JPH04335338A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance rapid processability and sensitivity and to reduce fluctuation of gradation by incorporating silver chlorobromide grains containing silver chloride in an amount of >=80mol% and silver bromide in a localized phase in an amount of >=10mol%, and sensitizing silver halide by a selenium compound. CONSTITUTION:The silver halide emulsion layer contains the silver halide in an average silver halide composition of >=80mol% silver chloride and <=1mol% silver iodide, preferably, substantially no silver iodide, and preferably, silver chlorobromide containing >=95mol% silver chloride. The silver halide grains has a localized phase containing at least >10mol% silver bromide in a layer state or nonlayer state in the inside of each grain or near the surface, preferably, in the inside by <=1/5 the grain diameter apart from the surface.

Description

Detailed Description of the Invention [0001] The present invention relates to a silver halide photographic light-sensitive material, and more specifically, it has excellent rapid processability and high sensitivity, and changes in sensitivity and gradation due to changes in exposure time. The present invention relates to a silver halide photographic material that exhibits little variation in tone and also has little variation in sensitivity or gradation due to changes in time between exposure and processing. [0002]Currently commercially available silver halide photographic materials and image forming methods using the same are diverse and are used in all fields. Among these photosensitive materials, for products used in markets where there is a strong demand for large quantities of prints to be completed in short lead times, such as photosensitive materials for color photographic paper, silver bromide or chloride containing virtually no silver iodide is used. Silver bromide has been used. In recent years, there has been an increasing demand for improved rapid processing performance of color photographic paper, and much research has been conducted. It is known that increasing the silver chloride content of the silver halide emulsion used dramatically improves the development speed, and in reality, in the market, the high silver chloride content of the emulsion used in color photographic paper is is progressing. However, with conventional chemical sensitization, silver halide emulsions with a high silver chloride content are difficult to obtain high sensitivity and high gradations, and furthermore, they suffer from reciprocity failure, that is, changes in sensitivity and gradation due to changes in exposure illuminance. Various techniques have been disclosed to overcome these problems. [0003] JP-A-58-95736, JP-A No. 58-10
No. 8533, No. 60-222844, No. 60-222
No. 845 and No. 64-26837 disclose that high sensitivity and high contrast performance can be obtained by high silver chloride emulsions having silver bromide rich regions of various structures. However, although highly sensitive emulsions can certainly be obtained by following these techniques, the effect of improving reciprocity failure is slight. It is known that doping silver halide grains with iridium is effective in improving reciprocity law failure of silver halide emulsions. For example, Japanese Patent Publication No. 43-4935 states that a light-sensitive material using a silver halide emulsion with a trace amount of Ir compound added during precipitation or ripening produces images with almost constant gradation over a wide range of exposure time. It is disclosed that it can be obtained. However, in a silver halide emulsion doped with iridium with a high silver chloride content, latent image intensification occurs between 15 seconds and about 2 hours after exposure, as reported by Zwicky in Journal
of Photographic Science (Journa)
of Photographic Science
), volume 33, page 201. If this happens, the sensitivity and gradation will fluctuate due to changes in the time between exposure and processing, which is not desirable in practice. JP-A-1-105940 discloses that a high silver chloride emulsion having a silver bromide-rich region selectively doped with iridium has excellent reciprocity properties without impairing latent image stability for several hours after exposure. It is disclosed that an emulsion can be obtained. However, as the inventors investigated,
With this technology, latent image sensitization may occur depending on the reaction conditions when forming the silver bromide-rich region, and further improvements are required to fully achieve both latent image stability and reciprocity properties. It was found necessary. SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a high-sensitivity device with excellent rapid processing performance, little variation in sensitivity and gradation due to changes in exposure time, and furthermore, An object of the present invention is to provide a silver halide photographic material with little variation in sensitivity and gradation due to changes in time (improved latent image stability). [Means for Solving the Problems] The object of the present invention is to provide a silver halide photographic light-sensitive material having at least one light-sensitive emulsion layer containing a silver halide emulsion on a support.
At least one of the silver halide emulsion layers contains a silver halide emulsion consisting of silver chlorobromide grains having a silver chloride content of 80 mol% or more, and the grains have a localized phase having a silver bromide content of 10% or more. This was achieved by a silver halide photographic light-sensitive material having the following characteristics, and further characterized in that the grains are selenium-sensitized. The present invention will be explained in detail below. The silver halide emulsion used in the present invention "consists of silver chlorobromide grains having a silver chloride content of 80 mol% or more" means that the average halogen composition of the silver halide grains contained in the emulsion of the present invention is 80 mol%.
The above is silver chloride, which means silver chlorobromide that does not substantially contain silver iodide. Here, "substantially no silver iodide" means that the silver iodide content is preferably 1.0 mol% or less. Further, the average halogen composition of the silver halide grains is preferably silver chlorobromide containing substantially no silver iodide, in which 95 mol % or more is silver chloride. Furthermore, it is most preferable to use silver chlorobromide, which is 99 mol % or more of silver chloride and is substantially free of silver iodide. The silver halide grains of the present invention must have localized phases with a silver bromide content of at least 10 mol % inside and/or on the surface of the silver halide grains in a layered or non-layered form. It is preferable that such a localized phase having a high silver bromide content be located near the grain surface in order to exhibit the effects of the present invention, as well as from the viewpoints of pressure resistance, treatment liquid composition dependence, and the like. Here, near the particle surface means
This refers to a position within 1/5 of the grain size of the silver halide grains used, measured from the outermost surface. More preferably, the position is within 1/10 of the grain size of the silver halide grains used, as measured from the outermost surface. The most preferred arrangement of the localized phase with a high silver bromide content is one in which the localized phase with a silver bromide content of at least 10 mol % is epitaxially grown at the corners of cubic or tetradecahedral silver chloride grains. The silver bromide content of the localized phase with a high silver bromide content must exceed 10 mol %, but if the silver bromide content is too high, it will decrease when pressure is applied to the photosensitive material. Undesirable characteristics may be imparted to the photographic material, such as the sensitivity and gradation greatly changing due to changes in the composition of the processing solution. Taking these points into consideration, the silver bromide content of the localized phase with a high silver bromide content is preferably in the range of 10 to 60 mol%, and 20 to 60 mol%.
The most preferred range is from 50% by mole. The silver bromide content of the localized phase with a high silver bromide content can be determined using the X-ray diffraction method (for example,
It can be analyzed using methods such as those described in "Structural Analysis", New Experimental Chemistry Course 6, edited by the Chemical Society of Japan, published by Maruzen. The localized phase having a high silver bromide content is preferably composed of 0.1 to 20% of silver, and 0.2 to 5% of the total silver amount constituting the silver halide grains of the present invention. More preferably, it is made of silver. The interface between such a localized phase with a high silver bromide content and other phases may have a clear phase boundary or a transition region where the halogen composition gradually changes. good. Various methods can be used to form such a localized phase with a high silver bromide content. for example,
A localized phase can be formed by reacting a soluble silver salt and a soluble halogen salt by a one-sided mixing method or a simultaneous mixing method. Furthermore, the localized phase can also be formed using a conversion method in which silver halide grains that have already been formed are converted into silver halide having a lower solubility product. or,
After mixing cubic or tetradecahedral silver halide host grains with silver halide fine grains having a smaller average grain size and a higher silver bromide content than the silver halide host grains,
It is also preferable to form a localized phase with a high silver bromide content by ripening. The emulsion grains of the present invention preferably contain an iridium compound. A water-soluble iridium compound can be used as the iridium compound used in the present invention. For example, iridium halide (II
I) compound, iridium (IV) halide compound,
Also, iridium complex salts having halogens, amines, oxalato, etc. as ligands, such as hexachloroiridium (III) or (IV) complex salts, hexaammineiridium (III) or (IV) complex salts, trioxalatoiridium (III) Alternatively, (IV) complex salts may be mentioned. In the present invention, among these compounds, III-valent compounds and IV-valent compounds can be used in any combination. These iridium compounds are used after being dissolved in water or a suitable solvent, but in order to stabilize solutions of iridium compounds, a commonly used method is to dissolve an aqueous hydrogen halide solution (e.g. hydrochloric acid,
A method of adding hydrochloric acid (bromic acid, hydrofluoric acid, etc.) or an alkali halide (eg, KCl, NaCl, KBr, NaBr, etc.) can be used. Instead of using a water-soluble iridium compound, it is also possible to add and dissolve other silver halide grains doped with iridium in advance during the preparation of silver halide grains according to the present invention. The total amount of iridium compound added during the preparation of silver halide grains according to the present invention is 5×10 −9 to 1×1 per mole of silver halide finally formed.
0-4 mol is suitable, preferably 1 x 10-8 to 1
x 10-5 mol, most preferably 5 x 10-8 to 5 x 1
0-6 mol. When the silver halide emulsion grains of the present invention contain an iridium compound, the localized phase having a high silver bromide content of the present invention accounts for at least 50% of the total iridium added during the preparation of the silver halide grains. Preferably, it is deposited with %. More preferably, the localized phase is deposited with at least 80% of the total iridium added, and most preferably with all the iridium added. Here, the expression "depositing the localized phase together with iridium" means that the iridium compound is supplied simultaneously with, immediately before, or immediately after supplying silver or halogen to form the localized phase. When a localized phase with a high silver bromide content is formed by mixing silver halide fine grains with a smaller average grain size and a higher silver bromide content than the silver halide host grains and then ripening the mixture, It is preferable that the silver halide fine particles having a high silver bromide content contain an iridium salt in advance. The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (grain size is defined as the diameter of a circle equivalent to the projected area of the grain, and the number average thereof is taken) is 0. 1μ to 2μ is preferable. Further, the particle size distribution thereof is preferably so-called monodisperse, with a coefficient of variation (standard deviation of particle size distribution divided by average particle size) of 20% or less, preferably 15% or less. At this time, in order to obtain a wide latitude, it is preferable to blend the above monodispersed emulsions in the same layer or to apply multilayer coating. The shapes of silver halide grains contained in photographic emulsions include regular crystal shapes such as cubes, tetradecahedrons, and octahedrons, and irregular crystal shapes such as spherical and plate shapes.
ar) A substance having a crystalline form or a compound form thereof can be used. Moreover, it may be made of a mixture of crystals having various crystal forms. In the present invention, it is preferable that particles having the above-mentioned regular crystal form be contained in an amount of 50% or more, preferably 70% or more, and more preferably 90% or more. [0015] In addition to these, the average aspect ratio (
An emulsion in which tabular grains having a diameter (diameter in terms of circle equivalent to thickness) of 5 or more, preferably 8 or more in terms of projected area exceeds 50% of the total grains can also be preferably used. The silver chlorobromide emulsion used in the present invention is P. Chim by Glafkides
ie et Physique Photography
ique (Paul Montel, 1967)
,G. F. Written by Duffin Photographic
Emulsion Chemistry (Focal
Press, 1966), V. L. Zelik
Makingand Coat by man et al.
ing Photographic Emulsion
(Focal Press, 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any method such as one-sided mixing method, simultaneous mixing method, or a combination thereof. May be used. A method in which particles are formed in an atmosphere containing excess silver ions (so-called back mixing method) can also be used. As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called controlled double jet method can also be used. According to this method,
A silver halide emulsion with a regular crystal shape and nearly uniform grain size can be obtained. In addition to the above-mentioned iridium salt, various polyvalent metal ion impurities can be introduced into the silver halide emulsion used in the present invention during the emulsion grain formation or physical ripening process. Examples of the compounds used include salts of cadmium, zinc, lead, copper, thallium, etc., or salts or complex salts of Group VIII elements such as iron, ruthenium, rhodium, palladium, osmium, platinum, etc. In particular, the Group VIII elements mentioned above can be preferably used. The amount of these compounds added varies widely depending on the purpose, but 10-
9 to 10-2 mol is preferred. Next, the selenium sensitization applied to the silver halide emulsion of the present invention will be explained in detail. As the selenium sensitizer used in the present invention, selenium compounds disclosed in conventionally known patents can be used. Selenium sensitization is usually carried out by adding an unstable selenium compound and/or a non-unstable selenium compound to a silver halide emulsion and stirring the emulsion at a high temperature, preferably 40° C. or higher, for a certain period of time. As an unstable selenium compound,
-15748, Japanese Patent Publication No. 43-13489, Japanese Patent Application No. 1998
It is preferable to use compounds described in Japanese Patent Application No. 2-130976 and Japanese Patent Application No. 2-229300. Specific unstable selenium sensitizers include isoselenocyanates (for example, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenamides, selenocarboxylic acids (for example, 2- selenopropionic acid, 2-selenobutyric acid), selenoesters, diacylselenides (e.g. bis(3-chloro-2,6
-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, and colloidal metal selenium. Although preferred types of unstable selenium compounds have been described above, these are not intended to be limiting. Those skilled in the art understand that when it comes to unstable selenium compounds used as sensitizers in photographic emulsions, the structure of the compound is not particularly important as long as selenium is unstable; It is generally understood that the moiety has no role other than to support the selenium and allow it to exist in an unstable form in the emulsion. In the present invention, unstable selenium compounds having such a broad concept are advantageously used. The non-unstable selenium compound used in the present invention is
No. 4553, Special Publication No. 52-34492 and Special Publication No. 5
The compound described in No. 2-34491 is used. Non-labile selenium compounds include, for example, selenite, potassium selenocyanide, selenazole compounds, quaternary salts of selenazole compounds, diaryl selenide, diaryl diselenide, dialkyl selenide, dialkyl diselenide, 2-selenazolidinedione, Examples include 2-selenoxazolidinethione and derivatives thereof. Among these selenium compounds, the following general formulas (I) and (II) are preferred.
) can be given. General formula (I) ##STR1## In the formula, Z1 and Z2 may each be the same or different and represent an alkyl group (for example, methyl, ethyl, t-butyl, adamantyl, t-octyl)
, alkenyl groups (e.g. vinyl, propenyl), aralkyl groups (e.g. benzyl, phenethyl), aryl groups (e.g. phenyl, pentafluorophenyl, 4-
chlorophenyl, 3-nitrophenyl, 4-octylsulfamoylphenyl, α-naphthyl), heterocyclic groups (e.g. pyridyl, thienyl, furyl, imidazolyl),
-NR1(R2), -OR3 or -SR4. R1, R2, R3 and R4 may each be the same or different and represent an alkyl group, an aralkyl group, an aryl group or a heterocyclic group. Examples of the alkyl group, aralkyl group, aryl group or heterocyclic group include the same examples as Z1. However, R1 and R2 may be a hydrogen atom or an acyl group (eg, acetyl, propanoyl, benzoyl, heptafluorobutanoyl, difluoroacetyl, 4-nitrobenzoyl, α-naphthoyl, 4-trifluoromethylbenzoyl). In the general formula (I), preferably Z1 represents an alkyl group, an aryl group or -NR1 (R2),
Z2 represents -NR5(R6). R1, R2, R
5 and R6 may each be the same or different and represent a hydrogen atom, an alkyl group, an aryl group, or an acyl group. In general formula (I), more preferably N,N-dialkylselenourea, N,N,N'-trialkyl-N
'-acylselenourea, tetraalkylselenourea, N
, N-dialkyl-arylselenoamide, N-alkyl-N-aryl-arylselenoamide. General formula (II) ##STR2## In the formula, Z3, Z4 and Z5 may be the same or different, and represent an aliphatic group, an aromatic group, a heterocyclic group, -OR7, -NR8 (R9), -SR1
0, -SeR11, -X or a hydrogen atom. R7
, R10 and R11 represent an aliphatic group, aromatic group, heterocyclic group, hydrogen atom or cation, R8 and R9
represents an aliphatic group, an aromatic group, a heterocyclic group, or a hydrogen atom, and X represents a halogen atom. In general formula (II),
Z3, Z4, Z5, R7, R8, R9, R
The aliphatic group represented by 10 and R11 is a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group, aralkyl group (for example, methyl, ethyl, n-propyl,
isopropyl, t-butyl, n-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopentyl, cyclohexyl, allyl, 2-butenyl, 3-pentenyl, propargyl, 3-pentynyl, benzyl, phenethyl). In general formula (II), Z3, Z4
, Z5 , R7 , R8 , R9 , R10 and R1
The aromatic group represented by 1 is a monocyclic or condensed aryl group (
For example, phenyl, pentafluorophenyl, 4-chlorophenyl, 3-sulfophenyl, α-naphthyl, 4-
methylphenyl). In the general formula (II), Z3, Z4
, Z5 , R7 , R8 , R9 , R10 and R1
The heterocyclic group represented by 1 is a 3- to 10-membered saturated or unsaturated heterocyclic group containing at least one of a nitrogen atom, an oxygen atom, or a sulfur atom (e.g., pyridyl, thienyl, furyl, thiazolyl, imidazolyl). , benzimidazolyl). In general formula (II), R7, R10 and R11
The cation represented by represents an alkali metal atom or ammonium, and the halogen atom represented by X represents, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. In general formula (II), preferably Z3, Z4 or Z5
represents an aliphatic group, an aromatic group, or -OR7, R7
represents an aliphatic group or an aromatic group. In general formula (II),
More preferably it represents trialkylphosphine selenide, triarylphosphine selenide, trialkylselenophosphate or triarylselenophosphate. Specific examples of compounds represented by general formulas (I) and (II) are shown below, but the present invention is not limited thereto. [Formula 3] [Formula 3] [Formula 4] [Formula 5] [Formula 5] [Formula 6] [Formula 7] [Formula 7] ##STR10## The amount of selenium sensitizer used depends on the selenium compound used, the silver halide grains (the type and content of halogen,
Although it varies depending on grain size, crystal shape, etc.), chemical ripening conditions, etc., it is generally 10-8 to 10-4 per mole of silver halide.
The amount used is preferably about 10-7 to 10-5 moles. The conditions for chemical sensitization in the present invention are not particularly limited, but the pAg is generally 5 to 10, preferably 5.
5 to 8, more preferably 6 to 7.5, and the temperature is generally 30 to 80°C, preferably 40 to 70°C. The pH is generally 4-10, preferably 5-8. The temperature is generally 30 to 80°C, preferably 40 to 70°C.
It is ℃. Regarding the chemical sensitization method applied to the silver halide emulsion used in the present invention, in addition to selenium sensitization alone using the selenium compound of the present invention, sulfur sensitization represented by the addition of an unstable sulfur compound, gold sensitization, etc. Noble metal sensitization represented by sensitization,
Alternatively, reduction sensitization or the like can be used in combination. Compounds used for chemical sensitization are described in JP-A-62-
Those described in the lower right column on page 18 to the upper right column on page 22 of Publication No. 215272 are preferably used. Spectral sensitization applied to the silver halide emulsion used in the present invention is carried out for the purpose of imparting spectral sensitivity in a desired light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention. In the present invention, it is preferable to add a dye-spectral sensitizing dye that absorbs light in a wavelength range corresponding to the desired spectral sensitivity. Spectral sensitizing dyes used at this time include, for example, F
．． M. Heterocyclic c by Harmer
compounds - Cyaninedyes and
related compounds (John Wi
ley & Sons New York, London
Examples include those described in 1964). Specific examples of compounds and spectral sensitization methods are described in the above-mentioned JP-A No. 62-215272, No. 2.
Those described in the upper right column of page 2 to page 38 are preferably used. Various compounds or their precursors are added to the silver halide emulsion used in the present invention for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of light-sensitive materials, or to stabilize photographic performance. be able to. Specific examples of these compounds are given in the aforementioned Japanese Patent Application Laid-Open No. 62-21527.
Those described on pages 39 to 72 of the specification of Publication No. 2 are preferably used. The emulsion used in the present invention is a so-called surface latent image type emulsion in which latent images are mainly formed on the grain surfaces. The photosensitive material according to the present invention has a hydrophilic colloid layer which can be decolorized by the treatment described on pages 27 to 76 of European Patent EP 0,337,490A2 for the purpose of improving image sharpness, etc. Dyes (especially oxonol dyes) are added to the sensitive material so that the optical reflection density at 680 nm is 0.70 or more, and di- to tetrahydric alcohols (among others) are added to the water-resistant resin layer of the support. For example, titanium oxide surface-treated with trimethylolethane)
The content is preferably 2% by weight or more (more preferably 14% by weight or more). Photographic additives such as cyan, magenta, and yellow couplers that can be used in the present invention are preferably used after being dissolved in a high-boiling organic solvent, and the high-boiling organic solvent has a melting point of 100°C or less and a melting point of 140°C. Any of the above water-immiscible compounds can be used as long as they are good solvents for couplers. The melting point of the high-boiling organic solvent is preferably 80°C or lower. The boiling point of the high boiling point organic solvent is preferably 160°C or higher,
More preferably, the temperature is 170°C or higher. Details of these high boiling point organic solvents are described in the lower right column on page 137 to the upper right column on page 144 of the specification of JP-A-62-215272. Cyan, magenta, or yellow couplers may also be impregnated into loadable latex polymers (e.g., U.S. Pat. No. 4,203,716) in the presence or absence of the high-boiling organic solvents mentioned above, or water-insoluble and organic It can be dissolved together with a solvent-soluble polymer and emulsified and dispersed in an aqueous hydrophilic colloid solution. Preferably columns 7 to 15 of U.S. Pat. No. 4,857,449.
Column and No. 12 of International Publication No. WO88/00723 Specification
Homopolymers or copolymers described on pages 30 to 30 are used, and methacrylate or acrylamide polymers, particularly acrylamide polymers, are preferably used from the viewpoint of color image stabilization. Further, in the light-sensitive material according to the present invention, it is preferable to use a color image preservation improving compound as described in European Patent EP 0,277,589A2 together with a coupler. Particularly preferred is the combination with a pyrazoloazole coupler. That is, a compound (F) that chemically bonds with the aromatic amine developing agent remaining after color development processing to produce a chemically inert and substantially colorless compound and/or an aroma remaining after color development processing. For example, in storage after processing, the compound (G) that chemically bonds with the oxidized form of a group amine color developing agent to produce a chemically inert and substantially colorless compound may be used simultaneously or singly. This is preferable in order to prevent the generation of stains and other side effects due to the formation of coloring dyes due to the reaction between the color developing agent or its oxidized product remaining in the film and the coupler. The photosensitive material of the present invention is also coated with anti-mildew agents as described in JP-A No. 63-271247 in order to prevent various types of mold and bacteria that grow in the hydrophilic colloid layer and degrade images. It is preferable to add an agent. The support used in the light-sensitive material according to the present invention may be a white polyester support for display purposes or a support on which a layer containing a white pigment is provided on the side having a silver halide emulsion layer. A support may also be used. In order to further improve sharpness, it is preferable to coat an antihalation layer on the side on which the silver halide emulsion layer is coated or on the back side of the support. In particular, the transmission density of the support was set to 0.3 so that the display can be viewed with both reflected and transmitted light.
It is preferable to set it in the range of 5 to 0.8. The photosensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be low-intensity exposure or high-intensity short-time exposure, and particularly in the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 -4 seconds is preferred. [0041] Also, upon exposure, US Pat. No. 4,88
Preferably, a band stop filter as described in US Pat. No. 0,726 is used. This removes light color mixing,
Color reproducibility is significantly improved. The exposed light-sensitive material may be subjected to conventional black-and-white or color development, but in the case of color light-sensitive materials, for the purpose of rapid processing, it is preferable to carry out bleach-fixing after color development. In particular, when the above-mentioned high silver chloride emulsion is used, the pH of the bleach-fix solution is approximately 6.5 for the purpose of promoting desilvering.
The following is preferable, and about 6 or less is more preferable. Silver halide emulsion and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) applied to the light-sensitive material according to the present invention, and the processing method applied to process this light-sensitive material As processing additives, the following patent publications, especially European Patent EP 0,355,660A2 (
Those described in JP-A-2-139544) are preferably used. [Table 1] [Table 2] [Table 2] [Table 3] [Table 3] [Table 4] [Table 5] [0049] In addition, as a cyan coupler,
In addition to the diphenylimidazole cyan coupler described in No. 33144, European Patent EP 0,333,185A2
3-hydroxypyridine cyan coupler (
Among them, 4 of couplers (42) listed as specific examples
Particularly preferred are equivalent couplers with a chlorine leaving group to make them di-equivalent, couplers (6) and (9), and cyclic active methylene cyan couplers described in JP-A No. 64-32260 (especially preferred). Particular preference is given to the couplers examples 3, 8, 34 listed by way of example). Further, as a method for processing silver halide color light-sensitive materials using a high silver chloride emulsion with a silver chloride content of 90 mol % or more, JP-A-2-207250, page 27, top left column to page 34, top right The method described in the column is preferably applied. [Example] Example 1 32 g of lime-treated gelatin was added to 800 cc of distilled water,
After dissolving at 40°C, 5.8 g of sodium chloride and N,
1.9 cc of N'-dimethylimidazolidine-2-thione (1% aqueous solution) was added and the temperature was raised to 72°C. Subsequently, a solution in which 80 g of silver nitrate was dissolved in 480 cc of distilled water and a solution in which 27.6 g of sodium chloride was dissolved in 480 cc of distilled water were added to and mixed with the above solution over 60 minutes while maintaining the temperature at 72°C. Next, add 80g of silver nitrate to 300cc of distilled water.
24.3 g of sodium chloride and 4 mg of potassium hexacyanoferrate (II) trihydrate were added to 30 g of distilled water.
0 cc of the solution was added and mixed over 20 minutes while maintaining the temperature at 72°C. After desalting and washing with water at 40°C, 90 g of lime-treated gelatin was added, and the pAg was adjusted to 7.4 with sodium chloride and sodium hydroxide.
H was adjusted to 6.4. After raising the temperature to 58 DEG C., triethylthiourea was added in an amount of 1.times.10@-5 mol per mol of silver halide to perform optimal sulfur sensitization. In addition, the blue-sensitive sensitizing dye shown below was added at 3×1 per mole of silver halide.
Spectral sensitization was performed by adding 0-4 mol. The silver chloride emulsion thus obtained was designated as Emulsion A. Emulsion A consists of sulfur sensitization using triethylthiourea, which has a sulfur sensitization of 1×10
Emulsion B was prepared, except that it was selenium sensitized with -5 moles of dimethylselenourea. What is emulsion A?
Before sulfur sensitization, potassium bromide aqueous solution was 0% compared to silver chloride.
．． Emulsion C was prepared, the only difference being that an amount was added to give a silver bromide content of 4 mol % to form a localized silver bromide phase. Emulsion A is made by adding silver bromide ultrafine grain emulsion (grain size 0.05 μm) in an amount to give a silver bromide content of 0.4 mol% relative to silver chloride before sulfur sensitization. Emulsion D was prepared, differing only in the formation of a localized phase. Emulsion C consists of silver halide 1 instead of sulfur sensitization using triethylthiourea.
Emulsion E was prepared, the only difference being that it was selenium sensitized with 1 x 10-5 moles per mole of dimethylselenourea. Emulsion D consists of 1×10 sulfur sensitization per mole of silver halide instead of sulfur sensitization with triethylthiourea.
Emulsion F was prepared, the only difference being that it was selenium sensitized with -5 moles of dimethylselenourea. For the six types of emulsions A to F prepared in this way, the grain shape, grain size, and grain size distribution were determined from electron micrographs. The particle size was expressed as the average value of the diameter of a circle equivalent to the projected area of the particle, and the particle size distribution was calculated by dividing the standard deviation of the particle size by the average particle size. All six types of emulsions from A to F have a grain size of 0.
．． The particles were cubic particles with sharp corners of 8 μm and a particle size distribution of 0.08. In addition, X-ray diffraction of Emulsions C, D, E, and F showed weak diffraction in a portion corresponding to a silver bromide content of 10 mol % to 40 mol %. Therefore, it can be said that in emulsions C, D, E, and F, a localized phase with a silver bromide content of 10 mol % to 40 mol % is epitaxially grown at the corners of the cubic silver chloride grains. Next, the surface of the paper support laminated on both sides with polyethylene was subjected to a corona discharge treatment, and then a gelatin undercoat layer containing sodium dodecylbenzenesulfonate was applied, and various photographic constituent layers were further coated. A multilayer color photographic paper (Sample 1) having the layer structure shown below was prepared. The coating solution was prepared as follows. First layer coating solution preparation Yellow coupler (ExY) 19.1g, color image stabilizer (
Cpd-1) 4.4g and color image stabilizer (Cpd-7)
To 1.4 g, 27.2 cc of ethyl acetate and solvent (So
4. lv-3) and solvent (Solv-7), respectively.
2g of gelatin was added and dissolved, and this solution was mixed with 18% of a 10% gelatin aqueous solution containing 8cc of sodium dodecylbenzenesulfonate.
After adding it to 5 cc, it was emulsified and dispersed using an ultrasonic homogenizer. The obtained dispersion was mixed and dissolved with the silver chloride emulsion A described above to prepare a first layer coating solution. Coating solutions for the second to seventh layers were also prepared in the same manner as the first layer coating solution. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. In addition, the total amount of Cpd-10 and Cpd-11 was 25% each in each layer.
．． It was added at a concentration of 0 mg/m2 and 50.0 mg/m2. The following spectral sensitizing dyes were used in the silver chlorobromide emulsion of each light-sensitive emulsion layer. ##STR11## ##STR12## For the red-sensitive emulsion layer, the following compound was added at 2.6 x 10-3 per mole of silver halide. Mol added. ##STR14## Further, the following dyes (the amounts in parentheses represent the coating amounts) were added to the emulsion layer to prevent irradiation. ##STR15## (Layer structure) The composition of each layer is shown below. The numbers represent the coating amount (g/m2). The silver halide emulsion represents the coated amount in terms of silver. Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (TiO2) and a bluish dye (ulmarine blue)] First layer (blue-sensitive yellow coloring layer) Said silver chlorobromide emulsion (A)

0.30 Gelatin

1.22 Yellow coupler (ExY)
0.82 Color image stabilizer (Cpd-1)
0.19
Solvent (Solv-3)

0.18 Solvent (Solv-7)

0.18 Color image stabilizer (Cpd-7)

0.06 0064 Second layer (color mixing prevention layer) Gelatin

0.64 Color mixing prevention agent (Cpd-5
)
0.10 Solvent
-1)
0.16 Solvent (Solv-4)
0
．． 08 Third layer (green-sensitive magenta coloring layer) Silver chlorobromide emulsion (cubic, 1:3 mixture of large size emulsion B with an average grain size of 0.55 μm and small size emulsion B with an average grain size of 0.39 μm (Ag mol) The coefficient of variation of the grain size distribution is 0.10 and 0.08, respectively, and each size emulsion is A.
0.12 gelatin (gBr0.8 mol% was locally contained on a part of the particle surface)

1.
28 magenta coupler (ExM)
0
．． 23 color image stabilizer (Cpd-2)

0.03 color image stabilizer (Cpd-3)

0.16 color image stabilizer (Cpd-4)

0.02 Color image stabilizer (Cpd-9)

0.02 solvent (Solv-2)

0.40 Fourth layer (ultraviolet absorption layer) Gelatin

1.41 Ultraviolet absorber (UV-1)

0.47 Color mixing prevention agent (Cpd-5)

0.05 solvent (Solv-5)

0.24 Fifth layer (red-sensitive cyan coloring layer) Silver chlorobromide emulsion (cubic, large size emulsion C with an average grain size of 0.58 μm and small size emulsion C with an average grain size of 0.45 μm): 4 mixture (Ag molar ratio).The coefficient of variation of particle size distribution is 0.09 and 0.11, each size emulsion is AgBr0
．． (6 mol% was locally contained on a part of the particle surface)
0.23 gelatin

1.04 Cyan coupler (ExC)

0.32 color image stabilizer (Cpd-2)

0.03 color image stabilizer (Cpd-4)

0.02 color image stabilizer (Cpd-6)

0.18 color image stabilizer (Cpd-7
)
0.40 color image stabilizer (Cpd
-8)
0.05 Solv.
-6)
0.14 Sixth layer (ultraviolet absorption layer) Gelatin

0.48 Ultraviolet absorber (UV-1)

0.16 color mixing inhibitor (Cpd-5)

0.02 solvent (Solv-5)

0.08 Seventh layer (protective layer) Gelatin

1.10 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.17 Liquid paraffin

0.03 22] [Chemical 23] [Chemical 24] [Chemical 24] Based on the photosensitive material obtained as above, a photosensitive material was prepared in which the emulsion in the blue-sensitive layer was replaced as shown in Table 1. These samples were designated as Samples 2 to 6. In order to investigate the sensitivity and gradation of the six types of photosensitive materials obtained in this way,
Exposure was applied for 10 seconds or 10-2 seconds through an optical wedge and a blue filter, and after about 1 hour, color development was performed using the processing steps and processing solution shown below. In order to examine the latent image storage properties of photosensitive materials, exposure was applied for 10-2 seconds through an optical wedge and a blue filter, and color development was performed after 10 seconds and 10 minutes using the processing steps and processing solution shown below. Ta. The reflection density of the treated sample thus prepared was measured to obtain a characteristic curve. The sensitivity is the reciprocal of the exposure amount required to give a density 0.5 higher than the fog density, and is expressed as a relative value with the sensitivity of Sample 1 at 10 seconds exposure as 100. The gradation is calculated from the exposure amount that determined the sensitivity.
It was expressed as the difference between the density for the exposure amount increased by 0.5 in ogE and the density for which the sensitivity was determined. As an evaluation of latent image preservation,
The density difference between the processed samples was measured 10 seconds and 10 minutes after exposure. The density difference is determined by calculating the density of the sample processed 10 minutes after exposure at the exposure amount required to give a density 0.5 higher than the fog density of the sample processed 10 seconds after exposure, and then calculating the density difference from the former. expressed. Positive values represent latent image sensitization and negative values represent latent image regression. These results are summarized in Table 2. [Table 6] (Development processing) The exposed sample is continuously processed (running) using a paper processing machine until twice the capacity of the color development tank is replenished in the next processing step. It was used after carrying out. Treatment process temperature
Time Replenisher* Tank capacity Color development 35℃ 45 seconds
161ml 17 liter bleach fixing
30~35℃ 45 seconds
215ml 17 liter rinse■
30-35℃ 20 seconds
- 10 liters rinse■
30-35℃ 20 seconds
- 10 liters rinse■
30-35℃ 20 seconds 350
ml 10 liters dry
70-80℃ 60 seconds *Replenishment amount is per 1 m2 of photosensitive material. (A 3-tank countercurrent system was used for rinsing ■ → ■.) The composition of each treatment liquid is as follows. color developer
tank liquid
replenisher water

800ml 800ml Ethylenediamine-N,N,N',N'- Tetramethylenephosphonic acid
1.5g 2.0g Potassium bromide
0.015g
- triethanolamine
8.0g
12.0g Sodium chloride

1.4g - potassium carbonate
25g
25g N-ethyl-N-(β-methanesulfona)
(midoethyl)-3-methyl-4-amino
Aniline sulfate
5.0g
7.0g N,N-bis(carboxymethyl)hydrazine

4.0g 5.0g N,N-di(sulfoethyl)hydroxylamine・1Na

4.0g 5.0g Fluorescent brightener (WHITEX 4B, manufactured by Sumitomo Chemical)
1.0g 2.0g Add water
1000ml
1000ml pH (25℃)

10.05 10.45 00
78] Bleach-fix solution (tank solution and refill solution are the same) Water


400ml ammonium thiosulfate (700ml)
g/liter)
100ml sodium sulfite

17g ethylenediaminetetraacetic acid iron(III) ammonium
55g Disodium ethylenediaminetetraacetate
5g ammonium bromide

40g
add water

1000ml pH (25℃)

6.0 Rinse solution (tank solution and refill solution are the same) Ion exchange water (calcium and magnesium are each 3
ppm or less) From the results in Table 2, the effects of the present invention are clear. That is, Samples 1 and 2 using pure silver chloride emulsions A and B cannot obtain sufficient sensitivity and are not suitable for practical use. Sample 3 using emulsion C and sulfur-sensitized emulsion C having a localized silver bromide phase and sample 4 using emulsion D
Although high sensitivity can be obtained with this method, the sensitivity is significantly lowered and the tone becomes softer during high-intensity, short-time exposure, and the latent image storage stability is also poor. For the first time, sample 5 using emulsion E, which has a localized silver bromide phase and is selenium-sensitized, and sample 6 using emulsion F, have high sensitivity and little variation in sensitivity gradation due to changes in exposure time. A silver halide photosensitive material having good latent image storage stability can also be obtained. Example 2 Emulsion D of Example 1 was prepared by adding potassium hexachloroiridate (IV) during the formation of fine silver bromide particles, so that the localized phase formed by the addition of fine silver bromide particles Emulsion G was prepared with the only difference being that the emulsion contained an iridium salt in an amount of 1.times.10@-7 mole of iridium salt per mole of total silver halide. Emulsion F of Example 1 is an emulsion in which potassium hexachloroiridate (IV) is added during the formation of silver bromide fine grains, so that iridium salt is contained in the localized phase formed by the addition of silver bromide fine grains. , 1 x 10- per mole of total silver halide
Emulsion H was prepared, the only difference being that it contained 7 moles of iridium salt. Emulsion I was prepared which differed from Emulsion G only in that the iridium salt content was 2.times.10@-5 moles per mole of total silver halide. Emulsion H
Emulsion J was prepared which differed only in that the iridium salt content was 2 x 10-5 mol per mol of total silver halide. Using the above emulsions G to J, multilayer color photographic papers 7 to 10 were prepared in the same manner as in Example 1 (see Table 3),
Together with Samples 4 and 6 of Example 1, exposure and development were performed in the same manner as in Example 1, and the photographic properties were evaluated. The results are shown in Table 4. [0081] [0082] From the results in Table 4, the effects of the present invention are clear. That is, in sample 7 containing sulfur-sensitized emulsion G having a localized phase containing iridium (iridium content: 1 x 10 -7 mol per mol of total silver halide), sample 4 containing no iridium Although the lower sensitivity and softer tone during high-intensity, short-time exposure are reduced compared to the above, it is not sufficient, and the latent image storage stability is not improved. Sample 9, which has an increased iridium salt content, hardly exhibits lower sensitivity and softer tone during high-intensity, short-time exposure compared to sample 7, but the latent image storage deteriorates and cannot be put to practical use. This was selenium sensitized and iridium was added to 1 x 10-7 mol/mol Ag.
Sample 8 containing the above-mentioned sample 8 can achieve both small fluctuations in sensitivity and gradation due to changes in exposure time and good latent image storage stability. Sample 10 of the present invention, in which the amount of iridium added was further increased, also had better latent image storage stability than sample 9, which was sensitized with sulfur, and exhibited less fluctuation in sensitivity and gradation due to changes in exposure time, and good latent image. Image preservability can be achieved at the same time. Effects of the Invention The present invention provides a silver halide that is excellent in rapid processing properties, has high sensitivity, and has both small fluctuations in sensitivity and gradation due to changes in exposure time, and good latent image storage stability. A photographic material is obtained.

Claims (1)

[Claims] Claim 1: A silver halide photographic material having at least one photosensitive emulsion layer containing a silver halide emulsion on a support, wherein at least one of the silver halide emulsion layers has a silver chloride content of 80 mol% or more. A silver halide emulsion consisting of silver chlorobromide grains of Silver halide photographic material.