JPH10301228A - Silver halide photographic sensitive material, and x-ray image forming unit and method, and its processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the photographic sensitive material capable of obtaining stable sensitivity and stable black tone even in the case of ultrahigh-speed processing by a low replenished development processing solution by incorporating a specified developer and a specified leuco compound in a hydrophilic colloidal layer. SOLUTION: This silver halide photographic sensitive material provided on a support with the hydrophilic colloidal layers including a silver halide emulsion layer and one of the hydrophilic colloidal layer contains the leuco compound and one of the developers respected by the formula in which each of R<1> and R<5> is, independently, an H atom or a group substitutable on a benzene ring but one of R<1> and R<3> is a hydroxy, sulfonamido, or carboxamide group; Z is an H atom or a group convertible into a nonprotected state; and each of R<1> -R<5> and the OZ group may combine with each other to form a ring together with each other, thus permitting the stable black tone to be obtained, without impairing sensitivity and storage stability.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, an X-ray image forming method using the same, and a processing method thereof. It relates to an excellent silver halide photographic material.

[0002]

2. Description of the Related Art In recent years, silver halide photographic light-sensitive materials for medical use (hereinafter, also simply referred to as light-sensitive materials) for X-rays,
In addition to the increase in the number of images taken due to the rapid increase in the number of diagnoses and the number of examination items, it is necessary to promptly inform the examinee of the diagnostic results, and further rapid processing is desired. In particular, for angiography, intraoperative imaging, and the like, it is necessary to see a photograph immediately after imaging.

On the other hand, in recent years, environmental regulations are strict,
Although replenishment has been progressing to reduce the amount of photographic processing waste liquid, furthermore, since the disposal of photographic processing waste liquid into the ocean has been banned since 1996, the development of a method to fundamentally reduce the amount of waste liquid is urgent. Have been.

[0004] Further, there is an increasing need to reduce pollution of developing solutions and fixing solutions, that is, to reduce and remove environmentally unfriendly components.

In order to solve such a problem, for example, a technology in which a developing agent is incorporated in a photosensitive material and development is performed using an alkaline liquid substantially containing no developer has been proposed by Research and Development.
Disclosure (Research Disclo
Sure) 173, 17364 (1978), JP-A-50-39928, JP-A-57-84448, and JP-A-63-44848.
228148 and the like.

However, in order to obtain a sufficient concentration by these techniques, development must be performed with an alkaline liquid having a high pH (pH = 12 to 14), which is not a preferable method from an environmental point of view.

When the replenishing amount of the developing solution is reduced to improve the environment, various inhibitors and additives eluted from the photosensitive material in the running process are accumulated in the developing solution (tank) in a large amount. The film treated with such a developing solution has a problem that the silver tone obtained is affected by how the silver filaments spread and the color tone of the obtained silver image becomes yellowish.

In the case of an X-ray photosensitive material, the color tone of the image is important for the observer to directly read the silver image visually, and the yellow tint is disliked because it gives an unpleasant feeling.
It is preferably a pure black tone.

Conventional techniques for improving silver tone include:
Many studies have been made from the light-sensitive material and developer side, but many of them have drawbacks that impair photographic performance and have not been satisfactory.

It has been strongly desired to develop a technique for effectively improving the color tone of a silver image without deteriorating photographic performance and under ultra-low replenishment of a developing solution and a fixing solution.

[0011]

Accordingly, a first object of the present invention is to provide a silver halide photographic light-sensitive material capable of obtaining a pure black tone even under ultra-low replenishment of a developing solution and a fixing solution. Is to do.

A second object of the present invention is to provide a photosensitive material which is free from deterioration in photographic performance during storage over time (raw storage), and which can be used under ultra-low replenishment and rapid processing of a developing solution and a fixing solution.
An object of the present invention is to provide a silver halide photographic light-sensitive material capable of obtaining stable sensitivity and silver tone. Another object is to provide a method for forming an X-ray image using a photosensitive material having the above-mentioned performance and a method for processing the same.

[0013]

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

(1) In a silver halide photographic material having a hydrophilic colloid layer including at least one silver halide emulsion layer on a support, at least one developer is contained in the hydrophilic colloid layer; At least one of the leuco compounds
A silver halide photographic light-sensitive material comprising a seed.

(2) In a silver halide photographic light-sensitive material having a hydrophilic colloid layer containing at least one silver halide emulsion layer on a support, the hydrophilic colloid layer contains the following general formula [1] or [ 2) A silver halide photographic material comprising at least one developer represented by the formula (2) and at least one leuco compound.

[0016]

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Wherein R ^{1 to} R ⁵ may be the same or different;
Represents a hydrogen atom or a group that can be substituted on a benzene ring. Here, at least one of R ¹ and R ³ is a hydroxy group, a sulfonamide group or a carbonamide group. Z
Represents a hydrogen atom or a group capable of deprotection under alkaline conditions.

R ^{1 to} R ⁵ and OZ may form a ring together.

[0019]

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In the formula, R ⁶ and R ⁷ each independently represent a hydroxy group, amino group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkoxycarbonylamino group, mercapto group or alkylthio group. Q represents an atomic group necessary for forming a 5- to 6-membered ring together with R ⁶ and R ⁷ .

(3) In a silver halide photographic material having a hydrophilic colloid layer including at least one silver halide emulsion layer on a support, at least one developer is contained in the hydrophilic colloid layer; A silver halide photographic material comprising at least one leuco compound represented by the following general formula [3].

[0022]

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In the formula, R ₁ and R ₂ each represent an alkyl group or an aryl group. R ₃ represents a hydrogen atom, a halogen atom or a monovalent substituent, and n represents an integer of 1 to 3. X, Z
₁ and Z _2, 5-6 together with the carbon atom adjacent to Z _1, Z ₂
Represents an atomic group necessary for forming a membered aromatic carbocycle or aromatic heterocycle. 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. CP represents the following group.

[0024]

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In the formula, R ₅ , R ₆ , R ₇ and R ₈ each represent a hydrogen atom, a halogen atom or a substituent which 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 and R ₁₂ have the same meaning as R ₄ . R ₁₀ and R ₁₁ each represent an alkyl group, an aryl group or a heterocyclic group. R ₁₃ , R ₁₄ and R ₁₅ have the same meanings as R ₁₀ , R ₁₁ and R ₁₂ , respectively. R ₁₆ represents an alkyl group, an aryl group, a sulfonyl group, a trifluoromethyl group, a carboxyl 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. R ₁₉ and R ₂₀ each represent an alkyl group or an aryl group. R ₂₁ and R ₂₄ have the same meanings as R _4, R ₂₂ and R ₂₃ have the same meanings as R ₁₉ and R _20, respectively. Y represents an atomic group necessary for forming a 5- or 6-membered monocyclic or condensed nitrogen-containing heterocyclic ring together with two nitrogen atoms. * Indicates a bonding point between CP and other partial structures 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 to 100. (1)
The silver halide photographic material according to any one of (3) and (3).

(5) The support according to any one of (1) to (4), wherein the support is polyethylene naphthalate.
6. The silver halide photographic light-sensitive material according to item 1.

(6) X-ray image formation characterized in that the silver halide photographic material according to any one of (1) to (5) is sandwiched between two fluorescent intensifying screens. unit.

(7) Using the X-ray image forming unit of (6) above, an X-ray having an X-ray energy of 80 kVp
An X-ray image forming method, comprising: a fluorescent intensifying screen having an absorption amount of 5% or more, a filling rate of the phosphor of 68% or more, and a thickness of the phosphor of 135 to 200 μm.

(8) The silver halide photographic material described in any one of (1) to (5) above, which is processed by an automatic developing machine including a development processing step. Processing method of photosensitive material.

(9) The method for processing a silver halide photographic material according to (8), wherein the processing is performed by an automatic developing machine having a mechanism for supplying a solid processing agent to a processing tank of the automatic developing machine.

(10) The silver halide photograph described in (8) or (9), wherein the amount of replenisher to be replenished to the developing tank or the fixing tank of the automatic developing machine is represented by the following formula (A). Processing method of photosensitive material.

Formula (A) 1 ≦ replenisher amount / amount taken out by photosensitive material ≦ 5 Hereinafter, the present invention will be described in detail.

The developer used in the silver halide photographic light-sensitive material of the present invention refers to a compound known as a developing agent or a development auxiliary agent, and a hydrophilic colloid layer such as an emulsion layer constituting the photographic material of the present invention. , A protective layer, an intermediate layer, and other non-photosensitive layers, but it is preferably contained in an emulsion layer or an intermediate layer or a protective layer farther from the support than the emulsion layer.

The developer used in the present invention must be a compound having a function of causing the leuco compound simultaneously used in the present invention to develop a blue color by an oxidation-reduction reaction of an oxidant generated by a development reaction. Hereinafter, the compound represented by formula (1) or (2) of the present invention will be described in more detail.

Preferred examples of the substituent represented by R ^{2 to} R ⁶ in the general formula [1] include a halogen atom (for example, chlorine and bromine), a hydroxy group, a sulfo group, a carboxyl group, a cyano group and an alkyl group. (C1-C30 linear, branched or cyclic ones such as methyl, sec-
Octyl, t-octyl, hexadecyl, cyclohexyl), alkenyl group (having 2 to 30 carbon atoms, for example, allyl, 1-octenyl), alkynyl group (having 2 to 30 carbon atoms, for example, propargyl), aralkyl group ( With 7 to 30 carbon atoms, for example, 1,1-dimethyl-1-phenylmethyl, 3,5-di-t-butyl-2-
Hydroxyphenylmethyl), aryl group (having 6 to 6 carbon atoms)
30, a 3- to 12-membered ring containing at least one of phenyl, naphthyl) and a heterocyclic group (oxygen, nitrogen, sulfur, phosphorus, selenium, or tellurium, for example, furfuryl, 2-pyridyl, morpholino, 1-tetrazolyl, 2-selenazolyl), alkoxy group (1 to 3 carbon atoms)
0, for example, methoxy, methoxyethoxy, hexadecyloxy, isopropoxy, allyloxy), aryloxy group (of 6 to 30 carbon atoms, for example, phenoxy, 4-nonylphenoxy), alkylthio group (1 to 30 carbon atoms) Such as butylthio, dodecylthio,
2-hexyldecylthio, benzylthio), arylthio group (having 6 to 30 carbon atoms, for example, phenylthio), carbonamido group (having 1 to 30 carbon atoms, for example, acetamide, 2- (2,4-di- t-pentylphenoxy) butanamide, benzamide, 3,5-bis (2-hexyldecanamido) benzamide), sulfonamide group (having 1 to 30 carbon atoms such as methanesulfonamide, 4- (2,4-di- (t-pentylphenoxy) butanesulfonamide, benzenesulfonamide, 4-dodecyloxybenzenesulfonamide), ureido group (having 1 to 30 carbon atoms such as N'-octadecylureido, N '-[3- (2 , 4-Di-t-pentylphenoxy) propyl] ureido, N '-(4-cyanophenyl) ureido, '-(2-tetradecyloxyphenyl) ureido), an alkoxycarbonylamino group (having 2 to 30 carbon atoms, for example, benzyloxycarbonylamino, ethoxycarbonylamino), an aryloxycarbonylamino group (having 7 to 30 carbon atoms) For example, phenoxycarbonylamino), acyloxy group (having 1 to 30 carbon atoms, for example, acetoxy, dichloroacetoxy, 4-oxopentanoyloxy,
(2,4-di-t-pentylphenoxy) hexanoyloxy, benzoyloxy, nicotinoyloxy), sulfamoylamino group (having 30 or less carbon atoms, for example, N'-benzyl-N'-methylsulfa Moylamino, N'-phenylsulfamoylamino), a sulfonyloxy group (having 1 to 30 carbon atoms, for example, methanesulfonyloxy, benzenesulfonyloxy), a carbamoyl group (having 1 to 30 carbon atoms, for example, N -Dodecylsulfamoyl, N- [3- (2,4-di-t-pentylphenoxy) propyl] carbamoyl, N- [2-chloro-5- (1-dodecyloxycarbonylethyloxycarbonyl) phenyl] carbamoyl ), Sulfamoyl group (having 30 or less carbon atoms, for example, ethylsulfamoyl, hexadecyl) Rufamoyl, 4- (2,4-di-t-pentylphenoxy) butylsulfamoyl, phenylsulfamoyl), acyl group (having 1 to 30 carbon atoms, for example, acetyl, octadecalyl, benzoyl), sulfonyl group ( Having 1 to 30 carbon atoms, for example, methanesulfonyl, octadecanesulfonyl, benzenesulfonyl, 4-dodecylbenzenesulfonyl), alkoxycarbonyl group (having 2 to 30 carbon atoms, for example, ethoxycarbonyl, dodecyloxycarbonyl, benzyloxy) Carbonyl), and an aryloxycarbonyl group (having 7 to 30 carbon atoms, for example, phenoxycarbonyl). These groups may be further substituted with the groups mentioned above.

Next, Z in the general formula [1] will be described. Z is a hydrogen atom or a protecting group that can be deprotected under alkaline conditions. Examples of the protecting group for Z include an acyl group (for example, acetyl, chloroacetyl, dichloroacetyl, benzoyl, 4-cyanobenzoyl, 4-oxopentanoyl), an oxycarbonyl group (for example, ethoxycarbonyl, phenoxycarbonyl, 4-methoxybenzyl) Oxycarbonyl), a carbamoyl group (for example, N-methylcarbamoyl, N- (4-nitrophenyl) carbamoyl, N (2-pyridyl) carbamoyl, N- (1-imidazolyl) carbamoyl), and JP-A-59-197.
Nos. 037, 59-201057, 59-1087
No. 76 and U.S. Pat. No. 4,473,537.

When OZ and R ^{2 to} R ⁶ together form a ring, preferably OZ and R ² , R ² and R ³ , R ³ and R ⁴ ,
R ⁴ and R ⁵ , R ⁵ and R ^6, or R ⁶ and O—Z combine to form a saturated or unsaturated 4- to 8-membered carbocyclic or heterocyclic ring.

The compound represented by the general formula [1] may form a bis-form, a tris-form, an oligomer or a polymer. The total number of carbon atoms of R ^{2 to} R ^{6 in} the general formula [1] is preferably 8 or more.

Of the general formula [1], the following general formulas [1-1] to [1-4] are preferred.

[0041]

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In the general formula [1-1], X represents a hydroxy group or a sulfonamide group, and R ² , R ³ , R ⁵ and R ⁶ have the same meanings as those in the general formula [1].

[0043]

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In the general formula [1-2], X is a hydroxy group or a sulfonamide group, and R ² to R ⁵ have the same meaning as in the general formula [1].

[0045]

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In the general formula [1-3], X is a hydroxy group or a sulfonamide group, Y is a carbamoyl group,
Oxycarbonyl, acyl group or sulfonyl group,
R ³ and R ⁵ have the same meanings as those in formula [1].

[0047]

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In the general formula [1-4], R ^{51 to} R ⁵⁸ have the same meaning as R ^{2 in the} general formula [1], and R ^{59 to} R ⁶² are a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. , N is an integer of 0 to 50.

In the general formula [1-1], R ² , R ³ , R
⁴ , R ⁵ are preferably a hydrogen atom, a halogen atom, a sulfo group, an alkyl group, an ether group, a thioether group, a carbonamide group, a sulfonamide group, a ureido group, a sulfonyl group, a carbamoyl group, an acyl group, and more preferably A hydrogen atom, a halogen atom, a sulfo group, an alkyl group, a carbonamide group, a sulfonamide group, a sulfonyl group, and most preferably, one of R ² and R ⁵ is an alkyl group, a carbonamide group, or a sulfonamide group. The other is a hydrogen atom, a halogen atom, a sulfo group, a sulfonyl group, or an alkyl group. X is preferably a hydroxy group.

In the general formula [1-2], R ^{2 to} R ⁵ are preferably a hydrogen atom, an alkyl group, an ether group, a thioether group, a carbonamide group, a sulfonamide group, a ureido group, a sulfonyl group, a carbamoyl group, an oxy group. Carbonyl, an acyl group, more preferably a hydrogen atom,
An alkyl group, an ether group, a thioether group, a carbonamide group, and a sulfonamide group, most preferably a hydrogen atom, an alkyl group, and an ether group. R ³ , R ⁴
Are preferably a hydrogen atom, an alkyl group, a halogen atom, and an ether group, more preferably a hydrogen atom and an alkyl group, and most preferably a hydrogen atom. X is preferably a hydroxy group.

In the general formula [1-3], X is preferably a hydroxy group, and Y is preferably a carbamoyl group or an oxycarbonyl group.

In the general formula [1-4], R ^{51 to} R ⁵⁸ are preferably a hydrogen atom, a halogen atom, an alkyl group,
Ether group, thioether group, carbonamide group, sulfonamide group, sulfonyl group, acyl group, carbamoyl group, more preferably hydrogen atom, halogen atom, alkyl group, carbonamide group, sulfonamide group, ether group, thioether group And most preferably a hydrogen atom, a halogen atom, an alkyl group, and a carbonamido group. When n = 0, R ⁵² and R ⁵⁴ are preferably an alkyl group, a carbonamide group, or a sulfonamide group. n is 0
In other ^cases , R ⁵² and R ⁵⁴ are preferably hydrogen atoms. n is 0
Alternatively, an integer of 20 to 50 is preferable.

Specific examples of the compound represented by the general formula [1] according to the present invention are shown below, but the present invention is not limited thereto.

[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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The compound represented by the general formula [1] according to the present invention can be synthesized by the methods described in the following patents and the patents cited therein, and methods analogous thereto.

Among the compounds represented by the general formula [1-1], monoalkyl-substituted hydroquinones are disclosed in US Pat.
Nos. 60,290, 2,419,613, 2,40
3,721, 3,960,570, 3,70
No. 0,453, JP-A-49-106329 and JP-A-49-106329.
No. 156438, dialkyl-substituted hydroquinones are disclosed in U.S. Pat. Nos. 2,728,659 and 2,732,300.
No. 3,243,294, 3,700,453
No., JP-A-50-156438 and JP-A-53-9528.
Nos. 53-55121, 54-29637 and 60-55339, hydroquinone sulfonates are disclosed in U.S. Pat. No. 2,701,197, and JP-A-60-1.
No. 72040, No. 61-48855, No. 61-488
No. 56, amide hydroquinones are disclosed in U.S. Pat.
Nos. 8,239 and 4,732,845;
150346 and 63-309949, hydroquinones having an electron-withdrawing group are disclosed in JP-A-55-4352.
No. 1, No. 56-109344, No. 57-22237
And No. 58-21249.

Compounds represented by the general formula [1-2] are disclosed in US Pat. Nos. 4,447,523 and 4,525,451;
JP-A-4,530,899, JP-A-4,584,264, JP-A-4,717,651, JP-A-59-220733,
Nos. 61-169845, JP-B-62-1386 and West German Patent 2,732,971 disclose compounds represented by the general formula [I-3] in U.S. Pat. Nos. 4,474,874 and 4,476. No. 219, JP-A-59-133544, compounds represented by the general formula [I-4] are described in U.S. Pat. Nos. 2,710,801, 2,816,028, 4,717,651, It is described in JP-A-57-17949 and JP-A-61-169844.

Further, examples of the alkali precursor of hydroquinone are described in US Pat. No. 4,443,537 and JP-A-59-108776.

Next, the compound of the general formula [2] of the present invention will be described in detail.

In the general formula [2], R ⁶ and R ⁷ are each independently a hydroxy group, -OM (M represents an alkali metal atom or an ammonium group), an amino group (a methyl group, an ethyl group as a substituent) , N-butyl group, hydroxyethyl group and the like having an alkyl group having 1 to 10 carbon atoms), acylamino group (acetylamino group, benzoylamino group and the like), alkylsulfonylamino group (methanesulfonylamino group and the like) ), Arylsulfonylamino group (benzenesulfonylamino group, p-toluenesulfonylamino group, etc.), alkoxycarbonylamino group (methoxycarbonylamino group, etc.), mercapto group, alkylthio group (methylthio group, ethylthio group, etc.), Is hydroxy, amino, alkylsulfonylamino, aryl It is a sulfonylamino group. Q is -O
_{-, - C (R 1)} (R 2) -, - C (R 3) =, - C (=
O) -, - N (R 4) -, - N = , etc., preferably a carbon atom, an oxygen atom or a nitrogen atom, jointly with two vinyl carbon and carbonyl carbon R ⁶ and R ⁷ is substituted Form a 5- to 6-membered ring. Here, R _{1 to} R ₄ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent (such as a hydroxy group, a carboxy group, or a sulfo group); , A hydroxy group, a carboxy group, a sulfo group, etc.)
Represents an aryl group, a hydroxy group, or a carboxy group. A saturated or unsaturated condensed ring may be formed on the constituent 5- to 6-membered ring, and a dihydrofuranone ring, a dihydropyrone ring,
Pyranone ring, cyclopentenone ring, cyclohexenone ring, pyrrolinone ring, pyrazolidone ring, pyridone ring, azacyclohexenone ring, uracil ring and the like, preferably dihydrofuranone ring, cyclopentenone ring, cyclohexenone ring, pyrazolidone ring Azacyclohexenone ring and uracil ring.

Specific examples of the compound represented by the general formula [2] are shown below, but it should not be construed that the invention is limited thereto.

[0066]

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[0067]

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[0068]

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[0069]

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In the present invention, the above general formula [1],
The amount of the developer [2] added may be 0.01 to 10 mol, preferably 0.05 to 2 mol, more preferably 0.1 to 1 mol per mol of silver halide contained in the silver halide emulsion layer. １1 mol. The developers used in the present invention may be used in combination of two or more kinds.

The timing of adding the developer represented by the above general formulas [1] and [2] may be any time during the chemical ripening step when it is added to the silver halide emulsion. It is preferably added to the steps from to the coating, and when it is used for a hydrophilic colloid other than an emulsion, it is preferably added to a coating solution.

The emulsion layer and / or hydrophilic colloid layer of the light-sensitive material of the present invention contains a leuco compound. Hereinafter, the leuco compound represented by the general formula [3] will be described in detail.

In the general formula [3] of the present invention, the alkyl group represented by R ₁ and R ₂ is preferably methyl,
Examples include groups such as ethyl, propyl, and butyl. These may be further substituted, and preferred substituents include a hydroxyl group and a sulfonamide group. R ₁ and R ₂
The aryl group represented by preferably a phenyl group. Examples of the monovalent substituent represented by R ₃ include an alkyl group (methyl, ethyl, i-propyl, hydroxyethyl, methoxymethyl, trifluoromethyl, t-butyl and the like), a cycloalkyl group (cyclopentyl, cyclohexyl and the like), Aralkyl groups (benzyl, 2-phenethyl, etc.), aryl groups (phenyl, naphthyl, p-tolyl, p-chlorophenyl, etc.), alkoxy groups (methoxy, ethoxy, i-propoxy, butoxy, etc.), aryloxy groups (phenoxy, etc.) , Cyano group, acylamino group (acetylamino, propionylamino, etc.), alkylthio group (methylthio, ethylthio, butylthio, etc.),
Arylthio groups (phenylthio, p-tolylthio, etc.),
Sulfonylamino group (methanesulfonylamino, benzenesulfonylamino, etc.), ureido group (3-methylureide, 3,3-dimethylureide, 1,3-dimethylureide, etc.), sulfamoylamino group (dimethylsulfamoylamino, etc.) ), Carbamoyl groups (methylcarbamoyl, ethylcarbamoyl, dimethylcarbamoyl, etc.), sulfamoyl groups (ethylsulfamoyl, dimethylsulfamoyl, etc.), alkoxycarbonyl groups (methoxycarbonyl, ethoxycarbonyl, etc.), aryloxycarbonyl groups (phenoxycarbonyl) ), Sulfonyl group (methanesulfonyl, butanesulfonyl, phenylsulfonyl, etc.), acyl group (acetyl, propanoyl, butyroyl, etc.), amino group (methylamino, ethylamino, dimethylamido) Etc.), a hydroxyl group, a nitro group, an imido group (phthalimide), a Hajime Tamaki (pyridyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, etc.).

[0074] X, Z ₁ and Z ₂ and Z _1, benzene ring as the aromatic carbon ring 5-6 membered formed by a carbon atom adjacent to Z _2, a naphthalene ring and the like, preferably benzene And a 5- or 6-membered aromatic heterocycle, similarly, pyridine, pyrimidine, pyridazine, pyrazine,
Each ring of triazine, tetrazine, pyrrole, furan, thiophene, thiazole, oxazole, imidazole, thiadiazole, oxadiazole and the like,
Preferably it is a pyridine ring.

Examples of the substituent that can be substituted on the benzene ring represented by R _{5 to} R ₈ include the aforementioned monovalent substituents. Preferably it is an alkyl group.

The 5- to 7-membered ring formed by bonding R ₅ and R ₆ and R ₇ and R ₈ to each other includes an aromatic carbon ring and an aromatic heterocyclic ring, and is preferably a benzene ring.

Examples of the alkyl group represented by R ₁₀ and R ₁₁ include methyl, ethyl, propyl, butyl and the like. Examples of the aryl group include a phenyl group and a naphthyl group, and examples of the heterocyclic group include a 5- to 6-membered aromatic heterocycle (pyridine, pyrazine, pyrimidine ring) having at least one of oxygen, sulfur and nitrogen atoms in the ring. 6-membered ring azines and their benzerogues; pyrrole, thiophene, furan and their benzerogues; imidazole, pyrazole, triazole, tetrazole, thiazole, oxazole, thiadiazole, oxadiazole and other 5-membered ring azoles and their residues Is mentioned. R
Preferably as ₁₀ and R ₁₁ phenyl, pyrazolyl,
And groups such as pyridyl.

Examples of the alkyl group represented by R ₁₆ include groups such as methyl, i-propyl, pentyl and t-butyl, and examples of the aryl group include phenyl and naphthyl groups. Examples of the sulfonyl group include benzenesulfonyl and the like, examples of the aryloxycarbonyl group include phenoxycarbonyl and the like, examples of the alkoxycarbonyl group include ethoxycarbonyl and the like, and examples of the carbamoyl group include diethylaminocarbonyl and the like.

Examples of the nitrogen-containing heterocyclic ring represented by Y include imidazole, triazole and tetrazole rings and benzo-fused rings thereof.

The alkyl group represented by R ₁₉ and R ₂₀ includes methyl, pentyl, t-butyl and the like, and the aryl group includes phenyl and naphthyl.

Hereinafter, typical specific examples of the leuco compound represented by the general formula [3] will be listed, but the present invention is not limited thereto.

[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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The amount of the leuco compound represented by the general formula [3] of the present invention may be 1 × 10 ^{-6 to} 5 × 10 ^-1 mol per mol of silver in a medical light-sensitive material. The effect of the present invention is preferable, and when less than 1 × 10 ⁻⁶ mol per mol of silver, the effect of improving silver tone is small,
On the other hand, if it exceeds 5 × 10 ^-1 mol, the whole image is undesirably dark. Therefore, the addition amount of the leuco compound,
5 × 10 ^{-5 to} 5 × 10 ^-2 mol, especially 5 ×, per mol of silver
Most preferably, it is contained in an amount of 10 ^-4 to 1 × 10 ^-2 mol.

As the method of adding the leuco compound, any method is used depending on the properties of the compound. For example, a method of adding as a solid fine particle dispersion, a method of dissolving in a high boiling point solvent and performing the above dispersion and then adding, a method of dissolving in a water-miscible organic solvent (methanol, ethanol, acetone, etc.) and adding the same are included. No.

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 (methanol, ethanol, acetone, etc.) 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, and the average particle size of the dye fine particles to be solid-dispersed may take an arbitrary value. It is preferably 0.01 to 20 μm, more preferably 0.03 to 2 μm.

The leuco compound can be contained in any layer in the photographic constituent layers. However, from the viewpoint of intensifying screen contamination, for X-ray photography, the emulsion layer or the layer between the emulsion layer and the support is used. Is preferably contained in the hydrophilic colloid layer.

The silver halide emulsion layer of the present invention is preferably an emulsion layer having a silver chloride content of 30 to 70 mol%, and a silver iodide content of 1.0 mol% or less.
More preferably, the emulsion is 0.5 mol% or less.

The silver halide grains according to the present invention are preferably tabular grains having two parallel (100) planes as main planes. The aspect ratio is preferably from 2.0 to 15.0. The term "principal plane" used herein refers to 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 relative to the thickness between the principal planes. It refers to the ratio of the average edge length forming a plane.

The average edge length of the main plane can be determined, for example, by photographing the particles with an electron microscope at a magnification of 10,000 to 50,000 times, and measuring the edge length of the particles 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 according to the present invention, but preferably 80% or more.

The maximum adjacency ratio of the tabular silver halide grains of the present invention is the maximum adjoining side length ratio of the (100) main plane. The coefficient of variation (P) represents the width of the grain size distribution of silver halide grains, and P = {(standard deviation of grain size distribution) / (average grain size)} × 10
The maximum adjacency ratio and the coefficient of variation are both measured using an electron microscope.

The silver halide emulsion according to the present invention includes:
Silver iodochloride, silver chloroiodobromide having a silver chloride content of 20 mol% or more can be used, and a silver chloride content of 30 to 7 is preferred.
0 mol% and a silver iodide content of 1.0 mol% or less (more preferably 0.5 mol% or less).

The emulsion containing the tabular silver halide grains of the present invention can be obtained by the following steps: (a) a step of introducing a silver salt and a halide salt into a dispersion medium to form nuclei of the tabular grains; Subsequently, it is prepared by a step of performing Ostwald ripening under conditions that maintain the (100) main surface of the tabular grains, and (c) a step of growing grains so as to obtain 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 simultaneous mixing method is also used during grain growth, but as one type of the simultaneous mixing method, a method of keeping the pAg in a liquid phase in which silver halide is formed constant, that is, a so-called controlled double jet method may be used. it can. 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. Since the particle size of the fine particles governs the supply rate of the halide ions, the preferred particle size varies depending on the size and halogen composition of the silver halide grains of the host, but those having an average equivalent sphere diameter of 0.3 μm or less are used. More preferably, it is 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 desirably smaller than the equivalent sphere diameter of the host particles, and more preferably 1/10 or less of the equivalent sphere diameter.

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 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 Desalting method using the exemplified G-3, G-8, etc. Also, Research Disclosure (RD) Vol. 102, 1972, 10
Monthly, Item 10208 and Vol. 131, 197
Desalination may be carried out using an ultrafiltration method described in the May 13 issue, Item 13122.

In the silver halide emulsion of the silver halide photographic light-sensitive material of the present invention, various hydrophilic colloids (hydrophilic binder) for enclosing the silver halide are used as a binder. For this purpose, gelatin and synthetic polymers such as polyvinyl alcohol and polyacrylamide, and photographic binders such as colloidal albumin, polysaccharides and cellulose derivatives may be used.

The amount of the hydrophilic binder per one side of the hydrophilic colloid layer is preferably 1.0 to 3.0 g / m ² , more preferably 1.5 to 3.0 g / m ^2.
２．５2.5 g / m ² .

Next, polyethylene naphthalate, which is a preferred support of the silver halide photographic light-sensitive material of the present invention, will be described.

The polyethylene naphthalate referred to in the present invention is polyethylene-2,6-naphthalate, which is a polymer whose constituent units are substantially composed of ethylene-2,6-naphthalate units. For example, 10 mol% or less, preferably 5 mol% or less of the third
Also included are ethylene-2,6-naphthalate polymers modified by the component.

Polyethylene-2,6-naphthalate is
In general, it is prepared 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,
Dicarboxylic acids such as 7-dicarboxylic acid and diphenyl ether dicarboxylic acid or lower alkyl esters thereof, p
Dicarboxylic acids such as oxybenzoic acid and p-ethoxybenzoic acid, or lower alkyl esters thereof, or dihydric alcohols such as propylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, diethylene glycol, and polyethylene; And polyalkylene glycols such as glycol and polytetramethylene glycol.

Further, during 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 an intrinsic 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.

The polyethylene-2,6-naphthalate film of the present invention can be used in applications where dust is deposited during use, which reduces its commercial value, so that its surface specific resistance value is 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) 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.

When the silver halide photographic light-sensitive material of the present invention is applied to medical X-ray radiography, for example, a fluorescent material mainly composed of a phosphor which generates near-ultraviolet light or visible light upon exposure to penetrating radiation. An intensifying screen is used. This is adhered to both surfaces of a light-sensitive material obtained by coating the silver halide emulsion layer of the present invention on both surfaces and X-ray irradiation is performed to perform imagewise exposure.

Here, the penetrating radiation is a high-energy electromagnetic wave and means X-rays and γ-rays.

The image forming unit referred to in the present invention includes a silver halide photographic material obtained by coating the silver halide emulsion layer of the present invention on both sides, and a specific silver halide photographic material of the present invention disposed in close contact with both sides thereof. It refers to a combination with a fluorescent intensifying screen.

The specific fluorescent intensifying screen of the present invention is X
It refers to those having an absorption of 45% or more with respect to X-rays having a line energy of 80 kVp, a filling factor of the phosphor of 68% or more, and a thickness of the phosphor of 135 μm to 200 μm.

Preferred phosphors for use in the fluorescent intensifying screen of the present invention 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, LaOCl: Tb. Tm. LaOBr: Tb
GdOBr: TbGdOCl: Tb), thulium-activated rare earth oxyhalide-based phosphor (LaOBr: T
m, LaOCl: Tm, etc.), barium sulfate-based phosphor [B
aSO ₄ : Pb, BaSO ₄ : Eu ²⁺ , (Ba.Sr) S
O ₄ : Eu ²⁺ etc.] divalent eurobium-activated alkaline earth metal phosphate-based phosphor [(Ba ₂ PO ₄ ) ₂ : Eu ²⁺ ,
(Ba ₂ PO ₄ ) ₂ : Eu ²⁺ etc.] divalent eurobium-activated alkaline earth metal fluorinated halide-based phosphor [BaF
Cl: Eu ²⁺ , BaFBr: Eu ²⁺ , BaFCl: Eu
²⁺ . Tb, BaFBr: Eu ²⁺ . Tb, BaF ₂ · Ba
Cl · KCl: Eu ²⁺ , (Ba · Mg) F ₂ · BaCl
.KCl: Eu ²⁺ etc.], iodide-based phosphor (CsI: N
a, CsI: Tl, NaI, KI: Tl, etc.), sulfide-based phosphor [ZnS: Ag (Zn.Cd) S: Ag, (Z
n. Cd) S: Cu, (Zn. Cd) S: Cu. Al
Etc.), a hafnium phosphate-based phosphor (HfP ₂ O ₇ : Cu
Etc.) However, the phosphor used in the present invention is not limited to these, and any phosphor that emits light in the visible or near ultraviolet region upon irradiation with radiation can be used.

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

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 in which a phosphor is uniformly dispersed in a binder solution onto a temporary support for forming a phosphor sheet, and drying the coating solution. Then, it can be manufactured by peeling off from the temporary support. That is, first, a binder and phosphor particles are added to an appropriate organic solvent, and the mixture is stirred and mixed to prepare a coating solution in which the phosphor is uniformly dispersed in the binder.

The binder has a softening temperature or a melting point of 30.
A thermoplastic elastomer at ~ 150 ° C 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, fluororubber, polyisoprene, chlorinated polyethylene, styrene-butadiene rubber and silicone rubber. At least one thermoplastic elastomer selected from the group consisting of: The mixing ratio of the thermoplastic resin in the binder may be from 10 to 100% by weight, but the binder is preferably composed of as many thermoplastic elastomers as possible, particularly preferably 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 1-1: 100 (weight ratio), particularly 1:
It is preferable to select from the range of 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 bonding agent between the binder and the phosphor in the formed phosphor layer is used. Various additives such as a plasticizer may be mixed.

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

Examples of the plasticizer include phosphoric esters such as triphenyl phosphate, tricresyl phosphate and diphenyl phosphate; phthalic esters such as diethyl phthalate and dimethoxyethyl phthalate; ethyl phthalyl ethyl glycolate; butyl phthalbutyl 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 sheet formation to form a coating film of the coating solution.

As the application 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, aluminum foil,
Metal sheets such as aluminum alloy foil, general paper and printing base paper such as photographic base paper, coated paper or art paper, baryta paper, resin coated paper, described in Belgian Patent 784,615. Particularly preferred are papers sized with such polysaccharides, pigment papers containing pigments such as titanium dioxide, and papers sized with polyvinyl alcohol.

After a coating solution for forming a phosphor layer is applied on 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.

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

The fluorescent intensifying screen is provided with an 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 obtained as described above is placed on a support, and the phosphor sheet is bonded to the support while being compressed at a temperature not lower than the softening temperature or the melting point of the binder.

As described above, by utilizing the method of pressing the sheet without previously fixing it on the phosphor sheet support, 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.

Usually, the fluorescent intensifying screen is provided with a transparent protective film for physically and chemically protecting the phosphor layer on the surface of the phosphor layer opposite to the side 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 μm.

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

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

The fluorine-based resin is a polymer of a fluorine-containing olefin (fluoroolefin) or a copolymer containing a fluorine-containing olefin as a copolymer component, such as polytetrafluoroethylene, polychlorotrifluoroethylene, or polyfluoroethylene. Examples include ethylene fluoride, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, and fluoroolefin-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 resin, and may contain a crosslinking agent, a hardener, a yellowing inhibitor 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.
It is preferably at least 50% by weight, more preferably at least 70% by weight.

Examples of the resin other than the fluorine-based 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 made of either a polysiloxane skeleton-containing oligomer or a perfluoroalkyl group-containing oligomer.
Alternatively, it may be formed from a coating film containing both.

The polysiloxane skeleton-containing oligomer has, for example, a dimethylpolysiloxane skeleton.
It preferably has at least one functional group, for example, a hydroxyl group, and has a molecular weight of 500 to 100,000.
It is preferably in the range of 0. Especially when the molecular weight is 1,000
It is preferably in the range of 0 to 100,000, and more preferably in the range of 3,000 to 10,000.
The oligomer containing a perfluoroalkyl group, for example, a tetrafluoroethylene group, preferably has at least one functional group, for example, a hydroxyl group in the molecule, and preferably has a molecular weight of 500 to 100,000. . In particular, the molecular weight is 1,000-100,
000, preferably 100 to 1
It is preferably in the range of 00,000.

If an oligomer containing a functional group is used, a crosslinking reaction occurs between the oligomer and the resin for forming the protective layer 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 even by long-term repeated use of the fluorescent intensifying screen or the operation of cleaning the protective film surface, and the effect of adding the oligomer is effective for a long time. 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 perfluoroolefin resin powder or 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 μm to 10 μm are preferable, and the average particle diameter is particularly preferably 0.3 μm.
m to 5 μm. The perfluoroolefin resin powder or the silicone resin powder is preferably contained in the protective film in an amount of 0.5 to 30% by weight, more preferably 2 to 20% by weight, based on the weight of the protective film. Preferably, it is most preferably in an amount of from 5 to 15% by weight.

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

The filling rate of the phosphor in the phosphor layer of the fluorescent intensifying screen of the present invention is at least 68%, and when it is less than 68%, the fluorescent sensitizing effect becomes insufficient.

The filling factor T of the phosphor in the phosphor layer of the fluorescent intensifying screen is measured as follows.

That is, after the protective layer of the phosphor layer of the fluorescent intensifying screen was peeled off and removed, the phosphor layer was eluted with methyl ethyl ketone, filtered, dried, and further dried with an electric furnace.
By baking at 0 ° C. for 1 hour to remove the resin component, only the phosphor was taken out of the phosphor layer. The weight of this phosphor is measured, and is defined as Wg. Further, the thickness Pcm, the area Qcm ² and the density Rg / cm ³ of the phosphor layer are measured. From these measured values, the phosphor filling rate T of the phosphor layer is calculated by the following equation.

T = {W} (P × Q × R)} × 100% In the present invention, the specific filtration is 2.2 mm of aluminum.
It is preferable to use a fluorescent intensifying screen that shows an absorption of 45% or more, and more preferably 50% or more, of X-rays having an X-ray energy of 80 kVp in a considerable X-ray generator. 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.

The thickness of the phosphor layer is 135 to 200 μm, and the filling rate of the phosphor in the phosphor layer is 68% or more.

If the thickness of the phosphor layer is less than 135 μm, the sensitizing effect of the fluorescent intensifying screen becomes insufficient, and
If it exceeds m, the sensitizing effect is saturated and the material is wasted. On the other hand, if the filling rate of the phosphor is less than 68%, the sensitizing effect of the fluorescent intensifying screen is still insufficient, which is not preferable.

The processing method and apparatus after the silver halide photographic light-sensitive material of the present invention has been subjected to image exposure by X-ray irradiation will be described.

In the developer used in the processing method of the present invention, in addition to dihydroxybenzenes, aminophenols and pyrazolidones as developing agents, JP-A-5-1651
Reductones described in JP-A-61-61 may also be used. 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.

The light-sensitive material of the present invention is preferably subjected to development processing even when a developing solution substantially free of a developing agent such as hydroquinone which is oxidized to a black-brown tar is used. The term "developer substantially free of a developing agent" as used herein refers to a developer which does not contain a hydroxybenzene-based developing agent such as hydroquinone in an amount of 0.03 mol or more per liter of the developing solution.

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. Further, a silver sludge inhibitor, a cyclodextrin compound, an amine compound described in U.S. Pat. No. 4,269,929, and the like can be added.

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

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

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

Further, the developer composition includes methyl cellosolve, methanol, acetone, dimethylformamide, cyclodextrin compound, JP-B-47-33378,
The compounds described in JP-A-44-9509 and the like can be used as an organic solvent for increasing the solubility of a developing agent, and other stain inhibitors, sludge inhibitors, and multilayer effect promoters can also be used. .

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 or the like, and in the case of granules or powders, Japanese Utility Model Laid-Open Nos. 62-81964 and 6
3-84151, JP-A-1-292375, etc.
Nos. 63-195345, etc., but reference can be made to a method using a screw or a screw, but the 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.

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 10 to 45 seconds,
When processed in seconds, the effect can be demonstrated without regret. If the total processing time (Dry tory) is less than 10 seconds, processing such as development, fixing, washing and drying is insufficient, which is not preferable.

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

In the processing of the silver halide photographic light-sensitive material of the present invention, it is preferable to use an automatic developing machine to which a member for charging a solid processing agent is connected. It is preferable from the viewpoint of drying efficiency to employ a transport roller (heat roller) whose outer periphery is heated by the above. Further, the transport roller preferably has a heat source inside the roller.

In the process of processing the silver halide photographic light-sensitive material of the present invention, the replenisher amounts of processing solutions such as a developing solution and a fixing solution must satisfy the following formula (A).

Formula (A) 1 ≦ Amount of replenisher / Amount taken out by photosensitive material ≦ 5 In the above formula (A), when (Amount of replenisher / Amount taken out by photosensitive material) is less than 1, the processing solution becomes insufficient. If the number exceeds 5, the processing liquid is wasted and the cost is increased. 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.

[0181]

Hereinafter, the present invention will be described with reference to examples.
Embodiments of the present invention are not limited to this.

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

[0183] A1 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% aqueous methanol solution 5.6 ml KBr 26.8 g 10% H ₂ SO ₄ 144 ml B1 silver nitrate 1487.5 g Make up to 3500 ml with distilled water C1 KBr 1050 g Make up to 3500 ml with distilled water D1 1.75 N aqueous KBr solution Silver below Potential control amount At 35 ° C., using a mixing stirrer described in JP-B-58-58288, 64.1 ml of each of the solution B1 and the solution C1 were added to the solution A1 by a simultaneous mixing method over a period of 2 minutes. And nucleation.

After the addition of the solution B1 and the solution C1 was stopped, the temperature of the solution A1 was raised to 60 ° C. over a period of 60 minutes, and the solution B1 and the solution C1 were again mixed by the simultaneous mixing method.
Each was added at a flow rate of 68.5 ml / min for 50 minutes.
During this time, the silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) was measured at +6 mV using the solution D1.
It controlled so that it might become. After completion of the addition, the pH was adjusted to 6 with 3% KOH, and immediately after desalting and washing, the seed emulsion EM was added.
-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. Electron microscopy revealed that the average diameter (in terms of circular diameter) was 0.07 μm, the average diameter was 0.5 μm, and the coefficient of variation was 25%.

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

[0186] A2 ossein gelatin _{29.4g 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 1.25 ml seed emulsion Em-1 2.65 mol equivalent Make up to 3000 ml with distilled water B2 3.50 N AgNO ₃ aqueous solution 1760 ml C2 KBr 737 g Make up to 1760 ml with distilled water D2 1.75 N KBr aqueous solution Below silver potential control amount At 60 ° C., using a mixing stirrer described in JP-B-58-58288, the total amount of the solution B2 and the solution C2 was added to the solution A2 by the simultaneous mixing method (double jet method), so that the flow rate at the end of the addition was the flow rate at the start of the addition. A growth time of 110 minutes was required so as to be three times as large as that described above.

During this period, the silver potential was increased by +40 using solution D2.
It controlled so that it might be set to mV. After completion of the addition, precipitation and desalting were performed using an aqueous solution of Demol (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 with an electron microscope and analyzed for their shapes, they were hexagonal tabular grains having an average equivalent circle diameter of 0.59 μm and an average thickness of 0.17 μm. The coefficient of variation was 24%.

(Preparation of AgBrCl (100) tabular emulsion EM-2 having a silver chloride content of 30 mol%) Solution A3 Ossein gelatin 37.5 g KI 0.625 g KBr 23.6 g NaCl 5.0 g 7500 ml with distilled water Solution B3 Silver nitrate 1500 g Make up to 2500 ml with distilled water Solution C3 KI 4 g KBr 200 g NaCl 42 g Make up to 684 ml with distilled water Solution D3 KBr 535 g NaCl 113 g Make up 1816 ml with distilled water At 40 ° C., the mixture described in JP-B-58-58288 Add 684 ml of B3 and the total amount of C3 to A3 in the stirrer.
It was added over a minute. EAg was adjusted to 220 mV and 2
After 0 min of Ostwald ripening, all remaining B3 and D3
Was added over 40 minutes. Meanwhile, EAg is 22
It was controlled at 0 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, it was determined that the average diameter of the circles was 0.8 μm and the average thickness was 0.1 μm.
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 A4 Ossein gelatin 37.5 g KI 0.625 g KBr 16.8 g NaCl 8.3 g 7500 ml with distilled water Solution B4 Silver nitrate 1500 g Make up to 2500 ml with distilled water Solution C4 KI 4 g KBr 143 g NaCl 70 g Make up to 684 ml with distilled water Solution D4 KBr 382 g NaCl 188 g Make up 1816 ml with distilled water EM-2 using the above additives A4 to D4 Emulsion EM-3 was obtained in the same manner as described above. About 3,000 of the obtained emulsions EM-3 were observed and measured by an electron microscope, and the shape was analyzed. The average circle equivalent diameter was 0.8 μm and the average thickness was 0.3 μm.
These were tabular grains having a (100) plane of 1 μm as the main plane, and the coefficient of variation was 20%.

(Preparation of Pure Silver Chloride (100) Tabular Emulsion EM-4) Solution A5 Ossein gelatin 37.5 g KI 0.625 g NaCl 16.5 g Make up to 7500 ml with distilled water Solution B5 1500 g with silver nitrate 2500 ml with distilled water Solution C5 KI 4 g NaCl 140 g Make 684 ml with distilled water Solution D5 375 g Make 1816 ml with distilled water Emulsion by the same method as EM-2 except that EAg is adjusted to 150 mV using the above-mentioned additives A5 to D5. EM-
3 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%.

(Preparation of Silver Iodide Fine Particles) A6 Ossein gelatin 100 g KI 8.5 g Make up to 2000 ml with distilled water B6 AgNO ₃ 360 g Make up to 605 ml with distilled water C6 KI 352 g Make up 605 ml with distilled water Solution A6 in a reaction vessel The solution B6 and the solution C6 were added at a constant rate over 30 minutes by a simultaneous mixing method while stirring at 40 ° C.

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 to water previously adjusted to 27 ° C. at a ratio of 100: 1, 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 3,3'-di- (4-sulfobutyl) -benzimidazolocarbocyanine-sodium salt anhydride (selenium sensitized) Emulsions EM-1 to EM-4 are subjected to spectral sensitization and chemical sensitization in the following manner. As a result, 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 per mol of 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) was stabilized at 3 × 10 ^-2 mol.

(Synthesis Example of Colloidal Tin Oxide Sol Dispersion) A stannic chloride hydrate (65 g) 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 cc 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-ray having a thickness of 175 μm and colored to a density of 0.17. (Support 2) Thickness of 100 to a density of 0.17.
μm polyethylene naphthalate film base for X-rays (preparation of tin oxide sol-subbed support)
Is subjected to a corona discharge treatment of 0.5 kV · A · min / m ² on each side, and then the undercoat latex liquid shown in the following (L-2) is dried so that the film thickness becomes 0.2 μm. The following (L-1) was sequentially applied so that the film thickness after drying was 0.053 μm, and dried at 123 ° C. for 2 minutes.

(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%).

[0203]

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In the lower layer on the other side of the same base, the SnO ₂ sol synthesized in the above (Synthesis Example) and the (L-
2) Solution and the following (L-4) solution in a volume ratio of 35: 15: 5
The above (L-1) and the following (L-3) solutions were placed in the upper layer so that the coating solution mixed at 0 was dried to a film thickness of 0.20 μm and an applied amount of the sol component of 400 mg / m ^2. 7 by ratio
The coating liquid mixed at 0:30 is dried to a thickness of 0.053 μm.
m and dried at 120 ° C. for 1 minute. Before coating, a corona discharge treatment of 0.5 kV · A · min / m ² was performed.

(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 the mixture was 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.

[0208]

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(Preparation of photosensitive material) The following coating solutions were simultaneously coated on the both surfaces of the support shown in Table 2 so as to have the following coating amounts, and dried to prepare samples.

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 mg / m ² Compound (G) 0.5 mg / m ² 2,6-bis (human peroxyamino) -4-diethylamino-1,3 5,5-Triacid 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 5 mg / m ² compound (H) 0.5mg / m ² n- _{4 H 9 OCH 2 CH (OH} ) CH 2 N (CH 2 COOH) 2 20mg / m 2 Compound (M) 5mg / m ² Compound (N) 5mg / m ² Colloidal silica 0.5 g / m ² Latex (L) 0.5 g / m ² composite latex (FG) 1.0 g / m ² dextran (molecular weight: about 100,000) 0.5 g / m ² Leuco compounds of the type and amount shown in Table 1 below were added.

Third layer (lower layer of protective layer) Gelatin 0.3 g / m ² Dioctyl phthalate 0.2 g / m ² Fourth layer Gelatin 0.3 g / m ² Matting agent composed of polymethyl methacrylate 27 mg / m ² (area average) Particle size 7.0 μm) Formaldehyde 20 mg / m ² 2,4-Dichloro-6-hydroxy-1,3,5-triazine sodium salt 10 mg / m ² latex (L) 0.2 g / m ² composite latex (Lx-1 ) 0.2 g / m ² polysiloxane (SI) 50 mg / m ² Compound (I) 30 mg / m ² Compound (S-1) 7 mg / m ² Hardener (B) 2 mg / m ² Compound (S-2) 2 mg / m ^{2 The} amount of the material applied was one side, and the amount of silver applied was adjusted so as to be 1.5 g / m ² per side.

To each of the second to fourth layers, the type and amount of developer shown in Table 1 below were added.

[0214]

[Table 1]

[0215]

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[0216]

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[0219]

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(Production of Fluorescent Intensifying Screen 1 of the Present Invention) Phosphor Gd ₂ O ₂ S: Tb (average particle size 1.8 μm) 200 g Combined polyurethane-based thermoplastic elastomer (Demolac TPKL-5-26 25 solid content) ) 40% (manufactured by Sumitomo Bayer Urethane Co., Ltd.) 20 g Nitrocellulose (digestion degree: 11.5%) 2 g To the above, a methyl ethyl ketone solvent was added and dispersed with a propeller type mixer to form a phosphor layer having a viscosity of 25 ps (25 ° C.). A coating solution was prepared. (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).

Thickness of 250 μm incorporating titanium dioxide
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 to 100 ° C to 100 ° C to form an undercoat layer on the support. The thickness of the coating film is 15 μm
Met.

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

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

(Production of Fluorescent Intensifying Screen 2 for Comparison) In the production of the fluorescent intensifying screen 1, the thickness of the coating solution for forming the phosphor layer was set to 15
A comparative fluorescent intensifying screen 2 comprising a support, an undercoat layer, a phosphor layer and a transparent protective film was produced in the same manner as the fluorescent intensifying screen 1 except that the coating was performed at 0 μm and no compression was performed.

(Measurement of Characteristics of Fluorescent Intensifying Screen) 1) Measurement of Sensitivity A fluorescent intensifying screen to be measured was exposed on an MRE single-sided silver halide photographic material manufactured by Eastman Kodak Co. in front of an X-ray source. 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.
Step exposure was performed with a width of 0.15. The exposed silver halide photographic light-sensitive material was subjected to development processing by the method described below for the method described in "Measurement of characteristics of silver halide photographic light-sensitive material" to obtain a measurement sample.

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

2) Measurement of X-ray absorption The intrinsic filtration operated at 80 kVp with three-phase power supply allows X-rays generated from a tungsten target tube equivalent to 2.2 mm of aluminum to pass through a 3 mm-thick aluminum plate. From the target tube tungsten anode
The sample was allowed to reach the sample fluorescent intensifying screen fixed at a position of 0 cm, and then the X-ray dose transmitted through the screen was measured using an ionizing dosimeter at a position 50 cm behind the phosphor layer of the fluorescent intensifying screen. , X-ray absorption was determined. In addition, the X-ray dose at the above measurement position measured without passing through the fluorescent intensifying screen was used as a reference.

X-ray absorption amounts of the obtained two fluorescent intensifying screens,
Table 2 shows the values of the phosphor filling factor, the thickness, and the sensitivity.

[0227]

[Table 2]

(Preparation of Tablet for Replenishment of Development) Tablets for replenishment of development were 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 size becomes 10 μm. 2000 g of sodium sulfite, 2700 g of dimesone S (1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone), 1250 g of DTPA (pentasodium diethylenetriaminepentaacetate), 5250 g
-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, 30 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.

The granules thus prepared were uniformly mixed with 1670 g of polyethylene glycol # 6000 and 1670 g of mannitol in a room conditioned at 25 ° C. and 40% RH for 10 minutes using a mixer. Thereafter, the obtained mixture was subjected to Tough Presto Collect 15 manufactured by Kikusui Seisakusho Co., Ltd.
Compression tableting was performed using a modified tableting machine of 27HU with a filling amount per tablet of 8.77 g to produce 2500 tablets A for development replenishment.

Operation (B) 4000 g of potassium carbonate, 2100 g of mannitol, and 2100 g of polyethylene glycol # 6000 are ground 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. Next, the obtained mixture was subjected to compression tableting using the above-mentioned tableting machine at a filling amount per tablet of 3.28 g to prepare 2500 tablets B for development replenishment.

(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): 1000 g of boric acid, 150 parts of aluminum sulfate / 18 hydrate
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 1 liter.

At the start of the processing of the developer (start of running), a liquid obtained by adding 330 ml of a starter to 16.5 liters of a developer 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 tank was filled with 11.0 L of a fixing solution prepared by diluting the fixing agent replenishing tablet with 298 g of the replenishing tablet and 149 g of the D agent with diluting water.

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

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 . The pH when the agents A and B were dissolved in 20 ml of water 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 sample was sandwiched between fluorescent intensifying screens 1 and irradiated with X-rays through a penetrometer type B (manufactured by Konica Medical Co., Ltd.).
The charging member for the solid processing agent was attached to the automatic developing machine SRX-701, and processing was performed using the solid processing agent at a development temperature of 35 ° C. for a total processing time of 30 seconds.

At this time, the replenishing amounts of the processing solutions were the amounts shown in Tables 3 and 4 for both the developing solution and the fixing solution. The sensitivities in the table indicate the sample numbers. 1 is a relative value with the reciprocal of the amount of X-ray exposure required to obtain a density of minimum density +1.0 being 100.

Developing time: 8.0 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 <silver tone Evaluation> 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 evaluation of sensitometry was performed, and the evaluation was visually performed in the following five stages. Table 3 shows the obtained results.

5: No yellowishness, pure black tone 4: Slightly yellowish, but barely noticeable 3: Yellowish, but no practical problem Yes 2: Strong yellowishness, which is problematic for practical use 1: Extremely strong yellowishness, not suitable for practical use <Evaluation of raw storage stability> The coated sample is cut into 10 cm × 10 cm, and is cut under the following two conditions. It was stored for 3 days to prepare a substitute evaluation sample for raw preservability.

Condition A: 23 ° C., 55% RH Condition B: After storage at 55 ° C., 55% RH, the obtained sample was treated under the same conditions as in the sensitometric evaluation, and the fog density was measured. Table 3 shows the value obtained by subtracting the fog density under the condition A from the fog density under the condition B as the evaluation of raw preservability. A smaller value indicates better raw preservability.

[0245]

[Table 3]

[0246]

[Table 4]

As is clear from Table 3, the sample of the present invention has higher sensitivity as compared with the comparative example, and all silver tone is excellent in pure black tone. In addition, there was no practical problem with respect to storage stability over time.

The fluorescent intensifying screen was used for comparison as No. With respect to the photographic performance when exposed at 2, the relative sensitivity value of the sample of the present invention did not increase as shown in Table 3, and the unit with the high-sensitivity intensifying screen (No. 1) of the present invention was It turned out that the effect of the invention is exhibited.

Table 4 shows that the sample of the present invention did not deteriorate in photographic performance upon low replenishment and ultra-rapid processing.

[0250]

As demonstrated in the examples, according to the present invention, a pure black tone can be obtained without deteriorating the sensitivity and the storability. Further, according to the present invention, a silver halide photographic light-sensitive material capable of obtaining stable sensitivity and silver tone even in ultra-rapid processing by low replenishment of a developing solution and a fixing solution was obtained.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03C 1/35 G03C 1/35 1/795 1/795 5/17 5/17 5/26 520 5/26 520 5/31 5/31 5 / 395 5/395 G21K 4/00 G21K 4/00 B

Claims (10)

[Claims] 1. A silver halide photographic material having a hydrophilic colloid layer including at least one silver halide emulsion layer on a support, wherein at least one of a developer and leuco A silver halide photographic material comprising at least one compound. 2. A silver halide photographic material having a hydrophilic colloid layer including at least one silver halide emulsion layer on a support, wherein the hydrophilic colloid layer contains the following general formula [1] or [2]. At least one of the developers represented by
And a silver halide photographic material comprising at least one of a leuco compound. Embedded image In the formula, R ^{1 to} R ⁵ may be the same or different and represent a hydrogen atom or a group that can be substituted on a benzene ring. However, R ¹ and R ³
At least one of them is a hydroxy group, a sulfonamide group or a carbonamide group. Z represents a hydrogen atom or a group capable of deprotection under alkaline conditions. R ^{1 to} R ⁵ , O
-Z may form a ring together. Embedded image In the formula, R ⁶ and R ⁷ are each independently a hydroxy group, an amino group,
Represents an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group or an alkylthio group. Q is R
⁶ represents an atomic group necessary to form a 5- or 6-membered ring together with R ^7. 3. A silver halide photographic material having a hydrophilic colloid layer including at least one silver halide emulsion layer on a support, wherein at least one of a developer is contained in the hydrophilic colloid layer; A silver halide photographic material comprising at least one leuco compound represented by the general formula [3]. Embedded image In the formula, R ₁ and R ₂ each represent an alkyl group or an aryl group. R ₃ represents a hydrogen atom, a halogen atom or a monovalent substituent, and n represents an integer of 1 to 3. X, Z ₁ and Z ₂ are
It represents an atomic group necessary for forming a 5- to 6-membered aromatic carbon ring or aromatic heterocyclic ring together with carbon atoms adjacent to Z ₁ and Z ₂ . 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. C
P represents the following group. Embedded image In the formula, R ₅ , R ₆ , R ₇ and R ₈ each represent a hydrogen atom, a halogen atom or a substituent capable of substituting on a benzene ring. or,
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 and R ₁₂ have the same meaning as R ₄ . R
₁₀ and R ₁₁ each represent an alkyl group, an aryl group or a heterocyclic group. R ₁₃ , R ₁₄ and R ₁₅ are respectively R ₁₀ , R ₁₁
And R ₁₂ . R ₁₆ represents an alkyl group, an aryl group, a sulfonyl group, a trifluoromethyl group, a carboxyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group or a cyano group. R ₁₇ is R
Has the same meaning as ₄ , R ₁₈ has the same meaning as R ₃ , and m represents an integer of 1 to 3. R ₁₉ and R ₂₀ each represent an alkyl group or an aryl group. R ₂₁ and R ₂₄ have the same meanings as R _4, R ₂₂
And R ₂₃ have the same meanings as R ₁₉ and R ₂₀ respectively. Y represents an atomic group necessary for forming a 5- or 6-membered monocyclic or condensed nitrogen-containing heterocyclic ring together with two nitrogen atoms. * Indicates a bonding point between CP and other partial structures 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 1%.
The amount is from 0 to 100 mol%.
6. The silver halide photographic light-sensitive material according to any one of the above. 5. The silver halide photographic material according to claim 1, wherein the support is polyethylene naphthalate. 6. An X-ray image forming unit comprising the silver halide photographic material according to claim 1 sandwiched between two fluorescent intensifying screens. 7. An X-ray image forming unit according to claim 6, wherein X-ray energy is 45 kVp for X-rays of 80 kVp.
An X-ray image forming method, characterized in that the screen is a fluorescent intensifying screen having an absorption amount of at least 68%, a filling rate of the phosphor of 68% or more, and a thickness of the phosphor of 135 to 200 μm. 8. The processing of a silver halide photographic light-sensitive material, wherein the silver halide photographic light-sensitive material according to claim 1 is processed by an automatic developing machine including a development processing step. Method. 9. The method for processing a silver halide photographic material according to claim 8, wherein the processing is performed by an automatic developing machine having a mechanism for supplying a solid processing agent to a processing tank of the automatic developing machine. 10. The silver halide photographic light-sensitive material according to claim 8, wherein the amount of replenisher replenished to the developing tank or the fixing tank of the automatic developing machine is represented by the following formula (A). Processing method. Formula (A) 1 ≦ Amount of replenisher / Amount taken out by photosensitive material ≦ 5