JP2009086332A - Industrial x-ray sensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an industrial X-ray sensitive material using high-sensitivity and high-contrast tabular grains. <P>SOLUTION: The industrial X-ray sensitive material has at least one silver halide emulsion layer on each of both surfaces of a transparent support, wherein the silver halide emulsion layer contains at least first tabular silver halide grains having an average grain thickness of <0.13 μm and an aspect ratio of ≥10 and second tabular silver halide grains having an average grain thickness of ≥0.13 μm and an aspect ratio of <10. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an industrial X-ray photosensitive material, and particularly to an industrial X-ray photosensitive material having high sensitivity and high contrast.

An industrial X-ray photosensitive material is a photosensitive material used to detect the intensity of transmitted X-rays by irradiating an object with X-rays in order to detect internal and surface defects of industrial members. is there. For this purpose, in addition to X-rays, γ-rays from radioactive isotopes, other high-energy rays and particle beams from accelerators are used as recording radiation sources. Further, when recording with these light-sensitive materials, it is often performed to irradiate the radiation with the light-sensitive material being adhered to a light-sensitive material with a thin metal foil such as a lead foil. The metal foil and the coated silver halide grains themselves absorb the energy to emit secondary electron beams and the like, and finally the photosensitive material is exposed using the secondary lines. Therefore, these are all image recordings by irradiation with radiation other than light. The latent image formed by irradiation with radiation or the like is developed with a developing solution to become a blackened silver image. The industrial X-ray photosensitive material is designed to extract a slight defect of an industrial member, and extremely high contrast is required to detect a small defect. In order to achieve a high contrast, increasing the amount of coated silver has been a conventional technique for industrial X-ray photosensitive materials. Therefore, the industrial X-ray photosensitive material product has a large amount of coated silver and is required to be improved in terms of resource saving. Also, the cost of the industrial X-ray photosensitive material product depends on silver. It was difficult to reduce and provide products at a more reasonable price.
In addition, the industrial X-ray photosensitive material is handled as a sensitive material in various harsh environments. That is, it is required to have a constitution that is strong in bending, adhesion, scratches, and raw storage of the photosensitive material, and also has high sensitivity and high contrast photographic characteristics.

  It is known to use tabular silver halide grains as means for increasing the sensitivity of silver halide. For example, an industrial X-ray photosensitive material using tabular silver halide grains in which 50% or more of the total grain projected area has an average aspect ratio of 2 or more used non-tabular silver halide grains having the same grain volume. It is disclosed that the radiographic sensitivity is higher than the case, and the sensitivity can be obtained without increasing the silver amount (see, for example, Patent Document 1).

  In order to increase photographic sensitivity, various means for preparing silver halide grains having a higher aspect ratio have been studied so far. By using these means, tabular grains having a high aspect ratio can be prepared relatively easily. Became possible.

  However, silver halide grains having a high aspect ratio give high sensitivity, but have various problems when introduced into industrial X-ray photosensitive materials.

Silver halide grains having a high aspect ratio do not have the high gradation required for industrial X-ray films. Further, when the aspect ratio is increased, pressure sensitization, scratch resistance, etc. are extremely deteriorated, so that it is not suitable as a defect detection means like the industrial X-ray photosensitive material. Patent Document 5 discloses silver halide tabular grains having a high aspect ratio of 7.5 to 26, but an industrial X-ray photosensitive material using silver halide tabular grains having a high aspect ratio of 10 or more. Has not yet been put to practical use because it includes many technical problems to be solved.
JP-A-9-106018

In view of the above conventional problems, an object of the present invention is to provide an industrial X-ray photosensitive material having high sensitivity and high contrast. In particular, this is achieved by using two types of tabular grains in combination.
<1> An industrial X-ray photosensitive material having at least one silver halide emulsion layer on each side of a transparent support, wherein the silver halide emulsion layer has an average grain thickness of at least less than 0.13 μm and an aspect ratio And a first tabular silver halide grain having an average grain thickness of 0.13 μm or more and an aspect ratio of less than 10 for industrial use. Ray photosensitive material.
<2> The silver halide emulsion layer according to <1>, wherein the silver halide emulsion layer contains a compound represented by the following general formula (1) in an amount of 3 mg to 10 mg per 1 g of silver in the silver halide emulsion layer. Industrial X-ray photosensitive material:

(In the formula, Q represents an atomic group necessary for forming a nitrogen-containing aromatic heterocycle. M represents a hydrogen atom or a cation).
<3> The ratio of the aspect ratio of the first tabular silver halide grain to the aspect ratio of the second tabular silver halide grain is 1.2 or more and 4.5 or less <1 > Or <2> Industrial X-ray photosensitive material.
<4> The ratio of the coating amount of the first tabular silver halide grains to the second tabular silver halide grains is 0.7 to 2.0 in terms of silver ratio < The industrial X-ray photosensitive material according to any one of 1> to <3>.
<5> The industrial X according to any one of <2> to <4>, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2): Ray photosensitive material:

(In the formula, R ₁ represents a hydrogen atom or a substituent that can be substituted on the benzene ring. N represents an integer of 1 to 5).
<6> The silver halide emulsion layer contains 3 to 10 mg of the compound represented by the general formula (1) per 1 g of silver in the silver halide emulsion layer. <2> to <5 > The industrial X-ray photosensitive material according to any one of the above.

  According to the present invention, a high-sensitivity and high-contrast industrial X-ray photosensitive material can be provided. In particular, according to the present invention, it is possible to provide an industrial X-ray photosensitive material capable of obtaining an image having a sufficient image density and an excellent image tone with a small amount of coated silver.

  Hereinafter, the present invention will be described in detail.

1. Industrial X-ray Photosensitive Material The industrial X-ray photosensitive material of the present invention has at least one silver halide emulsion layer on each side of a transparent support, and the silver halide emulsion layer has an average grain thickness of at least 0. 1st tabular silver halide grains having an aspect ratio of 10 or more and less than .13 μm and second tabular silver halide grains having an average grain thickness of 0.13 μm or more and an aspect ratio of less than 10.

  The inventors of the present invention have made diligent efforts to solve the technical problems with the aim of commercializing an industrial X-ray photosensitive material using tabular silver halide grains having a high aspect ratio exceeding 10 in aspect ratio. Among them, in addition to the above problems of insufficient gradation, defects such as pressure sensitization and scratch resistance, it was found that the obtained image color tone has an unexpected problem of becoming reddish brown. did. Since an image of an industrial X-ray photosensitive material is visually observed by humans and information is judged, the image color tone is an important characteristic, and an image color tone that deviates from pure black tone reduces diagnostic accuracy. Can also have an effect.

The present inventors have found that these problems are the first tabular silver halide grains having an average grain thickness of less than 0.13 μm and an aspect ratio of 10 or more and an average grain thickness of 0.13 μm or more and an aspect ratio of less than 10. It has been found that the problem can be solved by using the second tabular silver halide grains in combination, and has led to the invention of the present application. When the first tabular silver halide grains are used alone, high sensitivity can be obtained, but defects such as deterioration of image color tone, pressure sensitization, and scratch resistance increase. Further, when the second tabular silver halide grains are used alone, an improvement in sensitivity cannot be expected.
One of the effects of using the first tabular silver halide grains and the second tabular silver halide grains in the present application is to obtain a pure black tone image in which the image tone that cannot be obtained independently is preferable. It is.

Another effect of the combined use of the first tabular silver halide grains and the second tabular silver halide grains in the present application is that the gradation is harder than expected and the gradation preferable as an industrial X-ray photosensitive material is obtained. It is to be obtained. The gradation in this application is defined by the following.
When the radiation energy necessary for obtaining the density of (fog + optical transmission density 1.5) is E0, and the radiation energy E1 necessary for obtaining the density of (fog + optical transmission density 3.5) is a gradation. (G) = (3.5-1.5) / (logE1-logE0).
A preferable gradation (G) for the industrial X-ray photosensitive material of the present application is 4.0 or more and less than 5.5. More preferably, it is 4.2 or more and less than 5.5.

6) Application amount of each layer According to the present application, an image density can be sufficiently obtained with a small amount of applied silver. Therefore, the amount of applied silver is preferably 2.0 g / m ² or more and 6.0 g / m ² or less per side, More preferably, the applied silver amount can be reduced to 2.5 g / m ² or more and 5.5 g / m ² or less. As a result, when the applied silver amount is A (g / m ² ), the ratio (G / A value) of the gradation (G) to the applied silver amount is 0.8 or more, preferably 1.0 or more.

  Further, in the present application, another effect of using the first tabular silver halide grains and the second tabular silver halide grains in combination is unexpectedly superior in pressure sensitization and scratches compared to the case where each is used alone. It is to improve defects such as resistance.

  Furthermore, in the present invention, by containing the compound represented by the general formula (1) in an amount of 3 mg to 10 mg per 1 g of the silver halide emulsion layer, defects such as pressure sensitization and scratch resistance are further improved. . Further, the effect of improving the raw storage stability of the industrial X-ray photosensitive material was shown. Conventionally, it has been known to add the compound represented by the general formula (1) to the silver halide emulsion layer as an antifogging agent, but it has a harmful effect of lowering the sensitivity, so that only in a limited addition amount range. Has been used. The addition amount of the compound represented by the general formula (1) is 1.5 mg or less per 1 g of silver, and the addition amount in this application is an extremely large region. By adding a large amount of the compound represented by the general formula (1), it is possible to maintain high sensitivity, improve defects such as pressure sensitization and scratch resistance, and further improve the raw storage stability of the photosensitive material. It was totally unexpected.

2. Photosensitive silver halide emulsion The silver halide emulsion used in the invention will be described.
1) Halogen composition The silver halide emulsion grains of the present invention have any silver halide composition such as silver chloride, silver chlorobromide, silver chloroiodide, silver chloroiodobromide, silver bromide and silver iodobromide. You may have. Silver bromide and silver iodobromide are preferable from the viewpoint of obtaining high sensitivity.
The silver iodide content is preferably 2 mol% or less, particularly 0.05 mol% or more and 0.45 mol% or less with respect to the silver content contained in the silver halide emulsion grains from the viewpoint of rapid development processing suitability. preferable.

2) Grain shape The aspect ratio of the silver halide emulsion grains in the invention is defined as a value obtained by dividing the equivalent circle diameter of the projected area of one grain by the thickness of the grain.
The first tabular silver halide grains in the present invention are high aspect grains having an average grain thickness of less than 0.13 μm and an average aspect ratio of 10 or more. Preferably, the average particle thickness is 0.03 μm or more and 0.13 μm or less, and the average aspect ratio is 15 or more and 25 or less.
The second tabular silver halide grains in the present invention have an average grain thickness of 0.13 μm or more and an aspect ratio of less than 10. Preferably, the average particle thickness is 0.15 μm or more and 0.2 μm or less, and the average aspect ratio is 6 or more and 8 or less.

  In the present invention, the silver halide emulsion grains may be double twin grains having two parallel twin planes. Further, it may be a tabular grain having a {111} plane as a main plane or a tabular grain having a {100} plane as a main plane.

3) Combination ratio The combination ratio of the first tabular silver halide grains and the second tabular silver halide grains of the present invention will be described. The first tabular silver halide grains in the present invention preferably have an area ratio of 40% or more and 90% or less, more preferably 50% or more and 85% or less, and still more preferably, with respect to the projected area of the total silver halide. Is used at an area ratio of 55% to 80%. The second tabular silver halide grains have an area ratio of 10% or more and 60% or less, more preferably 15% or more and 50% or less, and still more preferably 20% or more with respect to the projected area in the total silver halide. The area ratio is 45% or less.

4) Layer structure The first tabular silver halide grains and the second tabular silver halide grains in the present invention may be used as a mixture of different photosensitive layers, even if they are used in the same photosensitive layer. It doesn't matter.

5) Manufacturing method As a manufacturing method of tabular silver halide grains, methods known in the art can be used in appropriate combination.
Further, tabular grains having parallel twin planes and having a {111} plane as a main plane are described in JP-A-58-127927, JP-A-58-11939, and JP-A-58-113928. It can be easily prepared by referring to the prepared methods.
In addition, a seed crystal in which tabular grains are present in a mass of 40% or more in an atmosphere having a relatively low pBr value of pBr 1.3 or less is formed, and silver and a halogen solution are added simultaneously while maintaining the same pBr value. It can also be obtained by growing seed crystals.
In this grain growth process, it is desirable to add silver and halogen solutions so that new crystal nuclei are not generated.
The size of the tabular silver halide grains can be adjusted by adjusting the temperature, selecting the type and amount of the solvent, controlling the addition amount and addition rate of the silver salt and halide used during grain growth.

Further, in the present invention, among the tabular silver halide grains, monodispersed hexagonal tabular grains are particularly useful grains.
Details of the structure and production method of monodispersed hexagonal tabular grains are as described in JP-A No. 63-151618.

  The silver halide emulsion preferable in the present invention may have a uniform crystal structure, but may have a halogen composition different from the inside and the outside, and may have a layered structure. Moreover, it is preferable that the reduction sensitized silver nucleus is included during grain formation.

  In the present invention, so-called halogen conversion type (conversion type) particles as described in British Patent No. 635841 and US Pat. No. 3,622,318 can be used particularly effectively. The halogen conversion amount is preferably 0.05 mol% to 0.45 mol%, more preferably 0.1 mol% to 0.3 mol%, based on the silver amount.

In the silver iodobromide emulsion, grains having a structure having a high iodine layer on at least one of the inside and the surface are particularly preferable.
Further, by converting the surface of the tabular silver halide grains preferable in the present invention into a high iodine type, a silver halide emulsion with higher sensitivity can be obtained.

  When halogen conversion is performed by the above method, a method in which a silver halide solvent is present is particularly effective. Preferred solvents include thioether compounds, thiocyanates, and tetrasubstituted thioureas. Of these, thioether compounds and thiocyanates are particularly effective. It is preferred to use 0.5 g to 5 g of thiocyanate per mole of silver halide and 0.2 g to 3 g of thioether.

  As a method for growing silver halide grains of the present invention, any known method can be used. That is, an aqueous silver salt solution and an aqueous halogen salt solution are added to the reaction vessel under efficient stirring. As a specific method, P.I. By Glafkides, Chemie et Physique Photographic (published by Paul Montel, 1967), G.K. F. Duffin, Photographic Emulsion Chemistry (published by The Focal Press, 1966), V.D. L. It can be prepared using the method described in Zelikman et al, Making and Coating Photographic Emulsion (published by The Focal Press, 1964). That is, any of an acidic method, a neutral method, an ammonia method, etc. may be used, and a method of reacting a soluble silver salt and a soluble halogen salt may be any one of a one-side mixing method, a simultaneous mixing method, and a combination thereof. Good.

As one form of the simultaneous mixing method, a method of maintaining a constant pAg in a liquid phase in which silver halide is generated, that is, a so-called controlled double jet method can be used.
Further, the addition rate of silver nitrate or an aqueous alkali halide solution is changed according to the grain growth rate, as described in British Patent No. 153516, JP-B-48-36890, JP-A-52-16364, etc. It is also preferable that the growth is carried out rapidly within a range not exceeding the critical supersaturation degree using a method or a method of changing the concentration of an aqueous solution as described in US Pat. No. 4,242,445, JP-A-55-158124.

  Tabular grains are preferably grown by physical ripening (fine grains dissolve and substrate grains grow) in the presence of silver halide fine grains.

In the fine grain emulsion addition method, an AgX fine grain emulsion having a diameter of 0.15 μm or less, preferably 0.1 μm or less, more preferably 0.06 μm to 0.006 μm is added, and tabular grains are grown by Ostwald ripening. The fine grain emulsion can be added continuously or continuously. The fine-grain emulsion can be prepared continuously by supplying AgNO ₃ solution and X-salt solution in a mixer provided near the reaction vessel, and can be added to the reaction vessel immediately, or in a separate vessel in advance. It can also be added continuously or continuously after preparing in a batch mode.
Such a fine grain emulsion can be added in a liquid state or as a dry powder. Also, the dry powder can be mixed with water just before the addition and liquefied for addition. The added fine particles are preferably added in such a manner that they disappear within 20 minutes, more preferably 10 seconds to 10 minutes. When the disappearance time is long, aging occurs between the fine particles, and the particle size increases, which is not preferable. Therefore, it is preferable not to add the whole amount at once. Such fine particles are preferably substantially free of multiple twin particles. Here, the multiple twin grain refers to a grain having two or more twin planes per grain. “Substantially free” refers to a multiple twin grain number ratio of 5% or less, preferably 1% or less, more preferably 0.1% or less. Furthermore, it is preferable that the single twin grain is not substantially contained. Furthermore, it is preferable that substantially no screw dislocation is contained. Here, “substantially free” follows the above definition.

In the step of nucleation of tabular silver halide grains, gelatin having a low methionine content described in US Pat. Nos. 4,713,320 and 4,942,120 is used, and US Pat. No. 4,914. , 014 and nucleation at a high pBr as described in JP-A-2-222940 are very effective in the nucleation step of the particles used in the present invention. In particular, gelatin having a methionine content of preferably 0 μmol / g to 50 μmol / g, more preferably 0 μmol / g to 40 μmol / g can be preferably used. When such gelatin is used during ripening and growth, thinner tabular grains having a uniform diameter size distribution are formed, which is preferable.
In the present invention, the silver nitrate aqueous solution, the halogen aqueous solution and the low molecular weight oxidized gelatin are preferably added within one minute while stirring in the presence of low molecular weight oxidized gelatin at a temperature of 20 ° C. to 40 ° C. At this time, the pBr of the system is preferably 2 or more, and the pH is preferably 7 or less. The concentration of the aqueous silver nitrate solution is preferably 0.6 mol / L or less. The gelatin preferably has a molecular weight smaller than that of a normal one, particularly preferably 10,000 to 50,000.
Gelatin in which the amino group has been modified by 90% or more to phthalation, succination or trimellitation and at least one of oxidized gelatin having a reduced methionine content are particularly preferably used.

Further, the aging step can be performed in the presence of a low concentration base described in US Pat. No. 5,254,453, or at a high pH described in US Pat. No. 5,013,641. Also, U.S. Pat. Nos. 5,147,771, 5,147,772, 5,147,773, 5,171,659, 5,210,013, and The polyalkylene oxide compound described in US Pat. No. 5,252,453 can be added in the aging step or the subsequent growth step.
In the present invention, the aging step is preferably performed at a temperature of 60 ° C. or higher and 80 ° C. or lower. It is preferable to reduce pBr to 2 or less immediately after nucleation or during aging. Further, additional gelatin is preferably added immediately after nucleation until the end of ripening. Particularly preferred gelatin has 95% or more of amino groups modified to succination or trimellitation.

  The pH during growth by adding fine particles needs to be 2.0 or more, but is preferably 6 or more and 10 or less. More preferably, the pH is 6 or more and 9 or less.

  The pCl needs to be 1.0 or more, but is preferably 1.6 or more. More preferably, it is 1.8 to 3.0.

6) Dislocation lines The tabular grains of the present invention preferably use silver halide grains having dislocation lines.

  The dislocation lines of tabular grains are described in, for example, J.A. F. Hamilton, Photo. Sci. Eng. 11, 57 (1967) and T.W. Shiozawa, J. et al. Soc. Photo. Sci. It can be observed by a direct method using a transmission electron microscope at a low temperature described in Japan, 35, 213 (1972). In other words, the silver halide grains taken out carefully so as not to apply a pressure that causes dislocation to the grains from the emulsion are placed on a mesh for electron microscope observation, and the sample is placed to prevent damage (printout, etc.) due to electron beams. Observation is performed by the transmission method in the cooled state. At this time, the thicker the particle, the more difficult it is to transmit the electron beam. Therefore, it is possible to observe more clearly using a high-pressure type electron microscope (200 kV or more for particles having a thickness of 0.25 μm). From the photograph of particles obtained by such a method, the position and number of dislocations for each particle when viewed from the direction perpendicular to the main plane can be obtained.

7) Heavy metal dope In the process of silver halide grain formation or physical ripening, cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or complex salt thereof, rhodium salt or complex salt thereof, iron salt or complex salt thereof, etc. are allowed to coexist. May be.

8) Chemical sensitization The silver halide grains of the present invention are preferably subjected to chemical sensitization. As chemical sensitization, chalcogen sensitization such as sulfur sensitization, selenium sensitization, and tellurium sensitization, gold sensitization, and reduction sensitization can be used. Preferably, chalcogen sensitization and gold sensitization can be used in combination.

  In sulfur sensitization, unstable sulfur compounds are used. The unstable sulfur compounds described in Grafkides, Chimie et Physique Photographic (published by Paul Momtel, 1987, 5th edition), Research Disclosure, Vol. 307, No. 307105 can be used. Specifically, thiosulfate (for example, hypo), thioureas (for example, diphenylthiourea, triethylthiourea, N-ethyl-N ′-(4-methyl-2-thiazolyl) thiourea, carboxymethyltriurea. Methylthiourea), thioamides (eg, thioacetamide), rhodanines (eg, diethylrhodanine, 5-benzylidene-N-ethyl-rhodanine), phosphine sulfides (eg, trimethylphosphine sulfide), thiohydantoins, Known sulfur compounds such as 4-oxo-oxazolidine-2-thiones, disulfides or polysulfides (eg, dimorpholine disulfide, cystine, lenthionine), mercapto compounds (eg, cysteine), polythionates, elemental sulfur And active gelatin It can be also used.

  In selenium sensitization, unstable selenium compounds are used, and Japanese Patent Publication Nos. 43-13489, 44-15748, JP-A-4-25832, JP-A-4-109240, JP-A-4-271341 and 5 The unstable selenium compound described in each specification of -40324 can be used. Specifically, colloidal metal selenium, selenoureas (eg, N, N-dimethylselenourea, trifluoromethylcarbonyl-trimethylselenourea, acetyl-trimethylselenourea), selenoamides (eg, selenoacetamide, N, N-diethylphenylselenamide), phosphine selenides (eg triphenylphosphine selenide, pentafluorophenyltriphenylphosphine selenide), selenophosphates (eg tri-p-tolylselenophosphate, Tri-n-butylselenophosphate), selenoketones (for example, selenobenzophenone), isoselenocyanates, selenocarboxylic acids, selenoesters, diacylselenides and the like may be used. Furthermore, non-labile selenium compounds described in JP-B Nos. 46-4553 and 52-34492, such as selenious acid, potassium selenocyanide, selenazoles, and selenides can also be used.

  In the tellurium sensitization, unstable tellurium compounds are used, and Canadian Patent No. 80000958, British Patent Nos. 1,295,462 and 1,396,696, JP-A-4-204640, and 4-271341. Nos. 4-3333043 and 5-303157 can be used. Specifically, telluroureas (eg, tetramethyltellurourea, N, N′-dimethylethylenetellurourea, N, N′-diphenylethylenetellurourea), phosphine tellurides (eg, butyl-diisopropylphosphine) Telluride, tributylphosphine telluride, tributoxyphosphine telluride, ethoxy-diphenylphosphine telluride), diacyl (di) tellurides (eg bis (diphenylcarbamoyl) ditelluride, bis (N-phenyl-N-methyl) Carbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) telluride, bis (N-phenyl-N-benzylcarbamoyl) telluride, bis (ethoxycarbonyl) telluride), isosterulocyanates, telluramides, tellurohydrazides, Te Lose esters (for example, butylhexyl telluroester), telluroketones (for example, telluroacetophenone), colloidal tellurium, (di) tellurides, other tellurium compounds (potassium telluride, telluropentathionate sodium salt), etc. Good.

  Regarding the gold sensitization, the aforementioned P.P. Gold salts described in Grafkides, Chimie et Physique Photographic (published by Paul Momtel, 1987, 5th edition), Research Disclosure 307, 307105, and the like can be used. Specifically, in addition to chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide and gold selenide, U.S. Pat. Nos. 2,642,361, 5,049,484, and 5,049,485. Gold compounds described in the specification and the like can also be used. Moreover, you may add noble metal salts, such as platinum, palladium, and iridium.

The amount of chalcogen sensitizer used in the present invention varies depending on the silver halide grains used, chemical sensitization conditions, etc., but is 10 ⁻⁸ mol to 10 ⁻² mol, preferably 10 mol, per mol of silver halide. ^-7 mol to 5 × using ^{10 -3} mol.

The amount of the gold sensitizer and the noble metal sensitizer used in the present invention is about 10 ⁻⁷ mol to 10 ⁻² mol per mol of silver halide. Although there is no restriction | limiting in particular in the conditions of the chemical sensitization in this invention, 6-11 are preferable as pAg, More preferably, it is 7-10, As pH, 4-10 are preferable, As temperature, 40 degreeC-95 degreeC However, 45 ° C to 85 ° C is more preferable.

  Regarding reduction sensitization, the above-mentioned P.I. Known reducing compounds described in Grafkides, Chimie et Physique Photographic (published by Paul Momtel, 1987, 5th edition), Research Disclosure, Vol. 307, No. 307105 can be used. Specifically, aminoiminomethanesulfinic acid (also known as thiourea dioxide), borane compound (eg, dimethylamine borane), hydrazine compound (eg, hydrazine, p-tolylhydrazine), polyamine compound (eg, diethylenetriamine, triethylene) Tetramine), stannous chloride, silane compounds, reductones (eg, ascorbic acid), sulfites, aldehyde compounds, hydrogen gas, and the like may be used. Further, reduction sensitization may be performed in an atmosphere of high pH or excessive silver ions (so-called silver ripening).

In the silver halide emulsion of the present invention, the surface of the grain or a part thereof may be subjected to halogen conversion in the chemical sensitization step. As a method for performing halogen conversion, water-soluble bromide salts such as potassium bromide and sodium bromide, water-soluble iodide salts such as potassium iodide and the like can be used alone or in combination, and they can be used as solids or It can be added as an aqueous solution or a gelatin dispersion. Further, addition of silver bromide fine grains of silver bromide, silver iodobromide and silver iodide is also preferably used, and these can be used alone or in combination.
When added as fine particles, the average equivalent sphere diameter of the fine particles is preferably 0.1 μm or less, and more preferably 0.05 μm or less. The fine particles can be continuously adjusted by supplying a silver nitrate aqueous solution and an alkali halide aqueous solution having an arbitrary composition with a mixer provided in the vicinity of the reaction vessel, and can be immediately added to the reaction vessel. It can also be added after adjusting to a batch type. Further, if necessary, the silver halide fine particles may contain ions or compounds of heavy metals such as iridium, rhodium and platinum.

In preparation of the emulsion of the present invention, for example, at the time of grain formation, desalting step, chemical sensitization, it is preferable that a metal ion salt is present before coating, depending on the purpose. When the particles are doped, it is preferably added after the formation of the particles, before the completion of the chemical sensitization after the formation of the particles when used as a particle sensitizer or a chemical sensitizer. A method of doping the entire particle, a method of doping only the core part, only the shell part, only the epitaxial part, or only the base particle of the particle can also be selected. Mg, Ca, Sr, Ba, Al, Sc, Y, LaCr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ru, Rh, Pd, Re, Os, Ir, Pt, Au, Cd, Hg, Tl, In, Sn, Pb, Bi, or the like can be used. These metals can be added in the form of a salt that can be dissolved during particle formation, such as ammonium salt, acetate salt, nitrate salt, sulfate salt, phosphate salt, hydrate salt, hexacoordinated complex salt, and tetracoordinated complex salt. For example, CdBr ₂ , CdCl ₂ , Cd (NO ₃ ) ₂ , Pb (NO ₃ ) ₂ , Pb (CH ₃ COO) ₂ , K ₃ [Fe (CN) ₆ ], (NH ₄ ) ₄ [Fe (CN) _{6 ],} K ₃ IrCl _6, and the like _(NH 4) 3 RhCl _6, and _K 4 Ru _{(CN) 6.} The ligand of the coordination compound can be selected from halo, aco, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo, or carbonyl.
These may use only one kind of metal compound, but may be used in combination of two or more kinds.

  A method of adding a chalcogen compound during preparation of an emulsion as described in US Pat. No. 3,772,031 may be useful. In addition to S, Se, or Te, cyanate, thiocyanate, selenocyanic acid, carbonate, phosphate, or acetate may be present.

  Chemical sensitization can also be performed in the presence of a so-called chemical sensitization aid. Useful chemical sensitization aids include compounds known to suppress fogging and increase sensitivity during the process of chemical sensitization, such as azaindene, azapyridazine, and azapyrimidine. Examples of chemical sensitization aid modifiers include U.S. Pat. Nos. 2,131,038, 3,411,914, 3,554,757, JP-A-58-126526, and the above-mentioned Daphin, "Photographic emulsion chemistry", pages 138-143.

9) Oxidizing agent treatment It is preferable to use an oxidizing agent for silver during the production process of the emulsion of the present invention. The oxidizing agent for silver means a compound having an action of acting on metallic silver and converting it into silver ions. In particular, a compound that converts very fine silver grains by-produced in the process of forming silver halide grains and chemical sensitization into silver ions is effective. The silver ions generated here may form a silver salt that is hardly soluble in water such as silver halide, silver sulfide, and silver selenide, or may form a silver salt that is easily soluble in water such as silver nitrate. Also good. The oxidizing agent for silver may be an inorganic substance or an organic substance. Examples of the inorganic oxidizing agent include ozone, hydrogen peroxide and adducts thereof (for example, NaBO ₂ .H ₂ O ₂ .3H ₂ O, 2NaCO ₃ .3H ₂ O ₂ , Na ₄ P ₂ O ₇ .2H ₂ O _{2 , 2Na 2 SO 4 · H 2} O 2 · 2H 2 O), peroxy acid salts (e.g., _{K 2 S 2 O 8, K} 2 C 2 O 6, K 2 P 2 O 8), peroxy complex compounds (e.g., K2 [Ti (O ₂ ) C ₂ O ₄ ] .3H ₂ O, 4K ₂ SO ₄ .Ti (O ₂ ) OH.SO ₄ .2H ₂ O, Na ₈ [VO (O ₂ ) (C ₂ H ₄ ) ₂ 6H ₂ O], permanganate (eg, KMnO ₄ ), oxyacid salts such as chromate (eg, K ₂ Cr ₂ O ₇ ), halogen elements such as iodine and bromine, and perhalogenates (eg, Potassium periodate) a salt of a high-valent metal (eg, Kisashiano potassium ferric acid) and thiosulfonate, and the like.

Examples of organic oxidizing agents include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogens (for example, N-bromosuccinimide, chloramine T, chloramine B). ) As an example.
It is a preferred embodiment to use the aforementioned reduction sensitization in combination with an oxidizing agent for silver.

10) Spectral sensitization The silver halide photographic light-sensitive material of the present invention is preferably spectrally sensitized. Examples of spectral sensitizing dyes that can be used for spectral sensitization include cyanine dyes, merocyanine dyes, composite cyanine dyes, composite merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful spectral sensitizing dyes are those belonging to cyanine dyes, merocyanine dyes and complex merocyanine dyes. For these dyes, any of nuclei commonly used for cyanine dyes can be applied as the basic heterocyclic nucleus. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, selenazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, tellurazole nucleus, etc .; Condensed nuclei; and nuclei in which aromatic hydrocarbon rings are condensed to these nuclei, ie, indolenine nuclei, benzindolenine nuclei, indole nuclei, benzoxazole nuclei, naphthoxazole nuclei, benzimidazole nuclei, naphthimidazole nuclei, A benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a naphthoselenazole nucleus, a quinoline nucleus, a benzotelazole nucleus, or the like can be applied. These heterocyclic nuclei may be substituted on carbon atoms.

  For the merocyanine dye or the composite merocyanine dye, any of nuclei usually used for merocyanine dyes can be applied as the nucleus having a ketomethylene structure. Particularly useful nuclei include pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidine-2,4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbituric acid nucleus, 2-thio A 5-membered or 6-membered heterocyclic nucleus such as a selenazolidine-2,4-dione nucleus can be applied.

  There is no restriction | limiting in particular as an addition time of a spectral sensitizing dye, It can add at arbitrary time from a particle formation process to just before application | coating. Specifically, a method of adding at the time of silver halide grain formation, a method of adding at the silver halide emulsion desalting step, a method of adding just before the silver halide emulsion chemical ripening (chemical sensitization) step, silver halide emulsion chemistry There is a method of adding at the time of ripening, after silver halide emulsion chemical ripening, and at the time of preparing a coating solution, but preferably before adding the gold sensitizer and chalcogen sensitizer described above, that is, before chemical sensitization with these compounds. Add to. It is also possible to uniformly attach each halogenated particle by adding the spectral sensitizing dye at a temperature of 25 ° C. or higher and lower than 55 ° C. and then performing chemical ripening by raising the temperature from the addition temperature.

  In order to contain the spectral sensitizing dye used in the present invention in the silver halide emulsion of the present invention, they may be dispersed directly in the emulsion, or water, methanol, ethanol, propanol, acetone, methyl cellosolve, 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, 1-methoxy-2-propanol, N, N- A solvent such as dimethylformamide alone or in a mixed solvent may be added to the emulsion. Further, as described in US Pat. No. 3,469,987, etc., a dye is dissolved in a volatile organic solvent, and this solution is dispersed in water or a hydrophilic colloid, and this dispersion is dispersed in an emulsion. As described in JP-B-46-24185, etc., in which a water-insoluble dye is dispersed in a water-soluble solvent without dissolving it, and this dispersion is added to the emulsion. No. 23389, JP-B-44-27555, JP-B-57-22091 and the like, a dye is dissolved in an acid and this solution is added to an emulsion, or an acid or a base is allowed to coexist to form an aqueous solution. As described in U.S. Pat. No. 3,822,135, U.S. Pat. No. 4,006,025, etc., a surfactant is allowed to coexist to form an aqueous solution or colloidal dispersion. Add to the emulsion As described in JP-A-53-102733 and JP-A-58-105141, a method in which a dye is directly dispersed in a hydrophilic colloid, and the dispersion is added to an emulsion. As described in US Pat. No.-74624, a method of dissolving a dye using a compound that shifts red and adding this solution to an emulsion can also be used. In addition, ultrasonic waves can be used for dissolution.

  Spectral sensitizing dye combinations are often used, particularly for the purpose of supersensitization. Typical examples thereof are U.S. Pat. Nos. 2,688,545, 2,977,229, 3,397,060, 3,522,052, 3,527,641, 3, 617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703,377, 3,769, No. 301, No. 3,614,609, No. 3,837,862, No. 4,026,707, British Patent Nos. 1,344,281, No. 1,507,803 JP-A-43-4936, JP-A-53-12375, JP-A-52-110618, JP-A-52-109925, and the like.

  Furthermore, these sensitizing dyes themselves exhibit no significant increase in spectral sensitization when combined with sensitizing dyes that do not exhibit spectral sensitizing effects themselves or are substances that do not substantially absorb visible light. They may be used in combination with any compound known as a so-called supersensitizer. Representative examples of supersensitizers include bispyridinium salt compounds described in JP-A-59-142541, stilbene derivatives described in JP-B-59-18691, JP-B-49-46932, and the like. Water-soluble bromides such as potassium bromide and potassium iodide, water-soluble iodides, condensates of aromatic compounds and formaldehyde described in US Pat. No. 3,743,510, etc., and cadmium salts And azaindene compounds. The spectral sensitizing dye is added to the emulsion after chemical ripening or before chemical ripening. For the silver halide grains of the present invention, the spectral sensitizing dye is most preferably added during chemical ripening or before chemical ripening (for example, during grain formation or physical ripening).

3. Compound Represented by General Formula (1) The compound represented by General Formula (1) in the present invention will be described.

In the formula, Q represents an atomic group necessary for forming a nitrogen-containing aromatic heterocycle.
M represents a hydrogen atom or a cation.

  Examples of the nitrogen-containing aromatic heterocycle formed by Q include pyrrole, imidazole, pyrazole, pyridine, pyrimidine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiazole, thiadiazole, oxazole, oxadiazole, and quinoline. Phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, benzimidazole, benzoxazole, benzthiazole, benzselenazole, and tetraazaindene, preferably imidazole, pyrazole, pyridine , Pyrimidine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiazole, thia Azole, oxazole, oxadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, tetrazole, benzimidazole, benzoxazole, benzthiazole, benzselenazole, and tetraazaindene are preferable. Is imidazole, triazole, thiazole, thiadiazole, oxazole, oxadiazole, tetrazole, benzimidazole, benzoxazole, or benzthiazole, more preferably benzimidazole, benzoxazole, or benzthiazole, particularly preferably benzimidazole. is there.

  The nitrogen-containing aromatic heterocycle formed by Q may have a substituent. Examples of the substituent include an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably C1-C8, for example, methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.) and alkenyl. A group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, and examples thereof include vinyl, allyl, 2-butenyl, and 3-pentenyl). Alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, such as propargyl, 3 Pentynyl, etc.), aryl groups (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenyl, p-methylphenyl, naphthyl, etc. An amino group (preferably having 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms, such as amino, methylamino, dimethylamino, diethylamino, and dibenzyl. Amino, etc.), an alkoxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, and examples thereof include methoxy, ethoxy, butoxy and the like. ), An aryloxy group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 6 carbon atoms). 2, for example, phenyloxy, 2-naphthyloxy and the like), an acyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, For example, acetyl, benzoyl, formyl, pivaloyl, etc.), an alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, for example, methoxycarbonyl , Ethoxycarbonyl, etc.), aryloxycarbonyl groups (preferably having 7 to 20 carbon atoms, more preferably having 7 to 16 carbon atoms, particularly preferably having 7 to 10 carbon atoms, such as phenyloxycarbonyl). An acyloxy group (preferably having 2 to 20 carbon atoms, more preferably 2 to 1 carbon atoms). 6, Particularly preferably, it has 2 to 10 carbon atoms, and examples thereof include acetoxy and benzoyloxy. ), An acylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include acetylamino and benzoylamino), alkoxycarbonylamino group (Preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 12 carbon atoms, and examples thereof include methoxycarbonylamino).

An aryloxycarbonylamino group (preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonylamino), a sulfonylamino group ( Preferably it is C1-C20, More preferably, it is C1-C16, Most preferably, it is C1-C12, for example, methanesulfonylamino, benzenesulfonylamino, etc.), a sulfamoyl group (preferably carbon number). 0-20, more preferably 0-16 carbon atoms, particularly preferably 0-12 carbon atoms, such as sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl, etc.), carbamoyl groups (Preferably 1-20 carbon atoms, more preferably 1-16 carbon atoms, Preferably have 1 to 12 carbon atoms, such as carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl, etc.), an alkylthio group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, especially Preferably it is C1-C12, for example, methylthio, ethylthio, etc. are mentioned, for example, Arylthio group (Preferably C6-C20, More preferably C6-C16, Especially preferably C6-C12 Yes, such as phenylthio, etc.), a sulfonyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as mesyl, tosyl, etc.). ), A sulfinyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, Preferably have 1 to 12 carbon atoms, such as methanesulfinyl, benzenesulfinyl, etc.), ureido groups (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 carbon atom). For example, ureido, methylureido, phenylureido, etc.), phosphoric acid amide group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms). For example, diethylphosphorus amide, phenylphosphoric acid amide, etc.), hydroxy group, mercapto group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl Groups, nitro groups, hydroxamic acid groups, sulfino groups, hydrazino groups, heterocyclic groups (eg imidazo Examples include ril, pyridyl, furyl, piperidyl, morpholino and the like. ) And the like. These substituents may be further substituted. Moreover, when there are two or more substituents, they may be the same or different.

  The substituent is preferably an alkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, aryloxy A carbonylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, a ureido group, a hydroxy group, a halogen atom, a cyano group, or a heterocyclic group, more preferably an alkyl group, an aryl group, an alkoxycarbonyl group, an aryloxycarbonyl group An acyloxy group, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, a ureido group, a halogen atom, or Tero ring group, more preferably alkyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, ureido group , A halogen atom or a heterocyclic group, particularly preferably an alkyl group.

The cation represented by M represents an organic or inorganic cation, for example, alkali metal ions (Li ⁺ , Na ⁺ , K ⁺ , Cs ⁺ etc.), alkaline earth metal ions (Mg ²⁺ , Ca ²⁺ etc.), ammonium (Ammonium, trimethylammonium, triethylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, or 1,2-ethanediammonium etc.), pyridinium, imidazolium, phosphonium (tetrabutylphosphonium etc.), etc. are mentioned. M is preferably a hydrogen atom or an alkali metal ion, and more preferably a hydrogen atom.

Preferably, the compound represented by the general formula (1) is a compound represented by the following general formula (2).

In the formula, R ₁ represents a hydrogen atom or a substituent that can be substituted on the benzene ring. n represents an integer of 1 to 5. The substituent that can be substituted on the benzene ring can be selected from the substituents described as the substituent that Q in the general formula (1) can have.

  Specific examples of the compound represented by formula (I) are shown below, but the present invention is not limited thereto.

  The addition amount of the compound represented by the general formula (1) is preferably 3 mg or more and 10 mg or less, more preferably 3.5 mg or more and 5 mg or less, per 1 g of silver in the silver halide emulsion layer.

The compound represented by the general formula (1) can be added after being dissolved in a water-soluble solvent such as water, methanol, or ethanol, or a mixed solvent thereof. At this time, the pH may be appropriately adjusted with an acid or a base, and a surfactant may be allowed to coexist. Furthermore, it can also be dissolved in a high boiling point organic solvent and added as an emulsified dispersion.
The reducing agent may be contained in the coating solution by any method such as a solution form, an emulsified dispersion form, or a solid fine particle dispersion form, and may be contained in the photosensitive material.
Well-known emulsification and dispersion methods include oils such as dibutyl phthalate, tricresyl phosphate, dioctyl sebacate or tri (2-ethylhexyl) phosphate, and an auxiliary solvent such as ethyl acetate and cyclohexanone, and dodecylbenzene. Examples thereof include a method of mechanically preparing an emulsified dispersion by adding a surfactant such as sodium sulfonate, oleoyl-N-methyl taurate, sodium di (2-ethylhexyl) sulfosuccinate. At this time, it is also preferable to add a polymer such as α-methylstyrene oligomer or poly (t-butylacrylamide) for the purpose of adjusting the viscosity and refractive index of the oil droplets.

Further, as a solid fine particle dispersion method, a reducing agent powder is dispersed in an appropriate solvent such as water by a ball mill, a colloid mill, a vibration ball mill, a sand mill, a jet mill, a roller mill, or an ultrasonic wave to produce a solid dispersion. A method is mentioned. In this case, a protective colloid (for example, polyvinyl alcohol) or a surfactant (for example, an anionic surfactant such as sodium triisopropylnaphthalenesulfonate (a mixture of three isopropyl groups having different substitution positions)) may be used. Good. In the mills, beads such as zirconia are usually used as a dispersion medium, and Zr and the like eluted from these beads may be mixed in the dispersion. Although it depends on the dispersion conditions, it is usually in the range of 1 ppm to 1000 ppm.
If the Zr content in the light-sensitive material is 0.5 mg or less per 1 g of silver, there is no practical problem.
The aqueous dispersion preferably contains a preservative (for example, benzoisothiazolinone sodium salt).

4). Photographic Additives The silver halide emulsion used in the present invention contains various compounds for the purpose of preventing fogging during the production process, storage or photographic processing of light-sensitive materials, or stabilizing photographic performance. be able to. That is, thiazoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrine thione; For example, triazaindenes, tetraazaindenes (especially 4-hydroxy-6-methyl (1,3,3a, 7) tetraazaindene), pentaa Known as antifoggants or stabilizers, such as indene, it may be added to many compounds. For example, those described in US Pat. Nos. 3,954,474, 3,982,947, and Japanese Patent Publication No. 52-28660 can be used. One preferred compound is a compound described in JP-A-63-212932. Antifoggants and stabilizers are available in various forms before particle formation, during particle formation, after particle formation, desalting process, during dispersion after desalting, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. Depending on the purpose, it can be added at any time.

In the present invention, it is also preferable to perform chemical sensitization in the presence of a nucleic acid or a decomposition product thereof before completion of chemical sensitization. As the nucleic acid or its degradation product, those described in JP-A-62-267541 can be used.
Nucleic acids used in the present invention include deoxyribonucleic acid (DNA) and ribonucleic acid (RNA), and nucleic acid degradation products include those in the middle of degradation and simple substances such as adenine, guanine, uracil, cytosine and thymine. It is done. In particular, adenine is a preferable nucleic acid degradation product. These can be used alone or in combination. In this case, it goes without saying that the nucleic acid and the nucleic acid degradation product may be used in combination. The amount of the nucleic acid or its degradation product added varies depending on the type of the nucleic acid degradation product, but is 20 mg or more, preferably 100 mg to 1 g, per mole of silver halide. These nucleic acids or nucleic acid degradation products may be used alone or in combination of two or more as described above.

5). Other Components The silver halide photographic light-sensitive material of the present invention may have a non-light-sensitive layer such as a crossover cut layer and a surface protective layer in addition to the light-sensitive silver halide emulsion layer. The non-photosensitive layer may contain a dye, colloidal silica, polymer latex, matting agent and the like in addition to the above-mentioned surfactants such as fluorine-containing compounds and non-fluorine compounds.
1) Crossover Cut Layer The photosensitive material of the present invention can be provided with a crossover light cut layer between the photosensitive emulsion layer and the support, if necessary, for the purpose of sharpening the image. The crossover cut layer is unique to medical X-ray photographic materials having silver halide emulsion layers on both sides, and light from one side affects the silver halide emulsion layer on the other side through the support. This is a means for solving the problem of degrading the image quality. The crossover cut layer can also serve as the non-photosensitive hydrocolloid layer of the present application. A dye corresponding to the photosensitive wavelength region is added to the crossover light cut layer. Any dye can be used as long as it does not leave harmful absorption after development.
In particular, it is preferable to add the dye in a solid fine particle dispersed state. The method of adding the dye in a state of solid fine particle dispersion is disclosed in JP-A-2-264936, JP-A-3-210553, JP-A-3-210554, JP-A-3-238447, JP-A-4-14038, JP-A-4-14038. -14039, JP-A-4-125635, JP-A-4-338747, JP-A-6-27589, and the like. Usable dyes are, for example, dyes of the general formulas (I) to (VII) described in JP-A-4-21542, Compound Examples I-1 to I-37, II-1 to II-6, III-1 to III. -36, IV-1 to IV-16, V-1 to V-6, VI-1 to VI-13, VII-1 to VII-5. Dye of general formula (1) described in JP-A-8-73767, Compound Examples 1-6. Dyes of general formulas (VIII) to (XII) described in JP-A-8-87091, compound examples VIII-1 to VIII-5, IX-1 to IX-10, X-1 to X-21, XI-1 to XI-6, XII-1 to XII-7.

  In addition to these, a method of adsorbing a known dye on a mordant, a method of dissolving a known dye in oil and emulsifying and dispersing it in the form of oil droplets, a method of adsorbing the dye described in JP-A-3-5748 on the surface of an inorganic substance, A method of adsorbing a dye described in Kaihei 2-298939 to a polymer can also be used. As the method for adding the crossover light cut layer to the photosensitive material, those described in each specification can be used.

2) Dye A dye may be added to the photosensitive material of the present invention for the purpose of detecting the position of the photosensitive material. The dye desirably has an absorption spectrum corresponding to the sensitivity maximum wavelength of the detection sensor, and any dye that does not leave harmful absorption after development processing can be used. Preferably, a dye having an absorption maximum at 700 nm to 1400 nm or a fine particle dispersion thereof is used.
For example,
(1) Examples of water-soluble dyes that can be decolored during processing include cyanine dyes, pyrylium dyes and aminium dyes represented by general formulas (I) to (IV) described in JP-A-3-211542, Compound Examples I-1 to I-6 II-1 to II-4, III-1 to III-4, IV-1 to IV-5,

(2) Solid fine particle dispersed dyes that can be decolored during processing include cyanine dyes, pyrylium dyes and aminium dyes of the general formulas (I) to (IV) described in JP-A-3-138640, Compound Examples I-1 to I -28, II-1 to II-10, III-1 to III-6, IV-1 to IV-7,

(3) Examples of dyes that do not decolorize during the treatment include tricarbocyanine dyes having a carboxyl group of general formula (I) to general formula (II) described in Japanese Patent Application No. 6-227983; No. 6-279297, tetracarbocyan dye having a carboxyl group of general formula (I) to general formula (II), compound examples 1 to 19, and general formula (1) to general formula described in Japanese Patent Application No. 7-208569 (3) Cyanine dye having no acid group, Compound Examples 1 to 63, Lake type cyanine dye of the general formula [1] described in JP-A-8-333519, Compound Example No. 1-No. 37, and the like.

Besides these, pyrylium dyes described in JP-A-62-299959, light scattering particles described in JP-A-63-131135, cyanine dyes described in JP-A-1-266536, and oxonols described in JP-A-2-282244. Solid fine particle dispersions of dyes, holopolar cyanine dyes described in JP-A-3-13638, polymer-type cyanine dyes described in JP-A-7-253039, tin-doped indium oxide (ITO) powders described in JP-A-7-113072, Yb ³⁺ compounds described in Kaihei 9-5913 can also be used.

  There is no particular limitation on the layer to which the dye for the purpose of detecting the position of the photosensitive material is added, and it can be added to the silver halide emulsion layer, the non-photosensitive hydrophilic colloid layer of the present invention, the surface protective layer, etc. As the method, those described in each specification can be used.

  In the light-sensitive material of the present invention, a compound represented by the general formula (I) of JP-A-2004-094083 may be used for the purpose of improving the color tone of the silver image. In addition, a dye may be added. The dye has a predetermined maximum absorption wavelength among pyrazoloazole dyes, anthraquinone dyes, azo dyes, azomethine dyes, oxonol dyes, carbocyanine dyes, styryl dyes, triphenylmethane dyes, indoaniline dyes and indophenol dyes. What you have is selected. Among them, anthraquinone dyes of the general formula (I) described in JP-A-5-34858, azomethine dyes of the general formula (I) described in JP-A-4-247449, and general formula (I) described in JP-A-4-296845, Indoaniline dyes contained in the general formula (I) described in Kaihei 5-43809 and azo dyes described in JP-A-5-341441 are useful.

  Specific examples of anthraquinone dyes include compounds 1 to 9 described in JP-A-5-341441, and compounds 3-6 to 3-18 and 3-23 to 3-38 described in JP-A-5-165147. . Specifically, compounds 17 to 46 described in JP-A-5-341441 can be used as the azomethine dye. Specifically, compounds 11 to 19 described in JP-A-5-289227, compound 47 described in JP-A-5-341441 and compounds 2-10 to 2-11 described in JP-A-5-165147 are used as indoaniline dyes. can do. Specifically, compounds 10 to 16 described in JP-A-5-341441 can be used as the azo dye.

  As a method for adding a dye for the purpose of improving the color tone of a silver image to a light-sensitive material, those described in each specification can be used.

3) Colloidal silica The silver halide photosensitive material of the invention may contain colloidal silica. Colloidal silica has an average particle diameter of 1 nm to 1000 nm, preferably 5 nm to 500 nm, more preferably 5 nm to 100 nm, and its main component is made of silicon dioxide, and may contain alumina or sodium alginate as a minor component. Good.
Specific examples of colloidal silica include SNOWTEX 20, SNOWTEX 30, SNOWTEX C, SNOWTEX O and the like under the trade name of Nissan Chemical Co., Ltd. (Tokyo, Japan).
The colloidal silica-containing layer may be any hydrophilic colloid layer such as a surface protective layer, an intermediate layer, a silver halide emulsion layer, an antihalation layer, an undercoat layer, a filter layer, or a backing layer. In the case where it is intended, it is preferably contained in the surface protective layer or the silver halide emulsion layer.
As content of colloidal silica, 1 mass%-200 mass% are preferable with respect to the hydrophilic colloid mass of the hydrophilic colloid layer to contain, and 10 mass%-100 mass% are the most preferable especially.
The layer containing colloidal silica preferably contains a plastic polymer latex in combination as necessary.

4) Polymer Latex The silver halide photographic light-sensitive material of the present invention may contain a polymer latex obtained by polymerizing a monomer that is hardly soluble in water.

  As such a monomer, for example, acrylic acid esters, methacrylic acid esters, divinylbenzene and the like described in JP-A-7-230135, page 2, 2nd line, 5th line to 17th line can be used.

Such a polymer latex may copolymerize the above monomer with another monomer. Examples of the monomer at this time include, for example, JP-A-7-230135, page 2, line 2, line 32 to page 4, line 1 35. The monomers described in the line can be used, and among them, acrylic acid esters, methacrylic acid esters, vinyl esters, styrenes, or olefins are preferably used.
Examples of the polymer latex include Lx-1 to Lx-21 of JP-A-7-230135.

5) Matting agent The silver halide photographic light-sensitive material of the present invention is obtained from No. 1 described in Example 1 of JP-A-6-19479. 1-No. Eight matting agents can be preferably used. Further, preferred compound examples 1 to 9 described in paragraph 0023 of JP-A-6-138572 can be preferably used.

  With regard to the size and the like of these matting agents, they can be preferably used in the sizes and usage amounts described in paragraph 0049 of JP-A No. 6-194779. Two or more kinds of particle size matting agents can be mixed and used. Regarding the particle size distribution of the matting agent, monodisperse particles having a coefficient of variation of 3% to 30% can be used depending on the purpose, or polydisperse particles having 30% or more can be used.

The coating amount of the total gelatin of the non-photosensitive hydrophilic colloid layer in the present invention is 2.5 g or less (total coating amount per side), preferably 0.5 g / m ² or more and 2.5 g / m ² or less, Particularly preferably, it is 1.0 g / m ² or more and 2.1 g / m ² or less. In this case, the gelatin coating amount of the protective layer is preferably 0.2 g / m ² or more and 1.0 g / m ² or less.

6) Swelling rate of coating film In the present invention, the swelling rate of the photosensitive material is a value obtained by subtracting the dry film thickness value from the film thickness value after the photosensitive material is immersed in distilled water at 21 ° C. for 3 minutes. The value is defined as (%) by multiplying 100 by the value obtained by dividing the value by the film thickness value in the dry state. The range of a preferable swelling rate is 20% to 220%, more preferably 40% to 150%.

7) Coating and drying step In general, a silver halide photographic light-sensitive material is coated on a support with an aqueous coating solution containing a hydrophilic colloid such as gelatin on a support, followed by low-temperature air having a dry bulb temperature of -10 ° C to 20 ° C. Allow to cool and solidify in, then dry at elevated temperature. The mass ratio of gelatin to moisture immediately after coating is usually around 3000%.
This coating solution usually contains various additives such as hydrophilic colloid binders, silver halide grains, surfactants, plasticizers such as polymer latex, gelatin hardeners, dyes, sensitizing dyes and matting agents. Yes.
In the present invention, when the hydrophilic colloid layer coating solution is applied and then dried, wet bulbs are used until the moisture content becomes 100% or less based on the dry amount of binder in the entire coating layer on the side having the silver halide emulsion layer. It is preferable to dry at a temperature of 20 ° C. or lower, preferably 19 ° C. to 10 ° C.
When two or more hydrophilic colloid layers are simultaneously applied and dried (that is, when there are two or more coating layers to be dried), the amount of water is the sum of the moisture in all layers, the binder drying The amount represents the sum of the dry weight (dry mass) of the binder in all layers.
The wet bulb temperature is the temperature of water droplets in an equilibrium state of humid air, and is lower as the humidity of the air is lower. In the constant rate drying period of the drying process, the wet bulb temperature of the drying air is substantially equal to the surface temperature of the coated sample.

Moreover, it is preferable that the environmental conditions at the time of winding in roll shape after application | coating and drying are 1.4 mass% or less, Preferably it is 1.3 mass%-0.6 mass%, and is wound up. In the present invention, the product processing of the silver halide photographic light-sensitive material wound in a roll after coating and drying is an environment having an absolute humidity of 1.4% by mass or less, preferably 1.3% by mass to 0.6% by mass. It is preferably processed below.
Absolute humidity (wt%) represents the state of wet air, and is a percentage of the ratio of the amount of water vapor (kg) in the humid air to the mass (kg) of dry air in the wet air.
8) Processing and packaging The silver halide photographic light-sensitive material is placed in a moisture-proof packaging so that the absolute humidity in the packaging is 1.4% by mass or less, preferably 1.1 to 0.6% by mass. Further, the mouth is sealed by a method such as heat sealing, and the photosensitive material is in equilibrium at the absolute humidity.

  Further, it is particularly preferable that after processing is seasoned in an environment with an absolute humidity of 1.4% by mass or less, and then heat-sealed and sealed in the package in the same environment.

9) Other additives There are no particular restrictions on the various additives used in the silver halide photographic emulsion and silver halide photographic light-sensitive material of the present invention. For example, the additives described in JP-A-2-68539 are described below. Things can be used.

(1) Silver halide emulsion and production method thereof JP-A-2-68539, page 8, lower right column, line 6 from the lower right column to page 10, upper right column, line 12.
(2) Chemical sensitization method From page 13, upper right column, No. 13 to lower left column, 16th line.
(3) Antifogging agent / stabilizer Same page, lower left column, line 17 to page 11, upper left column, line 7 and third page, lower left column, line 2 to page 4, lower left column (4) Spectral increase Sensitizing dye, page 4, lower right column, line 4 to page 8, lower right column.
(5) Surfactant / Antistatic Agent Same page, upper left column, line 14 to page 12, upper left column, line 9 (6) Matting agent / Slip agent Same page, upper left column, line 10 to upper right column 10th line.
Plasticizer, page 14, lower left column, line 10 to lower right column, line 1.
(7) Hydrophilic colloid, page 12, upper right column, line 11 to lower left column, line 16.
(8) Hardener From page 12, lower left column, line 17 to page 13, upper right column, line 6.
(9) Support The upper right column on page 13, line 7 to line 20.
(10) Dye / Mordant: From page 13, lower right column, line 1 to page 14, lower left column, line 9.

6). Phosphor screen The photographic light-sensitive material of the present invention is preferably image-exposed using a lead foil metal intensifying screen. For example, a fluorescent intensifying screen containing the following phosphor is used as a phosphor screen for X-ray photography. It can be carried out.

(Blue light emitting phosphor)
Y ₂ O ₂ S: Tb, LaOBr: Tb, BaFCl: Eu
(Green light emitting phosphor)
Gd ₂ O ₂ S: Tb, LaO ₂ S: Tb

As the UV-emitting phosphor, M ′ phase YTaO ₄ alone or a compound to which Gd, Bi, Pb, Ce, Se, Al, Rb, Ca, Cr, Cd, Nb, etc. are added, LaOBr with Gd, Tm, Gd and Tm , Gd and Ce, Tb added compounds, HfZr oxide alone or Ge, Ti alkali metal added compounds, Y ₂ O ₃ alone or Gd, Eu added compounds, Y ₂ O ₂ S with Gd There are compounds added, compounds using Gd, Tl, and Ce as activators in the matrix of various phosphors. Particularly preferable compounds include M ′ phase YTaO ₄ alone or a compound to which Gd, Sr is added, a compound in which LadBr is added with Gd, Tm, Gd, and Tm, an oxide of HfZr or a compound in which Ge, Ti alkali metal, or the like is added. It is.

The particle size of the phosphor is preferably 1 μm or more and 20 μm or less, but can be changed according to required sensitivity and manufacturing problems. The coating amount is preferably 400 g / m ² or more and 2000 g / m ² or less, but it cannot be said unconditionally depending on the required sensitivity and image quality. Further, the particle size distribution may be given from the vicinity of the support to the surface with a single intensifying screen. In this case, it is generally known to enlarge the surface particles. The space filling factor of the phosphor is 40% or more, preferably 60% or more.

  When photographing with the phosphor layers on both sides of the photosensitive material, the amount of phosphor applied on the X-ray incident side and the opposite side can be changed. In general, since the screen is shielded by the intensifying screen on the X-ray incident side, it is known that the application amount of the intensifying screen on the X-ray incident side is reduced particularly when a high sensitivity system is required.

  Examples of the support used for the screen used in the present invention include paper, a metal plate, and a polymer sheet. Generally, a flexible sheet such as polyethylene terephthalate is used. If necessary, the support may be provided with a reflective layer or a light absorber, or may be provided as a separate layer on the surface.

  If necessary, the support surface can be slightly uneven, or an adhesive layer for increasing the adhesion to the phosphor layer or a conductive layer can be provided as an undercoat. Examples of the reflective agent include zinc oxide, titanium oxide, and barium sulfate. Titanium oxide and barium sulfate are preferred because the phosphor has a short emission wavelength. The reflective agent may be present not only in the support or between the support and the phosphor layer, but also in the phosphor layer. When it exists in a fluorescent substance layer, it is preferable to make it unevenly distribute in the support body vicinity.

  Examples of the binder used in the screen of the present invention include proteins such as gelatin, polysaccharides such as dextran and corn starch, and natural high molecular substances such as gum arabic; polyvinyl butyral, polyvinyl acetate, polyurethane, polyalkyl acrylate, vinylidene chloride, nitro Examples thereof include synthetic polymer materials such as cellulose, fluorine-containing polymers, and polyesters, and mixtures and copolymers thereof. As a preferable binder, the basic performance includes a high transmittance with respect to light emitted from the phosphor. In this respect, gelatin, corn starch, acrylic polymers, fluorine-containing olefin polymers, polymers containing fluorine-containing olefins as copolymer components, styrene / acrylonitrile copolymers, and the like can be mentioned. These binders may have a functional unit that is crosslinked by a crosslinking agent. Further, depending on the required image quality performance, an absorber for light emission from the phosphor may be added to the binder, or a binder having low transmittance may be used. Examples of the absorbent include pigments, dyes, and ultraviolet absorbing compounds. The ratio of phosphor to binder is generally 1: 5 to 50: 1, preferably 1: 1 to 5: 1 in volume ratio. The ratio between the phosphor and the binder may be uniform or non-uniform in the thickness direction.

The phosphor layer is usually formed by a coating method using a coating liquid in which a phosphor is dispersed in a binder solution. Examples of the solvent for the coating solution include water or alcohol, organic solvents such as chlorine-containing hydrocarbons, ketones, esters, ether aromatic compounds, and mixtures thereof.
In the coating solution, dispersion stabilizers such as phthalic acid, stearic acid, caproic acid, and surfactant for phosphor particles, and plasticizers such as phosphoric acid ester, phthalic acid ester, glycolic acid ester, polyester, and polyethylene glycol are added. May be.

The screen used in the present invention can be provided with a protective layer on the phosphor layer. As the protective layer, a method of coating on the phosphor layer and a method of separately forming a protective layer film and laminating are generally used. In the application method, it may be applied simultaneously with the phosphor layer, or may be applied after the phosphor layer is applied and dried. The protective layer may be the same material as the binder of the phosphor layer or a different material. Examples of the substance used for the protective layer include cellulose derivatives, polyvinyl chloride, melamine, phenol resins, epoxy resins and the like in addition to the substances mentioned as the binder for the phosphor layer. Preferred materials include gelatin, corn starch, acrylic polymers, olefin polymers containing fluorine, polymers containing fluorine-containing olefins as copolymer components, and styrene / acrylonitrile copolymers. The thickness of the protective layer is generally from 1 μm to 20 μm, preferably from 2 μm to 10 μm, and more preferably from 2 μm to 6 μm.
It is preferable to emboss the surface of the protective layer of the present invention. Further, a matting agent may be present in the protective layer, or a substance having a light scattering property for light emission, such as titanium oxide, may be present depending on the desired image.

  In the protective layer of the screen used in the present invention, surface slipperiness may be imparted. Preferable slip agents include polysiloxane skeleton-containing oligomers and perfluoroalkyl group-containing oligomers.

You may provide electroconductivity to the protective layer of this invention. Examples of the conductivity imparting agent include white and transparent inorganic conductive materials and organic antistatic agents. Preferred inorganic conductive materials include ZnO powder, whiskers, SnO ₂ and ITO.

7). Development and Fixing Processing System 1) Development The development processing method of the present invention includes US Pat. No. 5,498,511, JP-A-7-16832, JP-A-8-54712, JP-A-9-329875, and JP-A-9-329875. The method described in No. 10-26815 can be referred to.

In the developing solution for processing the light-sensitive material of the present invention, hydroquinone, ascorbic acid, erythorbic acid (a diastereomer of ascorbic acid) or a derivative thereof is preferably used.
Ascorbic acid used in the present invention and derivatives of at least one of them are described in US Pat. No. 2,688,549, Japanese Patent Publication No. 36-17599, Japanese Patent Laid-Open No. 3-249756, Japanese Patent Laid-Open No. 4-270343, and the like.

  Specifically, compounds described in US Pat. No. 2,688,549, page 22, first column, line 22 to page 1, second column, line 33, Japanese Patent Publication No. 36-17599, page 1, left column 21 Compounds described in lines 26 to 26, compounds I-1 to I-8 and II-1 to II-4 described in JP-A-3-249756, page 4, JP-A-4-270343, page 4 The compounds described in 5th column, 40th line to 50th line can be used.

Of these, ascorbic acid or erythorbic acid (a diastereomer of ascorbic acid) and alkali metal salts such as lithium salts, sodium salts and potassium salts thereof are preferable.
The developing agent is usually preferably used in an amount of 0.01 mol / L to 0.8 mol / L, particularly preferably in an amount of 0.1 mol / L to 0.4 mol / L.

In the present invention, it is desirable to use an auxiliary developing agent exhibiting superadditivity together with the developing agent.
As an auxiliary developing agent exhibiting superadditivity, there is a 1-phenyl-3-pyrazolidone auxiliary developing agent.
1-Phenyl-3-pyrazolidones auxiliary developing agents include 1-phenyl-3-pyrazolidone, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4- Methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-4,4-dimethyl Examples include -3-pyrazolidone, 1-p-tolyl-4,4-dimethyl-3-pyrazolidone, or 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone. Of these, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone is preferred.
In the present invention, when a 1-phenyl-3-pyrazolidone auxiliary developing agent is used in combination with a developing agent, it is preferably used in an amount of 0.001 mol / L to 0.1 mol / L, particularly the latter. Is preferably used in an amount of 0.005 mol / L to 0.05 mol / L.

Further, as an auxiliary developing agent showing superadditivity, there is a p-aminophenol auxiliary developing agent. Examples of auxiliary developing agents for p-aminophenols include N-methyl-p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, N- (4-hydroxyphenyl) -glycine, and 2-methyl-p. -Aminophenol, p-benzylaminophenol and the like, among which N-methyl-p-aminophenol is preferable.
In the present invention, when a p-aminophenol auxiliary developing agent is used in combination with a developing agent, it is preferably used in an amount of 0.001 mol / L to 0.1 mol / L, particularly p-amino. Phenol auxiliary developing agents are preferably used in an amount of 0.005 mol / L to 0.05 mol / L.

Antifoggants added to the developer include azole compounds (for example, benzothiazoliums, benzimidazoliums, imidazoles, benzimidazoles, nitroindazoles, triazoles, benzotriazoles, tetrazoles, triazines, etc. ), Mercapto compounds (for example, mercaptothiazoles, mercaptobenzothiazoles, mercaptoimidazoles, mercaptobenzimidazoles, mercaptobenzoxazoles, mercaptothiazoles, mercaptooxadiazoles, mercaptotetrazoles, mercaptopyrimidines, mercaptotriazines Etc.).
In particular, examples of benzotriazoles include 5-methylbenzotriazole, 5-bromobenzotriazole, 5-chlorobenzotriazole, 5-butylbenzotriazole, and benzotriazole. As nitroindazoles, 5-nitroindazole, 6-nitroindazole, 4-nitroindazole, 7-nitroindazole, 3-cyano-5-nitroindazole and the like can be used.

  In the present invention, as a silver stain preventing agent in the developer, JP-B-56-46585, JP-B-62-4702, JP-B-62-4703, U.S. Pat. No. 4,252,215, U.S. Pat. The compounds described in JP-A No. -203439, JP-A No. 62-56959, JP-A No. 62-178247, JP-A No. 1-200249, JP-A No. 5-503179 and JP-A No. 5-53257 can be used.

2) Fixing In the present invention, various known liquids can be used as the fixing liquid. For example, it is a well-known aqueous solution containing thiosulfate, and has a pH of 3.8 or more, preferably 4.2 to 6.2. Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate. The concentration of the fixing agent can be changed as appropriate, and the fixing solution may contain a water-soluble aluminum salt that acts as a hardener, and examples thereof include aluminum chloride, aluminum sulfate, and potassium alum. In the fixing solution, tartaric acid, citric acid, gluconic acid, or derivatives thereof can be used alone or in combination of two or more. These compounds are preferably added in an amount of 0.005 mol or more per liter of the fixing solution, and it is particularly effective to add 0.01 mol / L to 0.03 mol / L. In the fixing solution, sulfite or bisulfite as a preservative is optionally 10 g or more, preferably 50 g or more, and more preferably 0.2 g or more of acetic acid or boric acid as a pH buffering agent per liter of use solution. Is preferably contained in an amount of 0.5 mol or more. Moreover, a pH adjuster (for example, sulfuric acid), a chelating agent capable of softening water, and compounds described in JP-A-62-278551 can be included.

  Examples of fixing accelerators include thiourea derivatives described in JP-B-45-35754, JP-A-58-122535, and 58-122536, alcohols having a triple bond in the molecule, and thioethers described in US Pat. No. 4,126,459. Or cyclodextran ethers that free anions, crown ethers, diazacycloundecene, di (hydroxyethyl) butamine, and the like. Mesoionic compounds described in JP-A-7-5654 and 6-273898 can be contained.

3) Washing with water and stabilization It is preferable to apply anti-fouling means to the water washing bath or stabilization bath. As an anti-fouling means, an ultraviolet irradiation method described in JP-A-60-263939, a method using a magnetic field described in JP-A-60-263940, and an ion exchange resin described in JP-A-61-131632. The method of using the antibacterial agent described in JP-A-61-115154, JP-A-62-153952, JP-A-62-2220951, and JP-A-62-209532 can be used in combination.

  Furthermore, L.M. F. West, “Water Quality Criteria”, Photo. Sci. & Eng. , Vol. 9 (1965), M.M. W. Beach, “Microbiological Growth in Motion-picture Processing”, SMTPE Journal Vol. 85 (1976), R.A. D. Deegan, “Photo Processing Wash Water Biocides”, J. Am. Imaging Tech. , Vol. 10, no. 6 (1984) and JP-A-57-8542, 57-58143, 58-105145, 57-132146, 58-18631, 57-97530, 57-157244, Antibacterial agents, antifungal agents, surfactants, and the like described in Kaihei Nos. 6-118583 and 8-248589 can be used in combination.

Further, R.C. T.A. Kreinan, J .; Image. Tech. 10 (6), page 242 (1984), isothiazoline-based compounds, Research Disclosure, Vol. No. 20526 (May 1981), isothiazoline-based compound, Vol. An isothiazoline compound described in 22845 (April 1983), a compound described in JP-A No. 62-209532, and the like can also be used in combination as a fungicide (Microbiocide).
Other compounds as described in “Chemistry of Antibacterial and Antifungal” written by Hiroshi Horiguchi, Mitsui Publishing (Showa 57), “Handbook of Antibacterial and Antifungal Technology”, This Society of Antibacterial and Antifungal, Hakuhodo (Showa 61) May be included.

  Further, Japanese Patent Application Laid-Open No. 60-235133 discloses a part or all of overflow from the water washing or stabilizing bath caused by replenishing the water washing or stabilizing bath with anti-corrosive means depending on the treatment. Thus, it can be used for diluting a processing solution having a fixing ability, which is the pretreatment step.

4) Processing system In the processing system of the present invention, the amount of liquid carried out by the photosensitive material from the developing tank to the fixing tank and from the fixing tank to the washing tank is preferably 0.2 mL to 4 mL per sheet. 0.2 mL or more and 2.4 mL or less are preferable, and 0.4 mL or more and 2.0 mL or less are more preferable.
When the washing tank is multistage, the amount taken out from the washing tank to the washing tank is preferably 0.2 mL or more and 4 mL or less, more preferably 0.2 mL or more and 2.4 mL or less per 4 sheets. More preferably, 0.21 mL or more and 1.6 mL or less are preferable.
The amount of washing water taken out from the washing tank when entering the drying zone is preferably 0.2 mL or more and 4 mL or less, more preferably 3 mL or less, and even more preferably 2.5 mL or less per 4 pieces of sensitive material. .

The light-sensitive material of the present invention is suitable for rapid processing, and the total processing time (Dry to Dry) from when it is carried into the developing tank until the drying step is completed is preferably 11 minutes or less, and more preferably 5 minutes or less. . When the total processing time is 5 minutes or less, development is at 30 ° C. to 40 ° C. for 15 seconds to 75 seconds, fixing is 15 seconds to 75 seconds, water washing is at 0 ° C. to 40 ° C. for 15 seconds to 75 seconds, and drying is 15 ° C. It is preferably performed at ˜75 ° C. for 1 second to 30 seconds. The replenishment rate, each photosensitive material 1 m ² per developer 3.5ML～650mL, fixer 3.5ML～650mL, it is preferable washing water is 30ML～650mL.

  For details of such processing, reference can be made to the description in the above-mentioned JP-A-9-329875.

  The following examples illustrate the invention.

Example 1
1. Preparation of silver halide emulsion (Preparation of silver halide emulsion A1)
1178 mL of an aqueous solution containing 0.8 g of KBr and 3.2 g of gelatin having an average molecular weight of 20000 was kept at 35 ° C. and stirred. An aqueous AgNO ₃ (0.8 g) solution, an aqueous KBr (0.58 g) solution and an aqueous gelatin (1.1 g) solution having an average molecular weight of 20000 were added over 45 seconds by the triple jet method. The concentration of AgNO ₃ solution with a solution of 0.3 mol / L. Thereafter, the temperature was raised to 68 ° C. over 3.5 minutes, and 26 g of gelatin having an average molecular weight of 100,000 was added. An aqueous solution of AgNO ₃ (209 g) and an aqueous KBr solution were added over 75 minutes while accelerating the flow rate by the control double jet method while maintaining pAg 7.7. Gelatin having an average molecular weight of 100,000 was added and then desalted according to a conventional method. Thereafter, gelatin having an average molecular weight of 100,000 was added and dispersed, and adjusted to pH 5.8 and pAg 8.0 at 40 ° C. to prepare an emulsion.

  This emulsion contains 1 mol of Ag and 60 g of gelatin per 1 kg of emulsion. The silver halide emulsion grains have an average equivalent circle diameter of 2.0 μm, a variation coefficient of equivalent circle diameter of 25%, an average thickness of 0.25 μm, and an aspect ratio. The tabular grains were 8.0. The particle shape was measured by observing a transmission electron micrograph image of the replica of the particle.

(Preparation of silver halide emulsion A2)
Silver halide emulsion A2 was prepared using a seed crystal growth method. This will be described below.

<Seed crystal formulation>
<< Emulsion T-1 >>
Grafted polyalkylene oxide polymer having a molecular weight of 30,000 (compound) in an aqueous solution of 0.8 g of low molecular weight gelatin (average molecular weight 15000) and 1.2 g of potassium bromide kept at 3.5 ° C. in 1.5 L of water 2 g of A-21) was added. Further, an aqueous solution containing 18 g of silver nitrate, 12.6 g of potassium bromide and 2.4 g of gelatin (average molecular weight 15000) were added in 60 seconds by the double jet method while stirring. Subsequently, after adding an aqueous solution containing 10 g of potassium bromide, the temperature was raised to 50 ° C. over 20 minutes. After that, 1 mL of an aqueous solution of 1N caustic soda was added. Thereafter, an aqueous solution containing 200 g of silver nitrate and an aqueous solution containing 138 g of potassium bromide were added over 32 minutes by the control double jet method while maintaining pAg 8.2. The flow rate at this time was accelerated so that the flow rate at the end of addition was 6.8 times the flow rate at the start of addition. After physical ripening at the same temperature for 8 minutes, the temperature was lowered to 35 ° C. and the soluble salts were removed by precipitation. Then, the temperature was raised to 40 ° C. and 50 g of gelatin, 4.7 g of phenoxyethanol, and 1 mg of sodium thiosulfonate were added. And the pH was adjusted to 5.7 with caustic soda. Thereafter, it was rapidly solidified to prepare an emulsion T-1.

  Thus, the silver halide grains in the resulting emulsion T-1 were tabular grains having a total number average sphere equivalent diameter of 0.23 ± 0.03 μm and a thickness of 0.1 μm.

<< Emulsion F-1 >>
24 g of gelatin was added to 840 mL of water and kept at 74 ° C. 20 g of seed crystals (emulsion T-1) were added to such a formulation. Three minutes after the addition, 2.6 g of potassium bromide was added. Next, an aqueous solution containing 32.7 g of silver nitrate and 188 mL of a halogen solution containing 22.3 g of KBr and 0.63 g of KI were added over 25 minutes to obtain the first stage growth. The flow rate at this time is a constant flow rate. After that, after adding 10 mg of sodium ethylthiosulfonate, 0.9 mg of thiourea dioxide was added. Further, an aqueous solution containing 161.5 g of silver nitrate and a halogen solution containing 110 g of KBr and 3.15 g of KI were added over 50 minutes by a control double jet while keeping the pAg at 8.00, and a second stage growth was performed. The flow rate at this time was accelerated so that the flow rate at the end of the addition was 5.7 times the flow rate at the beginning of the addition. After the addition, 12 mL of 1N potassium thiocyanate solution was added.

  After physical aging at the same temperature for 5 minutes, the temperature was lowered to 35 ° C. to remove soluble salts by precipitation. Thereafter, the temperature was raised to 40 ° C., 61 g of gelatin, 3.3 g of phenoxyethanol and a thickener were added, and the pH was adjusted to 6.1 and pAg 7.8 with sodium hydroxide and potassium bromide.

  The emulsion thus prepared was heated to 50 ° C., and 4.8 mg of sodium ethylthiosulfonate was added. Two minutes later, 150 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene was added, and four minutes later, Compound A-1 (the same as Exemplified Compound D-1) was used as a sensitizing dye. After adding 353 mg, 2.2 mg of chloroauric acid and 73 mg of potassium thiocyanate were added, and further 1 mg of sodium thiosulfate and 1.8 mg of selenium compound A-3 were added, followed by aging for 27 minutes. Thereafter, 22 mg of sodium sulfite was added for further ripening, and after 40 minutes, 1.8 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene was added, followed by rapid solidification. In this way, Emulsion F-1 was prepared.

  The total projected area of 80% is composed of grains having an aspect ratio of 5 or more, the average projected area diameter of all the grains is 1.25 μm, the dispersion coefficient is 28%, and the average thickness is 0.2 μm. The average aspect ratio was 7.

(Preparation of silver halide emulsion B1)
1178 mL of an aqueous solution containing 0.8 g of KBr and 3.2 g of oxidized gelatin having an average molecular weight of 20000 was kept at 35 ° C. and stirred. An aqueous AgNO ₃ (0.7 g) solution, an aqueous KBr (0.5 g) solution, and an oxidized gelatin (1.1 g) aqueous solution having an average molecular weight of 20000 were added over 45 seconds by the triple jet method. As the concentration of the AgNO ₃ solution, a solution having a concentration of 0.07 mol / L was used. Thereafter, the temperature was raised to 68 ° C. over 3.5 minutes, and 26 g of succinylated gelatin having an average molecular weight of 100,000 was added. An aqueous AgNO ₃ (237 g) solution and an aqueous KBr solution were added over 75 minutes while accelerating the flow rate by the control double jet method while maintaining pAg 8.5. Gelatin having an average molecular weight of 100,000 was added and then desalted according to a conventional method. Thereafter, gelatin having an average molecular weight of 100,000 was added and dispersed, and adjusted to pH 5.8 and pAg 8.0 at 40 ° C. to prepare an emulsion.

  This emulsion contains 1 mol of Ag and 60 g of gelatin per 1 kg of emulsion. The silver halide emulsion grains have an average equivalent circle diameter of 2.0 μm, a variation coefficient of equivalent circle diameter of 25%, an average thickness of 0.12 μm, and an aspect ratio. It was 16.7 tabular grains.

(Preparation of silver halide emulsion B2)
In the preparation method of B2, silver halide emulsion B2 having different average equivalent circle diameter and average thickness was prepared by changing the first addition amount of AgNO ₃ and KBr and the pAg of the control double jet method. B2 was a tabular grain having an average equivalent circle diameter of 2.0 μm, a variation coefficient of equivalent circle diameter of 25%, an average thickness of 0.09 μm, and an aspect ratio of 22.2.

(Chemical sensitization)
Each of the emulsions prepared as described above was chemically sensitized while being kept at 56 ° C. with stirring. First, 7.5 × 10 ⁻⁵ mol of the following thiosulfonic acid compound-I was added per mol of silver halide, and then 0.15 mol% of AgI fine particles having a diameter of 0.03 μm were added to the total silver amount. . Then potassium thiocyanate was added 6.5 × 10 ^-4 mol equivalent per 1 mol of silver halide per mole of silver halide dispersions of sensitizing dyes I-1 as the amount of sensitizing dye I-1 1.0 × 10 ⁻³ mol was added, and an aqueous solution of sensitizing dye II-1 was added in an amount corresponding to 3.5 × 10 ⁻⁶ mol per mol of silver halide, and calcium chloride was further added.

Subsequently, chloroauric acid was added in an amount equivalent to 2.2 × 10 ⁻⁵ mol per mol of silver halide and potassium thiocyanate was added in an amount equivalent to 6.5 × 10 ⁻⁴ mol per mol of silver halide, and then sodium thiosulfate was added to the silver halide. The equivalent of 1.1 × 10 ⁻⁵ mole per mole and selenium compound-1 were added in an amount equivalent to 7.0 × 10 ⁻⁶ mole per mole of silver halide. After 40 minutes, 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene was added in an amount equivalent to 5 × 10 ⁻⁴ mole per mole of silver halide and cooled to 35 ° C. Thus, chemical sensitization of the emulsion was completed.

2. 2. Preparation of coated sample 2-1. Preparation of Support A 175 μm-thick blue dyed biaxially stretched (containing 1,4-bis (2,6-diethylanilinoanthraquinone) polyethylene terephthalate support was subjected to corona discharge, and the following main components Each coating solution containing was applied to both sides of the support by a wire bar coater in the order of the first undercoat layer and the second undercoat layer.

・ First undercoat layer (support side)
The amount of the coating solution per 1 m ² on one side of the support was 4.9 mL. The amount of each additive material applied per 1 m ² on one side of the support is as follows.
・ Styrene-butadiene copolymer latex (as solid content) 0.31 g
・ 2,4-Dichloro-6-hydroxy-s-triazine sodium 8mg
Drying temperature 190 ° C

-Second undercoat layer The amount of the coating solution per 1 m ² on one side of the support was 7.9 mL. The amount of each additive material applied per 1 m ² on one side of the support is as follows.
・ Gelatin 80mg
_{· C 12 H 25 O (CH} 2 CH 2 O) 10 H 1.8mg
・ Preservative D 0.27mg
・ Polymethylmethacrylate 2.5mg matting agent 2.5mg
Drying temperature 185 ° C

2-2. Coating of Emulsion Layer and Protective Layer Coating was carried out on the both sides of the undercoat coated support prepared as described above from the support side by the simultaneous extrusion coating method so as to form the following emulsion layer and surface protective layer. Table 1 shows the sample numbers and their contents.

(Surface protective layer coating solution)
A surface protective layer coating solution was prepared and applied so that each component had the following coating amount. The pH was adjusted to 6.0 with NaOH.
Gelatin 1.2g / m ²
Sodium polyacrylate (average molecular weight 400,000) 60 mg / m ²
Butyl acrylate / methacrylic acid (6/4 mass ratio) copolymer 66.9 mg / m ²
Coating aid-1 15.8 mg / m ²
Application aid-2 29.5 mg / m ²
Coating aid-3 7.7 mg / m ²
Coating aid-4 1.4 mg / m ²
Coating aid-5 3.6 mg / m ²
Additive-5 2.4 mg / m ²
Matting agent-1 (number average particle diameter 3.8 μm) 54.2 mg / m ²
Proxel 1.1mg / m ²

(Preparation method of lower emulsion layer coating solution)
Each compound was added so that the coating amount of the lower layer emulsion subjected to chemical sensitization was as follows. It was written in terms of the amount of material applied per 1 m ^{2 on} one side.

Silver halide emulsion (types are shown in Table 1) (Amount of coated silver) 4.0 g
Gelatin 6.0g
1-phenyl-5-mercaptotetrazole compound (addition amount is shown in Table 1)
Additive-1 68.4mg
Additive-2 1.6mg
Additive-3 5.32mg
Additive-4 5.1mg
Dye-1 (blue tinting dye) 3.5mg
Dye-2 0.41g
1,2-bis (vinylsulfonylacetamido) ethane 42.3 mg

(Measurement of swelling rate of coating material)
First, the photographic material to be measured was aged for 7 days under the conditions of 40 ° C. and 60% relative humidity. Next, this sensitive material was immersed in distilled water at 21 ° C. for 3 minutes, and this state was frozen and fixed with liquid nitrogen. The photographic material was cut with a microtome so as to be perpendicular to the surface of the photographic material, and then freeze-dried at -90 ° C. What performed the above process was observed with the scanning electron microscope, and swelling film thickness Tw was calculated | required. On the other hand, the film thickness Td in the dry state was also determined by cross-sectional observation using a scanning electron microscope. A value obtained by dividing the difference between Tw and Td thus determined by Td and multiplying by 100 was defined as a swelling ratio (unit%). When each photographic material was measured by this method, the swelling rate of all the samples was 170%.

3. Evaluation of photographic performance Each of these photographic materials was evaluated for each item by the following method.
<X-ray photographic sensitivity and gradation>
Put each coating material in the cassette together with the lead foil intensifying screen, and X-ray irradiation takes 10 ^0.2 times longer by 1 second, 1.6 seconds, 2.5 seconds, ... Step by step. This sample was developed using an automatic self-machine FIP4000 using a developer and a fixing solution having the following composition, and the relationship between the optical density of the obtained sample and the log (X-ray irradiation time) vs. optical density was expressed. A characteristic curve is obtained. The X-ray irradiation time (E0) at the point where the optical density is (fog + 1.5) and the X-ray irradiation time (E1) at the point where the optical density is (fog + 3.5) are obtained, Relative sensitivity and gradation (G) were determined from the values.
Gradation (G) = (3.5-1.5) / (logE1-logE0)

<Developer solution>
Hydroquinone 20g
1-phenyl-3-pyrazolidinone 0.8 g
Potassium bromide 10g
Potassium iodide 0.1g
Phenyl mercaptotetrazole 0.03g
Potassium thiocyanate 2.5g
Polyglycol (molecular weight 400) 10mL
Aqueous potassium sulfite (655 g / l) 150 mL
Aqueous potassium carbonate (765 g / l) 40 mL
Aqueous potassium hydroxide (755 g / l) 10.4 mL
Trilon B (trade name of Na4EDTA from BASF) 4mL
Turpinal 2NZ (trade name of 1-hydroxy-ethyl diphosphonate disodium from HENKEL) 1 g
pH 10.85
1L of water

<Fixing solution>
200g sodium thiosulfate
Potassium metabisulfite 25g
pH 4.9-5.2
1L of water

<Evaluation of Image Tone -Evaluation of Reflective Silver Tone->
The silver tone of developed silver in reflected light was observed for the sample subjected to development processing. Evaluation was made according to the following criteria.
○: Metallic luster is weak and the reflection color tone is close to black.
X: Metallic luster is strong and the reflection color tone is close to brown.

<Evaluation of pressure sensitization>
The photosensitive material was folded 360 ° in accordance with a stainless steel pipe having a diameter of 6 mm. The same process as when the photographic performance was evaluated 30 minutes after the folding was performed.
Thereafter, the density increase (excluding the original fog and the base density of the emulsion) of the blackened portion along the stainless steel pipe was visually evaluated according to the following criteria.
○: Blackening density is low and there is no desensitization.
X: Strong blackening or desensitization remains.

The obtained results are shown in Table 2.
The coated sample according to the present invention had a high G / A ratio, had good contrast as an industrial X-ray photosensitive material, and was excellent in silver tone. In particular, Samples 15, 18, 21, 24, and 27 have a gradation of 4 and exhibit extremely high contrast as an industrial X-ray photosensitive material, with a G / A ratio of 0.8 or higher and extremely high pressure sensitization and sensitization resistance. It was excellent. Samples 15,18,21,24,27 are both samples with the addition of 1-phenyl-5-mercaptotetrazole in a large amount as 35 mg / ^{m 2,} by addition of a large amount of 1-phenyl-5-mercaptotetrazole, high It was completely unexpected to achieve high contrast and satisfy excellent pressure sensitization resistance.

  The structures of the compounds used in the examples are shown below.

Claims (6)

  An industrial X-ray light-sensitive material having at least one silver halide emulsion layer on each side of a transparent support, the silver halide emulsion layer having an average grain thickness of less than 0.13 μm and an aspect ratio of 10 or more The first tabular silver halide grains and the second tabular silver halide grains having an average grain thickness of 0.13 μm or more and an aspect ratio of less than 10 are used. . 2. The industrial X according to claim 1, wherein the silver halide emulsion layer contains a compound represented by the following general formula (1) in an amount of 3 mg to 10 mg per gram of silver in the silver halide emulsion layer. Ray photosensitive material:

(In the formula, Q represents an atomic group necessary for forming a nitrogen-containing aromatic heterocycle. M represents a hydrogen atom or a cation).   The ratio of the aspect ratio of the first tabular silver halide grains to the aspect ratio of the second tabular silver halide grains is 1.2 or more and 4.5 or less. Item 3. The industrial X-ray photosensitive material according to Item 2.   The ratio of the coating amount of the first tabular silver halide grains to the second tabular silver halide grains is 0.7 to 2.0 in terms of silver ratio. The industrial X-ray photosensitive material according to claim 3. The industrial X-ray according to any one of claims 2 to 4, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2). Photosensitive material:

(In the formula, R ₁ represents a hydrogen atom or a substituent that can be substituted on the benzene ring. N represents an integer of 1 to 5).   The silver halide emulsion layer contains the compound represented by the general formula (1) in an amount of 3 mg to 10 mg per gram of silver in the silver halide emulsion layer. 2. The industrial X-ray photosensitive material according to item 1.