JPH06148788A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent the sensitizing paper from being stained by adding at least one specific compound to a silver halide emulsion layer. CONSTITUTION:The silver halide photographic sensitive material contains at least one photosensitive silver halide emulsion layer on each of the both surfaces of the substrate and also one of the compounds represented by the formula I in this silver halide emulsion layer. In the compounds represented by the formula I, the compounds represented by the formula II are particularly preferred. In the formulas, Q1 is an atomic group necessary for forming a 5or 6-membered nitrogen heterocycle; X is a subtitutent; (n) is 0 or 1; Z1 is an atomic group necessary for forming a 5 or 6membered nitrogen heterocycle; Z2 is an oxygen, sulfur, selenium, tellurium or nitrogen atom; R1 is an alkyl group; L1-L4 are methylene groups. (n1) is 0, 1, 2 or 3; (n1) is 0 or 1; M1 is a charge neutralizing counter ion; (n1) is the number of the counter ions.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an industrial X-ray silver halide photographic light-sensitive material (hereinafter referred to as industrial X-ray sensitive material) and an exposure method therefor. Regarding Ray sensitive material.

[0002]

2. Description of the Related Art An industrial X-ray sensitive material irradiates an object with X-rays or the like to detect internal and surface defects of an industrial member and detects the intensity of the transmitted X-rays or the like. It is a sensitive material used to Objects that are usually inspected are
Most of them are metals such as iron and aluminum. On the other hand, as the radiation used, any radiation can be used as long as it can be absorbed to some extent by these objects and penetrate to some extent, and the silver halide grains can be exposed to light, but usually it can penetrate metals. X-rays and γ-rays are often used in the sense that they have the ability.

However, since X-rays, γ-rays and the like have a high penetrating ability, they easily penetrate silver halide grains, and particularly when they have high energy rays, their photosensitivity becomes low. Therefore, it is preferable that the object can be penetrated and that the silver halide grains are less likely to penetrate, that is, it is easier to be exposed to light,
For this purpose, X-rays penetrating an object are absorbed by a thin metal foil before reaching the silver halide photosensitive material and converted into secondary electron beams, whereby the silver halide grains are exposed to light. Is commonly used.

Actually, a lead foil having a thickness of about 0.01 mm to several mm is closely attached to a sensitive material and put in a shielding container such as a cassette, and in that state, X-rays transmitted through an object are irradiated. become. In this case, it is necessary to pay attention so that the sensitive material and the lead foil are in close contact with each other in order to prevent the deterioration of the image.

However, since lead is a fairly soft metal, it is likely that lead will be easily scraped off and adhere to the photosensitive material. When the developing process is performed in this state, the lead-attached portion is often blackened. Although it is a blackening unevenness usually called "intensifying screen stain", this not only erases necessary information, but in some cases it may be regarded as a defect of the object, which is very serious. It's a problem.

In order to improve the "staining on the intensifying screen", for example, a method for increasing the surface iodine content of silver halide grains is described in Japanese Patent Application No. 3-250815, which is treated separately by tank treatment. It made the unevenness worse, and it was necessary to incorporate another measure for this.

It is also possible to reduce the amount of the matting agent in the surface layer from the viewpoint of reducing the adhesion of lead, but it has been found that the adhesiveness becomes worse under high humidity, and the sliding is prevented from scratching. It is conceivable to add the agent to the surface layer, but the improvement effect is unexpectedly small, and conversely, it is difficult to handle because it is too slippery.

On the other hand, there is also a method of improving with an additive, and a method disclosed in, for example, Japanese Patent Application No. 4-104545 is known in this regard. When these additives are actually tested, it can be said that they are good additives with no adverse effects up to a certain amount, but when the amount is increased, the harmful effects still occur.
Therefore, in order to improve the quality with additives, the important factor is how few adverse effects and how large effects can be obtained.

[0009]

SUMMARY OF THE INVENTION The object of the present invention is to substantially eliminate the problem of "sensitizing screen stain" in an industrial X-ray sensitive material in which the photosensitive material is exposed and used in close contact with a lead foil. The present invention is to supply an X-ray sensitive material for industrial use which is substantially free from other problems.

[0010]

SUMMARY OF THE INVENTION The above-mentioned object is to provide an industrial X-ray photosensitive material which is exposed to X-rays or the like while being in direct contact with a metallic lead foil, the photosensitive material comprising at least one photosensitive layer on each side of a support. Industrial X having a soluble silver halide emulsion layer and containing at least one compound represented by the general formula (I) in the silver halide emulsion layer.
I was able to solve it by using the ray sensitive material.

[0011]

[Chemical 2]

In the formula, Q ₁ represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle, X represents a substituent,
n is 0 or 1.

The general formula (I) will be described in more detail. Q ₁ represents a 5- or 6-membered carbon, nitrogen or chalcogen (typically an atomic group necessary for forming a nitrogen-containing heterocycle consisting of oxygen, ion, selenium and tellurium atoms, and is generally called an acidic nucleus). The acidic nucleus mentioned here is, for example, "The Theory of the Photograp" edited by TH James.
hic Process) ", 4th Edition, Chapter 8, pages 198-200, published by Macmillan, 1977. The following nuclei are preferable. 2 or 4-thiohydantoin, 2-thiooxazolidine-
2,4-dione, the core of rhodanin. More preferably, it is a rhodamine nucleus.

Among the compounds represented by the general formula (I), the compound represented by the general formula (II) is particularly preferable.

[0015]

[Chemical 3]

In the formula, Z ₁ represents a group of atoms necessary for forming a 5- or 6-membered nitrogen-containing heterocycle. Z ₂ represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or a nitrogen atom. R ₁ represents an alkyl group. L ₁ , L ₂ , L
₃ and L ₄ represent a methine group. n ₁ represents 0, ₁ , 2 or 3. n ₂ represents 0 or 1. M ₁ represents a charge-neutralizing counterion, and m ₁ is a number of 0 or more necessary for neutralizing the charge in the molecule.

The general formula (II) will be described in more detail. The nucleus formed by Z ₁ includes a thiazole nucleus (thiazole nucleus (for example, thiazole, 4-methylthiazole, 4-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole), benzothiazole nucleus (for example, , Benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-
Chlorobenzothiazole, 5-nitrobenzothiazole, 4-methylbenzothiazole, 5-methylthiobenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 4-bromobenzothiazole, 6
-Bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 6-methylthiobenzothiazole, 5-ethoxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-
Carboxybenzothiazole, 5-phenethylbenzothiazole, 4-fluorobenzothiazole, 5-chloro-6-methylbenzothiazole, 5,6-dimethylbenzothiazole, 5,6-dimethylthiobenzothiazole 5,6-dimethoxybenzothiazole, 5-hydroxy-6-methylbenzothiazole, tetrahydrobenzothiazole, 4-phenylbenzothiazole), naphthothiazole nucleus (for example, naphtho [2,1-d] thiazole, naphtho [1,2-d] thiazole, naphtho [2] , 3
-D] thiazole, 5-methoxynaphtho [1,2-d]
Thiazole, 7-ethoxynaphtho [2,1-d] thiazole, 8-methoxynaphtho [2,1-d] thiazole,
5-methoxynaphtho [2,3-d] thiazole)}, thiazoline nucleus (for example, thiazoline, 4-methylthiazoline, 4-nitrothiazoline), oxazole nucleus {oxazole nucleus (for example, oxazole, 4-methyloxazole, 4- Nitroxazole, 5-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole), benzoxazole nucleus (for example, benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5
-Bromobenzoxazole, 5-fluorobenzoxazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole, 5-nitrobenzoxazole, 5-trifluoromethylbenzoxazole, 5-
Hydroxybenzoxazole, 5-carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6-nitrobenzoxazole, 6-methoxybenzoxazole, 6-hydroxybenzoxazole, 5,6-dimethylbenzoxazole, 4, 6-dimethylbenzoxazole, 5-ethoxybenzoxazole), naphthoxazole nucleus (for example, naphtho [2,1-d] oxazole, naphtho [1,2-d] oxazole, naphtho [2,3-d] oxazole, 5 -Nitronaphtho [2,1-d] oxazole)} oxazoline nucleus (eg, 4,4-dimethyloxazoline), selenazole nucleus {selenazole nucleus (eg, 4-methylselenazole, 4-nitroselenazole, 4-phenylselena) ), A benzoselenazole nucleus (for example, benzoselenazole, 5-chlorobenzoselenazole, 5-nitrobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, 6-nitrobenzoselenazole, 5-chloro-
6-nitrobenzoselenazole, 5,6-dimethylbenzoselenazole), naphthoselenazole nucleus (for example, naphtho [2,1-d] selenazole, naphtho [1,2-
d] selenazole)}, selenazoline nucleus (eg, selenazoline, 4-methylselenazoline), tellurazole nucleus {(terrazole nucleus (eg, tellurazole, 4-methylterrazole, 4-phenylterrazole), benzoterrazole nucleus (eg, , Benzoterrazole, 5-chlorobenzoterrazole, 5-methylbenzoterrazole, 5,6-dimethylbenzoterrazole, 6-methoxybenzoterrazole), naphthoterrazole nucleus (for example, naphtho [2,1-d ] Tellurazole, naphtho [1,
2-d] terrazole)}, a tellrazoline nucleus (for example,
Tellrazoline, 4-methyltelrazoline), 3,3-dialkylindolenine nucleus (eg, 3,3-dimethylindolenine, 3,3-diethylindolenine, 3,3-
Dimethyl-5-cyanoindolenine, 3,3-dimethyl-6-nitroindolenine, 3,3-dimethyl-5-nitroindolenine, 3,3-dimethyl-5-methoxyindolenine, 3,3,5- Trimethyl indolenine,
3,3-dimethyl-5-chloroindolenine), imidazole nucleus {imidazole nucleus (eg, 1-alkylimidazole, 1-alkyl-4-phenylimidazole,
1-arylimidazole), benzimidazole nuclei (for example, 1-alkylbenzimidazole, 1-alkyl-5-chlorobenzimidazole, 1-alkyl-
5,6-dichlorobenzimidazole, 1-alkyl-
5-methoxybenzimidazole, 1-alkyl-5-
Cyanobenzimidazole, 1-alkyl-5-fluorobenzimidazole, 1-alkyl-5-trifluoromethylbenzimidazole, 1-alkyl-6-chloro-5-cyanobenzimidazole, 1-alkyl-6
-Chloro-5-trifluoromethylbenzimidazole, 1-allyl-5,6-dichlorobenzimidazole, 1-allyl-5-chlorobenzimidazole, 1-
Arylbenzimidazole, 1-aryl-5-chlorobenzimidazole, 1-aryl-5,6-dichlorobenzimidazole, 1-aryl-5-methoxybenzimidazole, 1-aryl-5-cyanobenzimidazole), naphthimidazole nucleus (For example, alkylnaphtho [1,2-d] imidazole, 1-arylnaphtho [1,2-d] imidazole), the above-mentioned alkyl group has 1 to 8 carbon atoms, for example, methyl, ethyl, propyl. Unsubstituted alkyl groups such as isopropyl, butyl and hydroxyalkyl groups (eg, 2-hydroxyethyl, 3-hydroxypropyl) are preferable. Particularly preferred are methyl group and ethyl group. The aforementioned aryl group represents phenyl, halogen (eg chloro) substituted phenyl, alkyl (eg methyl) substituted phenyl, alkoxy (eg methoxy) substituted phenyl. }, Pyridine nucleus (for example, 2-pyridine, 4-pyridine, 5-methyl-2-pyridine, 3-methyl-4-pyridine), quinoline nucleus {quinoline nucleus (for example, 2-quinoline, 3-methyl-2-) Quinoline, 5-ethyl-2-quinoline, 6-
Methyl-2-quinoline, 6-nitro-2-quinoline, 8
-Fluoro-2-quinoline, 6-methoxy-2-quinoline, 6-hydroxy-2-quinoline, 8-chloro-2-
Quinoline, 4-quinoline, 6-ethoxy-4-quinoline, 6-nitro-4-quinoline, 8-chloro-4-quinoline, 8-fluoro-4-quinoline, 8-methyl-4-
Quinoline, 8-methoxy-4-quinoline, 6-methyl-
4-quinoline, 6-methoxy-4-quinoline, 6-chloro-4-quinoline), isoquinoline nucleus (for example, 6-nitro-1-isoquinoline, 3,4-dihydro-1-isoquinoline, 6-nitro-3-) Isoquinoline)}, an imidazo [4,5-b] quinoxaline nucleus (for example, 1,3-diethylimidazo [4,5-b] quinoxaline, 6-chloro-1,3-diallylimidazo [4,5-b] quinoxaline. ), An oxadiazole nucleus, a thiadiazole nucleus, a tetrazole nucleus, and a pyrimidine nucleus.

The nucleus formed by Z ₁ is preferably a thiazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzimidazole nucleus, a 2-quinoline nucleus or a 4-quinoline nucleus. More preferably, it is a thiazole nucleus.
Z ₂ is preferably an oxygen atom, a sulfur atom or a nitrogen atom (N—R ₂ ). R ₂ is a hydrogen atom, having 1 to
18, preferably 1 to 7, particularly preferably 1 to 4 alkyl groups (eg methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl), substituted alkyl groups {eg aralkyl groups (eg , Benzyl, 2-phenylethyl), hydroxyalkyl groups (eg, 2-hydroxyethyl,
3-hydroxypropyl), carboxyalkyl group (for example, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, carboxymethyl), alkoxyalkyl group (for example, 2-methoxyethyl, 2-
(2-methoxyethoxy) ethyl), sulfoalkyl group (for example, 2-sulfoethyl, 3-sulfopropyl, 3
-Sulfobutyl, 4-sulfobutyl, 2- [3-sulfopropoxy] ethyl, 2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl), sulfatoalkyl group (for example, 3-sulfatopropyl, 4
-Sulfatobutyl), a heterocyclic-substituted alkyl group (for example, 2- (pyrrolidin-2-one-1-yl) ethyl, tetrahydrofurfuryl, 2-morpholinoethyl), 2-acetoxyethyl, carbomethoxymethyl, 2-methane. Sulfonylaminoethyl}, allyl group, aryl group (eg phenyl, 2-naphthyl), substituted aryl group (eg 4-carboxyphenyl, 4-sulfophenyl, 3
-Chlorophenyl, 2-methylphenyl) and a heterocyclic group (for example, 2-pyridyl, 2-thiazolyl) are preferable.
More preferably, a hydrogen atom or an unsubstituted alkyl (eg, methyl, ethyl, n-propyl, n-butyl, n-
Pentyl, n-hexyl), carboxyalkyl group (for example, carboxymethyl, 2-carboxyethyl) and sulfoalkyl group (for example, 2-sulfoethyl).

Z ₂ is more preferably a sulfur atom. R ₁ is preferably an unsubstituted alkyl group having 18 or less carbon atoms (for example, methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, octadecyl), or a substituted alkyl group (for example, as a substituent,
A carboxy group, a sulfo group, a cyano group, a halogen atom (for example, fluorine, chlorine or bromine), a hydroxy group,
Alkoxycarbonyl group having 8 or less carbon atoms (eg, methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl), alkoxy group having 8 or less carbon atoms (eg, methoxy, ethoxy, benzyloxy, phenethyloxy), 10 or less carbon atoms A monocyclic aryloxy group (eg, phenoxy, p-tolyloxy), an acyloxy group having 3 or less carbon atoms (eg, acetyloxy, propionyloxy), an acyl group having 8 or less carbon atoms (eg, acetyl, propionyl, benzoyl). , Mesyl), a carbamoyl group (eg, carbamoyl, N, N-dimethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl), a sulfamoyl group (eg, sulfamoyl, N, N-dimethylsulfamoyl, morpholinosul). Sulfonyl, piperidinosulfonyl),
An aryl group having 10 or less carbon atoms (eg, phenyl, 4-
Chlorphenyl, 4-methylphenyl, α-aphtyl)
And an alkyl group having 18 or less carbon atoms substituted with. Preferably an unsubstituted alkyl group (for example, a methyl group,
Ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group), carboxyalkyl group (for example, 2-carboxyethyl group, carboxymethyl group), sulfoalkyl group (for example, 2-sulfoethyl group) , 3-sulfopropyl group, 4-sulfobutyl group, 3-sulfobutyl group) and methanesulfonylcarbamoylmethyl group.

L ₁ , L ₂ , L ₃ and L ₄ are methine groups or substituted methine groups (eg substituted or unsubstituted alkyl groups (eg methyl, ethyl, 2-carboxyethyl), substituted or unsubstituted aryl groups ( For example, phenyl, o-carboxyphenyl), heterocyclic group (eg barbituric acid), halogen atom (eg chlorine atom, bromine atom), alkoxy group (eg methoxy, ethoxy), amino group (eg N, N-diphenyl). Amino, N
-Methyl-N-phenylamino, N-methylpiperazino), those substituted with an alkylthio group (eg, methylthio, ethylthio), etc.}, and may form a ring with another methine group, or It is also possible to form a ring with the chromophore. Preferably an unsubstituted methine group,
It is a methine group substituted with an alkyl group (eg, methyl, ethyl). L ₁ and L ₂ form zeromethine, dimethine, tetramethine, hexamethine and the like. L ₁ and L
_{If the two} units are repeated, they need not be identical.
n ₁ is preferably 0.

M ₁ and m ₁ are included in the formula to indicate the presence or absence of a cation or anion, as required to neutralize the ionic charge of the dye. Whether a dye is a cation, an anion, or has a net ionic charge depends on its auxochrome and substituents. Typical cations are inorganic or organic ammonium and alkali metal ions, while the anion may be either an inorganic or organic anion, for example a halogen anion (eg a fluoride ion, (Chlorine ion, bromine ion, iodine ion), substituted aryl sulfonate ion (for example, p-toluene sulfonate ion, p-chlorobenzene sulfonate ion), aryl disulfonate ion (for example, 1,3-benzene disulfonate ion, 1, 5-naphthalenedisulfonate ion, 2,6-naphthalenedisulfonate ion), alkyl sulfate ion (for example, methyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetic acid Ion, trifluoromethane Sulfonic acid ions. Typical examples of the compounds represented by formula (I) or (II) are shown below, but the invention is not limited thereto.

[0022]

[Chemical 4]

[0023]

[Chemical 5]

[0024]

[Chemical 6]

[0025]

[Chemical 7]

[0026]

[Chemical 8]

The addition amount of the compound represented by formula (I) or (II) of the present invention is 1 × 10 ^-6 to 1 × 10 ^-3 mol, and particularly 1 × 10 ^-5 to 1 mol per mol of silver halide. 1 x 1
It is preferably 0 ^-4 mol. The silver halide emulsion layer is most preferable as a place of addition.

The compounds of the present invention are described in "Heterocyclic Compounds" by FM Hamer.
Heterocyclic Compounds-Cyanine Dyes and Relat
ed Compounds) (John Willie and Sons J)
ohn & Sons-New York, London, 1964). ， By D M Sturmer,
"Heterocyclic Compounds-Special Topics in Heterocyclic Chemistry
− (Heterocyclic Compounds−Special topics in hete
rocyclic chemistry-) ", Chapter 18, Section 14, Section 4
Pages 82-515, John Wiley & Sons, New York, London,
(Published in 1977). , "Rods Chemistry of
Carbon Compounds (Rodd's Chemistry of Carbon
Compounds) ", (2nd.Ed.vol.IV, part B, 1977), Chapter 15, 369-422; (2nd.Ed.vol.I.
V, part B, 1985), Chapter 15, 267-2
Page 96, Elsvier Science Publishing Compa
ny Inc.), New York, etc. for the synthesis.

As the silver halide of the photosensitive silver halide emulsion used in the present invention, silver chlorobromide, silver bromide, silver iodobromide and silver chloroiodobromide can be used. Here, the content of silver iodide is preferably 30 mol% or less, and particularly preferably 10 mol% or less. The distribution of iodine in the silver iodobromide grains may be uniform or may be different between the inside and the surface. The silver halide grains in the emulsion may have a regular crystal form such as a cube, an octahedron, a tetrahedron and a rhombohedron, or an irregular shape such as a sphere, a plate or a potato. It may have an irregular crystal form or a composite form of these crystal forms,
It may consist of a mixture of particles of various crystal forms. Further, tabular grains having a grain size of 5 times or more the grain thickness are preferably used in the present invention (specifically, RESEARCH DI
SCLOSURE 225 Volume Item 2534P. 20 ~
P. 58, January issue, 1983, and JP-A-58-12.
7921 and 58-113926).

The average grain size of the silver halide grains is defined as the grain size, with the diameter of a sphere having the same volume as that of the grain being defined as the average grain size. The average particle size is 0.1 μm to 3.0 μm, preferably 0.1.
15 μm to 2.0 μm is preferable. In the present invention, the photosensitive silver halide emulsion may be a mixture of two or more kinds of silver halide emulsions. Grain size of emulsion to be mixed
The halogen composition, sensitivity, etc. may be different. The light-sensitive emulsion may be mixed with a substantially non-light-sensitive emulsion (the surface or inside may or may not be fogged), or it may be divided into separate layers (details). Are described in US Pat. Nos. 2,996,382 and 3,397,987). For example, the same layer as a light-sensitive silver halide emulsion comprising a spherical or potato-shaped photosensitive emulsion and a tabular grain having a grain size of 5 times or more the grain thickness or a different layer as described in JP-A-58-127921. May be used for. When used in different layers, the light-sensitive silver halide emulsion consisting of tabular grains may be on the side closer to the support or conversely on the side farther from the support.

The photographic emulsion used in the present invention is P. Glafki.
des by Chimie et Physique Photographique (Paul Mon
tel, 1967), GF Duffin, Photograp
hicEmulsion Chemistry (The Focal Press, 196
6 years), by VL Zelikman et al Makig and Coting Pho
tographic Emulsion (The Focal Press, 1964
Year), JP-A-58-127921 and 58-1139.
It can be adjusted using the method described in Japanese Patent Publication No. 26, etc. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a method of reacting a soluble silver salt and a soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. .

It is also possible to use a method of forming silver halide grains in the presence of excess silver ions (so-called reverse mixing method). As one form of the simultaneous mixing method, a method of keeping pAg constant in the liquid phase in which silver halide is produced, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion comprising silver halide grains having a regular crystal form and a substantially uniform grain size can be obtained.

Even if the crystal structure of the silver halide grains is uniform to the inside, it has a layered structure in which the inside and the outside are different, British Patent 635,841 and US Pat. No. 3,622,318. It may be of the so-called conversion type as described in No. Further, silver halides having different compositions may be joined by epitaxial joining, or may be joined with compounds other than silver rhodanide and silver oxide, for example. Further, it may be either a surface latent image type or an internal latent image type. In the process of silver halide grain formation or physical ripening during the production of silver halide, cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt,
An iron salt or an iron complex salt may coexist.

During grain formation, a so-called silver halide solvent such as ammonia, thioether compound, thiazolidine-2-thione, tetrasubstituted thiourea, rhodancali, rhodammone, and amine compound may be present to control grain growth. The silver halide emulsion used in the present invention may or may not be chemically sensitized. Chemical sensitization methods include sulfur sensitization, reduction sensitization,
Known methods such as gold sensitization can be used,
Used alone or in combination.

Among the noble metal sensitization methods, the gold sensitization method is a typical one and a gold compound, mainly a gold complex salt is used. Noble metals other than gold, for example, complex salts of platinum, palladium, iridium, etc. may be contained. Specific examples are US Patent 2,
No. 448,060, British Patent No. 618,061 and the like. As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanins and the like can be used in addition to the sulfur compounds contained in gelatin. As the reduction sensitizer, a primary tin salt, an amine, formamidinesulfinic acid, a silane compound or the like can be used. Further selenium compounds,
Sensitization with a tellurium compound is also preferably used.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. . That is, azoles {eg, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, nitroindazoles, benzotriazoles, aminotriazoles, etc.); mercapto compounds {eg mercapto Thiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles,
Mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines, mercaptotriazines, etc .; thioketo compounds such as oxadrinethione; azaindenes {eg triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes), pentaazaindenes, etc.}; As an antifoggant or stabilizer such as benzenethiosulfonic acid, benzenesulfinic acid, and benzenesulfonic acid amide Many known compounds can be added.

Specifically, RESERCH DISCLO
SER Item 17643 VI (December 1978 issue, P. 24 to P. 25) or cited therein. In particular, JP-A-60-76743 and 6
Nitron and its derivatives described in JP-A-0-87322, mercapto compounds described in JP-A-60-80839, heterocyclic compounds described in JP-A-57-164735, and complex salts of heterocyclic compounds with silver. (Eg 1
-Phenyl-5-mercaptotetrazole silver) and the like can be preferably used.

In the photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material produced by using the present invention, coating aids, antistatic agents, slipperiness improvement, emulsion dispersion, adhesion prevention and photographic property improvement (for example, development acceleration) , Contrast enhancement, sensitization), and various other surfactants may be included. For example, saponin (steroidal), alkylene oxide derivative (eg polyethylene glycol, polyethylene glycol /
Nonionic surfactants such as polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene oxide adducts of silicones), alkyl esters of sugars; alkyl sulfonates, alkylbenzene sulfonates , Alkylnaphthalene sulfonate, alkyl sulfates, N-acyl-N
Anionic surfactants such as alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers; amphoteric surfactants such as alkyl betaines, alkyl sulfobetaines;
Cationic surfactants such as aliphatic or aromatic quaternary ammonium salts, pyridinium salts and imidazolium salts can be used.

Among them, saponin, dodecylbenzenesulfonic acid Na salt, di-2.ethylhexyl α-sulfosuccinic acid Na salt, p-octylphenoxyethoxyethanesulfonic acid Na salt, dodecyl sulfate Na salt, triisopropylnaphthalenesulfonic acid Na salt Salt, anion such as N-methyl-oleoyl taurine Na salt, dodecyltrimethylammonium chloride, N-oleoyl-N ',
Cations such as N ′, N′-trimethylammoniodiaminopropane bromide and dodecylpyridinium chloride, betaines such as N-dodecyl-N, N-dimethylcarboxybetaine and N-oleyl-N, N-dimethylsulfobutylbetaine, and polyynes. (Average degree of polymerization n = 10) oxyethylene cetyl ether, poly (n = 25) oxyethylene p-nonylphenol ether, bis (1-poly (n = 15) oxyethylene-oxy-2,4-di-t
Nonionics such as -pentylphenyl) ethane can be used particularly preferably.

As the antistatic agent, perfluorooctanesulfonic acid K salt, N-propyl-N-perfluorooctanesulfonylglycine Na salt, N-propyl-N-perfluorooctanesulfonylaminoethyloxypoly (n = 3) oxy Ethylene butanesulfonic acid Na salt, N
-Perfluorooctanesulfonyl-N ', N', N '
-Trimethylammoniodiaminopropane chloride,
N-perfluorodecanoylaminopropyl N ', N'
Fluorine-containing surfactants such as dimethyl-N'-carboxybetaine, JP-A-60-80848 and 61-112.
144, Japanese Patent Application Nos. 61-13398 and 61-160.
Nonionic surfactants, nitrates of alkali metals, conductive tin oxide, zinc oxide, vanadium pentoxide, or complex oxides obtained by doping antimony or the like as described in No. 50 can be preferably used.

In the present invention, a homopolymer of polymethylmethacrylate or a polymer of methylmethacrylate and methacrylic acid, organic compounds such as starch, and fine particles of inorganic compounds such as silica and titanium dioxide can be used as a matting agent. . The particle size is 1.0-1
It is preferably 0 μm, particularly preferably 2 to 5 μm. Silicone compounds described in U.S. Pat. Nos. 3,489,576 and 4,047,958 are used as a slip agent in the surface layer of the photographic light-sensitive material of the present invention, and colloidal silica described in JP-B-56-23139. Other than these, paraffin wax, higher fatty acid ester, den powder derivative and the like can be used.

Polyols such as trimethylolpropane, pentanediol, butanediol, ethylene glycol and glycerin can be used as a plasticizer in the hydrophilic colloid layer of the photographic light-sensitive material of the present invention. Furthermore, the hydrophilic colloid layer of the photographic light-sensitive material of the present invention preferably contains a polymer latex for the purpose of improving pressure resistance. As the polymer, a homopolymer of an alkyl ester of acrylic acid, a copolymer with acrylic acid, a styrene-butadiene copolymer, or a polymer or copolymer comprising a monomer having an active methylene group can be preferably used.

The photographic emulsion and the non-photosensitive hydrophilic colloid of the present invention may contain an inorganic or organic hardener. For example, chromium salts, aldehydes (formaldehyde, glitalaldehyde, etc.), N-methylol compounds (dimethylolurea, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,
3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N,
N'-methylenebis- [β- (vinylsulfonyl) propionamide] etc.), active halogen compounds (2,4-
Dichloro-6-hydroxy-s-triazine etc.), mucohalogen acids (mucochloric acid etc.), N-carbamoylpyridinium salts (1-morpholinocarbonyl-3-
(Pyridinio) methanesulfonate, etc.), haloamidinium salts (1- (1-chloro-1-pyridinomethylene))
Pyrrolidinium, 2-naphthalene sulfonate, etc.) can be used alone or in combination. Among them, JP-A-53-41220, JP-A-53-57257, and JP-A-53-57257.
Active vinyl compounds described in 9-162546 and 60-80846 and active halides described in U.S. Pat. No. 3,325,287 are preferable.

The hydrophilic colloid layer of the light-sensitive material of the present invention is preferably hardened with these hardeners so that the swelling ratio in water is 280% or less. As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

For example, dextran, polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-
A wide variety of synthetic hydrophilic polymeric substances such as vinylpyrrolidone, polyacrylic acid, polyacrylamide, polyvinyl imidazole, single or copolymers can be used. As the gelatin, besides lime-processed gelatin, acid-processed gelatin or enzyme-processed gelatin may be used, and a hydrolyzate of gelatin may also be used. Among these, it is preferable to use dextran and potaacrylamide together with gelatin.

The photosensitive silver halide emulsion layer of the present invention may be one layer, or may be divided into two layers or three layers. In this case, it is necessary that at least one of them contains the compound shown in the present invention. The layer containing the compound shown in the present invention may be on the side close to the surface layer, may be on the most support side, or may be any layer. However, the effect is larger on the surface layer side, which is most strongly affected by Pb attached to the surface. The silver halide light-sensitive material of the present invention may have a non-light-sensitive layer such as a surface protective layer in addition to the silver halide emulsion layer.

A cellulose triacetate film is preferable as a support for a general light-sensitive material, and either of them may be colored or may not be colored for antihalation. X
A polyethylene terephthalate film or a cellulose triacetate film is preferable as the support for the radiographic light-sensitive material, and it is particularly preferably colored in blue.

The support is preferably subjected to a corona discharge treatment, a glow discharge treatment or an ultraviolet irradiation treatment for improving the adhesion to the hydrophilic colloid layer, or a styrene butadiene latex or a vinylidene chloride latex. May be provided with a subbing layer, and a gelatin layer may be further provided thereon.
An undercoat layer using an organic solvent containing a polyester swelling agent and gelatin may be provided. By applying a surface treatment to these undercoat layers, the adhesion with the hydrophilic colloid layer can be further improved.

As a method of exposing the silver halide light-sensitive material of the present invention, X of a lead foil of 0.1 mm to several mm is used.
A method is preferably used in which a lead foil having a thickness suitable for the ray and γ-ray energy is selected, the lead foil is closely adhered to both sides of the photosensitive material, and in that state, X-rays or the like that have passed through the object are irradiated. In addition to X rays, γ rays are usually used as a radiation source.

For photographic processing of the light-sensitive material of the present invention, for example, Research Disclosure (RESEARCH D
ISCLOSURE) No. 176, pp. 28-30 (RD-
Any of known methods and known processing solutions as described in 17643) can be applied. The treatment temperature is usually chosen between 18 ° C and 50 ° C.

The developing solution used for photographic processing may contain a known developing agent. Examples of developing agents include dihydroxybenzenes (for example, hydroquinone) and 3-pyrazolidones (for example, 1-phenyl-3).
-Pyrazolidone), aminophenols (eg N-
(Methyl-p-aminophenol) and the like can be used alone or in combination. For the photographic processing of the light-sensitive material of the present invention, it is also possible to carry out processing with a developing solution containing imidazoles as a silver halide solvent described in JP-A-57-78535. Further, it can be processed with a developing solution containing a silver halide solvent described in JP-A-58-37643 and an additive such as indazole or triazole. The developer generally contains other known preservatives, alkali agents, pH buffers, antifoggants, and the like, and if necessary, a dissolution aid, a color tone agent, a development accelerator, a surfactant,
A defoaming agent, a water softening agent, a film hardening agent (eg, glutaraldehyde), a viscosity imparting agent and the like may be included.

As the fixing liquid, those having a generally used composition can be used. Thiosulfate as a fixing agent,
In addition to thiocyanate, an organic sulfur compound known to be effective as a fixing agent can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

[0053]

The present invention will be further described with reference to the following examples. Example 1 Ammonia was used as a silver halide solvent, and cubic silver bromide grains having a side length of 0.32 μ were prepared by a control double jet method. Further, grain formation was continued in the same manner as this time to form shell grains containing 1.0 mol% of silver iodide, and finally 0.40 µ cubic silver iodobromide grains were prepared. After desalting this emulsion in the usual way,
β-oxyethyl phenyl ether, 1-phenyl-5
-Addition of mercaptotetrazole, chemical sensitization using gold and sulfur sensitization together, and as a stabilizer 4-
Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added. The compounds shown in Table 1 were added to this emulsion, and sodium 3- (5-mercaptotetrazole) -benzenesulfonate, polyacrylamide, colloidal silica, 2,4-dichloro-6-hydroxy- was added.
Each sample was prepared by adding s-triazine. At this time, a surface protective layer evolved from gelatin, matting agent, anionic surfactant, polyethylene oxide nonionic surfactant, fluorine-containing compound, organopolysiloxane, composite latex (VONCOAT DV-759 manufactured by Dainippon Ink and Chemicals, Inc.) It was applied simultaneously, and this was applied to both sides of the polyethylene terephthalate support. At this time, the coated silver amount was set to 7 g / m ^{2 on} one side. (Sample a ~
h)

The following evaluations were performed on these samples. <Staining on intensifying screen> The method described on page 15 of Japanese Patent Application No. 3-250815. <Roller Mark> The method described on pages 29 to 30 of JP-A-63-259652. <Sensitivity> Pages 28 to 2 of JP-A-63-259652.
The method described on page 9.

The results thus obtained are shown in Table 1.

[0056]

[Table 1]

The following is clear from this table. During X-ray irradiation, the sensitivity is extremely reduced unless lead foil is used. It can be seen that the addition of the compound example (1) disclosed in the present invention improves "intensifying screen stains" and makes this problem less likely to occur even in exposure using a lead foil.

When the compound example (1) is added in a large amount, the roller mark gradually deteriorates.
For example, in Experiment No. 5, the roller mark is at a level where there is almost no problem, and the stain on the intensifying screen is at a fairly good level. Similarly, Comparative Compound III is shown as an example of a compound not included in the present invention, but also in this compound, when the addition amount is increased, the roller mark becomes worse. However, the stain on the intensifying screen is improved only slightly, and when this compound is used, the problem of the roller mark is only increased, and the stain on the intensifying screen is hardly improved, which is not preferable. It can be seen that the addition of the compound example (1) disclosed in the present invention greatly decreases the sensitivity, and is also preferable in this respect.

Example 2 Next, an example of comparison with another compound which is said to have the same effect will be shown. An aqueous solution of thioether HO (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) ₂ OH was added to the gelatin aqueous solution, and the particle shape was about 0.35 by the usual control double jet method.
Tetrahedral grains with rounded corners of μ were prepared. Phthalated gelatin was used as the gelatin used, and the gelatin was precipitated only by lowering the pH and a desalting step was performed.

This emulsion was subjected to ordinary gold and sulfur sensitization, and then 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, 3- (5-mercapto) was prepared in the same manner as in Example 1. Tetrazole) -sodium benzenesulfonate, polyacrylamide, colloidal silica, 2,4
-Dichloro-6-hydroxy-s-triazine was added, and the compounds shown in Table 2 were further added to perform coating simultaneously with the same surface protective layer as in Example 1 to prepare samples i to q.

The samples of these samples were tested for sensitivity, stain on the intensifying screen, and roller mark in the same manner as in Example 1, and the results shown in Table 2 were obtained.

[0062]

[Table 2]

In Table 2, compound IV is represented by Japanese Patent Application No. 4-10.
No. 4545, and V is a compound known to improve intensifying screen stains. When any of the compounds is added, the stains on the intensifying screen are improved, the sensitivity is lowered, and the roller mark is deteriorated when the addition amount is increased. However, the way of changing them is slightly different depending on the compound.

First, in the comparison between compound IV and compound example (3) of the present invention, the deterioration of the roller mark was almost the same when the decrease in sensitivity was about the same, but intensifying screen stains were observed in the compound example of the present invention. It turns out that (3) is better.

On the other hand, in the case of the comparative compound V and the compound of the present invention (3), when the roller marks were deteriorated to the same degree, the stains on the intensifying screen were improved to about the same level, but the sensitivity was not lowered at this time. There is a difference that the compound example (3) of the present invention is smaller. From the above, from the comparison of these compounds, when the compound of the present invention is used, a light-sensitive material with the least adverse effect can be achieved when comprehensively evaluated from the three viewpoints of sensitivity-roller mark intensifying screen stain. Recognize.

[Procedure amendment]

[Submission date] January 21, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0056

[Correction method] Change

[Correction content]

[0056]

[Table 1]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0058

[Correction method] Change

[Correction content]

When the compound example (1) is added in a large amount, the roller mark gradually deteriorates.
For example, in Experiment No. 5, the roller mark is at a level where there is almost no problem, and the stain on the intensifying screen is at a fairly good level. Similarly, Comparative Compound III is shown as an example of a compound not included in the present invention, but also in this compound, when the addition amount is increased, the roller mark becomes worse. However, the stain on the intensifying screen is improved only slightly, and when this compound is used, the problem of the roller mark is only increased, and the stain on the intensifying screen is hardly improved, which is not preferable. It can be seen that the compound example (1) disclosed in the present invention causes a small decrease in sensitivity when added, and is also preferable in this respect.

Claims (1)

[Claims] 1. An industrial X-ray sensitive material which is irradiated with X-rays or the like in a state of being in direct contact with a metallic lead foil, wherein the sensitive material has at least one photosensitive silver halide emulsion layer on each side of a support. An industrial-use X characterized by containing at least one compound represented by the following general formula (I) in the silver halide emulsion layer or other hydrophilic colloid layer.
Ray photosensitive material. [Chemical 1]