JP2811265B2 - Silver halide photographic material - Google Patents

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 has excellent suitability for rapid processing, improves the occurrence of roller marks and the residual color of a sensitizing dye when processed by an automatic developing machine, and has an improved processing ability. The present invention relates to a photographic light-sensitive material in which photographic performance hardly changes with a change in liquid composition.

[0002]

2. Description of the Related Art In recent years, high-speed rapid processing by an automatic developing machine has rapidly spread in the developing process of photographic light-sensitive materials (hereinafter referred to as "light-sensitive materials"), and the processing time of various light-sensitive materials has been greatly reduced. In order to achieve rapid processing, a developer for achieving sufficient sensitivity in a short time, a photosensitive material having a rapid progress of development and giving a sufficient degree of blackening in a short time, and drying in a short time after washing with water Characteristic is required. Techniques utilizing tabular grains for the purpose of improving the viewpoints described above are described in U.S. Pat. Nos. 4,439,520 and 4,425,425. In JP-A-63-305343 and JP-A-1-77047, the development progress and the sensitivity / fog ratio are improved by controlling the development start point of a silver halide grain having a (111) plane near the top of the grain. A technique for performing this is disclosed. Further, JP-A-58-111933 discloses a photographic element for radiography in which tabular grains are used to reduce the swelling of the hydrophilic colloid layer to 200% or less, thereby having high covering power and requiring no additional hardening during processing. Is disclosed. These known techniques are excellent in improving the development progress of the light-sensitive material and have high utility values. However, if the processing time of each process of development, fixing and washing is shortened, residual silver and residual hypo increases due to deterioration of fixability and washing ability, in addition to reduction of photographic sensitivity,
Significant problems occur in the preservation of the finished image. Also,
In the case of a light-sensitive material which has been spectrally sensitized with a sensitizing dye, the problem of residual color also appears. These problems other than photographic properties are limited in the improvement by the modification of silver halide emulsions, and when the processing speed is reduced to a certain degree or more (specifically, for example, when the development and fixing times become 10 seconds or less, respectively). ) Eventually results in a problem of film quality. That is, the thickness of the hydrophilic colloid layer determines fixing and residual color, which is an obstacle to speeding up.

With respect to this viewpoint, Japanese Patent Application Laid-Open No.
3, JP-A-64-86133, JP-A-1-105524
4, JP-A-1-158435, JP-A-1-15843
6. JP-A-63-221341 discloses that the amount of gelatin on the side having a hydrophilic colloid layer including a silver halide emulsion layer is 2.
There is disclosed a means of preparing the composition in the range of 0 to 3.5 g / m ² to achieve rapid processing with a total processing time of 20 seconds or more and less than 60 seconds. However, these prior arts are accompanied by the disadvantage that the amount of gelatin is reduced, and as a result, abrasion blackening and roller mark are significantly deteriorated. Abrasion blackening refers to a phenomenon in which, when a film is handled, when the film is rubbed together or the film is rubbed with another substance, abrasion-like blackening occurs after development processing. Further, the roller mark refers to a phenomenon in which, when the photosensitive material is processed by an automatic developing machine, pressure is applied to the photosensitive material due to fine irregularities on the surface of a transport roller, thereby causing spot-like density unevenness.

[0004] As a technique for improving such disadvantages caused by reducing the amount of gelatin applied, Japanese Patent Application Laid-Open No. H4-1288 has been disclosed.
No. 32 discloses a light-sensitive material technique in which the silver iodide content of silver halide grains contained in a photosensitive emulsion layer is set to 0.6 mol% or less. Due to the decrease in silver iodide content, abrasion blackening and roller marks have been improved, and the total processing time can be further reduced, but on the other hand, photographic properties are liable to change with changes in developer composition. The drawback is that a new problem has arisen. For example, when iodine ions accumulate in the developing solution, sensitization and fogging occur, and for example, when the fixing solution is mixed into the developing tank, low sensitivity softening becomes severe.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide no problem in fixing property and residual color even when subjected to rapid processing, no problem in roller mark and abrasion blackening performance, and a developer solution. Another object of the present invention is to provide a light-sensitive material which realizes stable photographic performance even with respect to the composition fluctuation.

[0006]

The object of the present invention has been attained as follows. In a medical silver halide photographic material having at least one silver halide emulsion layer on a support, the silver halide grains are silver iodobromide grains , and the silver iodide content is 0.01 mol%. and less than 0.5 mol%, medical, characterized by containing a compound represented by the following general formula in the emulsion layer and / or a hydrophilic colloid layer of the silver halide photographic light-sensitive material (I) Silver halide photographic material. General formula (I)

[0007]

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A particularly preferred embodiment is a case where the silver halide photographic light-sensitive material has an average size of silver halide grains of less than 0.25 μm ³ contained in the emulsion layer. Hereinafter, a specific configuration of the present invention will be described in detail.

With respect to the compounds of general formula (I), R ₁
And R ₂ represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group and a heterocyclic group. These groups may be substituted, and as a substituent, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, a carbamoyl group, an amide group, a cyano group, a nitro group, an amino group, a sulfonyl group, an acyl group, an alkylthio group , Arylthio group,
Represents an alkoxycarbonyl group, an aryloxycarbonyl group, an alkoxycarbonylamino group, or an allyloxycarbonylamino group. Two or more of these substituents may be substituted, and when two or more are substituted, they may be the same or different. M represents a hydrogen atom, an alkali metal atom, a quaternary ammonium group or a group that can be a hydrogen atom or an alkali metal atom under alkaline conditions.

More specifically, R ₁ and R ₂
Is a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms (for example, a methyl group, a propyl group, a hexyl group, a dodecyl group, an isopropyl group, etc.), a cycloalkyl group having 3 to 20 carbon atoms (for example, a cyclopropyl group, A cyclohexyl group), an aromatic group having 6 to 20 carbon atoms such as a phenyl group and a naphthyl group,
Specific examples of the 20 aralkyl groups (eg, benzyl group, phenethyl group, etc.) and heterocyclic groups include 5-, 6-, or 7-membered heterocycles containing at least one nitrogen, oxygen, sulfur atom, or the like. And further include those forming a condensed ring at an appropriate position (for example, a pyridine ring,
Quinoline ring, pyrimidine ring, isoquinoline ring, etc.).

The straight-chain or branched alkyl group, cycloalkyl group, aryl group, aralkyl group and heterocyclic group may be further substituted. Specifically, a halogen atom (F, Cl, Br, etc.), an alkyl group ( Methyl, ethyl, isopropyl, etc.), alkoxy (phenoxy, etc.), carbamoyl (unsubstituted carbamoyl,
Dimethylcarbamoyl group, diethylcarbamoyl group, etc.), amide group (acetamido group, benzamide group, etc.), cyano group, nitro group, amino group (unsubstituted amino group, dimethylamino group, etc.), sulfonyl group (methanesulfonyl group, p- Toluenesulfonyl group, acyl group (acetyl group, benzoyl group, etc.), alkylthio group (methylthio group, etc.), arylthio group (phenylthio group, etc.), alkoxycarbonyl group (methoxycarbonyl group, etc.), aryloxycarbonyl group (phenoxycarbonyl group, etc.) Group), alkoxycarbonylamino group (such as methoxycarbonylamino group), allyloxycarbonylamino group (such as phenoxycarbonylamino group)
Can be given. These substituents may be substituted two or more, and when substituted two or more, they may be the same or different. Particularly preferred as R ₁ is an unsubstituted phenyl group, and particularly preferred as R ₂ is a hydrogen atom.

M is a hydrogen atom, an alkali metal atom (eg, a sodium atom, a potassium atom, etc.), a quaternary ammonium group (eg, a trimethylammonium group, a dimethylbenzylammonium group, a tributylammonium group, etc.), and M is a hydrogen atom or a hydrogen atom under alkaline conditions. Represents a group that can be an alkali metal atom (for example, an acetyl group, a cyanoethyl group, a methanesulfonyl group, and the like). Hereinafter, specific examples of the compound represented by formula (I) used in the present invention will be shown.

[0013]

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[0014]

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[0015]

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The amount of the compound represented by the formula (I) is preferably 1 × 10 ^-6 mol to 1 × 10 ^-3 mol, more preferably 5 × 10 ^-6 mol, per mol of silver. ５5 × 10 ^-4 mol. The addition site is a silver halide emulsion layer or another hydrophilic colloid layer, and the other hydrophilic colloid layer is a hydrophilic colloid layer on the side where the silver halide emulsion layer is present, such as a surface protective layer and an intermediate layer. It is. Although there is no particular limitation on the timing of addition, for example, when it is added to a silver halide emulsion layer, the time from completion of chemical sensitization to coating is preferable. In the light-sensitive material of the present invention, a light-sensitive material in which the photosensitive silver halide emulsion layer is provided on one side of the support or a light-sensitive material provided on both sides of the support may be used. The light-sensitive material of the present invention may have a hydrophilic colloid layer in addition to the silver halide emulsion layer, if necessary, and it is preferable to provide a surface protective layer according to a known method. The amount of gelatin on the side having the hydrophilic colloid layer including the emulsion layer is preferably in the range of 2.0 g / m ² or more and less than 3.2 g / m ² , particularly 2.4 g / m ² or more and 3.0 g.
/ M ² is desirable. The melting time of the light-sensitive material of the present invention is preferably set to 8 minutes or more and 45 minutes or less. The measuring method of the melting time referred to in the present invention follows the method described in JP-A-63-221341.

Next, the emulsion grains used in the present invention will be described. The size of the particles used in the present invention is preferably 0.01 [mu] m ³ or more 1 [mu] m ³ as an average of the volume of each particle, a significant improvement effect is obtained in particular 0.03 .mu.m ³ or 0.25 [mu] m ³ or less. The silver halide grains in the emulsion may have a regular crystal form such as cubic, octahedral, spherical,
It may have an irregular crystal form such as a plate-like or potato-like form, or may consist of a mixture of particles of various crystal forms.

The silver halide grains of the present invention have a silver iodide content of 0.01 mol% or more and less than 0.5 mol%.
Silver iodobromide long, silver bromide, silver iodochlorobromide, silver chlorobromide, silver iodochloride, may be any of silver chloride, but in achieving high sensitivity silver iodobromide Preferably, silver iodochlorobromide or silver chlorobromide is suitable for a photosensitive material for high illuminance exposure such as a laser imager. Silver iodide content should be 0.5 mol% MatsuMitsuru 0.01 mol%, based on total silver as an average of the individual particles, especially below 0.1 mol% 0.4 mol% Is good. The silver iodide distribution between individual grains may be present or uniform.

The use of monodisperse emulsions is a preferred embodiment for the present invention. The method for producing a monodispersed emulsion is known, for example
J. Photo. Sci. 12, 242 to 251 (1963),
JP-B-48-36890, JP-B-52-16364
JP-A-55-142329, JP-A-57-179
835, etc., can be used as appropriate.
The emulsion of the present invention may be a core-shell type emulsion. The core-shell type emulsion is known from JP-A-54-48521.

Tabular grains are preferably used in the present invention. For tabular grains, RESEARCH DISCLOSURE 22
Vol. 5, Item 22534, 20-58, January issue (198
3) and JP-A-58-127921 and JP-A-58-127921.
No. 113926, JP-A-58-113927, JP-A-58-113928, and U.S. Pat. No. 4,439,520 can be referred to. The projected area diameter of the tabular emulsion of the present invention is preferably from 0.3 to 2.0 μm, particularly preferably from 0.5 to 1.2 μm. Particle thickness is 0.05-0.3μ
m, particularly particles having a particle size of 0.1 to 0.25 μm are preferred, and those having an aspect ratio of 3 or more and less than 20 and particularly 4 or more and less than 8 are preferred. Among the tabular grains, monodisperse tabular grains are particularly useful grains. Details of the structure and production method of monodisperse tabular grains referred to in the present invention are described in JP-A-63-1516.
18, according to the description in JP-A-1-158426.

There are no particular restrictions on the various additives used in the light-sensitive material of the present invention, and for example, those described in the following applicable places can be used. Item: This section 1) Chemical sensitization method: JP-A-2-68539, page 10, right upper column, line 13 to upper left column, line 16, Japanese Patent Application No. 3-105035. 2) Antifoggant JP-A-2-68539, page 10, lower left column, line 17 and stabilizers, page 11, upper left column, line 7 and page 3, lower left column, line 2 to page 4, lower left Column. 3) Color tone improver JP-A-62-276439, page 2, lower left column, line 7 to page 10, lower left column, line 20; JP-A-3-94249, page 6 lower left column, line 15 Page 11, upper right column, line 19. 4) Spectral sensitizing dyes JP-A-2-68539, page 4, lower right column, line 4 to page 8, lower right column. 5) Surfactant JP-A-2-68539, page 11, upper left column, line 14 or antistatic agent, page 12, upper left column, line 9; 6) Matting agent, slip agent JP-A-2-68539, page 12, upper left column, line 10 or plasticizer from line 10, upper right column, line 10 from line 10, lower left column, line 14 to line 1, lower right column. . 7) Hydrophilic colloid From page 11, upper right column, line 11 to lower left column, line 16 of JP-A-2-68539. 8) Hardener From page 17, lower left column, line 17 to page 13, upper right column, line 6 of JP-A-2-68539. 9) Support 10) Crossover Japanese Patent Application Laid-Open No. 2-264944, page 4, upper right column, line 20 or cut method, page 14 upper right column. 11) Dyes and mordants JP-A-2-68539, page 13, lower left column, line 1 to page 14, lower left column, line 9. JP-A-3-24537, page 14, lower left column to page 16, lower right column. 12) Polyhydroxyl JP-A-3-39948, from page 11, upper left column to the first benzenes, page 2, lower left column, EP Patent No. 452772A. 13) Layer structure JP-A-3-198041. 14) Development processing method JP-A-2-103737, page 16, upper right column, line 7 to page 19, lower left column, line 15 and JP-A-2-115837, page 3, lower right column, line 5 From page 10, line 10 in the upper right column. Next, the present invention will be described more specifically with reference to examples.

[0022]

【Example】

Example 1 Preparation of emulsions 1 to 5 (octahedral grains of uniform composition) 25 g of inert gelatin, 0.76 g of potassium bromide, 50
10 cc of 10% ammonium nitrate and 5.5 cc of 25% aqueous ammonia were dissolved in 1 liter of distilled water and kept at 52 ° C. with stirring. To this, 600 cc of an aqueous solution of silver nitrate having a concentration of 0.98 mol / liter was added over 50 minutes. One minute after the start of the addition of the aqueous silver nitrate solution, a mixed aqueous solution of potassium bromide and potassium iodide (total halogen concentration of bromine and iodine: 0.98 mol / liter) was controlled so that the pAg was constant at 9.2. While adding. Silver iodobromide grains having different compositions were prepared by changing the mixing ratio of potassium bromide and potassium iodide. After the addition of the aqueous silver nitrate solution and the aqueous halogen solution is completed, potassium thiocyanate (2N
Solution) was added. After 3 minutes, the mixture was cooled to 35 ° C., washed by flocculation, 30 g of inert gelatin was added, and the mixture was heated to 40 ° C. and adjusted to pH 6.5 and pAg 8.2. The resulting emulsion had an equivalent sphere diameter of 0.6.
It consisted of octahedral particles of 2 μm (= 0.125 μm ³ ) and had a coefficient of variation of 17%.

Emulsions 1 to 5 were subjected to the following chemical sensitization. 6
With stirring at 0 ° C, first, 0.02mg of thiourea dioxide
Was added and held for 20 minutes to effect reduction sensitization.
Next, 0.1 mol of 0.03 μm AgI fine particles was added, and 5
After separating, 4-hydroxy-6-methyl-1,3,3
120 mg of a, 7-tetraazaindene and 240 mg of the sodium salt of the sensitizing dye anhydro-5,5'-dichloro-9-ethyl-3,3'-di (3-sulfopropyl) -oxacarbocyanine were added. Subsequently, 1.5 mg of sodium thiosulfate and triphenyl-phosphinic selenide 3
mg, 2.6 mg chloroauric acid and potassium thiocyanate 20
mg was added and cooled to 35 ° C. 25 minutes later. Thus, Emulsions 1 to 5 were obtained. Table 1 shows the silver iodide contents of Emulsions 1 to 5.

Preparation of Coating Solution for Emulsion Layer The following chemicals were added per mole of silver halide to the emulsions 1 to 5 which had been subjected to chemical sensitization to prepare a coating solution. -2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 72 mg-trimethylolpropane 9 g-dextran (average molecular weight 39,000) 18.5 g-potassium polystyrene sulfonate (average molecular weight 60) 1.8 g)

[0025]

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Snowtex C (manufactured by Nissan Chemical Industries, Ltd.) 29.1 g Gelatin The amount of gelatin in the emulsion layer was adjusted to 1.6 g / m ² . Hardener (1,2-bis (vinylsulfonyl zetamido) ethane in hydrophilic colloid layer) 8 × 10 ^-3 mol per 100 g of latin

Preparation of Surface Protective Layer Coating Solution A surface protective layer coating solution was prepared and prepared such that each component had the following coating amount. Gelatin 0.60 g / m ² · Sodium polyacrylate (average molecular weight 400,000) 0.023 g / m ² · polymethylmethacrylate (average particle size 3.7μm) 0.087g / m ² · Proxel 0.0005 g / m ^Two

[0028]

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(Prepared to pH 7.4 with NaOH)

Preparation of Photographic Material As a support, a biaxially stretched polyethylene terephthalate having a thickness of 185 μm and having an undercoat layer previously coated on both sides was prepared. The polyethylene terephthalate used contained a dye having the following structure at 0.04% by weight.

[0031]

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The emulsion layer and the surface protective layer were coated on both sides of the support by a coextrusion method. The coated silver amount per one side was 2.15 g / m ² . Thus, photographic materials 1-1
0 was obtained.

Table 1----------------------------------------------------------photographic material Content Exemplified compound (3) of the present invention (3) (mol%) (mg / Ag1 mol)----------------. 1 Comparison 1 0.1 No addition 2 Comparison 2 0.2 No addition 3 Comparison 3 0.4 No addition 4 Comparison 4 0.6 No addition 5 Comparison 50 0.8 No addition 6 invention 10.1 177 invention 20.2 178 invention 30.4 179 invention 40.6 1710 comparison 5 0.8 17 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−

Evaluation of standard photographic performance Photographic materials 1 to 10 were measured from both sides using a direct medical fluorescent intensifying screen HR-4 manufactured by Fuji Photo Film Co., Ltd.
Gave a second exposure. After the exposure, the following processing was performed to evaluate the sensitivity. The sensitivity was represented by the reciprocal ratio of the amount of exposure that gives a density of 1.5 in addition to fog, with photographic material 1 as 100. For the fog, the net fog value of the developed silver from which the base density was subtracted was used.

<Automatic Developing Machine> CEPROS (manufactured by Fuji Photo Film Co., Ltd.) (The number of rotations of the drive motor is made variable so that the film transport speed can be increased.)

Preparation of Concentrate <Developer> Parts A A 270 g of potassium hydroxide 1125 g of potassium sulfite 450 g of sodium carbonate 75 g of boric acid 150 g of diethylene glycol 30 g of diethylenetriaminepentaacetic acid 1- (N, N-diethylamino) ethyl 1.5 g of 5-mercaptotetrazole 405 g of hydroquinone 30 g of 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 4500 ml by adding water

Parts agent B • 750 g of tetraethylene glycol • 3 g of 3,3′-dithiobishydrocinnamic acid • 75 g of glacial acetic acid • 4.5 g of 5-nitroindazole • 67.5 g of 1-phenyl-3-pyrazolidone 1000ml

Parts agent C 15 g potassium bromide 120 g potassium metabisulfite 750 ml with water

<Fixing solution> • Ammonium thiosulfate (70 wt / vol%) 3.0 liters • Ethylenediaminetetraacetic acid disodium dihydrate 0.45 g • Sodium sulfite 225 g • Boric acid 60 g • 1- (N, N- Dimethylamino) ethyl 15 g-5-Mercaptotetrazole Tartaric acid 48 g Glacial acetic acid 675 g Sodium hydroxide 225 g Sulfuric acid (36N) 58.5 g Aluminum sulphate 150 g Add water to 6000 ml, pH 4.68

Preparation of Processing Solution The above processing concentrate was filled into a CEPROS replenisher container. The developer replenisher container has parts A, B, and C connected together by the container itself. A processing agent having the following mixing ratio is filled in the developing and fixing tanks of the automatic developing machine. Developing solution Parts agent A 60 ml Parts agent B 13.4 ml Parts agent C 10 ml water 116.6 ml (pH 10.50) Fixer concentrate 80 ml water 120 ml (pH 4.62) The washing tank was filled with tap water.

Developing temperature 35 ° C. Fixing temperature 35 ° C. Washing temperature 15 ° C. Drying temperature 50 ° C. Processing speed 30 seconds at Top to Top The results of photographic fog and sensitivity are summarized in Table 2.

Evaluation of Photographic Performance when Iodine Ion Accumulates in Developer Under the conditions for evaluating the standard photographic performance described above, 20 mg / kg of KI was contained in the developer in the developing tank of the automatic developing machine.
The photographic performance was evaluated in the same manner as described above. Table 2 summarizes the results of fog and sensitivity.

Evaluation of photographic performance when fixing solution is mixed in developing solution Under the conditions for evaluating the standard photographic performance described above, 4 cc of the fixing solution in the fixing bath was used in the developing solution of the developing tank of the automatic developing machine. The photographic performance was evaluated in the same manner as described above. Table 2 summarizes the results of fog and sensitivity.

Evaluation of Roller Mark Photographic materials 1 to 10 were uniformly exposed to a size of 10 × 12 inches so as to have a density of 1.0, and then processed under the same conditions as in the evaluation of standard photographic performance. However, the rollers used for transporting the developing tank and the crossover roller from development to fixing used here were intentionally fatigued.
The surface of the roller had irregularities of ± 10 μm. Some photographic materials after processing had many fine spots. The state was sensory evaluated in the following four stages, and the results are summarized in Table-2. A: Almost no spots are observed. : Spots are slightly generated, but are not bothersome for practical use. Δ: Spots are generated but not generated on a roller with little fatigue. Acceptable level. ×: Many spots. It occurs even with rollers with low fatigue and is not practical.

[0045]

As can be seen from the experimental results in Table 2, the developer used in this experiment may not contain a processing hardener, and as the silver iodide content of the grains increases, the roller mark deteriorates. The photographic materials 5 and 10 having a silver iodide content of 0.8 mol% are not practical. On the other hand, as the silver iodide content decreases, the photographic performance in the case where the fixing solution is mixed into the developing tank is increased in desensitization and fog. However, the photographic materials 6 to 8, which are a combination of the compound of the present invention and the silver iodide content, have practically no problem in roller marks, have little fluctuation in sensitivity and fog even in the development mixed with a fixing solution, and have a developed KI. It can be seen that the liquid is an extremely stable light-sensitive material with little change in sensitivity and fog. The effect of the present invention is clear from this embodiment.

Example 2 Photographic materials 11 to 18 were prepared in the same manner as in Example 1.
However, in preparing the monodisperse octahedral emulsion, the particle size was changed by adjusting the temperature during the preparation and the addition amount of the 25% aqueous ammonia solution. Further, as the compound of the present invention, Exemplified compound (8) was used instead of Exemplified compound (3). Table 3 summarizes the silver iodide content, the grain size, and the amount of the exemplary compound (8) of the present invention for the photographic materials 11 to 18.

Photographic materials 11 to 18 were evaluated in the same manner as in Example 1, and the results are summarized in Table 4. Although not shown in Table 4, the roller marks of the photographic materials 11 to 18 were all in the range of ◎ to ○ and were in a state without any problem.

Table 3-----------------------------------------------------------------------------| Silver halide content Exemplified compound (8) of the present invention (μm ³ ) (mol%) (mg / Ag 1 mol) ------------------------------------ −−−−−−−−−−−− 11 Comparison 6 0.270 0.25 Not added 12 Comparison 7 0.125 0.25 Not added 13 Comparison 8 0.065 0.25 Not added 14 Comparison 9 0.035 0.25 Not added 15 Invention 6 0.270 0.25 20 16 present invention 7 0.125 0.25 20 17 present invention 8 0.065 0.25 20 18 present invention 9 0.035 0.25 20 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−− −−−−−−−−

Table 4------------------------------------------------------------- Accumulated state Fixer mixed state Sensitivity Fog Sensitivity Fog Sensitivity Fog ---------------------------------------------------- Comparison 160 0.055 180 0.080 135 0.075 12 Comparison 110 0.025 130 0.060 95 0.080 13 Comparison 80 0.020 100 0.040 55 0.035 14 Comparison 55 0.015 75 0.030 25 0.035 15 Invention 145 0.035 160 0.040 135 0.040 16 Invention 100 0.020 105 0.020 100 0.020 17 Present invention 75 0.015 80 0.015 75 0.015 18 Present invention 50 0.010 50 0.010 50 0.010 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− −−−−−−−

From the results shown in Table 4, the particle size was 0.25
[mu] m ³ or more in the photographic material 11 and 15 has a large desensitization of photographic properties due to the addition of the compound of the present invention, KI accumulated developer in sensitivity and graininess material change suppression is less than 0.25 [mu] m ³ of fog Is inadequate compared to Further, even in the development in a state where the fixing solution is mixed, the effect of suppressing desensitization and fogging is smaller than that of a particle photosensitive material having a particle size of less than 0.25 μm ³ . This experiment shows that the effect of the present invention is remarkable when the particle size is less than 0.25 μm ³ .

Example 3 Preparation of tabular grain emulsion a 6 g of potassium bromide and 6 g of low molecular weight gelatin having an average molecular weight of 20,000 obtained by enzymatically treating alkali-treated gelatin in 1 liter of water were added to a container kept at 55 ° C. While stirring, 5.56 g of an aqueous solution of silver nitrate and 9.4 g of an aqueous solution were added over 45 seconds by a double jet method. Subsequently, after adding 20 g of gelatin having a normal molecular weight, the temperature was raised to 62 ° C., and an aqueous solution of 11.11 g of silver nitrate was added over 12 minutes. Next, 6 cc of a 25% aqueous NH ₃ solution was added, and 5 minutes later, 5.6 cc of a 100% aqueous acetic acid solution was added to neutralize. Thereafter, an aqueous solution of 150 g of silver nitrate and a mixed aqueous solution of potassium bromide and potassium iodide were added over 25 minutes by a control double jet method while keeping the potential at pAg 8.5.
The flow rate at this time was linearly accelerated so that the flow rate at the end of the addition was eight times the flow rate at the start of the addition. 23 minutes after the start of the accelerated flow addition, K ₃ IrCl ₆ was added to 5
× 10 ^-5 g was added. After the addition by the control double jet method for 25 minutes was completed, 15 cc of a 2N potassium thiocyanate solution was added. After this, the temperature is 35 ° C
To 40 ° C after removing the soluble salts by the sedimentation method.
The temperature was raised to 41 g of gelatin and phenoxyethanol.
5 g was added and the pH was adjusted to 5.95 with NaOH. Thus, tabular grains a were prepared. The resulting emulsion had a silver iodide content of 1.1 mol% and an average projected area diameter of 0.
63 μm (standard deviation: 9.2%), average thickness is 0.10
The aspect ratio was 6 at 5 μm.

Preparation of Tabular Particles (b) 6 g of potassium bromide and 6 g of low molecular weight gelatin having an average molecular weight of 20,000 obtained by enzyme treatment of alkali-treated gelatin were added to 1 liter of water, and stirred in a container kept at 55 ° C. An aqueous solution of 5.56 g of silver nitrate and an aqueous solution of 9.4 g were added by a double jet method over 45 seconds. Subsequently, after adding 20 g of gelatin having a normal molecular weight, the temperature was raised to 62 ° C., and an aqueous solution of 11.11 g of silver nitrate was added over 12 minutes. Next, 6 cc of a 25% aqueous NH ₃ solution was added, and 5 minutes later, 5.6 cc of a 100% aqueous acetic acid solution was added to neutralize. Thereafter, an aqueous solution of 150 g of silver nitrate and an aqueous solution of potassium bromide were added over 25 minutes by a control double jet method while maintaining the potential at pAg 8.8. The flow rate at this time was linearly accelerated so that the flow rate at the end of the addition was eight times the flow rate at the start of the addition. 23 minutes after the start of the flow rate acceleration addition, 5 × 10 ⁻⁵ g of K ₃ IrCl ₆ was added.
After the addition by the control double jet method for 25 minutes was completed, 15 cc of a 2N potassium thiocyanate solution was added. Thereafter, 0.25 mol of a silver iodide fine grain emulsion having an average diameter of 0.03 μm was added. Lower the temperature to 35 ° C,
After removing soluble salts by the sedimentation method, the temperature was raised to 40 ° C., 41 g of gelatin and 2.5 g of phenoxyethanol were added, and the pH was adjusted to 5.95 with NaOH. Thus, tabular grains b were prepared. The resulting emulsion had a silver iodide content of 0.255 mol% and an average projected area diameter of 0.62 μm.
m (standard deviation: 9.0%), the average thickness was 0.10 μm, and the aspect ratio was 6.2.

Preparation of Tabular Particles c In a liter of water, 6 g of potassium bromide and 6 g of low molecular weight gelatin having an average molecular weight of 20,000 obtained by enzymatically treating alkali-treated gelatin were added, and stirred in a container kept at 55 ° C. An aqueous solution of 5.56 g of silver nitrate and an aqueous solution of 9.4 g were added by a double jet method over 45 seconds. Subsequently, after adding 20 g of gelatin having a normal molecular weight, the temperature was raised to 62 ° C., and an aqueous solution of 11.11 g of silver nitrate was added over 12 minutes. Next, 6 cc of a 25% aqueous NH ₃ solution was added, and 5 minutes later, 5.6 cc of a 100% aqueous acetic acid solution was added to neutralize. Thereafter, an aqueous solution of 150 g of silver nitrate and an aqueous solution of potassium bromide were added in 25 minutes by a control double jet method while maintaining the potential at pAg 8.8. The flow rate at the end of the addition was 8 times the flow rate at the start of the addition. And accelerated linearly. 23 minutes after the start of the flow rate acceleration addition, 5 × 10 ⁻⁵ g of K ₃ IrCl ₆ was added. 2
After the addition by the control double jet method for 5 minutes was completed, 15 cc of a 2N potassium thiocyanate solution was added. Thereafter, the temperature was lowered to 35 ° C, and soluble salts were removed by a sedimentation method.
g and 2.5 g of phenoxyethanol, and adjusted to pH 5.95 with NaOH. The temperature was raised again to 56 ° C., and a silver iodide fine grain emulsion having an average diameter of 0.03 μm was added to 0.1 g.
After adding 05 mol, the mixture was allowed to stand for 10 minutes. Thus, tabular grains c were prepared. The resulting emulsion had a silver iodide content of 0.051 mol% and an average projected area diameter of 0.62.
μm (standard deviation 9.0%), average thickness 0.10 μm
And the aspect ratio was 6.2.

These emulsions a to c were subjected to the following chemical sensitization. With stirring maintained at 56 ° C., 0.043 mg of thiourea dioxide was added, and the mixture was kept as it was for 15 minutes to perform reduction sensitization. Next, 4-hydroxy-6-methyl-
160 mg of 1,3,3a, 7-tetraazaindene and sensitizing dye anhydro-5,5'-dichloro-9-ethyl-
350 mg of the sodium salt of 3,3'-di (3-sulfopropyl) -oxacarbocyanine were added. Subsequently, chemical sensitization was carried out using sodium thiosulfate in combination with triphenylphosphinic acid selenide, chloroauric acid and potassium thiocyanate. After the completion of the chemical sensitization, the emulsion was cooled to obtain an emulsion.

(Preparation of emulsion layer coating solution) Tabular grains ac
The following chemicals were added per 1 mol of silver halide to prepare an emulsion layer coating solution.・ 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 72 ・ Gelatin Add gelatin so that the coating amount of the emulsion layer becomes 2.5 g / m ²・ Dextran (average molecular weight of 3. 90,000) 18.5 g ・ Sodium polystyrene sulfonate (average molecular weight: 600,000) 1.8 g ・ Hardener 1,2-bis (vinylsulfonylacetamide) ethane Addition amount is adjusted so that the swelling ratio becomes 230%.

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-Snowtex C (manufactured by Nissan Chemical Industries, Ltd.) 9.6 g as solid content-dextran (average molecular weight 39,000) 5.8 g-Exemplified compound (3) of the present invention Amount shown in Table 5 Used here The swelling ratio is the same as that specified in JP-A-58-111933.

(Preparation of Surface Protective Layer of Emulsion Layer) The surface protective layer of the emulsion layer was prepared and prepared so that each component had the following coating amount.・ Gelatin 0.97 g / m ²・ Sodium polyacrylate (average molecular weight: 400,000) 0.018 g / m ²・ 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 0.003 g / m ^2-polymethyl methacrylate (average particle size 2.5 [mu] m) 0.05 g / m ² · Proxel 0.0005 g / m ²

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Adjustment to pH 7.2 with NaOH A prepared emulsion layer coating solution and surface protective layer coating solution were simultaneously extruded onto a 183 μm-thick polyethylene terephthalate film which had been biaxially stretched and preliminarily coated with an undercoat layer. , On one side. The coated silver amount is 2.75.
g / m ² . The polyethylene terephthalate used contained a dye having the following structure at 0.04% by weight.

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(Adjustment of Antihalation Layer) An antihalation layer and a surface protection layer of an antihalation layer were coated on the side where the emulsion layer and the surface protection layer were coated and on the side opposite to the support. Each layer was prepared so as to have the following coating amount. (Antihalation layer) Gelatin 1.5 g / m ² Phosphoric acid 5.2 g / m ² Snowtex C (Nissan Chemical Co., Ltd.) 0.5 g / m ² as solid content. Potassium polystyrene sulfonate (average molecular weight) 600,000) 25 mg / m ² · polymer latex (poly (ethyl acrylate / methacrylic acid) = 97/3)

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(Surface protective layer of antihalation layer) Gelatin 0.66 g / m ² Polymethyl methacrylate (average particle size 3.5 μm) 65 mg / m ²

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C ₈ F ₁₇ SO ₃ K 1.7 mg / m ² potassium polystyrene sulfonate (average molecular weight 600,000) 2 mg / m ² NaOH 2.5 mg / m ^{2 The} antihalation layer and the surface protection layer Co-extrusion was applied and dried simultaneously. Swelling ratio of antihalation layer and surface protective layer measured by cryo-SEM method 1
30%. Photographic materials 19-24 completed in this way
Are summarized in Table 5.

Table 5 -------------------------------------------------------- Material Photograph Emulsion No. Silver iodide Content Exemplified compound (3) of the present invention (3) (mol%) (mg / Ag1 mol)----------------. −−−−− 19 Comparison a 1.1 No addition 20 Comparison b 0.255 No addition 21 Comparison c 0.051 No addition 22 Comparison a 1.1 20 23 Invention b 0.255 20 24 The present invention c 0.051 20 ------------------------------------------------------------------------------------

The single-sided light-sensitive material for CRT photography thus obtained was evaluated in the same manner as in Example 1. However, the exposure was performed by setting the exposure time to 2 seconds from the emulsion surface side with 545 nm monochromatic light by an interference filter. Sensitivity is photographic material 1
9 is displayed as 100. The results are summarized in Table-6.

Table 6 -------------------------------------------------------------------------------------------------------- Photographic material Standard photographic performance KI accumulation state Fixer-mixed state Roller sensitivity Fog sensitivity Fog sensitivity Fog mark −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 19 ratio Comparison 100 0.025 120 0.040 95 0.030 × 20 Comparison 100 0.020 115 0.030 85 0.035 ◎ 21 Comparison 100 0.015 110 0.020 70 0.040 ◎ 22 Comparison 90 0.020 100 0.030 100 0.020 × 23 Invention 95 0.015 100 0.020 100 0.015 ◎ 24 Invention 95 0.015 95 0.015 95 0.015 ◎ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−

From the results shown in Table 6, it was found that the effect of the present invention was remarkable even in a single-sided photosensitive material comprising tabular grains.

Claims (2)

(57) [Claims] 1. A medical silver halide photographic material having at least one silver halide emulsion layer on a support, wherein the silver halide grains are silver iodobromide grains and contain silver iodide. the amount is 0.5 mol% MatsuMitsuru 0.01 mole%, contains a compound represented by the following general formula in the emulsion layer and / or a hydrophilic colloid layer of the silver halide photographic light-sensitive material (I) A silver halide photographic light-sensitive material for medical use , characterized in that: General formula (I) In the formula, R ₁ and R ₂ represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group or a heterocyclic group. These groups may be substituted, and as a substituent, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, a carbamoyl group, an amide group, a cyano group, a nitro group, an amino group, a sulfonyl group, an acyl group, an alkylthio group , An arylthio group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkoxycarbonylamino group or an aryloxycarbonylamino group. Two or more of these substituents may be substituted, and when two or more are substituted, they may be the same or different. M represents a hydrogen atom, an alkali metal atom, a quaternary ammonium group or a group that can be a hydrogen atom or an alkali metal atom under alkaline conditions. 2. A medical silver halide photographic material as claimed in claim 1, wherein the average size of the silver halide grains contained in the emulsion layer is 0.25 [mu] m ³ MatsuMitsuru.