Silver halide emulsion, process for producing silver halide emulsion, and silver halide photographic material

Abstract

 The invention is directed to a silver halide photographic emulsion having a silver chloride content of 90 mol% or more is disclosed, wherein the silver halide emulsion contains a gelatin having an absorbance by a silver colloid test of lower than 0.25, to a process for producing the silver halide emulsion and to a silver halide photographic material containing the silver halide emulsion.

Description

[0001] The present invention relates to a silver halide emulsion, a process for producing the silver halide emulsion, and a silver halide photographic material using the silver halide emulsion, and more specifically, the invention relates to a silver halide emulsion excellent in shelf life with a lapse of time and wet abrasion resistance; a process for producing the silver halide emulsion and a silver halide photographic material using the silver halide emulsion.

[0002] A silver halide color photographic material of the related art is sensitized during the storage with a lapse of time, and thus has been embarrassed by the problem of the occurrence of fog and the problem of the deterioration of wet abrasion resistance. As one of the causes of deteriorating the shelf life with a lapse of time and wet abrasion resistance, it is related with the existence of fine silver nuclei existing in the insides and on the surfaces of silver halide grains. The fine silver nuclei are formed without intentionally adding a reducing agent during the production of a silver halide emulsion.

[0003] On the other hand, gelatin, which is used as a binder for silver halide grains, contains photographically active substances such as inhibiting substances, reducing substances, etc., and give various influences on the photographic characteristics. As trace components contained in gelatin, for example, inorganic salts, sulfur-containing components, saccharides, aldehydes, and nucleic acid are known.

[0004] Hitherto, for reducing the photographic activity of gelatin, it has been attempted to oxidize gelatin. For example, in U.S. Patent 2,890,215, it is described that by treating gelatin with peracetic acid, cysteine and aldehyde in gelatin were completely eliminated. However, because peracetic acid is a self-reactive substance having a dangerous property of explosively proceeding the reaction and thus is a substance of requiring a cautious safety countermeasure at transporting and handling the substance, an improvement countermeasure has been desired. Also, according to the paper abstract by Suzuki, et al. described in the preprint of the 1998 Meeting of The Society of Photographic Science and Technology of Japan, page 50,it is described that gelatin was oxidized by each of hydrogen peroxide, chloric acids, and peracetic acid, the influences of the kind of each oxidizing agent on methionine, aldehyde, and the physical inhibiting degree were determined, and when gelatin was treated using sodium chlorite, the amount of aldehyde was reduced. Also, according to the report by F.J. Moll described in Journal of Photographic Sciences, Vol. 34, page 47, it is described that in the oxidation of gelatin with an aqueous solution of hydrogen peroxide, when the extent of the oxidation is increased, the formation of fog is increased and the grain growth inhibiting force is reduced, and by the oxidation, the amount of aldehyde in the gelatin is not reduced, but the amount of methionine is reduced. Also, in Japanese Patent Laid-Open No. 157024/1987, it is described that by the treatment of an aqueous solution of hydrogen peroxide, the amount of methionine in gelatin is reduced.

[0005] Though in the above-cited patents and reports, the amount of aldehyde or methionine, that is considered to be one of reductive substances of gelatin, is reduced by the oxidation of gelatin, these patents and reports do not at all mention a silver ion reducing capability of oxidized gelatin obtained by the oxidation, and therefore, the silver ion reducing capability is unknown. Moreover, these patents and reports are quite silent as to the problem of shelf life with a lapse of time and the wet abrasion resistance.

[0006] As described above, the technique of improving the shelf life with a lapse of time, the wet abrasion resistance, etc., of gelatin by inactivating the silver ion reducing property of gelatin has not yet been known.

[0007] The present invention has been made in view of the foregoing various circumstances. A first object of the invention is to provide a silver halide emulsion excellent in shelf life with a lapse of time and wet abrasion resistance. A second object of the invention is to provide a process for producing a silver halide emulsion excellent in shelf life with a lapse of time and wet abrasion resistance. A third object of the invention is to provide a silver halide photographic material, and particularly a silver halide color photographic material excellent in shelf life with a lapse of time and wet abrasion resistance. The fourth object of the invention is to provide gelatin having a low silver ion reducing property.

[0008] The above-described and other objects and the characteristics and advantages will be made clear by the following description.

[0009] The present inventors made extensive and intensive investigations. As a result, it has been found that the above-described objects can be attained by the following means of the invention.

(1) A silver halide emulsion having a silver chloride content of 90 mol% or more, characterized in that the emulsion contains gelatin having an absorbance by a silver colloid test of lower than 0.25.

(2) The silver halide emulsion as set forth in (1), wherein the gelatin as set forth in (1) is used at the formation of silver halide grains.

(3) The silver halide emulsion as set forth in (1) or (2), wherein the gelatin is a gelatin subjected to an oxidation treatment with a chlorite.

(4) A process for producing a silver halide emulsion having a silver chloride content of 90 mol% or more, characterized by using gelatin having an absorbance by a silver colloid test of lower than 0.25.

(5) A process for producing a silver halide emulsion, characterized by using the gelatin as set forth in (4) at the formation of silver halide grains.

(6) The process as set forth in (4) or (5), wherein the gelatin is a gelatin subjected to an oxidation treatment with a chlorite.

(7) The process as set forth in any one of (4) through (6), wherein the addition amount of a thiosulfonic acid compound during after-ripening is from 0 to 1 µmol/mol-Ag.

(8) A silver halide photographic material characterized by containing the silver halide emulsion as set forth in any one of (1) through (6).

[0010] Then, the present invention will be described below in detail.

[0011] The silver colloid test for measuring the silver ion reducing force prescribed in the invention is as follows.

[0012] Gelatin having a dry weight of 5 g is mixed with 17 g of silver nitrate and deionized water to make to 100 ml in total. In the case of using a set of 10% by weight gelatin, 50 g of 10% by weight gelatin is mixed with 17 g of silver nitrate and deionized water to make to 100 ml in total. These solutions are each ripened for 2 hours at 60 °C, and by using a reducing force of gelatin, a silver ion of silver nitrate is reduced to form a silver colloid. After ripening, the absorbance of the solution at 430 nm is measured by a spectrophotometer (a trade name: U-4300 Type Recording Spectrophotometer, manufactured by Hitachi, Ltd.) using a cell having a cell length of 1 cm. Also, a sample prepared by adding the same amount of deionized water in place of the silver nitrate is prepared as a blank sample, and the absorbance thereof at 430 nm is measured by the same way. Then, the absorbance obtained by subtracting the absorbance of the blank sample from the absorbance of the gelatin sample is defined as the absorbance of the silver colloid formed by the reduction.

[0013] In the invention, the silver halide emulsion contains gelatin having an absorbance by the silver colloid test of lower than 0.25, preferably lower than 0.2, and more preferably lower than 0.18. The absorbance of gelatin is preferably as near 0.0 as possible.

[0014] For obtaining the gelatin having the absorbance defined as described above, an oxidation treatment may be applied, or other treatments such as a chemical treatment may be applied. That is, in the invention, to lower the silver ion reducing property of gelatin, any method may be used. Gelatin may be subjected to an oxidation treatment or treatments other than the oxidation treatment, such as a chemical treatment, but a method of applying an oxidation treatment to gelatin is preferred.

[0015] Then, a preferred oxidation method in the invention is explained.

[0016] First, gelatin is swollen with and dissolved in water. The concentration of gelatin is preferably from 5 to 15% by weight from the viewpoint of workability. After dissolving gelatin, an oxidizing agent is added. There is no problem on the temperature of adding the oxidizing agent if gelatin is dissolved in water, but for avoiding the gelatin from being damaged by heat, the temperature is preferably from 30°C to 50°C. There is no particular restriction on the ripening time with the oxidizing agent, but for avoiding the gelatin from being damaged, the ripening time is preferably within 48 hours, and more preferably within 4 hours.

[0017] After ripening with the oxidizing agent, the excessive oxidizing agent is removed. The excessive oxidizing agent may be decomposed with an enzyme or an equivalent or excessive amount of a reducing agent, or may be removed by carrying out dialysis or ultrafiltration.

[0018] There is no particular restriction on the oxidizing agent if the oxidizing agent can make the absorbance by the silver colloid test of lower than 0.25. Specifically, any oxidizing agents capable of oxidizing organic aldehydes or reducing sugars may be used. Examples of such an oxidizing agent are described, for example, in Experimental Chemistry Series; Organic Synthesis V, Fourth Edition, Vol. 23, edited by The Chemical Society of Japan, ibid.; Organic Synthesis IV, pages 1 to 6 (published in 1992), R.C. Larock, Comprehensive Organic Transformations, Second Edition, pages 1653 to 1657 (published in 1999), and they can be used in the invention. Specific examples of the oxidizing agent include sodium permanganate, iodine, N-bromosuccinimide, silver oxide, sodium chlorite, iodobenzene, iodobenzene diacetate, sodium metaperiodate and sodium peroxoborate. In the invention, oxidizing agents which can oxidize organic aldehydes are preferred, and among them, chlorites and peroxoborates are more preferred, and chlorites are most preferred.

[0019] In the case of oxidizing gelatin, because it is preferred to treat an aqueous solution of gelatin with an oxidizing agent, it is advantageous that the oxidizing agent is water-soluble, and sodium chlorite is preferred in the point. Also, even when the oxidizing agent is insoluble in water, if necessary, after oxidation treatment, the oxidizing agent can be removed by filtration, and thus, even such an oxidizing agent can be used in the invention.

[0020] After oxidative ripening, the gelatin may be cooled to form a set product (a coagulated gel material, meaning a gel material in a gel state by sol-gel conversion), or may be dried.

[0021] Also, the specific gelatin as described above can be used together with gelatin which is usually used in the field of the art.

[0022] The gelatin prepared in the invention can be added from the beginning of precipitation of a silver halide emulsion or on the way of the precipitation of a silver halide emulsion. Also, the gelatin can be added in the midst of sedimentation and washing with water for desalting, can be added at re-dispersing thereafter, or can be added after chemical ripening. Moreover, the gelatin can be added before coating. In each case, the whole amount of the gelatin can be replaced with ordinary gelatin, or only a part of the gelatin can be replaced with ordinary gelatin. Also, directly before initiating the precipitation of a silver halide emulsion, the oxidation treatment of gelatin can be carried out, or simultaneously with the precipitation of a silver halide emulsion, the oxidation treatment of gelatin can be carried out. Preferably, the gelatin is added at the beginning or on the way of the grain formation, or at dispersing of sedimentation and washing with water for desalting. It is more preferred to add the gelatin at the beginning or on the way of the grain formation. Most preferably, the gelatin is added at the beginning of the grain formation. About the using amount of the gelatin of the invention, it is preferred that the whole amount of the gelatin is replaced with ordinary gelatin.

[0023] Also, in the case of using the gelatin of the invention at the grain formation, it is preferred that the addition amount of a thiosulfonic acid compound at after-ripening, that is, at chemical sensitization, is from 0 to 1 µm/mol-Ag, and it is more preferred that no thiosulfonic acid compound is added. It sometimes happens that the thiosulfonic acid compound adsorbs on the surfaces of the silver halide emulsion grains at the chemical sensitization to restrain the development and lower the photographic sensitivity. In this case, the thiosulfonic acid compound includes salts of alkylthiosulfonic acids (for example, sodium ethanethiosulfonate), salts of arylthiosulfonic acids (for example, sodium benzenethiosulfonate). Specifically, the compounds shown by the general formula (XX), that is, the illustrative compounds (XX-1) to (XX-33) described in Japanese Patent Laid-Open No. 90819/1998 are enumerated. Accordingly, the descriptions of the compounds shown by the general formula (XX) in paragraph Nos. 0074 to 0089 of Japanese Patent Laid-Open No. 90819/1998 are preferably incorporated into the specification of the present application.

[0024] As the silver halide grains in the silver halide emulsion of the invention, cubic or tetradecagonal crystal grains substantially having the {100} plane (these grains may be rounded at the apexes of the grains and may have higher degree planes), octagonal crystal grains, or tabular grains having an aspect ratio of 2 or more, in which at least 50% of the total projected areas are made of the {100} plane or the {111} plane, are preferred.

[0025] The aspect ratio is a value obtained by dividing the diameter of the circle corresponding to the projected area by the thickness of the grain. In the invention, the cubic crystal grains, the tabular grains having the {100} plane as the main plane, or the tabular grains having the {111} plane as the main plane, are preferably used.

[0026] As the silver halide emulsion, a silver chloride emulsion, a silver bromide emulsion, a silver iodobromide emulsion, a silver chloro(iodo)bromide emulsion, etc., are generally used, but in the invention, from also the viewpoint of quick processing property, a silver chloride emulsion, a silver chlorobromide emulsion, a silver chloroiodide emulsion, or a silver chlorobromoiodide emulsion, each having a silver chloride content of 90 mol% or more, is used. Also, the silver chloride content of the silver chloride emulsion, the silver chlorobromide emulsion, the silver chloroiodide emulsion, or the silver chlorobromoiodide emulsion is more preferably 95 mol% or more, and most preferably 98 mol% or more. Of these silver halide emulsions, those having, at the shell portions of the silver halide grains, a silver iodochloride phase of preferably from 0.01 to 0.50 mol%, and more preferably from 0.05 to 0.40 mol%, per total moles of silver are preferred because a high sensitivity is obtained, and the emulsion is excellent in high-illumination light-exposure aptitude. Also, silver halide emulsions having, on the surfaces of the silver halide grains, a silver bromide local phase of preferably from 0.2 to 5 mol%, and more preferably from 0.5 to 3 mol% per total moles of silver are particularly preferred because a high sensitivity is obtained, and the photographic performance can be stabilized.

[0027] When the silver halide emulsion of the invention contains silver iodide, the introduction of an iodide ion may be carried out by adding a solution of the iodide singly or by adding an iodide solution together with the addition of a silver salt solution and a high-chloride salt solution. In the latter case, the iodide solution and the high-chloride salt solution may be separately added, or a mixed solution of the iodide and the high-chloride salt may be added. The iodide is added in the form of a soluble salt such as an alkali metal iodide or an alkaline earth metal iodide. Or, by cleaving an iodide ion from the organic molecule described in U.S. Patent 5,389,508, an iodide can be introduced. Also, as other iodide ion source, fine silver iodide grains can be used.

[0028] The addition of the iodide solution may be carried out by a concentrated way for a period of time of the grain formation, or may be carried out over a certain period of time. The introducing position of the iodide ion into the high-chloride silver halide emulsion is restrained for obtaining the silver halide emulsion having a high sensitivity and giving less fog. When the iodide ion is introduced into the inside of the silver halide emulsion grains, the sensitivity is less increased. Therefore, the addition of the iodide solution is carried out to the outer side than preferably 50%, more preferably 70%, and most preferably 80% of the grain volume. Also, it is preferred that the addition of the iodide solution is finished at the inner side than preferably 98%, and most preferably 96% of the grain volume. That is, when the addition of the iodide solution is finished at an inner side a little from the surface of the grain, the silver halide emulsion having a higher sensitivity and giving less fog can be obtained.

[0029] The distribution of the iodide ion concentration to the depth direction of the inside of the grain can be measured by an etching/TOF-SIMS (Time of Flight-Secondary Ion Mass Spectrometry) method, for example, using TRIFT II Type TOF-SIMS (manufactured by Phi Evans Corporation). The TOF-SIMS method is Specifically described in Surface Analytical Technique Book; Secondary Ion Mass Analytical Method, edited by The Surface Science Society of Japan, published by Maruzen Co., Ltd. in 1999. When the silver halide emulsion grains are analyzed by the etching/TOF-SIMS method, even when the addition of the iodide solution is finished at the inner side of the grains, it can be analyzed that the iodide ion oozes towards the surfaces of the grains. When the silver halide emulsion of the invention contains silver iodide, it is preferred that by the analysis of the etching/TOF-SIMS method, the iodide ion has a concentration maximum at the surfaces of the grains and the concentration of the iodide ion attenuates towards the inside of the grains.

[0030] When the silver halide emulsion of the invention has a silver bromide local phase, it is preferred to form the silver bromide local phase having the silver bromide content of 10 mol% or more at the surfaces of a silver halide grains by epitaxial growing. The silver bromide content of the silver bromide local phase is more preferably in the range of from 10 to 60 mol%, and most preferably from 20 to 50 mol%. Also, it is preferred that the silver bromide local phase is constituted of silver of from 0.1 to 5 mol% of the total silver amount constituting the silver halide grains in the invention, and it is more preferred that the silver bromide local phase is constituted of silver of from 0.3 to 4 mol% of the total silver amount. It is preferred that the silver bromide local phase contains a complex ion of a metal belonging to the Group VIII of the periodic table, such as iridium(III) chloride, iridium(III) bromide, iridium(IV) chloride, sodium hexachloroiridate(III), potassium hexachloroiridate(IV), hexaammineiridium(III) salt, trioxalatoiridium(III) salt, and trioxalatoirdium(IV) salt. The addition amount of the compound is in a wide range according to the purposes but is preferably in the range of from 10^-9 to 10^-2 mol per mole of the silver halide.

[0031] In the invention, by adding a transition metal ion in the step of forming and/or growing the silver halide grains, the metal ion can be incorporated in the insides and/or on the surfaces of the silver halide grains. As the metal ion used, a transition metal ion is preferred, and of the transition metals, iron, ruthenium, iridium, osmium, lead, cadmium, and zinc are preferable. Furthermore, it is more preferable that the metal ion has a ligand and is used as a six-coordinate octahedron-type complex. In the case of using an inorganic compound as the ligand, it is preferred to use a cyanide ion, a halide ion, thiocyane, a hydroxide ion, a peroxide ion, an azide ion, a nitrite ion, water, ammonia, a nitrosyl ion, or a thionitrosyl ion. Also, it is preferred to use the above inorganic compound upon coordination with any one of the above-described metal ions including iron, ruthenium, iridium, osmium, lead, cadmium, and zinc, and furthermore, it is preferred to use plural kinds of ligands in one complex molecule. Also, as the ligand, an organic compound can be used, and as a preferred organic compound, there are chain-form compounds having a carbon atom number of the main chain of not more than 5 and/or 5-membered or 6-membered heterocyclic compounds. A more preferable organic compound is a compound having a nitrogen atom, a phosphorus atom, an oxygen atom, or a sulfur atom in the molecule as a coordination atom to a metal, and most preferable organic compounds are furan, thiophene, oxazole, isooxazole, thiazole, isothiazole, imidazole, pyrazole, triazole, furazane, pyran, pyridine, pyridazine, pyrimidine, and pyrazine, and further, compounds having such a compound as a fundamental skeleton and a substituent introduced thereinto are also preferred.

[0032] A preferred combination of the metal ion and the ligand is a combination of an iron ion or a ruthenium ion and a cyanide ion. In these compounds, it is preferred that the cyanide ion occupies a greater part of the coordination site to iron or ruthenium, which is a central metal, and it is also preferred that the residual coordination site is occupied by thiocyane, ammonia, water, nitrosyl ion, dimethyl sulfoxide, pyridine, pyrazine, or 4,4'-bipyridine. It is most preferred that the 6 coordination sites of the central metal are all occupied by the cyanide ions to form a hexacyanoiron complex or hexacyanoruthenium complex. The complex having the cyanide ions as the ligand is added during the grain formation in an amount of preferably from 1 × 10^-8 mol to 1 × 10^-2 mol, and most preferably from 1 × 10^-6 mol to 5 × 10^-4 mol, per mole of silver. In the case of using iridium as the central metal, it is preferred to use a fluoride ion, a chloride ion, a bromide ion, or an iodide ion as the ligand, and of these ions, the use of the chloride ion or the bromide ion is more preferred. Specific examples of the preferred iridium complex include [IrCl₆]^3-, [IrCl₆]^2-, [IrCl₅(H₂O)]^2-, [IrCl₅(H₂O)]^-, [IrCl₄(H₂O)₂]^-, [IrCl₄(H₂O)₂]⁰, [IrCl₃(H₂O)₃]⁰, [IrCl₃(H₂O)₃]⁺, [IrBr₆]^3-, [IrBr₆]^2-, [IrBr₅(H₂O)]^2-, [IrBr₅(H₂O)]^-, [IrBr₄(H₂O)₂]^-, [IrBr₄(H₂O)₂]⁰, [IrBr₃(H₂O)₃]⁰, and [IrBr₃(H₂O)₃]⁺. The iridium complex is added during the grain formation in an amount of preferably from 1 × 10^-10 mol to 1 × 10^-3 mol, and most preferably from 1 × 10^-8 mol to 1 × 10^-5 mol, per mole of silver. In the case of using ruthenium or osmium as the central metal, it is preferred to use a nitrosyl ion, a thionitrosyl ion, or a water molecule and a chloride ion together as the ligand. It is more preferable to form a pentachloronitrosyl complex, a pentachlorothionitrosyl complex, or a pentachloroaqua complex, and it is also preferred to form a hexachloro complex. The complex is added during the grain formation in an amount of from 1 × 10^-10 mol to 1 × 10^-6 mol, and more preferably from 1 x 10^-9 mol to 1 × 10^-6 mol, per mole of silver.

[0033] In the invention, it is preferred that the above-described complex is directly added to the reaction solution at the formation of the silver halide grains, to an aqueous solution of a halide for forming the silver halide grains, or other solution, which is then added to the silver halide grain forming solution, thereby incorporating the complex in the silver halide grains. Furthermore, it is preferred that by combining these methods, the complex is incorporated in the silver halide grains.

[0034] In the case of incorporating the complex in the silver halide grains, it is preferred that the complex uniformly exists in the insides of the silver halide grains, but it is also preferable that the complex exists only at the surface layers of the silver halide grains, as disclosed in Japanese Patent Laid-Open Nos. 208936/1992, 125245/1990 and 188437/1991. Also, it is preferred that the complex exists only in the insides of the silver halide grains, while a layer which does not contain the complex is added to the surfaces of the silver halide grains. Also, it is preferred that the surface phase of the silver halide grains is modified by carrying out physical ripening with fine silver halide grains having the complex incorporated therein, as disclosed in U.S. Patents 5,252,451 and 5,256,530. Furthermore, these methods can be used as the combination thereof, and also, plural kinds of complexes may be incorporated in one silver halide grain. There is no particular restriction on the halogen composition of the position in which the complex is incorporated, and the complex is preferably incorporated in any one of a silver chloride layer, a silver chlorobromide layer, a silver bromide layer, a silver iodochloride layer, and a silver iodobromide layer.

[0035] An average grain size of the silver halide grains (the diameters of the circles equivalent to the projected areas of the silver halide grains are defined as the grain sizes, and the number average is employed as the average grain size) contained in the silver halide emulsion of the invention is preferably from 0.1 µm to 2 µm.

[0036] Also, as the grain size distribution, a so-called monodispersed one, wherein a variation coefficient (one obtained by dividing the standard deviation of the grain size distribution by the average grain size) is preferably not larger than 20%, more preferably not larger than 15%, and most preferably not larger than 10%, is preferred. In this case, for the purpose of obtaining a wide latitude, it is preferred that the monodispersed silver halide emulsions are blended in the same layer, or the monodispersed silver halide emulsions are subjected to multilayer coating.

[0037] The silver halide emulsion of the invention can contain various compounds or precursors thereof for the purposes of preventing the occurrence of fog in the production process or in the storage of the silver halide photographic material, or during the photographic processing, or stabilizing the photographic performance. As specific examples of the compounds, the compounds described in Japanese Patent Laid-Open No. 215272/1987 (described above), pages 39 to 72 are preferably used. Furthermore, the 5-arylamino-1,2,3,4-thiatriazole compounds (the aryl residue has at least one electron releasing group) described in EP0447647 are also preferably used.

[0038] Also, in the invention, for increasing the shelf life of the silver halide emulsion of the invention, the hydroxamic acid derivatives described in Japanese Patent Laid-Open No. 109576/1999, the cyclic ketones having a double bond, both ends of which are substituted with amino groups or hydroxyl groups, adjacent to the carbonyl group described in Japanese Patent Laid-Open No. 327094/1999 (particularly, the compounds shown by the general formula (S1); those in paragraph Nos. 0036 to 0071 can be incorporated into the specification of the present application), the sulfo-substituted catechols or hydroquinones (for example, 4,5-dihydroxy-1,3-benzenedisulfonic acid, 2,5-dihydroxy-1,4-benzenedisulfonic acid, 3,4-dihydroxybenzenesulfonic acid, 2,3-dihydroxybenzenesulfonic acid, 2,5-dihydroxybenzenesulfonic acid, 3,4,5-trihydroxybenzenesulfonic acid, and salts of these acids) described in Japanese Patent Laid-Open No.143011/1999, and the water-soluble reducing agents shown by the general formulae (I) to (III) of Japanese Patent Laid-Open No. 102045/1999 are preferably used in the invention.

[0039] Spectral sensitization is usually carried out for imparting a spectral sensitivity in a desired light wavelength region to the silver halide emulsion of each layer in the photosensitive material of the invention.

[0040] In the photosensitive material of the invention, as spectral sensitizing dyes used for the spectral sensitization of the blue, green, and red regions, there are the compounds described, for example, in F.M. Harmer, Heterocyclic Compounds-Cyanine Dyes and Related Compounds (published by John Willey & Sons Co., 1964 [New York, London]). Specific examples of the compounds and the spectral sensitization method preferably used in the invention are described in Japanese Patent Laid-Open No. 215272/1987 (cited above), page 22, right upper column to page 38. Also, as red-sensitive spectral sensitizing dyes for the silver halide emulsion grains having a particularly high silver chloride content, the spectral sensitizing dyes described in Japanese Patent Laid-Open No. 123340/1991 are very preferable from the viewpoints of the stability, the strength of adsorption, the temperature reliance of light exposure, etc.

[0041] The addition amount of these spectral sensitizing dyes is in a wide range according to the cases, and is preferably in the range of from 0.5 × 10^-6 mol to 1.0 × 10^{- 2} mol, and more preferably from 1.0 × 10^-6 to 5.0 × 10^-3 mol, per mole of the silver halide.

[0042] The silver halide emulsion of the invention is usually subjected to chemical sensitization. As the chemical sensitization method, sulfur sensitization represented by the addition of an unstable sulfur compound, noble metal sensitization represented by gold sensitization, and reduction sensitization can be used singly or as a combination of them. As the compound used for the chemical sensitization, the compounds described in Japanese Patent Laid-Open No. 215272/1987, page 18, right lower column to page 22, right upper column are preferably used. Among them, those subjected to gold sensitization are preferred in the invention. By applying the gold sensitization, the fluctuation of the photographic performance in the case of carrying out a scanning exposure by a laser light, etc., can be further reduced, and such is also preferred in the effects of the invention.

[0043] For applying the gold sensitization to the silver halide emulsion of the invention, various inorganic gold compounds, gold(I) complexes having an inorganic ligand, and gold(I) compounds having an organic ligand can be utilized. As the inorganic gold compounds, for example, chloroauric acid or the salts thereof can be used. As the gold(I) complexes having an inorganic ligand, for example, gold dithiocyanate compounds such as potassium gold(I) dithiocyanate and gold dithiosulfate compounds such as trisodium gold(I) dithiosulfate can be used.

[0044] As the gold(I) compounds having an organic ligand, the bis gold(I) mesoion heterocyclic compounds such as gold(I) tetrafluoroborate bis(1,4,5-trimethyl-1,2,4-triazolium-3-thiorate), as described in Japanese Patent Laid-Open No. 267249/1992; the organic mercapto gold(I) complexes such as potassium bis(1-[3-(2-sulfonatobenzamido)phenyl]-5-mercaptotetrazole potassium salt) aurate(I) pentahydrate, as described in Japanese Patent Laid-Open No. 218870/1999; and the gold(I) compounds coordinated with a nitrogen compound anion, such as bis(1-methylhydantoinate) gold(I) sodium salt tetrahydrate, as described in Japanese Patent Laid-Open No. 268550/1992, can be used. Also, the gold(I) thiorate compounds described in U.S. Patent 3,503,749; the gold compounds described in Japanese Patent Laid-Open Nos. 69074/1996, 69075/1996 and 269554/1997; and the compounds described in U.S. Patents 5,620,841, 5,912,112, 5,620,841, 5,939,245 and 5,912,111 can be used.

[0045] The addition amount of these compounds can be changed according to the cases, but is usually from 5 × 10^-7 to 5 × 10^-3 mol, and preferably from 5 × 10^-6 to 5 × 10^-4 mol, per mole of the silver halide.

[0046] Also, colloidal gold sulfide can be used and the production method thereof is described in Research Disclosure, 37154; Solid State Ionics, Vol. 79, pages 60 to 66, published in 1995; Compt. Rend. Hebt. Seances Acad. Sci. Sect. B, Vol. 263, page 1328, published in 1966, etc. As the colloidal gold sulfide, those having various sizes can be used, and colloidal gold sulfide having particle sizes of not larger than 50 nm can be used. The addition amount thereof can be changed in a wide range according to the cases but is usually from 5 × 10^-7 to 5 × 10^-3 mol, and preferably from 5 × 10^-6 to 5 × 10^-4 mol, in terms of a gold atom per mole of the silver halide.

[0047] In the invention, the gold sensitization may be combined with other sensitization method such as sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization, and noble metal sensitization using other noble metal compound than the gold compound.

[0048] For the silver halide photographic material of the invention, the photographic materials and additives, which have hitherto been known in the field, can be used.

[0049] For example, as the photographic support, a transmission -type support and a reflection-type support can be used. As the transmission-type support, a transparent film such as a cellulose nitrate film and a polyethylene terephthalate film; and further films of a polyester of 2,6-naphthalene dicarboxylic acid (NDCA) and ethylene glycol (EG) or a polyester of NDCA, terephthalic acid and EG, having an information-recording layer such as a magnetic layer, formed thereon, are preferably used. As the reflection-type support, a reflection-type support laminated with plural polyethylene layers or polyester layers, at least one layer of the waterproof resin layers (laminated layers) containing a white pigment such as titanium oxide, is preferred.

[0050] As the more preferred reflection support in the invention, there is a paper support having a polyolefin layer having fine holes formed on the side of forming a silver halide emulsion layer. The polyolefin layer may be composed of multilayers, and in this case, it is preferred that the polyolefin (e.g., polypropylene and polyethylene) layer adjacent to the gelatin layer of the silver halide emulsion side does not have fine holes, and the polyolefin (e.g., polypropylene and polyethylene) layer adjacent to the paper support has fine holes. The density of the polyolefin layer of multilayers or single layer disposed between the paper support and the photographic constituting layers is preferably from 0.40 to 1.0 g/ml, and more preferably from 0.50 to 0.70 g/ml. Also, a thickness of the polyolefin layer of multilayers or single layer disposed between the paper support and the photographic constituting layers is preferably from 10 to 100 µm, and more preferably 15 to 70 µm. Also, a ratio of the polyolefin layer to the paper support is preferably from 0.05 to 0.5, and more preferably from 0.1 to 0.2.

[0051] Also, it is preferred to form a polyolefin layer on the opposite side (back surface) of the paper support to the side of the photographic constituting layers from the viewpoint of increasing the rigidity of the reflection-type support, and in this case, as the polyolefin layer formed on the back surface, a polyethylene or polypropylene layer, whose surface is matted, is preferred, with the polypropylene layer being more preferred. A thickness of the polyolefin layer at the back surface is preferably from 5 to 50 µm, and more preferably from 10 to 30 µm. Also, a density of the polyolefin layer is preferably from 0.7 to 1.1 g/ml.

[0052] In the reflection-type support used in the invention, preferred embodiments about the polyolefin layers formed on the paper support are described in Japanese Patent Laid-Open Nos. 333277/1998, 333278/1998, 52513/1999 and 65024/1999, EP0880065 and EP0880066.

[0053] Furthermore, it is preferred that the above-described waterproof resin layer contains a fluorescent brightening agent. Also, the fluorescent brightening agent may be dispersed in the hydrophilic colloid layer of the photosensitive material. As the fluorescent brightening agent, benzoxazole-based, coumarin-based, or pyrazoline-based fluorescent brightening agent can be preferably used, and a benzoxazolyl naphthalene-based and benzoxazolyl stilbene-based fluorescent brightening agents are more preferably used. There is no particular restriction on the using amount thereof, but the using amount is preferably from 1 to 100 mg/m². In the case of mixing with the waterproof resin, a mixing ratio is preferably from 0.0005 to 3% by weight, and more preferably from 0.001 to 0.5% by weight to the resin.

[0054] As the reflection-type support, a transmission-type support or the reflection-type support as described above having a hydrophilic colloid layer containing a white pigment formed thereon may be used.

[0055] Also, the reflection-type support may be a support having a mirror plane-reflective or second kind diffusion-reflective metal surface.

[0056] Also, as the support used for the photosensitive material of the invention, a white polyester-based support or a support having a layer containing a white pigment on the support of the side having a silver halide emulsion layer may be used for display. Furthermore, for improving the sharpness, it is preferred that an antihalation layer is coated on the support of the side of coating the silver halide emulsion or the back surface of the support. Particularly, in order to appreciate a display by a reflected light or a transmitted light, it is preferred to set a transmission density of the support within the range of from 0.35 to 0.8.

[0057] In the silver halide photographic material of the invention, for the purpose of improving the sharpness of images, it is preferred that the dye (particularly, an oxonole-based dye) capable of being decolored by treatment described in EP0337490A2, pages 27 to 76 is added to the hydrophilic colloid layer of the photosensitive material such that the optical reflective density of the photosensitive material at 680 nm is 0.70 or more, or that titanium oxide subjected to a surface treatment with a dito tetrahydric alcohol (for example, trimethylolethane), etc. is incorporated in the waterproof resin layer of the support in an amount of 12% by weight or more (more preferably 14% by weight or more).

[0058] In the photosensitive material of the invention, for the purposes of preventing irradiation and halation and improving the safelight safety, etc., it is preferred to add the dye (particularly, an oxonole dye and a cyanine dye) capable of being decolored by treatment described in EP0337490A2, pages 27 to 76 to the hydrophilic colloid layer. Furthermore, the dyes described in EP0819977 can be preferably added in the invention.

[0059] Of these water-soluble dyes, there are the dyes, which deteriorate the color separation or the safelight safety when the using amount is increased. As the dyes, which can be used without deteriorating the color separation, the water-soluble dyes described in Japanese Patent Laid-Open Nos. 127324/1993, 127325/1993 and 216185/1993 are preferable.

[0060] In the invention, in place of the water-soluble dyes, or together with the water-soluble dyes, a colored layer capable of being decolored by treatment is used. The colored layer capable of being decolored by treatment used may be formed in direct contact with a silver halide emulsion layer or may be disposed in contact with the silver halide emulsion via an interlayer containing a treatment color mixing inhibitor such as gelatin and hydroquinone. It is preferred that the colored layer is disposed as the under layer (support side) of the silver halide emulsion layer which is colored in the same kind of the elementary color as the colored color. It is possible to dispose all the colored layers each corresponding to each of the elementary colors, or to dispose optionally selecting a part of the elementary colors. Also, it is possible to dispose the colored layer colored corresponding to plural elementary color regions. In the optical reflection density of the colored layer, it is preferred that an optical density value in the wavelength of the highest optical density in the wavelength region used for the light exposure (in an ordinary printer exposure, the visible light region of from 400 nm to 700 nm, and in the case of a scanning exposure, the wavelength of the scanning exposure light source used) is from 0.2 to 3.0. Also, the optical density value is more preferably from 0.5 to 2.5, and particularly preferably from 0.8 to 2.0.

[0061] For forming the colored layer, a method, which has hitherto been known, can be applied. For example, there are a method of incorporating a dye in the hydrophilic colloid layer in the state of a solid fine particle dispersion as in the dyes described in Japanese Patent Laid-Open No. 282244/1990, page 3, right upper column to page 8 and the dyes described in Japanese Patent Laid-Open No. 7931/1991, page 3, right upper column to page 11, left lower column; a method of mordanting a cationic polymer with an anionic dye; a method of adsorbing a dye to fine grains such as silver halide grains, and fixing the grains in the layer; and a method of using the colloid silver as described in Japanese Patent Laid-Open No. 239544/1989. As the method of dispersing the fine powder of the dye in a solid state, for example, a method of incorporating a finely divided dye, which is substantially insoluble in water at a pH of 6 or lower but is substantially soluble in water at a pH of 8 or higher, is described in Japanese Patent Laid-Open No. 308244/1990, page 4 to page 13. Also, the method of mordanting the cationic polymer with the anionic dye is described in Japanese Patent Laid-Open No. 84637/1990, pages 18 to 26. The preparation method of colloidal silver as a light absorbent is described in U.S. Patents 2,688,601 and 3,459,563. Of these methods, the method of incorporating the finely divided dye and the method of using colloidal silver, etc. are preferred.

[0062] The silver halide photographic material of the invention is used as a color negative film, a color positive film, a color reversal film, a color reversal photographic printing paper, a photosensitive material for display, a photosensitive material for digital color proof, a color photographic printing paper, etc., and in these uses, it is preferred to use as a color photographic printing paper.

[0063] It is preferred that the color photographic printing paper has at least one layer of each of a yellow color-forming silver halide emulsion layer, a magenta color-forming silver halide emulsion layer, and a cyan color-forming silver halide emulsion layer, and in general, these silver halide emulsion layers are successively disposed in the order of the yellow color-forming silver halide layer, the magenta color-forming silver halide layer, and the cyan color-forming silver halide layer from the side near the support.

[0064] However, other different layer construction may be employed.

[0065] The silver halide emulsion layer containing a yellow coupler may be disposed in any position on the support, but when the yellow coupler-containing silver halide emulsion layer contains tabular silver halide grains, it is preferred that the yellow coupler-containing layer is formed at the position far from the support than at least one layer of the magenta coupler-containing silver halide emulsion layer and the cyan coupler-containing silver halide emulsion layer. Also, from the viewpoints of the color development acceleration, the desilvering acceleration, and the reduction of the residual color by a sensitizing dye, it is preferred that the yellow coupler-containing silver halide emulsion layer is formed at the position farthest from the support than other silver halide emulsion layers. Furthermore, from the viewpoint of reducing the occurrence of the blix fading, it is preferred that the cyan coupler-containing silver halide emulsion layer is disposed between other two color-forming silver halide emulsion layers, and further from the viewpoint of the reduction of the occurrence of light fading, it is preferred that the cyan coupler-containing silver halide emulsion layer is formed as a lowermost layer. Also, each of the yellow color-forming layer, the magenta color-forming layer, and the cyan color-forming layer may be composed of 2 layers or 3 layers. For example, as described in Japanese Patent Laid-Open Nos. 75055/1992, 114035/1997 and 246940/1998, and U.S. Patent 5,576,159, it is preferred that a coupler layer, which does not contain a silver halide emulsion, is formed adjacent to a silver halide emulsion layer as a color-forming layer.

[0066] As the materials used for the silver halide emulsions of the invention, other materials (additives, etc.), the photographic constituting layers (layer alignment, etc.) used in the invention, processing methods and additives for the processing applied for processing the silver halide photographic materials, those described in Japanese Patent Laid-Open Nos. 215272/1987 and 33144/1990, and EP0355660A2 are preferably used, and particularly, those described in EP0355660A2 are preferably used. Furthermore, the materials for the silver halide color photographic materials and the processing methods described in Japanese Patent Laid-Open Nos. 34889/1993, 359249/1992, 313753/1992, 270344/1992, 66527/1993, 34548/1992, 145433/1992, 854/1990, 158431/1989, 90145/1990, 194539/1991 and 93641/1990, and EP0520457A2, can be preferably used.

[0067] Particularly, in the invention, as the above-described reflection-type support and silver halide emulsions, different kinds of metal ion species doped in the silver halide grains, the storage stabilizers and antifogging agents for silver halide emulsions, the chemical sensitization methods (sensitizers), the spectral sensitization methods (spectral sensitizers), cyan, magenta and yellow couplers and emulsion-dispersing methods thereof, the color image storage improving agents (stain inhibitors and fading inhibitors), dyes (colored layers), gelatin species, the layer structures of the photosensitive materials and the pH of the coating of the photosensitive materials, etc., those described in Japanese Patent Laid-Open gazettes shown in Table 1 below are preferably applied.

Table 1

Elements	Laid-Open No. 104448/1995	Laid-Open No. 77775/1995	Laid-Open No. 301895/1995
Reflective-type support	Col. 7, line 12 to col. 12, line 19	Col. 35, line 43 to col. 44, line 1	Col..5, line 40 to col. 9, line 26
Silver halide emulsion	Col. 72, line 29 to col. 74, line 18	Col. 44, line 36 to col. 46, line 29	Col. 77, line 48 to col. 80, line 28
Different metal ion species	Col. 74, line 19 to same col., line 44	Col. 46, line 30 to col. 47, line 5	Col. 80, line 29 to col. 81, line 6
Storage stabilizer or antifogging agent	Col. 75, line 9 to same col., line 18	Col. 47, line 20 to same col., line 29	Col. 18, line 11 to Col. 31, line 37 (particularly, mercapto heterocyclic compounds)
Chemical sensitization method (chemical sensitizer)	Col. 47, line45 to col. 75, line 6	Col. 47, line 7 to same col., line 17	Col. 81, line 9 to same col., line 17
Spectral sensitization method (spectral sensitizer)	Col. 75, line 19 to col. 76, line 45	Col. 47, line 30 to col. 49, line 6	Col. 81, line 21 to col. 82, line 48
Cyan coupler	Col. 12, line 20 to col. 39, line 49	Col. 62, line 50 to col. 63, line 16	Col. 88, line 49 to col. 89, line 16
Yellow coupler	Col. 87, line 40 to col. 88, line 3	Col. 63, line 17 to same col., line 30	Col. 89, line 17 to same col., line 30
Magenta coupler	Col. 88, line 4 to same col., line 18	Col. 63, line 3 to col. 64, line 11	Col. 31, line 34 to col. 77, line 44 and col. 88, line 32 to same col., line 46
Emulsion-dispersing method of couplers	Col. 71, line 3 to col. 72, line 11	Col. 61, line 36 to same col., line 49	Col. 87, line 35 to same col., line 48
Color image storage improving agent (stain inhibitor)	Col. 39, line 50 to col. 70, line 9	Col. 61, line 50 to col. 62, line 49	Col. 87, line 49 to col. 88, line 48
Fading inhibitor	Col. 70, line 10 to col. 71, line 2
Dye (colorant)	Col. 77, line 42 to col. 78, line 41	Col. 7, line 14 to col. 19, line 42 and col. 50, line 3 to col. 51, line 14	Col. 9, line 27 to col. 18, line 10
Gelatin species	Coll. 78, line 42 to same col., line 48	Col. 51, line 15 to same col., line 20	Col. 83, line 13 to same col., line 19
Layer construction of photosensitive material	Col. 39, line 11 to same col., line 26	Col. 44, line 2 to same col., line 35	Col. 31, line 38 to col. 32, line 33
pH of the coating of photosensitive material	Col. 72, line 12 to same col., line 28
Scanning exposure	Col. 76, line 6 to col. 77, line 41	Col. 49, line 7 to col. 50, line 2	Col. 82, line 49 to col. 83, line 12
Preservative in developer	Col. 88, line 19 to col. 89, line 22
(*):

[0068] As the cyan, magenta and yellow couplers used in the invention, other couplers described in Japanese Patent Laid-Open No. 215272/1987, page 91, right upper column, line 4 to page 121, left upper column, line 6; Japanese Patent Laid-Open No. 33144/1990, page 3, right upper column, line 14 to page 18, left upper column, last line and page 30, right upper column, line 6 to page 35, right lower column, line 11; EP0355660 A2, page 4, lines 15 to 27, page 5, line 30 to page 28, last line, page 45, lines 29 to 31, and page 47, line 23 to page 63, line 50 are useful.

[0069] Also, in the invention, the compounds of the general formulae (II) and (III) described in WO98/33760 and the compounds shown by the general formula (D) of Japanese Patent Laid-Open No. 221825/1998 may be added, and the addition thereof is preferred.

[0070] Then, the couplers used in the invention will be described more Specifically.

[0071] As the cyan couplers, which can be used in the invention, pyrrolotriazole-based couplers are preferably used, and the couplers shown by the general formula (I) or (II) of Japanese Patent Laid-Open No. 313324/1993, the couplers shown by the general formula (I) of Japanese Patent Laid-Open No. 347960/1994, and the illustrative couplers described in these patents are particularly preferred.

[0072] Also, phenol-based and naphthol-based cyan couplers are preferably used, and the cyan couplers shown by the general formula (ADF) described in Japanese Patent Laid-Open No. 333297/1998 are preferred.

[0073] As other cyan couplers than those described above, there are the pyrroloazole-type cyan couplers described in EP0488248 and EP0491197A1; the 2,5-diacylaminophenol couplers described in U.S. Patent 5,888,716; the pyrazoloazole-type cyan couplers having an electron releasing group and a hydrogen bond group at the 6-position as described in U.S. Patents 4,873,183 and 4,916,051, and particularly, the pyrazoloazole-type cyan couplers each having a carbamoyl group at the 6-position described in Japanese Patent Laid-Open Nos. 171185/1996, 311360/1996, and 339060/1996 are preferred.

[0074] Also, the diphenylimidazole-based cyan couplers described in Japanese Patent Laid-Open No. 33144/1990, the 3-hydroxypyridine-based cyan couplers [of these couples, the two-equivalent coupler obtained by bonding a chlorine-splitting group to the four-equivalent coupler of the coupler (42) enumerated as a specific example, and the couplers (6) and (9) are particularly preferred] described in EP0333185A2, the cyclic active methylene-based cyan couplers (of these couplers, the couplers 3, 8 and 34 enumerated as specific examples are particularly preferred) described in Japanese Patent Laid-Open No. 32260/1989, the pyrrolopyrazole-type cyan couplers described in EP0456226A1, and the pyrroloimidazole-type cyan couplers described in EP0484909 can be used.

[0075] As the magenta coupler used in the invention, the 5-pyrazolone-based magenta couplers and the pyrazoloazole-based magenta couplers described in Table 1 described above can be used, but from the viewpoints of the hue, the image stability, the color formation property, etc., the pyrazolotriazole couplers wherein a secondary or tertiary alkyl group is directly bonded to the 2, 3 or 6-position of the pyrazolotriazole ring as described in Japanese Patent Laid-Open No. 65245/1986, the pyrazoloazole couplers containing a sulfonamide group in the molecule as described in Japanese Patent Laid-Open No. 65246/1986, the pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in Japanese Patent Laid-Open No. 147254/1986, and the pyrazoloazole couplers having an alkoxy group or an aryloxy group at the 6-position as described in EP226849A and EP294785A are preferably used.

[0076] In particular, as the magenta coupler, the pyrazoloazole couplers shown by the general formula (M-I) described in Japanese Patent Laid-Open No. 122984/1996 are preferred, and the couplers of paragraph Nos. 0009 to 0026 of this patent are applied to the invention of this application and are incorporated as a part of the specification of this application.

[0077] In addition, the pyrazoloazole couplers having a steric hindrance group at both the 3-position and the 6-position described in EP854384 and EP884640 are preferably used.

[0078] Also, as the yellow coupler, in addition to the couplers described in the above-described table, the acylacetamide-type yellow couplers having a 3- to 5-membered ring structure at the acryl group described in EP0447969A1, the malondianilide-type yellow couplers having a cyclic structure described in EP 0482552A1, and the acylacetamide-type yellow couplers having a dioxane structure described in U.S. Patent 5,118,599 are preferably used. Of these couplers, the use of the acylacetamide-type yellow couplers wherein the acyl group is a 1-alkylcyclopropane-1-carbonyl group, and the malondianilide-type yellow couplers wherein one of the anilides constitutes an indoline ring is particularly preferred. These couplers can be used singly or as a combination of them.

[0079] It is preferred that the coupler used in the invention is emulsion-dispersed in an aqueous hydrophilic colloid solution by impregnating in a loadable latex polymer (e.g., see U.S. Patent 4,203,716) in the presence (or in the absence) of the high-boiling organic solvent described in Table 1 described above, or by dissolving together with a polymer, which is insoluble in water but soluble in an organic solvent.

[0080] As the polymer insoluble in water but soluble in an organic solvent, which can be preferably used, there are the homopolymers or the copolymers described in U.S. Patent 4,857,449, columns 7 to 15 and WO88/00723, pages 12 to 30. More preferably, there are a methacrylate-based polymer or an acrylamide-based polymer. Particularly, the use of the acrylamide-based polymer is preferred from the viewpoint of the color image stability, etc.

[0081] In the invention, known color mixing inhibitors can be used, but of these compounds, the following compounds are preferred.

[0082] For example, the redox compounds of high molecular weight described in Japanese Patent Laid-Open No. 333501/1993, the phenidone-based or hydrazine-based compounds described in WO98/33760 and U.S. Patent 4,923,787, and the white couplers described in Japanese Patent Laid-Open Nos. 249637/1993 and 282615/1998, German Patent 19629142A1 can be used. Also, in the case of particularly carrying out quickening of the development by increasing the pH of a developer, it is preferred to use the redox compounds described in German Patent 19618786A1, EP839623A1, EP842975A1, German Patent 19806846A1, and French Patent 2760460A1.

[0083] In the invention, it is preferred to use a compound having a triazine skeleton having a high molar extinction coefficient as a ultraviolet absorbent, and for example, the following compounds can be used.

[0084] That is, there are the compounds described in Japanese Patent Laid-Open Nos. 3335/1971, 152776/1980, 197074/1993, 232630/1993, 307232/1993, 211813/1994, 53427/1996, 234364/1996, 239368/1996, 31067/1997, 115898/1998, 147577/1998 and 182621/1998, German Patent 19739797A, EP711804A, and International Patent Publication No. 501291/1996.

[0085] As the binder or the protective colloid, which can be used for the silver halide photographic material of the invention, gelatin is advantageously used, but other hydrophilic colloids can be used singly or together with gelatin. In preferred gelatin, the content of heavy metals such as iron, copper, zinc, and manganese, contained as impurities is preferably not more than 5 ppm, and more preferably not more than 3 ppm.

[0086] Also, the amount of calcium contained in the photosensitive material of the invention is preferably not more than 20 mg/m², more preferably not more than 10 mg/m², and most preferably not more than 5 mg/m².

[0087] In the invention, for preventing the growth of various kinds of molds and bacteria deteriorating images by growing in the hydrophilic colloid layers, it is preferred to add the antifungal/antibacterial agent as described in Japanese Patent Laid-Open No. 271247/1988.

[0088] Furthermore, the pH of the coating of the photosensitive material is preferably from 4.0 to 7.0, and more preferably from 4.0 to 6.5.

[0089] In the invention, from the viewpoints of improving the coating stability of the photosensitive material, preventing the generating static electricity, controlling the electrostatic-charging amount, etc., a surfactant can be added. As the surfactant, there are an anionic surfactant, a cationic surfactant, a betain-based surfactant, and a nonionic surfactant, and they are described, for example, in Japanese Patent Laid-Open No. 333492/1993. As the surfactant used in the invention, a fluorine atom-containing surfactant is preferred.

[0090] There is no particular restriction on the addition amount of the surfactant, but the addition amount is generally from 1 × 10^-5 to 1 g/m², preferably from 1 × 10^-4 to 1 × 10^-1 g/m², and more preferably from 1 × 10^-3 to 1 × 10^-2 g/m².

[0091] The fluorine atom-containing surfactant may be used singly or together with other known surfactant, but it is preferred to use it together with other known surfactant.

[0092] The photosensitive material of the invention is used, in addition to printing system using an ordinary negative printer, for a scanning light exposure system using a cathode ray tube (CRT). The cathode ray tube light-exposure apparatus is simple and compact, and is low in cost as compared with the apparatus using a laser light. Also, the control of the optical axis and color is easy.

[0093] For the cathode ray tube used for image exposure, various kinds of illuminants showing emissions in spectral regions are used according to the necessary. For example, one kind of a red color illuminant, a green color illuminant, or a blue color illuminant, or a mixture of two or more kinds of these illuminants is used. The spectral regions are not limited to the red, green, and blue regions described above, but an illuminant emitting in a yellow, orange, purple or infrared region is used. In particular, the cathode ray tube emitting in white by mixing these illuminants is frequently used.

[0094] When the photosensitive material has plural photosensitive layers each having a different spectral sensitivity distribution, and the cathode ray tube has illuminants showing emissions of plural spectral regions, plural colors may be exposed at a time, that is, as image signal of plural colors is supplied to the cathode ray tube, and plural colors may be emitted from the cathode ray tube. A method of successively supplying image signals each having a respective color to a cathode ray tube, carrying out successively the emission of each color, and exposing through filter films by cutting other colors than the supplied colors (plane successive exposure) may be employed, and in general, the plane successive exposure is preferred for a high image quality since a cathode ray tube having a high resolution can be used.

[0095] The photosensitive material of the invention is preferably used for a digital scanning exposure system using a gas laser, a light emitting diode, a semiconductor laser, or a monochromatic high-density light such as a secondary higher harmonics generating light source (SHG), etc., obtained by combining a semiconductor laser or a solid laser using a semiconductor laser as the exciting light source and a non-linear optical crystal. For making the system compact and inexpensive, it is preferred to use a semiconductor laser or the secondary higher harmonic generating light source (SHG) obtained by combining a semiconductor laser or a solid laser and the non-linear optical crystal. In particular, for designing an apparatus, which is compact and inexpensive, has a long life, and further has a high stability, the use of a semiconductor laser is preferred, and it is preferred that as at least one of the exposure sources, a semiconductor laser is used.

[0096] In the case of using such a scanning exposure light source, the spectral sensitivity maximum wavelength of the photosensitive material of the invention can be optionally established according to the wavelength of the scanning exposure light source used. Because in the SHG light source obtained by combining a solid laser using a semiconductor laser as the exciting light source or a semiconductor laser and a non-linear optical crystal, the oscillation wavelength of the laser can be divided into halves, a blue light or a green light is obtained. Accordingly, it is possible that the spectral sensitivity maximum of the photosensitive material is in usual three wavelength regions of blue, green, and red.

[0097] When the light-exposure time in such scanning exposure is defined to be the time of exposing a pixel size when the pixel density is 400 dpi, the exposure time is preferably not longer than 10^-4 second, and more preferably not longer than 10^-6 second.

[0098] The scanning exposure system, which can be preferably applied to the present invention, is described in detail in the patents shown in Table 1 described above.

[0099] For processing the photosensitive material of the invention, the processing materials and the processing methods described in Japanese Patent Laid-Open No. 207250/1990, page 26, right lower column, line 1 to page 34, right upper column, line 9 and Japanese Patent Laid-Open No. 97355/1992, page 5, left upper column, line 17 to page 18, right lower column, line 20 can be preferably applied. Also, as preservatives used for the developers, the compounds described in the patents shown in Table 1 described above can be preferably used.

[0100] The present invention can also be preferably applied to the photosensitive material having a quick processing aptitude.

[0101] The color development time is a time from when a photosensitive material enters a color developer until when the photosensitive material enters a bleach-fix solution (blix solution) of the subsequent processing step. For example, in the case where it is processed by an automatic processor, the sum total of the time when the a photosensitive material is immersed in a color developer (so-called in-liquid time) and the time when the photosensitive material leaves from the color developer and is transported in air towards a blix bath of the subsequent processing step (so-called in-air time) is defined to be a color development time. Similarly, the blix time is a time from when the photosensitive material enters a blix solution until when the photosensitive material enters a subsequent water-washing bath or a stabilization bath. Also, the water-washing time or the stabilization time is a time from when the photosensitive material enters the water-washing or stabilization solution until when the photosensitive material is in the solution towards a drying step (so-called in-liquid time).

[0102] In the case of carrying out quick processing in the invention, the color development time is preferably not longer than 60 seconds, more preferably not longer than 50 seconds but not shorter than 6 seconds, and most preferably not longer than 30 seconds but not shorter than 6 second. Similarly, the blix time is preferably not longer than 60 seconds, more preferably not longer than 50 seconds but not shorter than 6 seconds, and most more preferably not longer than 30 seconds but not shorter than 6 seconds. Also, the time for water washing or stabilization is preferably not longer than 150 seconds, and more preferably not longer than 130 seconds but not shorter than 6 seconds.

[0103] As a method of developing the photosensitive material of the invention after exposure, a wet system such as a method of developing a developer containing an alkaline agent and a developing agent of the related art and a method of incorporating a developing agent in the photosensitive material and developing the photosensitive material with an activator solution such as an alkaline solution free from a developing agent, as well as a heat developing method without using a developer, can be used. Particularly, because in the activator method, the processing solution does not contain a developing agent, the management and handling of the processing solution are easy, and a load at the waste liquid processing is less, and thus, the activator method is preferred in the point of the environmental safety.

[0104] In the activator method, as the developing agent or the precursor thereof, which is incorporated in the photosensitive material, the hydrazine-type compounds described, for example, in Japanese Patent Laid-Open Nos. 234388/1996, 152686/1997, 152693/1997, 211814/1997 and 160193/1997 are preferably used.

[0105] Also, a development method of reducing the coated silver amount of the photosensitive material and carrying out an image amplification processing (intensification processing) using hydrogen peroxide is preferably used. In particular, it is preferred to use the above-described method for the activator method. Specifically, the image-forming method using the activator solution containing hydrogen peroxide described in Japanese Patent Laid-Open Nos. 297354/1996 and 152695/1997 is preferably used.

[0106] In the activator method, after processing with the activator solution, the photosensitive material is usually subjected to a desilvering treatment, but in the image amplification processing method using the photosensitive material of a low silver content, a simple method of water washing or a stabilization treatment while omitting the desilvering treatment can be carried out. Also, in a system of reading image information from a photosensitive material by a scanner, etc., even in the case of using a high-silver content photosensitive material such as a photosensitive material for photographing, a processing mode without need of the desilvering treatment can be employed.

[0107] As the activator solution, the desilvering solution (bleach/fixing solution), the processing materials for water washing and the stabilization solution and the processing method, known materials and methods can be used. Preferably, those described in Research Disclosure, Item 36544 (September 1994), pages 536 to 541 and Japanese Patent Laid-Open No. 234388/1996 can be used.

[0108] When the photosensitive material of the invention is subjected to a printer exposure, it is preferred to use the band stop filter described in U.S. Patent 4,880,726, whereby light color mixing is removed, and the color reproductivity is greatly improved.

[0109] In the invention, as described in EP0789270A1 and EP0789480A1, before giving image information, a yellow micro dot pattern is pre-exposed in advance, whereby the copying may be regulated.

[0110] According to the invention, a silver halide emulsion excellent in shelf life with a lapse of time and excellent in wet abrasion resistance, a process for producing the silver halide method having the excellent performance, and a silver halide photographic material showing the excellent performance can be provided.

[0111] Then, the invention is described in more detail-based on the following Examples, but the invention is not limited to these Examples.

Reference Example 1:

[0112] Silver colloid tests of various gelatins usually used were carried out. The results are shown in Table 2 below. As the result, it is shown that as gelatins usually used, there are no gelatins having an absorbance by the silver colloid test showing a silver ion reducing property of lower than 0.25.

Table 2

	Gelatin Name	Silver colloid test Absorbance (430 nm)
1	No. 1 extracted gelatin made by A Co.	0.389
2	No. 2 extracted gelatin made by A Co	0.420
3	No. 3 extracted gelatin made by A Co.	0.530
4	No. 4 extracted gelatin made by A Co.	0.984
5	Mixture of No. 1 + No. 2 + No. 3 + No. 4 extracted gelatins made by A Co.	0.884
6	No. 1 extracted gelatin made by B Co.	0.346
7	No. 1 extracted gelatin made by C Co.	0.325
8	Diluted mixture of No. 1 + No. 2 + No. 3 + No. 4 extracted gelatins made by A Co.	0.605
9	Mixture of No. 1 + No. 2 + No. 3 + No.4 extracted gelatins made by D Co.	0.580
10	Oxidation-treated mixture of No. 1 + No. 2 + No. 3 + No. 4 extracted gelatins made by B Co.	0.803
11	Deionized mixture of No. 1 + No. 2 + No. 3 extracted gelatins made by C Co.	0.391
12	No. 1 extracted gelatin made by E Co.	0.322
13	Gelatin prepared by strongly oxidizing No. 1 extracted gelatin made by E Co. by H2O2*	0.455
14	Gelatin prepared by weakly oxidizing No. 1 extracted gelatin made by E Co. by H2O2*	0.384
15	Mixture of No. 1 + No. 2 extracted gelatins made by A Co.	0.437
16	No. 1 extracted gelatin made by A Co.	0.321
17	Mixture of No. 1 + No. 2 + No. 3 + No. 4 extracted gelatins made by A Co.	0.771

(*) : H2O2 is one decomposed using catalase.

Example 1

(Preparation of gelatins)

Comparative gelatin A:

[0113] Deionized gelatin

Comparative gelatin B:

[0114] Gelatin obtained by dissolving deionized gelatin in water at a concentration of 10% by weight and heating at 50°C for 4 hours

Comparative gelatin C:

[0115] Gelatin obtained by dissolving deionized gelatin in water at a concentration of 10% by weight, adding 88 µ mol/g-gel of aqueous hydrogen peroxide, ripening for 16 hours at 40°C, and thereafter decomposing the residual aqueous hydrogen peroxide with a catalase

[0116] (This gelatin was treated according to the oxidation treatment method by hydrogen peroxide described in Japanese Patent Laid-Open No. 157024/1987.)

Gelatin D of the invention:

[0117] Gelatin obtained by dissolving deionized gelatin in water at a concentration of 10% by weight, adding 9.1 µ mol/g-gel of sodium chlorite, ripening for 4 hours at 50° C, and thereafter removing the sodium chlorite by ultrafiltration.

Gelatin E of the invention:

[0118] Gelatin obtained by dissolving deionized gelatin in water at a concentration of 10% by weight, adding 9.1 µ mol/g-gel of sodium peroxoborate(NaBO₃.4H₂O), ripening for 4 hours at 50°C, and thereafter removing the sodium peroxoborete by ultrafiltration.

(Silver colloid test)

[0119] For determining the silver ion reducing property of these gelatins, a silver colloid test was carried out. From the comparative gelatin C corresponding to the gelatin of Japanese Patent Laid-Open No. 157024/1987 by Maskasky, it was shown that the silver ion reducing property of the gelatin subjected to the hydrogen peroxide treatment, which has hitherto been known, was almost the same as that of the gelatin not subjected to the hydrogen peroxide treatment, and the silver reducing property was not reduced. On the other hand, it was shown that in the gelatin D and E used for the invention, the silver ion reducing property was clearly lower than that of other gelatins.

Table 3

Gelatin	Silver Colloid Test (at 430 nm)
A (Comparative)	0.338
B (Comparative)	0.339
C (Comparative)	0.359
D (Invention)	0.153
E (Invention)	0.197

Example 2

(Preparation of emulsions)

(Preparation of Emulsion A used for blue-sensitive emulsion layer)

[0120] A 1: 1 mixture (silver molar ratio) of a cubic large-sized emulsion A1 having an average grain size of 0.70 µm and a small-sized emulsion A2 having an average grain size of 0.50 µm was prepared as an emulsion A.

[0121] The variation coefficient of the grain size distribution of the emulsion A1 and the emulsion A2 was 0.09 and 0.11, respectively. In each size emulsion, 0.5 mol% silver bromide was locally incorporated into a part of the surfaces of the grains made of silver chloride as the base material. To the site corresponding to 10% in the volume from the outermost surface layers of the grains was added an iodine ion of 0.1 mol% to the total halogens, and also, K₄Ru(CN)₆ of 1 × 10^-6 mol per mole of the silver halide, potassium ferrocyanide of 1 × 10^-7 mol per mole of the silver halide and K₂IrCl₅(H₂O) of 1 × 10^-8 mol per mole of the silver halide were added thereto.

[0122] In the emulsions, the following blue-sensitive sensitizing dyes A and B were added to the emulsion A1 in the amount of 3.2 × 10^-4 mol per mole of the silver halide and to the emulsion A2 in the amount of 4.4 × 10^-4 mol per mole of silver halide, respectively, followed by applying a spectral sensitization.

Sensitizing dye A

[0123] 

Sensitizing dye B

[0124] 

(Preparation of emulsion B used for green-sensitive emulsion layer)

[0125] A cubic emulsion B having an average grain size of 0.38 µm and a variation coefficient of the grain size distribution of 0.09 was prepared.

Liquid I	Water	800 ml
	Gelatin A described above	38 g
	NaCl	16 mmol
Liquid II	Silver nitrate	1.40 mol
	Water to make	540 ml
Liquid III	NaCl	1.40 mol
	Water to make	540 ml
Liquid IV	KBr	28 mmol
	Water to make	20 ml

[0126] To the liquid I heated to 50°C were simultaneously added equal amounts of the liquid II and the liquid III while vigorously stirring. In the first 24 minutes, the liquid II and the liquid III were added at an addition rate of 2.2 ml/min., respectively. After an interval of 10 minutes, in the 40 minutes thereafter, the liquid II and the liquid III were added at 12 ml/min., respectively. Also, during the time of from 31 minutes to 36 minutes after the initiation of the second addition, the liquid IV was added at 4 ml/min. Thereafter, the temperature was lowered, and sedimentation and water washing were carried out for desalting. After water washing, the temperature was fixed to 40°C, 12 g of the above-described gelatin A1 was added, the pH was adjusted to 5.6, and the pAg was adjusted to 7.3.

[0127] To the emulsion was added the green-sensitive sensitizing dye D described below in an amount of 2.9 × 10^-4 mol per mole of the silver, and spectral sensitization was carried out.

Sensitizing dye D

[0128] 

(Preparation of emulsion C used for red-sensitive emulsion layer)

[0129] A 1: 1 mixture (silver molar ratio) of a cubic large-sized emulsion C1 having an average grain size of 0.40 µm and a small-sized emulsion C2 having an average grain size of 0.30 µm was prepared. The variation coefficient of the grain size distribution was 0.09 and 0.11, respectively. The respective emulsions contained 0.1 mol% of silver iodide at the vicinity of the grain surface and contained 0.8 mol% of silver bromide locally at the grain surface. Also, like the emulsion A, K₄Ru(CN)₆, potassium ferrocyanide, and K₂IrCl₅(H₂O) were incorporated into the emulsion grains.

[0130] The following sensitizing dyes G and H were added to the emulsions in an amount of 8.0 × 10^-5 mol per mole of the silver halide to the large-sized emulsion and in an amount of 10.7 × 10^-5 mol per mole of the silver halide to the small-sized emulsion, respectively. Furthermore, the following compound I was added to the red-sensitive emulsion layer in an amount of 3.0 × 10^-3 mol per mole of the silver halide.

Sensitizing dye G

[0131] 

Sensitizing dye H

[0132] 

(Preparation of coated sample of color photographic material)

[0133] After applying a corona discharging treatment to both surfaces of a paper support, both surfaces of which were coated with a polyethylene resin, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was formed, and further, by successively coating the photographic constituting layers of the first layer to the seventh layer, a sample A1 of a silver halide color photographic material having the layer construction shown below was prepared. The coating liquid for each photographic constituting layer was prepared as follows.

Preparation of the coating liquid for the first layer:

[0134] In 21 g of a solvent (Solv-1) and 80 ml of ethyl acetate were dissolved 57 g of a yellow coupler (ExY), 7 g of a color image stabilizer (Cpd-1), 4 g of a color image stabilizer (Cpd-2), 7 g of a color image stabilizer (Cpd-3), and 2 g of a color image stabilizer (Cpd-8). The solution obtained was emulsion-dispersed in 220 g of an aqueous solution of 23.5% by weight gelatin containing 4 g of sodium dodecylbenzenesulfonate by a high-speed stirring emulsifier (dissolver), and 900 g of water was added thereto, to prepare an emulsified dispersion A

[0135] The above-described emulsified dispersion A and the above-described emulsion A were mixed to prepare the coating liquid for the first layer such that the liquid had the composition described below. The coating amount of the emulsion is shown by a silver amount-converted coating amount.

[0136] The coating liquids for the second layer to the seventh layer were also prepared by the same manner as in the coating liquid for the first layer described above. As the gelatin hardener for each layer, sodium (2,4-dichloro-6-oxide-1,3,5-trazine) (H-1), (H-2), and (H-3) shown below were used. Also, to each layer, were added the following antiseptics Ab-1, Ab-2, Ab-3 and Ab-4 such that the total amount was 15.0 mg/m², 60.0 mg/m², 5.0 mg/m² and 10.0 mg/m², respectively.

(H-1) Hardener

[0137] 

(H-2) Hardener

[0138] 

(H-3) Hardener

[0139] 

(Ab-1) Antiseptic

[0140] 

(Ab-2) Antiseptic

[0141] 

(Ab-3) Antiseptic

[0142] 

(Ab-4) Antiseptic

[0143] 

[0144] Then, a chemical sensitization process is explained. Each of the above-described emulsions (A, B, and C) was heated to 40°C, and sodium benzenethiosulfonate, bis(1,4,5-trimethyl-1,2,4-triazolium-3-thiolate gold(I) tetrafluoroborate, and an optimum amount of sodium thiosulfate pentahydrate were added to the emulsion. After heating at 60°C for 30 minutes, the above-described sensitizing dyes were added, and after cooling to 40°C, 1-(3-methylureidophenyl)-5-mercaptotetrazole was added to each emulsion (3.3 × 10^-4 mol for the emulsion A, 1.0 × 10^-3 mol for the emulsion B, and 5.9 × 10^-4 mol for the emulsion C, respectively per mole of the silver halide).

[0145] Also, 1-(3-methylureidophenyl)-5-mercaptotetrazole was added to the second layer, the fourth layer, the sixth layer, and the seventh layer such that the addition amount was 0.2 mg/m², 0.2 mg/m², 0.6 mg/m² and 0.1 mg/m², respectively.

[0146] Also, to the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was added in an amount of 1 × 10^-4 mol and 2 × 10^-4 mol, respectively per mole of the silver halide.

[0147] Also, to the red-sensitive emulsion layer, a copolymer latex of methacrylic acid and butyl methacrylate (weight ratio 1 : 1, average molecular weight 200,000 to 400,000) was added in an amount of 0.05 g/m².

[0148] Also, sodium catechol-3,5-disulfonate was added in an amount of 6 mg/m² for the second layer, 6 mg/m² for the fourth layer, and 18 mg/m², respectively.

[0149] Also, for irradiation prevention, the following dyes (the numerals in the parentheses show the coating amounts).

(Layer construction)

[0150] Then, the construction of each layer is shown. The numeral shows the coating amount (g/m²). The coating amount of the silver halide emulsion shows the silver-converted coating amount.

Support: Polyethylene resin-laminated paper

[0151] [The polyethylene resin of the first layer (Layer 1) side contains white pigments (TiO₂, content: 16% by weight; ZnO₂, content: 4% by weight), a fluorescent brightening agent (4,4'-bis(5-methylbenzoxazolyl)stilbene, content 0.03% by weight), and a blue dye (ultramarine blue).]

Layer 1 (Blue-sensitive emulsion layer):
Emulsion A	0.24
Gelatin	1.25
Yellow Coupler (ExY)	0.57
Color image stabilizer (Cpd-1)	0.07
Color image stabilizer (Cpd-2)	0.04
Color image stabilizer (Cpd-3)	0.07
Color image stabilizer (Cpd-8)	0.02
Solvent (Solv-1)	0.21

Layer 2 (Color mixing inhibiting layer):
Gelatin	0.99
Color mixing inhibitor (Cpd-4)	0.09
Color image stabilizer (Cpd-5)	0.018
Color image stabilizer (Cpd-6)	0.13
Color image stabilizer (Cpd-7)	0.01
Solvent (Solv-1)	0.06
Solvent (Solv-2)	0.22

Layer 3 (Green-sensitive emulsion layer):
Emulsion B	0.21
Gelatin	1.36
Magenta coupler (ExM)	0.15
Ultraviolet absorbent (UV-A)	0.14
Color image stabilizer (Cpd-2)	0.02
Color image stabilizer (Cpd-4)	0.002
Color image stabilizer (Cpd-6)	0.09
Color image stabilizer (Cpd-8)	0.02
Color image stabilizer (Cpd-9)	0.03
Color image stabilizer (Cpd-10)	0.01
Color image stabilizer (Cpd-11)	0.0001
Solvent (Solv-3)	0.11
Solvent (Solv-4)	0.22
Solvent (Solv-5)	0.20

Layer 4 (Color mixing inhibiting layer):
Gelatin	0.71
Color mixing inhibitor (Cpd-4)	0.06
Color image stabilizer (Cpd-5)	0.013
Color image stabilizer (Cpd-6)	0.10
Color image stabilizer (Cpd-7)	0.007
Solvent (Solv-1)	0.04
Solvent (Solv-2)	0.16

Layer 5 (Red-sensitive emulsion layer):
Emulsion C	0.12
Gelatin	1.11
Cyan coupler (ExC-2)	0.13
Cyan coupler (ExC-3)	0.03
Color image stabilizer (Cpd-1)	0.05
Color image stabilizer (Cpd-6)	0.06
Color image stabilizer (Cpd-7)	0.02
Color image stabilizer (Cpd-9)	0.04
Color image stabilizer (Cpd-10)	0.01
Color image stabilizer (Cpd-14)	0.01
Color image stabilizer (Cpd-15)	0.12
Color image stabilizer (Cpd-16)	0.03
Color image stabilizer (Cpd-17)	0.09
Color image stabilizer (Cpd-18)	0.07
Solvent (Solv-5)	0.15
Solvent (Solv-8)	0.05

Layer 6 (Ultraviolet absorption layer):
Gelatin	0.46
Ultraviolet absorbent (UV-B)	0.45
Compound (S1-4)	0.0015
Solvent (Solv-7)	0.25

Layer 7 (Protective layer):
Gelatin	1.00
Acrylic-modified copolymer of polyvinyl alcohol (degree of modification: 17%)	0.04
Liquid paraffin	0.02
Surfactant (Cpd-13)	0.01

[0152] The compounds used in the above-described layer constructions are shown below.

(ExY) Yellow coupler: A 70:30 mixture (molar ratio) of

[0153] 

and

(ExM) Magenta coupler: A 40:40:20 mixture (molar ratio) of

[0154] 

and

(ExC-2) Cyan coupler:

[0155] 

(ExC-3) Cyan coupler: A 50:25:25 mixture (molar ratio) of

[0156] 

and

and

(Cpd-1) Color image stabilizer:

[0157] 

Number average molecular weight: 60,000

(Cpd-2) Color image stabilizer:

[0158] 

(Cpd-3) Color image stabilizer:

[0159] 

(Cpd-4) Color mixing inhibitor:

[0160] 

(Cpd-5) Color image stabilizer:

[0161] 

(Cpd-6) Color image stabilizer:

[0162] 

Number average molecular weight: 600; m/n = 10/90

(Cpd-7) Color image stabilizer:

[0163] 

(Cpd-8) Color image stabilizer:

[0164] 

(Cpd-9) Color image stabilizer:

[0165] 

(Cpd-10) Color image stabilizer:

[0166] 

(Cpd-11)

[0167] 

(Cpd-13) Surfactant: A 7:3 mixture (molar ratio) of

[0168] 

and

(Cpd-14)

[0169] 

(Cpd-15)

[0170] 

(Cpd-16)

[0171] 

(Cpd-17)

[0172] 

(Cpd-18)

[0173] 

(Cpd-19) Color mixing inhibitor:

[0174] 

(UV-1) Ultraviolet absorbent:

[0175] 

(UV-2) Ultraviolet absorbent:

[0176] 

(UV-3) Ultraviolet absorbent:

[0177] 

(UV-4) Ultraviolet absorbent:

[0178] 

(UV-5) Ultraviolet absorbent:

[0179] 

(UV-6) Ultraviolet absorbent:

[0180] 

(UV-7) Ultraviolet absorbent:

[0181] 

UV-A: A mixture of UV-1/UV-2/UV-3/UV-4 = 4/2/2/3 (weight ratio)

UV-B: A mixture of UV-1/UV-2/UV-3/UV-4/UV-5/UV-6 = 9/3/3/4/5/3 (weight ratio)

UV-C: A mixture of UV-2/UV-3/UV-6/UV-7 = 1/1/1/2 (weight ratio)

(Solv-1)

[0182] 

(Solv-2)

[0183] 

(Solv-3)

[0184] 

(Solv-4)

[0185] 

        O=P(̵OC₆H_.3(n))₃

(Solv-5)

[0186] 

(Solv-7)

[0187] 

(Solv-8)

[0188] 

(S1-4)

[0189] 

[0190] By following the same procedures as above, Samples A2 to A3, B1 to B3, C1 to C3, D1 to D3, and E1 to E3 were prepared by changing the gelatin and the addition amount of the sodium benzenethiosulfonate used in the case of preparing the emulsion B of Sample B1 as shown in Table 4 below. In the cases of preparing samples B1 to B3, C1 to C3, D1 to D3, and E1 to E3, the amount of gelatin in the liquid I was changed to 380 g of 10% gelatin, and also, the amount of water was changed to 470 ml.

Table 4

Sample No.	Gelatin	Sodium benzenethiosulfonate
A1 (Comparison)	Gelatin A	40 µmol/mol-Ag
A2 (Comparison)	Gelatin A	1 µmol/mol-Ag
A3 (Comparison)	Gelatin A	0 µmol/mol-Ag
B1 (Comparison)	Gelatin B	40 µmol/mol-Ag
B2 (Comparison)	Gelatin B	1 µmol/mol-Ag
B3 (Comparison)	Gelatin B	0 µmol/mol-Ag
C1 (Comparison)	Gelatin C	40 µmol/mol-Ag
C2 (Comparison)	Gelatin C	1 µmol/mol-Ag
C3 (Comparison)	Gelatin C	0 µmol/mol-Ag
D1 (Invention)	Gelatin D	40 µmol/mol-Ag
D2 (Invention)	Gelatin D	1 µmol/mol-Ag
D3 (Invention)	Gelatin D	0 µmol/mol-Ag
E1 (Invention)	Gelatin E	40 µmol/mol-Ag
E2 (Invention)	Gelatin E	1 µmol/mol-Ag
E3 (Invention)	Gelatin E	0 µmol/mol-Ag

[0191] For determining the photographic characteristics of these samples, the following tests were carried out.

Test 1: Sensitometry

[0192] To each coated sample, using an actinometer (FWH-type, manufactured by Fuji Photo Film Co., Ltd.), gradation exposure for sensitometry was applied. An SP-2 filter was mounted, and at a low illumination, the sample was exposed for 10 seconds.

[0193] After the exposure, color development processing A shown below was carried out.

[0194] The processing steps are shown below.

[Processing A]

[0195] The above-described photosensitive material A1 was worked to a roll form having a width of 127 mm, after imagewise exposing using a mini-labo printer processor, PP1258AR (a trade name, manufactured by Fuji Photo Film Co., Ltd.), continuous processing (running test) was carried out by the following processing steps until a replenisher was replenished to 2 times the volume of the color development tank. The processing using the running liquid was defined to be processing A.

Processing step	Temperature	Time	Replenishing amount*
Color development	38.5°C	45 sec.	45 ml
Blix	38.0°C	45 sec.	35 ml
Rinse (1)	38.0°C	20 sec.	-
Rinse (2)	38.0°C	20 sec.	-
Rinse (3)	**38.0°C	20 sec.	-
Rinse (4)	**38.0°C	30 sec.	121 ml

*: The replenishing amount per m2 of the photosensitive material. **: A rinse cleaning system, RC50D (a trade name, manufactured by Fuji Photo Film Co., Ltd.) was equipped to the rinse (3), and a rinse liquid was taken out from the rinse (3) and sent to a reverse osmosis film module (RC50D) by a pump. The permeated water obtained by the same tank was supplied to the rinse (4), and the concentrated water was returned to rinse (3). The pump pressure was controlled such that the permeated water amount to the reverse osmosis module was maintained at from 50 to 300 ml/min., and the water was circulated while controlling the temperature for 10 hours per day. (The rinse was a tank counter-current system from the rinses(1) to (4).)

[0196] The composition of each processing liquid was as follows.

[Color developer]	[Tank liquid]	[Replenisher]
Water	800 ml	800 ml
Dimethylpolysiloxane-based surfactant (a trade name: Silicone KF351A, made by Shin-Etsu Chemical Co., Ltd.)	0.1 g	0.1 g
Tri(isopropanol)amine	8.8 g	8.8 g
Ethylenediaminetetraacetic acid	4.0 g	4.0 g
Polyethylene glycol (molecular weight: 300)	10.0 g	10.0 g
Sodium 4,5-dihydroxybenzene-1,3-disulfonate	0.5 g	0.5 g
Potassium chloride	10.0 g	-
Potassium bromide	0.040 g	0.010 g
Triazinylaminostilbene-based fluorescent brightening agent (a trade name: Hakkol FWA-SF, made by Showa Chemical Co., Ltd.)	2.5 g	5.0 g
Sodium sulfite	0.1 g	0.1 g
Disodium-N,N-bis(sulfonatoethyl)hydroxylamine	8.5 g	11.1 g
N-Ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-amino-4-aminoaniline·3/2 sulfate·monohydrate	5.0 g	15.7 g
Potassium carbonate	26.3 g	26.3 g
Water to make	1,000 ml	1,000 ml
pH (adjusted with potassium hydroxide or sulfuric acid at 25°C)	10.15	12.50

[Blix solution]	[Tank liquid]	[Replenisher]
Water	700 ml	600 ml
Ethylenediaminetetraacetic acid iron(III) ammonium	47.0 g	94.0 g
Ethylenediaminetetraacetic acid	1.4 g	2.8 g
m-Carboxybenzenesulfinic acid	8.3 g	16.5 g
Nitric acid (67%)	16.5 g	33.0 g
Imidazole	14.6 g	29.2 g
Ammonium thiosulfate (750 g/liter)	107.0 ml	214.0 ml
Ammonium sulfite	16.0 g	32.0 g
Ammonium bisulfite	23.1 g	46.2 g
Water to make	1,000 ml	1,000 ml
pH (adjusted with acetic acid or ammonia at 25°C)	6.0	6.0

[Rinse liquid]	[Tank liquid]	[Replenisher]
Chlorinated sodium isocyanurate	0.02 g	0.02 g
Deionized water (conductivity: 5 µS/cm or lower)	1,000 ml	1,000 ml
pH	6.5	6.5

[0197] The magenta color density of each sample after the processing was measured, and the 10-seconds exposure low-illumination sensitivity of the emulsion A1 was determined. The sensitivity was defined as a reciprocal of the exposure amount of giving a higher color density by 1.0 than the lowest colored density and was shown by a relative value when the sensitivity of the developed sample A1 was defined as 100. Also, the fog was shown by a lowest density of each sample.

Test 2: Shelf life with a lapse of time

[0198] Each coated sample was stored for two days under the atmosphere of 60°C and a humidity of 55%, thereafter, the sample was light-exposed and subjected to color development processing, and the sensitivity and the fog thereof were compared with those of the sample before storing.

[0199] The sensitivity of each sample was defined as in Test 1 by defining the sensitivity of the developed sample A1 before storing as 100, and the numerical value obtained by subtracting the sensitivity before storing from the sensitivity after storing is defined as the sensitivity with a lapse of time. Also, the fog of each same was defined as in Test 1, and similarly, the numerical value obtained by subtracting the fog before storing from the fog after storing is defined as the fog with a lapse of time.

Test 3: Wet abrasion resistance

[0200] Each coated sample was light-exposed and subjected to development processing by applying the following operation to the color development processing A. That is, 10 seconds after carrying out the color development in the color development processing A, writing on the emulsion layer surface of the same by a stylus having a diameter of 1.6 mm equipped with a load of 30 g, and thereafter, the sample was blixed. When the coated sample showed a mark by the load, the sample was shown as "bad" and when the sample did not show a mark, the sample was shown as "good".

[0201] Tests 1 to 3 were carried out, the magenta color density of each sample after the processing was measured, and each of the 10-seconds exposure low-illumination sensitivity, the fog density, and the wet abrasion resistance were determined. The results obtained are shown in Table 5 below.

[0202] From the results shown in the above table, it can be seen that in the emulsions D1 to D3, and E1 to E3 of the invention prepared using gelatin having a low silver ion reducing property according to the invention, the shelf life with a lapse of time and the wet abrasion resistance are greatly improved as compared with the emulsions C1 to C3 prepared using gelatin subjected to an oxidation treatment with aqueous hydrogen peroxide, which have hitherto been known, and the emulsions A1 to A3 and B1 to B3 prepared using gelatin not subjected to an oxidation treatment. Also, from the emulsions D2, D3, E2 and E3, it can be seen that even when the addition amount of sodium benzenethiosulfonate is reduced to 1 µmol/mol-Ag or less, a good photographic property can be obtained. This is considered to be caused by the matter that because in the emulsions of the invention, silver nuclei scarcely exist in the silver halide emulsion, even when gold sensitization is carried out, the fog is not generated. Also, by comparing the emulsion D1 with the emulsion D3 or the emulsion E1 with the emulsion E3, it can be seen that by adding the oxidizing agent at the chemical ripening, the sensitivity is lowered. This is considered to be caused by the matter that the oxidizing agent added at chemical ripening attaches to the surfaces of the silver halide grains to cause the development restraint. Incidentally, as is seen from the comparison of the samples B1 to B3 with the samples A1 to A3, the heat treatment itself at oxidizing gelatin gives no influence on the photographic properties.

Claims

1. A silver halide emulsion having a silver chloride content of 90 mol% or more, characterized in that said silver halide emulsion contains gelatin having an absorbance by a silver colloid test of lower than 0.25.

2. The silver halide emulsion as claimed in claim 1, wherein said gelatin is used at the formation of silver halide grains.

3. The silver halide emulsion as claimed in claim 1 or 2, wherein said gelatin is a gelatin subjected to an oxidation treatment with a chlorite or a peroxoborate.

4. A process for producing a silver halide emulsion having a silver chloride content of 90 mol% or more, characterized by using a gelatin having an absorbance by a silver colloid test of lower than 0.25.

5. A process for producing a silver halide emulsion, characterized by using the gelatin as claimed in claim 4 at the formation of silver halide grains.

6. The process as claimed in claim 4 or 5, wherein the gelatin is a gelatin subjected to an oxidation treatment with a chloriteor a peroxoborate.

7. The process as claimed in any one of claims 4 through 6, wherein the addition amount of a thiosulfonic acid compound during after-ripening is from 0 to 1 µ mol/mol-Ag.

8. A silver halide photographic material, characterized by containing the silver halide emulsion as claimed in any one of claims 1 through 3.

9. Use of a gelatin having an absorbance by a silver colloid test of lower than 0.25, for preparing a silver halide emulsion having a silver chloride content of 90 mol% or more.