JPH0764240A - Silver halide photographic sensitive material and its processing method - Google Patents

Abstract

PURPOSE:To provide a silver halide photographic sensitive material enhanced in sharpness without drop of sensitivity and to provide its processing method. CONSTITUTION:This silver halide photographic sensitive material has at least each one photosensitive silver halide emulsion layer on both sides of a transparent support, and it is characterized by that the emulsion layer comprises flat silver halide grains having an aspect ratio of 1-5 in the >=50% projection areas of the total silver halide grains and the support is substantially composed of polyethylene-2, 6-naphthalate, and the sensitivities of the emulsion layers on both sides are different from each other by 2-10 times, and this photosensitive material is processed with a developing solution substantially not containing a hardener and replenished by <=25ml per a quarter size (10X12 inches).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material which is suitable for rapid processing and has improved sharpness.

[0002]

2. Description of the Related Art In medical light-sensitive materials, the sharpness of the image of X-ray film is extremely important in order to detect fine lesions at an early stage and appropriately diagnose them.

As a conventional sharpness improving means, for example,
A method in which a water-soluble dye is contained in the photosensitive layer and its adjacent layer (JP-A-50-28827, JP-A-57-185038, JP-A-1-15843).
0), but these cause a decrease in sensitivity, an increase in exposure dose, and when a high-sensitivity intensifying screen is used, the graininess deteriorates and the total image quality deteriorates.

When the main cause of sharpness deterioration is crossover light, it is considered that the emulsion is coated not on both sides but on only one side, but this method softens the photographic characteristics and processing. There is a large amount of residual silver and residual hypo after that, and deterioration (discoloration) of the silver image occurs when left after development, which is not preferable.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-mentioned drawbacks and to provide a silver halide photographic light-sensitive material having improved sharpness and a method of processing the same without causing a decrease in sensitivity.

[0006]

The above object of the present invention is to provide a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on both sides of a transparent support, wherein the emulsion layer has a projected area. Of tabular silver halide emulsion having an aspect ratio of 1 or more and less than 5 at least 50% of
And the support consists essentially of polyethylene-2,6-naphthalate, and the sensitivity of the emulsion layers on both sides of the support is
It has been solved by a silver halide photographic light-sensitive material characterized by a difference of 2 to 10 times.

Preferably, in the silver halide photographic light-sensitive material, the photographic characteristics of the emulsion on the high sensitivity side are such that the average contrast between the densities of 0.25 and 2.0 is 2 or less and the density of the emulsion on the low sensitivity side is 0.25 to 2.0. The average contrast between them is 2.5 or more.

In another embodiment, the silver halide photographic light-sensitive material is processed with a developer containing substantially no hardening agent, and the replenishing amount of the developer is cut into four and 25 ml or less per sheet. And a method of processing a silver halide photographic light-sensitive material characterized by

The present invention will be described in detail below.

The tabular silver halide grains according to the present invention have an average grain size of preferably 0.3 to 3.0 μm, particularly preferably 0.5 to 3.0 μm.
It is 1.5 μm.

The tabular silver halide grain of the present invention has an average value of grain diameter / thickness (called aspect ratio) (called average aspect ratio) of 1 to 5, preferably 2.5 to 4
Is.

The average thickness of the tabular silver halide grains of the present invention is preferably 0.5 μm or less, particularly preferably 0.3 μm or less.

In the present invention, the diameter of the silver halide grain is defined as the diameter of a circle having an area equal to the projected area of the grain from the observation of an electron micrograph of the silver halide grain. In the present invention, the thickness of a silver halide grain is defined as the minimum distance between two parallel planes constituting a tabular silver halide grain.

The thickness of tabular silver halide grains can be determined from electron micrographs of silver halide grains with shadows or electron micrographs of sample slices obtained by coating a support with a silver halide emulsion and drying. .

To obtain the average aspect ratio, the minimum
Measure 100 samples. In the silver halide emulsion of the present invention, the effect is obtained when the tabular silver halide grains account for 50% or more of all the light-sensitive silver halide grains.

The emulsion used in the present invention may be a single emulsion or a mixture of two or more kinds of emulsions.
The emulsions to be mixed may be emulsions according to the present invention, or may be normal crystals or twinned grains having an aspect ratio of less than 2.

The tabular silver halide emulsion of the present invention is preferably monodisperse, and the average grain size is ±
It is particularly preferable that the silver halide grains contained in the grain size range of 20% are 50% by weight or more.

The tabular silver halide emulsion of the present invention may have any halogen composition such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. Silver iodide or silver iodobromide is preferable, and the average silver iodide content is 0 to 5.0 mol%, particularly preferably 0.1 to 3.0 mol%.

The tabular silver halide emulsion of the present invention comprises
The halogen composition may be uniform within the grain or silver iodide may be localized, but those localized in the central portion are also preferably used.

A method for producing a tabular silver halide emulsion is described in, for example, JP-A Nos. 58-113926, 58-113927 and 58-113934.
No. 62-1855, European Patents 219,849, 219,85
You can refer to No. 0 etc. A method for producing a monodisperse tabular silver halide emulsion is disclosed in JP-A-61-664.
You can refer to issue 3.

As a method for producing a tabular silver iodobromide emulsion having a high aspect ratio, a silver nitrate aqueous solution or a silver nitrate aqueous solution and a halide aqueous solution are simultaneously added to a gelatin aqueous solution having a pBr of 2 or less to generate seed crystals. And then grown by the double jet method.

The size of tabular silver halide grains can be controlled by the temperature at the time of grain formation and the rate of addition of an aqueous silver salt and halide solution. The aspect ratio is calculated by the seed crystal preparation method, the thickness and the pAg, pH, and halogen composition during growth.
It can be controlled by aging time and temperature.

The average silver iodide content of the tabular silver halide emulsion can be controlled by changing the composition of the aqueous halide solution to be added, that is, the ratio of bromide to iodide.

For the tabular silver halide grains, a silver halide solvent such as ammonia, thioether or thiourea can be used at the time of production, if necessary. The grain growth may be carried out by supplying an aqueous solution containing silver ions and an aqueous solution containing halogen ions, or may be supplied as fine particles of silver halide. In this case, a combination of silver iodide, silver iodobromide, silver bromide, silver chlorobromide, silver chloride, a halogen ion-containing solution, a silver ion-containing solution and the like can be supplied.

The silver halide emulsion according to the present invention includes
Core / shell type or double structure type grains having a silver halide composition whose surface is different from the inside of the grain are also preferably used. The emulsion may be subjected to a water washing method such as a Noudel water washing method and a flocculation sedimentation method in order to remove soluble salts. As a preferred washing method, for example, Japanese Examined Patent Publication No. 35-160
Particularly preferable desalting method is a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in JP-A No. 86 or a method using G3, G8, etc., as an aggregation polymer agent described in JP-A-63-158644. .

The chemical sensitization method includes so-called sulfur sensitization,
Sensitization by Se compound, Te compound, gold sensitization,
Sensitization with a noble metal of Group VIII of the Periodic Table (for example, Pd, Pt, Id, etc.) and a combination of these can be used. Above all, a combination of gold sensitization and sulfur sensitization, or a combination of gold sensitization and Se compound is preferable. Further, it is also preferable to use it in combination with reduction sensitization.

It is preferable to supply iodine ions at the time of chemical sensitization or at the end of chemical sensitization from the viewpoint of sensitivity and dye adsorption. A method of adding in the form of fine grains of silver iodide is particularly preferable.

It is also preferable to carry out the chemical sensitization in the presence of a compound having adsorptivity to silver halide. Particularly preferred compounds are azoles, diazoles, triazoles, tetrazoles, indazoles, thiazoles, pyrimidines, azaindenes, particularly compounds having a mercapto group and compounds having a benzene ring.

The silver halide photographic light-sensitive material of the present invention is subjected to a reduction treatment, so-called reduction sensitization method, in which a reducing compound is added, and a silver ion excess state of pAg = 1 to 7 called silver ripening is passed. Method, p called high pH aging
It may be applied to the silver halide emulsion by a method of allowing a high pH state of H = 8 to 11 to pass. Further, these two or more methods can be used in combination.

The method of adding a reducing compound is preferable because the degree of reduction sensitization can be finely adjusted. The reducing compound may be an inorganic or organic compound, such as thiourea dioxide, stannous salt, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds, borane compounds, ascorbic acid and its derivatives, and sulfite. Examples thereof include salts, and particularly preferable examples include thiourea dioxide, stannous chloride and dimethylamine borane. The addition amount of these reducing compounds varies depending on the reducing property of the compound, the type of silver halide, the emulsion production conditions such as the dissolution conditions, and is 1 × 10 ⁻⁸ per mol of silver halide.
A range of up to 1 × 10 ^-2 mol is suitable. These reducing compounds are dissolved in water or an organic solvent such as alcohols and added during the growth of silver halide grains.

The silver halide photographic light-sensitive material of the present invention comprises
It is spectrally sensitized with methine dyes and other spectral sensitizing dyes. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. For these spectral sensitizing dyes, any of the heterocyclic nuclei and the like commonly used for dyes can be applied. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus,
Pyrrole nuclei, oxazole nuclei, thiazole nuclei, selenazole nuclei, imidazole nuclei, tetrazole nuclei, pyridine nuclei, etc., and nuclei in which an aliphatic hydrocarbon ring is fused to these nuclei,
That is, indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus,
A benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms.

The merocyanine dye or the complex merocyanine dye contains pyrazoline as a core having a ketomethine structure.
5-6 membered heterocyclic nuclei such as -5-one nucleus, thiobitantoin nucleus, 2-thiooxazolidine-2,4-dione nucleus, thiazoline-2,4-dione nucleus, rhodanine nucleus and thiobarbituric acid nucleus Can be applied.

These dyes are described, for example, in German Patent No. 929,
080, U.S. Patent No. 2,231,658, No. 2,493,748, No. 2,503,776, No. 2,519,001, No. 2,912,329,
No. 3,655,394, No. 3,656,959, No. 3,672,897
No. 3,649,217, British Patent No. 1,242,588, Japanese Patent Publication Sho
44-14030.

These sensitizing dyes may be used alone or in combination. Sensitizing dyes are often used in combination. As typical examples thereof, U.S. Pat.Nos. 2,688,545, 2,977,299, and 3,
397,060, 3,522,052, 3,527,641, 3,6
No. 17,293, No. 3,628,964, No. 3,666,480, No. 3,
No. 679,428, No. 3,703,377, No. 3,837,862, British Patent No. 1,344,281, and Japanese Patent Publication No. 43-4936. The sensitizing dye may be added at any time during grain formation, before and after chemical sensitization, during the sensitization, and before coating, but it is preferably added at several points.

Gelatin can be used as the hydrophilic colloid or binder used in the light-sensitive material of the present invention, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, hydroxyethyl cellulose, carboxymethyl cellulose, cellulose derivatives such as cellulose sulfates, sugar derivatives such as sodium alginate, dextran and starch derivatives. Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be used. In particular, it is preferable to use dextran or polyacrylamide having an average molecular weight of 5000 to 100,000 together with gelatin. Examples of these are, for example, JP-A-1-307738, 2-62532, 2-24748, 2-
44445, 1-66031, JP-A-64-65540, JP-A-63-1
No. 01841, 63-153538, etc.

As gelatin, lime-processed gelatin, acid-processed gelatin, enzyme-processed gelatin as described in Bull. Soc. Sci. Phot, Japan. No. 16, page 30 (1966), and gelatin derivatives ( For example, those obtained by reacting various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleinimide compounds, polyalkylene oxides and epoxy compounds ) Is included.

The silver halide photographic light-sensitive material of the present invention is provided with a sensitivity difference between the A-side and the B-side with the support interposed, and the sensitivity difference is 2 to 10 times. Then, it is more preferable to expose the high-sensitivity side on the photographing side.

Next, the polyethylene-2,6-naphthalate which is the support of the silver halide photographic light-sensitive material of the present invention will be described.

The term "polyethylene-2,6-naphthalate" as used in the present invention means a polymer whose constituent units are substantially composed of ethylene-2,6-naphthalate units, but a small amount, for example, 10 mol% or less, preferably Is 5 mol% or less of the third
Also included are ethylene-2,6-naphthalate polymers modified with components.

Polyethylene-2,6-naphthalate is generally a suitable compound of naphthalene-2,6-dicarboxylic acid or a functional derivative thereof such as methyl naphthalene-2,6-dicarboxylate and ethylene glycol in the presence of a catalyst. It is prepared by condensation under reaction conditions. In that case, as the third component, for example, adipic acid, oxalic acid, isophthalic acid, terephthalic acid, naphthalene-2,7-dicarboxylic acid,
Dicarboxylic acids such as diphenyl ether dicarboxylic acid or lower alkyl esters thereof, p-oxybenzoic acid, p
Dicaponic acid such as ethoxybenzoic acid, or a lower alkyl ester thereof or a dihydric alcohol such as propylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, diethylene glycol, polyethylene glycol or polytetramethylene glycol. Examples thereof include polyalkylene glycol.

In the polymerization, a lubricant such as titanium dioxide,
Stabilizers such as phosphoric acid, phosphorous acid and ester salts thereof, antioxidants such as hindered phenols, polymerization regulators and plasticizers may be added. Further, the polyethylene naphthalate used in the present invention has a limiting viscosity of 0.4 or more, preferably 0.55 to 0.9, because the mechanical stability decreases if the degree of polymerization is too low. The crystallinity is not too low for dimensional stability, and is preferably 35% or more and 60% or less. It is preferable that the polyethylene-2,6-naphthalate film of the present invention has a surface resistivity of 10 ¹⁴ Ω · cm or less, because the commercial value of the polyethylene-2,6-naphthalate film is reduced when dust is used during use. As a method of obtaining such a film,
Method of applying antistatic agent, method of forming thin film layer of metal or metal compound on film surface, method of adding antistatic agent during polymerization of polyester raw material, mixing of polyester raw material and antistatic agent during film formation The method of doing is appropriately used. Among these, polyethylene-2,6-naphthalene obtained by polycondensation in the presence of sodium alkylbenzenesulfonate as a raw material and polyalkylene glycol may be used.

In the polyethylene-2,6-naphthalene used in the present invention, 40 mol% or more of the monomers to be polymerized is dimethyl naphthalene-2,6-dicarboxylate, but preferably 60 mol% or more, It is preferably 80 mol% or more.

The surface of these supports may be provided with an undercoat layer, corona discharge, or irradiation with ultraviolet rays in order to improve the adhesion of the coating layer.

A method for producing the support used in the present invention will be described.

<Preparation of support> After adding a transesterification catalyst to 100 parts of dimethyl naphthalene-2,6-dicarboxylate and 60 parts of ethylene glycol, 1.2 parts of sodium dodecylbenzenesulfonate and 0.8 part of polyethylene glycol having a molecular weight of 8000. Polyethylene-2,6-naphthalate obtained by polycondensation by adding 0.01 part of syloid was melt extruded and the unstretched film was stretched 4.2 times at 170 degrees and further stretched 4.2 times in the transverse direction at 150 degrees. did. Heat set to 25
It was 5 degrees for 10 seconds. Thus, a film having a thickness of 100 μm was obtained. 70μm, 120 by changing the degree of stretching
A support of μm and 180 μm was obtained.

Undercoating treatment An undercoating treatment was carried out according to the method of Sample No. 9 of Example 1 of JP-A-52-104913.

The above-described silver halide photographic light-sensitive material of the present invention is processed with a developing solution containing substantially no hardening agent, and the replenishment amount of the developing solution is 25 ml or less per quadrant film. It The term "substantially free of a hardener" means that the concentration of the hardener in the use liquid state is 0.05 mol / l or less.

Conventionally, in high-temperature rapid processing, a hardener for gelatin such as glutaraldehyde has been used in a developing solution. According to this method, there is an advantage that a gelatin physical property that can withstand high-speed transportation by an automatic processor at a high temperature of, for example, 35 ° C. or more can be provided. However, it cannot be denied that the developing speed is reduced to a considerable extent, and the sensitivity and the maximum density are deteriorated. Further, in recent years, market demands for the environment have increased, and the glutaraldehyde odor contained in the developer is disliked because it gives an unpleasant feeling.

Therefore, by imparting an appropriate hardenability to the light-sensitive material itself, hardening with a developing solution is substantially unnecessary, and as a result, deterioration of developability can be avoided.

In the present invention, a silver halide photograph having the photographic performance aimed at by the present invention is obtained by processing with a developer not containing a hardening agent and a developer replenishment amount of 25 ml or less per quadrant film. A photosensitive material can be obtained.

The developing replenisher used herein may have the same composition as that of a commonly used developing solution. In the present invention, the replenishing amount may be 25 ml or less per quadrant film, preferably 20 ml to 10 ml. The replenishment timing is preferably a method in which a sensor attached to the developing machine detects the area of the processed photosensitive material and replenishes when the processed area reaches a prescribed amount. The minimum area for replenishment is preferably a hexagonal size.

Photographic processing of the light-sensitive material of the present invention is carried out, for example, by RD-17643, XX to XXI, pages 29 to 30 or 308119, XX to X.
Treatment with a treatment solution as described in XI, pp. 1011-1012 may be performed. This process may be a black and white photographic process that forms a silver image. Processing temperature is usually 18 ℃ to 50 ℃
It is processed in the range of.

Developers for black and white photographic processing include dihydroxybenzenes (eg hydroquinone), 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone), aminophenols (eg N-methyl-P-aminophenol). Etc. can be used alone or in combination. For the developer, known agents such as preservatives, alkaline agents, pH buffers, antifoggants, development accelerators, surfactants, defoamers,
You may use a color tone agent, a water softener, a solubilizing agent, a viscosity imparting agent, etc. as needed.

A fixing agent such as thiosulfate or thiocyanate is used in the fixing solution, and a water-soluble aluminum salt such as aluminum sulfate or potassium alum may be contained as a hardening agent. In addition, it may contain a preservative, a pH adjuster, a water softener and the like.

[0056]

EXAMPLES Examples of the present invention will be described below. Naturally, the present invention is not limited to the examples described below.

Example 1 (Preparation of seed emulsion) A seed emulsion Em-A having a high degree of monodispersity was prepared by the following method.

A1 Hydrogen peroxide treated ossein gelatin 11.3 g Potassium bromide 6.72 g DF-1 1.2 ml Water to make 1.13 l

[0059]

[Chemical 1]

B1 silver nitrate 170 g water to 227.5 ml C1 ossein gelatin 4.56 g potassium bromide 119 g water to 227.5 ml D1 ammonia water (28%) 66.6 ml 40 ° C. The liquid B1 and the liquid C1 were added by the double jet method to the liquid A1 which was vigorously stirred in the above step to generate nuclei. After the addition, lower the temperature of the mixed solution to 20 ° C and adjust the potential to 40 mV, and
Was added in 20 seconds and aged for 5 minutes.

Then, 30 g of modified gelatin (substitution rate 80%) in which the amino group of gelatin was substituted with a phenylcarbamoyl group was added, and after stirring, the pH was lowered to 3.0 to cause aggregation, and the supernatant was decanted. 2000 ml of water was added again, the pH was raised to 6.0, and the mixture was stirred and dispersed. Then p
H was lowered to 3.0 and decantation was performed in the same manner.

Furthermore, the above seed emulsion washed with water was redispersed using 23 g of ossein gelatin. When the seed emulsion was observed with an electron microscope, it was a monodispersed AgBr emulsion having an average grain size of 0.28 μm and a width of 20%.

(Preparation of tabular grains) A silver halide emulsion Em-1 mainly composed of tabular twin crystals was prepared using the seed emulsion Em-a and the solution shown below.

E1 ossein gelatin 6.49 g DF-1 1.2 ml The above seed emulsion 0.62 mol equivalent F1 ossein gelatin 1.69 g potassium bromide 107.2 g potassium iodide 2.30 g with water 504 ml G1 Silver nitrate 170 g Water 504 ml Fluorine F1 and G
Solution 1 was added by the control double jet method. The addition flow rate was controlled to 80% of the flow rate at which new nuclei were generated. During addition, the potential was kept at −10 mV at 65 ° C. by using an aqueous KBr solution for control.

After the addition was completed, after adjusting the pH to 6.0,
As a spectral sensitizing dye, the following sensitizing dye A was used as silver halide 1
After adding 283 mg per mol and allowing sufficient adsorption, precipitation desalting and washing with water were performed using a Kao Atlas demol aqueous solution and a magnesium sulfate aqueous solution.

[0066]

[Chemical 2]

Further, the above-mentioned emulsion washed with water was redispersed using 23 g of ossein gelatin. Emulsion is 50 ℃
The potential was 50 mV and the pH was 5.85.

About 3000 particles of Em-1 were observed and measured by an electron microscope to analyze the shape. The results were as follows.

Proportion of hexagonal tabular plate to the total projected area; 80% Average particle diameter of hexagonal tabular crystal (circle conversion); 1.40 μm Average particle thickness of hexagonal tabular crystal; 0.7 μm Average aspect ratio of hexagonal tabular plate; 2.0 Monodispersity: 10% The amount of seed emulsion used was adjusted, and Em-2,3,4,5,6 was prepared in the same manner as in the preparation of Em-1 except for the above. However, the amount of the sensitizing dye added before desalting was adjusted to an amount proportional to the calculated surface area of the particles.

About 3000 particles of Em-2,3,4,5,6 were observed and measured by an electron microscope to analyze the shape. The results were as follows.

Ratio of hexagonal plate to total projected area: 80%, respectively Average particle diameter of hexagonal plate crystal (converted to yen); Average particle thickness of hexagonal plate crystal shown in Table 1; Average aspect ratio of hexagonal plate shown in Table 1 Monodispersity of 2.0 hexagonal flat plate; Em-a was prepared in the same manner as Em-a except that when 10% Em-a was prepared, D1 was added and aging was carried out for 5 minutes, followed by extending for 10 minutes.

When this seed emulsion was observed with an electron microscope,
It was a 30% -wide AgBr emulsion having an average grain size of 0.29 μm.

Em-7 was prepared in exactly the same manner as Em-1 except that the above Em-I was used. However, the amount of seed particles was adjusted to obtain the particle size shown in Table 1.

About 3000 particles of Em-7 were observed and measured by an electron microscope to analyze the shape. The results were as follows.

Ratio of hexagonal flat plate to total projected area; 80% Average particle diameter of hexagonal flat plate crystal (converted to a circle); Average particle thickness of hexagonal flat plate crystal shown in Table 1; Average aspect ratio of hexagonal flat plate shown in Table 1; 2.0 Mono-dispersion degree of hexagonal plate; When making 25% Em-a, Em-a was prepared in the same manner as Em-a except that the place of aging for 5 minutes after adding D1 was extended to 20 minutes.

When this seed emulsion was observed with an electron microscope,
It was a 40% wide AgBr emulsion having an average grain size of 0.31 μm.

Em-8 was prepared in exactly the same manner as Em-1 except that the above Em-C was used. However, the seed particle amount is shown in Table 1.
Was adjusted so as to obtain a particle size of.

About 3000 particles of Em-8 were observed and measured by an electron microscope to analyze the shape. The results were as follows.

Ratio of hexagonal tabular plate to total projected area: 80% Average grain diameter of hexagonal tabular crystal (converted to a circle); Average grain thickness of hexagonal tabular crystal shown in Table 1; Average aspect ratio of hexagonal tabular plate shown in Table 1; 2.0 Monodispersity of hexagonal plate: 35%

[0080]

[Table 1]

Chemical Sensitization of Tabular Emulsion Em-1 1% NH ₄ SCN per mol of silver was added to Em-1 prepared above;
Just before the addition of the chemical sensitizer consisting of 2 ml, 0.2% HAuCl ₄ ; 0.78 ml, 0.25% Na ₂ S ₂ O ₃ ; 5.6 ml, the spectral sensitizing dye (A); 127 mg
Was chemically sensitized at 48 ° C.

After the chemical sensitization is started, the average particle size is 0.04μ in 30 minutes.
0.002 mol of AgI fine particles of m was added per mol of silver halide. After continuing the chemical ripening for 20 minutes, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added in an amount of 2.4 g per mol of silver halide, and the temperature was lowered to stop the chemical ripening. .

With respect to Em-2 to 8, chemical sensitizers and sensitizing dyes in proportion to the surface area of grains were added, and chemical ripening was performed in the same manner as Em-1.

After mixing the chemically aged emulsions in the proportions shown in Table 2, the following various additives were added to prepare a coating emulsion solution, which was uniformly coated on both sides of the support and dried. To prepare a sample.

The amount of coated silver is 2.3 to 2.5 g per one side.
/ M ² , and the amount of gelatin is 3.0 g / m ² . The coated silver amount was adjusted within the above range to obtain a predetermined G (gamma value indicating contrast), and a sample was prepared. Within the above range, the sharpness is not affected.

[0086]

[Table 2]

Application No. 1-phenyl-5-mercaptotetrazole was added to the emulsion solutions on the low-sensitivity side of 10 and 11 to adjust the sensitivity.

1-phenyl-5-mercaptotetrazole 10 mg 1-trimethylolpropane 14 g t-butyl-catechol 68 mg polyvinylpyrrolidone (molecular weight 10,000) 850 mg styrene-maleic anhydride copolymer 2.0 g nitrophenyl-triphenyl- Phosphonium chloride 50 mg 1,3-dihydroxybenzene-4-ammonium sulfonate 1.7 g 1,1 dimethylol-1-bromure 1-nitromethane 6.2 mg nC ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 700 mg

[0089]

[Chemical 3]

The additives used in the protective layer solution are as follows. The added amount is shown as an amount per 1 g of gelatin.

Matting agent consisting of polymethylmethacrylate having an average particle diameter of 5 μm 21 mg Matting agent consisting of polymethylmethacrylate having an average particle diameter of 3 μm 28 mg

[0092]

[Chemical 4]

Glyoxal 15 mg / g Gel The obtained sample was processed using the following developer and fixer using an automatic processor SRX503 manufactured by Konica Corporation.

Developer Formulation Part-A (for finishing 10.8 l) Potassium hydroxide 340 g Potassium sulfite (50% solution) 2150 g Diethylenetetraamine pentaacetic acid 32.3 g Sodium hydrogencarbonate 108 g 5-Methylbenzotriazole 150 mg 1-phenyl-5- Mercaptotetrazole 15mg Hydroquinone 280g Add water to make 3600ml.

Part-B (for 10.8 l finishing) glacial acetic acid 158 g triethylene glycol 144 g 1-phenyl-3-pyrazolidone 19.5 g 5-nitroindazole 0.32 g n-acetyl-D, L-penicillamine 0.11 g Part-A and B Were mixed and made up to 10.8 l with water.

Starter formulation (1.0 l for finishing) Glacial acetic acid 138 g Potassium bromide 325 g 5-Methylbenzotriazole 1.5 g CH ₃ N (C ₃ H ₆ NHCONHC ₂ H ₄ SC ₂ H ₅ ) ₂ 20 mg Water was added to 1.0 l To finish.

20 ml of the starter was added per 1.0 l of the developing solution.

Fixer Formulation Part-A (16.4l for finishing) Ammonium thiosulfate (70wt / vol%) 3460g Sodium sulfite 150g Sodium acetate trihydrate 350g Sodium citrate 43g Gluconic acid 33g Boric acid 26g Glacial acetic acid 120g Part-B (For finishing 16.4l) Aluminum sulfate 56g Sulfuric acid (50wt%) 91g Part-A and B were mixed and finished to 16.4l with water.

Processing step Processing temperature (° C) Processing time (sec) Replenishment amount Insertion −− 1.2 Development + crossover 35 14.6 270 ml / m ² Fixing + crossover 33 8.2 430 ml / m ² Washing + crossover 18 7.2 7.0 l / min Squeeze 40 5.7 Drying 50 8.1 Total −− 45.0 The capacity of each tank of the automatic processor used was 16 liters for the developing tank,
Fixing tank 10 liters of water washing tank is 10 liters and clinker 205 (Co., Ltd. Date plate Laboratories manufacturing, sales, the main component SiO _2,
Grain size of Al ₂ O ₃ , Ag ⁺ ion ceramics 1.0 to 1.5 mm, specific gravity
2.5-2.6) 200 g was filled in a bag sewn with a 20-mesh polyethylene woven cloth and immersed in the vicinity of the washing water supply section of the washing tank. In addition, drying is done with an infrared heater (heater temperature
220 ℃) and warm air (60 ℃) were used together.

An infrared sensor was used to detect the insertion of the film. The film area for 10 quadrants was detected, and the replenishment amount (developer 210 ml, fixer 320 ml) for 10 quadrants was replenished.

(Evaluation of Sensitivity and G) The above coated sample was sandwiched with an intensifying screen for X-ray photography (for auroral LT-2 regular), and X was used.
It was placed at a distance of 2 m from the wire tube, and was irradiated with X-rays at 90 KVP and 50 mA for 0.08 seconds using an aluminum wedge, and then subjected to the above-mentioned development treatment. In order to measure the X-ray sensitivity of each surface, after processing, each of the A surface and the B surface was removed using a highter, and the density of only the A and B surfaces was measured.
From the obtained characteristic curve, the reciprocal of the exposure X-ray at the density of fog +0.1 was obtained, and the sensitivity of the high-sensitivity surface of Sample 1 was 10
The relative value as 0 was calculated.

G was calculated as the gamma of the density of optical density fog +0.25 and fog +2.0 on the characteristic curve.

(Evaluation of Sharpness) The above coated sample was sandwiched by an intensifying screen for X-ray photography (for auroral LT-2 regular), and a phantom for the chest placed at a distance of 2 m from the X-ray tube. I took a picture. The imaging conditions were 90 KVP and 50 mA, but the irradiation time was adjusted so that the concentration in the lung field was 1.8. Then, the development processing described above was performed, and the sharpness of the lung field and the depiction of the mediastinum of the film processed on Schaukasten were evaluated. In each case, the evaluation was done on a 5-point scale. 5 is the highest level, 3 is the diagnostically acceptable limit level, and levels less than 3 are levels that cannot be practically used for diagnosis. In general, a light-sensitive material with good sharpness in the lung field has a poor media delineation, resulting in poor depiction.

The results are shown in Table 3.

[0105]

[Table 3]

From Table 3, it can be seen that the present invention has good sharpness in the lung field and particularly excellent depiction in the mediastinum.

The replenishment amount of the developing solution is divided into four and is 30 per sheet.
After processing the above sample No.4 and No.10 with ml, the replenishment amount is 20 ml
Fog increased by 0.01 compared to.

Example 2 No. 1 of Example 1 When 8 was applied, it was applied in exactly the same manner as in Example 1 except that the base was changed as follows.

<Preparation of Support> In preparing the support of Example 1, dimethyl naphthalene-2,6-dicarboxylate and dimethyl terephthalate were added at 100: 0, 80:20, 60:40, 40: 60,
A support was prepared by changing the polymerization to 20:80 and 0: 100.

The obtained sample was evaluated in the same manner as in Example 1.

The results are shown in Table 4.

[0112]

[Table 4]

It can be seen from Table 4 that the present invention has excellent sharpness of the lung field and excellent depiction of the upper mediastinum.

[0114]

According to the present invention, a silver halide photographic light-sensitive material having improved sharpness and a method of processing the same can be obtained without lowering the sensitivity.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical indication G03C 5/31

Claims (3)

[Claims] 1. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on both sides of a transparent support, said emulsion layer comprising at least 5 projected areas.
0% consists of a tabular silver halide emulsion having an aspect ratio of 1 or more and less than 5, and the support is substantially polyethylene-
A silver halide photographic light-sensitive material comprising 2,6-naphthalate, wherein the emulsion layers on both sides of the support are different in sensitivity from 2 times to 10 times. 2. The photographic characteristics of the emulsion on the high sensitivity side have a density of 0.25.
2. The silver halide photographic light-sensitive material according to claim 1, wherein the average contrast between 2 and 2.0 is 2 or less, and the average contrast between the densities of the emulsions on the low sensitivity side is 0.25 and 2.0 is 2.5 or more. 3. The silver halide photographic light-sensitive material is treated with a developing solution containing substantially no hardening agent, and the replenishing amount of the developing solution is cut into four and is 25 ml or less per sheet. A method for processing a silver halide photographic light-sensitive material.