Silver halide photographic material

FIELD OF THE INVENTION
The present invention relates to a silver halide photographic material, and more specifically relates to a silver halide photographic material which has high sensitivity, generates less fog, exhibits excellent storage stability and generates less residual color after processing.
BACKGROUND OF THE INVENTION
Every endeavor has been made for enhancing sensitivity and for reduction of residual colors after processing of a silver halide photographic material. It is known that a sensitizing dye which is used for spectral sensitization largely affects capacities of a silver halide photographic material. A trace of structural difference of a sensitizing dye largely affects photographic capacities such as sensitivity, fog, storage stability and residual color after processing, but it is difficult to foresee its effect. Many engineers have hitherto synthesized various kinds of sensitizing dyes and endeavored to investigate photographic capacities thereby, but it is not possible to know photographic capacities in advance yet. Combined use of two or more sensitizing dyes also greatly influences photographic capacities, such as sensitivity, fog, storage stability and residual color after processing, but it is difficult to foresee its effect, therefore many engineers have examined combinations of a variety of sensitizing dyes and endeavored to investigate photographic capacities thereby, but it is not possible to know photographic capacities in advance yet.
Further, a trial of reduction sensitization for enhancing sensitivity of a silver halide photographic material has been studied heretofore. Various compounds are disclosed in many patents as useful reduction sensitizers, for example, tin compounds are disclosed in U.S. Pat. No. 2,487,850, polyamine compounds in U.S. Pat. No. 2,512,925, and thiourea dioxide compounds in British Patent 789,823. Further, in Photographic Science and Engineering, Vol. 23, p. 113 (1979), comparisons of natures of silver nuclei formed according to various reduction sensitizing methods are described and dimethylamineborane, stannous chloride, hydrazine, and methods of high pH ripening and low pAg ripening have been employed. Reduction sensitizing methods are also disclosed in U.S. Pat. Nos. 2,518,698, 3,201,254, 3,411,917, 3,779,777 and 3,930,867. Not only the selection of reduction sensitizers but contrivances of reduction sensitizing methods are disclosed in JP-B-57-33572 and JP-B-58-1410 (the term "JP-B" as used herein means an "examined Japanese patent publication").
From the above-described reasons, techniques of spectrally sensitizing silver halide grains (in particular, reduction sensitized silver halide grains) in a highly sensitive state and without causing malefic effects such as fog have been demanded.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a silver halide photographic material which has high sensitivity, generates less fog, is excellent in storage stability and generates less residual color after processing.
As a result of eager investigations, the above object of the present invention has been attained by the following means.
(1) A silver halide photographic material which contains at least one compound represented by the following formula (I) and at least one compound represented by the following formula (II): ##STR3## wherein Ar.sub.1 and Ar.sub.2 each represents an aryl group or a heterocyclic group; R.sub.1 and R.sub.2 each represents an alkyl group; M.sub.1 represents a counter ion for charge balance; and m.sub.1 represents a number of 0 or more necessary for balancing a charge in the molecule of the compound; ##STR4## wherein either Z.sub.1 or Z.sub.2 represents an oxygen atom and the other represents a sulfur atom; V represents a monovalent substituent; R.sub.3 and R.sub.4 each represents an alkyl group; M.sub.2 represents a counter ion for charge balance; and m.sub.2 represents a number of 0 or more necessary for balancing a charge in the molecule of the compound.
(2) A silver halide photographic material comprising a support having provided thereon at least one silver halide emulsion layer, wherein silver halide grains of the emulsion layer are reduction sensitized and the silver halide photographic material contains at least one compound represented by formula (I) and at least one compound represented by formula (II).
(3) The silver halide photographic material as described in (1) or (2), wherein the silver halide photographic material contains at least one compound represented by the following formula (XX), (XXI) or (XXII):
R.sub.101 --SO.sub.2 S--M.sub.101 (XX)
R.sub.101 --SO.sub.2 S--R.sub.102 (XXI)
R.sub.101 --SO.sub.2 S--(E)--.sub.a SSO.sub.2 --R.sub.103 (XXII)
wherein R.sub.110, R.sub.102 and R.sub.103 each represents an aliphatic group, an aromatic group or a heterocyclic group; M.sub.101 represents a cation; E represents a divalent linking group; and a represents 0 or 1.
DETAILED DESCRIPTION OF THE INVENTION
Compounds for use in the present invention are described in detail below.
In formula (II), the monovalent substituent represented by V is not particularly restricted and any group can be used so long as it is a monovalent substituent. Examples of monovalent substituents represented by V include, for example, a halogen atom (e.g., chlorine, bromine, iodine fluorine,), a mercapto group, a cyano group, a carboxyl group, a phosphoric acid group, a sulfo group, a hydroxyl group, a carbamoyl group (hereinafter, "a carbamoyl group" means a carbamoyl group which may have a substituent), for example, a carbamoyl group having from 1 to 10, preferably from 2 to 8, more preferably from 2 to 5, carbon atoms (e.g., methylcarbamoyl, ethylcarbamoyl, morpholinocarbonyl), a sulfamoyl group (which may be substituted), for example, a sulfamoyl group having from 0 to 10, preferably from 2 to 8, more preferably from 2 to 5, carbon atoms (e.g., methylsulfamoyl, ethylsulfamoyl, piperidinosulfonyl), a nitro group, an alkoxyl group (which may be substituted), for example, an alkoxyl group having from 1 to 20, preferably from 1 to 10, more preferably from 1 to 8, carbon atoms (e.g., methoxy, ethoxy, 2-methoxyethoxy, 2-phenylethoxy), an aryloxy group (which may be substituted), for example, an aryloxy group having from 6 to 20, preferably from 6 to 12, more preferably from 6 to 10, carbon atoms (e.g., phenoxy, p-methylphenoxy, p-chlorophenoxy, naphthoxy), an acyl group (which may be substituted), for example, an acyl group having from 1 to 20, preferably from 2 to 12, more preferably from 2 to 8, carbon atoms (e.g., acetyl, benzoyl, trichloroacetyl), an acyloxy group (which may be substituted), for example, an acyloxy group having from 1 to 20, preferably from 2 to 12, more preferably from 2 to 8, carbon atoms (e.g., acetyloxy, benzoyloxy), an acylamino group (which may be substituted), for example, an acylamino group having from 1 to 20, preferably from 2 to 12, more preferably from 2 to 8, carbon atoms (e.g., acetylamino), a sulfonyl group (which may be substituted), for example, a sulfonyl group having-from 1 to 20, preferably from 1 to 10, more preferably from 1 to 8, carbon atoms (e.g., methanesulfonyl, ethanesulfonyl, benzenesulfonyl), a sulfinyl group (which may be substituted), for example, a sulfinyl group having from 1 to 20, preferably from 1 to 10, more preferably from 1 to 8, carbon atoms (e.g., methanesulfinyl, benzenesulfinyl), a sulfonylamino group (which may be substituted), for example, a sulfonylamino group having from 1 to 20, preferably from 1 to 10, more preferably from 1 to 8, carbon atoms (e.g., methanesulfonylamino, ethanesulfonylamino, benzenesulfonylamino), an amino group (which may be substituted), for example, an amino group having from 1 to 20, preferably from 1 to 12, more Preferably from 1 to 8, carbon atoms (e.g., methylamino, imethylamino, benzylamino, anilino, diphenylamino), an ammonium group (which may be substituted), for example, an ammonium group having from 0 to 15, preferably from 3 to 10, more preferably from 3 to 6, carbon atoms (e.g., trimethylammonium, triethylammonium), a hydrazino group (which may be substituted), for example, a hydrazino group having from 0 to 15, preferably from 1 to 10, more preferably from 1 to 6, carbon atoms (e.g., trimethylhydrazino), a ureido group (which may be substituted), for example, a ureido group having from 1 to 15, preferably from 1 to 10, more preferably from 1 to 6, carbon atoms (e.g., ureido, N,N-dimethylureido), an imido group (which may be substituted), for example, an imido group having from 1 to 15, preferably from 1 to 10, more preferably from 1 to 6, carbon atoms (e.g., succinimido), an alkylthio- or arylthio group (which may be substituted), for example, an alkylthio-, arylthio- or heterocyclylthio group having from 1 to 20, preferably from 1 to 12, more preferably from 1 to 8, carbon atoms (e.g., methylthio, ethylthio, carboxyethylthio, sulfobutylthio, phenylthio, 2-pyridylthio), an alkoxycarbonyl group (which may be substituted), for example, an alkoxycarbonyl group having from 2 to 20, preferably from 2 to 12, more preferably from 2 to 8, carbon atoms (e.g., methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl), an aryloxycarbonyl group (which may be substituted), for example, an aryloxycarbonyl group having from 6 to 20, preferably from 6 to 12, more preferably from 6 to 8, carbon atoms (e.g., phenoxycarbonyl), an alkyl group (which may be substituted), for example, an unsubstituted alkyl group having from 1 to 18, preferably from 1 to 10, more preferably from 1 to 5, carbon atoms (e.g., methyl, ethyl, propyl, butyl), a substituted alkyl group having from 1 to 18, preferably from 1 to 10, more preferably from 1 to 5, carbon atoms (e.g., hydroxymethyl, trifluoromethyl, benzyl, carboxyethyl, ethoxycarbonylmethyl, acetylaminomethyl, in addition, an unsaturated hydrocarbon group preferably having from 2 to 18, more preferably from 3 to 10, particularly preferably from 3 to 5, carbon atoms (e.g., vinyl, ethynyl, 1-cyclohexenyl, benzylidyne, benzylidene) is also included in a substituted alkyl group), an aryl group (which may be substituted), for example, a substituted or unsubstituted aryl group having from 6 to 20, preferably from 6 to 15, more preferably from 6 to 10, carbon atoms (e.g., phenyl, naphthyl, p-carboxyphenyl, p-nitrophenyl, 3,5-di-chlorophenyl, p-cyanophenyl, m-fluorophenyl, p-tolyl), and a heterocyclic group (which may be substituted), for example, a heterocyclic group having from 1 to 20, preferably from 2 to 10, more preferably from 4 to 6, carbon atoms (which may be substituted) (e.g., pyridyl, 5-methylpyridyl, thienyl, furyl, morpholino, tetrahydrofurfuryl). The heterocyclic group may have the condensed structure of a benzene ring, a naphthalene ring and an anthracene ring.
These substituents may further be substituted with a substituent represented by V.
Preferred substituent of V is a halogen atom (e.g., fluorine, chlorine, bromine, iodine), more preferably chlorine or bromine, and particularly preferably bromine.
In formulae (I) and (II), R.sub.1, R.sub.2, R.sub.3 and R.sub.4 each represents an alkyl group, e.g., an unsubstituted alkyl group having from 1 to 18, preferably from 1 to 7, particularly preferably from 1 to 4, carbon atoms (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl), or a substituted alkyl group having from 1 to 18, preferably from 1 to 7, particularly preferably from 1 to 4, carbon atoms (any substituent can be used, for example, an alkyl group substituted with the substituent described above as substituents of V can be exemplified, preferably an aralkyl group (e.g., benzyl, 2-phenylethyl), an unsaturated hydrocarbon group (e.g., allyl), a hydroxyalkyl group (e.g., 2-hydroxyethyl, 3-hydroxypropyl), a carboxyalkyl group (e.g., 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, carboxymethyl), an alkoxyalkyl group (e.g., 2-methoxyethyl, 2-(2-methoxyethoxy)ethyl), an aryloxyalkyl group (e.g., 2-phenoxyethyl, 2-(1-naphthoxy)ethyl), an alkylthioalkyl group (e.g., 2-methylthioethyl, 2-(2-methylthioethylthio)ethyl), an arylthioalkyl group (e.g., 2-phenylthioethyl, 2-(1-naphthylthio)ethyl), a heterocyclylthioalkyl group (e.g., 2-pyridylthioethyl, 2-thienylthioethyl), an alkoxycarbonylalkyl group (e.g., ethoxycarbonylmethyl, 2-benzyloxycarbonylethyl), an aryloxycarbonylalkyl group (e.g., 3-phenoxycarbonylpropyl), an acyloxyalkyl group (e.g., 2-acetyloxyethyl), an acylalkyl group (e.g., 2-acetylethyl), a carbamoylalkyl group (e.g., 2-morpholinocarbonylethyl), a sulfamoylalkyl group (e.g., N,N-dimethylcarbamoylmethyl), a sulfoalkyl group (e.g., 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2-(3-sulfopropoxy)ethyl, 2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl), a sulfoalkenyl group (e.g., sulfopropenyl), a sulfatoalkyl group (e.g., 2-sulfatoethyl, 3-sulfatopropyl, 4-sulfatobutyl), a heterocyclic group-substituted alkyl group (e.g., 2-(pyrrolidin-2-one-1-yl)ethyl, tetrahydrofurfuryl), or an alkylsulfonylcarbamoyl-methyl group (e.g., methanesulfonylcarbamoylmethyl)).
Preferred alkyl groups represented by R.sub.1, R.sub.2, R.sub.3 and R.sub.4 is an alkyl group substituted with an acid radical (e.g., carboxyalkyl, sulfoalkyl), more preferably 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl or 4-sulfobutyl, and particularly preferably 3-sulfopropyl or 3-sulfobutyl.
In formula (I), Ar.sub.1 and Ar.sub.2 each represents an aryl group (which may be substituted, and those described above as substituents of V can be cited as examples of substituents of the aryl group), for example, a substituted or unsubstituted aryl group having from 6 to 20, preferably from 6 to 15, more preferably from 6 to 10, carbon atoms (e.g., phenyl, naphthyl, p-carboxyphenyl, p-chlorophenyl, 3,5-dichlorophenyl, p-cyanophenyl, p-bromophenyl, p-tolyl), or a heterocyclic group (which may be substituted, and those described above as substituents of V can be cited as examples of substituents of the heterocyclic group), for example, a heterocyclic group having from 1 to 20, preferably from 2 to 10, more preferably from 4 to 6, carbon atoms (e.g., pyridyl, 5-methylpyridyl, thienyl, furyl). Ar.sub.1 and Ar.sub.2 each more preferably represents an aryl group, particularly preferably a phenyl group.
In formula (II), either Z.sub.1 or Z.sub.2 represents an oxygen atom and the other represents a sulfur atom, preferably Z.sub.1 represents a sulfur atom and Z.sub.2 represents an oxygen atom.
In formulae (I) and (II), M.sub.1 and M.sub.2 are included in the formulae to show the presence of a cation or an anion when a counter ion is necessary to neutralize the ionic charge of the dye. Representative examples of cations include an inorganic cation such as a hydrogen ion (H.sup.+), an alkali metal ion (e.g., a sodium ion, a potassium ion, a lithium ion), and an alkaline earth metal ion (e.g., a calcium ion), and an organic ion such as an ammonium ion (e.g., an ammonium ion, a tetraalkylammonium ion, a pyridinium ion, an ethylpyridinium ion). Anions may be either inorganic or organic, and examples include a halogen anion (e.g., a fluorine ion, a chlorine ion, an iodine ion), a substituted arylsulfonate ion (e.g., a p-toluenesulfonate ion, a p-chlorobenzenesulfonate ion), an aryldisulfonate ion (e.g., a 1,3-benzenedisulfonate ion, a 1,5-naphthalenedisulfonate ion, a 2,6-naphthalenedisulfonate ion), an alkylsulfate ion (e.g., a methylsulfate ion), a sulfate ion, a thiocyanate ion, a perchlorate ion, a tetrafluoroborate ion, a picrate ion, an acetate ion, and a trifluoromethanesulfonate ion. In addition, ionic polymers or other dyes having a counter charge to the dye may be used.
In the present invention, a sulfo group is described as SO.sub.3.sup.-, but it can be described as SO.sub.3 H when a hydrogen ion is present as a counter ion.
m.sub.1 and m.sub.2 each represents a number necessary to balance a charge in the molecule and it represents 0 when an inner salt is formed. m.sub.1 and m.sub.2 each preferably represents from 0 to 4.
Besides the compounds represented by formula (I) or (II) according to the present invention, other sensitizing dyes may also be used. Sensitizing dyes are often used in combination, in particular, for the purpose of supersensitization. Representative examples thereof are disclosed in U.S. Pat. Nos. 2,688,545, 2,977,229, 3,397,060, 3,522,052, 3,527,641, 3,617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703,377, 3,769,301, 3,814,609, 3,837,862, 4,026,707, British Patents 1,344,281, 1,507,803, JP-B-43-4936, JP-B-53-12375, and JP-A-52-110618 and JP-A-52-109925 (the term "JP-A" as used herein means an "unexamined published Japanese patent application").
Specific examples of the compounds represented by formula (I) or (II) according to the present invention are shown below, but it should not be construed as the present invention is limited thereto.
Compounds Represented by Formula (I):
______________________________________ ##STR5##No. R =______________________________________(1) .paren open-st. CH.sub.2).sub.2 --CH(CH.sub.3)--SO.sub.3.su p.-(2) .paren open-st. CH.sub.2).sub.3 SO.sub.3.sup.-(3) .paren open-st. CH.sub.2).sub.2 SO.sub.3.sup.-(4) .paren open-st. CH.sub.2).sub.4 SO.sub.3.sup.-(5) --CH.sub.2 CO.sub.2.sup.-(6) .paren open-st. CH.sub.2).sub.2 CO.sub.2.sup.-______________________________________ ##STR6## No. n______________________________________ (7) 1 (8) 2 (9) 3______________________________________ ##STR7##No. V.sub.1______________________________________(10) Cl(11) Br(12) OH(13) OCH.sub.3______________________________________ ##STR8##No. V.sub.1______________________________________(14) ##STR9##(15) ##STR10##(16) ##STR11##(17) ##STR12##(18) ##STR13##______________________________________(19) ##STR14##(20) ##STR15##______________________________________
Compounds Represented by Formula (II):
______________________________________ ##STR16##No. X n______________________________________(51) F 3(52) " 4(53) Cl 3(54) " 4(55) Br 3(56) " 4(57) I 3(58) " 4______________________________________ ##STR17##No. X n______________________________________(59) F 3(60) " 4(61) Cl 3(62) " 4(63) Br 3(64) " 4(65) I 3(66) " 4______________________________________ ##STR18##No. V.sub.1______________________________________(67) OCH.sub.3(68) CH.sub.3(69) OH(70) CO.sub.2 H______________________________________ ##STR19##No. V.sub.1______________________________________(71) OCH.sub.3(72) CH.sub.3(73) OH(74) CO.sub.2 H______________________________________ ##STR20##No. R______________________________________(75) CH.sub.2 CO.sub.2 H(76) (CH.sub.2).sub.2 CO.sub.2 H(77) (CH.sub.3).sub.3 CO.sub.2 H______________________________________ ##STR21## No. n______________________________________ (78) 1 (79) 2 (80) 3______________________________________
The compounds represented by formula (I) or (II) can be synthesized according to the methods described in the following literature: F. M. Harmer, Heterocyclic Compounds--Cyanine Dyes and Related Compounds, John Wiley & Sons, New York, London (1964), D. M. Sturmer, Heterocyclic Compounds--Special Topics in Heterocyclic Chemistry, Chap. 18, Clause 14, pp. 482 to 515, John Wiley & Sons, New York, London (1977), Rodd's Chemistry of Carbon Compounds, 2nd Ed., Vol. IV, Part B, Chap. 15, pp. 369 to 422, Elsevier Science Publishing Company Inc., New York (1977).
For the inclusion of the compounds represented by formula (I) or (II) according to the present invention in the silver halide emulsion for use in the present invention, they may be directly dispersed in the emulsion, or they may be dissolved in a single or mixed solvent of water, methanol, ethanol, propanol, acetone, methyl cellosolve, 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, 1-methoxy-2-propanol, N,N-dimethylformamide, etc., and then added to the emulsion.
In addition, various methods can be used for the inclusion of the dyes in the emulsion, e.g., a method in which the dyes are dissolved in a volatile organic solvent, the solution is dispersed in water or hydrophilic colloid and this dispersion is added to the emulsion as disclosed in U.S. Pat. No. 3,469,987, a method comprising dispersing the water-insoluble dyes in a water-soluble solvent without dissolution and adding the dispersion to the emulsion as disclosed in JP-B-46-24185, a method in which the dyes are dissolved in an acid and the solution is added to the emulsion, or the dyes are added to the emulsion as an aqueous solution coexisting with acid or base as disclosed in JP-B-44-23389, JP-B-44-27555 and JP-B-57-22091, a method in which the dyes are added to the emulsion as an aqueous solution or colloidal dispersion coexisting with a surfactant as disclosed in U.S. Pat. Nos. 3,822,135 and 4,006,026, a method in which the dyes are directly dispersed in a hydrophilic colloid and the dispersion is added to the emulsion as disclosed in JP-A-53-102733 and JP-A-58-105141, or a method comprising dissolving the dyes using a compound capable of red-shifting and adding the solution to the emulsion as disclosed in JP-A-51-74624 can be used. Further, ultrasonic waves can be used for dissolution.
The time of the addition of the compounds for use in the present invention to the silver halide emulsion for use in the present invention may be at any stage of the preparation of the emulsion recognized as useful hitherto. For example, they may be added at any stage if it is before coating, i.e., before grain formation stage of silver halide grains and/or before desalting stage, during desalting stage and/or after desalting and before beginning of chemical sensitization, as disclosed in U.S. Pat. Nos. 2,735,766, 3,628,960, 4,183,756, 4,225,666, JP-A-58-184142 and JP-A-60-196749, or immediately before or during chemical ripening, after chemical ripening and before coating of the emulsion as disclosed in JP-A-58-113920. Also, as disclosed in U.S. Pat. No. 4,225,666 and JP-A-58-7629, the sensitizing dyes can be used as a single compound alone or in combination with compounds having different structures, and they can be divided and added separately, for example, one part of them is added during grain formation stage and the remaining is added during chemical ripening stage or after the completion of chemical ripening, otherwise one part is added prior to chemical ripening or during ripening stage and the remaining after completion of chemical ripening. The kinds of compounds added separately and combinations of compounds may be varied.
Although the use amount of the compound represented by formula (I) or (II) according to the present invention varies depending on the shapes and the sizes of silver halide grains to be used, but is generally from 0.1 to 4 mmol, preferably from 0.2 to 2.5 mmol, per mol of the silver halide. They may be used in combination with other sensitizing dyes.
The silver halide emulsion prepared according to the present invention can be used in color photographic materials, e.g., a color paper, a color film for photographing, and a color reversal film, and black-and-white photographic materials, e.g., an X-ray film, a general film for photographing, and a photographic film for photomechanical process.
Exposure methods of silver halide photographic materials according to the present invention are described. Photographic images can be obtained by usual exposure methods. That is, any of well-known various light sources can be used as exposure light sources, e.g., natural light (sunlight), a tungsten lamp, a fluorescent lamp, a mercury lamp, a xenon arc lamp, a carbon arc lamp, a xenon flash lamp, a laser light, an emission diode, and CRT. Exposure time of shorter than 1/1,000 sec., e.g., from 1/10.sup.4 to 1/10.sup.6 sec. using a xenon flash lamp, and longer than 1 sec. can be used, as well as exposure of from 1/1,000 to 1 sec. used in usual cameras. If necessary, spectral composition of the light for use in exposure can be adjusted using a color filter. Exposure can be effected using light emitted from fluorescent materials excited by an electron beam, an X-ray, a .gamma.-ray or an .alpha.-ray.
It is preferred to use an oxidizing agent for silver during the production process of the emulsion for use in the present invention. An oxidizing agent for silver is a compound having a function of acting on metal silver and converting it to a silver ion. In particular, a compound which can convert superminute silver grains by-produced in the course of the formation of silver halide grains and chemical sensitization to a silver ion is effective. The silver ion formed may form hardly water-soluble silver salt such as silver halide, silver sulfide or silver selenide, or may form easily water-soluble silver salt such as silver nitrate. The oxidizing agent for silver may be inorganic or organic. Examples of inorganic oxidizing agents include ozone, oxyacid salt, such as hydrogen peroxide and addition. products thereof (e.g., NaBO.sub.2.H.sub.2 O.sub.2.3H.sub.2 O, 2Na.sub.2 CO.sub.3.3H.sub.2 O.sub.2, Na.sub.4 P.sub.2 O.sub.7.2H.sub.2 O.sub.2, 2Na.sub.2 SO.sub.4.H.sub.2 O.sub.2.2H.sub.2 O), peroxyacid salt (e.g, K.sub.2 S.sub.2 O.sub.8, K.sub.2 C.sub.2 O.sub.6, K.sub.2 P.sub.2 O.sub.8), a peroxy complex compound (e.g., K.sub.2 [Ti(O.sub.2)C.sub.2 O.sub.4 ].3H.sub.2 O, 4K.sub.2 SO.sub.4.Ti(O.sub.2)OH.SO.sub.4.2H.sub.2 O, Na.sub.3 [VO(O.sub.2) (C.sub.2 H.sub.4).sub.2 ].6H.sub.2 O), permanganate (e.g., KMnO.sub.4), and chromate (e.g., K.sub.2 Cr.sub.2 O.sub.7), a halogen element such as iodine and bromine, perhalogen acid salt (e.g., potassium periodate), a metal salt of high valency (e.g., potassium hexacyanoferrate(III)), and thiosulfonate. Further, examples of organic oxidizing agents include quinones such as p-quinone, an organic peroxide such as peracetic acid and perbenzoic acid, a compound which releases active halogen (e.g., N-bromosuccinimide, chloramine T, chloramine B).
Disulfide compounds disclosed in EP-A-627657 are more preferred oxidizing agents.
The oxidizing agents which are preferably used in the present invention are inorganic oxidizing agents such as ozone, hydrogen peroxide and addition products thereof, a halogen element, and thiosulfonate, and organic oxidizing agents such as quinones. It is preferred to use the above-described reduction sensitization in combination with an oxidizing agent for silver. The method of usage can be selected from a method in which an oxidizing agent is used and then reduction sensitization is carried out, an inverse method thereof, or a method in which both are concurred with. These methods can be used selectively in a grain formation process or in a chemical sensitization process.
The silver halide photographic material of the present invention preferably contains at least one compound selected from the compounds represented by formula (XX), (XXI) or (XXII).
R.sub.101 --SO.sub.2 S--M.sub.101 (XX)
R.sub.101 --SO.sub.2 S--R.sub.102 (XXI)
R.sub.101 --SO.sub.2 S--(E)--.sub.a SSO.sub.2 --R.sub.103 (XXII)
wherein R.sub.101, R.sub.102 and R.sub.103 each represents an aliphatic group, an aromatic group or a heterocyclic group, Mio, represents a cation, E represents a divalent linking group, and a represents 0 or 1.
Formulae (XX), (XXI) and (XXII) are described in detail below. When R.sub.101, R.sub.102 and R.sub.103 each represents an aliphatic group, the aliphatic group is preferably an alkyl group having from 1 to 22 carbon atoms, an alkenyl group having from 2 to 22 carbon atoms, or an alkynyl group having from 2 to 22 carbon atoms, and these groups may be substituted. Examples of alkyl groups include, e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, isopropyl and t-butyl.
Examples of alkenyl groups include, e.g., allyl and butenyl.
Examples of alkynyl groups include, e.g., propargyl and butynyl.
When R.sub.101, R.sub.102 and R.sub.103 each represents an aromatic group, the aromatic group is preferably an aromatic group having from 6 to 20 carbon atoms, e.g., phenyl and naphthyl. These groups may be substituted.
When R.sub.101, R.sub.102 and R.sub.103 each represents a heterocyclic group, the heterocyclic group is a 3 to 15-membered ring having at least one element selected from nitrogen, oxygen, sulfur, selenium or tellurium. Examples of heterocyclic rings include, e.g., a pyrrolidine ring, a piperidine ring, a pyridine ring, a tetrahydrofuran ring, a thiophene ring, an oxazole ring, a thiazole ring, an imidazole ring, a benzothiazole ring, a benzoxazole ring, a benzimidazole ring, a selenazole ring, a benzoselenazole ring, a tellurazole ring, a triazole ring, a benzotriazole ring, a tetrazole ring, an oxadiazole ring, and a thiadiazole ring.
Examples of substituents for R.sub.101, R.sub.102 and R.sub.103 include, e.g., an alkyl group (e.g., methyl, ethyl, hexyl), an alkoxyl group (e.g., methoxy, ethoxy, octyloxy), an aryl group (e.g., phenyl, naphthyl, tolyl), a hydroxyl group, a halogen atom (e.g., fluorine, chlorine, bromine, iodine), an aryloxy group (e.g., phenoxy), an alkylthio group (e.g., methylthio, butylthio), an arylthio group (e.g., phenylthio), an acyl group (e.g., acetyl, propionyl, butyryl, valeryl), a sulfonyl group (e.g., methylsulfonyl, phenylsulfonyl), an acylamino group (e.g., acetylamino, benzamino), a sulfonylamino group (e.g., methanesulfonylamino, benzenesulfonylamino), an acyloxy group (e.g., acetoxy, benzoxy), a carboxyl group, a cyano group, a sulfo group, and an amino group.
E preferably represents a divalent aliphatic group or a divalent aromatic group. Examples of divalent aliphatic groups represented by E include, e.g., --(CH.sub.2).sub.n --(n is from 1 to 12), --CH.sub.2 --CH.dbd.CH--CH.sub.2 --, ##STR22## --CH.sub.2 --C.tbd.C--CH.sub.2, a xylylene group, etc. Examples of divalent aromatic groups represented-by E include, e.g., phenylene and naphthylene.
These substituents may further be substituted with a substituent described above as the substituents of V.
M.sub.101, preferably represents a metal ion or an organic cation. Examples of metal ions include a lithium ion, a sodium ion, and a potassium ion. Examples of organic cations include an ammonium ion (e.g., ammonium, tetramethylammonium, tetrabutylammonium), a phosphonium ion (e.g., tetraphenylphosphonium), a guanidine group, etc. Specific examples of the compounds represented by formula (XX), (XXI) or (XXII) are shown below, but the present invention is not limited to these compounds.
__________________________________________________________________________(XX-1) CH.sub.3 SO.sub.2 SNa (XX-2) C.sub.2 H.sub.5 SO.sub.2 SNa(XX-3) C.sub.3 H.sub.7 SO.sub.2 SK (XX-4) C.sub.4 H.sub.9 SO.sub.2 SLi(XX-5) C.sub.6 H.sub.13 SO.sub.2 SNa (XX-6) C.sub.8 H.sub.17 SO.sub.2 SNa(XX-7) ##STR23## (XX-8) C.sub.10 H.sub.21 SO.sub.2 SNa(XX-9) C.sub.12 H.sub.25 SO.sub.2 SNa (XX-10) C.sub.16 H.sub.33 SO.sub.2 SNa(XX-11) ##STR24## (XX-12) t-C.sub.4 H.sub.9 SO.sub.2 SNa(XX-13) CH.sub.3 OCH.sub.2 CH.sub.2 SO.sub.2 S.Na (XX-14) ##STR25##(XX-15) CH.sub.2 .dbd.CHCH.sub.2 SO.sub.2 SNa (XX-16) ##STR26##(XX-17) ##STR27## (XX-18) ##STR28##(XX-19) ##STR29## (XX-20) ##STR30##(XX-21) ##STR31## (XX-22) ##STR32##(XX-23) ##STR33## (XX-24) ##STR34##(XX-25) ##STR35## (XX-26) ##STR36##(XX-27) ##STR37## (XX-28) ##STR38##(XX-29) KSSO.sub.2 (CH.sub.2).sub.2 SO.sub.2 SK (XX-30) NaSSO.sub.2 (CH.sub.2).sub.4 SO.sub.2 SNa(XX-31) NaSSO.sub.2 (CH.sub.2).sub.4 S(CH.sub.2).sub.4 SO.sub.2 SNa (XX-32) ##STR39##(XX-33) ##STR40##(XXI-1) C.sub.2 H.sub.5 SO.sub.2 S--CH.sub.3 (XXI-2) C.sub.8 H.sub.17 SO.sub.2 SCH.sub.2 CH.sub.3(XXI-3) ##STR41## (XXI-4) ##STR42##(XXI-5) C.sub.2 H.sub.5 SO.sub.2 SCH.sub.2 CH.sub.2 CN (XXI-6) ##STR43##(XXI-7) ##STR44## (XXI-8) ##STR45##(XXI-9) ##STR46## (XXI-10) ##STR47##(XXI-11) ##STR48## (XXI-12) ##STR49##(XXI-13) ##STR50## (XXI-14) ##STR51##(XXI-15) ##STR52## (XXI-16) ##STR53##(XXI-17) ##STR54## (XXI-18) C.sub.2 H.sub.5 SO.sub.2 SCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 OH(XXI-19) ##STR55## (XXI-20) ##STR56##(XXI-21) CH.sub.2 SSO.sub.2 (CH.sub.2).sub.4 SO.sub.2 SCH.sub.3 (XXI-22) CH.sub.3 SSO.sub.2 (CH.sub.2).sub.2 SO.sub.2 SCH.sub.3(XXI-23) ##STR57## (XXI-24) ##STR58##(XXI-25) ##STR59##(XXII-1) ##STR60##(XXII-2) C.sub.2 H.sub.5 SO.sub.2 SCH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.2 SSO.sub.2 C.sub.2 H.sub.5 (XXII-3) ##STR61##(XXII-4) ##STR62## (XXII-5) ##STR63##(XXII-6) ##STR64## (XXII-7) C.sub.2 H.sub.5 SO.sub.2 SSSO.sub.2 C.sub.2 H.sub.5(XXII-8) (n)C.sub.3 H.sub.7 SO.sub.2 SSSO.sub.2 C.sub.3 H.sub.7 (n) (XXII-9) ##STR65##__________________________________________________________________________
The compound represented by formula (XX) can be easily synthesized according to the methods disclosed in JP-A-54-1019 and British Patent 972,211.
The compound represented by formula (XX), (XXI) or (XXII) is preferably added in an amount of from 10.sup.-7 to 10.sup.-1 mol, more preferably from 10.sup.-6 to 10.sup.-2 mol, and particularly preferably from 10.sup.-5 to 10.sup.-3 mol, per mol of the silver halide.
For adding the compound represented by formula (XX), (XXI) or (XXII) to an emulsion during the production process thereof, methods usually used for adding additives to a photographic emulsion can be used. For example, a compound which is soluble in water is added as an aqueous solution having proper concentration, and a compound which is insoluble or hardly soluble in water is dissolved in an appropriate organic solvent which is miscible with water and does not adversely affect photographic properties and which is selected from alcohols, glycols, ketones, esters or amides, and added as a solution.
The compound represented by formula (XX), (XXI) or (XXII) can be added to an emulsion at any stage such as during the grain formation of a silver halide emulsion, before or after chemical sensitization. The compound is preferably added before reduction sensitization is conducted or during reduction sensitization is being conducted. The compound is particularly preferred added during grain growing.
The compound may be previously added to a reaction vessel but it is more preferred to be added at an appropriate stage during grain formation. Further, the method comprising previously adding the compound represented by formula (XX), (XXI) or (XXII) to an aqueous solution of water-soluble silver salt or an aqueous solution of water-soluble alkali halide and forming grains using these aqueous solutions can be employed. In addition, the solution of the compound represented by formula (XX), (XXI) or (XXII) may be divided to several parts and added in several times or may be added continuously over a long period of time with the degree of the grain formation.
Of the compounds represented by formula (XX), (XXI) or (XXII), the compounds represented by formula (XX) are most preferably used in the present invention.
With respect to various techniques and inorganic and organic materials which can be used in the silver halide photographic emulsion and the silver halide photographic material using the silver halide photographic emulsion according to the present invention, in general, those disclosed in Research Disclosure, No. 308119 (1989), ibid., No. 37038 (1995) can be used.
In addition to these, more specifically, for example, techniques and inorganic and organic materials which can be used in the color photographic material to which the silver halide photographic emulsion of the present invention is applicable are disclosed in the following places of EP-A-436938 and the patents cited in the following places.
______________________________________Item Place______________________________________ 1) Layer Structure line 34, page 146 to line 25, page 147 2) Silver Halide line 26, page 147 to line 12, page Emulsion 148 3) Yellow Coupler line 35, page 137 to line 33, page 146, lines 21 to 23, page 149 4) Magenta Coupler lines 24 to 28, page 149; line 5, page 3 to line 55, page 25 of EP-A- 421453 5) Cyan Coupler lines 29 to 33, page 149; line 28, page 3 to line 2, page 40 of EP-A- 432804 6) Polymer Coupler lines 34 to 38, page 149; line 39, page 113 to line 37, page 123 of EP-A-435334 7) Colored Coupler line 42, page 53 to line 34, page 137, lines 39 to 45, page 149 8) Other Functional line 1, page 7 to line 41, page 53, Coupler line 46, page 149 to line 3 page 150; line 1, page 3 to line 50, page 29 of EP-A-435334 9) Preservative lines 25 to 28, page 15010) Formalin lines 15 to 17, page 149 Scavenger11) Other Additives lines 38 to 47, page 153; line 21, page 75 to line 56, page 84 of EP-A- 42145312) Dispersion Method lines 4 to 24, page 15013) Support line 32 to 34, page 15014) Film Thickness, lines 35 to 49, page 150 Physical Proper- ties of Film15) Color Development line 50, page 150 to line 47, page Process 15116) Desilvering line 48, page 151 to line 53, page Process 15217) Automatic line 54, page 152 to line 2, page 153 Processor18) Washing and lines 3 to 37, page 153 Stabilizing Processes______________________________________

The present invention will be illustrated specifically with reference to examples below, but these are not to be construed as limiting the invention.
EXAMPLE 1
Preparation of Sample No. 101:
A multilayer color photographic material was prepared as Sample No. 101 by coating each layer having the following composition on an undercoated cellulose triacetate film support having the thickness of 127 .mu.m. The numeral corresponding to each component indicates the addition amount per m.sup.2. The function of the compounds added is not limited to the use described.
______________________________________First Layer: Antihalation LayerBlack Colloidal Silver silver amount: 0.28 gGelatin 2.20 gUltraviolet Absorber U-1 0.27 gUltraviolet Absorber U-3 0.08 gUltraviolet Absorber U-4 0.08 gHigh Boiling Point Organic Solvent Oil-1 0.29 gCoupler C-9 0.12 mgSecond Layer: InterlayerGelatin 0.38 gCompound Cpd-K 5.0 mgUltraviolet Absorber U-2 3.0 mgHigh Boiling Point Organic Solvent Oil-3 0.06 gDye D-4 10.0 mgThird Layer: InterlayerYellow Colloidal Silver silver amount: 0.007 gGelatin 0.40 gFourth Layer: First Red-Sensitive EmulsionLayerEmulsion A silver amount: 0.55 gEmulsion B silver amount: 0.23 gSurface Fogged Fine Grain silver amount: 0.07 gSilver Iodobromide Emulsion(average grain diameter: 0.11 .mu.m)Gelatin 1.11 gCoupler C-1 0.04 gCoupler C-2 0.09 gCompound Cpd-A 1.0 mgCompound Cpd-E 0.14 gCompound Cpd-K 2.0 mgCompound Cpd-H 4.4 mgHigh Boiling Point Organic Solvent Oil-2 0.09 gFifth Layer: Second Red-Sensitive EmulsionLayerEmulsion C silver amount: 0.14 gEmulsion D silver amount: 0.28 gGelatin 0.65 gCoupler C-1 0.05 gCoupler C-2 0.11 gCompound Cpd-E 0.10 gHigh Boiling Point Organic Solvent Oil-2 0.09 gSixth Layer: Third Red-Sensitive EmulsionLayerEmulsion E silver amount: 0.50 gGelatin 1.56 gCoupler C-3 0.63 gCompound Cpd-E 0.11 gPolymer Latex P-1 0.16 gHigh Boiling Point Organic Solvent Oil-2 0.04 gSeventh Layer: InterlayerGelatin 0.50 gCompound Cpd-D 0.04 gHigh Boiling Point Organic Solvent Oil-3 0.08 gEighth Layer: InterlayerYellow Colloidal Silver silver amount: 0.01 gGelatin 1.56 gCompound Cpd-A 0.12 gCompound Cpd-I 0.04 mgCompound Cpd-J 0.07 gHigh Boiling Point Organic Solvent Oil-3 0.15 gNinth Layer: First Green-Sensitive EmulsionLayerEmulsion F silver amount: 0.42 gEmulsion G silver amount: 0.38 gEmulsion H silver amount: 0.32 gSurface Fogged Core/Shell Type silver amount: 0.08 gFine Grain Silver Bromide Emulsion(average grain diameter: 0.11 .mu.m)Gelatin 1.53 gCoupler C-7 0.07 gCoupler C-8 0.17 gCompound Cpd-B 0.30 mgCompound Cpd-C 2.00 mgCompound Cpd-K 3.0 mgPolymer Latex P-2 0.02 gHigh Boiling Point Organic Solvent Oil-2 0.10 gTenth Layer: Second Green-SensitiveEmulsion LayerEmulsion I silver amount: 0.16 gEmulsion J silver amount: 0.34 gGelatin 0.75 gCoupler C-4 0.20 gCompound Cpd-B 0.03 gPolymer Latex P-2 0.01 gHigh Boiling Point Organic Solvent Oil-2 0.01 gEleventh Layer: Third Green-SensitiveEmulsion LayerEmulsion K silver amount: 0.44 gGelatin 0.91 gCoupler C-4 0.34 gCompound Cpd-B 0.06 gPolymer Latex P-2 0.01 gHigh Boiling Point Organic Solvent Oil-2 0.02 gTwelfth Layer: Yellow Filter LayerYellow Colloidal Silver silver amount: 0.02 gGelatin 0.73 gMicrocrystal Dispersion of Dye E-1 0.24 gCompound Cpd-G 0.02 gCompound Cpd-J 0.04 gHigh Boiling Point Organic Solvent Oil-3 0.08 gPolymer M-1 0.23 gThirteenth Layer: First Blue-SensitiveEmulsion LayerEmulsion L silver amount: 0.35 gGelatin 0.55 gCoupler C-5 0.20 gCoupler C-6 4.00 gCoupler C-10 0.02 gCompound Cpd-E 0.07 gCompound Cpd-K 0.03 mgFourteenth Layer: Second Blue-SensitiveEmulsion LayerEmulsion M silver amount: 0.06 gEmulsion N silver amount: 0.10 gGelatin 0.75 gCoupler C-5 0.35 gCoupler C-6 5.00 gCoupler C-10 0.30 gCompound Cpd-E 0.04 gFifteenth Layer: Third Blue-SensitiveEmulsion LayerEmulsion O silver amount: 0.20 gEmulsion P silver amount: 0.02 gGelatin 2.40 gCoupler C-6 0.09 gCoupler C-10 0.90 gCompound Cpd-E 0.09 gCompound Cpd-M 0.05 mgHigh Boiling Point Organic Solvent Oil-2 0.40 gPolymer Latex P-2 0.10 gSixteenth Layer: First Protective LayerGelatin 1.30 gUltraviolet Absorber U-1 0.10 gUltraviolet Absorber U-2 0.03 gUltraviolet Absorber U-5 0.20 gCompound Cpd-F 0.40 gCompound Cpd-J 0.06 gDye D-1 0.01 gDye D-2 0.01 gDye D-3 0.01 gDye D-5 0.01 gHigh Boiling Point Organic Solvent Oil-2 0.37 gSeventeenth Layer: Second Protective LayerFine Grain Silver Iodobromide silver-amount: 0.05 gEmulsion (average grain diameter:0.06 .mu.m, AgI content: 1 mol%)Gelatin 1.80 gCompound Cpd-L 0.8 mgPolymethyl Methacrylate 5.00 g(average particle diameter: 1.5 .mu.m)Copolymer of Methyl Methacrylate/Acrylic 0.10 gAcid in Proportion of 6/4 (average particlediameter: 1.5 .mu.m)Silicone Oil SO-1 0.030 gSurfactant W-2 0.030 g______________________________________
Further, Additives F-1 to F-11 were added to every emulsion layer in addition to the above components. Moreover, Gelatin Hardener H-1 and Surfactants W-1, W-3, W-4, W-5 and W-6 for coating and emulsifying were added to every layer in addition to the above components.
In addition, phenol, 1,2-benzisothiazolin-3-one, 2-phenoxyethanol, phenethyl alcohol, p-hydroxybenzoic acid butyl ester were added as antibacterial and antifungal agents.
Light-sensitive emulsions used in Sample No. 101 are shown in Table 1 below.
TABLE 1__________________________________________________________________________ Variation Coefficient Average of Aspect Sensitizing Dye Sensitizing Dye Sensitizing Dye Equivalent- Equivalent- Ratio Addition Addition Addition Sphere Circle of Iodide Amount Amount AmountEmul- Diameter Diameter Entire Content (.times.10.sup.-4 mol/ (.times.10.sup.-4 mol/ (.times.10.sup.-4 mol/sion (.mu.m) (%) Grains (mol %) Kind mol-Ag) Kind mol-Ag) Kind mol-Ag)__________________________________________________________________________A 0.20 16 1.6 4.0 S-1 8.1 S-3 0.3B 0.25 15 3.0 4.0 S-1 8.9 S-3 0.3C 0.22 14 2.5 4.0 S-1 8.8 S-2 0.2 S-3 0.2D 0.35 10 3.6 4.0 S-1 9.8 S-2 0.3 S-3 0.2E 0.49 16 5.0 2.0 S-1 6.7 S-2 0.5 S-3 1.2F 0.15 15 1.0 3.5 S-4 15.1 S-5 1.5G 0.23 14 1.9 3.5 S-4 10.4 S-5 2.0H 0.32 11 2.4 3.5 S-4 7.5 S-5 1.4I 0.28 11 4.5 3.3 S-4 7.7 S-5 1.4J 0.40 16 4.0 3.3 S-4 7.2 S-5 1.4K 0.59 20 5.9 2.8 S-4 6.4 S-5 1.2L 0.24 14 3.4 4.6 S-6 6.5 S-7 2.5M 0.30 10 3.0 4.6 S-6 6.2 S-7 2.0N 0.40 9 4.5 1.6 S-6 5.6 S-7 1.8O 0.60 15 5.5 1.0 S-6 4 S-7 1.5P 0.80 18 2.5 1.0 S-6 3.4 S-7 1.1__________________________________________________________________________ Note 1) All of the above emulsions were chemically sensitized using gold, sulfur and selenium. Note 2) All of the above emulsions were added with sensitizing dyes before chemical sensitization. Note 3) Appropriate amounts of Compounds F5, F7, F8, F9, F10, F11, F12, F13, F14 and F15 were respectively added to the above emulsions. Note 4) Emulsions A, B, I and J comprise triple structure tabular grains having major faces comprising {100} faces and other emulsions having major faces comprising {111} faces. Note 5) Emulsions A, B, E, F, I and P are emulsions whose internal sensitivities are higher than surface sensitivities. Note 6) Emulsions E, I and P are emulsions comprising silver chloride grains epitaxially grown after chemical sensitization. Note 7) Emulsions other than A, E and F comprise grains having 50 or more dislocation lines per one grain observed by a transmission electron microscope. Note 8) Sensitizing Dye S6 is exemplified Compound (55) and Sensitizing Dye S7 is exemplified Compound (1) according to the present invention.
Preparation of Dispersion of Organic Solid Dispersion Dye
Dye E-1 shown below was dispersed according to the following method. That is, water and 70 g of W-4 were added to 1,400 g of a wet cake of the dye containing 30% of water, and stirred to obtain a slurry having 30% dye concentration. Next, 1,700 ml of zirconia beads having an average diameter of 0.5 mm were filled in an ultravisco mill (UVM-2) manufactured by Aimex Co., the slurry was passed and the content was pulverized at a peripheral speed of about 10 m/sec and discharge amount of 0.5 l/min for 8 hours. Beads were removed by filtration and the resulting dispersion was heated at 90.degree. C. for 10 hours for stabilization, then water and gelatin were added to dilute the dispersion to dye concentration of 3%. The average grain diameter of the obtained fine grains of the dye was 0.4 .mu.m and the extent of distribution of grain diameters ((standard deviation of grain diameters)/(average grain diameter).times.100) was 18%.
Preparation of Sample No. 102 (Brownie film):
A photographic material was prepared as Sample No. 102 by coating the backing layer having the following composition (A) on one side of a cellulose triacetate film support having the thickness of 95 .mu.m and the same layers as Sample No. 101 on the other side of the support.
The numeral corresponding to each component indicates the coated weight in unit of g/m.sup.2.
______________________________________Composition of Backing Layer (A):______________________________________First LayerBinder: Acid-Processed Gelatin 1.00(isoelectric point: 9.0)Polymer Latex: P-1 0.13(average particle diameter: 0.1 .mu.m)Polymer Latex: P-2 0.23(average particle diameter: 0.2 .mu.m)Ultraviolet Absorber: U-1 0.03Ultraviolet Absorber: U-3 0.01Ultraviolet Absorber: U-4 0.02High Boiling Point Organic Solvent: Oil-1 0.03Surfactant: W-3 0.01Surfactant: W-6 3.0 .times. 10.sup.-3Sodium Hydroxide 0.10Second LayerBinder: Acid-Processed Gelatin 3.10(isoelectric point: 9.0)Polymer Latex: P-2 0.11Ultraviolet Absorber: U-1 0.03Ultraviolet Absorber: U-3 0.01Ultraviolet Absorber: U-4 0.02Dye: D-2 0.09Dye: D-6 0.12High Boiling Point Organic Solvent: Oil-1 0.03Surfactant: W-3 0.01Surfactant: W-6 3.0 .times. 10.sup.-3Potassium Sulfate 0.27Sodium Hydroxide 0.05Third LayerBinder: Acid-Processed Gelatin 3.30(isoelectric point: 9.0)Surfactant: W-3 0.02Potassium Sulfate 0.30Sodium Hydroxide 0.05Fourth LayerBinder: Lime-Processed Gelatin 1.15(isoelectric point: 5.4)Matting Agent: B-1 0.04(average particle diameter: 2.0 .mu.m)Matting Agent: B-2 0.03(average particle diameter: 2.3 .mu.m)Gelatin Hardener: H-1 0.21Surfactant: W-3 0.06Surfactant: W-2 6.0 .times. 10.sup.-3______________________________________
Preparation of Sample No. 103 (sheet):
A photographic material was prepared as Sample No. 103 by coating the backing layer having the following composition (B) on one side of a cellulose triacetate film support having the thickness of 205 .mu.m and the same layers as Sample No. 101 on the other side of the support.
The numeral corresponding to each component indicates the coated weight in unit of g/m.sup.2.
Composition of Backinq Layer (B):
______________________________________First LayerBinder: Acid-Processed Gelatin 0.70(isoelectric point: 9.0)Polymer Latex: P-1 0.08(average particle diameter: 0.1 .mu.m)Polymer Latex: P-2 0.15(average particle diameter: 0.2 .mu.m)Ultraviolet Absorber: U-1 0.02Ultraviolet Absorber: U-3 5.0 .times. 10.sup.-3Ultraviolet Absorber: U-4 0.01High Boiling Point Organic Solvent: Oil-1 0.02Surfactant: W-3 0.01Surfactant: W-6 2.0 .times. 10.sup.-3Sodium Hydroxide 0.07Second LayerBinder: Acid-Processed Gelatin 5.60(isoelectric point: 9.0)Polymer Latex: P-2 0.20Ultraviolet Absorber: U-1 0.05Ultraviolet Absorber: U-3 0.01Ultraviolet Absorber: U-4 0.03Surfactant: W-3 0.03Surfactant: W-6 5.0 .times. 10.sup.-3High Boiling Point Organic Solvent: Oil-1 0.06Potassium Sulfate 0.50Sodium Hydroxide 0.09Third LayerBinder: Acid-Processed Gelatin 5.00(isoelectric point: 9.0)Surfactant: W-3 0.02Potassium Sulfate 0.43Sodium Hydroxide 0.08Fourth LayerBinder: Acid-Processed Gelatin 0.80(isoelectric point: 9.0)Matting Agent: B-1 0.02(average particle diameter: 2.0 .mu.m)Matting Agent: B-2 0.02(average particle diameter: 2.3 .mu.m)Gelatin Hardener: H-1 0.35Surfactant: W-3 0.03Surfactant: W-2 4.0 .times. 10.sup.-3______________________________________ ##STR66## P-2 Polybutyl acrylate/acrylic acid copolymer in proportion of 95/5
______________________________________B-1 ##STR67## x/y = 90/10 (by mole)B-2 ##STR68## x/y = 60/40 (by mole)______________________________________
Samples Nos. 101 to 103 obtained were subjected to wedge exposure and color reversal process according to the following processing steps.
______________________________________Processing Processing Processing Tank Replenish- Time Temperature Capacity ing RateProcessing Step (min) (.degree. C.) (liter) (ml/m.sup.2)______________________________________First Development 6 38 12 2,200First Washing 2 38 4 7,500Reversal 2 38 4 1,100Color Development 6 38 12 2,200Pre-bleaching 2 38 4 1,100Bleaching 6 38 2 220Fixing 4 38 8 1,100Second Washing 4 38 8 7,500Final Rinsing 1 25 2 1,100______________________________________
The composition of each processing solution used was as follows.
______________________________________ Tank Solution Replenisher______________________________________First Developing SolutionPentasodium Nitrilo-N,N,N- 1.5 g 1.5 gtrimethylenephosphonatePentasodium Diethylene- 2.0 g 2.0 gtriaminepentaacetateSodium Sulfite 30 g 30 gPotassium Hydroquinone- 20 g 20 gmonosulfonatePotassium Carbonate 15 g 20 gSodium Bicarbonate 12 g 15 g1-Phenyl-4-methyl-4- 1.5 g 2.0 ghydroxymethyl-3-pyrazolidonePotassium Bromide 2.5 g 1.4 gPotassium Thiocyanate 1.2 g 1.2 gPotassium Iodide 2.0 mg --Diethylene Glycol 13 g 15 gWater to make 1,000 ml 1,000 mlpH (adjusted with sulfuric 9.60 9.60acid or potassium hydroxide)Reversal SolutionPentasodium Nitrilo-N,N,N- 3.0 g same as thetrimethylenephosphonate tank solutionStannous Chloride 1.0 gDihydratep-Aminophenol 0.1 gSodium Hydroxide 8 gGlacial Acetic Acid 15 mlWater to make 1,000 mlpH (adjusted with acetic 6.00acid or sodium hydroxide)Color Developing SolutionPentasodium Nitrilo-N,N,N- 2.0 g 2.0 gtrimethylenephosphonateSodium Sulfite 7.0 g 7.0 gTrisodium Phosphate 36 g 36 gDodecahydratePotassium Bromide 1.0 g --Potassium Iodide 90 mg --Sodium Hydroxide 3.0 g 3.0 gCitrazinic Acid 1.5 g 1.5 gN-Ethyl-N-(.beta.-methanesulfon- 11 g 11 gamidoethyl)-3-methyl-4-aminoaniline.Sesquisulfate.Monohydrate3,6-Dithiaoctane-1,8-diol 1.0 g 1.0 gWater to make 1,000 ml 1,000 mlpH (adjusted with sulfuric 11.80 12.00acid or potassium hydroxide)Pre-bleaching SolutionDisodium Ethylenediamine- 8.0 g 8.0 gtetraacetate DihydrateSodium Sulfite 6.0 g 8.0 g1-Thioglycerol 0.4 g 0.4 gSodium Bisulfite Addition 30 g 35 gProduct of FormaldehydeWater to make 1,000 ml 1,000 mlpH (adjusted with acetic 6.30 6.10or sodium hydroxide)Bleaching SolutionDisodium Ethylenediamine- 2.0 g 4.0 gtetraacetate DihydrateAmmonium Ethylenediamine- 120 g 240 gtetraacetato FerrateDihydratePotassium Bromide 100 g 200 gAmmonium Nitrate 10 g 20 gWater to make 1,000 ml 1,000 mlpH (adjusted with nitric 5.70 5.50acid or sodium hydroxide)Fixing SolutionAmmonium Thiosulfate 80 g same as the tank solutionSodium Sulfite 5.0 g same as the tank solutionSodium Bisulfite 5.0 g same as the tank solutionWater to make 1,000 ml same as the tank solutionpH (adjusted with acetic 6.60acid or aqueous ammonia)Final Rinsing Solution1,2-Benzisothiazolin-3-one 0.02 g 0.03 gPolyoxyethylene-p- 0.3 g 0.3 gmonononylphenyl Ether(average polymerizationdegree: 10)Polymaleic Acid (average 0.1 g 0.15 gmolecular weight: 2,000)Water to make 1,000 ml 1,000 mlpH 7.0 7.0______________________________________
As for the sensitivity of the BL layer of the sample obtained, the reciprocal of the exposure required to give a density of Dmax-0.2 was taken as fresh sensitivity and this was shown as a relative sensitivity. Further, the unexposed film was stored at 60% RH, 60.degree. C. for 3 days, then the film was exposed, development processed and evaluated for sensitivity in the same manner as above.
The results obtained are shown in Table 2. The results of valuation of samples prepared in the same manner. as above exept for replacing the sensitizing dyes used in Emulsions L, M, N, O and P with the following dyes are also shown in table 2.
TABLE 2______________________________________ Relative RelativeSample Sensitivity, Sensitivity,No. Fresh Aged Remarks______________________________________101 100 90 Invention (control)102 101 91 Invention103 100 90 Invention104 85 63 Comparison105 85 64 Comparison106 86 63 Comparison______________________________________
Comparisons were made between Sample Nos. 101 and 104, between Sample Nos. 102 and 105 (Brownie films), and between Sample Nos. 103 and 106 (sheets).
Dye SD-6 (in place of S-6) ##STR69## Dye SD-7 (in place of S-7) ##STR70##
As is apparent from Table 2, Sample Nos. 101, 102 and 103 in which dyes according to the present invention were used in combination showed higher sensitivity and excellent storage stability as compared with Comparative Sample Nos. 104, 105 and 106.
Further, residual color after processing was evaluated visually. With respect to Comparative Sample Nos. 104, 105 and 106 in which Comparative Dyes (SD-6) and (SD-7) were used as BL dyes, there were observed yellow residual color. On the contrary, Sample Nos. 101, 102 and 103 in which Dyes (S-6) and (S-7) according to the present invention were used generated no residual color.
According to the present invention, silver halide photographic materials which have high sensitivity, exhibit excellent storage stability and generate less residual color can be obtained.
While the invention has been described in detail and with reference to specific examples thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

Number	Name	Date	Kind
4960689	Nishikawa et al.	Oct 1990
5582960	Nielsen et al.	Dec 1996

Silver halide photographic material

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