JPH0227340A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To decrease the fogging of images and to enhance gradation and graininess by subjecting the photosensitive material contg. specific compds. to image exposing then to auxiliary exposing. CONSTITUTION:One or more kinds of the compds. expressed by the formula I or II are incorporated into the emulsion layers of the title photosensitive material or the adjacent layers thereof. The images are formed by subjecting this photosensitive material to image exposing then to auxiliary exposing. In the formulas, R<1>, R<2> denote H, hydroxy, etc.; Z<1> denotes H, amino, etc.; M denotes H, ammonium, etc.; n<1> denotes 1-6; Z<2> denotes H, -COOM, etc.; m denotes 0-10. The addition of the above-mentioned compds. at a desired ratio in the stage from chemical maturation before coating is possible and the execution of the auxiliary exposing just before the development is possible as well.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material, and relates to the processing of a silver halide photographic light-sensitive material to obtain an image with less fog and improved gradation and graininess. It is about the method.

[Background of the invention]

There are known methods for changing the contrast of silver halide photographic materials, such as post-exposure during the photographic processing process, pre-exposure before photographing, and sub-exposure after image exposure. When a photographic light-sensitive material is irradiated with negative light, it adds to the original exposure for recording an image.
It is well known that fog development occurs and images with low contrast are obtained.

[Purpose of the invention]

A drawback of providing a second exposure or sub-exposure other than the original exposure as described above is that it increases fog on the photosensitive material. A second drawback is that the image becomes too soft in tone than necessary.

The present invention has been made in view of these drawbacks, and it is an object of the present invention to provide a method for processing a silver halide photographic light-sensitive material in which fog is less likely to occur in a sub-exposure method for tone adjustment.

A second object is to provide a method for processing a silver halide photographic light-sensitive material that does not cause the gradation to become too soft and does not change the photographic properties in the region of medium density or higher.

A third object is to provide a method for processing a silver halide photographic light-sensitive material that produces an image after development with good graininess.

[Structure of the invention]

In order to achieve the above-mentioned object, the inventors of the present invention have conducted a wide range of studies and found that a 10-silver-genide photographic light-sensitive material No. 2 having at least one layer of 10-silver-genide emulsion on a support has the emulsion The layer and/or its adjacent layer is a silver oxide photographic material containing at least one compound represented by the following general formula CI) or (II), and after imagewise exposure, sub-exposure is performed. This was achieved using a silver halide photographic material that is characterized in that it is developed after being given a .

In the formula, R1 is a hydrogen atom, a hydroxy group, an alkyl group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, etc.), and these alkyl groups are substituted. It may have a group (e.g. carboxymethyl group, carboxyethyl group, etc.), an aryl group (e.g. 1f phenyl group, etc.), -000M group, -3
03M group, M represents a hydrogen atom, an alkali metal atom (eg, sodium, potassium, etc.) or an ammonium group.

Zl is a hydrogen atom, an amino group (for example, an unsubstituted amine group,
Alternatively, the substituted amino group may include a dimethylamino group, diethylamino group, methylamino group, dicarboxyethylamino group, etc., and may also include a nitrogen atom to form a heterocycle (for example, a pyrrolidine ring, an imidazole ring, a morpholine ring, etc.)
000M group, -SO,M group (M represents a hydrogen atom, an ammonium group, or an alkali metal atom (eg, sodium, potassium, etc.). n I represents an integer of 1 to 6.

These compounds are described, for example, in JP-A No. 51-102639, JP-A No. 53-28426, JP-A No. 57-16734, JP-A No. 5
It can be easily obtained by the general synthesis method described in Japanese Patent Publication No. 7-26848 and Japanese Patent Publication No. 48-35494.

Next, specific examples of the compounds represented by the general formulas [■] and (II) of the present invention are shown below, but the present invention is not limited thereto.

The general formula (1) of the present invention can be simplified to the following general formula (
Since it can be represented by I[), the general formula [I[[) is used as the basic skeleton of the specific compound example.

General formula [■] General formula (I [I) R2 in the formula represents the same meaning as RI shown in the above general formula (1), and z2 represents a hydrogen atom, -C00M group, -3O,M group. where M has the same meaning as M in the above-mentioned general formula [I].

nl represents O or 1 to 6, and m represents an integer from θ to lO.

Compounds of general formula (It) When using the compounds of general formulas CI) and (I[) according to the present invention in a silver halide emulsion, it is preferable to dissolve them in water or a suitable organic solvent before adding them. .

Although it may be added at any time during the emulsion manufacturing process, it is preferably added during chemical ripening, particularly during the process from chemical ripening to coating.

Although the amount added is not uniform depending on the compound, it may be 1xlO-2 mol-1XlO-11 mol per mol of silver halide, particularly preferably 2 x 10-' mol to 7X1().
It's a bow mole.

Next, as a sub-exposure method of the present invention, it may be carried out at any time after imagewise exposure of the light-sensitive material and before it is placed in a developing bath, but preferably immediately before development.

The exposure condition is to use light of 600 nm or more (preferably, but not necessarily limited). Exposure amount (high sensitivity) The silver halide grains contained in the silver halide photographic light-sensitive material of the present invention are silver halide containing silver iodide, and can be any of silver iodochloride, silver iodobromide, and silver chloroiodobromide. In particular, silver iodobromide is preferred from the standpoint of obtaining high sensitivity.

The average silver iodide content in such silver halide grains is 0.5 to 10 mol%, preferably 1 to 8 mol%,
Inside the grain, there is a localized portion in which silver iodide is localized at a high concentration of at least 20 mol %.

In this case, the inside of the particle is preferably located as far inward as possible from the outer surface of the particle, particularly within 0.000 m from the outer surface. O
It is preferable that the localized portion exists at a distance of 1 μm or more.

Further, the localized portion may exist in a layered manner inside the particle, or may have a so-called core-shell structure, with the entire core serving as the localized portion. In this case, it is preferable that part or all of the core part of the grain, excluding the inner part with a thickness of 0.01 μm or more from the outer surface, is a localized part with a silver iodide concentration of 20 mol % or more.

In addition, the concentration of silver iodide in the localized portion is 30 to 40
The preferred range is mole %.

The outside of such localized areas is usually coated with silver halide without silver iodide.

That is, in a preferred embodiment, the distance from the outer surface is 0.0
1μm or more, especially 0. Silver halide (usually silver bromide) in which the shell portion of ~1.5 μm thick does not contain silver iodide
is formed.

In the present invention, from the inside of the particle (preferably from the outer wall of the particle)
．． At least 2
A method for forming a localized portion of silver iodide at a high concentration of 0 mol % or more may be one that does not use seed crystals.

If seed crystals are not used, the reaction liquid phase containing the protected gelatin (
Since there is no silver halide that can serve as growth nuclei in the mother liquor (hereinafter referred to as mother liquor) before the start of ripening, first, silver ions and halide ions containing high concentration iodine ions of at least 20 mol % are supplied to form growth nuclei. let Then, addition and supply are continued to grow particles from the growth nuclei. Finally, a shell layer having a thickness of 0.1 μm or more is formed from silver halide containing no silver iodide.

If seed crystals are used, at least 20 mol% of the seed crystals alone
The above silver iodide may be formed and then covered with a shell layer. Alternatively, the amount of silver iodide in the seed crystal is set to 0 or within the range of 10 mol % or less, and at least 20 mol % of silver iodide is formed inside the grain in the step of growing the seed crystal, and then the shell layer is formed. It may be coated with

In the silver halide photographic light-sensitive material according to the present invention, at least 50% of the silver halide grains present in the emulsion layer are
% of grains having localized silver iodide portions as described above.

A preferred embodiment of the silver halide photographic light-sensitive material of the present invention uses silver halide grains having a regular structure or morphology and having localized silver iodide portions as described above.

The term "silver halide grains with a regular structure or morphology" as used herein means grains that grow isotropically without including anisotropic growth such as twin planes, such as cubic, tetradecahedral, octahedral, It has a shape such as a spherical shape.

A method for producing such regular silver halide grains is known, for example, as described in J. Phot, Sci., 5, 332 (1
961), Ber.

Bunsenges, Phys, Chem, 67, 94
9 (1963), Int-ern.

Congress Photo, Sei, Tokyo (
1967) and others.

Such regular silver halide grains can be obtained by adjusting the reaction conditions when growing silver halide grains using a simultaneous mixing method. In such a simultaneous mixing method, silver halide grains are produced by adding approximately equal amounts of a silver nitrate solution and a silver halide solution to an aqueous solution of a protective colloid while stirring vigorously.

The supply of silver ions and halide ions is necessary and sufficient for the growth of only existing grains, without dissolving the existing crystal grains as the crystal grains grow, and conversely not allowing the generation and growth of new grains. The critical growth rate to supply silver 10genide,
Alternatively, it is preferable to increase the growth rate continuously or stepwise within the allowable range. As for this increasing method, Japanese Patent Publications No. 48-36890 and No. 52-163
No. 64 and JP-A-55-142329.

This critical growth rate is determined by the temperature, pH, pAg, degree of stirring,
Composition, solubility, particle size, interparticle distance of silver halide grains,
Although it varies depending on crystal habit, type of protective colloid, temperature, etc., it can be easily determined experimentally by methods such as microscopic observation of emulsion particles suspended in a liquid phase and turbidity measurement.

In a preferred embodiment of the present invention, it is desirable that at least 50% by weight of the silver halide grains contained in the silver halide emulsion layer be regular grains as described above.

Another preferred embodiment of the present invention is to use a monodisperse emulsion having a localized silver iodide portion as described above.

The monodisperse emulsion referred to herein means, for example, Tbe
Photographic Journal, 79
．． Trivelli in 330-338 (1939),
At least 95% of the particles, by number or weight, are within ±40% of the mean particle diameter, preferably ±30%, when the mean particle diameter is measured by the method reported by
A silver halide emulsion that is within the range of

Such monodisperse emulsion grains are made using simultaneous mixing techniques, similar to ordered silver halide grains. The conditions for simultaneous mixing are the same as those for producing regular silver halide grains.

Methods for producing such monodispersed emulsions are known, for example, J. Ph.
ot, Sic, 12.242-251 (1963
) JP-A-48-36890, JP-A No. 52-16364,
JP-A-55-142329, JP-A-58-49938
It is stated in each publication of the issue.

In order to obtain the above-mentioned monodispersed emulsion, it is particularly preferable to use seed crystals and to supply silver ions and halide ions using the seed crystals as growth nuclei to grow grains.

The broader the particle size distribution of this seed crystal, the wider the particle size distribution of the particle growth nuclei. Therefore, in order to obtain a monodisperse emulsion, it is preferable to use seed crystals with a narrow particle size distribution at the seed crystal stage.

The silver halide grains as described above used in the silver halide photographic light-sensitive material of the present invention include, for example, T, H, J am
“The Theory or the Ph” by es
otographic Process” 4th edition, Ma
Neutral method, acidic method, ammonia method, forward mixing, back mixing, double jet method, control daughter full jet method, conversion method, core/ It can be manufactured by applying a method such as the Fell method.

Further, the silver halide emulsion containing these silver halide grains or shiso grains may contain various heavy metal salts such as iridium salts and rhodium salts to improve photographic characteristics.

Furthermore, during the growth process of these silver halide grains, the outer surface of the grains is improved by temporarily placing the pAg of the mother liquor containing the protective colloid in a state of excess bromine ions of at least 10.5, particularly preferably 11.5 or more. of (11
1) The effects of the present invention can be further enhanced by rounding the particles by increasing the surface area by 5% or more.

In this case, the increase rate of the (Ill) plane is relative to that before passing through the above-mentioned I) Ag atmosphere of 10.5 or more, and especially the increase rate of the (111) plane is 10% or more, more preferably It is preferably 10 to 20%.

The outer surface of the silver halide grain is the (111) plane or the (10
0) Which side is covered, or how to measure the ratio, can be found in the report by Ma Hirata, “
Butylene of Japan” (Bu
letin of the 5ociety ofS
scientific photography of
Japan) No., pages 13.5-15 (1963
)It is described in.

In the present invention, during grain growth before chemical sensitization, the mother liquor containing protective colloid is passed once through an atmosphere in which I)Ag is at least 10.5, so that the (111) plane is It can be easily confirmed whether the increase is 5% or more.

In this case, the above f) Ag is added before chemical sensitization, but preferably from the time when silver ions are subjected to cold force a for the growth of silver halide grains to before the desalting process, especially when silver ions are added. It is preferable to do this after the completion of the sensitization, but before the so-called desalting step which is usually carried out before chemical sensitization. This is because it is easy to obtain a monodispersed emulsion with a narrow particle size distribution.

In addition, aging in an atmosphere where pAg is 10.5 or more,
It is preferable to do this for 2 minutes or more.

By controlling pAg in this manner, the number of (111) planes increases by 5% or more, resulting in a rounded shape.

When the average grain size of the silver halide grains used in the present invention is larger than 3.0μ, the graininess deteriorates significantly;
Furthermore, the sensitizing effect cannot necessarily be obtained, and the object of the present invention cannot be achieved. On the other hand, when the average particle size is smaller than 0.2 μ, the sensitivity decreases significantly, making it impossible to obtain the desired sensitivity and monolithic curve. The average grain size of the silver halide grains in the present invention is preferably in the range of 0.4 to 1.7 microns.

The silver halide emulsion of the present invention is prepared by adding a pAg suitable for chemical sensitization by an appropriate method after the growth of silver halide grains is completed.
or ion concentration. For example, the flocculation method and the noodle washing method, Research Disclosure 17643
Research Disclosure No. 176
No. 43).

Further, in the present invention, an emulsion may be used alone,
Two or more types of silver halide emulsions having different average grain sizes may be used in combination.

In this case, the silver halide composition of each emulsion may be different or the same.

Chemical sensitization methods applied to silver halide grains as described above include, for example, sulfur sensitization methods using sodium thiosulfate, thiourea compounds, etc., and gold sensitization methods using chlorauric acid salts, gold trichloride, etc. There are reduction sensitization methods using , thiourea dioxide, stannous chloride, silver ripening, etc., palladium sensitization methods, selenium sensitization methods, etc., and these methods can be used alone or in combination of two or more. It's a monkey. In this case, it is particularly preferable to use gold sensitization and sulfur sensitization together.

In addition to the above-mentioned sulfur sensitization method, selenium sensitization method can also be used for the silver halide emulsion used in the present invention. For example, U.S. Pat.
The method described in Japanese Patent Publication No. 44-15748 can be used.

When a mixture of two or more emulsions is used, the emulsions may be mixed and chemically sensitized, or each emulsion may be chemically sensitized individually and then mixed.

The silver halide grains of the present invention have I
Noble metal ions such as r, Rh, Pt, and Au can be added and included inside the particles, and also have a low pA
Reduction-sensitizing nuclei can be provided inside the particles using a g atmosphere or a suitable reducing agent. Furthermore, if the sensitivity of the optically sensitized material is kept at the same sensitivity level as that before sensitization, it is possible to make the silver halide grains finer, thereby obtaining products with excellent image quality, pressure resistance, etc. I can do it.

In the silver halide photographic material of the present invention, the emulsion can be optically sensitized. There are no particular limitations on the optical sensitizer, and for example, known optical sensitizers commonly used for optical sensitization of silver halide emulsions, such as cyanine dyes and merocyanine dyes, can be used.

The hydrophilic colloid for dispersing the silver halide grains used in the present invention is most preferably gelatin, but in order to further improve the binder properties, gelatin derivatives, other natural hydrophilic colloids such as albumin, casein, agar, etc. may be used. , gum arabic, alginic acid and its derivatives such as salts, amides and esters, starch and its derivatives, cellulose derivatives such as cellulose ethers, partially hydrolyzed cellulose acetate, carboxymethyl cellulose etc., or synthetic hydrophilic resins such as polyvinyl alcohol, polyvinyl Homo- and copolymers of pyrrolidone, acrylic acid and methacrylic acid or derivatives thereof, such as esters, amides and nitriles, vinyl polymers,
For example, vinyl ethers and vinyl esters can be used.

During rapid processing using an automatic processor, it is desirable that the amount of gelatin in the silver rodanide photographic light-sensitive material be as small as possible in order to improve drying properties. On the other hand, when the amount of gelatin decreases, its protective colloidal properties decrease, making pressure marks more likely to occur during roller conveyance. Therefore, the amount of gelatin used in the silver halide photographic light-sensitive material according to the present invention is based on the weight of silver corresponding to the silver halide used.
The weight ratio (gelatin amount/silver amount) is preferably 0.4 to 0.8.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention has stabilizers and fog suppressants such as those described in US Pat. No. 2,444,607 and US Pat. No. 2,716.
No. 062, No. 3,512,982, No. 3,342
, No. 596, German Patent No. 1,189,380, German Patent No. 2
Specifications of No. 05,862 and No. 211.841, Japanese Patent Publication No. 43-4183, Japanese Patent Publication No. 39-2825, and Japanese Patent Publication No. 1977-5
0-22626, 50-25218, etc. may be applied, and a particularly preferred compound is 4-hydroxy-6-methyl-1,3. ,3a,7-chitrazaindene,
5.6-drimethylene-7-hydroxy-S-triazolo(1,5,-a)pyrimidine, 5.6-titramethylene-7-hydroxy-s-triazolo(1°5-a)pyrimidine, 5-methyl-7-hydroquine-S Triazolo (
1,5-a) pyrimidines, 7- and droxys-triazolo(1,5-a) pyrimidines, gallic acid esters (e.g. isoamyl gallate, dodecyl gallate, propyl gallate, sodium gallate, etc.), mercaptans (
For example l-7enyl-5-mercaptotetrazole, 2
-mercaptobenzthiazole, etc.), benztriazoles (e.g., 5-bromobenztriazole, 4-methylbenztriazole, etc.), benzimidazoles (e.g., 6-nidropenzimidazole, etc.), and the like.

The silver halide photosensitive material according to the present invention can be prepared using a photographic hardening agent commonly used in its coating solution, such as an aldehyde-based hardener or an aziridine-based hardener (for example, PB Report, 19.921. U.S. Pat. No. 2,950.197, Same No. 2,964,404
No. 2.983,611, No. 3,271,17
Specifications of No. 5, Japanese Patent Publication No. 46-40898, Japanese Patent Application Publication No. 1973
No. 0-91315), inoxazole systems (for example, those described in U.S. Pat. No. 331.609), and epoxy systems (for example, U.S. Pat. No. 3.04).
7,394, West German Patent No. 1,085,663, British Patent No. 1.033,518, and Japanese Patent Publication No. 1973-
35495), vinyl sulfone type (e.g. 1fPB Revoto 19,920. West German Patent No. 1)
, 100,942, British Patent No. 1,251,091, Japanese Patent Application Publication No. 45-54236, Japanese Patent Application Publication No. 48-110996, US Patent No. 353.964, Japanese Patent No. 3.490,91.
1), acryloyl type (e.g. Japanese Patent Application No. 48-27949, U.S. Patent No. 3,640,
No. 720), carbodiimides (for example, those described in U.S. Patent No. 2.938.892, Japanese Patent Publication No. 46-38715, and Japanese Patent Application No. 15095-1982) , other maleimide-based, acetylene-based, methanesulfonic acid ester-based, triazine-based, and polymer hardening agents can be used. In addition, thickeners such as those described in U.S. Pat.
0,404 specification, Japanese Patent Publication No. 43-4939, and Japanese Patent Application Laid-Open No. 48-63716), as well as Latin laths such as U.S. Patent No. 766.979 and French Patent No. 1,395,554. Specifications of each issue, Special Publication No. 1973-
43125, and as a matting agent, those described in British Patent No. 1,221.980 can be used.

Desired coating aids can be used in the constituent layers of the silver halide photographic material according to the present invention, such as saponin or sulfosuccinic acid surfactants, such as those described in British Patent No. 548,532, esp. Gansho 47-89630
or as anionic surfactants, for example, Japanese Patent Publication No. 43-18166,
U.S. Patent No. 3,514,293, French Patent No. 2,
Specifications of No. 025,688, ``Special Publication No. 43-1024
Those described in Publication No. 7 etc. can be used.

In the silver halide photographic material according to the present invention, a dye can be used in the layer below the emulsion layer of the present invention in contact with the support in order to reduce the so-called crossover effect, and also to improve the sharpness of the image. Dyes can be added to the protective layer and/or the emulsion layer of the present invention to improve the properties or reduce capri caused by safe light. As such a dye, any known dye for the above purpose can be used.

In addition, in order to apply the emulsion of the present invention to a color photosensitive material, the emulsion of the present invention adjusted to have red sensitivity, green sensitivity, and blue sensitivity is combined with cyan, magenta, and yellow couplers to be contained in the color photosensitive material. The methods and materials used should be appropriate.

Useful couplers include closed methylene-based yellow couplers, pyrazolone-based magenta couplers, and 7-enol-based or naphthol-based cyan couplers.These couplers can be combined with colored couplers for automasking (e.g., when the active site of the coupler has a bonding group). couplers with a split-off group having an azo group), osazone-type compounds, development-diffusive dye-releasing couplers, development inhibitor-releasing compounds (development-inhibiting compounds that react with the oxidized form of an aromatic primary amine developing agent) compounds that release compounds, including both so-called DIR couplers, which react with oxidized forms of aromatic primary amine developing agents to form colored dyes, as well as so-called old R substances, which form colorless compounds)
It is also possible to use Further, in order to incorporate these couplers into a silver halide color photographic light-sensitive material, various known techniques conventionally used for couplers can be applied.

The silver halide photographic material of the present invention can be obtained by coating the above-mentioned emulsion on a support.

In the silver halide photographic material according to the present invention, when two or more types of silver halide emulsions having different average grain sizes are used, they can be individually decomposed into films and coated on the support. , or can be mixed and applied.

The support used in the silver halide photographic emulsion of the present invention is
It includes all known materials, such as polyester films such as polyethylene terephthalate, polyamide films, polycarbonate films, styrene films, baryta paper, and papers coated with synthetic polymers. The emulsion of the present invention can be coated on one or both sides of the support, and when coated on both sides, the emulsion can be applied symmetrically or asymmetrically with respect to the support.

Although the present invention is applicable to all silver halide photographic materials, it is particularly suitable for high-sensitivity black-and-white or color negative photographic materials. When applied to medical X-ray radiography, for example, a fluorescent intensifying screen whose main component is a phosphor that emits near-ultraviolet to visible light upon exposure to penetrating radiation is coated on both sides with the emulsion of the present invention. It is desirable that both surfaces of the silver halide material according to the present invention are exposed to light. The penetrating radiation herein refers to high-energy electromagnetic waves, and means X-rays and γ-rays. And here, the fluorescent intensifying screen refers to, for example, an intensifying screen whose main fluorescent component is tungsten oxide (CaWO*),
It is a fluorescent intensifying screen whose main fluorescent component is a rare earth compound activated with terbium.

The silver halide photographic material according to the present invention can be developed by a commonly used known method. The black and white developer is a commonly used developer such as hydroquinone, l-phenyl-3-pyrazolidone, N-methyl-p-
Those containing aminophenol or p-phenyl diamine alone or in combination of two or more thereof are used, and other commonly used additives can be used.

Further, when the light-sensitive material is for color use, color development can be carried out by a commonly used color development method.

Developers containing aldehyde hardeners can also be used in the silver halide photosensitive material of the present invention, such as dialdehydes such as maleic dialdehyde, glutaraldehyde and their sodium bisulfite salts, etc. Developers known in the photographic field may also be used.

〔Example〕

Examples of the present invention will be described in detail below. Note that, as a matter of course, the present invention is not limited to the embodiments described below.

Example - ■ Monodisperse cubic silver iodobromide containing 2.0 mol% of silver iodide with an average grain size of 0.28 μm was prepared by the double jet method while controlling 60° CSpAg-8.0 and pH = 2.0. A crystal emulsion was obtained. A portion of this emulsion was used as a core and grown as follows. That is, an ammoniacal silver nitrate solution and a solution containing potassium iodide and potassium bromide were added to the solution containing the core particles and gelatin at 40°C, pAg 9.0, pH 9.0 using a double jet method, and silver iodide was added at 30°C. 1st containing mol%
A coating layer was formed. Further, I) Add an ammoniacal silver nitrate solution and a potassium bromide solution using a double jet method at Ag=9.0 to form two coating layers of pure silver bromide, with an average silver iodide content of 2.0 mol%. Cubic monodisperse silver iodobromide emulsions with various average grains were prepared.

The particle size of the silver halide grains was controlled by adjusting the amount of core grains and the amount of silver halide added. Table 1 shows the average grain sizes of these emulsions.

Next, in water IQ, 30 g of gelatin 1 10.5 g of potassium bromide
g, thioether (110(CFIz)xs(CHz)zs(CL)is
(CL)zol() 0.5wt% water-soluble 10Il+2 was added and dissolved in the solution kept at 65 °C (pAg = 9
．． A mixed solution of 0.88 mol silver nitrate solution (30 ml) and 0.88 mol potassium iodide and potassium bromide (molar ratio 96.5:3.5) was added to pH-6.5) with stirring.
After simultaneously adding 30ml of silver nitrate for 15 seconds, 1mol of a mixed solution of 600N+12 of silver nitrate and potassium bromide and potassium iodide in a molar ratio of 96.5:3.5 was added over 70 minutes. When added at the same time, the average particle size is 1.
The volume is 18 μl, the thickness is 0.15 μm, and the silver iodide content is 3.
A 5 mol % tabular silver iodobromide emulsion was prepared. Next, tabular silver iodobromide emulsions having various average grain sizes were prepared in the same manner by adjusting the amounts of silver and halide added and the temperature during grain formation. Table below shows the average particle size of these particles.
Shown in 2.

After removing excess salt by coagulation-precipitation, 8X of chloroauric acid per mole of silver halide was added to these emulsions.
10-' mol, sodium thiocyanate 7X 10-'
Add 7 x 10-' mol of ammonium thiocyanate, perform optimal gold/sulfur sensitization, and further add the following sensitizing dyes (A) and (B) and potassium iodide I x 10-'
Optimal spectral sensitization by adding 1 mol AgX? Where was it?

Sensitizing dye (A) 600 mg/AgX mol Sensitizing dye (B) 20 mg/AgX mol C2H6CxHs After completion of spectral increment sensitization, all emulsions were mixed at the weight ratio shown in 3, and then halogenated as an emulsion layer additive. 90 g lime-processed ossein gelatin, 40 g tert-butyl-catechol (1++ g, 4-hydroxy-6-
Methyl-1,3,3a,7-chitrazaindene 3g, polyvinylpyrrolidone (molecular weight 10,000) 1.0g
, 2.5 g of styrene/maleic anhydride copolymer, 10 g of trimethylolpropane, 5 g of diethylene glycol
g1 Nitrophenyl-triphenylphosphonium chloride 50 mg% 1.3-dihydroxybenzene-4-ammonium sulfonate 4 g12-Mercaptobenzimidazole-5-sulfonate sodium 15 mg.

sodium chloride mg 10mg.

rags 0■ O3Na 1,1-dimethylol-1-bromo-1-nitromethane IO mg.

In addition, the compounds shown in Table 4 were added to prepare an emulsion layer coating solution.

In addition, the following compounds were added as protective layer additives to prepare a protective layer coating solution. That is, 1g of gelatin, C4FISO3K

3+*gCsF + so(CH
*CHZOu”TTCH,CH,OH
511g Glyoxal 30mg Matting agent consisting of polymethyl methacrylate with an average particle size of 5 μm 7 rig
, 70mg of colloidal silica with an average particle size of 0.023μm
etc. were added.

Each of the above-mentioned emulsion layer coating solutions, together with this protective layer coating solution, were coated on both sides of a 180 μm thick undercoated, blue-colored polyethylene terephthalate support with a silver content of 2.4 g/m'' on one side. Gelatin is 3 on one side.

Sample 1-13 was obtained by coating at a concentration of 8 g/l.

These samples were exposed using an X-ray photographic intensifying screen Ko-250 (Konica Corporation) using scissors and an aluminum wedge under X-ray exposure conditions of 80 KV, 100 mA, and 0.04 sec at a distance of 2.7 m from the X-ray tube. It was exposed using

After exposure, each sample was divided into two parts, one of which was exposed to KX manufactured by Konica Corporation.
-500 automatic processor, and on the other hand, a Hi-Vision Safelight HVS-15FL manufactured by Kyoritsu Medical Electric Co., Ltd. with a compensation filter attached is installed in the insertion opening of the KS500, and the sub-exposure is performed when inserting the film. was given and processed.

From the obtained characteristic curve, the pace density and fog density 10, l
Let the absolute value of the logarithm of the exposed X-ray dose be S, and the absolute value of the logarithmic value of the exposed X-ray dose that gives the pace density +1.0 be S2, and the points of density 1.0 and 2.0. When the slope of the straight line connecting the two is θ, tan θ was determined as γ (gamma) and is shown in Table 4 below.

In addition, the graininess is rR measured with an aperture diameter of 48μ.
Evaluation was made based on MsJ graininess (however, at an optical density of 1.2). Regarding rRMsJ granularity, see T.H. James (ed.): The Theory.
Of the Photographic Process (The T
theory of Photographic Pro
cess) (1977, Macmillan)pp
619-620.

Note that the lower the RMS value, the better the graininess.Table 4
As shown in Figure 2, comparative samples 1.2.5 and 12 had F.
Since the increase in og is significant and the decrease in γ is large, the gradation becomes extremely soft. Further, the graininess does not change before and after sub-exposure.

On the other hand, the sample of the present invention has almost no change in Fog,
Only the sensitivity at the base of the characteristic curve increases, and no decrease in γ is observed. That is, it can be seen that according to the present invention, the gradation in the middle density area remains unchanged, but the gradation in the low density area is improved.

Furthermore, as can be seen from the RMS value, the sample of the present invention has improved graininess.

〔Effect of the invention〕

As described above, according to the processing method of the present invention, an image with sharp gradations can be obtained without increasing Fog,
Moreover, a silver halide photographic material with improved graininess can be obtained.

Procedural amendment November 9, 1986

Claims (1)

[Scope of Claims] In a silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer on a support, the emulsion layer and/or its adjacent layer has the following general formula [I] or [ II
] A silver halide photographic light-sensitive material containing at least one of the compounds represented by:
1. A method for processing a silver halide photographic material, which comprises subjecting it to sub-exposure and then developing it. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (R^1 in the formula is a hydrogen atom, hydroxy group, alkyl group, aryl group, acyl group, -COOM group, -SO_3M
group, Z^1 is a hydrogen atom, an amino group, -COOM group, -S
represents an O_3M group, M represents a hydrogen atom, an ammonium group, or an alkali metal atom, and n^1 represents an integer of 1 to 6. ) General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (R^2 in the formula has the same meaning as R^1 in general formula [I], and Z^2 is a hydrogen atom, -COOM group, - In the SO_3M group, M has the same meaning as M in general formula [I]. n^1 represents 0 or 1 to 6, m represents 0 to 10.)