JPS60151637A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To enhance the sensitivity, and to prevent an increase in fogs in preservation under high temps. by sensitizing with at least three kinds of different sensitizers, and incorporating simultaneously flat plate-shaped particles of silver iodobromide having specified thickness and specified diameter. CONSTITUTION:A silver halide photosensitive material is prepared by sensitizing the material with at least three kinds of different sensitizers such as an unstable selenium sensitizer, a noble metal sensitizer, and a sulfur sensitizer, and incorporating flat plate-shaped particles of silver iodobromide whose at least 50% by number of the particles has <0.5mu thickness and whose particles having >=0.6mu diameter has the diameter >=5 times said particle thickness. Isoselenocynate, methylselenourea, etc. are used as siad selenium sensitizer, and sodium chloroaurate and potassium aurithiocyanate, etc. are used as the noble metal sensitizer. And a thiourea derivative, thiocyanate, etc. are used as the sulfur sensitizer.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Use) The present invention relates to a silver halide photographic material, and more particularly to a silver halide photographic material that is highly sensitive, has little fog, and has excellent thermal stability. .

(Prior art) Recently, silver halide photographic M&optical materials have become available for a wide range of photography, such as being able to take photographs in the dark and accurately photographing fast-moving subjects. There is a strong demand for highly sensitive photosensitive materials that can respond to various conditions. Therefore, useful chemical ripening methods such as sulfur sensitization and selenium sensitization have been developed to increase the sensitivity of silver halide emulsions used in the above-mentioned light-sensitive materials. It has attracted attention as being suitable for sensitization.

Regarding such selenium sensitization methods, the list includes U.S. Pat. No. 1.574.944, U.S. Pat.
Same No. 2,739,060g, Same No. 3,2947,446
No. 3,420,670, No. 3,320,06
No. 9, No. 3,658,540-Q, No. 3,408,
No. 196, No. 3,408,197, No. 3,442
．． 653g, German Patent No. 3,591,385, British %FF No. 255,846, German Patent No. 861,984, German Patent No. 1,033,510, German Patent No. 1,547,762,
French special ff No. 2゜093.038, same No. 2,09
No. 3,209, Special Publication No. 43-13489, No. 44-1
No. 5748, No. 52-34491, No. 52-3449
No. 2, No. 53-295, No. 52-36009, No. 5
Although it is described in various specifications and publications such as No. 2-38408 and No. 57-22090, conventional selenium sensitization is not considered to be useful for improving the sensitizing effect, especially the foot sensitivity. However, it has the drawback that it is accompanied by the occurrence of fog, and the fog further increases when the photosensitive material is stored at high temperatures.

(Object of the Invention) Therefore, an object of the present invention is to provide a silver halide photographic photosensitive material which has high sensitivity, low fog, and suppresses increase in fog when stored at high temperatures.

(Structure of the Invention) The object of the present invention is to reduce the number of particles sensitized with a small number of unstable selenium sensitizers, noble metal sensitizers, and sulfur sensitizers (all three different sensitizers). % or thickness 0.5μ
This can be achieved by using a silver halide photographic material containing tabular silver iodobromide grains with a diameter of 0.6 μm or more or a diameter of 5 times or more the grain thickness.

The invention will now be described in more detail.

In the silver halide photographic light-sensitive material of the present invention (hereinafter referred to as the light-sensitive material of the present invention), at least 3fiI11 of an unstable selenium sensitizer, a noble metal sensitizer and a sulfur sensitizer are used.
The silver halide grains sensitized with a different sensitizer have a thickness of less than 0.5μ and a diameter of 0.6tr or more, and the grain size is at least 5 times the thickness of the above grains. Tabular silver iodobromide grains such as
It includes.

In general, regarding plate-shaped silver halide grains, the list is reported in the Journal of the Photographic Society of Japan, Vol. It is also stated in official gazettes, etc.

Such plate-shaped silver halide grains do not exhibit any particular sensitization when subjected to gold-sulfur sensitization;
Spherical or potato-shaped silver saponide particles and fW
It only shows a sensitizing effect of about I.

On the other hand, selenium sensitization is known from the above-mentioned various publications, but it is known that selenium sensitization is carried out using emulsions containing spherical or potato-shaped halogenated catfish grains as mentioned above, as well as silver iodobromide emulsions. Sensitization seems to increase fog due to chemical ripening, and the increase in fog is noticeable during storage at temperatures between 40°C and ω°C.

The above-mentioned tabular silver halide grains having a grain size of 5 times or more the grain thickness as used in the present invention can be produced by a known method.

For example, Kodaira-shaped silver halide grains prepared at a low pBr v- as described in the dissertation by Shukaku Sakai titled ``Study on the manufacturing method of photodevelopable silver halide photosensitive materials.'' A method is also known in which grains are grown by adding ungrown fine halogenated i'8 particles precipitated under scouring conditions.

Also, as described in JP-A-58-113928, unsweetened silver halide grains having a pBr of 0.6 to 1.6 and containing substantially iodide ions were prepared first in a water bath. A method of growing silver halide grains by adding a silver salt, a beautide, and an iodide, and furthermore, JP-A-58-1279
Seed crystals containing tabular grains in an amount of 40% or more by weight based on the total grains as described in Publication No. 21 are used as pBr 1.3.
A method is also known in which seed crystals are grown while simultaneously adding Km to a water-soluble silver salt and a halogen salt solution while maintaining the pBrf as described above.

In the preparation of tabular silver halide grains according to the present invention, it is preferable to increase the prefectural rate of water-bathable silver salt and water-soluble halide as the silver halide grains grow. When the rate of addition of water-soluble silver salt and water-soluble halide is increased in this manner, the particle size distribution of silver halide grains becomes monodisperse, and the mixing time by dipping is shortened.

Therefore, it is advantageous for industrial production and is preferable in that it reduces the chance of structural defects being formed inside the silver halide grains.

For information on how to increase the rate of addition of water-bathable silver salts and water-temperature halides as described above, see Seiban 11848-3689.
No. 0, 52-16364-1? , Japanese Patent Publication No. 55-142
As described in each publication of No. 329, the addition rate of the water-bathable silver salt and the water-soluble halide may be increased continuously or may be increased stepwise.

The upper limit of the above addition rate is the flow rate just before new nuclei of silver halide grains are generated. It changes depending on various conditions such as the composition, solubility, particle size, interparticle distance, type of colloid, and *i.

In preparing the tabular silver halide grains according to the present invention, the pH value is about 1.5 to IO1, preferably pH 2 to IO1.
9, and in this case, as a growth promoter for silver halide grains, ammonia, thiocyanate, thioethers, thiourea, etc. are preferably used, and the temperature during preparation is 35
It ranges from 90°C to 90'C.

The thickness of the tabular silver halide grains according to the present invention prepared by the above-mentioned method is less than 0.5ρ, preferably 0.
．． less than 3μ, the diameter is 0.6μ or more, preferably Oo8μ or more, the particle size is 5 times or more, preferably 8 times or more the thickness, and 50% or more of the total number of particles, preferably 75 % or more of the grains are composed of tabular silver halide grains. Furthermore, the tabular silver halide grains according to the present invention have a halocarbon bride composition of silver iodobromide, and further have a silver iodide content of 0.1 to 10 mol %, preferably 0.3 mol %.
~6 mol% silver iodobromide.

The tabular silver iodobromide grains according to the present invention having the above-mentioned shape and composition are chemically sensitized using three kinds of sensitizers: an unstable selenium sensitizer, a Kaede sensitizer, and a sulfur sensitizer. First, when the unstable selenium heat enhancer according to the present invention is added to a silver nitrate aqueous solution, which is generally called an active selenium compound, it becomes water-insoluble A at room temperature (20"C).
It is a compound that causes precipitation of g2S e. For example, isoselenocyanate, methylselenourea, ethylselenourea, pro, birselenoIy, N,N-dimethylselenourea, N',N-dimethylselenourea, selenoketone,
Triphenyltumesphine selenide and the like can be mentioned. And the amount used is 1 mole 1111r8
-1'4 moles, preferably IF5-1'6 moles.

Next, examples of the prize range sensitizer according to the present invention include gold salt sensitizers such as sodium chloroaurate and potassium aurithiocyanate, as well as palladium salts such as palladium chloride. The amount of these sensitizers used is silver 1
It is preferable to use the gold salt sensitizer and the palladium salt sensitizer in combination.

As the sulfur sensitizer related to the present invention, thiourea derivatives, thiocyanates, thiobinates, etc. can be used, and the amount used is in the range of +o-8 to 14 moles per mole of silver. It is.

In the present invention, rhodan salt, which is a sulfur-containing compound, can also be used in excess. - Chemical ripening using the three sensitizers mentioned above is carried out at a temperature of 40
It is preferable that the reaction be carried out under the following conditions: °C to (capital) °C, pH value 5 to 8, and pAgAg-8.

The light-sensitive material of the present invention containing tabular silver iodobromide grains sensitized by the above sensitization method exhibits effective sensitization with a selenium sensitizer, has high sensitivity, low capri, and high temperature. It has excellent stability even when stored at low temperatures (40°C to 0°C).

The emulsion containing tabular silver iodobromide grains according to the present invention is subjected to chemical ripening for the purpose of preventing fog during its manufacturing process, storage, or development processing, or to stabilize photographic performance. Afterwards, various compounds may be added.

For example, azoles, such as benzothiazolium salts, nitroindazoles, nitropene imidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzimidazoles, aminotriazoles, benzotriazoles, nitrobenzodiazoles, etc. Trianoles, mercaptothiazoles (especially l-phenyl-5-mercaptotetrazole)
etc., as well as mercaptopyrimidines, mercaptopyrimidines, thioketo compounds such as oxazolinthione, benzenethiosulfinic acid, pensenesulfinic acid, benzenesulfonic acid amide, hydroquinone hinderer, aminophenol fat conductor, gallic acid, etc. Acid conductor,
A number of compounds known as anti-capri agents and stabilizers can be added, such as ascorbic acid derivatives and the like.

It is preferable to add these # agents after chemical ripening or before coating.

As the binder for the silver halide emulsion according to the present invention, various hydrophilic colloids including gelatin can be used. Examples of gelatin include seratin, which includes 4-body gelatin, and 4-body seratin, which includes reaction products with gelatin anhydride, reaction products of seratin and incyanate, or gelatin and benzenesulfonyl chloride. Reaction products with compounds containing active halogs/atoms, etc., are included. Examples of acid anhydrides used in the reaction with seratin include maleic anhydride,
Phthalic anhydride, benzoic anhydride, acetic anhydride, isatoic anhydride, succinic anhydride, etc. are included, and isocyanate compounds include phenyl isocyanate, p-promophenyl incyane), p-10 lophenyl, etc. Isocyanate, p-tolyl isocyanate, p-nitrophenyl isocyanate, naphthylisocyanate and the like can be mentioned.

In addition to the above-mentioned derivative gelatin and ordinary photographic gelatin, as hydrophilic colloids for preparing silver halide emulsions, colloidal albumin, kanfu, gum arabic, dextran, alginic acid, such as acetyl Cellulose derivatives of cellulose acetate hydrolyzed to a content of 19-26%, polyacrylamide, imidized polyacrylamide, casein; Containing vinyl arsil polymers, polyvinyl alcohol-boribi, nylpyrrolidone, hydrolyzed polyvinyl acetate, polymers obtained by polymerization of proteins or saturated acylated proteins with monomers having vinyl groups, polyvinylpyridine, polyvinylamine, polyaminoethyl methacrylate Alternatively, polyethyleneimine or the like may be used instead.

The silver halide emulsion used in the present invention can be used for various purposes such as coating aid, antistatic, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (for example, development acceleration, high contrast, and sensitization). It may also contain a known surfactant.

That is, these surfactants, for example, as described in U.S. Pat.
, No. 240,472, No. 2,831,766, No. 3,158,484, No. 3,210,191, No. 3,294,540, No. 3,507,660 ,
British Patent No. 1,012,495, British Patent No. 1,022,8
No. 78, No. 1,179,290, No. 1,198,
No. 450, U.S. Patent i2,7a9. s91, same no. 2,
823゜123, same No. 1,179,290, same No. 1
, No. 198,450, No. 2,739,891, No. 2.823.123, No. 3,068,101, No. 3,415,649, No. 3,666.478 ,
No. 3,756,828, British Patent No. 1,397,2
No. 18, No. 3,113゜816'75, No. 3,41
1.4139, same No. 3,473,174, same No. 3,3
No. 45,974, No. 3,726,683, No. 3,
No. 843,368, Belgian Patent No. 731°126,
British Patent No. 1,138,514, British Patent No. 1.159,8
No. 25, No. 1,374,780, U.S. Patent No. 2,2
No. 71,623, No. 2,288,226, No. 2,
No. 944,900, No. 3,235,919, No. 3
, 671,247, 3,722,021, 3,589,906, 3,666.478, 3,754.924, West German patent application OL81. .

961.683-1 specification and JP 50-1174
No. 14, 5o-59o25-1, Special Publication No. 40-378
No. 40-379 and No. 1 Martyr 43-13822. For example, saponin (steroid thread), alkylene oxide conductor (for example, polyethylene glycol, polyethylene glycol/polypropylene f
9 ” ” m compounds, positive ethylene glycol alkyl or alkylaryl ether polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkyl amines or amides, polyethylene oxide adducts of silicone], glycidol derivatives (monomers) (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polymonocarbons, alkyl esters of sugars, nonionic surfactants such as urethanes or ethers, triterpenoid thread saponins, alkyl carboxylates , alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-furkyltaurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, poly Carboxy, sulfo group, phosphor group such as oxyethylene alkyl phosphate esters,
Anionic surfactants containing acidic groups such as sulfate ester groups and phosphate ester groups, amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphate esters,
Ampholytic surfactants such as alkyl betaines, amine imides, and amine oxides, alkyl amine salts, aliphatic or aromatic quaternary ammonium salts, and complex quaternary ammonium salts or sulfonium salts such as pyridium and imidazolium. Cationic surfactants such as can be used.

In addition to the above-mentioned surfactant as a development accelerator, the above-mentioned silver halide photographic emulsion contains OLS 2,0
No. 02,871, No. 2,445,611, No. 2,
It may contain imidazoles, thioethers, selenoethers, etc., which are described in British Patent No. 360,878 and British Patent No. 1, 352,196.

In addition, in order to apply the silver halide emulsion according to the present invention to a color photosensitive material, a combination of yellow, macenta and cyan couplers may be added to a silver halide emulsion screened to have evening sensitivity, green sensitivity and red sensitivity, respectively. The method and wood used for color photosensitive materials may be used, and the coupler is preferably a non-diffusible coupler having a hydrophobic group called a ballast group in the molecule. Turnip 2- may be either 4-equivalent or 2-equivalent to silver ions.

It may also be enriched with a colored coupler that has a color correction effect or a coupler that releases an image inhibitor (so-called DIR color) during development. Furthermore, the coupler is a coupling reaction product or nothing.

It may be a coupler that is a color.

A known closed ketomethylene thread coupler may be used as the yellow coloring coupler. Among these, benzoylacetanilide group and pivaloylacetanilide type compounds are monovalent. A specific example of the yellow coupler used is Ki LI! 1% Permit No. 2,875,057, Same No. 3.256
, No. 506, No. 3,408,194, No. 3,55
No. 1,155, No. 3,582,322, No. 3,7
No. 25,072, No. 3,891,445, West German Patent No.], No. 547.868, West Fox'f! J application (OL)
S) No. 2.213,461, No. 2.219.917, No. 2.261,361, No. 2,414. oo6
g, No. 2.263,875, etc.

It is possible to use macenta color-forming couplers, pyrazolone compounds, inks, nolon thread compounds, anoacetyl compounds, etc., and pyrazolone threads are also available.Specific examples of macenta color-forming couplers include: U.S. Patent No. 2,600,788, U.S. Patent No. 2,983,608
%, No. 113,062,653, No. 3,127,2
No. 69, No. 3,311,476, No. 3,419,
No. 391, No. 3,519,429, No. 3,558
, No. 319, No. 3,582,322, No. 3,61
No. 5,506, No. 3,834,908, No. 3,8
91,445, West German Patent No. 1,810.46'4, West German Patent tF+H (OLS) No. 2,408,665, West German Patent No. 2,417,945, West German Patent No. 2,418,959,
It is described in Japanese Patent Publication No. 2,424,467, Japanese Patent Publication No. 40-6031, etc.

As the cyan color-forming coupler, a phenol compound, a naphthol thread compound, etc. can be used. Specific examples include U.S. Patent Nos. 2,369,929 and 2,434.
, No. 272, No. 2,474,293, No. 2,52
No. 1,908, No. 2,895,826, No. 3,0 of the same prefecture
No. 34,892, No. 3,311,476, No. 3,
No. 458,315, No. 3,476.563, No. 3
, No. 583,971, No. 3,591,383.

No. 3,767.411, West German Percentage Permit J14 (OLS
) No. 2,414,830, No. 2,454,329, and Japanese Unexamined Patent Publication No. 591338/1983.

As for the blade φ coupler, for example, US Patent Nos. 3 and 4
No. 76.560, No. 2,521,908, No. 3.
(No. 134,892, Special Publication No. 44-2016, No. 38
-22335, 42-11304, 44-32
No. 461, Patent Application No. 1984-98469, Ming #I, same Seki-
No. 118029 #11, West German patent application (OLS) 2
．． 418,959 M° can be used.

As a DIR coupler, for example, US%
No. 27,554, No. 3,617,291, No. 3.
No. 701,783, No. 3,790,384, No. 3
．． No. 632,345, West German Patent Application (OLS) 2゜41
4.0 (No. 16, No. 2,454,301, No. 2,454,329, British Patent No. 953,454, and Japanese Patent Application No. 50-1+6570) can be used.

In addition to the DIR coupler, the light-sensitive material may contain a compound that releases a visual image inhibitor upon development, such as those described in U.S. Pat.
No. 529, West German Patent Application (OLS) 2°417.91
Those listed in No. 4 can be used. Other JP-A-55-8
No. 5549, No. 57-94752-j5', No. 56-6
No. 5134, No. 56-135841, No. 54-130
No. 716, No. 56-133734, No. 56-1358
No. 41, U.S. Patent No. 11g4,310,618, British Patent @2,083,640, Research Tisfroger, 418360 (1979), $14850
(1980), Ya39033 (19/80), Ya19146 (1980), Bian20525 (198
The couplers described in 1 χ A 21728 (1982) may also be used.

Two or more types of the above-mentioned force 7 lars can be included in the same layer. Further, the same compound may be contained in two or more different layers.

A coupler can be introduced into the silver halide emulsion layer by a known method, such as the method described in US Pat. No. 2,322,027. For example, phthalate alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.),
Phosphate ester (diphenylphosphny), ) IJ phenyl phosphate, tricresyl phosphate,
Dioctylbutyl phosphate), citric acid ester <51 is acetyl citrate tribunal), benzoic acid ester (ρ1 is octyl benzoate), alkyl amide (relative is diethyl laurylamide), etc., or boiling point 30'C to 150°C, for example, lower alkyl acetate such as ethyl acetate, butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., and then hydrophilic Dispersed into colloids. The above-mentioned high boiling point organic bath medium and low boiling point bath medium may be mixed and used.

When the coupler has a carboxylic acid group, such as a sulfonic acid group, it is introduced into the hydrophilic colloid as an alkaline solution.

These couplers are generally m in the silver halide emulsion layer.
2 X I (r'' moles to 5 X If' moles, preferably I X I (12 moles to 5 X Iff' moles) per mole.

Examples of antistatic agents include diacetylcellulose, styrene perfluoroalkylridium maleate copolymers, and alkali salts of reaction products of styrene-maleic anhydride copolymers and p-aminobenzenesulfonic acid. Examples of the matting agent include polymethacrylic acid methyl, polystyrene, and alkali polyester posimer. It is also possible to use colloidal silicon oxide. Further, examples of the latex added to improve the physical properties of the film include copolymers of acrylic esters, vinyl esters, etc. and other monomers having ethylene groups. Examples of gelatin plasticizers include glycerin and glycol thread compounds, and examples of thickeners include styrene-sodium maleate copolymers, alkyl vinyl ether-maleic acid copolymers, and the like.

The support for the photosensitive material made of the silver halide emulsion prepared as described above is not particularly limited, and examples include baryta paper, positive ethylene stoppered paper, polypropylene synthetic paper, glass paper, cellulose acetate, and cellulose nitrate. , polyvinyl acetal, polypropylene, polyester films such as polyethylene terephthalate, polystyrene, etc., and these supports are appropriately selected depending on the purpose of use of each photosensitive material.

These supports are subjected to F drawing processing as required.

After exposure, the light-sensitive material prepared using the silver halide emulsion of the present invention can be developed by a commonly used known method.

m white yj1. ise is an alkali metal containing visual herbal medicines such as hydroxybenzenes, aminophenols, and aminebenzenes, and also includes alkali metal salts such as sulfites, carbonates, monosulfites, bromides, and iodides. be able to. Further, when the light-sensitive material is for color use, color development can be carried out by the commonly used color development #L1 station method. In the reversal method, the material is first developed with a black negative developer *I solution, then exposed to white light in a blur or treated with a bath containing Kabu IJ MJ, and then color developed using an alkaline development method including color development.

There are no particular restrictions on the processing method, and any processing method can be applied.For example, a typical method is to carry out bleach-fixing treatment after color development, and if necessary, wash with water and perform stabilization treatment. Alternatively, it is possible to apply a method in which the fixing and fixing processes are performed separately in one area of the coloring machine, and further water washing and stabilization treatment are performed as necessary.

The iron halide emulsion according to the present invention is suitable for photographic purposes only.
, and has little fog, so it can be preferably used in many photosensitive materials.

■Eha, the photosensitive materials related to the present invention include monochrome general use, X-ray use, color use, infrared use, micro use, scissor color light and white use,
It can be effectively applied to IP and original materials for various uses such as inversion and diffusion transfer methods.

Next, the non-invention will be explained in detail with reference to Examples, and the non-invention will not be limited by these. water 720
A solution containing silver nitrate in 240 ml of water and an f# solution containing 25.4 # of potassium bromide in 2,401 ntcf2 of water were simultaneously added to a solution at 70°C containing phosphorus for 5 minutes. Ripening was performed to obtain a tabular silver bromide grain emulsion (A) as a seed crystal.

After adjusting the pBr O,H by adding potassium bromide water ME to a part of the hole MJ (AJ), the remaining part of the emulsion (A) was gradually cooled as a source emulsion, and further Ostwald ripened. A tabular conjugated silver grain emulsion (B) having an average grain size of 1.75ρ and a thickness of 0.1μ was prepared.

On the other hand, potassium iodide was added to a part of the emulsion (A) to adjust the pBr to 0.8, and the potassium iodide was added to a part of the emulsion (A) to adjust the pBr to 0.8.
．． 39 and then the remaining portion of emulsion CA) was gradually added as a source emulsion, with an average grain size of 1.53p and a thickness of 0.
．． A tabular silver iodobromide emulsion EC) having a diameter of 15 ρ was obtained.

Next, as a comparative emulsion, 1 mol% of iodide was added by the ammonia method (direct mixing method) (111).
I got it.

(1) The milk oki obtained above [B] to [D] are
Chemical sensitization (temperature 60°C) using gold-sulfur sensitization most suitable for Tani emulsion was carried out by adding sodium thiosulfate, strong acid chloride and ammonium thiocyanate adjusted to pAg 7.8, I)) 16.0. did.

Then 4-hydroxy-6-methyl-1 as a stabilizer,
3, 3a, ? - Added tetrazaindene, added 6-nitro-benzimidazole as an antifoggant, and then added Ceratin coating aid, hard #MJ1, converted to silver per 1m. The emulsion was coated in a coating amount corresponding to 4y, and the emulsion was kept dry to prepare a sample.

[2] N per mole of the other emulsion CB) to [1].

N'-dimethylselenourea], 1 x 1 ff mol, strong acid chloride 1.5 x L (l mol, sodium thiosulfate 6.3 'Add 7ru, 4
Selenium sensitization was performed at 5°C.

(3) When carrying out this selenium sensitization, add 1 mol of silver to 5 x 1 (J"-7 mol) of palladium chloride, then add chloroauric acid corresponding to the above h amount to combine selenium-palladium. Chemical ripening (45°C) was performed by sensitization.

These chemically sensitized samples were treated with stabilizers and
Add an antifoggant, a coating aid, a hardening agent, etc., apply the emulsion, dry it, and test the sample.

The coating samples obtained above each had a 3.2 CMS
The film was exposed to tungsten light for 0.01 seconds through an optical wenge, and developed using a QX-1200 automatic processor using an XD-90 developer (manufactured by Konishiroku Photo Industries (Kyu)). The results are shown in Table 1 below.The sensitivity in the table is the reciprocal of the exposure lid that gives an optical density of fog + 0.5. Sensitivity was expressed as a relative value when the sensitivity of 100 was taken as 100.

In addition, the fog in light is the fog when each sample is left for two days under the conditions of humidity mark % and temperature 50°C. Sample (C) corresponding to the silver oxide emulsion was prepared by filtering selenium-enhanced M [2J and selenium-palladium sensitization (3J), resulting in low fog in the tube sensitivity (and storage under hot, humid and vermilion conditions). It can be seen that it is stable and the occurrence of fog is suppressed even when exposed to water.

Example 11112 Tabular silver bromide grain emulsion prepared in Example 1 (
A silver nitrate solution and a potassium bromide water bath solution containing 2.0 mol % potassium iodide were added to A) by the Doublege-Cyto method. During this time, the pBr decreased to 0.7 and the pH decreased to 2.
I kept it at 0. Thus, the average grain size is 1.23p and the thickness is 0.
A temporary silver iodide grain emulsion (E) of 23 p was obtained.

The above emulsion (E) was subjected to (IJ gold-sulfur sensitization, [2J selenium sensitization and (3) selenium-palladium sensitization) in the same manner as in Example N1.

Next, emulsions (B), (C) and (
D) and the sensitizing dye shown below in addition to the Taniho-added pongee used in Example N1 in the emulsion (E) above, 1 per mole of silver.
50~ was added to perform optical sensitization.

(Sensitizing dye) 〒・1・ Next, the same test as in Example 1 was conducted on the valley sample, and the results obtained are shown in Table 2 below.

From the results in the table above, it can be seen that the tabular silver iodobromide grain pores M (C) and (E) according to the present invention are formed by the sensitizing dye after selenium sensitization (21 and selenium-palladium sensitization t31). It can be seen that even when optically sensitized, the sensitivity is high and the fog is low (and it is stable and the occurrence of fog is suppressed even when stored under hot and humid conditions).

(Effects of the Invention) The light-sensitive material containing tabular silver grains according to the present invention can effectively exhibit selenium sensitization, and can still maintain sensitivity and reduce fog.
It also has a wide range of storage stability.

Agent: Masu-shi No 1) Parent: Kou

Claims (1)

[Claims] at least (3)% of the particles have a thickness of less than 0.5μ, sensitized with three different sensitizers, including unstable selenium sensitizers, precious metal sensitizers, and sulfur sensitizers; A silver halide photographic material comprising tabular silver iodobromide grains having a diameter of 0.6 μm or more and a grain size of 5 times or more the grain thickness.