JPH02103535A - Silver halide photographic sensitive material improved to eliminate roughness of image - Google Patents

Abstract

PURPOSE:To obtain high-quality images free from image roughness, etc., by providing hydrophilic colloidal layers contg. specific compds. to the photosensitive material and incorporating internally fogged metal salt particles into at least one layer thereof. CONSTITUTION:Photosensitive silver halide emulsion layers contg. photosensitive silver halide particles are formed on both sides of a base. The hydrophilic colloidal layers contg. at least the compds. expressed by the formula I are provided between the photosensitive silver halide emulsion layers and the base and the internally fogged metal salt particles are incorporated into at least one layer of the hydrophilic colloidal layers and/or at least one layer of the photosensitive silver halide emulsion layers. In the formula I, R<1>, R<6>, R<7> denote an alkyl group, aryl group, etc.; R<2> denotes H, alkyl group or benzyl group; R<3> denotes H, alkyl group or aryl group, R<4>, R<5> respectively denote H or an atom group necessary for forming 5- 6-membered rings. Sharpness and graininess are improved in this way and the high sensitivity is obtd.; in addition, the color tones of developing silver is improved.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a silver halide photographic material (hereinafter sometimes simply referred to as a "photographic material"). In particular, in photographic materials having light-sensitive silver halide emulsion layers on both sides of the support, sharpness is improved by reducing crossover light, high sensitivity and high contrast are maintained, and images are less rough. It provides photographic materials.

[Background of the invention]

A photographic material having a light-sensitive emulsion layer on both sides of a support is
Even if you try to expose only the emulsion layer on one side of the support, the light that passes through the support (crossover light) may also expose the emulsion layer on the opposite side, and this is known as the old crossover effect. known from. Since the crossover effect reduces sharpness, it is desirable to reduce the crossover light that causes this as much as possible.

Examples of photographic materials having light-sensitive emulsion layers on both sides of the support include radiation-sensitive materials, particularly X-ray-sensitive materials.

For example, when directly projecting medical X-ray images, an X-ray film with emulsion layers formed on both sides of a support is placed in close contact between fluorescent intensifying screens. Not only the emulsion layer of the X-ray film in contact with the intensifying screen is exposed by the light emitted from the intensifying screen, but also the emulsion layer on the opposite side is simultaneously exposed by the crossover light. This crossover effect reduces sharpness.

The deterioration of sharpness due to the above-mentioned crossover light becomes more significant as the amount of silver in the light-sensitive emulsion layer decreases.

On the other hand, the supply of metallic silver, which is essential as a raw material for photographic materials, is decreasing. On the other hand, the demand in various industries is increasing, and attempts are being made to reduce the amount of silver used in photographic materials.

Furthermore, various demands are placed on the performance of photographic materials, and in particular, highly sensitive photographic materials with stable photographic performance are required. In particular, X-ray photosensitive materials are required to have higher sensitivity in order to reduce the amount of X-ray exposure to the human body, and high-quality photographic materials are also required to ensure reliable diagnosis.

In photographic materials, high sensitivity can generally be achieved by increasing the size of the halogen northern limit emulsion grains. However, according to this method, the blackening density per unit of developed silver decreases, and the gamma (the slope of the linear portion of the characteristic curve) decreases. In order to improve these problems, it is necessary to increase the amount of silver per unit area of the photosensitive material, but this goes against the above-mentioned demand for silver saving.

As a method that achieves high sensitivity and saves silver, U.S. Patent No. 2
, No. 996,382 and No. 3,178,282 disclose a photographic light-sensitive material in which surface latent image type silver halide grains and silver halide grains having fog nuclei inside the grains are present adjacent to each other. A method is described for obtaining photographic images with relatively high sensitivity and high covering power. Although this is desirable from the standpoint of saving silver, a small amount of silver in such a photographic light-sensitive material increases the problem of the above-mentioned crossover effect and has the disadvantage of deteriorating sharpness.

It has been known to provide a filter dye between an emulsion layer and a support in order to cut crossover light. Generally, it is preferable that filter dyes be decolored during the development process, and this property is particularly required for X-ray films. Therefore, a water-soluble filter dye is used, but in this case, the filter dye may diffuse into the emulsion layer and cause a decrease in sensitivity. Additionally, fog may increase during storage.

For example, as one of the prior art, British patent 821,352
A technique using dyes is described in the patent specification. However, simply applying the method described herein has the disadvantage that the sensitivity decreases due to the dye, problems occur in processability, and, for example, roller marks are generated by the developing machine during development, deteriorating the image. .

- [Object of the Invention] The present invention has been made in view of the above-mentioned circumstances, and is capable of reducing cross-over light without causing a decrease in sensitivity, and is applicable to photographic light-sensitive materials using a high-intensity, low-III amount emulsion. It is an object of the present invention to provide a photographic material that can prevent deterioration in processability even in the case of high-quality images without image roughness or the like.

[Structure of the invention]

A photographic light-sensitive material according to the present invention which achieves the above object is a silver halide photographic light-sensitive material having a light-sensitive silver halide emulsion layer containing light-sensitive silver halide grains on both sides of a support. At least I of the silver emulsion layer
Between Ji and the support, at least the following - formation (I)
At least one of the hydrophilic colloid layers and/or at least one of the photosensitive silver halide emulsion layers has a hydrophilic colloid layer containing a compound represented by: It is characterized by containing metal salt particles.

General formula (1) RI, an alkyl group having 1 to 6 carbon atoms, an aryl group.

Ester group or carboxyl group R'', H, alkyl group or benzyl group having 1 to 4 carbon atoms R3, H, alkyl group or aryl group R', R5; H1 or R4 is R6, R5 is R'7 and 5 ~Atom group R'lR7 necessary to form a 6-membered ring; each an alkyl group or an aryl group.

ester group n; 1, 2 or 3 m; 0 or 1 represents.

However, each of the above groups includes those having a substituent.

The present invention will be explained in detail below.

Typical specific examples of the compound represented by general formula (1) contained in the photographic material of the present invention are shown below, but the present invention is not limited thereto.

For each compound, the maximum absorption wavelength λ□ in aqueous solution,
and the molar extinction coefficient ε+aax.

Exemplary compound εn*x =3.73X lo4 ε,, □-5,20X 10' ε□, = 3.34X10'! -4 ■ ε11□=3.78X10' ε11. l1 = 3.81X10' I-7 ■ ■ ε Hiden X 6.22X10' 618M 4.58X10' ■ -12 ε -11X 5.25X10' ε□ 47xlO' The compound represented by the general formula (1) is, for example, BP276.
It can be easily synthesized by the method described in Japanese Patent No. 566. - The compound represented by Formation [■] is contained in the hydrophilic colloid layer existing between any layer of the photosensitive silver halide emulsion layer and the support, but the means for containing this compound is arbitrary. It is. For example, these compounds are often dissolved in water, an organic solvent miscible with water (eg, methanol, ethanol, acetone, etc.), or a mixture thereof.

The amount of the compound represented by general formula (1) may be such that it gives a density of at least 1.00 at the wavelength of light at which the photosensitive silver halide emulsion exhibits maximum sensitivity. Specifically,
It is preferable to add 0.1 mg to 100 mg/rrf on both sides, more preferably 0.5 to 80 mg/rr, particularly preferably 1 to 50 mg/rrf.

The compounds represented by the general formula 11) may be used alone or in combination of two or more.

When there are two or more hydrophilic colloid layers containing the compound represented by the general formula [I], the compounds contained in each layer may be the same or different. It has a photosensitive silver halide emulsion layer on both sides of the body, and the photosensitive silver halide emulsion layer contains photosensitive silver halide grains.

In the present invention, "photosensitivity" means that the sensitivity of the photosensitive silver halide grains is higher than that of the metal salt grains covered inside. More specifically, it means having a sensitivity that is preferably 10 times or more, more preferably 100 times or more, the sensitivity of the metal salt particles covered inside. The sensitivity here has the same meaning as the sensitivity shown below.

As the photosensitive silver halide emulsion, a conventional photosensitive silver halide emulsion such as a surface latent image type emulsion is used.

The surface latent image type silver halide emulsion that can be used in the present invention refers to a surface latent image type silver halide emulsion that, after exposure for 1 to 1/100 seconds, is developed by the method of surface development (A) and method of internal development (B) shown below. The sensitivity obtained in surface development (A) is the same as that obtained in internal development (B).
), preferably an emulsion in which the sensitivity of the former is more than twice that of the latter. Here, sensitivity is defined as follows.

S is the sensitivity, and Eh is the maximum density (Da+ax) and the maximum density (
(Dmax
+Dmin).

Surface Development (A)> Developed for 10 minutes at 20°C in a developer with the following formulation.

N-methyl-p-aminophenol (hemisulfate) 2.57τ ascorbic acid 10° Sodium metaborate tetrahydrate 35 f? potassium bromide
Add 1g water
1β internal development (B)> Red blood salt 3g/It and phenosafranin 0.0126g
/β for 10 minutes at 20°C, then washed with water for 10 minutes, and developed in a developer having the following formulation at 20°C for 10 minutes.

N-Methyl-p-aminophenol (hemiborate> 2.5g Ascorbic acid 10g Sodium metaborate tetrahydrate 35g Bromide "J Lamb"
1g sodium thiosulfate
Add 3g water 1
As the one-surface latent image type silver halide emulsion, silver iodobromide or silver chloroiodobromide is preferable. The content of silver iodobromide is preferably 0.1 to 30 mol%, particularly preferably 0.5 to 10 mol%, and it is preferable that silver iodide is formed inside the grains.

The average particle diameter of the surface latent image type silver halide grains is preferably larger than that of the internally capped metal salt grains, for example, preferably 066 μm or more gives good results.

In this specification, the average particle diameter refers to the particle diameter in the case of particles that are spherical or approximately spherical, and in the case of particles with a shape other than spherical, the average particle diameter based on the diameter when the projected image is converted to a circular image of the same area. This is the expressed value.

The average particle size is measured by direct measurement from an electron microscope, by a Coulter counter, by using a centrifugal particle size distribution measuring device based on the liquid phase sedimentation method, or the like.

The surface latent image type silver halide emulsion grains that can be used in the present invention may have a regular crystal shape such as a cube, an octahedron, a dodecahedron, a rhombidodecahedron, or a spherical, potato-shaped, etc. Irregular (irregu) shape, plate shape, etc.
It may be in a crystalline form (lar). Furthermore, it may consist of a mixture of particles of various crystal forms.

Further, an emulsion may be used in which ultratabular silver halide grains having a grain diameter of three times or more the grain thickness occupy 50% or more of the total projected area.

The silver halide grains may have different layers inside and on the surface. .

The surface latent image type silver halide emulsion may be a monodisperse emulsion. Here, the monodisperse emulsion is one in which □≦0.20, where r is the average grain size of silver halide grains and σ is its standard deviation.

r When silver iodobromide grains are used as silver halide grains in a surface latent image type silver halide emulsion, the distribution of silver iodide inside the grains may be uniform, and the concentration may be higher as the inner part of the grain approaches, and the silver iodide distribution may be localized within the grains. may be done. Note that when referring to localizing silver iodide inside the grain, the inside refers to the range from the center of the grain to 2/3 of the total iml contained in the grain.

The intragrain silver iodide distribution of silver halide grains can be determined, for example, by a method combining ion etching and X-ray photoelectric distribution.

The photographic emulsion used to form the photographic light-sensitive material of the present invention may be prepared by any of the acidic method, neutral method, ammonia method, etc., and the reaction between the soluble root salt and the soluble halogen salt can be carried out by the one-sided mixing method or the simultaneous mixing method. Any method or combination thereof may be used.

Alternatively, a method in which grains are formed in an excess of silver ions (so-called back mixing method) may be used.As a form of simultaneous mixing method, a method of controlling pAg and pH in the liquid phase in which silver halide is produced, so-called chondrold method, may also be used.・Double jet method can also be used.

In order to control the grain growth of silver halide, various silver halide solvents, crystal control compounds described in JP-A-62-42148, and various sensitizing dyes can be used. In the process of silver halide grain formation or physical ripening, various sensitizing dyes, cadmium salts, zinc salts, lead salts,
A thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or a complex salt thereof, etc. may be coexisting.

Surface latent image type silver halide emulsions can be chemically sensitized by various methods.

Photographic emulsions may be spectrally sensitized with methine dyes and others.

Next, the internally capped metal salt particles used in the photographic material of the present invention will be described. In the present invention, the internally covered metal salt particles are at least one of the hydrophilic colloid layers containing the compound represented by the above-mentioned form CI),
It is contained in at least one of the photosensitive silver halide emulsion layers or in at least one of both layers. As such metal salt particles, Japanese Patent Application Laid-Open No. 57-138
No. 633, No. 57-140317, No. 57-1542
Although there are photosensitive cuprous halide particles described in No. 33 and thallium (1) compounds (eg, T7!Br, Tju, etc.), silver halide particles are preferable.

The internally capped metal salt particles described above may also be stabilized using a compound having a mercapto functional group.

Compounds having a mercapto functional group that can be used in this case include, for example, heterocyclic nitrogen compounds having a mercapto functional group, where the mercapto functional group is a carbon atom located α-position with respect to the nitrogen atom of the heterocyclic ring. or tetrazaindenes with at least one mercapto function, purines with at least one mercapto function, triazaindene neck with at least one mercapto function, at least one mercapto function. Mention may be made of pentazaindenes having groups.

When carrying out the photographic light-sensitive material of the present invention specifically, 3
By using a silver iodobromide emulsion containing more than mol % of silver iodide and an internally fogged metal salt emulsion, it is possible to satisfactorily increase the intensity, contrast, and covering power.

For example, the internally covered metal salt particle emulsion used in the photographic light-sensitive material of the present invention may have a coated metal salt amount of 2 g/rr.
Transparent density (excluding the density of the support itself) when a test specimen of is 0.5 or less, and the same test piece was not exposed to light D-19
35℃ with a developer containing 0.5g/l of potassium iodide.
An emulsion can be used which has a clear fog density (excluding the density of the support itself) of at least 1.0 when developed for 2 minutes.

Emulsions containing capped metal salt particles can be prepared by various methods,
For example, it can be obtained by a known method.

For example, it can be obtained by preparing a core emulsion having fog nuclei according to the core-shell emulsion preparation method described in US Pat. No. 3,206,313, and then coating the core emulsion grains with a shell emulsion.

Methods for fogging the core emulsion include irradiation with light, chemical fogging with a reducing agent, unstable sulfur compound, or gold compound, and ripening at low pAg and high pH. Among these, methods using a reducing agent and methods using a reducing agent and a gold compound in combination are preferred.

The silver halide composition of the silver halide emulsion in which the inside of the grain is covered includes silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide,
Any silver iodobromide or the like may be used. Further, the silver halide grains may have regular crystals such as cubic, octahedral, dodecahedral, or dodecahedral, or irregular crystals such as spherical, potato-shaped, tabular, etc. i rregu
It may have a jar crystal shape.

The internally capped metal salt grains preferably have an average grain size smaller than that of the photosensitive silver halide grains, preferably from 1.0 to 0.05 μm, and preferably from 1.0 to 0.05 μm. It is more preferred to have an average particle size of 6 to 0.1 .mu.m, with 0.5 .mu.m or less particularly preferred and gives good results.

The content ratio of the photosensitive silver halide grains and the internally capped metal salt particles in the photographic light-sensitive material of the present invention is determined by the type of emulsion used (for example, halogen composition), the type or purpose of the light-sensitive material used, and the use of the photosensitive material. Although it can be changed depending on the contrast of the emulsion to be used, the ratio is preferably 100:1 to 1:100, and particularly preferably 10:1 to 1:10.

In addition, the total amount of metal applied is 0.5 to 10 g/d.
is preferred.

As the binder or protective colloid for the photographic emulsion, it is preferable to use gelatin such as lime-treated gelatin, acid-treated gelatin, derivative gelatin, or gelatin graft polymer.
Hydroxyethyl cellulose, polyvinyl alcohol,
Hydrophilic colloids such as polyvinylimidazole can be used.

The above-mentioned hydrophilic colloids can also be used as the hydrophilic colloid for forming the hydrophilic colloid layer containing the compound represented by the general formula [I] according to the present invention.

In the photographic light-sensitive material, a dispersion of a water-insoluble or sparingly soluble synthetic polymer can be contained in the photographic emulsion layer and other hydrophilic colloid layers to improve dimensional stability.

In the present invention, various compounds can be contained in order to prevent stagnation and stabilize photographic performance during the manufacturing process, storage, or photographic processing of the photographic light-sensitive material.

In the light-sensitive material of the present invention, the silver halide emulsion layer and other hydrophilic colloid layers can be hardened with a suitable hardener.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioethers, thiomorpholines, quaternary Ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, etc. may be included.

Furthermore, the photographic emulsion layer or other water-based colloid layer of the photographic light-sensitive material may contain coating aids, antistatic properties, slipperiness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (e.g. development acceleration, hardening, aggravation). etc., a surfactant may be included.

There are several embodiments regarding the layer structure of the photosensitive material of the present invention, but representative ones include (1) containing a compound represented by the general formula (1) according to the present invention on a support; A structure in which a lignophilic colloid layer is coated, and a surface latent image type silver halide emulsion and metal salt particles (emulsion) such as silver halide whose interiors are covered are mixed and coated on the layer (
2) A layer containing the compound represented by the general formula (I) according to the present invention and metal salt particles such as silver halide (emulsion) coated inside the particles is coated on a support, and further on this layer. A structure in which a layer containing a surface latent image type silver halide emulsion is coated, (3) a hydrophilic colloid layer containing a compound represented by the general formula (1) according to the present invention is coated on a support, and On top of this, a layer containing a surface latent image type silver halide emulsion and a metal salt grain (emulsion) such as silver halide with the inside of the grain covered is coated, and a surface latent image type silver halide emulsion is further applied on this layer. (4) A hydrophilic colloid layer containing a compound represented by the general formula (1) according to the present invention is coated on a support, and a surface latent image type layer is further applied on the support. A layer containing a silver halide emulsion and a metal salt grain (emulsion) such as silver halide with a cloudy interior is coated, and a surface latent image type silver halide emulsion and a layer containing a grain interior are coated on top of this. Metal salt particles such as silver halide (
(5) A structure in which a gelatin coating layer is applied as a protective layer on the compositions (1) to (4) above, etc. can be mentioned. However, the present invention is not limited to this, and for example, when two or more photosensitive silver halide emulsion layers are present, the compound represented by the general formula (I) according to the present invention may be on the side closer to the support than any of them.

In the photographic material of the present invention, light-sensitive silver halide emulsion layers are provided on both sides of the support.

The hydrophilic colloid layer containing the compound represented by the general formula (I) according to the present invention may be present on at least one surface, but it is preferably present on both surfaces.

The photographic material of the present invention is preferably provided with a protective layer. The protective layer is generally a layer made of a hydrophilic colloid, and the hydrophilic colloid used can be those mentioned above.

Further, the protective layer may be a single layer or a multilayer structure.

The protective layer may contain an antistatic agent.

The emulsion layer or protective layer may contain at least one type selected from matting agents and smoothing agents;
It is preferable to include it in the protective layer.

The photographic material of the present invention may be provided with an antihalation layer, an intermediate layer, a filter layer, etc., if necessary.

The photographic light-sensitive material of the present invention can be applied to any light-sensitive material such as an Xray5 light-sensitive material, a Lith light-sensitive material, a black-and-white photographic light-sensitive material, a color light-sensitive material, and the like.

The photographic light-sensitive material of the present invention may contain dyes other than those represented by formula (I), a fluorescent whitening agent, a color cast inhibitor, an ultraviolet absorber, and the like, if necessary.

The photographic light-sensitive material of the present invention uses a photographic emulsion or other coating liquid,
on flexible supports such as plastic films, paper, cloth, or rigid supports such as glass, ceramic, metal, etc.
It can be obtained by coating by a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, or the like.

For photographic processing of the photographic light-sensitive material of the present invention, various methods can be applied using various processing solutions depending on the specific light-sensitive material. That is, the photographic processing may be black-and-white processing or color photographic processing depending on the purpose [Examples] The present invention will be described in detail below with reference to Examples.

However, as a matter of course, the present invention is not limited to the examples.

Example-1 (1) Preparation of photosensitive emulsion 2.0 mol % of silver iodide with an average grain size of 0.20 μm was prepared by the double jet method at 60°C, while controlling pAg=a, o, and pH=2.0. A silver iodobromide monodisperse cubic emulsion containing the following was obtained. A portion of this emulsion was used as a core and grown as follows. That is, in a solution containing core particles and gelatin, 4
At 0°C, pAg = 8.0, pH = 9.5, an ammoniacal silver nitrate solution and a solution containing potassium iodide and potassium bromide were added using a double jet method, and a first solution containing 25 mol% silver iodide was added. A covering calendar was formed.

Note that the addition rate was gradually increased as the particles grew.

The resulting emulsion was an octahedral monodisperse emulsion with an average grain size of 0.38 μm. Using this emulsion grain as a core, further p A g
= tt, o, pH = 9.0 by adding ammoniacal silver nitrate solution and potassium bromide solution by double jet method,
A second coating layer was formed. The obtained emulsion had an average grain size of 0.
It was an octahedral monodispersed emulsion of 70 μm. The silver iodide content at this time was 4 mol%.

(σ/r = 0.12).

Next, the above emulsion was desalted by a conventional agglomeration method, and then added to the desalted emulsion, containing 9 chloroauric acid per mole of silver halide.
X10-' mol, sodium 1,000 sulfate 8XIO-' mol, and ammonium thiocyanate 8x lQ-4 mol were added to optimally sensitize gold and sulfur, and 4-hydroxy-6
-Methyl-1,3,3a,7-chitrazyden 2X10
A photosensitive silver iodobromide emulsion was obtained, which was stabilized at 100 molar.

(2) Preparation of emulsion with internal fog A silver nitrate aqueous solution and a potassium bromide aqueous solution were simultaneously added to a 2.5% by weight gelatin solution kept at 55°C. After the addition, the temperature of the solution was maintained at 70° C., potassium hydroxide and silver nitrate were added, and the solution was aged for 20 minutes to form a fog. The solution is then kept at 55°C, neutralized by adding acetic acid, and then simultaneously added with an aqueous solution of silver nitrate and potassium bromide to form a coating, desalted by the usual flocculation method, and redispersed in an aqueous gelatin solution. As a result, an emulsion having an internal fog core with an average grain size of 0.40 μm was obtained. To this emulsion was added 5-mercapto-1-phenyltetrazole at 120 µm per mole of silver halide to obtain an emulsion having internal pores.

(3) Preparation of test sample From the support side, add a hydrophilic colloid layer to which the compound represented by the general formula (1) according to the present invention (or comparative compound) as shown in Table 1, and then add the above (1) above to the hydrophilic colloid layer. Angry light consisting of an emulsion prepared by mixing the prepared photosensitive silver halide emulsion and the emulsion with internal fog prepared in (2) above at a weight ratio of 2:1 (however, the following additives were contained) A protective layer described below was coated on the northern limit emulsion layer of halogen and layer 5 by the method shown below.

That is, the emulsion layer contains 400 mg of t-butyl-catechol as an additive per mole of silver halide.

Polyvinylpyrrolidone (molecular weight 10,000) 1.0
g.

Styrene-maleic anhydride copolymer 2.5g.

Trimethylolpropane Log.

Diethylene glycol 5 g.

Nitrophenyl-triphenylphosphonium chloride 50 mg.

Ammonium 1.3-dihydroxybenzene-4-sulfonate 4 g.

Sodium 2-mercaptobenzimidazole-5-sulfonate 1.5 mg.

H 1,1-dimethylol-1-bromo-1-nitromethane 70 mg.

etc. were added.

Also, The following is added to the protective layer: 1 part gelatin I got a star per g.

That is, CHzCOO(CHz)Jll.

CHzcOO(CHz) zcH(CI:l) zm
g SO, Na :4aSOz CHCOOCH2(Cal4) 3t
lCIIZCOOC)+2 (Cal(,,) 3H5
mgFl 9C9-0+CH2CH,O+y-vcH2
cH2-OH3mgC,F,503K
In addition to adding 2 mg, 7 mg of a matting agent made of polymethylmethanol with an average particle size of 7 μm, 70 mg of colloidal silica with an average particle size of 09O13 μm, 3 μm of formaldehyde, 2 mg of glyoxal, and 2-hydroxy-4,6-dichloro-
An aqueous gelatin solution to which 1,3,5-triazine sodium salt, etc. was added was used as a protective layer solution. The three layers mentioned above,
At the same time, it was coated on a polyester film base that had been undercoated using the method described in JP-A-59-19941 at a coating speed of 90 m/min and dried in 2 minutes and 30 seconds. A sample was obtained by coating and drying. The coated silver π is 4.0 g/m on both sides, the gelatin coating amount of the protective layer is 2.4 g/m2 on both sides, the gelatin coating amount of the emulsion layer is 4.0 g/m on both sides, and the general formula according to the present invention is The gelatin coating amount of the hydrophilic colloid layer containing the compound represented by (1) was 1.2 g/m on both sides.

In addition, in sample preparation, the following compounds were used as comparative compounds for the compound represented by the general formula N) according to the present invention.

(a) (b) (4) Test sample test method a, sensitometry The sample was sandwiched between X-ray photographic intensifying screens NR-100 (manufactured by Konica Corporation), and the tube voltage was set at 80 KVp while changing the distance. Irradiate with X-rays, and use XD-3R (manufactured by Konica Corporation) as a developer and XF-3R (manufactured by Konica Corporation) as a fixer, and process at 35°C for 45 seconds with a roller conveyance automatic development 1sRX-501 (manufactured by Konica Corporation). Processing (Dry-t.

Dry).

Sensitivity evaluation was performed for each sample developed as described above. Sensitivity is fog + L of sample ml.

The sensitivity is expressed as a relative value, with the reciprocal of the X-ray dose giving a blackening density of 0 being 100.

b. Measurement of MTF The obtained sample was subjected to intensifying screen NR-
100, a square wave chart was photographed, and the MTF was measured by the contrast method. In addition, MTF is spatial frequency 2
．． The value of 0 wood/mrn is shown. The higher the MTF value, the higher the sharpness.

Judgment of C3 image quality Similarly to sensitometry, using an intensifying screen NR-100, X-rays were irradiated at 80 KVp at a distance that gave a blackening density of 0.5 ± 0.1 after development, and the image was heated at 38°C. 5RX-50
1 Processed with an automatic processor.

When processed at a high temperature of 38°C, so-called roller marks are likely to form due to convex parts such as foreign matter attached to the roller.
Then, the silver image becomes rough, and an image that looks grainy to the naked eye is obtained. This rough texture was judged as roughness.

The following sublimation was used as a criterion.

O No roughness △ Beginning of roughness. Limit to withstand use × Rough and unbearable to use (results) As understood from the data in Table 1, the sample of the present invention has
The MTF value is high, so the sharpness is good, the sensitivity is maintained, and the roughness of the image is improved.

Example-2 (1) Preparation of photosensitive emulsion 30 g of gelatin in 11 water, thioether (HO(CHI)ZS(CH2)2S(C)12)25
(CH2), OR) 10 ml of a 0.5% aqueous solution was added and dissolved, and the mixture was kept at 65°C.

In this solution (pAg = 9.1, pH = 6.5), 0.88 mol of nitric acid was dissolved with stirring; 30 mβ and 0.
A mixed solution of 88 mol of potassium iodide and potassium bromide (
Molar ratio 96.5: 3.5) 30ml! and 1 molar silver nitrate solution 600 IIIE simultaneously for 15 seconds.
and potassium bromide and potassium iodide in a molar ratio of 96.5:3.5 M600+nj! and 70
A tabular ashy odor northern limit emulsion was prepared by adding them in portions. The obtained tabular silver halide grains had an average grain size of 1.
18 μm, thickness 0.15 μm, silver iodide content 3.
It was 5 mol%. This emulsion was desalted in the same manner as in Example 1, and then chemically sensitized using gold and sulfur sensitization.
Chloro-3-potassium bromide 10.5g, (3-sulfonatepropyl)benzoxapurine-2
-ylidenemethyl-1-butene)-3=penzooxazoliopropanesulfnate) 150 mol/1 mole of halogenated compound was added, and then 4-hydroxy-6-methyl-1° was added in the same manner as in Example 1. 3.3a,? - Tetrazyden was added to obtain a green-sensitive silver iodobromide emulsion.

(2) Preparation of emulsion with internal pores CuBr1 grains containing 3.0 mol % of Cur with an average grain size of 0.2 μm were prepared by the method of Example 2 of JP-A-58-116535. It was subsequently covered with light without washing with water or desalting. After that, the same
A coating was formed by the same operation using an appropriate amount of the solution, followed by water washing and desalting treatment as in Example 1 in JP-A-58-116.535, redispersion in an aqueous gelatin solution, and then mercapto of the following formula. 200 per mole of silver halide compound
(3) Preparation of test sample A test sample was prepared in the same manner as in Example-1.

(4) Test method for test sample The sample prepared as described above was used in Example 1 using the X-ray photographic intensifying screen NR-100 as KO-250 (Konica Corporation).
A test was conducted in the same manner as in Example 1, except that the material was changed to (manufactured by). Further, a 30 cm x 3 Q cm sample was uniformly exposed to light so that the transmitted light blackening density was 1.0 under the above processing conditions, and the color tone of the sample developed under the same conditions was visually observed.

In this example, the following compounds were used for comparison with the compound represented by the general formula (1) according to the present invention.

(c) As can be understood from the data in Table 2, the samples of the present invention have a high MTF value, therefore have good sharpness, maintain sensitivity, and have improved image roughness. [Effects of the Invention] According to the present invention, it is possible to provide a photographic material that has improved sharpness and graininess, has high sensitivity, and has a good developed silver tone.

Claims (1)

[Scope of Claims] 1. In a silver halide photographic material having a light-sensitive silver halide emulsion layer containing light-sensitive silver halide grains on both sides of a support, at least one of the light-sensitive silver halide emulsion layers A hydrophilic colloid layer containing at least a compound represented by the following general formula [I] is provided between the layer and the support, and at least one of the hydrophilic colloid layers and/or the photosensitive halogen 1. A silver halide photographic light-sensitive material, wherein at least one of the silver halide emulsion layers contains internally covered metal salt particles. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ R^1; Alkyl group, aryl group, ester group, or carboxyl group having 1 to 6 carbon atoms R^2; H, alkyl group having 1 to 4 carbon atoms or benzyl group R^3: H, alkyl group or aryl group R^4, R^5; each H or R^4 is R^6, R
^5 is an atomic group necessary to form a 5- to 6-membered ring with R^7 R^6, R^7; each alkyl group or aryl group, ester group n; 1, 2 or 3 m; 0 or 1 represents. However, each of the above groups includes those having a substituent.