JP2702001B2 - 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 emulsion, and more particularly to a photographic light-sensitive material having improved sensitivity, graininess and contrast.

[0002]

2. Description of the Related Art In recent years, demands for photographic light-sensitive materials have become increasingly severe, and there has been an ever-higher demand for photographic light-sensitive performance such as high sensitivity, high contrast, and excellent granularity. Various studies have been made to answer these demands.

[0003] For example, a laminated silver halide grain having a plurality of outer shells (shells) on the outer side of an inner shell,
To increase the development activity and to increase the sensitivity is disclosed in
-22408, JP-B-43-1316, J.P. Photo. Sci. ,twenty four
(1976) 198 etc. JP-A-60-143331,
J. Imaging Sci. 29 (1985) 193 and the like disclose that a high iodine phase is provided inside the grains to increase the sensitivity. JP-A-60-143332 discloses that an emulsion having a high sensitivity and a high contrast can be obtained by using an emulsion having a small iodine distribution between grains.

Japanese Patent Application Laid-Open Nos. 60-35726 and 63-220238
And the like disclose that by providing a portion having a high silver iodide content inside a grain, a silver halide emulsion having a small pressure fog and a high sensitivity granularity ratio can be obtained.

It is easily presumed that these techniques can be diversified for normal-crystal (regular) silver halide grains to increase the sensitivity. However, in practice, for example, the silver iodide content of the regular grains is increased inside the regular grains. When a high part is provided and a dislocation line is introduced,
Although the sensitivity is increased, even when used in a practical silver halide photographic material, the graininess of a highlight portion is deteriorated due to a decrease in contrast, and high sensitivity, high contrast, and good graininess cannot be achieved. Thus, satisfactory results have not always been obtained with respect to the current high requirements.

The present inventors have conducted intensive studies. As a result, when dislocations were introduced by providing a portion having a high silver iodide content in regular grains, there was a large variation in the intergranular iodine distribution of emulsion grains. Clarified that the photographic performance was impaired.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a light-sensitive silver halide emulsion having high sensitivity, good granularity and high contrast.

[0008]

As a result of diligent research conducted by the present researchers, the object of the present invention is mainly that of the (111) plane and the (100) plane.
In a silver halide photographic light-sensitive material provided on a support, a silver halide emulsion layer containing a silver halide emulsion containing normal-crystal silver halide grains comprising regular silver halide grains is provided. Regarding the normal crystal silver halide grains, the ratio (crystal habit ratio) of the (100) plane to the (111) plane is 0.5 or more on average, the average silver iodide content is 2 mol% or more, and 50 % Or more has 10 or more dislocation lines per particle from the inside of the particle to the particle surface,
It has been found that a silver halide photographic material is characterized in that the relative standard deviation of the silver iodide content between grains is 30% or less.

Here, the photosensitive silver halide emulsion is
The silver halide grains preferably have a portion having a higher silver iodide content than the grain surface.

In the present invention, the normal crystal silver halide grains mainly composed of the (111) plane and the (100) plane are (1) on the entire surface of the grains.
The ratio of the (11) plane and the (100) plane is 60% or more.

The regular silver halide emulsion used in the present invention mainly comprises (111) planes and (100) planes.
Ratio of (100) plane to (111) plane (crystal habit ratio)
Is 0.5 or more on average, preferably 1 or more, more preferably 2 or more.

The silver halide grains of the present invention may be octahedral, cubic, or tetradecahedral. Also, EP
Particles having rounded corners, such as those disclosed in US Pat. Nos. 0,096,727 B1 and EP-0064412 B1, or DE-2306647C2, JP-A-60-221320.
The surface-modified particles as disclosed in the above-mentioned publication may be used.

The dislocations of regular silver halide grains are described, for example, in J. Am. F. Hamilton, Photo. Sci. Eng. , 1
1, 57, (1967); Shiozawa, J.A. Soc. Phot
o. Sci. Japan, 35, 213, (1972) can be observed by a direct method using a transmission electron microscope at a low temperature. That is, the silver halide grains taken out from the emulsion so as not to apply enough pressure to generate dislocations on the grains are placed on a mesh for observation with an electron microscope, and the sample is prepared so as to prevent damage (print-out, etc.) by an electron beam. Observation is performed by a transmission method in a state of cooling. From the photograph of the particles obtained by such a method, the number and position of dislocation lines of each particle can be obtained.

Regarding the number of dislocation lines of the particles of the present invention, 10
It is preferable that particles containing 50 or more dislocation lines exist in an amount of 50% by number or more. More preferably, the number of particles containing 10 or more dislocation lines is 80% by number or more, and particularly preferably the number of particles containing 20 or more dislocation lines is 80% by number or more.

The silver halide grains of the present invention may be fine grains having a grain size of about 0.1 μm or less, or large grains having a projected area diameter up to about 10 μm.

In the present invention, the relative standard deviation of the silver iodide content of each grain is 30% or less, preferably 20% or less, more preferably 15% or less.

The silver iodide content of each emulsion grain can be measured, for example, by analyzing the composition of each grain using an X-ray microanalyzer described in JP-A-60-254032. Here, the "relative standard deviation of the silver iodide content of each grain" means, for example, the silver iodide content of at least 100 emulsion grains measured by an X-ray microanalyzer. It is a value obtained by multiplying the value obtained by dividing the standard deviation by the average silver iodide content by 100. Specific methods for measuring the silver iodide content of individual emulsion grains are described in, for example, European Patent No. 1
47,868A.

In the present invention, the particle surface is defined as 50
It refers to a region up to a depth of about A. The silver halide emulsion composition in such a region can be usually measured by the ESCA method. The inside of the particle refers to a region other than the above-described surface region.

In the present invention, the dislocation line extends from the inside of the particle to a surface of 0.1 μm or more from the surface, and the dislocation line exists at any position on a plane, a side, or a vertex. Good.

In order to narrow the intergrain iodide distribution of the silver iodide content, the size distribution of the regular silver halide grains used in the present invention is desirably as narrow as possible.
Specifically, the relative standard deviation of the particle size is preferably 20% or less, particularly preferably 10% or less.

The silver halide emulsion composition of the grains of the present invention is preferably silver iodobromide or silver chloroiodobromide, and more preferably has a silver iodide content of 2 to 20 mol%, preferably 2 to 10 mol%. %, More preferably 2 to 5 mol% of silver iodobromide.

The production method of the regular silver halide grains of the present invention can be constituted by appropriately combining methods known in the art. For example, the method described in Research Disclosure, vol. 176, No. 17643 (November 1979), page 648 can be used.

The dislocation lines of the regular silver halide grains of the present invention can be introduced by a known method, and can be controlled, for example, by providing a specific high iodine phase inside the grains. The internal high iodine phase refers to a silver halide solid solution containing iodine. The silver halide in this case is preferably silver iodide, silver iodobromide, or silver chloroiodobromide, and is preferably silver iodide or silver iodobromide (iodine content: 20 to 40 mol%). More preferably, silver iodide is particularly preferred.

The internal high iodine phase may be uniformly deposited on the plane of the substrate grains, or may be locally present. Such localization may occur anywhere on the plane, side, or corner of the substrate particle. Further, the internal high iodine phase may be selectively epitaxially coordinated at such a site.

As a method for this purpose, for example, a so-called conversion method in which an iodide salt is added alone, for example, JP-A-59-133540, JP-A-58-108526, JP-A-59-108526,
An epitaxial junction method as described in 162540 may be used. PAg when adding iodide salt is 8.5 to 1
A range of 0.5 is more preferable, and a range of 9.0 to 10.5 is particularly preferable. Preferably, the temperature is kept in the range from 50 ° C to 30 ° C. The silver iodide content of the substrate grains is lower than that of the high iodide phase, preferably 0 to 12 mol%, more preferably 0 to 10 mol%.

The outer phase covering the high iodine phase is lower than the iodine content of the high iodide phase, preferably 0 to 12 mol%, more preferably 0 to 10 mol%, most preferably. Is 0 to 3 mol%.

The internal high iodine phase is preferably present in the range of 5 mol% to 80 mol%, more preferably 20 mol% to 70 mol% in terms of the total silver amount from the center of the regular silver halide grains.
It is more preferably present in the range of mol%, particularly preferably in the range of 30 to 70 mol%.

The iodide content of the internal high iodide phase is higher than the average iodide content of silver iodide, silver iodobromide or silver chloroiodobromide present on the grain surface, preferably 5 times or more. It is particularly preferably at least 20 times.

Further, the amount of silver halide forming the internal high iodide phase is not more than 50 mol%, more preferably not more than 10 mol%, particularly preferably not more than 5 mol% of the silver amount of the whole grains in terms of silver amount. It is as follows.

In the present invention, the properties of silver halide grains can be controlled by allowing various compounds to be present in the process of silver halide precipitation. Such a compound may be initially present in the reactor.

Further, according to a conventional method, one or more salts may be added and added. U.S. Patent No.
2,448,060, 2,628,167, 3,737,313, 3,
No. 772,031, and Research Disclosure, 13
Vol. 4, June 1975, 13752, as described in copper, iridium, lead, bismuth, cadmium, zinc (eg, chalcogen compounds of sulfur, selenium and tellurium), gold and compounds of noble metals of Group VII. The characteristics of silver halide can be controlled by allowing such a compound to be present during the process of silver halide precipitation. Japanese Patent Publication No. 58-1410
No. 5, Moisar et al., Journal of Photographic Science, Vol. 25, 1977, pp. 19-27. Reduction sensitization can be performed.

In the regular silver halide grains used in the present invention, silver halides having different compositions may be bonded by epitaxial bonding. For example, silver halides other than silver halides such as rhodan silver and lead oxide may be used. They may be joined. These emulsion grains are described, for example, in U.S. Patent Nos. 4,094,684, 4,142,900, and 4,459,353.
No., UK Patent No. 2,038,792, US Patent No. 4,349,622
Nos. 4,395,478, 4,433,501, 4,463,087
Nos. 3,656,962 and 3,852,067, JP-A-59-1625
No. 40.

The regular silver halide grains of the present invention include:
Usually, it is chemically sensitized.

Chemical sensitization is described in James (TH Jam).
es), The Theory of Photographic Process, 4th Edition, Macmillan, 1977, (TH.
James, The Theory of the Photographic Proce
ss, 4th ed, Macmillan, 1977), pages 67-76, using active gelatin.
Research Disclosure, Volume 120, April 1974
Mon, 12008; Research Disclosure, 34, 19
June 1975, 13452, U.S. Patent Nos. 2,642,361, 3,29
7,446, 3,772,031, 3,857,711, 3,901,
PAg as described in US Pat. Nos. 714, 4,266,018, and 3,904,415, and British Patent 1,315,755.
Chemical sensitization can be carried out using sulfur, selenium, tellurium, gold, platinum, palladium, iridium or combinations of these sensitizers at 5-10, pH 5-8 and temperature 30-80 ° C. Chemical sensitization is optimally performed in the presence of a gold compound and a thiocyanate compound, or as described in U.S. Patent Nos. 3,857,711, 4,266,018 and 4,054,457, such as sulfur containing compounds or hypo, thiourea. The reaction is performed in the presence of a sulfur-containing compound such as a rhodanine-based compound.

The chemical sensitization can be carried out in the presence of a chemical sensitization auxiliary. As the chemical sensitization aid, compounds known to suppress fog and increase sensitivity in the process of chemical sensitization, such as azaindene, azapyridazine and azapyrimidine, are used. Examples of chemical sensitization aid modifiers include:
U.S. Pat.Nos. 2,131,038, 3,411,914, 3,554,7
No. 57, JP-A-58-126526, and "Photographic Emulsion Chemistry" by Duffin, pp. 138-143. In addition to or as an alternative to chemical sensitization, reduction sensitization can be performed, for example, with hydrogen, as described in US Pat. Nos. 3,891,446 and 3,984,249. Also, U.S. Pat.
As described in US Pat. Nos. 18,698, 2,743,182 and 2,743,183, using reducing agents such as stannous chloride, thiourea dioxide, polyamines, or using low pAg (eg, less than 5) and / or high pH (eg, Greater than 8)
Reduction sensitization can be achieved by the treatment. Further, the color sensitization can be improved by the chemical sensitization method described in U.S. Pat. Nos. 3,917,485 and 3,966,476.

The sensitization method using an oxidizing agent described in JP-A-61-3134 and JP-A-61-3136 can also be applied to the chemical sensitization of the present invention.

The emulsion comprising regular silver halide grains of the present invention is used in combination with an emulsion comprising ordinary chemically sensitized silver halide grains (tabular grains and nontabular grains) in the same silver halide emulsion layer. be able to.

Here, as the silver halide of the tabular grains, any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used. Preferred silver halide is silver iodobromide or silver iodochlorobromide containing 30 mol% or less of silver iodide. Particularly preferably, 2 mol%
Silver iodobromide containing from 1 to 25 mol% of silver iodide.

The particle size of the tabular grains used here is as follows:
Fine particles having a diameter of 0.1 μm or less, large-sized grains having a projected area diameter of up to 10 μm may be used, and a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution may be used.

General methods for producing the above tabular grains include those described in US Pat. Nos. 4,434,226, 4,439,520 and 4,441,310.
No. 4399215, No. 4433048, No. 4386156
, No. 4400463, No. 4414306, and No. 4435501 can be achieved by appropriately combining the methods. Examples of the non-tabular grains include regular grains having regular crystals such as cubic, octahedral and tetradecahedral grains, and grains having irregular crystalline forms such as spherical and potato-like. be able to.

The non-tabular grains used in the present invention are described, for example, in "Physics and Chemistry of Photography" by Grafkid, published by Paul Montell (P. Glafkides, Chimie et.
tographique Paul Montel, 1967), "Photographic Emulsion Chemistry" by Daffin, published by Focal Press (GF Duffi).
n, Photographic Emulsion Chemistry (FocalPre
ss, 1966), "Production and Coating of Photographic Emulsions", by Zerikman et al., Focal Press (VL Zelikman et al.)
al, Making and Coating Photographic Emulsion
Focal Press, 1964). That is, any of an acidic method, a neutral method, an ammonia method, etc. may be used, and a method of reacting a soluble silver salt and a soluble halide salt may be any one of a one-sided mixing method, a simultaneous mixing method, and a combination thereof. You may. A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a control double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

Two or more silver halide emulsions formed separately may be used as a mixture.

The silver halide emulsion comprising the regular grains can be obtained by controlling pAg and pH for grain formation. For details, for example,
Science and Engineering (Photographi
c Science and Engineering, Vol. 6, 159-165
(1962); Journal of Photographic Science,
12, 242-251 (1964), U.S. Patent No. 3,655,394
And British Patent 1,413,748.

The monodispersed emulsions are described, for example, in JP-A-48-8600, JP-A-51-39027, JP-A-51-83097 and JP-A-51-83097.
53-137133, 54-48521, 54-99419, 58
Nos. 37635, 58-49938, JP-B-47-11386, U.S. Pat. No. 3,655,394 and British Patent 1,413,748.

The crystal structure of these non-tabular grains may be uniform, may have a different halogen composition inside and outside, or may have a layered structure. These emulsion grains are described, for example, in British Patent No. 1,027,146, U.S. Patent Nos. 3,505,068 and 4,444,877 and JP-A-60-1433.
No. 31.

In the present invention, 0.6 μm or less, preferably 0.2 μm
A non-light-sensitive fine particle emulsion having a size of not more than μm may be added to a silver halide emulsion layer, an intermediate layer or a protective layer for the purpose of accelerating development, improving storage stability, and effectively utilizing reflected light.

The regular silver halide grains of the present invention include:
Preferably used for color photographic materials.

Known photographic additives which can be used in the present invention are Research Disclosure No. 17643 and No. 187.
16 and the locations described in Table 1 are shown.

The photographic light-sensitive material of the present invention contains various colors.
Couplers can be used. A specific example is the above-mentioned Research Disclosure (RD) No. 17643, VI
It is described in the patents described in IC-G. As the dye-forming coupler, a coupler that provides the three primary colors of the subtractive color method (that is, yellow, magenta, and cyan) by color development is important. Specific examples of the diffusion-resistant 4-equivalent or 2-equivalent coupler include RD No. 17643, VII-
In addition to the couplers described in the patents described in C and D, the following can be preferably used in the present invention.

Typical yellow couplers usable in the photographic light-sensitive material of the present invention include hydrophobic acylacetamide couplers having a ballast group. Specific examples thereof are described in, for example, U.S. Patent Nos. 2,407,210, 2,875,057, and 3,265,506. In the present invention, the use of 2-equivalent yellow couplers is preferred. For example, US Pat. Nos. 3,408,194 and 3,447,928
Nos. 3,933,501 and 4,022,620, each of which is an oxygen atom desorbable yellow coupler or, for example, Japanese Patent Publication No. 58-10739, U.S. Pat.Nos. 4,401,752,
No. 4,326,024, RD No. 18035 (April 1979), UK Patent No. 1,425,020, West German Application Publication No. 2,219,917,
2,261,361, 2,329,587 and 2,433,812
The nitrogen-elimination type yellow coupler described in No.
Typical examples are given below. α-pivaloyl acetanilide couplers are excellent in the fastness of a coloring dye, especially in light fastness, while α-benzoylacetanilide couplers provide a high color density.

The magenta coupler which can be used in the photographic light-sensitive material of the present invention includes a hydrophobic, indazolone-based or cyanoacetyl-based, preferably 5-pyrazolone- or pyrazoloazole-based coupler having a ballast group. Is mentioned. The 5-pyrazolone coupler is 3-
A coupler substituted with an arylamino group or an acylamino group is preferred from the viewpoint of the hue and color density of a coloring dye. Representative examples thereof include, for example, US Pat. No. 2,311,082
No. 2,343,703, No. 2,600,788, No. 2,90
Nos. 8,573, 3,062,653, 3,152,896 and 3,936,015. As a leaving group of a 2-equivalent 5-pyrazolone coupler, US Pat. No. 4,310,61
A nitrogen atom leaving group described in No. 9 or U.S. Pat.
The arylthio group described in 1,897 is particularly preferred.
Further, a 5-pyrazolone-based coupler having a ballast group described in European Patent No. 73,636 can obtain a high color density. U.S. Pat. No.
Pyrazolobenzimidazoles described in 3,061,432, preferably pyrazolone [5,1-c] [1,2,4] triazoles described in U.S. Pat. No. 3,725,067, Research Disclosure J.P. 24220 (June 1984) and pyrazolotetrazols and research disclosure jars 24230 (June 1984) described in JP-A-60-33552.
) And pyrazolopyrazoles described in JP-A-60-43659. The imidazo [1,2-b] pyrazols described in U.S. Pat. No. 4,500,630 are preferred from the viewpoint of low yellow side absorption and light fastness of the coloring dye, and the pyrazolo [1] described in U.S. Pat. No. 4,540,654 are preferred. , 5-
b] [1,2,4] triazole is particularly preferred.

Cyan couplers which can be used in the photographic light-sensitive material of the present invention include hydrophobic and diffusion-resistant naphthol-based and phenol-based couplers.
No. 2,474,293, naphthol-based couplers, preferably U.S. Pat.Nos. 4,052,212, 4,146,396,
Representative examples thereof include an oxygen atom-eliminating 2-equivalent naphthol-based coupler described in 4,228,233 and 4,296,200. Specific examples of phenol couplers are described in, for example, U.S. Pat. Nos. 2,369,929 and 2,801,171.
Nos. 2,772,162 and 2,895,826.

Couplers capable of forming cyan dyes which are robust to humidity and temperature are preferably used in the present invention,
Typical examples are, for example, phenolic cyan couplers having an alkyl group of ethyl or more at the meta position of the phenol nucleus described in U.S. Pat.No. 3,772,002, such as U.S. Pat.Nos. 2,772,162 and 3,758,308. Id 4,126,396
Nos. 4,334,011, 4,327,173, German Patent Publication No. 3,329,729 and European Patent 121,365, for example, 2,5-diacylamino-substituted phenolic couplers, for example, U.S. Pat. No. 4,333,999
Nos. 4,451,559 and 4,427,767 which are phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position. Cyan couplers in which a sulfonamide group or an amide group is substituted at the 5-position of naphthol described in EP 161 626A, for example, have excellent color image fastness and can be preferably used in the present invention.

In order to correct the unnecessary absorption of the coloring dye, it is preferable to perform masking by using a color coupler in combination with the color photographic material for photography. For example, U.S. Pat.
No. 63,670 and Japanese Patent Publication No. 57-39413, yellow-colored magenta couplers or, for example, U.S. Pat.
4,929, 4,138,258 and British Patent 1,146,36
The magenta colored cyan coupler described in No. 8 is a typical example. Other color couplers are RD 1
7643, paragraphs VII-G.

Coupler whose coloring dye has moderate diffusibility
Can be used together to improve the graininess. As such couplers, specific examples of a magenta coupler are disclosed in U.S. Pat. No. 4,366,237 and British Patent No. 2,125,570.
EP 96,570 and German Offenlegungsschrift 3,234,533 describe specific examples of yellow, magenta or cyan couplers.

The dye-forming coupler and the above-mentioned special coupler may form a polymer of a dimer or more. Polymer
A typical example of a dyed coupler is described in U.S. Pat.
Nos. 51,820 and 4,080,211. Specific examples of polymerized magenta couplers are described in UK Patent No. 2,1
02,173 and U.S. Pat. No. 4,367,282.

Couplers which release a photographically useful residue upon coupling can also be preferably used in the present invention. The DIR coupler that releases the development inhibitor is the above-mentioned R
D 17643, the couplers of the patents described in VII-F are useful.

Preferred combinations with the present invention include:
Developer deactivated type represented by JP-A-57-151944; Timing type represented by U.S. Pat. No. 4,248,962 and JP-A-57-154234; Reaction type represented by JP-A-60-184248 Particularly preferred are, for example, JP-A-57-1519.
No. 44, No. 58-217932, JP-A-60-218645, No. 60-22
No. 5156, No. 59-82214 and No. 60-233650.
No. 184248, which is a reactive DIR coupler.

In the photographic light-sensitive material of the present invention, a coupler capable of releasing a nucleating agent or a development accelerator or a precursor thereof imagewise during development can be used. Specific examples of such compounds are described in British Patent Nos. 2,097,140 and 2,197.
No. 31,188. Particularly preferred are couplers which release a nucleating agent having an adsorbing effect on silver halide, and specific examples thereof are described in, for example, JP-A-59-157638.
And 59-170840.

The coupler used in the present invention can be introduced into a light-sensitive material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in, for example, US Pat. No. 2,322,027.

Specific examples of the steps and effects of the latex dispersion method and examples of the latex for impregnation are described in US Pat.
No. 99,363 and West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

Suitable supports that can be used in the present invention are described, for example, in RD. No. 17643, p. 28 and No. 187116
On page 647, right column to page 648, left column.

The color photographic light-sensitive material according to the present invention is prepared by using the RD. No. 17643, pp. 28-29, and No. 18716, No. 6
The development can be carried out by the usual method described on page 51, left column to right column.

The color photographic light-sensitive material of the present invention is usually subjected to a washing treatment or a stabilization treatment after development, bleach-fixing or fixing.

In the water washing step, two or more tanks are generally countercurrently washed to save water. As stabilization processing,
Instead of the water washing step, a multi-stage countercurrent stabilization treatment as described in JP-A-57-8543 is mentioned as a typical example. In the case of this step, 2 to 9 countercurrent baths are required. Various compounds are added to the stabilizing bath for the purpose of stabilizing an image. For example, adjusting the membrane pH (for example, pH 3 to
8) Various buffering agents (eg, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid) Are used in combination) and formalin. In addition, if necessary, for example, a water softener (for example, inorganic phosphoric acid,
Aminopolycarboxylic acid, organic phosphoric acid, aminopolyphosphonic acid, phosphonocarboxylic acid), disinfectant (for example, benzoisothiazolinone, isothiazolone, 4-thiazoline benzimidazole, halogenated phenol), surfactant Various additives such as a fluorescent whitening agent and a hardening agent may be used, or two or more of the same or different target compounds may be used in combination.

It is preferable to add, for example, various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate as the membrane pH adjuster after the treatment.

The present invention can be applied to various color light-sensitive materials. For example, general or movie color negative films, slide or TV color
Reversal films, color papers, color-positive films and color reversal papers can be mentioned as typical examples. The present invention also provides, for example,
It can also be applied to a black-and-white light-sensitive material using a mixture of three-color couplers described in J. No. 17123 (July 1978).

[0069]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Example 1 (Preparation of Emulsion A) An aqueous silver nitrate solution and an aqueous potassium bromide solution were added to an aqueous gelatin solution kept at 75 ° C. by a double jet method at a pAg of 7.0. As a result, 0.24 μm silver iodobromide core grains were obtained (core formation step).

Subsequently, at 75 ° C., an aqueous solution containing silver nitrate and an aqueous solution containing potassium bromide and potassium iodide were added to pAg
At 7.7, added by the double jet method (particle growth stage 1).

Further, at 75 ° C., an aqueous silver nitrate solution and an aqueous potassium bromide solution were added at a pAg of 7.7 by a double jet method (particle growth stage 2). The emulsion thus obtained was named Emulsion A.

(Preparation of Emulsion B) Core grains were formed in the same manner as Emulsion A, and grain growth stage 1 was carried out in the same manner as Emulsion A, except that an aqueous solution of silver nitrate and an aqueous solution of potassium bromide were used.

Further, an aqueous solution of potassium iodide was added at a temperature of 75 ° C. and a pAg of 7.7 (conversion).

Further, the grain growth stage 2 was carried out in the same manner as in the case of Emulsion A to obtain Emulsion B.

(Preparation of Emulsion C) Emulsion C was prepared in exactly the same manner as Emulsion B, except that the temperature during the addition of the potassium iodide aqueous solution (conversion) was changed to 40 ° C.

(Preparation of Emulsion D) Emulsion D was prepared in exactly the same manner as Emulsion B except that the pAg at the time of adding the aqueous solution of potassium iodide (conversion) was changed to 9.5.

(Preparation of Emulsion E) Emulsion E was prepared in exactly the same manner as Emulsion B except that the pAg at the time of addition of the potassium iodide aqueous solution (conversion) was changed to 9.5 and the temperature was changed to 40 ° C.

(Preparation of Emulsion F) Grain Growth Stages 1 and 2
Emulsion F was prepared in exactly the same manner as Emulsion E except that the pAg of was changed to 9.5.

(Preparation of Emulsion G) An aqueous silver nitrate solution was added to a gelatin aqueous solution containing potassium bromide kept at 75 ° C. by a single jet method.

Further, an emulsion G was prepared in exactly the same manner as in Emulsion E, by carrying out grain formation step 1, conversion and grain formation step 2.

In the emulsions A to F thus obtained, the ratio of the (111) and (100) planes to the total surface was 60%.
% Or more of the particles.

Thereafter, for each of emulsions A to G, 35
After washing with water by a known flocculation method at ℃, gelatin was added, and potassium chloroaurate and sodium thionitrate were added in optimal amounts to perform chemical sensitization. Then, sensitizing dye S-
After adding the optimum amount of 1,2, the emulsions A to G were subjected to direct dislocation lines using a transmission electron microscope according to the method described in Example 1- (2) of JP-A-63-220238. Was observed. Further, with respect to emulsions A to G, the intergranular iodine distribution was determined according to the method described in EP 147868A. Table 2 shows the respective results.

To each of the obtained emulsions, dodecylbenzenesulfonate as a coating aid, p-vinylbenzenesulfonate as a thickener, a vinylsulfone compound as a hardener, and polyethylene as a photographic property improver. An oxide coating solution was prepared by adding an oxide compound. Subsequently, the coating solutions were separately applied evenly on a polyester base which had been separately processed, and a surface protective layer mainly composed of an aqueous gelatin solution was applied thereon to prepare coating samples A to G. did. At this time, the coated silver amount of each of Samples A to G was 4.0 g / m ² , and the gelatin coated amount of the protective layer was:
Each was 1.3 g / m ² , and the coated amount of gelatin in the emulsion layer was 2.7 g / m ² .

The following experiment was conducted in order to evaluate the coated product thus obtained.

First, the sample pieces of the coating samples A to G were 1/100
Exposure time for 10 seconds Wedge exposure at 10 CMS, development with a processing solution of the following composition at 20 ° C. for 4 minutes, fixing, washing and drying, sensitometry, and fog +
The sensitivity was determined by the reciprocal of the exposure amount giving a density of 0.1, and gamma was determined from the slope of a straight line connecting points D = 0.2 and D = 1.0 on the characteristic curve.

Treatment liquid 1-phenyl-3-pyrazolidone 0.5 g hydroquinone 10 g ethylenediaminetetraacetic acid / sodium sodium 2 g potassium sulfite 60 g boric acid 4 g potassium carbonate 20 g sodium bromide 5 g diethylene glycol 20 g adjusted to pH 10.0 with sodium hydroxide One liter was obtained by adding water. Table 3 shows the obtained results.

From these results, it can be seen that, even when dislocation lines such as emulsion B are present, when the intergrain iodine distribution is wide, sensitivity is increased but only soft gradation is obtained, and the object cannot be achieved. From the results of emulsions F and G, the crystal habit ratio,
It can be seen that it is preferable to specify the size distribution and the iodine distribution in order to achieve the purpose. In contrast, when the emulsion of the present invention is used, it is apparent that a highly sensitive emulsion can be obtained and the object can be achieved.

Example 2 Preparation of Sample 201 A multilayer color photographic material comprising the following layers was prepared on an undercoated 127 μm thick cellulose triacetate film support to obtain Sample 201. . The numbers represent the amount added per m ² . The effect of the added compound is not limited to the use described.

First layer: Anti-halation layer Black colloidal silver 0.20 g Gelatin 1.9 g UV absorber U-1 0.04 g UV absorber U-2 0.1 g UV absorber U-3 0.1 g UV absorber U-4 0.1 g UV absorber U-6 0.1 g High-boiling organic solvent Oil-1 0.1 g Microcrystalline solid dispersion of dye E-1 0.1 g.

Second layer: Intermediate layer Gelatin 0.40 g Compound Cpd-D 5 mg Compound Cpd-L 5 mg Compound Cpd-M 3 mg High boiling organic solvent Oil-3 0.1 g Dye D-4 0.4 mg.

Third layer: Intermediate layer A fine-grain silver iodobromide emulsion whose surface and inside are fogged (average particle size: 0.06 μm, variation coefficient: 18%, AgI content: 1 mol%) Silver amount: 0.05 g Gelatin: 0.4 g.

Fourth layer: low-sensitivity red-sensitive emulsion layer Emulsion 1 silver amount 0.1 g Emulsion 2 silver amount 0.4 g gelatin 0.8 g coupler C-1 0.15 g coupler C-2 0.05 g coupler C-9 0.05 g compound Cpd-D 10 mg High boiling organic solvent Oil-2 0.1 g.

Fifth layer: middle-sensitivity red-sensitive emulsion layer Emulsion 2 Silver amount 0.2 g Emulsion 3 Silver amount 0.3 g Gelatin 0.8 g Coupler C-1 0.2 g Coupler C-2 0.05 g Coupler C-3 0.2 g High Boiling organic solvent Oil-2 0.1 g.

Sixth layer: high-sensitivity red-sensitive emulsion layer Emulsion 4 Silver amount 0.4 g Gelatin 1.1 g Coupler C-1 0.3 g Coupler C-3 0.7 g Additive P-1 0.1 g. 7th layer: Intermediate layer Gelatin 0.6 g Additive M-1 0.3 g Color mixing inhibitor Cpd- 2.6 mg UV absorber U-1 0.1 g UV absorber U-6 0.1 g Dye D-1 0.02 g Compound Cpd-D 5 mg Compound Cpd-L 5 mg Compound Cpd-M 5 mg.

Eighth Layer: Intermediate Layer A silver iodobromide emulsion having a fogged surface and inside (average particle size 0.06 μm, variation coefficient 16%, AgI content 0.3 mol%) Silver content 0.02 g Gelatin 1.0 g Additive P- 1 0.2 g 0.1 g of a color mixture inhibitor Cpd-N 0.1 g of a color mixture inhibitor Cpd-A.

Ninth layer: low-sensitivity green-sensitive emulsion layer Emulsion 5 Silver content 0.1 g Emulsion 6 Silver content 0.2 g Emulsion 7 Silver content 0.2 g Gelatin 0.5 g Coupler C-7 0.05 g Coupler C-8 0.20 g Compound Cpd -B 0.03 g Compound Cpd-D 10 mg Compound Cpd-E 0.02 g Compound Cpd-F 0.02 g Compound Cpd-G 0.02 g Compound Cpd-H 0.02 g High boiling organic solvent Oil-1 0.1 g High boiling organic solvent Oil-2 0.1 g.

10th layer: Medium-sensitive green-sensitive emulsion layer Emulsion 7 Silver amount 0.3 g Emulsion 8 Silver amount 0.1 g Gelatin 0.6 g Coupler C-7 0.2 g Coupler C-8 0.1 g Compound Cpd-B 0.03 g Compound Cpd -E 0.02 g Compound Cpd-F 0.02 g Compound Cpd-G 0.05 g Compound Cpd-H 0.05 g High boiling organic solvent Oil-2 0.01 g.

Eleventh layer: High-sensitivity green-sensitive emulsion layer Emulsion 9 Silver amount 0.5 g Gelatin 1.0 g Coupler C-4 0.3 g Coupler C-8 0.1 g Compound Cpd-B 0.08 g Compound Cpd-E 0.02 g Compound Cpd -F 0.02 g Compound Cpd-G 0.02 g Compound Cpd-H 0.02 g High boiling organic solvent Oil-1 0.02 g High boiling organic solvent Oil-2 0.02 g.

12th layer: Intermediate layer Gelatin 0.6 g Dye D-1 0.1 g Dye D-2 0.05 g Dye D-3 0.07 g.

13th layer: Yellow filter layer Yellow colloidal silver Silver amount 0.07 g Gelatin 1.1 g 0.01 g of color mixing inhibitor Cpd-A 0.01 g of high boiling organic solvent Oil-1 0.01 g Microcrystalline solid dispersion of dye E-2 0.05 g.

Fourteenth layer: Intermediate layer 0.6 g of gelatin.

Fifteenth layer: low-sensitivity blue-sensitive emulsion layer Emulsion 10 Silver amount 0.2 g Emulsion 11 Silver amount 0.3 g Emulsion 12 Silver amount 0.1 g Gelatin 0.8 g Coupler C-5 0.2 g Coupler C-10 0.4 g.

Sixteenth layer: medium-sensitivity blue-sensitive emulsion layer Emulsion 12 silver amount 0.1 g emulsion 13 silver amount 0.4 g gelatin 0.9 g coupler C-5 0.3 g coupler C-6 0.1 g coupler C-10 0.1 g.

Seventeenth layer: high-sensitivity blue-sensitive emulsion layer Emulsion 14 Silver amount 0.4 g Gelatin 1.2 g Coupler C-6 0.6 g Coupler C-10 0.1 g.

18th layer: 1st protective layer Gelatin 0.7 g UV absorber U-1 0.04 g UV absorber U-2 0.01 g UV absorber U-3 0.03 g UV absorber U-4 0.03 g UV absorber U -5 0.05 g UV absorber U-6 0.05 g High boiling organic solvent Oil-1 0.02 g Formalin Scavenger-Cpd-C 0.2 g Formalin Scavenger-Cpd-I 0.4 g Dye D-3 0.05 g Compound Cpd-N 0.02 g.

Nineteenth layer: Second protective layer Colloidal silver Amount of silver 0.1 mg Fine grain silver iodobromide emulsion (average particle size 0.06 μm, AgI content 1 mol%) Silver amount 0.1 g Gelatin 0.4 g.

20th layer: 3rd protective layer Gelatin 0.4 g Polymethyl methacrylate (average particle size 1.5 μ) 0.1 g Copolymer of methacrylate and acrylic acid 4: 6 (average particle size 1.5 μ) 0.1 g Silicone oil 0.03 g Surfactant W-1 3.0 mg Surfactant W-2 0.03 g.

To all the emulsion layers, additives F-1 to F-8 were added in addition to the above composition. Further, in addition to the above composition, gelatin hardener H-1 and surfactants for coating and emulsification W-3, W-4, W-5, W-
6, W-7 was added.

Further, as antiseptic and antifungal agents, phenol and 1,
2-Benzisothiazolin-3-one, 2-phenoxyethanol and phenethyl alcohol were added.

The silver iodobromide emulsions 1 to 14 used in Sample 201 were
Table 4 shows the results.

Sensitizing dyes S-1 to S-8 were added as shown in Table 5.

The names or chemical structural formulas of the compounds used for preparing the samples of Examples 1 and 2 are as shown in Chemical Formulas 1 to 16 below.

(Preparation of Samples 202 to 207) In preparation of Sample 201, Emulsion A used for the fifth medium-speed red-sensitive emulsion layer and the tenth medium-speed green-sensitive emulsion layer was prepared as shown in Table 6. Samples 202 to 207 were prepared by substituting the emulsions BG.

(Evaluation of Coated Sample) The sample pieces of the coated samples 201 to 207 obtained as described above were subjected to white wedge exposure at an exposure time of 1/100 second and an exposure amount of 20 CMS. After development processing, sensitometry was performed.

Further, the sample exposed through a pattern for RMS measurement was subjected to the following processing and subjected to RMS measurement.

(Processing step) Processing step Time Temperature Tank capacity Replenishment amount Black-and-white development 6 minutes 38 ° C 12 liters 2.2 liters / m ² First rinse 2〃 38〃 4 〃 7.5 〃 Inversion 2〃 38〃 4 〃 1.1 色 Coloring Developing 6〃 38〃 12〃 2.2〃 Adjustment 2〃 38〃 4〃 1.1 白 Bleaching 6〃 38〃 122 0.22〃 Fixed 4〃 38〃 8〃 1.1〃 Second washing 4〃 38〃 8〃 7.5〃 Stable 1〃2〃2〃1.1〃 The composition of each treatment solution was as follows.

Black-and-white development Mother liquor Replenisher Nitrilo-N, N, N- 2.0 g 2.0 g Trimethylene phosphonic acid pentasodium salt Sodium sulfite 30 g 30 g Potassium hydroquinone monosulfonate 20 g 20 g Potassium carbonate 33 g 33 g 1-phenyl-4- Methyl-4-hydroxy 2.0g 2.0g Cimethyl-3-pyrazolidone Potassium bromide 2.5g 1.4g Potassium thiocyanate 1.2g 1.2g Potassium iodide 2.0mg ... Add water 1000ml 1000ml pH 9.60 9.60 pH is hydrochloric acid or hydroxylated Adjusted with potassium.

Reversal solution Mother liquor Replenisher Nitrilo-N, N, N-3.0 g To the mother liquor Trimethylenephosphonic acid / pentasodium salt Same stannous chloride / dihydrate 1.0 g p-Aminophenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 ml Water was added to 1000 ml pH 6.00 The pH was adjusted with hydrochloric acid or sodium hydroxide.

Color developing solution Mother liquor Replenisher Nitrilo-N, N, N-2.0 g 2.0 g Trimethylenephosphonic acid / pentasodium salt Sodium sulfite 7.0 g 7.0 g Trisodium phosphate / 12 hydrate 36 g 36 g Potassium bromide 1.0 g ... Potassium iodide 90mg ... Sodium hydroxide 3.0g 3.0g Citrazinic acid 1.5g 1.5g N-ethyl- (β-methanesulfonamide 11g 11g ethyl) -3-methyl-4-aminoaniline sulfate 3.6-dithia-1.8- Octanediol 1.0 g 1.0 g Water was added to 1000 ml 1000 ml pH 11.80 12.00 The pH was adjusted with hydrochloric acid or potassium hydroxide.

Adjustment solution Mother liquor Replenisher Ethylenediaminetetraacetic acid disodium salt 8.0 g To the mother liquor Disodium salt Same sodium sulfite 12 g 1-thioglycerin 0.4 ml Sorbitan ester (compound shown below) 0.1 g Water In addition, 1000 ml pH 6.20 pH was adjusted with hydrochloric acid or sodium hydroxide.

Bleaching solution Mother liquor Replenisher Ethylenediaminetetraacetic acid disodium salt 2.0 g 4.0 g dihydrate Ethylenediaminetetraacetic acid Fe (III) A 120 g 240 g ammonium dihydrate 100 g potassium bromide 200 g ammonium nitrate 10 g 20 g water In addition, 1000 ml 1000 ml pH 5.70 5.50 pH was adjusted with hydrochloric acid or sodium hydroxide.

Fixer mother liquor replenisher ammonium thiosulfate 8.0 g sodium sulphite 5.0 g same mother liquor 5.0 g water was added to mother liquor 1000 ml pH 6.60 pH was adjusted with hydrochloric acid or aqueous ammonia.

Stabilizing solution Mother liquor Replenishing solution Formalin (37%) 5.0 ml Polyoxyethylene-p-monononylfe 0.5 ml to the same mother liquor Nyl ether (average degree of polymerization 10) Water was added 1000 ml without pH adjustment.

Table 7 shows the results. Here, each sensitivity represents a relative sensitivity at a density of 1.0.

From these results, it is clear that the use of the emulsion of the present invention makes it possible to obtain a photographic material having high sensitivity and good graininess.

[0127]

According to the present invention, a photographic material having high sensitivity, good granularity, and excellent contrast can be obtained.

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[Table 1]

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Claims (2)

(57) [Claims] 1. A halogenated silver halide emulsion layer comprising a silver halide emulsion layer containing a silver halide emulsion containing normal crystal (regular) silver halide grains mainly comprising (111) and (100) planes is provided on a support. In the silver photographic light-sensitive material, the ratio of the (100) plane to the (111) plane (crystal habit ratio) of the normal crystal silver halide grains in the silver halide emulsion
Is 0.5 or more on average, the average silver iodide content is 2 mol% or more, and 50% or more in number has 10 or more dislocation lines per grain from the inside of the grain to the grain surface. Wherein the relative standard deviation of the silver iodide content is 30% or less. 2. The silver halide photographic material according to claim 1, wherein the silver halide photographic material is a normal crystal silver halide grain having a relative standard deviation of grain size distribution of 20% or less.