JPH1124197A - Silver halide photographic sensitive material, x-ray image forming unit and method, and method for processing silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the silver halide photographic sensitive material forming a cold black tone silver image and superior silver image storage stability incorporating specified water-insoluble compound grains and a leuco compound for forming a blue dye by reaction with the oxidation product of a developing agent in a hydrophilic colloidal layer. SOLUTION: The silver halide photographic sensitive material is provided on a support with the hydrophilic colloidal layers including at least one silver halide emulsion layer, and the hydrophilic colloidal layer includes at least one of the leuco compounds for forming a blue dye by reaction with the oxidation product of the developing agent and one of the compounds represented by formulae I and II in which each of R1a and R2a is an optionally substituted alkyl or alkoxy or alkylthio group or the like; n1 is an integer of >=1 and when n1 is >=2, each of R1a and R2a becomes plural and each of the plural of them may be same or different; in formula II, each of R3a and R4a is same as R1a and R2a in formula I: n2 is an integer of >=3, and each of R3a and R4a and each of the plural of them may be same or different.

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 (hereinafter, also simply referred to as a "light-sensitive material"). The present invention relates to a photosensitive material having excellent image storability, an X-ray image forming unit using the same, an X-ray image forming method and a processing method.

[0002]

2. Description of the Related Art In recent years, regarding development processing of photosensitive materials,
There is a demand for a reduction in processing time and a reduction in the amount of waste liquid accompanying the processing.

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

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

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

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

[0007] When a silver image has a yellow tint, a medical photosensitive material has a drawback of giving an unpleasant impression to an image observer. Such a phenomenon is often observed in fine grain emulsions and tabular grains having a small grain thickness.

However, conventionally known color toning agents (for example, certain mercapto compounds, etc.) are not practically applicable to high-sensitivity emulsions because of their desensitization.

On the other hand, in emergency medical care in the medical field, rapid processing is essential because it is necessary to quickly grasp the condition of the patient, and ultra-rapid processing systems with a total processing time of 30 seconds or less have already been developed. Further, from the viewpoint of environmental conservation, there is a demand for an improved processing system, such as a reduction in the amount of waste liquid due to a low replenishment of the processing liquid and a reduction in the burden on the processing operation.

Accordingly, a silver halide photographic light-sensitive material which can stably provide high sensitivity and high contrast even in rapid processing, has a pure black tone in silver tone, and has no problem from the viewpoint of environmental protection, and its processing. A way was desired.

In recent years, as a technique for improving the color tone of image silver, a specific dye is dissolved in a water-insoluble high-boiling organic solvent as described in, for example, JP-A-5-165147, and it is reduced to a minute size in an aqueous solvent. Techniques for dispersing and incorporating the light-sensitive material into light-sensitive materials have been proposed, but the sensitivity fluctuates depending on storage conditions before exposure. In particular, in the case of a medical X-ray photosensitive material, there has been a problem that the intensifying screen which is brought into contact with the photosensitive material at the time of exposure is stained. In addition, this technique also has a disadvantage that the fog density increases because the same amount of dye is contained in the unexposed portion as in the exposed portion.

In order to solve this drawback, a technique in which a dye image corresponding to silver development is formed by a diffusion-resistant compound which releases a diffusible dye by the action of silver ions while forming a silver image is disclosed in JP-A-3-157645. However, the effect of improving the color tone of image silver and the effect of reducing fog were insufficient.

Further, Japanese Patent Application Laid-Open No. 3-153234 has proposed a technique using a leuco dye which gives a blue image corresponding to a silver image. According to this technique, contamination of the developer and generation of stain are suppressed, but the color tone of the blue dye formed from the leuco dye has a long wavelength and has a greenish tint, so that the effect of improving the black tone of the image silver is reduced. It was not enough. Further, the leuco dye remaining in the unexposed areas of the processed photographic material is liable to develop color with the passage of time and has a drawback that fog rises.

On the other hand, the phenomenon that a silver image takes on a yellow tint also occurs when the silver image is stored for a long time after processing.
The reason for this is that the super-rapid processing causes the silver halide remaining in the fixing solution not sufficiently fixed and the silver halide solvent in the fixing solution remaining without being sufficiently washed to react during storage, and the silver ions are converted. It is believed to change the shape of the formed and developed silver filament.

There has been a strong demand for a light-sensitive material which is free from yellowish tint and has a cool black tone immediately after the development processing, and has no discoloration even when the image is stored for a long period of time, and stably maintains the cool black tone. . However, a corresponding technology for simultaneously improving both of them has not yet been disclosed.

[0016]

SUMMARY OF THE INVENTION Accordingly, it is a first object of the present invention to provide a silver halide photographic light-sensitive material having a silver image with a cool black tone and excellent silver image storability. . A second object of the present invention is to provide a silver halide photographic light-sensitive material capable of obtaining the above-mentioned performance by ultra-rapid and low replenishment processing,
An object of the present invention is to provide a line image forming unit, an X-ray image forming method and a processing method.

[0017]

The object of the present invention has been solved by the following constitution.

In a silver halide photographic 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): And a leuco compound which forms a blue dye by reacting with an oxidized form of a developing agent.

[0019]

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In the formula (1), R _1a and R _2a each represent a substituted or unsubstituted alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, alkenyl group, alkynyl group, amino group, alkyl group. Represents an imino group, an arylimino group, an alkylthio group, an arylthio group, an acyl group, a cyanide group, or an azide group, and R _1a and R _2a may be the same or different. n ₁ represents a positive integer of 1 or more, and when n ₁ is plural, R _1a and R _2a may be the same or different.

[0021] wherein in the general formula _{(2), R 3a, R} 4a represents R _1a, R _2a group having the same meaning as in the general formula (1), R _3a, R
_4a may be the same or different. n ₂ represents a positive integer of 3 or more, and when n ₂ is plural, R _3a and R _4a may be the same or different.

The leuco compound has the following general formula (3)
The silver halide photographic material as described in the above item, which is a compound represented by (6).

[0023]

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Wherein W is -NR ₁ R ₂ , -OH or -O
Z is represented, R ₁ and R ₂ represent an alkyl group or an aryl group, respectively, and Z represents an alkali metal ion or a quaternary ammonium ion. R ₃ represents a hydrogen atom, a halogen atom or a monovalent substituent, and n represents an integer of 1 to 3. Z ₁ and Z ₂ are each a nitrogen atom or ＣC
(R ₃ ) —. X represents an atomic group necessary for constructing a 5- to 6-membered aromatic heterocyclic ring together with Z ₁ , Z ₂ and carbon atoms adjacent thereto. R ₄ is a hydrogen atom, an acyl group,
Represents a sulfonyl group, a carbamoyl group, a sulfo group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. R represents an aliphatic group or an aromatic group, and p represents an integer of 0 to 2. CP1 represents the following groups.

[0025]

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[0026]

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

[0028]

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Wherein R ₁ , R ₂ , R ₃ , R ₄ , CP1, n,
R and p are R ₁ , R ₂ , R ₃ ,
R _4, CP1, n, is the same as R and p.

[0030]

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Wherein R ₃ , n, R ₄ , W, X, Z ₁ , Z ₂ ,
And CP1 represent R ₃ , n, R ₄ ,
W, X, same meaning as Z _1, Z _2, and CP1.

[0032]

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In the formula, R ₁ , R ₂ , R ₃ , R ₄ , CP1 and n represent R ₁ , R ₂ , R ₃ , R ₄ , CP ₁ in the general formula (3).
And n are synonymous.

The silver halide grains in the silver halide emulsion layer are tabular silver halide grains having a main plane composed of two parallel (100) planes, and have a silver chloride content of 10 to 100 mol. %, Or a silver halide photographic light-sensitive material as described in the above item.

The amount of silver per side is 1.0 to 2.0 g
/ M ² , the silver halide photographic light-sensitive material as described in any one of the above items.

The silver halide photographic material as described in any one of the above items, wherein the support is polyethylene naphthalate.

The silver halide photographic material as described in any one of the above items, wherein the thickness of the polyethylene naphthalate support is 70 to 170 μm.

An X-ray image forming unit, wherein the surface of the silver halide photographic light-sensitive material according to any one of the above-mentioned items having an emulsion layer and the fluorescent surface of a fluorescent intensifying screen are brought into close contact with each other.

In the above X-ray image forming unit, the X-ray energy of the fluorescent intensifying screen shows an absorption of 45% or more with respect to X-rays of 80 kVp, and the filling rate of the phosphor is 6%.
An X-ray image forming method, wherein the fluorescent intensifying screen is 8% or more and the thickness of the phosphor is 135 to 200 μm, and the fluorescent intensifying screen is irradiated with X-rays to perform imagewise exposure.

A method for processing a silver halide photographic light-sensitive material, characterized by processing the silver halide photographic light-sensitive material according to any one of the above-mentioned items in a photographic processing step including a development step.

(10) The method for processing a silver halide photographic material as described in (1), wherein the processing is carried out by an automatic developing machine having a mechanism for supplying a solid processing agent to a processing tank.

(11) The method for processing a silver halide photographic material as described in (10), wherein the amount of replenisher to be replenished in the developing step and / or the fixing step is represented by the following formula.

1 ≦ replenisher amount / amount taken out of photosensitive material ≦ 7 12 Processing time required for all processing steps (Dry to Dr)
12. The method for processing a silver halide photographic light-sensitive material according to any one of items 11 to 11, wherein y) is within 30 seconds.

Hereinafter, the present invention will be described in detail.

The hydrophilic colloid layer of the light-sensitive material of the present invention contains the compound represented by the general formula (1) or (2). The compound can exert its effect when contained in any of the layers in the light-sensitive material of the present invention, but is preferably a silver halide grain emulsion layer or a hydrophilic colloid layer adjacent to the emulsion layer.

The amount of addition is from 0.001 to 0.1 per mol of silver.
It may be 1 mol, preferably 0.003 to 0.01 mol.

The compounds represented by the general formulas (1) and (2) of the present invention are phosphazene derivatives whose basic skeleton is composed of P = N bonds, and some of the substituents are ionic side-chain groups or It is the case of a pi-electron compound side chain group, a polyether side chain group, or the like.

These compound groups include a high molecular weight compound group in which the P = N bond is linear, and a cyclic compound group and a cyclic chain compound group. The method of synthesizing these compounds is described in more detail as follows: (PNF ₂ ) ₃ , (PNF ₂ ) ₄ , (PNF ₂ ) n
And the like, in which the side group such as is a trimer, tetramer, or n-mer of an F atom, (PNCl ₂ ) ₃ , (PNCl ₂ ) ₄ , (PNCl ₂ )
Compounds in which the side group such as n (n <15) is a Cl atom trimer, tetramer, n-mer, (PNBr ₂ ) ₃ , (PNB
(Pr ₂ ) ₄ , (PNBr ₂ ) n, etc., a compound in which the side chain group is a Br atom trimer, tetramer, n-mer, (PNI ₂ ) ₃ , (PNI)
₂ ) ₄ , (PNI ₂ ) n or the like has a side chain group which is a halogen atom of a trimer, tetramer, or n-mer compound of I atom, and is represented by C ₆ H ₅ ON.
a, CH ₃ C ₆ H ₄ ONa, (C ₆ H ₅ O) ₂ Ca, CF ₃ C
Reaction with a metal salt of an aromatic organic compound such as H ₂ ONa, an aromatic compound having a hydroxyl group such as C ₆ H ₅ OH or a fat such as CH ₂ (CH ₃ ) = C—COOCH ₂ CH ₂ OH Aromatic compounds capable of nucleophilic substitution with a halogen atom on the P atom, such as aromatic alcohols, aromatic amines such as C ₆ H ₅ NH ₂ , amines such as aniline, sodium hydroxide, sodium carbonate, etc. And a method of mixing with a halogen acceptor compound.

The phosphazene derivative is generally synthesized in this manner, but the synthesis method based on the substitution reaction is not particularly limited.

Further, the combination of the side chain groups may not necessarily be composed of a single group, but may be a combination selected from a plurality of these groups.
It can be arbitrarily selected to have a solubility of 1 g or less in 100 g of a 40 ° C. aqueous solution adjusted to H10.00.
In addition, Chem. Rev .. , 1972, vol72,
No. And functional groups contained in the compounds shown in Nos. 4,315 to 356, and these functional groups may further have a hydrophilic substituent such as a carboxyl group, a sulfate group, and a phosphate group. .

Next, specific examples of the compounds represented by formulas (1) and (2) are shown, but the present invention is not limited to these. In the following specific examples, L is a chain compound, C
Represents a cyclic compound, and H represents a cyclic compound having a structure in which the cyclic compound is further connected in a chain or network.

L-1 [NP (NCS) ₂ ] _n L-2 [NP (NCO) ₂ ] _n L-3 [NP (COCH ₃ ) ₂ ] _n L-4 [NP (COC ₁₇ H ₃₅ ) ₂ ] _n L-5 [NP (CN) ₂ ] _n L-6 [NP (OMe) ₂ ] _n L-7 [NP (OEt) ₂ ] _n L-8 [NP (OCH ₂ CF ₃ ) ₂ ] _n L- 9 [NP (OCH ₂ C ₂ F ₅ ) ₂ ] _n L-10 [NP (OCH ₂ CF ₂ CF ₂ H) ₂ ] _n L-11 [NP (OCH ₂ C ₃ H ₇ ) ₂ ] _n L-12 [NP (OCH ₂ CF ₃ ) (OCH ₂ C
_{3 F 7)] n L-} 13 [NP (OCH 2 (CF 2) 6 CF 3) 2] n L-14 [NP (OCH 2 C 2 F 5) (OCH 2 C
_{3 F 7)] n L-} 15 [NP (OCH 2 CF 2 CF 2 H) (OCH 2 C
₆ F ₁₂ H)] _n L-16 [NP (OPh) ₂ ] _n L-17 [NP (OC ₆ H ₄ F-p) ₂ ] _n L-18 [NP (OC ₆ H ₄ CF ₃ -m) ₂ ] _n L-19 [NP (OC ₆ H ₄ Cl-p) ₂ ] _n L-20 [NP (OC ₆ H ₃ Cl ₂ -2, 4) ₂ ] _n L-21 [NP (OC ₆ H _{4 CH 3 -p) 2] n L} -22 [NP (OC 6 H 4 C 6 H 5 -p) 2] n L-23 [NP (NHMe) 2] n L-24 [NP (NHEt) 2] n L-25 [NP (NHPr-n) ₂ ] _n L-26 [NP (NHBu-n) ₂ ] _n L-27 [NP (NHPh) ₂ ] _n L-28 [NP (NMe ₂ ) ₂ ] _n L −29 [NP (NC ₅ H ₁₀ ) ₂ ] _n L-30 [NP (NEt ₂ ) Cl] _n L-31 [NP (NEt ₂ ) (NH ₂ )] _n L-32 [NP (NEt ₂ ) ( NHMe) _{n L-33 [NP (NEt} 2) (NHEt)] n L-34 [NP (NEt 2) (NHPr-n)] n L-35 [NP (NEt 2) (NHBu-n)] n L-36 (NPPh ₂ ) _n L-37 [NP (SEt) ₂ ] _n L-38 [NP (N ₃ ) ₂ ] _n L-39 [NP (NH ₂ ) ₂ ] _n

[0053]

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C-1 [NP (CF ₃ ) ₂ ] ₃ C-2 (NPPh ₂ ) ₃ C-3 (NPPh ₂ ) ₄ C-4 [NP (C ₆ H ₄ Cl-p) ₂ ] ₃ C- 5 [NP (OC ₆ H ₄ F-p) ₂ ] ₃ C-6 [NP (OC ₆ H ₄ F-p) ₂ ] ₄ C-7 (NPET ₂ ) ₃ C-8 (NPet ₂ ) ₄ C- 9 [NP (COCH ₃ ) ₂ ] ₃ C-10 [NP (COC ₁₇ H ₃₅ ) ₂ ] ₃ C-11 [NP (COCH ₃ ) ₂ ] ₄ C-12 [NP (COC ₁₇ H ₃₅ ) ₂ ] ₄ C-13 [NP (OCH ₂ CF ₃ ) ₂ ] ₃ C-14 [NP (OCH ₂ CF ₃ ) ₂ ] ₄ C-15 [NP (OMe ₂ ) ₂ ] ₃ C-16 [NP (OMe ₂ ) ₂ ] ₄ C-17 [NP (OEt ₂ ) ₂ ] ₃ C-18 [NP (OEt ₂ ) ₂ ] ₄ C-19 [NP (OPr-i) ₂ ] ₃ C-20 [NP (OPr-i) ₂ ] ₄ C-21 [N _{P (OBu-n) 2]} 3 C-22 [NP (OBu-n) 2] 4 C-23 [NP (OCH 2 Ph) 2] 3 C-24 [NP (OCH 2 Ph) 2] 4 C- 25 [NP (OPh) ₂ ] ₃ C-26 [NP (OPh) ₂ ] ₄ C-27 [NP (OC ₆ H ₄ CH ₃ -p) ₂ ] ₃ C-28 [NP (OC ₆ H ₄ CH ₃₎ -P) ₂ ] ₄ C-29 [NP (SEt) ₂ ] ₄ C-30 [NP (SPh) ₂ ] ₃ C-31 [NP (SPh) ₂ ] ₄ C-32 [NP (NHMe) ₂ ] ₃ C-33 [NP (NHMe) ₂ ] ₄ C-34 [NP (NHEt) ₂ ] ₃ C-35 [NP (NHEt) ₂ ] ₄ C-36 [NP (NHBu-n) ₂ ] ₃ C-37 [ NP (NHBu-n) ₂ ] ₄ C-38 [NP (NMe ₂ ) ₂ ] ₃ C-39 [NP (NMe ₂ ) ₂ ] ₄ C-40 [NP (NEt ₂ ) ₂ ] ₃ C-41 [NP (NEt ₂ ) ₂ ] ₄ C-42 [NP (NMePh) ₂ ] ₃ C-43 N ₃ P ₃ Ph ₃ (NHMe) ₃ (cis) C-44 N ₃ P ₃ Ph ₃ (NHMe) ₃ (trans) C-45 N ₃ P ₃ Ph ₃ (NHEt) ₃ (cis) C-46 N ₃ P ₃ Ph ₃ (NHEt) ₃ (trans) C-47 N ₃ P ₃ (NHEt) ) ₄ (OCH ₂ CF ₃ ) ₂ (g
em) C-48 N ₃ P ₃ (NHEt) ₄ (OCH ₂ CF ₃ ) ₂ (n
on-gem) C-49 N ₃ P ₃ (OC ₆ H ₅ ) ₄ (NH ₂ ) ₂ (gem) C-50 N ₃ P ₃ (OC ₆ H ₅ ) ₄ (NH ₂ ) ₂ (non-
gem) C-51 [NP (NCS) ₂ ] ₃ C-52 [NP (NCO) ₂ ] ₃ C-53 [NP (CN) ₂ ] ₃ C-54 [NP (N ₃ ) ₂ ] ₃ C-55 _{[NP (OPr-n) 2} ] 3 C-56 [NP (OCH 2 CF 3) 2] 3 C-57 [NP (SEt) 2] 3 C-58 [NP (NH 2) 2] 3 C-59 [NP (CF ₃ ) ₂ ] ₄ C-60 [NP (NCS) ₂ ] ₄ C-61 [NP (NCO) ₂ ] ₄ C-62 [NP (CN) ₂ ] ₄ C-63 [NP (OPr- n) ₂ ] ₄ C-64 [NP (NH ₂ ) ₂ ] ₄ C-65 [NP (OMe) ₂ ] ₅ C-66 [NP (NMe ₂ ) ₂ ] ₅ C-67 [NP (OPh) ₂ ] _{5 C-68 N 5 P 5} (OC 6 H 5) 8 (NH 2) 2 (gem) C-69 [NP (OMe) 2] 6 C-70 [NP (NMe 2) 2] 6 C-7 1 [NP (OPh) ₂ ] ₆ C-72 N ₆ P ₆ (OC ₆ H ₅ ) ₁₀ (NH ₂ ) ₂ (gem) C-73 [NP (OMe) ₂ ] ₈ C-74 [NP (NMe ₂ ) ₂ ] ₈ C-75 [NP (OPh) ₂ ] ₈ C-76 N ₈ P ₈ (OC ₆ H ₅ ) ₁₄ (NH ₂ ) ₂ (gem)

[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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The compound represented by the general formula (1) or (2) of the present invention traps dissolved silver in a silver halide photographic light-sensitive material so as to trap the dissolved silver on the light-sensitive material or in a processing solution for a silver halide photographic light-sensitive material. Has the function of preventing the generation of silver stains.

Next, the leuco compound of the present invention will be described in detail.

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

As the monovalent substituent represented by R ₃ , an alkyl group (eg, methyl, ethyl, isopropyl, hydroxyethyl, methoxymethyl, trifluoromethyl,
t-butyl group, etc.), cycloalkyl group (eg, cyclopentyl, cyclohexyl group, etc.), aralkyl group (eg, benzyl, 2-phenethyl group, etc.), aryl group (eg, phenyl, naphthyl, p-tolyl, p-chlorophenyl group, etc.) , An alkoxyl group (eg methoxy, ethoxy,
Isopropoxy, n-butoxy group, etc.), aryloxy group (eg, phenoxy group, etc.), cyano group, acylamino group (eg, acetylamino, propionylamino group, etc.), alkylthio group (eg, methylthio, ethylthio, n-butylthio group, etc.) An arylthio group (eg, phenylthio group, etc.), a sulfonylamino group (eg, methanesulfonylamino, benzenesulfonylamino group, etc.),
Ureido group (eg, 3-methylureide, 3,3-dimethylureide, 1,3-dimethylureide group, etc.), sulfamoylamino group (dimethylsulfamoylamino group, etc.), carbamoyl group (eg, methylcarbamoyl, ethylcarbamoyl) , Dimethylcarbamoyl group, etc.), sulfamoyl group (eg, ethylsulfamoyl, dimethylsulfamoyl group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.), Sulfonyl group (for example, methanesulfonyl group,
Butanesulfonyl group, phenylsulfonyl group, etc.), acyl group (eg, acetyl, propanoyl, butyroyl group, etc.), amino group (eg, methylamino, ethylamino,
A dimethylamino group, a hydroxy group, a nitro group, an imide group (eg, a phthalimido group), and a heterocyclic group (eg, a pyridyl group, a benzimidazolyl group, a benzothiazolyl group, a benzoxazolyl group).

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

Preferred examples of the alkoxycarbonyl group include methoxycarbonyloxy and ethoxycarbonyloxy groups. Preferable examples of the aryloxycarbonyl group include a phenoxycarbonyloxy group.

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

The 5-, 6-membered aromatic heterocyclic ring constituted by X, Z ₁ , Z ₂ and carbon atoms adjacent thereto is a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a triazine ring, a tetrazine ring, a pyrrole ring. Ring, furan ring, thiophene ring, thiazole ring, oxazole ring, imidazole ring, thiadiazole ring, oxadiazole ring and the like. Preferably it is a pyridine ring.

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

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

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

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

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

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

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

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

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

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

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

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

The structure was confirmed by NMR spectrum and Mass spectrum.

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

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

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

The structure was confirmed by NMR spectrum and Mass spectrum.

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

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

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

The structure was confirmed by NMR spectrum and Mass spectrum.

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

The addition amount of the compounds represented by formulas (3) to (6) of the present invention is 1 × 10 ^-6 mol to 5 × 10 ^-1 mol per mol of silver in the light-sensitive material of the present invention. This is preferable for achieving the effects of the present invention. Below this, the effect of improving the silver tone is small, and above this, the entire image is dark, which is not preferable. Particularly preferred is 5 to 1 mole of silver.
× well 10 ^-5 mol to 5 × 10 ^-2 mol, it may be 5 × 10 ^-4 mol to 1 × 10 ^-2 mol containing more preferred in the expression of the effect.

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

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

The silver halide grains of the light-sensitive material of the present invention include:
More preferably, it is a flat plate having two parallel (100) planes as main planes. The average aspect ratio of the particles is 2.
0 to 15.0. The principal plane referred to herein is a set of parallel planes having the largest area among the crystal surfaces forming substantially rectangular parallelepiped emulsion grains, and the aspect ratio refers to the principal plane of the grain with respect to the thickness between the principal planes. It refers to the ratio of the average edge length to be formed.

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

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

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

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

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

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

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

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

The preferred particle size depends on the size and the halogen composition of the silver halide grains of the host, since the grain size of the fine grains governs the supply rate of the halide ions. However, those having an average equivalent sphere diameter of 0.3 μm or less are preferred. Used. It is more preferably 0.1 μm or less. In order for the fine particles to be deposited on the host particles by recrystallization,
The fine particle size is desirably smaller than the equivalent sphere diameter of the host particles, and more preferably, 1% of the equivalent sphere diameter.
/ 10 or less.

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

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

The emulsion used in the silver halide photographic light-sensitive material of the present invention can use various photographic additives before and after physical ripening or chemical ripening. Compounds used in such a process include, for example, Research Disclosure (RD) No. No. 17643, ibid. 18
716 and No. 716. Various compounds described in 308119 can be used.

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

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

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

The support of the light-sensitive material of the present invention is preferably polyethylene naphthalate. Polyethylene naphthalate is specifically polyethylene-2,6-naphthalene, wherein 40 mol% or more of the monomer to be polymerized is dimethyl naphthalene-2,6-dicarboxylate, preferably 60 mol% or more, more preferably It refers to one that is 80 mol% or more.

The surface of the support may be provided with an undercoat layer, or subjected to corona discharge, ultraviolet irradiation, etc. in order to improve the adhesion of the coating layer. Hereinafter, a method for preparing the support used in the present invention will be described.

After adding a transesterification catalyst to 100 parts of dimethyl naphthalene-2,6-dicarboxylate and 60 parts of ethylene glycol, 1.2 parts of sodium dodecylbenzenesulfonate, 0.8 parts of polyethylene glycol having a molecular weight of 8000, and thyroid 0.01 part was added, and the polyethylene-2,6-naphthalate obtained by polycondensation was melt-extruded, and the unstretched film was stretched 4.2 times at 170 °, and further stretched at 150 ° in the transverse direction. .2
It was stretched twice. Heat set was at 255 degrees for 10 seconds.

In the present invention, the polyethylene-2,6-
The thickness of the naphthalene support is 70 to 170 μm,
Preferably it is 90 to 150 μm.

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

In the present invention, the image forming unit is one in which the photosensitive material of the present invention is sandwiched between two fluorescent intensifying screens for imagewise exposure by X-ray irradiation.

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

Preferred phosphors used in the fluorescent intensifying screen include the following.

Tungstate phosphors (CaWO ₄ ,
MgWO ₄ , CaWO ₄ : Pb, etc.), terbium-activated rare earth oxysulfide-based phosphor [Y ₂ O ₂ S: Tb, Gd ₂ O ₂ S: T
b, La ₂ O ₂ S: Tb, (Y.Gd) ₂ O ₂ S: Tb,
(Y. Gd) O ₂ S: Tb. Tm, etc.], terbium-activated rare earth phosphate-based phosphors (YPO ₄ : Tb, GdPO ₄ : T
b, LaPO ₄ : Tb, etc.), terbium-activated rare earth oxyhalide phosphor (LaOBr: Tb, LaOB)
r: Tb. Tm, LaOCl: Tb, LaOCl: T
b. Tm, 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, BaSO4: Eu} 2+, (Ba.Sr)
SO ₄ : Eu ²⁺ etc.], divalent eurobium-activated alkaline earth metal phosphate phosphor [(Ba ₂ PO ₄ ) ₂ : Eu ²⁺ ,
(Ba ₂ PO ₄ ) ₂ : Eu ²⁺ etc.] divalent eurobium-activated alkaline earth metal 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 obtained by uniformly dispersing a phosphor in a binder solution onto a temporary support for forming a phosphor sheet, and drying. Then, it can be manufactured by peeling off from the temporary support. That is, first, a binder and phosphor particles are added to an appropriate organic solvent, and the mixture is stirred and mixed to prepare a coating solution in which the phosphor is uniformly dispersed in the binder.

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

Examples of the solvent for preparing the coating liquid 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 kind of the phosphor, and the like. In general, the mixing ratio between the binder and the phosphor is 1: 1.
It is selected from the range of 1 to 1: 100 (weight ratio), and particularly preferably selected from the range of 1: 8 to 1:40 (weight ratio).

[0141] The coating solution may be a dispersant for improving the dispersibility of the phosphor in the coating solution or a binding agent between the binder and the phosphor in the formed phosphor layer. Various additives such as a plasticizer may be mixed.

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

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

The coating solution containing the phosphor and the binder prepared as described above is uniformly applied to the surface of the temporary support for 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. What can be processed into is preferred. From this point, for example, cellulose acetate film, polyester film, polyethylene terephthalate film, polyamide film, polyimide film, triacetate film, plastic film such as polycarbonate film, metal sheet such as aluminum foil and aluminum alloy foil, general paper and photographic base paper Base paper for printing, such as coated paper or art paper, baryta paper, resin coated paper, paper sized with polysaccharide as described in Belgian Patent No. 784,615, titanium dioxide, etc. Pigmented paper containing pigments, and processed paper such as paper sized with polyvinyl alcohol are particularly preferred.

After the coating solution for forming a phosphor layer is applied to the temporary support and dried, the coating solution 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 to strengthen the bond between the support and the phosphor layer, and to improve sensitivity and sensitivity.
In order to improve image quality (sharpness, granularity), a light reflecting layer made of a light reflecting material such as titanium dioxide or a light absorbing layer made of a light absorbing material such as carbon black may be provided.

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

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

As described above, by using the method of pressing the sheet without fixing it to the phosphor sheet support in advance, the sheet can be spread thinly and not only can prevent the phosphor from being damaged but also fix 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 apparatus used for the compression processing include generally known apparatuses such as a calender roll and a hot press. For example, the compression treatment using a calender roll is performed by placing the phosphor sheet obtained on a support and passing the phosphor sheet at a constant speed between rollers heated to a temperature higher than the softening temperature or melting point of the binder. The pressure during compression is 50 kg / cm ²
It is preferable that this is the case.

Usually, a 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 on the side opposite to the side in contact with the support described above. . Such a transparent protective film is preferably provided also for the fluorescent intensifying screen of the present invention. The thickness of the protective film is generally in the range of 0.1 to 20 μ.

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

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

In the present invention, as the protective layer used in the fluorescent intensifying screen, a film formed by a coating film containing a fluorine-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 an olefin containing fluorine (fluoroolefin) or a copolymer containing an olefin containing fluorine as a copolymer component, such as polytetrafluoroethylene, polychlorotrifluoroethylene, or polyfluorene. 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 the organic solvent by a structural unit other than the fluoroolefin to be copolymerized. A protective layer can be easily formed by applying a solution prepared by dissolving in a suitable solvent on the phosphor layer and drying. Examples of such a copolymer include a fluoroolefin-vinyl ether copolymer. Also, polytetrafluoroethylene and its modified products are soluble in a suitable fluorine-based organic solvent such as a perfluoro solvent, and thus are protected by coating in the same manner as the copolymer containing the above-mentioned fluoroolefin as a copolymer component. A film can be formed.

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

Examples of the resin other than the fluorine-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 formed from a coating film containing one or both of a polysiloxane skeleton-containing oligomer and a perfluoroalkyl group-containing oligomer.

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

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

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

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.

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

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

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

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

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

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

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

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

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

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

[0178]

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

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

[0181]

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[0182]

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[0183]

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[0184]

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

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

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

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

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

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

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

Prior to the treatment, it is also preferable to add a starter, and it is preferable to add the starter after solidifying it. As the starter, in addition to an organic acid such as a polycarboxylic acid compound, a halide of an alkaline earth metal such as KBr, an organic inhibitor, and a development accelerator are used.

The silver halide photographic light-sensitive material of the present invention can be subjected to a total processing time (dry to dry) using an automatic processor.
The treatment is preferably performed within 30 seconds. The treatment is preferably performed in 5 to 30 seconds, but the treatment in 10 to 30 seconds is preferably performed without any change.

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 2 to 10 seconds), development temperature 25 to 50 ° C
(Further 30 to 40 ° C.), fixing time 2 to 12 seconds (further 1 to 10 seconds), fixing temperature 20 to 50 ° C. (further 30 to 4 ° C.).
0 ° C), water washing time (stabilization) 3 to 15 seconds (further 1 to 8
Second), water washing temperature (stabilization) 0 to 50 ° C (moreover 15 to 4
0 ° C), a drying time of 3 to 12 seconds (more preferably 2 to 8 seconds), and a drying temperature of 35 to 100 ° C (more preferably 40 to 80 ° C). The silver halide photographic light-sensitive material of the present invention is developed, fixed and washed (or stabilized), dried with a squeeze roller, and then dried.

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

In the process of processing the light-sensitive material of the present invention, it is necessary that the replenisher amounts of the developing solution and the fixing solution satisfy the following formula.

1 ≦ amount of replenisher / amount taken out by photosensitive material ≦ 7 If the above (amount of replenisher / amount taken out by photosensitive material) is 1
When the value is less than 7, the processing liquid becomes insufficient and an image defect occurs. When the value exceeds 7, 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.

[0199]

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

Example 1 (Preparation of hexagonal tabular pure silver bromide seed emulsion Em-A) A1 ossein gelatin 60.2 g distilled water 20.0 l HO (CH ₂ CH ₂ O) _n- [CH (CH ₃ ) _{CH 2 O] 17 - (CH} 2 CH 2 O) m H (n + m = 5~7) 3500ml in a 10% methanol aqueous solution _{5.6ml KBr 26.8g 10% H 2 SO} 4 144ml B1 Silver nitrate 1487.5g distilled water C1 KBr 1050 g Make up to 3500 ml with distilled water D1 1.75 NKBr aqueous solution At the following silver potential control amount at 35 ° C., using a mixing stirrer described in JP-B-58-58288, solution B1 and solution C1 were added to solution A1. 64.1 ml was added by the simultaneous mixing method over a period of 2 minutes to form nuclei.

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 the completion of the addition, the pH was adjusted to 6 with 3% KOH, and immediately after desalting and washing, a seed emulsion EM-A was obtained.
The seed emulsion EM-A thus prepared has a maximum adjacent side ratio of 1.0 to 90% of the total projected area of the silver halide grains.
2.0 hexagonal tabular grains having an average thickness of 0.07 μm and an average diameter (converted to circular diameter) of 0.5 μm;
The coefficient of variation was found to be 25% by electron microscope observation.

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

[0204] 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-A 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 The following silver potential control amount 60 At ° C., the flow rate at the end of addition was determined by the simultaneous mixing method (double jet method) using the mixing stirrer described in JP-B-58-58288, by the simultaneous mixing method (double jet method). 110 so that it becomes three times
Minutes of time was required for addition growth. During this time, the silver potential was controlled to be +40 mV using the solution D2.

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

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

(Preparation of AgBrCl (100) tabular emulsion EM-2 having a silver chloride content of 30 mol%) A3 ossein gelatin 37.5 g KI 0.625 g KBr 23.6 g NaCl 5.0 g Make up to 7,500 ml with distilled water. 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., a stirrer described in JP-B-58-58288. In A3, add 684 ml of B3 and the total amount of C3 to 1
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 prepare emulsion E.
M-2. When about 3000 of the obtained emulsion EM-2 were observed and measured by an electron microscope to analyze the shape,
(1) having an average equivalent circle diameter of 0.8 μm and an average thickness of 0.1 μm
(00) A tabular grain having a plane as a main plane, and the coefficient of variation was 20%.

(Preparation of AgBrCl (100) tabular emulsion EM-3 having a silver chloride content of 70 mol%) A4 ossein gelatin 37.5 g KI 0.625 g KBr 16.8 g NaCl 8.3 g Make up to 7,500 ml with distilled water. B4 Silver nitrate 1500 g Make 2500 ml with distilled water C4 KI 4 g KBr 143 g NaCl 70 g Make 684 ml with distilled water D4 KBr 382 g NaCl 188 g Make 1816 ml with distilled water The same method as EM-2 using the above solutions A4 to D4. Thus, emulsion EM-3 was obtained. Approximately 3,000 of the obtained emulsions EM-3 were observed and measured by an electron microscope, and analyzed for their shapes.
a tabular grain having a (100) plane of μm as a main plane,
The coefficient of variation was 20%.

(Preparation of Pure Silver Chloride (100) Tabular Emulsion EM-4) 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 Make up to 2500 ml with distilled water Solution C5 KI 4 g NaCl 140 g Distilled water to 684 ml Solution D5 NaCl 375 g distilled water to 1816 ml Emulsion EM- by the same method as EM-2 except that EAg was adjusted to 150 mV using the above-mentioned solutions A5 to D5. 3
I got Approximately 3,000 of the obtained emulsions EM-4 were observed and measured by an electron microscope to analyze the shape. (100) with an average circle equivalent diameter of 0.8 μm and an average thickness of 0.1 μm
These are tabular grains having a major surface as the plane, and the coefficient of variation is 20%
Met.

(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 with 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 at a ratio of 100: 1 to water previously adjusted to 27 ° C., and a high-speed stirrer ( (Dissolver) at 3,500 rpm for 30 to 120 minutes to obtain a solid fine particle dispersion of the spectral sensitizing dye. At this time, the sensitizing dye (A) was adjusted to have a concentration of 2%.

Sensitizing dye (A): 5,5'-dichloro-9
-Ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine sodium salt anhydrous Sensitizing dye (B): 5,5'-di- (butoxycarbonyl) -1,1'-diethyl-3 , 3'-Di- (4-sulfobutyl) benzimidazolocarbocyanine sodium salt anhydride (Selenium sensitization) The above emulsions EM-1 to EM-4 were subjected to spectral sensitization and chemical sensitization by the following method. Chemically sensitized emulsions EM-A to EM-D were obtained.

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

(Synthesis Example of Colloidal Tin Oxide Sol Dispersion) Stannous 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.

Further, 40 ml of 30% aqueous ammonia is added and heated in a water bath to form a SnO ₂ sol solution. When used as a coating solution, the sol solution is concentrated to about 8% while blowing ammonia into the sol solution.
Regarding the volume resistivity of the particles contained in this sol solution, a thin film was formed on silica glass using the sol solution, and the value measured by the four probe method was defined as the volume resistivity of the particles. The measured volume resistivity was 3.4 × 10 ⁴ Ωcm.

(Support 1) Polyethylene terephthalate film base for X-rays (PET) having a thickness of 175 μm and colored to a density of 0.170 (Support 2)
0 μm X-ray polyethylene naphthalate film base (PEN) (Preparation of tin oxide sol-subbed support) Supports 1, 2
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 to a thickness of 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.

[0219]

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

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

(L-3) Dimethyl terephthalate 34.0
2 parts by weight, 25.52 parts by weight of dimethyl isophthalate, 5
-Sulfoisophthalic acid dimethyl sodium salt 12.97
Parts by weight, 47.85 parts by weight of ethylene glycol, 1,4
Cyclohexanedimethanol 18.95 parts by weight, calcium acetate monohydrate 0.065 parts by weight, manganese acetate tetrahydrate 0.022 parts by weight under a nitrogen stream 170 to 22 parts
After transesterification while distilling off methanol at 0 ° C., 0.04 parts by weight of trimethyl phosphate, 0.04 parts by weight of antimony trioxide as a polycondensation catalyst and 15.08 parts by weight of 1,4-cyclohexanedicarboxylic acid. Add part, 2
At a reaction temperature of 20 to 235 ° C., almost the theoretical amount of water was distilled off to carry out esterification. Thereafter, the pressure inside the reaction system was further reduced and the temperature was raised over about 1 hour, and finally polycondensation was performed at 280 ° C. and 1 mmHg or less for about 1 hour to obtain a polyester polymer.
(Intrinsic viscosity 0.35) 30 g of styrene, 30 g of butyl methacrylate, 20 g of glycidyl methacrylate, 20 g of acrylamide and 1.0 g of ammonium persulfate were added to 7300 g of an aqueous solution of the obtained polyester polymer, and 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. Then, the following surfactants 1.
3 g, ammonium persulfate 0.0 g as initiator
23 g were added, and then 8.0 g of vinyl pivalate and 4.6 g of vinyl acetate were added simultaneously, and reacted for 4 hours.
Thereafter, the mixture was cooled and adjusted to pH 6 with a sodium hydroxide solution to obtain a composite latex FG.

Surfactant

[0226]

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(Preparation of photosensitive material of the present invention) The following transverse light blocking layer, emulsion layer coating solution and protective layer coating solution were coated on both sides of supports 1 and 2 shown in Table 2, respectively, at the following prescribed coating amounts. At the same time, and dried.

First Layer (Transverse Light Blocking Layer) Gelatin 0.2 g / m ² Solid Fine Particle Dispersion Dye (AH) 20 mg / m ² Sodium Dodecylbenzenesulfonate 5 mg / m ² Compound (I) 5 mg / m ² 2, 4-Dichloro-6-hydroxy-1,3,5-triazine sodium salt 5 mg / m ² colloidal silica (average particle size 0.014 μm) 10 mg / m ² Second layer (emulsion layer) Emulsion EM-A obtained above To -D, the following various additives were added.

Gelatin (including those in emulsions EM-AD) 1.2 g / m ² Compound (G) 0.5 mg / m ² 2,6-bis (hydroxyamino) -4-diethylamino-1,3 5,5-triazine 5 mg / m ² t-butyl-catechol 5 mg / m ² polyvinylpyrrolidone (molecular weight 10,000) 20 mg / m ² styrene-maleic anhydride copolymer 80 mg / m ² sodium polystyrene sulfonate 80 mg / m ² tri Methylolpropane 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) 0.5 m _{^{/ M 2 nC 4 H 9 OCH}} 2 CH (OH) CH 2 N (CH 2 COOH) 2 20mg / m 2 Compound (M) 5mg / m ² Compound (N) 5mg / m ² Colloidal silica 0.5 g / m ² Latex (L) 0.5 g / m ² Composite latex (FG) 1.0 g / m ² Dextran (molecular weight about 100,000) 0.5 g / m ² Third layer (lower layer of protective layer) Gelatin 0.3 g / m ² dioctyl Phthalate 0.2 g / m ² Fourth layer (protective layer upper layer) Gelatin 0.3 g / m ² Polymethyl methacrylate matting agent (area average particle diameter 7.0 μm) 27 mg / m ² 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 (FG) 0.2 g / m ² Compound (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

[0230]

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[0231]

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[0232]

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The coating weight of the above material was for one side, and the coating amount was adjusted so that the amount of silver applied was 1.5 g / m ² per side. The phosphazene derivative and the leuco compound of the present invention were added to the second layer (emulsion layer) and the third layer (lower layer of the protective layer) as shown in Table 1.

(Production of Fluorescent Intensifying Screen 1) Phosphor Gd ₂ O ₂ S: Tb (average particle size 1.8 μm) 200 g Combined polyurethane-based thermoplastic elastomer Demolac TPKL-5-2625 solid content 40% (Sumitomo) Bayer Urethane Co., Ltd. 20 g Nitrocellulose (digestion degree: 11.5%) 2 g A methyl ethyl ketone solvent was added to the above and dispersed with a propeller mixer to prepare a coating solution for forming a phosphor layer having a viscosity of 25 ps (25 ° C.). . (Binder / Phosphor ratio = 1/2)
2) Separately, 90 g of a soft acrylic resin solid content and 50 g of nitrocellulose were added and dispersed and mixed as a coating liquid for forming an undercoat layer with methyl ethyl ketone to obtain a viscosity of 3 to 6 ps (25 g).
C).

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

The above-mentioned coating solution for forming a phosphor layer was uniformly coated with a doctor blade to a thickness of 240 μm and 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) In the production of the fluorescent intensifying screen 1, the same procedure as in the fluorescent intensifying screen 1 was applied except that the thickness of the coating solution for forming the phosphor layer was applied at 150 μm and no compression was performed. Thus, a fluorescent intensifying screen 2 comprising a support, an undercoat layer, a phosphor layer, and a transparent protective film was produced.

(Measurement of Characteristics of Fluorescent Intensifying Screen) 1) Measurement of Sensitivity A fluorescent intensifying screen to be measured is exposed to the front of an X-ray source on an MRE single-sided silver halide photographic material manufactured by Eastman Kodak Company. The material and then the fluorescent intensifying screen were placed in contact with each other, and the X-ray exposure was changed by the distance method, and log E = 0.
Step exposure was performed with a width of 15 mm. The exposed silver halide photographic light-sensitive material was subjected to development processing by the method described below for the method described in "Measurement of characteristics of silver halide photographic light-sensitive material" to obtain a measurement sample.

The concentration of the measurement sample 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 transmits X-rays generated from a tungsten target tube equivalent to 2.2 mm of aluminum through an aluminum plate having a thickness of 3 mm. From the tungsten anode of the target tube.
To reach the sample fluorescent screen fixed at the position of 00 cm,
Then, the X-ray dose transmitted through the intensifying screen was measured at a position 50 cm behind the phosphor layer of the fluorescent intensifying screen using an ionizing dosimeter, and the amount of X-ray absorption was determined. As a reference, X at the above measurement position measured without passing through a fluorescent intensifying screen was used.
Dose was used.

The measured values of the X-ray absorption of each of the obtained fluorescent intensifying screens are shown below.

X-ray absorption amount Phosphor filling rate Phosphor thickness Sensitivity Fluorescent intensifying screen No. (%) (%) (Μm) 1 55 72 154 100 2 37 65 105 61 (Preparation of Tablet for Replenishment of Development) A tablet for replenishment of development was prepared according to the following operations (A) and (B).

Operation (A) 12500 g of sodium erythorbate as a developing agent is ground in a commercially available bantam mill until the average particle diameter 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),
12.5 g of methylbenzotriazole, 1-phenyl-
5 g of 5-mercaptotetrazole, N-acetyl-D,
Add 60 g of L-penicillamine, mix in a mill for 30 minutes, and in a commercial stirring granulator at room temperature for about 10 minutes, 30 ml
After granulation by adding water, the granulated product is dried at 40 ° C. for 2 hours in a fluidized bed drier to almost completely remove the water content of the granulated product. 1670 g of polyethylene glycol # 6000 and 1670 g of mannitol are uniformly mixed with the granules thus prepared in a room humidified at 25 ° C. and 40% RH or less using a mixer for 10 minutes. Tough pre-collect 1 from Kikusui Seisakusho Co., Ltd.
527HU was compressed and compressed using a modified tableting machine with a filling amount per tablet of 8.77 g to prepare 2500 tablets A for replenishment of development.

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

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

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

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

Developer Starter Glacial acetic acid 2.98 g KBr 4.0 g Add water to make 1 liter.

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

The fixing tank was filled with 11.0 liters of a fixing solution prepared by diluting 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 the development processing was 1.0, and running was performed.

During the running, the photosensitive material was 0.6
4 pieces of the above A and B agents and 150 ml of water per 2 m ²
The addition was performed. When each of the agents A and B was dissolved in 20 ml of water, the pH was 10.70. Four fixing agents, two D agents, and 150 ml of water were added to the fixing solution per 0.62 m ² of the photosensitive material. The rate of addition of water to each processing agent was started almost simultaneously with the addition of the processing agent, and was added at a constant speed for 10 minutes in approximately proportion to the dissolution rate of the processing agent.

<Evaluation of Sensitometry> The obtained film sample was sandwiched between fluorescent intensifying screens 1 and irradiated with X-rays through a penetrometer type B (manufactured by Konica Medical Co., Ltd.), and then an automatic developing machine SRX-701 ( A component for charging a solid processing agent was attached to Konica Corporation, and the solid processing agent was used to perform processing at a development temperature of 35 ° C. for a total processing time of 30 seconds. In addition,
At this time, the replenishment amount of the processing solution was the amount shown in Table 2 for both the developer and the fixing solution.

<Evaluation of Silver Tone> Each of the coated samples was
After cutting into 0 cm × 30 cm, and sandwiching the fluorescent intensifying screen 1 and irradiating with X-rays, the same processing as in the evaluation of sensitometry was performed.
The evaluation was visually performed in five stages as follows.

5: Cool black tone without any yellowish color 4: Slightly yellowish color, but little noticeable 3: Yellowish color, but practically acceptable 2: The yellowish tint is strong and poses a practical problem. 1: The yellowish tint is remarkably strong and unsuitable for practical use. <Evaluation of Image Preservation> The developed sample was stored under the following conditions.

[A]. 60 g of a saturated aqueous solution of cobalt chloride (CoCl ₂ .6H ₂ O) in a sealable pressure vessel (FIG. 1)
And add 14 ml of pure water. ) Was placed, and the developed sample was placed on a mesh plate. Close the lid and replace with oxygen until the internal oxygen concentration becomes 90% or more, the pressure in the container is set to 2.3 kgW / cm ^2, and 55 ° C. (heating)
And stored tightly for one month.

[B]. The developed sample is immersed in a 0.2% hydrogen peroxide solution for 30 seconds and then dried at room temperature.
After the dried sample was conditioned for 1 hour at 23 ° C. and a relative humidity of 80%, it was sealed in a moisture-proof bag, heated to 55 ° C., and stored for 48 hours.

[C]. The developed sample was placed in a desiccator containing 3% aqueous hydrogen peroxide and stored at room temperature for one month.

Each sample stored under the above conditions was visually observed on a Schaukasten and evaluated according to the following evaluation criteria.

A: No discoloration is observed B: Discoloration is slightly observed C: Discoloration is clearly observed D: Discoloration is considerable.

The results obtained are shown in Tables 1 and 2 below.

[0263]

[Table 1]

[0264]

[Table 2]

As can be seen from the table, the sample of the present invention was excellent in the color tone of the silver image without a yellow tint with a cool black tone, and no discoloration was observed in the storage stability of the silver image.

Example 2 Sample No. 1 prepared in Example 1 10, 11, 12, 13
Was used to change the processing time and the replenishing amount, and evaluation was performed in the same manner as in Example 1.

<Change in processing time> The above-mentioned processing solution was used for processing under the following conditions.

(Normal Processing Conditions) Developing time: 12 seconds Fixing time: 9.3 seconds Washing time: 6 seconds Between washing and drying (squeeze): 4.8 seconds Drying time: 12.9 seconds Total processing time: 45 seconds (Rapid processing conditions) Developing time: 8 seconds Fixing time: 6.2 seconds Washing time: 4 seconds Between washing and drying (squeeze): 3.2 seconds Drying time: 8.6 seconds Total processing time: 30 seconds <Replenishment amount Change of developer and fixer: The replenishing amounts shown in Table 3 are used. 14 is a relative value when the reciprocal of the X-ray exposure required to obtain a density of minimum density +1.0 is 100.

The above results are shown in Table 3 below.

[0270]

[Table 3]

As is clear from Table 3, the sample of the present invention can obtain high sensitivity even at low replenishment and rapid processing.

[0272]

As has been demonstrated in the examples, according to the present invention, the color tone of the developed silver after the development processing and after the storage can be stably obtained without a yellow tint and with a cool black tone. Furthermore, the sample of the present invention was able to obtain high sensitivity even during low replenishment and rapid processing.

[Brief description of the drawings]

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

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Metal body part 2 Metal lid part 3 Oxygen gas introduction doorway 4 Oxygen gas introduction doorway 5 On-off valve 6 On-off valve 7 Sealing screw 8 Bottom part 9 Sample under test 10 Net plate 11 Barometer 12 Packing 13 Humidity control Agent 14 Petri dish

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03C 1/34 G03C 1/34 1/74 1/74 1/76 1/76 1/795 1/795 5/17 5/17 5/26 5/26 520 520 5/29 5/29 5/31 5/31 5/395 5/395 G21K 4/00 G21K 4/00 A

Claims (12)

[Claims] In a silver halide photographic material having a hydrophilic colloid layer including at least one silver halide emulsion layer on a support, the hydrophilic colloid layer contains the following general formula (1) or ( A silver halide photographic light-sensitive material comprising: particles of the water-insoluble compound represented by 2); and at least one leuco compound which reacts with an oxidized form of a developing agent to form a blue dye. Embedded image In the general formula (1), R _1a and R _2a each represent a substituted or unsubstituted alkyl group, alkoxy group, alkylthio group,
Aryl, aryloxy, alkenyl, alkynyl, amino, alkylimino, arylimino, alkylthio, arylthio, acyl, cyanide, azide; R _1a and R _2a are the same; Or different. n ₁ represents a positive integer of 1 or more;
When n ₁ is plural, R _1a and R _2a may be the same or different. In the general formula (2), R _3a ,
R _4a represents a group having the same _meaning as R _1a and R _{2a in} formula (1);
_3a and R _4a may be the same or different. n ₂ represents a positive integer of 3 or more, and when n ₂ is plural, R _3a , R _3
4a may be the same or different. 2. A leuco compound represented by the following general formula (3):
The silver halide photographic material according to claim 1, which is a compound represented by (6). Embedded image In the formula, W represents —NR ₁ R ₂ , —OH or —OZ;
₁ and R ₂ each represent an alkyl group or an aryl group, and Z represents an alkali metal ion or a quaternary ammonium ion. R ₃ is a hydrogen atom, a halogen atom or 1
And n represents an integer of 1 to 3. Z ₁ and Z ₂ each represent a nitrogen atom or ＣC (R ₃ ) —.
X is 5 together with Z ₁ , Z ₂ and carbon atoms adjacent thereto.
Represents a group of atoms necessary for constructing a 6-membered 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. R represents an aliphatic group or an aromatic group, and p represents an integer of 0 to 2. CP1 represents the following groups. Embedded image Embedded image In the formula, R _{5 to} R ₈ each represent a hydrogen atom, a halogen atom, or a substituent that can be substituted on a benzene ring. Also R ₅ and R ₆
And R ₇ and R ₈ may combine with each other to form a 5- to 7-membered ring. R ₉ has the same meaning as R ₄ . R ₁₀ and R ₁₁ each represent an alkyl group, an aryl group or a heterocyclic group.
R ₁₂ has the same meaning as R ₄ . R ₁₃ and R ₁₄ have the same meaning as R ₁₀ and R ₁₁ . R ₁₅ has the same meaning as R ₁₂ . R ₁₆ is an alkyl group, an aryl group, a sulfonyl group, a trifluoromethyl group, a carboxy group, an aryloxycarbonyl group,
Represents an alkoxycarbonyl group, a carbamoyl group or a cyano group. R ₁₇ has the same meaning as R ₄ . R ₁₈ has the same meaning as R ₃ , and m represents an integer of 1 to 3. Y1 represents an atomic group necessary for constructing a 5- or 6-membered monocyclic or condensed nitrogen-containing heterocyclic ring together with two nitrogen atoms. R ₁₉ and R ₂₀
Represents an alkyl group or an aryl group. R ₂₁ has the same meaning as R ₄ . R ₂₂ and R ₂₃ has the same meaning as R ₁₉ and R _20. R ₂₄ has the same meaning as R ₂₁ . R ₂₅ , R ₂₇ and R ₂₈ represent a hydrogen atom or a substituent. R ₂₆ has the same meaning as R ₄ . R ₂₉ , R ₃₁ and R ₃₂ have the same meanings as R ₂₅ , R ₂₇ and R ₂₈ . R ₃₀ has the same meaning as R ₂₆ . R _34, R ₃₅ and R ₃₆ have the same meanings as R _25, R ₂₇ and R _28. R ₃₃ is R ₂₆
Is synonymous with R ₃₈ , R ₃₉ and R ₄₀ have the same meaning as R ₂₅ , R ₂₇ and R ₂₈ . R ₃₇ has the same meaning as R ₂₆ . R ₄₁ ,
R ₄₂ and R ₄₃ have the same meanings as R _25, R ₂₇ and R _28.
R ₄₄ has the same meaning as R ₂₆ . ★ is C in general formula (3)
Represents a bonding point between P1 and another partial structure. Embedded image In the formula, R ₁ , R ₂ , R ₃ , R ₄ , CP 1, n, R, and p represent R ₁ , R ₂ , R ₃ , R ₄ , CP ₁ in general formula (3).
It is synonymous with n, R and p. Embedded image Wherein R ₃ , n, R ₄ , W, X, Z ₁ , Z ₂ , and CP 1
Is R ₃ , n, R ₄ , W, X, Z ₁ ,
It is synonymous with Z ₂ and CP1. Embedded image _{Wherein, R 1, R 2, R} 3, R 4, CP1 and n have the same meanings as _{R 1, R 2, R 3} , R 4, CP1 and n in the general formula (3). 3. The silver halide grains in the silver halide emulsion layer are tabular silver halide grains having a main plane composed of two parallel (100) planes and having a silver chloride content of 10 to 10. 4. The silver halide photographic material according to claim 2, wherein the amount is 100 mol%. 4. A silver coating weight per side of 1.0 to 2.0 g.
/ M < ² >, The silver halide photographic light-sensitive material according to any one of claims 1 to 3, wherein 5. The silver halide photographic light-sensitive material according to claim 1, wherein the support is polyethylene naphthalate. 6. The polyethylene naphthalate support has a thickness of 70 to 170 μm.
6. The silver halide photographic light-sensitive material according to any one of the above items 5. 7. An X-ray image, wherein the surface of the silver halide photographic material according to any one of claims 1 to 6 having an emulsion layer and the fluorescent surface of a fluorescent intensifying screen are adhered to each other. Line image forming unit. 8. The X-ray image forming unit according to claim 7, wherein the X-ray energy of the fluorescent intensifying screen exhibits an absorption of 45% or more with respect to X-rays of 80 kVp, and the filling rate of the phosphor is 6%.
An X-ray image forming method, wherein the fluorescent intensifying screen is 8% or more and the thickness of the phosphor is 135 to 200 μm, and the fluorescent intensifying screen is irradiated with X-rays to perform imagewise exposure. 9. A method for processing a silver halide photographic light-sensitive material, comprising processing the silver halide photographic light-sensitive material according to claim 1 in a photographic processing step including a development step. . 10. The processing is performed by an automatic developing machine having a mechanism for supplying a solid processing agent to a processing tank.
The method for processing a silver halide photographic light-sensitive material described in the above. 11. The method for processing a silver halide photographic light-sensitive material according to claim 9, wherein a replenisher amount to be replenished in the developing step and / or the fixing step is represented by the following formula. . 1 ≦ amount of replenisher / amount taken out by photosensitive material ≦ 7 12. A processing time (Dry) required for all processing steps.
The method for processing a silver halide photographic material according to any one of claims 9 to 11, wherein (to Dry) is within 30 seconds.