

Examples of the aliphatic group represented by R include a hexyl group and a dodecyl group. As the aromatic group, p
-Toluene, dodecylbenzene and the like.

The compounds represented by formulas (3) to (6) will be specifically described below, but the invention is not limited thereto.

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[0081]

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[0082]

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[0083]

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[0084]

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[0085]

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[0086]

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[0087]

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[0088]

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[0089]

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[0090]

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[0091]

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Synthesis Example 1 (Synthesis of Exemplified Compound 8) Reaction Route

[0093]

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(1) 3.9 g was dissolved in 50 ml of ethyl acetate, and 0.5 g of 5% Pd / C was added, and hydrogenation was carried out at normal pressure. The blue color of the reaction solution disappeared, and (2) was formed.

Next, 1.2 g of triethylamine was added to the reaction solution.
And 1.5 g of acetyl chloride were added, and the mixture was stirred at room temperature for 2 hours. The catalyst and insolubles were separated by filtration, and the residue was recrystallized from ethyl acetate to give 3.8 g of the desired Exemplified Compound 8 (yield: 89).
%)Obtained.

The structure was confirmed by NMR spectrum and Mass spectrum.

Synthesis Example 2 (Synthesis of Exemplified Compound 9) Reaction Route

[0098]

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3.9 g of Synthesis Example 1 (1) was added to ethyl acetate 5
The mixture was dissolved in 0 ml, and 0.5 g of 5% Pd / C was added thereto to carry out normal-pressure catalytic hydrogenation. The blue color of the reaction solution disappeared and (2)
Generated.

Next, 1.2 g of triethylamine was added to the reaction solution.
And 4.0 g of trifluoroacetic anhydride were added, followed by stirring at room temperature for 2 hours. The catalyst and insolubles were separated by filtration, and the residue was recrystallized from ethyl acetate to give 4.0 g of the desired Exemplified Compound 9 (yield 8
5%).

The structure was confirmed by NMR spectrum and Mass spectrum.

Synthesis Example 3 (Synthesis of Exemplified Compound 58) Reaction Route

[0103]

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2. Exemplified Compound 8 was added to 30 ml of methanol.
5 g was dissolved, and p-toluenesulfonic acid monohydrate 2.6
g and stirred.

Next, the reaction mixture was poured into 300 ml of water and collected by filtration to obtain 4.1 g of the desired Exemplified Compound 58 (yield: 87%).
Obtained.

The structure was confirmed by NMR spectrum and Mass spectrum.

Other compounds could be easily synthesized in the same manner as in the above synthesis examples.

The amount of the compound represented by formulas (3) to (6) of the present invention may be 1 m
It is preferable that the content of the present invention is 1 × 10 ^-6 mol or more and less than 5 × 10 ^-1 mol per ol, for the effect of the present patent to be exhibited. Below this, the effect of improving the silver tone is small, and above this, the whole image appears dark. Not preferred. More preferably, silver 1
In the case where it is contained in an amount of 5 × 10 ⁻⁵ mol or more and less than 5 × 10 ⁻² mol per mol, in particular, the case where it is contained in an amount of 5 × 10 ⁻⁴ mol or more and less than 1 × 10 ⁻² mol per 1 mol of silver is preferable in terms of achieving the effect.

In the present invention, any method of adding the compounds represented by the general formulas (3) to (6) may be used depending on the properties of each compound. For example, a method of adding as a solid fine particle dispersion, a method of dissolving in a high boiling point solvent and then adding after dispersing, a method of dissolving in a water-miscible organic solvent (for example, methanol, ethanol, acetone, etc.) and adding the same are exemplified. . As a preferable method, a method of adding as a solid fine particle dispersion or a method of dissolving in a water-miscible organic solvent (for example, methanol, ethanol, acetone or the like) and adding the same is used. When added as a solid fine particle dispersion, a known dispersion method such as an acid precipitation method, a ball mill, a jet mill or an impeller dispersion method can be applied. Although it can be taken, it is preferably 0.01 to 20 μm,
More preferably, it is 0.03 to 2 μm.

The molar ratio of the compound represented by the general formulas (5) and (6) to RSO ₃ H is 1 mole of the compound represented by the general formulas (5) and (6), and RS0 ₃ H1 It is preferably from 3 to 3 mol.

The compounds represented by the general formulas (3) to (6) of the present invention can be contained in any of the photographic constituent layers. The compound is preferably contained in an emulsion layer or a layer between the emulsion layer and the support, particularly preferably in a transverse light-blocking layer.

The silver halide grains according to the present invention are preferably in the form of a flat plate having two parallel (100) planes as main planes, and have an aspect ratio of 2.0 or more, preferably 15.
It is less than 0. The principal plane referred to herein is a set of parallel planes having the largest area among the crystal surfaces forming substantially rectangular parallelepiped emulsion grains, and the aspect ratio refers to the principal plane of the grain with respect to the thickness between the principal planes. It refers to the ratio of the average edge length to be formed.

The average edge length of the principal plane is determined, for example, by photographing the particle with an electron microscope at a magnification of 10,000 to 50,000 times, and measuring the edge length of the particle on the print or the area at the time of projection. It is obtained by doing. The particle thickness can also be obtained by actually measuring an electron micrograph.

The fact that the main plane is the (100) plane can be determined by an electron diffraction method or an X-ray diffraction method. In observation with an electron micrograph, particles having a (100) principal plane can be examined because the principal plane is an orthogonal square (square or rectangular) plane.

The tabular silver halide grains of the present invention account for 50% or more of the total projected area of the silver halide grains contained in the silver halide emulsion layer of the present invention, preferably 80%.
That is all.

The silver halide emulsion according to the present invention includes:
Silver iodochloride, silver chloroiodobromide, etc. having a silver chloride content of 10 mol% or more can be used, and preferably a silver chloride content of 30 mol% to 70 mol%, and a silver iodide content of 1.0 mol%. Or less (more preferably 0.5 mol% or less).

The emulsion having tabular silver halide grains of the present invention comprises (a) a step of introducing a silver salt and a halide salt into a dispersion medium to form nuclei of the tabular grains; And a step of performing Ostwald ripening under conditions that maintain the (100) major plane of the tabular grains, and (c) a step of growing grains so as to have a desired grain size and silver chloride content.

It is preferable to use a double jet method (simultaneous mixing method) as a method of reacting a silver salt and a halide salt during nucleation.

The double-jet method is also used during grain growth. One type of double-jet method is a method in which the pAg in the liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method. It can also be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

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 the halogen composition of the silver halide grains of the host, since the grain size of the fine grains governs the supply rate of the 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 the 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 water 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 added depends on the type of reduction sensitizer, the particle size of silver halide grains, composition and crystal habit, 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).

Silver nitrate is preferred as the water-soluble silver salt.
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, the selenium sensitizer used comprises a wide variety of selenium compounds. For example, U.S. Pat. Nos. 1,574,944, 1,602,592 and 16,234.
No. 99, JP-A-60-150046, JP-A-4-25
No. 832, No. 4-109240, No. 4-147250
No. etc.

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 based on the technique for using the selenium sensitizer.

In the present invention, it is also preferable to use reduction sensitization 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.
It is carried out by adding a reducing agent and / or a water-soluble silver salt to the silver halide emulsion.

The tabular silver halide photographic emulsion used in the light-sensitive material of the present invention is spectrally sensitized using methine dyes and other spectral sensitizing dyes. Dyes used include cyanine dyes, merocyanine dyes, composite cyanine dyes, composite merocyanine dyes, holoboralar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. These dyes can be applied to any of the nuclei commonly used. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, 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.

The merocyanine dye or the complex merocyanine dye includes pyrazoline- as a nucleus having a ketomethine structure.
5-6 nuclei, thiobitantoin nuclei, 2-thiooxazolidine-2,4-dione nuclei, thiazoline-2,4-dione nuclei, rhodanine nuclei, thioparbituric acid nuclei, etc.
Member heterocyclic nuclei can be applied. These spectral sensitizing dyes may be used alone or in combination. Often used in combination with spectral sensitizing dyes. These spectral sensitizing dyes and methods of use are known combinations.

It is preferable that supersensitization is carried out by using at least one of the compounds represented by the following formula (7) in combination with the spectral sensitizing dye.

[0142]

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In the formula, Z ⁷¹ represents a group of non-metallic atoms necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic ring, for example, thiazolium (for example, thiazolium, 4-methylthiazolium, benzothiazolium, 5-methylbenzothiazolium, 5-chlorobenzothiazolium, 5-methoxybenzothiazolium, 6-methylbenzothiazolium, 6-methylbenzothiazolium
Methoxybenzothiazolium, naphtho [1,2-d] thiazolium, naphtho [2,1-d] thiazolium and the like, oxazoliums (for example, oxazolium, 4-
Methyl oxazolium, benzoxazolium, 5-chlorobenzoxazolium, 5-phenylbenzoxazolium, 5-methylbenzoxazolium, naphtho [1,2-d] oxazolium and the like, imidazolium ( For example, 1-methylbenzimidazolium, 1-propyl-5-chlorobenzimidazolium, 1-ethyl-
5,6-dichlorobenzimidazolium, 1-allyl-
5-trichloromethyl-6-chloro-benzimidazolium, etc.), selenazoliums [for example, benzoselenazolium, 5-chlorobenzoselenazolium, 5-methylbenzoselenazolium, 5-methoxybenzoselenazolium, naphtho [ 1,2-d] selenazolium).

R ⁷¹ represents a hydrogen atom, an alkyl group (having 8 or less carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, etc.) and an alkenyl group (for example, an allyl group). R ⁷² is preferably an alkyl group or an alkenyl group. R ⁷² represents a hydrogen atom or a lower alkyl group (eg, a methyl group, an ethyl group, etc.). X ⁷¹ is an acid anion (e.g. ^{Cl -, Br -, I -} , ClO 4 -, p- toluenesulfonic acid, and the like), preferably thiazolium compounds are advantageously used in the Z ^71. More preferably, benzothiazolium or naphthothiazolium (including those having a substituent) is advantageously used.

Specific examples of the compound represented by formula (7) used in the present invention are shown below, but the present invention is not limited to these specific examples.

[0146]

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[0147]

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[0148]

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[0149]

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[0150]

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The compound represented by the above general formula (7) is advantageously used in an amount of about 0.01 to 5 g per mol of silver halide. The ratio (weight ratio) of the above-mentioned known sensitizing dye (for example, a cyanine dye) to the compound represented by the general formula (7) is expressed by the following formula: sensitizing dye of the present invention / compound represented by the general formula (7) = The range from 10/1 to 1/50 is advantageously used, especially the range from 5/1 to 1/10.

The compound represented by the general formula (7) used in the present invention can be directly dispersed in an emulsion, or can be dispersed in a suitable solvent (eg, water, methyl alcohol, ethyl alcohol, propyl alcohol, methyl cellosolve). , Acetone, etc.) or a mixed solvent using a plurality of these solvents, and then added to the emulsion.

Other sensitizing dyes can be added to an emulsion in the form of a solution or a dispersion in a colloid according to the method of adding a sensitizing dye. The compound represented by the general formula (7) may be added to the emulsion before the addition of the spectral sensitizing dye described above, or may be added after the addition. Further, the compound of the formula (7) and the sensitizing dye may be separately dissolved, and these may be separately and simultaneously added to the emulsion, or may be mixed and then added to the emulsion.

In the present invention, it is preferable to use the photosensitive dye in combination with at least one of the compounds represented by the following general formula (8).

[0155]

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In the formula, -A ^81- represents a divalent aromatic residue, and these are -SO ₃ M groups, wherein M represents a hydrogen atom or a cation that imparts water solubility (eg, sodium, potassium, etc.). ] May be included. As -A-, for example, those selected from the following -A ⁸¹ -or -A ^82- are useful. However, when the R ^81, R ^82, R ⁸³ or R ⁸⁴ do not contain -SO ₃ M is -A- is -A ⁸¹ - is selected from the group of.

[0157] -A ⁸¹ -

[0158]

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[0159] -A ⁸² -

[0160]

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R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ each represent a hydrogen atom, a hydroxy group or a lower alkyl group (having a carbon number of 1 to 1)
8 is preferred. For example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, etc., an alkoxy group (preferably having 1 to 8 carbon atoms, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc.), an aryloxy group ( For example, phenoxy group, naphthoxy group, o-troxy,
a p-sulfophenoxy group, a halogen atom (eg, a chlorine atom, a bromine atom, etc.), a heterocyclic nucleus (eg, a morpholinyl group, a piperidyl group, etc.), an alkylthio group (eg, a methylthio group, an ethylthio group, etc.), a heterocyclylthio group (eg, Benzothiazolylthio group, benzimidazolyl group, phenyltetrazolylthio group, etc., arylthio group (for example, phenylthio group, tolylthio group), amino group, alkylamino group (including substituted alkylamino group) (for example, methylamino group, ethylamino Group, propylamino group, dimethylamino group, diethylamino group, dodecylamino group, cyclohexylamino group, β-hydroxyethylamino group, di- (β-hydroxyethyl) amino group, β-sulfoethylamino group), arylamino group (Substituted arylua Roh containing groups) (e.g. anilino group, o- sulfoanilino group, m- sulfoanilino group, p
-Sulfoanilino group, o-toluidino group, m-toluidino group, p-toluidino group, o-carboxyanilino group,
m-carboxyanilino group, p-carboxyanilino group, o-chloroanilino group, m-chloroanilino group, p
-Chloroanilino group, p-aminoanilino group, o-anisidino group, m-anisidino group, p-anisidino group, o-
Acetaminoanilino group, hydroxyanilino group, disulfophenylamino group, naphthylamino group, sulfonaphthylamino group, etc., heterocyclylamino group (for example, 2
-Benzothiazolylamino group, 2-pyrazyl-amino group, etc., aralkylamino group (including substituted aralkylamino group) (for example, benzylamino group, o-anisylamino group, m-anisylamino group, p-anisylamino group, etc.) , An aryl group (for example, a phenyl group) and a mercapto group.

Each of R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ may be the same or different. -A- is -A ₂ - when selected from the group consisting of, R ^81, at least one of R ^82, R ^83, R ⁸⁴ may be one or more sulfo groups (free acid groups, to form a salt May be required). W ⁸¹
Represents -CH = or -N =.

Next, specific examples of the compound included in the general formula (8) used in the present invention will be described. However, the present invention is not limited only to these compounds.

8-1 4,4'-Bis [4,6-di (benzothiazolyl-2-thio) pyrimidin-2-ylamino] stilbene-2,2'-disulfonate disodium salt 8-2 4,4 ' -Bis [4,6-di (benzothiazolyl-2-amino) pyrimidin-2-ylamino] stilbene-2,2'-disulfonic acid disodium salt 8-3 4,4'-bis [4,6-di (naphthyl) -2-
Oxy) pyrimidin-2-ylamino] stilbene-
Disodium 2,2'-disulfonate 8-4 4,4'-bis [4,6-di (naphthyl-2-
Oxy) pyrimidin-2-ylamino] bibenzyl-
Disodium 2,2'-disulfonate 8-5 4,4'-bis (4,6-dianilinopyrimidin-2-ylamino) stilbene-2,2'-disulfonate disodium salt 8-6 4,4 '-Bis [4-chloro-6- (2-naphthyloxy) pyrimidin-2-ylamino] biphenyl-2,2'-disulfonic acid disodium salt 8-7 4,4'-bis [4,6-di ( 1-phenyltetrazolyl-5thio) disodium salt 8-8 4,4'-bis [4,6-di (benzimidazolyl-2-thio) pyrimidin-2-ylamino] stilbene-2,2'-disulfonic acid Disodium salt 8-9 4,4'-bis (4,6-diphenoxypyrimidin-2-ylamino) stilbene-2,2'-disulfonate disodium salt 8-10 4,4'-bis (4,6 Diphenylthiopyrimidin-2-ylamino) stilbene-2,2'-disulfonate disodium salt 8-11 4,4'-bis (4,6-dimercaptopyrimidin-2-ylamino) biphenyl-2,2'-disulfone Acid disodium salt 8-12 4,4'-bis (4,6-dianilino-triazin-2-ylamino) stilbene-2,2'-disulphonic acid disodium salt 8-13 4,4'-bis (4- Anilino-6-hydrokillertriazin-2-ylamino) stilbene-2,
Disodium 2-disulfonate 8-14 4,4'-bis (4-naphthylamino-6-
Anilino-triazin-2-ylamino) stilbene-
Disodium 2,2'-disulfonate salt In these specific examples, 2-1 to 8-12 are preferable,
Particularly preferred are 8-1 to 8-5 and 8-7.

The compound of formula (8) is advantageously used in an amount of about 0.01 to 5 grams per mole of silver halide in the emulsion. The ratio (weight ratio) of the sensitizing dye of the present invention to the compound represented by the general formula (8) is as follows: sensitizing dye / compound represented by the general formula (8) = 1/1 to 1 / 1
The range of 00 is advantageously used, in particular from 1/2 to 1/50
Is advantageously used. The compound represented by the general formula (8) used in the present invention can be directly dispersed in the emulsion, and a suitable solvent (eg, methyl alcohol,
(E.g., ethyl alcohol, methyl cellosolve, water) or a mixed solvent thereof, and then added to the emulsion. The sensitizing dye can be added to the emulsion in the form of a solution or a dispersion in a colloid according to the method of adding the sensitizing dye. Further, it can be dispersed and added to the emulsion by the same method as the alkali releasing agent described in JP-A-50-80119.

Various photographic additives can be used in the light-sensitive material of the present invention. Examples of known additives include, for example, the aforementioned (RD) 17643 (December, 1978) and No. 18716 (1979) And 308119 (19
(December 1989). The types and locations of the compounds shown in these three (RD) are shown below.

[0167]

[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 hydroxyethyl cellulose, sugar derivatives, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid, polyacrylamide and the like. 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.

Next, the polyethylene naphthalate of the present invention will be described.

[0172] The polyethylene naphthalate preferably used as the support is, more specifically, polyethylene-2,6.
-Naphthalate, a polymer whose constituent units are substantially composed of ethylene-2,6-naphthalate units, but modified by a small amount of, for example, 10 mol% or less, preferably 5 mol% or less of a third component. Ethylene
Also included are 2,6-naphthalate polymers.

Polyethylene-2,6-naphthalate is
In general, it is produced by condensing naphthalene-2,6-dicarboxylic acid or a functional derivative thereof, for example, methyl naphthalene-2,6-dicarboxylate and ethylene glycol under appropriate reaction conditions in the presence of a catalyst. In that case, as the third component, for example, adipic acid, oxalic acid, isophthalic acid, terephthalic acid, naphthalene-2,7
A dicarboxylic acid such as dicarboxylic acid, diphenyl ether dicarboxylic acid or a lower alkyl ester thereof, a dicarboxylic acid such as p-oxybenzoic acid or p-ethoxybenzoic acid, or a lower alkyl ester thereof, or propylene glycol, trimethylene glycol or tetramethylene glycol; And divalent alcohols such as pentamethylene glycol, hexamethylene glycol and diethylene glycol, and polyalkylene glycols such as polyethylene glycol and polytetramethylene glycol.

In the polymerization, a lubricant such as titanium dioxide,
Stabilizers such as phosphoric acid, phosphorous acid and ester salts thereof, antioxidants such as hindered phenol, polymerization regulators, plasticizers and the like may be added.

The polyethylene naphthalate used in the present invention has a limiting viscosity of 0.4 or more, preferably 0.55 to 5, since the mechanical stability is lowered if the degree of polymerization is too low.
0.9 is preferred. It is not preferable that the crystallinity is too low for dimensional stability.
5% or more and 60% or less are preferable.

[0176] intended use of the polyethylene-2,6-naphthalate film of the present invention, the surface resistivity for the the dust attached during use the product value decreases 10 ¹⁴
It is preferably Ω · cm or less. As a method of obtaining such a film, a method of applying an antistatic agent, a method of forming a thin layer of a metal or a metal compound on the film surface, a method of adding an antistatic agent during polymerization of polyester raw material, and a method of forming a film It is appropriately used such as a method of mixing a polyester raw material and an antistatic agent. Among them, polyethylene-2,6-naphthalene obtained by performing polycondensation in the presence of sodium alkylbenzenesulfonate and polyalkylene glycol as raw materials may be used.

Polyethylene-2,6 used in the present invention
-Naphthalene refers to a monomer in which 40 mol% or more of the monomer to be polymerized is dimethyl naphthalene-2,6-dicarboxylate, preferably 60 mol% or more, more preferably 80 mol% or more.

The surface of these supports may be provided with an undercoat layer, or subjected to corona discharge, ultraviolet irradiation, etc. in order to improve the adhesion of the coating layer.

A method for preparing a support used in the present invention will be described.

<Preparation of Support> 100 parts of dimethyl naphthalene-2,6-dicarboxylate, ethylene glycol 60
After adding a transesterification catalyst to 1.2 parts, 1.2 parts of sodium dodecylbenzenesulfonate, 0.8 parts of polyethylene glycol having a molecular weight of 8000, and 0.01 parts of thyroid
Parts obtained by performing polycondensation by adding
2,6-Naphthalate was melt-extruded and the unstretched film was stretched 4.2 times at 170 °, and then stretched 4.2 times in the transverse direction at 150 °.

The heat setting was at 255 ° C. for 10 seconds. Thus, supports having different thicknesses were obtained by changing the degree of stretching. In the present invention, a thickness of 70 to 170 μm, preferably 90 to 150 μm is preferable. If the thickness is smaller than this range, the required intensity cannot be obtained, and in the case of X-ray image diagnosis, there is a drawback that the waist is weak and the diagnosis is difficult. On the other hand, if the thickness is larger than this range, the effect of improving the color tone of the silver image of the present invention cannot be sufficiently obtained, and the curl tends to be easily formed.

(Underlining treatment) JP-A-52-104913
No. 1 of the sample No. Subbing was performed according to the method of Example 9 and used as a support. The thickness of the support is 70
To 170 μm, preferably 90 to 150 μm.

If the thickness is smaller than this range, the required intensity cannot be obtained, and in the case of X-ray image diagnosis, there is a disadvantage that the waist is weak and the diagnosis is difficult. On the other hand, if the thickness is larger than this range, the effect of improving the color tone of the silver image of the present invention cannot be sufficiently obtained, and the curl tends to be easily formed.

In the present invention, the image forming unit is one 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 by 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.

Preferred phosphors used in 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.

The fluorescent intensifying screen used in the present invention is preferably filled with a phosphor having 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.

The production of the fluorescent intensifying screen comprises the steps of forming a phosphor sheet comprising a binder and a phosphor, placing the phosphor sheet on a support, and setting the phosphor sheet at a temperature not lower than the softening temperature or the melting point of the binder. It is preferable to manufacture the phosphor sheet in a step of bonding the phosphor sheet to a support while compressing the phosphor sheet.

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, and 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 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 desired characteristics of the fluorescent intensifying screen, the type of the phosphor, and the like. In general, 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 improved. 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 phthalyl ethyl 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.

As the applying means, for example, a doctor blade, a roll coater, a knife coater or the like can be used.

As the temporary support, for example, those made of various materials such as glass, wool, cotton, paper, and metal can be used. A flexible sheet or roll for handling as an information recording material 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 to the 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.

The following is a description of the operation. 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 undercoating 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 thus obtained is placed on a support, and the phosphor sheet and the phosphor sheet are bonded to the support while being compressed at a temperature not lower than the softening temperature or the melting point of the binder.

In this way, by using the method of pressing the sheet without fixing it on the phosphor sheet support in advance, the sheet can be spread thinly and not only prevents the phosphor from being damaged but also fixes the sheet. 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 the compression device used for the compression process include generally known devices 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.

Normally, 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 in contact with the support described above. . 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 formed 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 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 the oligomer containing a functional group is used, a cross-linking reaction occurs between the oligomer and the resin for forming the protective layer when the protective film is formed, and the oligomer is incorporated into the molecular structure of the resin for forming the film. 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.

It is preferable that the protective film of the fluorescent intensifying screen is 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.

In the present invention, the filling rate of the phosphor 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 fluorescent filter exhibits an absorption amount of 45% or more, more preferably 50% or more, with respect to 80 kVp X-rays in an X-ray generator whose intrinsic filtration is 2.2 mm of aluminum. 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 is, for example, 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.

Examples of the developer for black-and-white photographic processing include dihydroxybenzenes (such as hydroquinone), 3-pyrazolidones (such as 1-phenyl-3-pyrazolidone), and aminophenols (such as N-methyl-aminophenol). 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, etc., and the gravity drop method described in JP-A-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.

[0231]

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In the general formula (A), R ⁹¹ and R ⁹² are each independently a hydroxy group, —OM ⁹¹ (M ⁹¹ represents an alkali metal atom or an ammonium group), an amino group (a methyl group as a substituent, Examples include those having an alkyl group having 1 to 10 carbon atoms such as an ethyl group, an n-butyl group, and a hydroxyethyl group.), An acylamino group (such as an acetylamino group and a benzoylamino group), and an alkylsulfonylamino group (such as methanesulfonylamino). An arylsulfonylamino group (benzenesulfonylamino group, p-toluenesulfonylamino group, etc.), an alkoxycarbonylamino group (methoxycarbonylamino group, etc.), a 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 ⁹¹ is ^{-O -, - C (R 93} ) (R 94) -, - C (R 95)
=, -C (= O)-, -N ( ^R96 )-, -N = and the like, preferably a carbon atom, an oxygen atom or a nitrogen atom, and ^R91
And ^R92 together with the two substituted vinyl and carbonyl carbons form a 5- to 6-membered ring. Where R ⁹³ -R
⁹⁶ 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.

[0234]

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[0235]

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[0236]

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[0237]

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The compound represented by formula (A) is
About 0.005 to 0.5 mol, preferably 0.1 to 0.5 mol per liter.
Used in the range of 02 to 0.4 mol.

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 JP-B-37-160.
Nos. 88, 37-5987, 38-7826, 44-12380, 45-9019 and U.S. Pat. No. 3,813,247; No. 50-15554
P-phenylenediamine-based compound described in
Quaternary ammonium salts described in JP-A-0-137726, JP-B-44-30074, JP-A-56-156826 and JP-A-52-43429; U.S. Pat.
P-aminophenols described in Nos. 122 and 4,119,462; U.S. Patent Nos. 2,482,546, 2,494,903, 2,596,926, and 3,128, No. 182, No. 3,582,346, No. 4,230,796, No. 3,253,919, amine compounds described in JP-B-41-11431, JP-B-37-16088, JP-B-41 -11431, 42
No. 23883, No. 42-25201, U.S. Pat. Nos. 3,128,183, 3,532,501, etc., polyalkylene oxides, and other 1-phenyl-
If necessary, 3-pyrazolidones, hydrozines, mesoionic compounds, ionic compounds, imidazoles, and the like can be added.

Examples of antifoggants include 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, the developer composition includes methyl cellosolve, methanol, acetone, dimethylformamide, a cyclodextrin compound, JP-B-47-33378,
The compounds described in JP-A-44-9509 can be used as an organic solvent for increasing the solubility of the developing agent, and other stain preventing agents, sludge preventing agents and layering effect promoters 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 also 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 can be subjected to a total processing time (dry to dry) using an automatic processor.
The treatment is preferably performed in 5 to 45 seconds, but the treatment is preferably performed without any change when the treatment is performed in 10 to 25 seconds. Here, the time from the time when the tip of the photosensitive material to be processed is immersed in the developing tank liquid of the automatic developing machine to the time when it comes into contact with the fixing tank liquid in the next process is referred to as “development time”. "Fixing time" refers to the time until contact with the washing tank solution (stabilizing solution), "Washing time" refers to the time of immersion in the washing tank solution, and "Drying time" refers to the time in the drying zone of the automatic processor. , The developing time is 3 to 15 seconds (further 2 to 10 seconds), the developing temperature is 25 to 50 ° C. (further 30 to 40 ° C.), the fixing time is 2 to 12 seconds (further 1 to 10 seconds).
Sec), fixing temperature 20-50 ° C (further 30-40 ° C),
Water washing (stabilization) time 3 to 15 seconds (further 1 to 8 seconds), water washing (stabilization) temperature 0 to 50 ° C (further 15 to 40 ° C),
Drying time 3-12 seconds (further 2-8 seconds), drying temperature 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 necessary 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 replenished, respectively, and the replenishing amount needs to satisfy the following formula.

1 ≦ (replenishment amount / carry-out amount by photosensitive material) ≦ 7 When (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.

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.

[0251]

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

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

[0253] The solution A ₁ ossein gelatin 60.2g Distilled water _{20.0l 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 aqueous solution 5.6 ml KBr 26.8 g 10% H ₂ SO ₄ 144 ml solution B ₁ silver nitrate 1487.5 g Make up to 3500 ml with distilled water Solution C ₁ KBr 1050 g Make up to 3500 ml with distilled water Solution D in ₁ 1.75 N KBr aqueous solution following silver potential control amount 35 ° C., using a mixing and stirring machine shown in 58-58288 Pat Sho, the solution a ₁ each 64.1ml of solution B ₁ and solution C ₁ It took 2 minutes to add by the double jet method to form nuclei.

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 prepared 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 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 kinds 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% aqueous 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. 75N KBr aqueous solution At the following silver potential control amount at 60 ° C., a simultaneous mixing method (double jet) using the mixing stirrer described in the specification of Japanese Patent Publication No. 58-58288, with the total amount of the solution B ₂ and the solution C _{2 in} the solution A ₂ Method), the addition growth was performed for 110 minutes so that the flow rate at the end of the addition became three times the flow rate at the start of the addition.

[0257] 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 carried out using an aqueous solution of Demol (manufactured by Kao Atlas) and an aqueous solution of magnesium sulfate in order to remove excess salts.

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

(Preparation of AgBrCl (100) tabular emulsion EM-2 having a silver chloride content of 30 mol%) Solution A ₃ Ossein gelatin 37.5 g KI 0.625 g KBr 23.6 g NaCl 5.0 g 7500 ml with distilled water Solution B ₃ Silver nitrate 1500 g Make up to 2500 ml with distilled water Solution C ₃ KI 4 g KBr 200 g NaCl 42 g Make up to 684 ml with distilled water Solution D ₃ KBr 535 g NaCl 113 g Make up 1816 ml with distilled water At 40 ° C., Japanese Patent Publication No. 58-58288 No. to a ₃ in the mixed agitator shown in the specification, were added the total amount of 684ml and C ₃ of the B ₃ over 1 minute. The EAg was adjusted to 220 mV, and after Ostwald ripening for 20 minutes, the entire remaining amount of B _{3 and} the entire amount of D ₃ were added over 40 minutes. Meanwhile, EA
g was controlled at 220 mV.

After completion of the addition, in order to remove excess salts,
After precipitation and desalting, a gelatin solution was added and dispersed to obtain emulsion EM-2.

When about 3,000 of the obtained emulsions EM-2 were observed and measured by an electron microscope, and analyzed for their shapes, a (10 μm) having an average equivalent circle diameter of 0.8 μm and an average thickness of 0.1 μm was obtained.
0) These are tabular grains having a plane as a main plane, and the coefficient of variation is 2
It was 0%.

(Preparation of AgBrCl (100) tabular emulsion EM-3 having a silver chloride content of 70 mol%) Solution A ₄ ossein gelatin 37.5 g KI 0.625 g KBr 16.8 g NaCl 8.3 g distilled water 7500 ml Solution B ₄ Silver nitrate 1500 g Make up to 2500 ml with distilled water Solution C ₄ KI 4 g KBr 143 g NaCl 70 g Make up to 684 ml with distilled water Solution D ₄ KBr 382 g NaCl 188 g Make up 1816 ml with distilled water The above solutions A _{4 to} D ₄ And EM-3 was obtained in the same manner as in EM-2.

When about 3,000 of the obtained emulsions EM-3 were observed and measured by an electron microscope, and analyzed for their shapes, (10 μm) having an average equivalent circle diameter of 0.8 μm and an average thickness of 0.1 μm was obtained.
0) These are tabular grains having a plane as a main plane, and the coefficient of variation is 2
It was 0%.

(Preparation of Pure Silver Chloride (100) Tabular Emulsion EM-4) Solution A ₅ Ossein gelatin 37.5 g KI 0.625 g NaCl 16.5 g Make up to 7500 ml with distilled water Solution B ₅ silver nitrate 1500 g with distilled water 2,500 ml Solution C ₅ KI 4 g NaCl 140 g Make 684 ml with distilled water Solution D ₅ NaCl 375 g Make 1816 ml with distilled water Except for adjusting EAg to 150 mV using additives A _{5 to} D ₅ above, EM- Emulsion EM-
4 was obtained.

When about 3,000 of the obtained emulsions EM-4 were observed and measured by an electron microscope, and analyzed for their shapes, (10 μm) having an average equivalent circle diameter of 0.8 μm and an average thickness of 0.1 μm was obtained.
0) These are tabular grains having a plane as a main plane, and the coefficient of variation is 2
It was 0%.

[0267] The reaction vessel to 605ml with C ₆ KI 352 g Distilled water to 605ml with B ₆ AgNO ₃ 360 g of distilled water to 2000ml with (silver iodide Preparation of fine particles) A ₆ ossein gelatin 100 g KI 8.5 g Distilled water in solution a ₆ while stirring maintaining the 40 ° C., it was added at a constant rate over a period of 30 minutes by double jet precipitation of a solution of B ₆ and solution C _6.

The pAg during the addition was kept at 13.5 by a conventional pAg control means. The formed silver iodide has an average grain size of 0.06.
It was a mixture of μm β-AgI and γ-AgI.

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 at a ratio of 100: 1 to water previously adjusted to 27 ° C., and a high-speed stirrer ( (Dissolver) 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'-dichloro-9
-Ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine salt anhydride Sensitizing dye (B): 5,5'-di- (butoxycarbonyl) -1,1'-diethyl-3, 3'-di- (4-sulfobutyl) benzimidazolocarbocyanine-sodium salt anhydride (selenium sensitized) Emulsions EM-1 to EM-4 were subjected to spectral sensitization and chemical sensitization by the following method, Chemically sensitized emulsions EM-A to EM-D 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) 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 1) Polyethylene terephthalate film base for X-rays having a thickness of 175 μm and colored blue at a concentration of 0.170.

(Support 2) Polyethylene naphthalate film base for X-rays having a thickness of 100 μm and colored blue at a concentration of 0.170.

(Preparation of Tin Oxide Sol Subbed Support)
0.5 kV · A · m on one side of each of supports 1 and 2
After performing the corona discharge treatment of in / m ² , the following (L−
The undercoat latex liquid shown in 2) has a thickness of 0.2 after drying.
The following (L-1) was sequentially applied so that the film thickness after drying was 0.053 μm so that
Dried for minutes.

[0277]

Embedded image

(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 liquid (L-2) and the liquid (L-4) described below 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. Then, the solid content was adjusted to 10% by weight to obtain a coating solution.

(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 ml of distilled water and a 30% by weight 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.

[0283]

Embedded image

(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 surfaces 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 trimethylo -Lupropane 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 Sodium ² -mercaptobenzimidazole-5-sulfonate 0.5 mg / m ² compound (H) / M ² nC ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 20 mg / m ² Compound (M) 5 mg / m ² Compound (N) 5 mg / m ² Colloidal silica 0.5 g / m ² latex (L) 0.5 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 (upper protective layer) Gelatin 0.3 g / m ² Matting agent composed of polymethyl acrylate 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) 50 m / M ² Compound (I) 30 mg / m ² Compound (S-1) 7mg / m 2 hardener (B) 2 mg / m ² Compound ^{(S-2) 2mg / m} 2

[0287]

Embedded image

[0288]

Embedded image

[0289]

Embedded image

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 and the third layer were added the leuco compounds and the compounds of the general formulas (1) and (2) of the types and amounts shown in Table 3, respectively.

(Production of Fluorescent Intensifying Screen 1) Phosphor Gd ₂ O ₂ S: Tb (average particle size 1.8 μm) 200 g Combined polyurethane-based thermoplastic elastomer Demolac TPKL-5-2625 Solid content 40% ( Sumitomo Bayer Urethane Co., Ltd. 20 g Nitrocellulose (digestibility: 11.5%) 2 g Add a methyl ethyl ketone solvent to the above and disperse it with a propeller 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) is placed horizontally on a glass plate, and the above-mentioned coating solution for forming an undercoat layer is 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, a transparent protective film having a thickness of 3 μm was formed by the method described in Example [1] of JP-A-6-75097.

As described above, a fluorescent intensifying screen 1 comprising a support, an undercoat layer, a phosphor layer and a transparent protective film was produced.

(Manufacture of Fluorescent Intensifying Screen 2) In the manufacture 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. 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 exposed to an X-ray source in front of an MRE single-sided silver halide photographic material manufactured by Eastman Kodak Company. The material and then the fluorescent intensifying screen were placed in contact with each other, and the X-ray exposure was changed by the distance method, and log E = 0.
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.

The measurement sample was measured for concentration 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 intrinsic filtration operated at 80 kVp with three-phase power supply transmits X-rays generated from a tungsten target tube equivalent to 2.2 mm of aluminum through an aluminum plate having a thickness of 3 mm. From 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.

[0301]

[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) 12500 g of sodium erythorbate as a developing agent is pulverized 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.
A 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 obtained 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 of the replenishing tablet 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 starter was filled with 11.0 liters of a fixing solution prepared by diluting the replenishment tablet with 298 g of the C agent and 149 g of the D agent with dilution water, and filled the fixing tank with the starting solution.

The photosensitive material prepared above was exposed to light so that the optical density after the development processing was 1.0, and running was performed.

During running, the photosensitive material contained 0.6 photosensitive material.
The above-mentioned four agents A and B and 150 ml of water were added per 2 m ² . 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 of Sensitometry> The obtained photosensitive material sample was sandwiched between fluorescent intensifying screens 1 and irradiated with X-rays through a penetrometer type B (manufactured by Konica Medical Co., Ltd.). A charging member for the solid processing agent was attached to the developing machine SRX-701, and the solid processing agent was used to perform processing at a development temperature of 35 ° C. for a total processing time of 45 seconds.

At this time, the replenishment amounts of the processing solutions were the amounts shown in Table 4 for both the developing solution and the fixing solution.

The sensitivity was shown as a relative value with the reciprocal of the X-ray exposure required for Sample 1 to obtain a density of minimum density +1.0 as 100.

<Processing time> Developing 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 < Evaluation of Silver Tone> Each of the coated samples was 10 cm × 30
After irradiating with X-rays while sandwiching the fluorescent intensifying screen 1, the same processing as in the sensitometric evaluation was performed, and the visual evaluation was performed in five steps as follows.

5: No yellow tint, cool black tone 4: Slight yellow tint, but barely noticeable 3: Yellow tint, no practical problem 2: Strong yellowish color, which is problematic in practical use 1: Extremely strong yellowish color, not suitable for practical use <Evaluation of image preservability> A saturated aqueous solution of cobalt chloride (CoCl _2. 60g a 6H ₂ O
And add 14 ml of pure water. ) Is placed thereon, the developed sample is placed on a mesh plate, the lid is closed and the inside is replaced with oxygen, the pressure in the container is set to 2.3 kgw / cm ^2, and the pressure is set to 1 at 55 ° C. (heating). Each sample sealed and stored for months was visually observed on a Shakasten and evaluated according to the following evaluation criteria.

A: no discoloration is observed B: slight discoloration is observed C: discoloration is clearly observed D: considerably discolored The obtained results are shown in Tables 3 and 4.

[0319]

[Table 3]

[0320]

[Table 4]

From Tables 3 and 4, the photosensitive material containing a sulfur compound having a water-soluble group in the hydrophilic colloid layer and a leuco compound in the hydrophilic colloid layer of the present invention uses a redox compound as a developing agent. It can be seen that the silver image is excellent in the processing, there is no contamination of the fluorescent intensifying screen and the developing solution, and there is little change in photographic performance even when stored over time.

Example 2 Sample No. 1 prepared in Example 1 10, 11, 12, 13
The processing time was 30 and 45 seconds described below, and the sensitivity at a replenishing amount / carrying out ratio of 7 or 2 was measured in the same manner as in Example 1 to evaluate quick processing. Table 5 shows the results.

<Processing time> Developing time: 8 seconds Fixing time: 6.2 seconds Washing time: 4 seconds Between washing and drying (squeeze): 3.2 seconds Drying time: 8.6 seconds Total processing time: 30 seconds

[0324]

[Table 5]

From Table 5, it can be seen that the sample of the present invention has a small sensitivity reduction and excellent processability even when processed for 30 seconds when the replenishment amount / the carry-out amount by the photosensitive material is 2 to 7.

[0326]

According to the present invention, a photographic material, a processing method, an image forming unit and an image forming method which are excellent in photographic performance and silver tone by rapid processing using a redox compound and which do not contaminate a fluorescent intensifying screen and a developing solution. was gotten.

[Brief description of the drawings]

FIG. 1 is a sectional view showing an example of a pressure-resistant container used in an embodiment of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Metal body part 2 Metal lid part 3 Oxygen gas inlet / outlet 4 Oxygen gas inlet / outlet 5 Open / close valve 6 Open / close valve 7 Open / close screw 8 Bottom 9 Sample under test 10 Net plate 11 Pressure gauge 12 Packing 13 Humidity control Agent 14 Petri dish

Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03C 1/09 G03C 1/09 1/34 1/34 1/795 1/795 5/17 5/17 5/26 5/26 520 520 5 / 31 5/31 5/395 5/395 G21K 4/00 G21K 4/00 B

Claims (13)

[Claims] 1. A silver halide photographic material having a silver halide emulsion layer and a hydrophilic colloid layer on a support, wherein the silver halide emulsion layer contains a sulfur-containing compound having a water-soluble group, and A silver halide photographic material characterized in that at least one layer selected from a hydrophilic colloid layer and / or the silver halide emulsion layer contains a leuco compound which reacts with an oxidized developing agent to form a blue dye. . 2. The silver halide photographic light-sensitive material according to claim 1, wherein the sulfur compound having a water-soluble group is a compound represented by the following general formula (1) or (2). material. Formula (1) R ^1- (S) _n -R ² (wherein, R ¹ and R ² each represent 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, and R ¹ and R ² may be the same or different, and n represents an integer of 2 or more and 6 or less.) General formula (2) R ³ -S (M) _x (wherein R ³ represents an aliphatic group, an aromatic group, a heterocyclic group or a cycloalkenyl group substituted with a water-soluble group;
(M) _x represents a group capable of adsorbing to silver halide, M represents a hydrogen atom, an alkali metal atom or a cationic group, x is 1 or 0, and when x is 0, the general formula (2) is R ³ =
S. ) 3. The leuco compound represented by the following general formula (3)
2. The silver halide photographic material according to claim 1, which is a compound represented by any one of (1) to (6). Embedded image [Wherein, W represents -NR ₁ R ₂ , -OH or -OZ;
R ₁ and R ₂ each represent an alkyl group or an aryl group, and Z represents an alkali metal ion or a quaternary ammonium ion. R ₃ represents a hydrogen atom, a halogen atom or a monovalent substituent, and n represents an integer of 1 to 3. Z ₁ and Z ₂ each represent a nitrogen atom or ＣC (R ₃ ) —. X represents an atomic group necessary for forming a 5- to 6-membered aromatic heterocycle together with Z ₁ , Z ₂ and carbon atoms adjacent thereto. R ₄ is a hydrogen atom, an acyl group, a sulfonyl group,
Represents a carbamoyl group, a sulfo group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. R represents an aliphatic group or an aromatic group. p represents an integer of 1 to 2. CP1 represents the following groups. [Chemical formula 2] Embedded image [Wherein, R _{5 to} R ₈ each represent a hydrogen atom, a halogen atom, or a substituent that can be substituted on a benzene ring. R ₅ and R ₆ and R ₇ and R ₈ may be bonded to each other to form a 5- to 7-membered ring. R ₉ has the same meaning as R ₄ . R ₁₀ and R ₁₁ each represent an alkyl group, an aryl group or a heterocyclic group. R ₁₂ has the same meaning as R ₄ . R ₁₃ and R ₁₄ have the same meaning as R ₁₀ and R ₁₁ . R ₁₅ has the same meaning as R ₁₂ . R ₁₆
Represents an alkyl group, an aryl group, a sulfonyl group, a trifluoromethyl group, a carboxy group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group or a cyano group. R ₁₇ has the same meaning as R ₄ . R ₁₈ has the same meaning as R ₃ , and m represents an integer of 1 to 3. Y1 represents an atomic group necessary for constructing a 5- or 6-membered monocyclic or condensed nitrogen-containing heterocyclic ring together with two nitrogen atoms. R ₁₉ and R ₂₀ represent an alkyl group or an aryl group. R ₂₁ has the same meaning as R ₄ . R ₂₂ and R ₂₃ has the same meaning as R ₁₉ and R _20. R ₂₄ has the same meaning as R ₂₁ . R ₂₅ , R ₂₇ and R ₂₈
Represents a hydrogen atom or a substituent. R ₂₆ has the same meaning as R ₄ . R ₂₉ , R ₃₁ and R ₃₂ have the same meanings as R ₂₅ , R ₂₇ and R ₂₈ . R ₃₀ has the same meaning as R ₂₆ . R _34, R ₃₅ and R ₃₆ have the same meanings as R _25, R ₂₇ and R _28. R ₃₃ is R ₂₆
Is synonymous with R ₃₈ , R ₃₉ and R ₄₀ have the same meaning as R ₂₅ , R ₂₇ and R ₂₈ . R ₃₇ has the same meaning as R ₂₆ . R ₄₁ ,
R ₄₂ and R ₄₃ have the same meanings as R _25, R ₂₇ and R _28.
R ₄₄ has the same meaning as R ₂₆ . ★ is C in general formula (3)
Represents a bonding point between P1 and another partial structure. [Formula 4] [Wherein R ₁ , R ₂ , R ₃ , R ₄ , CP1, n, R and p
Represents R ₁ , R ₂ , R ₃ , R ₄ , CP ₁ in the general formula (3).
It is synonymous with n, R and p. [Chemical formula 5] [Wherein R ₃ , n, R ₄ , W, X, Z ₁ , Z ₂ , and CP
1 represents R ₃ , n, R ₄ , W, X, or R ₃ in the general formula (3).
It is synonymous with Z ₁ , Z ₂ and CP1. [Formula 6] _{Wherein, R 1, R 2, R} 3, R 4, CP1 and n have the same meanings as _{R 1, R 2, R 3} , R 4, CP1 and n in the general formula (3). ] 4. The silver halide grains contained in the silver halide emulsion layer are tabular grains having a main plane composed of two parallel (100) planes, and having a silver chloride content of 10 mol% or more. The silver halide photographic light-sensitive material according to any one of claims 1 to 3, wherein 5. The silver halide grains contained in the silver halide emulsion layer are subjected to at least one kind of sensitization selected from reduction sensitization, selenium sensitization and tellurium sensitization in any step of emulsion production. The silver halide photographic light-sensitive material according to any one of claims 1 to 4, wherein 6. The silver halide photographic light-sensitive material according to claim 1, wherein the support is polyethylene naphthalate. 7. The silver halide photographic material according to claim 1, wherein the thickness of the polyethylene naphthalate support is 70 μm to 170 μm. 8. An X-ray image forming unit wherein the surface of the silver halide photographic material according to claim 1 having an emulsion layer and the fluorescent surface of a fluorescent intensifying screen are in close contact with each other. 9. The fluorescent intensifying screen according to claim 8, which exhibits an absorption amount of 45% or more with respect to X-rays having an X-ray energy of 80 kVp, a filling rate of the phosphor of 68% or more, and a fluorescent screen. An X-ray image forming method, wherein the thickness of the body is 135 to 200 μm, and imagewise exposure is performed by irradiating X-rays. 10. A silver halide photographic light-sensitive material characterized in that the silver halide photographic light-sensitive material according to claim 1 is processed in a processing step of an automatic developing machine including a development step. Processing method. 11. A method for processing a silver halide photographic light-sensitive material, wherein the automatic developing machine according to claim 10 has a mechanism for supplying a solid processing agent to a processing tank. 12. The method for processing a silver halide photographic light-sensitive material according to claim 10, wherein the replenisher amount replenished in the developing step and / or the fixing step is represented by the following formula. 1 ml / m ² ≤ replenisher volume / amount taken out of photosensitive material ≤
7 ml / m ² 13. A processing time required for all processing steps (Dry
13. The method for processing a silver halide photographic light-sensitive material according to claim 11, wherein (to Dry) is 30 seconds or less.