JPH04204937A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a photosensitive material having high sensitivity, little fogging and good picture sharpness by forming the material in a manner that the sensitivity of the one emulsion side is 1.5-10 times higher than that of the other emulsion side. CONSTITUTION:The photographic sensitive material is formed in a manner that the emulsion layer in one side has sensitivity 1.5-10 times higher than the other emulsion layer and that the amt. of silver halide in the high-sensitive emulsion layer is 1.1-5.0 times as much as the amt. of silver in the other side. This silver emulsion layer contains at least one compd. expressed by formulae I-VII. In the formulae, A is a group adsorbing to silver halide, Y is a bivalent joint group comprising atoms or atom groups selected from hydrogen, carbon, nitrogen, oxygen, and sulfur, R is an org. group containing at least one of thioether group, amino group, ammonium group, ether group, and heteroring group, n is 0 or 1, m is 1 or 2, Q is an atom group necessary to form 5- or 6-member heterocylic ring, X is sulfur, oxygen, or selenium, and R1 is hydrogen, or halogen elements.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention is directed to X
This invention relates to silver halide photographic materials for line printing. [Background of the Invention] X-ray photography used for medical diagnosis involves sandwiching a film coated with emulsion on both sides between two fluorescent intensifying screens and holding it in a cassette. Common. This takes into consideration the effect on the human body, and in order to effectively utilize a small amount of X-rays, the X-rays that have passed through the front intensifying screen are further used in the rear intensifying screen. Conventionally, when observing images with films that have emulsion layers on both sides of the support, one sees both the image on the front surface that enters the mouth directly, and the image on the back surface that passes through the base of the support and enters the eye. . Therefore, there is no problem when the image is viewed at right angles to the support, but when viewed from an angular position, the images on the front and back sides become "shifted" and the sharpness decreases. Also, when taking X-rays, the incident angle is 9 to the film surface.
It is common to take pictures so that the angle is 0 degrees, but even in this case
An angle of incidence spread of about 17 degrees from the source of the line is inevitable. Furthermore, in some cases, images may be taken at an oblique angle.
In such a case, in the case of a double-sided emulsion film, the "image shift" between the front and back sides is further magnified, resulting in a significant decrease in sharpness. In recent years, X-ray imaging systems have rapidly advanced in higher image quality and faster processing, and in particular higher sensitivity and sharpness have improved breast cancer,
It is an indispensable element in the diagnosis of diseases such as lung cancer. For this reason, attempts have been made to use films with single-sided emulsion for these diagnoses, but while this certainly improves sharpness, it results in a lack of sensitivity, so as mentioned above, light transmission to the back side (crossover light ), the reality is that a double-sided emulsion film with high sensitivity is unavoidably used even if "pocketed images" occur due to However, an increase in the amount of silver is undesirable because it reduces the marking speed, generates residual silver, and slows down the drying performance, which goes against the speed of processing.Especially, it is undesirable to reduce the processing time of X-ray film. Shortening is an essential condition for intra-operative imaging in the surgical field and blood-cured imaging in the radiological examination field, in order to prevent accidents caused by blood solidification caused by catheters in blood vessels. There is an urgent need to increase the sensitivity of photosensitive materials, which is an issue in the current X-ray scanner, and to establish new technology that can easily obtain high-sharp images through rapid processing. Various ha

[In the field of silver 1-genide photographic materials, various sensitization techniques have been proposed. For example, supersensitization methods using spectral sensitizing dyes, chemical sensitization methods or development acceleration methods using various compounds are known, but these conventional sensitization methods always Silver halide emulsions are not versatile, and it is difficult to say that they are particularly effective for highly sensitive silver halide photosensitive materials. That is, when these methods are applied to high-sensitivity emulsions, there is a problem that fogging tends to occur over time. On the other hand, there is an increasingly strong demand for rapid processing of silver halide photographic materials for X-rays. Rapid processing tends to increase fog and inevitably lowers sensitivity. That is, the current situation is that images with high sensitivity and low fog can be easily obtained through rapid processing, and those that are at a loss of 1-1 with medical cutting information are unprofitable. [Object of the Invention] Accordingly, the first object of the present invention is to provide a silver halide photographic material that is less likely to cause fog and has high sensitivity. The second object of the present invention is to achieve high sensitivity through high temperature rapid processing.
Another object of the present invention is to provide a silver halide photographic material that can provide images with high sharpness. Other objectives will become apparent from the description below. [Configuration of the Invention] It has been found that the above object of the present invention is achieved by the following configuration]7, and the present invention has been completed. That is, in a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on both sides of a transparent support, (a) the sensitivity of the emulsion surface on one side or the sensitivity of the emulsion layer on the other side is The sensitivity is 1.5 to 10 times higher than the sensitivity, and (1) the amount of silver halide on the high-sensitivity emulsion layer side is 1.1 to 5.0 times higher than the amount of silver halide on the other side. A certain old silver halide photographic material, (e) a silver halide containing at least one compound selected from the following formulas [1] to [7] in the silver halide emulsion layer: This is accomplished using photographic materials. General formula [1] A-f(Y)-R'l I11 In the formula, A represents a group adsorbed to silver halide. Examples of the group adsorbed on silver halide include compounds having a mercapto group bonded to a heterocycle, heterocyclic compounds capable of producing iminosilver, or hydrocarbon compounds having a mercapto group. Examples of mercapto compounds bonded to heterocycles include substituted or unsubstituted mercaptoazoles (e.g. 5-
mercap], tetrazoles, 3-mercapto-1,2
, 4-triazoles, 2-mercaptoimidazoles, 2-merno]but-1.3.4-thiadiazoles,
5-Mercap 1□-1,2,4-thiadiazoles, 2
-Mercapyl-1,3,4-oxadiazoles, 2
-Mercapto-1,3,4-selenacyazoles, 2-
mercaptoimidazoles, 2-mercaptothiazoles, 2-mercapto group〉zuoxazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzthiazoles, etc.), substituted or unsubstituted mercaptopyrimidines (e.g., 2-mercapto pyrimidines, etc.). Examples of heterocyclic compounds capable of forming iminosilver include substituted or unsubstituted indazoles, benzimidazoles, benzo[lyazoles, benzoxazoles, benzthiazoles, imidazoles, thiazoles, oxazoles, triazoles, and tetrazoles. Examples include azaindenes, pyrazoles, and indoles. Examples of the hydrocarbon compound having a mercapto group include alkyl mercaptans, aryl mercaptans, alkenyl mercaptans, and aralgyl mercaptans. Y represents a divalent linking group consisting of an atom or a group of atoms selected from a hydrogen atom, a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom. Examples of divalent linking groups include -5-1-〇-1-N-1 R,R. Rs Rs Rr. 11j These linking groups have a linear or branched alkylene group (for example, methylene group, ethylene group, propylene group, butylene group, hexylene group, ■-
methylethylene group, etc.), or a substituted or unsubstituted arylene group (phenylene group, naphthylene group, etc.). R-R2, R3, R-Rs, Ra, R7, Rs, R9
and R3° each represent a hydrogen atom, a substituted or unsubstituted alkyl group (e.g., methyl group, ethyl group, propyl group, butyl group, etc.), a substituted or unsubstituted aryl group (e.g., phenyl group, 2 -methylphenyl group, etc.),
It represents a substituted or unsubstituted alkenyl group (eg, propenyl group, l-methylvinyl group, etc.) or a substituted or unsubstituted aralkyl group (eg, benzyl group, phenethyl group, etc.). Rli represents an organic group containing at least one thioether group, amine group (including salt form), ammonium group, ether group, or heterocyclic group (including salt form). Examples of such organic groups include groups selected from substituted or unsubstituted alkyl groups, alkenyl groups, aralkyl groups, or aryl groups combined with the above groups; Good too. For example, hydrochloride of dimethylaminoethyl group, aminoethyl group, diethylaminoethyl group, dibutylaminoethyl group, dimethylaminopropyl group, dimethylaminoethylthioethyl group, 4-dimethylaminophenyl group, 4-dimethylaminobenzyl group, methylthioethyl group. group, ethylthiopropyl group, 4-methylthio-3-cyanophenyl group, methylthiomethyl group, trimethylammonioethyl group, methoxyethyl group, methoxyethoxyethoxyethyl group, methoxyethylthioethyl group, 3.4-dimethoxyphenyl group , 3-chloro-4-methoxyphenyl group, morpholinoethyl group, l-imitasolylethyl group, morpholinoethylthioethyl group, pyrrolidinoethyl group, piperidinopropyl group, 2-pyridylmethyl group, 2-(l -imidazolyl)ethylthioethyl group, pyrazolylethyl group, triazolylethyl group, methoxycarbonylaminoethyl group, and the like. n represents 0 or 1, m represents the general formula [2] MS -C=N In the general formula [2], Q is preferably a carbon atom, a nitrogen atom,
Represents a group of atoms necessary to form a 5- or 6-membered heterocycle composed of at least one of oxygen, sulfur, and selenium atoms. The heterocycle may also be fused with a carbon aromatic ring or a heteroaromatic ring. Examples of the heterocycle include tetrazoles, triazoles, imidazoles, thiadiazoles, oxadiazoles, selenadiazoles, oxazoles, thiazoles, benzoxazoles, benzthiazoles, benzimidazoles, pyrimidines, etc. can give. M is a hydrogen atom, an alkali metal atom (e.g., sodium atom, potassium atom, etc.), an ammonium group (e.g., trimethylammonium group, dimethylbenzylammonium group, etc.), a group that can become M=H or an alkali metal atom under alkaline conditions. (For example, it represents an acetyl group, a noanoethyl group, a methanesulfonylethyl group, etc.). In addition, these heterocycles include a nitro group, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), a mercapto group, an ano group,
Substituted or unsubstituted alkyl groups (e.g., methyl group, ethyl group, propyl group, E-butyl group, /anogel group, etc.), aryl groups (e.g., phenyl group, 4-
methanesulfo〉amidophenyl group, 4-methyltubonyl group, 3.4-dichlorophenyl group, naphthyl group, etc.), alkenyl group (e.g. allyl group, etc.), aralkyl group (e.g. benzyl group, 4-methylbenzyl group) , phenethyl group, etc.), sulfonyl group (e.g. methanesulfonyl group, ethanesulfonyl group, p-'l' luenesulfonyl group, etc.), carbamoyl group (e.g. unsubstituted carbamoyl group, methylcarbamoyl group, phenylcarbamoyl group) , etc.), sulfamoyl group (e.g. unsubstituted sulfamoyl group, methylsulfamoyl group, phenylsulfamoyl group, etc.), carbonamide group (e.g. acetamido group, benzamide group, etc.), sulfonamide group (e.g. N is a meta-7 sulfonamito group, a benzene) sulfonamido group, I) a river, luene sulfo) amide group, etc.), anluoki, ・ group (e.g., an aralkyl group, hensoyluo↓] group, etc.), a sulfonyloxy-7 group (e.g., methane or luponyl A key group, etc.), thioureido group (e.g. unsubstituted ureido group, methylureido group, ethyl ureide group, phenylureido group, etc.), thioureido group (e.g. (substituted thioureido group, melupureido group, etc.), anno-
group (e.g. acetyl group, hensoyl group, etc.), Ogi7
nonorponyl group (for example, methoxycarbonyl group, etc.), oxycarbonylamino group (for example, methoxycarbonylamino group, phenoxycarbonylamino group,
2-Utylhexyl, luogine, luponylamino group, etc.),
Although it may be substituted with carboxylic acid or its salt, sulfonic acid or its salt, hydroxyl group, etc., nucleation promoting effect is better if it is not substituted with carboxylic acid or its salt, sulfonic acid or its salt, hydroxyl group, etc. I like it because of this. Preferred examples of the heterocycle represented by Q include tetrazoles, triazoles, imidazoles, thiadiazoles, and oxadiazoles. Y,R. m and n have the same meanings as in formula [1], respectively. General formula [3], ・′-゛′・, N-M In the formula, YlR, m, n1M have the same meanings as those in general formula [1], and Q is a 5- or 6-membered group capable of forming iminosilver. Represents a group of atoms necessary to form a heterocycle. Preferably, 5 or 6 selected from carbon, nitrogen, oxygen, sulfur, and selenium.
Represents a group of atoms necessary to form a member heterocycle. Also,
The heterocycle may be fused as a carbon aromatic ring or a heteroaromatic ring. The heterocycle formed by Q is
For example, indazoles, pensimidazoles, benzotriazoles, pensoxazoles, benzthiazoles, imidazoles, thiazoles, oxazoles, triazoles, tetrazoles, tetraazaindenes, triazaines. Dens, diazine pres,
Examples include birasols and indoles. General formula [4] In the formula, M, R, Y, and n have the same meanings as in general formula [2]. X represents an oxygen atom, a sulfur atom or a sulfur atom, preferably a sulfur atom. -Math [5] R. (2) In the formula, R1 is a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), a nitro group, a mercapto group, an unsubstituted amino group, a substituted or unsubstituted alkyl group (
For example, methyl group, ethyl group, etc.), alkenyl group (e.g. propenyl group, I-methyl vinyl group, etc.), aralgyl group (e.g. benzyl group, phenethyl group, etc.), aryl group (e.g. phenyl group, 2-methyl phenyl group,
), or represents Y7TR. R2 is a hydrogen atom, an unsubstituted amino group, or 'fi Y'
)N R and R1 and R2 may be the same or different from each other. However, at least one of R1 and R2 is j Y '7T
Represents R. M, R, Y, and n each have the same meaning as in the general formula [2] above. General formula [6] (1) In the formula, R1 represents fY force R. However, M, R, Y, n
Each has the same meaning as the general formula [2]. In the formula, R2 and R3 are a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), a substituted or unsubstituted amino group (for example, an unsubstituted amine group, a methylamino group, etc.), a nitro group , substituted or unsubstituted alkyl groups (e.g. methyl group, ethyl group, etc.), alkenyl groups (
For example, propenyl group, -methylvinyl group, etc.), aralkyl group (e.g. benzyl group, phenethyl group, etc.)
Alternatively, it represents an aryl group (eg, phenyl group, 2-methylphenyl group, etc.). M, R, each have the same meaning as in the previous general formula [6]. The present invention will be explained in detail below. In the present invention, emulsion layers are coated on both sides of a support, and unlike conventional methods, the present invention is characterized in that a sensitivity difference is created between the photosensitive emulsions on both sides. Moreover, when photographing, exposure is done from only one side. The sensitivity difference referred to in the present invention is basically determined by the light source used to photograph the photosensitive material used in the present invention. For example, a regular X-ray film is measured using a fluorescent intensifying screen for regular X-ray film photography, and an ortho X-ray film is measured using a fluorescent intensifying screen for ortho X-ray film photography. In addition, if systems that use other light sources (panchromatic, infrared, etc.) appear in the future, measurements will be made using light sources that are used in combination with photosensitive materials. In the present invention, the difference in sensitivity between the high-speed emulsion side and the low-speed emulsion side is 4% of the maximum density (not including the support density) of each side of the light-sensitive material.
It can be determined as the ratio of the reciprocal of the amount of light required to obtain a density of 0%. In the present invention, the relative sensitivity of the emulsion surfaces on both sides of the support is:
It was obtained as follows. The relative sensitivity of the high-sensitivity emulsion side can be determined by developing a sample exposed from the high-sensitivity emulsion side, then wiping the back (low-sensitivity) emulsion side with a proteolytic enzyme or an alkaline aqueous solution. Prepare a sample for sensitivity measurement. Sensitivity is measured by subtracting the support concentration from the maximum concentration by 0.4.
The reciprocal of the exposure amount sA required to obtain a density equal to the sum of the support density and the support density is determined. The relative sensitivity of the low-speed emulsion side was determined by developing a sample exposed from the low-speed emulsion side, then wiping the back (high-speed) emulsion side in the same way to create a sensitivity measurement sample with an image of only the low-speed emulsion side. , the value obtained by subtracting the support density from the maximum density is multiplied by 0.4, and the reciprocal of the exposure amount sB required to obtain the density obtained by adding the support density is determined. The light-sensitive material of the present invention has a relative sensitivity ratio of sA/sB = 1.5 to 10 between the high-speed emulsion surface and the low-speed emulsion surface determined in this manner. In cases where the density of information from the photograph is concentrated below 2.0, such as in medical black-and-white photographs, the depiction of low-density areas is essentially done on the side facing the light source (high-sensitivity emulsion side). This method is very effective as a means of preventing deterioration in the sharpness of photographs during photographing and viewing. For the total amount of silver halide on the side constituting the high-sensitivity side of the photosensitive material of the present invention, it is necessary to use silver halide grains with a larger average grain size than on the low-sensitivity side, and it is necessary to form a density as high as possible. Therefore, it is necessary to increase the amount of silver halide on the high-sensitivity side. The incidence (f
! 'Light) The light transmittance is 12% or more, more preferably 2%.
It ranges from 0% to 90%. This is because if the transmittance is too low, the amount of light exposed from the high-sensitivity emulsion surface reaching the low-sensitivity surface will be small, making it impossible to efficiently expose the low-sensitivity emulsion surface. The transmittance from the high-sensitivity surface to the low-sensitivity surface of the photosensitive material of the present invention is the relative sensitivity of the low-sensitivity surface when exposed from the high-sensitivity surface (
sB') and the relative sensitivity (sB) of the low-sensitivity surface when exposed from the low-sensitivity surface. (sB'/sB)>0.12 is the photosensitive material of the present invention. The relative sensitivity is determined as the reciprocal of the exposure amount required to obtain a density equal to the value obtained by subtracting the support density from the maximum density of the low-speed surface, multiplied by 0.4, and then adding the support density. As the light source for determining the relative sensitivity of the sample of the present invention, it is preferable to use a light source that is optimal for exposing each photosensitive material. For example, with Regicolar X-ray film for direct photography,
A blue light-emitting intensifying screen (for example, sold by NR-1fiO Koniriki C stock) that uses CaWO as the phosphor and an ortho-X-ray film for direct imaging uses Gd0 as the phosphor.
2S: Using a green-emitting intensifying screen using Tb (full version is 5RO-160 sold by Konica Co., Ltd.), 0.02
It is preferable to obtain it with an exposure time of 0 to 0.20 seconds. C
The film for RT photography is C using P445 phosphor.
It is clever to calculate the RT time in the range of 1.5 to 2 seconds. If the film records laser light, it is preferable to use the laser light used to expose the film. If there is a film, it is preferable to obtain the II2I secondary surface light, and if it is a film for indirect photography using a mirror camera, it is preferable to obtain the light emission from the fluorescent screen used. It is preferable that the total silver halide iC on the side constituting the layer is 1.1 times or more, preferably 1.2 times or more, than that of the low-speed layer.The silver content ratio of both layers is 1:5. The following is preferable. If it is more than that, the advantage of providing silver halide on both sides of a photosensitive material intended for single-sided exposure as in the present invention will be reduced. - Applicable to conventional single-sided emulsion light-sensitive materials for photographing, mammography, etc. A further feature of the present invention is that when exposing the light-sensitive material according to the present invention, it is exposed only from one side. The film may be placed on either the front or back side with respect to the X-ray incident side, but it is preferable that the surface of the high-sensitivity layer be on the incident side.When using a fluorescent intensifying screen, either the front or back side of the film may be placed. Although it is preferable to set the fluorescent screen on the high-sensitivity emulsion layer side, it is preferable to set the fluorescent screen on the high-sensitivity emulsion layer side.As mentioned above, the silver halide photographic material according to the present invention has A silver halide emulsion layer is coated, and the sensitivity of the emulsion differs between the front and back sides.Therefore, the high-sensitivity silver halide emulsion according to the present invention has the following characteristics:
Compared to low-sensitivity surfaces, fogging is more likely to occur, and recent processing using automatic processors, in particular, typically involves high-temperature, rapid processing using highly active developers. Under these processing conditions, fogging can be kept low,
Maintaining higher sensitivity was difficult. As a result of a wide range of searches for anti-fogging agents, the inventor found that -
It is believed that this problem can be solved by using at least one compound selected from the compounds represented by formulas [1] to [7], and images with high sensitivity, low fog, and excellent sharpness can be obtained even under high-temperature rapid processing conditions. The fact that it had such an effect was something that we could not have predicted. Hereinafter, typical examples of compounds represented by formulas [1] to [7] according to the present invention will be listed, but the present invention is not limited thereto. CH2CH2SCH3 ■ CH2C82NHCO(CH2CH20)3CH3C1
(2SCH. CH2C820CH5 ・HCQ OCHz CH20CHs The above compounds can be synthesized, for example, by the method described in JP-A-63-106656 or a method analogous thereto. These compounds according to the present invention can be synthesized using water or a hydrophilic solvent. For example, it is dissolved in an organic solvent such as methanol or ethanol and added to the silver halide emulsion layer or its adjacent layer.In the present invention, it is added to the emulsion layer on the high-speed side as well as the emulsion layer on the low-speed side. By this, the desired effect of the present invention can be well achieved.The amount added to the silver halide emulsion is preferably 0.01 to 10 g per mole of silver halide grains, and particularly preferably 0.1 to 1 g. In order to incorporate the compound of the present invention into the silver halide emulsion layer, it can be added by any method at any time during emulsion preparation, preferably at the end of chemical ripening or at any time before coating. The emulsion used in the silver halide photographic light-sensitive material of the present invention may be any silver halide, such as silver iodobromide, silver iodochloride, or silver iodochlorobromide. Silver iodobromide is preferable in that it can be obtained.Silver halide grains in photographic emulsions are cubic, octahedral,
It may be one that has grown isochronically such as a tetrahedron, a polyhedral crystal type such as a sphere, one that consists of twins with planar defects, or a mixed or composite type thereof. Good too. The grain size of these silver halide grains is 0.1μ
It may be fine particles of less than a second size to large particles of up to 20 μm. The emulsion used in the silver halide photographic material of the present invention can be produced by a known method. For example, Research Disclosure (RD) No. 17643 (December 1978), pp. 22-23.
i. nPreparation and types) and the same (RD) No. 18716 (November 1979)
- Can be prepared by the method described on page 648. The emulsion of the silver halide photographic light-sensitive material according to the present invention is described, for example, in "The theory o" by T. H. James.
f thephotographic process
"4th edition, published by Macmillan (1977) 3
Method described on pages 8-104, G, F, Dauf fi
"Photographic Emulsion Chemistry J Photographic" by n.
emulsionChei+1try”, Foca
Published by l press (1966), Glafki, P.
“Physics and Chemistry of Photography” by Des
ysique photography″”P
Published by aul Mante1 (1967), V, L,
"Manufacture and Coating of Photographic Emulsions" by Zelikman et al.
king and coating photogra
phicea+ulsionNFocal press
It is prepared by the method described in Shakan (1964). That is, solution conditions such as neutral method, acidic method, ammonia method, etc.
It can be produced using mixing conditions such as forward mixing method, back mixing method, double jet method, Chondral double jet method, etc., particle preparation conditions such as conversion method, core/shell method, and combination methods thereof. A preferred embodiment of the present invention is a monodisperse emulsion in which silver iodide is localized inside the grains. Examples of silver halide emulsions preferably used in the present invention include JP-A-59-177535 and JP-A-61-802.
No. 237, No. 61-132943, No. 63-4975
1 and Japanese Patent Application No. 63-238225. The crystal habits are cubic, tetradecahedral, octahedral, and the intermediate (1, 1
, 1) plane and (1,0,0) plane may be arbitrarily mixed. A monodisperse emulsion as used herein means that when the average particle diameter is measured by a conventional method, at least 95% of the particles in terms of number or weight are within ±40% of the average particle diameter, preferably within ±30%. It is a certain silver halide grain. The grain size distribution of silver halide may be either a monodisperse emulsion with a narrow distribution or a polydisperse emulsion with a wide distribution. The crystal structure of silver halide may have different silver halide compositions inside and outside. The emulsion as a preferred embodiment of the present invention is a core/shell monodisperse emulsion having a clear two-layer structure consisting of a high iodine core portion and a low iodine shell layer. The silver iodide content of the high iodide portion is 20 to 40 mol%, particularly preferably 20 to 30 mol%. Methods for producing such monodispersed emulsions are known, for example, J. Ph.
ot, Sic, pp. 12.242-251 (1963)
, JP-A-48-36890, JP-A-52-16364,
It is described in publications such as No. 55-142329, No. 58-49938, Soft British Patent No. 1,413,748, U.S. Patent No. 3,574,628, and No. 3,655,394. The monodisperse emulsion mentioned above is particularly preferably an emulsion in which grains are grown by using seed crystals and supplying silver ions and halide A using the seed crystals as growth nuclei. In addition,
Methods for obtaining core Danuel emulsions and 1,2 are described, for example, in British Patent No. 1.027.146 and US Pat. No. 3,505.06.
No. 8, No. 4,444,877, JP-A-60-1433
It is detailed in the official bulletin number 1. The silver halide emulsion used in the present invention may be tabular grains having an asbec F ratio of 4 or more and less than 30. The advantages of such tabular grains include improved spectral sensitization efficiency, image graininess and sharpness, and are described in, for example, British Patent No. 2,112,157 and US Patent No. 4,43.
9, No. 520, No. 4,433.048, No. 4.41
No. 4,310, No. 4,434,226, JP-A-58-
No. 113927, No. 58-127921, No. 63-1
No. 38342, No. 63-284272, No. 63-30
No. 5343 and others, and emulsions can be prepared by method 1] described in these publications. Emulsions that have multiple particles can be either of the surface latent image type that forms a latent image on the grain surface, the internal latent image type that forms a latent image inside the grain, or the four type that forms a latent image on the surface and inside the grain. These emulsions may be mixed with cadmium salts, complex salts, zinc salts, thallium salts, iridium salts, or complex salts of 71, rhodium salts, or 2 at the stage of physical ripening or grain preparation. complex salts thereof, iron salts, or complex salts thereof may be used.The emulsion may be washed with water such as the tardel water washing method, the 70-kicore method, and the dipping method to remove soluble salts. However, if we use a water washing method, for example,
Particularly preferred is the method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in No. 86, or the method using the collection polymer agent examples G 3 and G 8 described in JP-A-63-158644. , is mentioned as a desalination method. In the emulsion according to the present invention, various photographic additives can be used in the steps before and after physical ripening and chemical ripening. Known additives, etc.]7, for example, Research Disclosure Soyer No. 17643 (1978, 1
February) and same No. 18716 (November 1979)
Examples include compounds described in . Compound types and additives shown in these two research disclosures RD-17643RD-1871
Page 6 Classification Page Classification Chemical Sensitizer 23111648-Right Sensitizing Dye 23TV648 Right--649 Left Development Accelerator 29 N+ 64L-Right-J-7 Antifoggant
24VI649-Lower right stabilizer /l 77
Color stain prevention agent 25 ■ 650 left-right image stabilizer 25 ■ Ultraviolet absorber 25-26 ■ 649 right-650 left filter dye // // Brightening agent 24 V hardening agent
Curing agent 26X651 left coating
Auxiliary agent 26-27 XI 650 right surfactant 26-27 n 650 right plasticizer 27 111 tt
Slip agent/f static prevention agent 27 X1ll ttman
G agent 28 XVI 65
0 Right Binder - 26ff651 Left Supports that can be used for the photosensitive material according to the present invention include, for example, the aforementioned RD-17643, page 28 and RD-187.
16, page 647, left column. Suitable supports include plastic films, and the surfaces of these supports may generally be provided with a subbing layer or subjected to corona discharge, ultraviolet irradiation, etc. in order to improve the adhesion of the coating layer. The emulsion according to the present invention can then be coated on both sides of the support thus treated. When applying the present invention to medical X-ray radiography,
For example, a fluorescent intensifying screen whose main component is a phosphor that generates near-ultraviolet light or visible light when exposed to penetrating radiation is used. It is desirable to expose this material in close contact with both surfaces of a light-sensitive material prepared by coating both surfaces with the emulsion of the present invention. The penetrating radiation herein refers to high-energy electromagnetic waves, and means X-rays and gamma rays. Further, the fluorescent intensifying screen refers to, for example, an intensifying screen whose fluorescent component is mainly calcium tungstate, or a fluorescent intensifying screen whose main component is a rare earth compound activated with terbium. [Examples] Examples of the present invention will be described below. However, it goes without saying that the present invention is not limited to the examples described below. Example 1 (1) Preparation of monodisperse grains Monodisperse grains of silver iodobromide containing 2.0 mol% of silver iodide with an average grain size of 0.2 μm are used as cores, and iodine containing 30 mol% of silver iodide is used as the nucleus. Silver bromide was grown at pH 9.8, pA g7.8,
After that, equal moles of potassium bromide and silver nitrate were added at pH 8.2, pA g 9.1, and the average silver iodide content was 2.2 mol%.
The average grain size is 0.375 μm (
(1)-1), 0.64. um((1)-2), 1
．． 22μ+m((1)-3), 0.88μm((1)
-4) Four types of monodispersed emulsion grains were prepared. The emulsion was desalted from excess salts using a conventional flocculation method. That is, the temperature was maintained at 40° C., and a formalin condensate of sodium naphthalene sulfonate and an aqueous solution of magnesium sulfate were added to cause coagulation, and the supernatant liquid was removed. The dispersibility of the four types of particle sizes obtained had good monodispersity with S/upper<0.16. (2) Preparation of tabular grains Potassium bromide was added to 5.5 ρ of a 1.5% gelatin solution containing 0.17 mol of potassium bromide by the double jet method while stirring at 80°C and pH 5.7. mol and the equivalent of 2.0 mol of silver nitrate were added in solution over a period of 3 minutes. pBr was maintained at 0.8. (0.53% of the total silver nitrate used was consumed.) The potassium bromide solution addition was stopped and the silver nitrate solution was continued to be added for 4.6 minutes. (Consuming 8.6% of all silver nitrate used.)
Then, potassium bromide solution and silver nitrate solution were added at the same time to 12
Added for 1 minute. During this period, par was maintained at 1.15, and the addition flow rate was accelerated so that the flow rate at the time of completion was 2.3 times that at the start. (43.6% of the total silver nitrate used was consumed.) The potassium bromide solution addition was stopped and the silver nitrate solution was added for 1 minute. (Consuming 4.7% of the total silver nitrate used.) A 2.1 molar solution of potassium bromide containing 0.55 mole of potassium iodide was added with the silver nitrate solution over a period of 12.0 minutes. During this time, the pBr was maintained at 1.7 and the flow rate was accelerated to be 1.5 times the starting rate upon completion. (35.9% of the total silver nitrate used was consumed.) To this emulsion was added 1.5 g of sodium thiocyanate, 1 mole of Ag, and held for 25 minutes. A solution of 0.60 mol of potassium iodide and silver nitrate were added by double jet method at equal flow rates for about 5 minutes until pBr reached 3.0. (About 6.6% of the total silver nitrate used was consumed.) The amount of total silver nitrate consumed was about 11 moles. In this way, an emulsion containing tabular silver iodobromide grains with an average grain diameter of 1.80 μm and an aspect ratio of about 9=1 was prepared.
was prepared. In these grains, tabular grains account for 80% or more of the total projected area of the silver iodobromide grains. Preparation, processing and evaluation of samples Obtained (1)-L (112, (1)-3, (1)-
Pure water was added to each of the silver halide grains in Step 4 so that the volume per mole of silver was 500 m12, and the temperature was then heated to 55°C. The amount of (1)-1 per mole of silver halide is 82
0 mg, (,l) −2 or 600 mg, (1) −
Added 360mg of 3, 500mg of (1)-4,
Tabular grain (2) contains 600+ng, addition 1. Ta. After 10 minutes, the ammonium thionate salt was added to (1)-1 or 4X10-' moles per mole of silver, and (1)-2 was 2X1 per mole of silver.
0-3 mol, (1)-3 or 1xlO-3 mol, (1)-
1.6X 10-'' moles of 4 and 3X1O-'' moles of (2) were added, and further I: Appropriate amounts of chloroauric acid and hypo were added to start chemical ripening. This was carried out under the conditions of pi (6.15) and silver potential of 50 mV. 15 minutes before the end of chemical ripening (70 minutes after the start of chemical ripening), 200 mg of potassium iodide was added per mole of silver. After 5 minutes, add 10% (wit/vol) acetic acid to
i was lowered to 5.6 and held at that pH value for 5 minutes, then a 0.5% (vt/vol) solution of potassium hydroxide was added to bring the pH back to 6.15, and then 4-hydroquine-6-
Chemical ripening was completed by adding methyl-1,3°3a,7-chitrazaindene. (1)-1, (1)-2, (1)-3 of the obtained particles,
(1)-4 and (2) were mixed as shown in Table 1, and then the emulsion additives listed below were added to prepare a preparation. The I)H after adjusting the photographic emulsion coating solution was 6.40. The silver potential was adjusted to 74 mV (35°C) using sodium carbonate and potassium bromide solution. Using this emulsion coating solution, samples were prepared as follows. That is, the amount of gelatin in the photographic emulsion layer was 2.0 g/m' for both the high-speed emulsion layer and the low-speed emulsion layer, and the amount of silver halide grains was set as shown in Table 1 in terms of silver. Also, prepare a protective layer solution using the additives listed below, so that the protective layer has a gelatin loading of 1.15 g/m2,
Subi 1 of 80m/min using two slide hopper type coaters! Coat both sides simultaneously on the support using
It dried in seconds to obtain a sample. As a support, glycidyl methacrylate) 5 (]yt%, methyl acrylate l
Qwt%, a copolymer consisting of three monomers of butyl methacrylate to 40wt% was diluted to a concentration of 1Qwt%, and an aqueous copolymer dispersion obtained was subbing and applied. , density 011 for X-ray film of 71175 μm
5, a blue-colored 1° polyethylene terephthalate film base was used. The spectral sensitizing dyes used for sample preparation are as follows. Spectral sensitizing dye A Spectral sensitizing dye B Additives used in the emulsion solution (photosensitive/silver halogenide coating solution) are as follows. The amount added is expressed per mole of silver halogenide. ], l-dimethylol-1-bromo-1-nitromethane 7 (Jmgt-butyl-catechol 400+++g polyvinylpyrrolidone (molecular Ji 10,000) 1.Og styrene-maleic anhydride copolymer 2.5g nitrophenyl-tri7 : Ruphosphonium chloride 50mg1.
Ammonium 3-di-hydroxybenzene-4-sulfonate 4gH The additives used in the protective layer solution are as follows. The amount added is expressed in liters per liter of coating solution.10 Lime-treated inert gelatin 68g Acid-treated gelatin
2g polymethyl methacrylate, matting agent with area average particle size of 3.5μm 161g silicon dioxide particles matting agent with area average particle size of 1.2μm 0.5g Ludox AM (manufactured by DuPont) (colloidal silica) 30g bisvinylsulfonyl methyl ether 11Ig (50:46:4) 10mg C,zHzicONH(C)I2CHzO)s[(2,
0g (dye emulsion dispersion) *0
．． A 4g* dye emulsion dispersion was prepared as follows. 10 kg of each of the above dyes was weighed and dissolved in a solvent consisting of 12 ff of tricresyl phosphate and 85 I2 of ethyl acetate at 55°C. This is called an oil-based solution. On the other hand, anionic surfactant (AS below) 1.35
kg, 9.3% aqueous gelatin solution dissolved at 45°C27
01 was prepared. This is called an aqueous solution. (AS) The above oil-based and water-based solutions were placed in a dispersion vessel and dispersed under reduced pressure under high speed rotation. The following additives and water were added to the resulting dispersion to give a total weight of 240 kg. Phenol (2.5% aqueous solution) 16Q NO+ r The sensitivity of each side of the obtained sample was determined using a fluorescent intensifying screen KO-250.
(manufactured by Konica Corporation) using the single-back method using only the back side, we created two samples, one photographed from the high-sensitivity emulsion layer side and the other photographed from the low-sensitivity emulsion layer side. The side of the cassette without the intensifying screen was painted black with high light absorption. For imaging, X-rays were irradiated for 0.05 seconds at a tube voltage of 90 KVP and 20 mA, and a sensitometric curve was created using the distance method to determine sensitivity, maximum density, and gamma. The development was carried out using an automatic developing machine 5RX-501 (manufactured by Konica Corporation) using a developing solution with the following composition, at a developing temperature of 35°C.
1 The fixing temperature is 33℃, the washing water temperature is 18℃, and the speed is 1.5 per minute.
1 and the entire process was run in 45 second mode. The relative sensitivity in Table 2 is calculated as the reciprocal of the X-ray dose required to obtain the concentration obtained by subtracting the support concentration from the maximum concentration, multiplied by 0.4, and adding the support concentration.
Expressed as relative sensitivity when 100. However, samples No. 1 and No. 002 were comparative samples and were exposed normally using a fluorescent intensifying screen on both sides. To evaluate the image quality of samples Nos. 1 to 23, sharpness and dryness are evaluated. Sharpness is Funkist Chart SM 55853
(Sold by Konica Medical Co., Ltd.) under the same tube voltage, intensifying screen, and processing conditions as the actual photo. Each sample was exposed to light such that the average density of shading determined by the Funkist chart was 0.8±0.02. Evaluation of sharpness A: Can distinguish up to 10 LP/mm with a magnifying glass. B: Up to 8 LP/+uo can be identified with a magnifying glass. C: Can be identified up to 6 LP/mm with a magnifying glass. D: Up to 5 LP/arm can be identified with a magnifying glass. E: Can be identified by 4 LP/+w in Roubaix. In the above, A is the most excellent, and E is not excellent. <Evaluation of drying property> The processing machine and processing agent were used in the same manner as in sensitometry, and the drying property of the obtained sample was evaluated in five stages according to the following criteria. Dryness Evaluation Criteria ○: Completely dry and the sample is warm. △: Completely dry and the sample is clean. ×: Slightly damp. (L/3 or less) XX: Moist. (2/3 or more) Developer composition Developer potassium sulfite 60.0g Hydroquinone 25゜0g 1-phenyl-3-pyrazolidone 1.5g Boric acid 10.0g Potassium hydroxide 23.0g Triethylene glycol 17.5g 5-Methylbenztriazole 0.04g5-nitrobene・
Tsuimitasol 0.11g1-7 J-=
4-5-Mercap) Tefrazole 0.015 g Glutaraldehyde bisulfite 8.0 g The results obtained are shown in Table 2 below. Margins below 3, ), ;' Table 2 [Effects of the Invention] As shown in Table 2, the silver halide photographic material according to the present invention is a light-sensitive material with high sensitivity and excellent sharpness. We were able to obtain a photographic material with high-temperature and high-speed processability.

Claims (1)

[Scope of Claims] A silver halide photographic material having at least one light-sensitive silver halide emulsion layer on both sides of a transparent support,
(a) The sensitivity of the emulsion side on one side is 1.5 to 10 times higher than the sensitivity of the emulsion side on the other side, and (b) and the amount of silver halide on the high-sensitivity emulsion side is A silver halide photographic material having an amount of silver halide of 101 to 5.0 times the amount of silver halide on the other side, wherein (c) the silver halide emulsion layer contains the following general formulas [1] to [7]. ] A silver halide photographic light-sensitive material characterized by containing at least one kind selected from the compounds represented by the following. General formula [1] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, A represents a group that adsorbs to silver halide, and Y is selected from a hydrogen atom, a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom. R represents an organic group containing at least one of a thioether group, an amino group, an ammonium group, an ether group, or a heterocyclic group. n represents 0 or 1, and m represents 1 or 2. General formula [2] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, Q represents the atomic group necessary to form a 5- or 6-membered heterocycle, and this heterocycle is fused with a carbocycle or a heterocycle. You can leave it there. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ is the general formula [1] above.
It is synonymous with that of M represents a hydrogen atom, an alkali metal atom, an ammonium group, or a group that cleaves under alkaline conditions. General formula [3] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, Q represents the atomic group necessary to form a 5- or 6-membered heterocycle capable of forming iminosilver, and Y, R, m, n and M
has the same meaning as that of the general formula [2] above. Also, ▲ includes mathematical formulas, chemical formulas, tables, etc. ▼ is synonymous with that of general formula [1]. General formula [4] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, X represents a sulfur atom, an oxygen atom, or a selenium atom. Y, R, m, n and M have the same meanings as in the general formula [2] above. General formula [5] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ In the formula, R_1 is a hydrogen atom, a halogen atom, a nitro group, a mercapto group, an unsubstituted amino group, respectively a substituted or unsubstituted alkyl group, alkenyl group, or aralkyl group. , aryl group, or ▲Represents a mathematical formula, chemical formula, table, etc.▼. R_2 represents a hydrogen atom, an unsubstituted amino group, or ▲a numerical formula, chemical formula, table, etc.▼. However, at least one of R_1 and R_2 is ▲There is a mathematical formula, chemical formula, table, etc.▼. Y, R, n and M each have the same meaning as in the general formula [2] above. General formula [6] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 represents ▲There are mathematical formulas, chemical formulas, tables, etc.▼. M, R, Y, and n each have the same meaning as in the general formula [2] above. General formula [7] ▲ Numerical formulas, chemical formulas, tables, etc. are included▼ In the formula, R_2 and R_3 represent a hydrogen atom, a halogen atom-substituted or unsubstituted alkyl group, alkenyl group, aralkyl group, or aryl group. However, M and R_1 each have the same meaning as each of the above general formula [6].