Negative silver halide photographic light-sensitive material capable of being handled in light room

Abstract: A silver halide light-sensitive photographic material having an improved safe-light insensitivity and, thererefore, capability of being easily handled in the light room is disclosed. The material comprises a support; at least one silver halide emulsion layer being provided on one side of the support and containing silver halide grains containing at least 50 mol % of silver chloride, 10⁻⁴ to 10⁻⁸ mol per 1 mol of silver halide of a rhodium salt and a desensitizing dye; and at least one hydrophilic colloidal layer being provided on the other side of the support and containing at least one dye so that the absorbancy of the dye at the maximum spectral sensitivity wavelength (λ max) of the desensitizing dye is not less than 0.3, and the absorbancy ratio at the maximum spectral sensitivity wavelength against that at 450 nm is not less than 0.2.

Description: NEGATIVE SILVER HALIDE PHOTOGRAPHIC LIGHT-SENSITIVE MATERIAL CAPABLE OF BEING HANDLED IN LIGHT ROOM The present invention relates to a negative silver halide photographic light-sensitive material, in particular, to a negative silver halide photographic light-sensitive material capable of being processed in an "illuminated room", or "light room". For the purposes of labor-saving, improved operational efficiency, and prevention of environmental contamination, there has been a demand for a technique that will enable the film-making, conventionally performed in a dark room (i.e. the so-called "reverse process"), to be performed in an illuminated room. As a result there have been improvements in light-sensitive materials as well as in hardware such as printers. Light-sensitive materials capable of being handled in an illuminated room include silver halide photographic light-sensitive materials that can be exposed by ultraviolet-rich light sources such as a high-voltage mercury-vapor lamp, metal halide light source, xenon lamp, or a halogen lamp. These silver halide photographic light-sensitive materials can be handled in a bright environment having an illumination of 100 to 500 luxes, for example a fluorescent lamp for general use, a fluorescent lamp of smaller ultraviolet emission designed for this purpose, or a fluorescent lamp in which the ultraviolet emission is eliminated. The known methods for preparing silver halide photographic light-sensitive materials being capable of handled in an illuminated room (hereinafter referred to as "sensitive materials for use in an illuminated room") are as follows: a method described for example in Japanese Patent Publication Open to Public Inspection (hereinafter referred to as Japanese Patent O.P.I. Publication) No. 125734/1981, wherein an inorganic desensitizer such as a rhodium salt, or a bismuth salt is added to an emulsion of high chloride content; a method described for example in Japanese Patent Examined Publication No. 17273/1970, wherein an organic desensitizer is added to an emulsion of high chloride content; a method described for example in Japanese Patent O.P.I. Publication Nos. 157633/1984, and 26041/1986, wherein a rhodium salt or an organic de-sensitizer is added to an emulsion of high silver chloride content. Recently, conflicting requirements of higher sensitivity, and a longer allowable duration where the light-sensitive material is handled, have been required of a sensitive material for use in an illuminated room. As a result of researches for satisfying these conflicting criteria, the inventors have confirmed that a conventional method where a rhodium salt, and an organic desensitizer, especially a desensitizing dye, are added to an emulsion whose silver halide content is virtually silver chloride only is favorable. However, it has been found that an illuminated room sensitive material prepared by such a method has the following disadvantages. Usually, a light-sensitive material for use in an illuminated room is, in order to prevent halation, provided with a hydrophilic colloid backing layer containing a dye that has a spectral absorption range within the characteristic spectral range of the silver halide. It is common knowledge that the safelight insensitivity of a sensitive material in an illuminated room is better when the backing layer is positioned upward. However, with a sensitive material, for use in an illuminated room, which contains a desensitizing dye, the safelight insensitivity deteriorates when the backing surface whilst facing upward is irradiated with a safelight, even though the safelight insensitivity of the material is significantly greater when the emulsion layer side is facing upward. Such loss in safelight insensitivity is particularly noticeable, when a sensitive material which has undergone exposure is irradiated with a safelight. This phenomenon occurs because a latent image formed by exposing is oxidised by a desensitizing dye when irradiated with a safelight, and the characteristic sensitivity of silver halide decreases due to the filtering effect of a backing dye. Thus the enhancement of the latent image with safelight irradiation decreases. The object of the present invention is to provide a highly sensitive negative silver halide photographic light-sensitive material that can be handled for an extended period in an illuminated room, regardless of which face of the material is exposed to the illuminated room environment. This object is achieved by a negative silver halide photographic light-sensitive material comprising a support which has provided thereon at least one silver halide emulsion layer, and on the other side of support, at least one hydrophilic colloid backing layer. In particular, according to the present invention, the negative silver halide photographic light-sensitive material is characterized in that the emulsion layer contains silver halide grains comprising at least 50 mol% of silver chloride, a rhodium salt in an amount of 10⁻⁴ to 10⁻⁸ mol per mol silver halide, and a desensitizing dye, and the backing layer contains at least one type of dye so that absorbency of this dye at the maximum spectral sensitivity wavelength of the desensitizing dye (λmax) is not less than 0.3 and the ratio of the absorbency of this dye at the maximum spectral sensitivity wavelength to the absorbency of the same dye at 450 nm is not smaller than 0.2. A hydrophilic colloid layer, which is adjacent to the emulsion layer above, is preferably formed in compliance with a specific requirement, and is preferably either a negative silver halide photographic emulsion layer or a non-light-sensitive layer. The examples of a non-light-sensitive layer include a subbing layer, intermediate layer, and a protective layer. Fig. 1 is a graph illustrating the characteristics of an electrodeless discharge tube manufactured by Fusion Co. The silver halide composition which forms at least one layer of the negative silver halide photographic light-sensitive material of the invention comprises at least 50 mol% silver chloride. The particularly preferred silver halide components are silver chloride and silver chloro-bromide. The preferable average grain size of the emulsion is less than 0.5 µ, and more preferably less than 0.3µ. These grains are most preferably of a "Lippmann type" with a preferable average grain size of less than 0.1µ. Various methods for preparing such super-fine silver halide grains are known in the art, and any may be used. However, more specifically, the preferred method is a "functional-addition controlled double jet process", wherein the rates for adding silver nitrate and halide are varied in proportion to the growth rate of the silver halide grains which are formed in a reaction vessel at a comparatively low temperature. The electrical potential of silver is maintained constant level where the solubility of grains is lowest i.e. 120 to 210 mV. Additionally, the pH level, while silver halide is generated in a reaction vessel, is at an arbitrary level. Preferably however, the method is an acid process, and more preferably one carried out at a pH level ranges from 1 to 4. Furthermore, in order to lower the solubility of the silver halide grains, the silver halide in the reaction vessel is preferably allowed to adsorb a nucleoside, for example adenine, benzyladenine, and adenocyine; or a tetrazaindene compound; or a mercapto compound. Incidentally, throughout this specification, the size of silver halide grain is represented, for convenience, by the edge length of a cubic grain having the same volume as the silver halide grain. The emulsion, as mentioned previously, contains a rhodium salt in an amount of 10⁻⁴ to 10⁻⁸ mol per mol silver halide. Various rhodium salts can be used. For example, the (preferably water-soluble) rhodium salt used in embodying the invention may be selected from conventionally known similar salts. Typical useful rhodium salts include [Na₃Rhcℓ₆], [K₃RhBr₆], rhodium chloride-amine complex, and rhodium trichloride. A water soluble rhodium salt is preferably employed, particularly when silver halide grains are generated. However, such a salt may be used thereafter, or in several steps. The rhodium salt may additionally be incorporated into a layer other than the emulsion layers formed with this emulsion, for example, a hydrophilic colloid layer on the same side where the silver halide emulsion layer is formed. Additionally, the quantity of the rhodium salt may be separated into several parts which are added to more than two layers. When incorporating the rhodium salt, another inorganic compound such as an iridium salt, platinum salt, thalium salt, cobalt salt, or a gold salt may be additionally used. The mono-dispersity of the silver halide grains contained in the emulsion above is, preferably, 5 to 60, more preferably, 8 to 30. The mono-dispersity is calculated by multiplying by 100 times the number obtained by dividing the standard deviation of the above defined grain size by an average grain size. For the silver halide grains in the emulsion mentioned above, grains having a multilayer structure comprising at least two layers can be used. The examples of such useful grains include silver chloro-bromide grains comprising silver chloride cores and silver bromide shells; and similar grains comprising silver bromide cores and silver chloride shells. Regardless of the nature of grains, it is mandatory that the silver chloride content in the emulsion is not less than 50 mol%. Additionally, any layer can contain iodide. However, the preferred iodide content is not more than 5 mol%. The desensitizing dye used in the present invention is preferably a compound in which the sum of the anode and cathode potential is positive when analyzed by polarography. This type of compound is described in various patent specifications and in the literature, and any of these desensitizing dyes may be used. However, the particularly preferred desensitizing dyes are those represented by the following general formulas [I] through [V]. These compounds can be synthesized by referring to specifications of U.S. Patent Nos. 3,567,456, 3,615,639, 3,579,345, 3,615,608, 3,598,596, 3,598,955, 3,592,653, and 3,582,343; Japanese Patent Examined Publication Nos. 26751/1965, 27332/1965, 13167/1968, 8833/1970, and 8746/1972. In formulas [I] and [II], R₁ and R₂ independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, or an alkyl group (e.g., -CF₃), or together represent a group necessary to complete a fused aromatic ring. R₃ and R₄ independently represent an alkyl group, on a (preferably lower) alkenyl group, phenyl group or a (preferably lower) hydroxylalkyl group. When neither R₁ nor R₂ is a hydrogen atom, R₃ and R₄ may independently be an aryl group. n is a positive integer from 1 to 4. R₅ represents a lower alkyl group or lower sulfonated alkyl group, and X represents an anion, preferably an acid anion. In formula [III], R₁ and R₂ independently represent a hydrogen atom or nitro group; and R₃ and R₄ independently represent a (preferably lower) alkyl group, allyl group or phenyl group. Z represents a group of atoms necessary for forming a nitrobenzothiazole nucleus, nitrobenzoxazole nucelus, nitrobenzoselenazole nucleus, imidazo[4·5-b]quinoxaline nucleus, 3·3-dimethyl-3H-pyrrolo[2·3-b]pyridine nucleus, 3·3-dialkyl-3H-nitroindole nucleus, thiazolo[4·5-b]quinoline nucleus, nitroquinoline nucleus, nitrothiazole nucleus, nitronaphthothiazole nucleus, nitroxazole nucleus, nitronaphthoxazole nucleus, nitroselenazole nucleus, nitronaphthoselenazole nucleus, or nitropyridine nucleus. X represents an anion; m and n independently represent an integer of 1 or 2. When the compound forms an inner salt, n is 1. In formula [IV], R₁, R₂, R₃ and R₄ independently represent a hydrogen atom, halogen atom, alkyl group, alkoxy group, aryloxy group, or nitro group. R₅ represents a hydrogen atom, alkyl group, or nitro group. Z represents a group of atoms necessary for forming a thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, oxazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, selenazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, thiazoline nucleus, pyridine nucleus, quinoline nucleus, isoquinoline nucleus, 3,3-dialkyl-3H-indole nucleus, imidazole nucleus, benzimidazole nucleus or naphthoimidazole nucleus, wherein each nucleus may be unsubstituted or have a substituent which is, for example, a lower alkyl group, phenyl group, thienyl group, halogen atom, alkoxy group, hydroxy group, cyano group, alkylsulfonyl group, alkoxycarbonyl group, phenylsulfonyl group and trifluoromethyl group. L₁ and L₂ respectively represent a methine chain that may be unsubstituted or lower alkyl-substituted or aryl-substituted. R₆ and R₇ independently represent an alkyl group, alkenyl group, aryl group, sulfoalkyl group or aralkyl group, each being unsubstituted or substituted. X represents an anion; and m and n are independently 1 or 2. When the compound has an inner salt, n is 1. In formula [V], R₁ and R₃ independently represent an alkyl group; and R₂ represents an aryl group. L₁ and L₂ independently represent a methine chain that is unsubstituted or lower alkyl-substituted or aryl-substituted. Z represents a group of atoms necessary for forming a thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, oxazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, selenazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, thiazoline nucleus, pyridine nucleus, quinoline nucleus, 3,3-dialkylindolenine nucleus, imidazole nucleus, or imidazo[4.5-b]quinoxaline nucleus. X represents an anion. m represents a positive integer 1 to 3, and n represents 1 or 2. Typical examples of compounds expressed by the above formulas [I] through [V] are as follows. In some of the following compounds, Pts ⊖ represents a paratoluenesulfonic acid anion. (Example componds) The desensitizing dye used in the invention is preferably used in an amount of 1 to 1,000 mg per mol silver halide, more preferably, 5 to 300 mg per mol silver halide. The desensitizing dye used in the invention may be incorporated into a light-sensitive material at any time selected from during formation of silver halide grains, during physical ripening, during chemical ripening, after the ripening, or during preparation of a coating solution. Further, in order to prevent loss in the sensitivity, the desensitizing dye is preferably a dye having low sensitivity in the 450 nm range and below, and whose maximum spectral sensitivity wavelength is higher than 500 nm. A silver halide emulsion used in the present invention is a negative type one, and not of positive type. The negative silver halide emulsion differs from the positive type one in that it has grains fogged in advance. The effects of the invention are promoted by chemical ripening. Any suitable method for chemical ripening may be used. Into the backing layer of a silver halide photographic light-sensitive material of the invention, various dyes may be incorporated. The examples of a dye useful in embodying the invention include the compounds represented by the following formulas [VI-a], [VI-b], [VI-c] and [VI-d]. In this formula, R₁ is a group represented by -OX or wherein X and Y independently represent a hydrogen atom, alkyl group, cyanoalkyl group, carboxyalkyl group, sulfoalkyl group, hydroxyalkyl group, halogenated alkyl group, or an optionally substituted alkyl group (or sodium- or potassium salt thereof). R₂ and R₃ independently represent a hydrogen atom, halogen atom, alkyl group, hydroxy group, alkoxy group, alkylthio group or a group similar to the previously defined -OX group. Q represents a phenyl group having, as a substituent group, at least one halogen atom, carboxy group, sulfo group, or sulfoalkyl group (or a sodium-salt or a potassium salt thereof); sulfoalkyl group, sulfoalkoxyalkyl group or sulfoalkylthioalkyl group. L represents a methine group optionally having a substituent group. R₄ represents an alkyl group, carboxy group, alkyloxycarbonyl group; or unsubstituted amino group, or acyl-substituted amino group. m is an integer of 1 or 2; and n is 0 or 1. In this formula, R₅, R₆, R₈, R₉ and R₁₀ independently represent a hydrogen atom, halogen atom, alkyl group, hydroxyl group, alkoxy group, amino group, acylamino group, carboxyl group; or sulfoalkyl group (or a sodium-salt or a potassium-salt thereof). R₇ represents an alkyl group, or carboxyl group. In this formula, R₁₁ and R₁₂ independently represent an alkyl group, substituted alkyl group, aryl group, alkoxycarbonyl group, or carboxyl group. R₁₃ and R₁₄ independently represent a sulfonic-substituted or carboxyl-substituted alkyl or sulfonic group; carboxyl-substitued or sulfonic-substituted aryl group (or a sodium-salt or a potassium salt thereof). L represents a substituted or unsubstituted methine chain. M represents a sodium, potassium or hydrogen atom. ℓ is 0 or 1. In this formula, R₁, R₂, R₃ and R₄ independently represent any of an alkyl group, hydroxyalkyl group, cyano group, alkylcyano group, alkoxy group, and sulfoalkyl group. R₅ and R₆ independently represent a sulfonic group, or alkylsulfonic group. The typical examples of compounds expressed by formula [VI-a] through [VI-d] are as follows. The examples of sensitizers which may be incorporated into the silver halide emulsion used in the invention include active gelatin; sulfur sensitizers such as sodium thiosulfate, allyl thiocarbamide, thiourea, and allyl isothiocyanate; selenium sensitizers such as N,N-dimethylseleno emulsion, and selenourea; reduction sensitizers such as triethylenetetramine, and stannous chlroride; and various noble metal sensitizers such as potassium chloroaurite, potassium aurithiocyanate, potassium chloroaurate, 2-aurosulfobenzothiazolemethyl chloride, ammonium chloropalladate, potassium chloroplatinate, or sodium chloropaladite may be used. Such sensitizers can be used singly or in combination. When using a gold sensitizer, ammonium thiocyanate can also be used. Of these sensitizers, a sulfur sensitizer is the most advantageous. The sulfur sensitizer is preferably used in an amount of 15 to 150 mg per mol silver halide. Favorable effects are attainable when the silver halide emulsion layer used in the invention contains a tetrazolium compound such as disclosed, for example, in Japanese Patent O.P.I. Publication Nos. 18317/1977, 17719/1978, 17720/ 1978 and 149946/1986. Those compounds are, for example, tetrazolium compounds expressed by the following general formulas [VII-1], [VII-2], and [VII-3]. In these formulas, R₅, R₇, R₈, R₉, R₁₂, R₁₃, R₁₄, and R₁₅ independently represent an alkyl group (such as a methyl group, ethyl group, propyl group, or a dodecyl group), allyl group, phenyl group (such as a phenyl group, tolyl group, hydroxyphenyl group, carboxyphenyl group, aminophenyl group, mercaptophenyl group, or a methoxyphenyl group), naphthyl group (such as α-naphthyl group, β-naphthyl group, hydroxynaphthyl group, carboxynaphthyl group, or an aminonaphthyl group), or a heterocyclic group (such as thiazolyl group, benzothiazolyl group, oxazolyl group, pyrimidinyl group, or a pyridyl group). Each of these groups may be a group capable of forming a metal chelate or complex. R₆, R₁₀, and R₁₁ independently represent any group selected from an allyl group, phenyl group, naphthyl group, heterocyclic group, alkyl group (such as methyl group, ethyl group, propyl group, butyl group, mercaptomethyl group, and mercaptoethyl group), hydroxyl group, alkylphenyl group, alkoxyphenyl group, carboxyl gropu (salt thereof), carboxyalkyl group (such as methoxycarbonyl group, and ethoxycarbonyl group), amino group (such as amino group, ethylamino group, and anilino group), mercapto group, nitro group, and hydrogen atom. D represents a bivalent aromatic group; and E represents any group selected from an alkylene group, allylene group, and aralkylene group. X ⊖ represents an anion; and n is 1 or 2. However, when the compound has an inner salt, n is 1. The typical examples of a cationic portion in a tetrazolium compound useful in the present invention are as follows. However, the examples of a cationic portion in a compound useful in the invention are not limited only to these examples. (T-1) 2-(benzothiazole-2-yl)-3-phenyl-5-dodecyl-2H-tetrazolium (T-2) 2,3-diphenyl-5-(4-t-octyloxyphenyl)-2H-tetrazolium (T-3) 2,3,5-triphenyl-2H-tetrazolium (T-4) 2,3,5-tri(p-carboxyethylphenyl)-2H-tetrazolium (T-5) 2-(benzothiazole-2-yl)-3-phenyl-5-(o-chlorophenyl)-2H-tetrazolium (T-6) 2,3-diphenyl-2H-tetrazolium (T-7) 2,3-diphenyl-5-methyl-2H-tetrazolium (T-8) 3-(p-hydroxyphenyl)-5-methyl-2-phenyl-2H-tetrazolium (T-9) 2,3-diphenyl-5-ethyl-2H-tetrazolium (T-10) 2,3-diphenyl-5-n-hexyl-2H-tetrazolium (T-11) 5-cyano-2,3-diphenyl-2H-tetrazolium (T-12) 2-(benzothiazole-2-yl)-5-phenyl-3-(4-tolyl)-2H-tetrazolium (T-13) 2-(benzothiazole-2-yl)-5-(4-chlorophenyl)-3-(4-nitrophenyl)-2H-tetrazolium (T-14) 5-ethoxycarbonyl-2,3-di(3-nitrophenyl)-2H-tetrazolium (T-15) 5-acetyl-2,3-di(p-ethoxyphenyl)-2H-tetrazolium (T-16) 2,5-diphenyl-3-(p-tolyl)-2H-tetrazolium (T-17) 2,5-diphenyl-3-(p-iodophenyl)-2H-tetrazolium (T-18) 2,3-diphenyl-5-(p-diphenyl)-2H-tetrazolium (T-19) 5-(p-bromophenyl)-2-phenyl-3-(2,4,6-trichlorophenyl)-2H-tetrazolium (T-20) 3-(p-hydroxyphenyl)-5-(p-nitrophenyl)-2-phenyl-2H-tetrazolium (T-21) 5-(3,4-dimethoxyphenyl)-3-(2-ethoxyphenyl)-2-(4-methoxyphenyl)-2H-tetrazolium (T-22) 5-(4-cyanophenyl)-2,3-diphenyl-2H-tetrazolium (T-23) 3-(p-acetamidophenyl)-2,5-diphenyl-2H-tetrazolium (T-24) 5-acetyl-2,3-diphenyl-2H-tetrazolium (T-25) 5-(flu-2yl)-2,3-diphenyl-2H-tetrazolium (T-26) 5-(thien-2yl)-2,3-diphenyl-2H-tetrazolium (T-27) 2,3-diphenyl-5-(pyrido-4yl)-2H-tetrazolium (T-28) 2,3-diphenyl-5-(quinole-2yl)-2H-tetrazolium (T-29) 2,3-diphenyl-5-(benzoxazole-2yl)-2H-tetrazolium (T-30) 2,3-diphenyl-5-nitro-2H-tetrazolium (T-31) 2,2′,3,3′-tetraphenyl-5,5′ 1,4-butylene-di-(2H-tetrazolium) (T-32) 2,2′,3,3′-tetraphenyl-5,5′-p-phenylene-di-(2H-tetrazolium) (T-33) 2-(4,5-dimethylthiazole-2yl)-3,5-diphenyl-2H-tetrazolium (T-34) 3,5-diphenyl-2-(triazine-2yl-2H-tetrazolium) (T-35) 2-(benzothiazole-2yl)-3-(4-methoxyphenyl)-5-phenyl-2H-tetrazolium (T-36) 2,3-dimethoxyphenyl-5-phenyl-2H-tetrazolium (T-37) 2,3,5-tris(methoxyphenyl)-2H-tetrazolium (T-38) 2,3-dimethylphenyl-5-phenyl-2H-tetrazolium (T-39) 2,3-hydroxyethyl-5-phenyl-2H-tetrazolium (T-40) 2,3-hydroxymethyl-5-phenyl-2H-tetrazolium (T-41) 2,3-cyanohydroxyphenyl-5-phenyl-2H-tetrazolium (T-42) 2,3-di(p-chlorophenyl)-5-phenyl-2H-tetrazolium (T-43) 2,3-di(hydroxyethoxyphenyl)-5-phenyl-2H-tetrazolium (T-44) 2,3-di(2-pyridyl)-5-phenyl-2H-tetrazolium (T-45) 2,3,5-tris(2-pyridyl)-2H-tetrazolium (T-46) 2,3,5-tris(4-pyridyl)-2H-tetrazolium Of tetrazolium compounds which can be used as nondiffusive compounds, a tetrazolium compound obtained by selecting relevant cationic and anioic portions is particularly useful. The examples of an anioic portion on a tetrazolium compound preferably used in the invention are as follows; halogen ions such as chloride ions, bromide ions, and iodide ions; acid radicals of inorganic acids such as sulfuric acid, nitric acid, and perchloric acid; acid radicals of organic acids such as sulfonic acid, and carboxylic acid; lower alkyl benzenesulfonic anions such as p-toluenesulfonic anions; higher alkylbenzenesulfonic anions such as p-dodecylbenzenesulfonic anions; higher alkylsulfate ester anions such as lauryl sulfate anions; dialkyl sulfosuccinate anions such as di-2-ethylhexyl sulfosuccinate anions; polyether alcohol-sulfate ester anions such as cetyl polyethenoxysulfate anions; higher fatty acid anions such as stearic anions; anions comprising polymers, such as polyacrylic anions, and those having acid radicals integrated. Further, a nondiffusive tetrazolium compound according to the invention can be synthesized by delibrately selecting its cationic and anioic portions. The thus synthesized compounds are those typified by a 2,3,5,-triphenyl-2H-tetrazolium-dioctyl succinate sulfonate salt. As detailed later in the Example, these compounds are prepared in a manner such as: the respective soluble salts of the anionic and cationic portions are independently dispersed into gelatin, the resultant gelatin solutions are blended together and dispersed in a gelatin matrix; or similar compounds are prepared by first preparing pure crystals of oxidants, then they are dissolved in appropriate solvents such as dimethyl sulfoxide, then each resultant solution is dispersed in a gelatin matrix. When the dispersion is not readily homogeneous, use of an appropriate homogenizer such as a supersonic homogenizer wave and Manton-Gohline homogenizer for emulsification and dispersion attains a favorable result. Further, the compounds can be first slightly dispersed in a high boiling solvent such as dioctylphthalate to prepare a protected emulsion, then the resultant emulsion can be dispersed in a hydrophilic colloidal layer. A preferred mode of embodying the invention is that a silver halide emulsion layer used in the invention incorporates a hydrazine compound instead of the above tetrazolium compound. The hydrazine compounds advantageous in embodying the invention include those represented by the following general formulas [VIII] and [IX]. Formula [VIII] R₁NHNHCHO Formula [IX] R₁NHNHCOR₂ In these formulas, R₁ and R₂ independently represent a pyridyl group, quinoline group, furan group, or thiophene group, wherein each of which is optionally substituted by, for example, an aryl group, alkyl group, substituted ureide group, aliphatic amino group, halogen atom, alkoxy group, and alkylamino group. R₁ and R₂ are preferably an optionally substituted aryl group (such as phenyl group or naphthyl group) or an optionally substituted alkyl group. The aryl group represented by R₁ or R₂ is preferably a benzene ring or naphthalene ring, which is optionally substituted by, for example, a straight-chained or branched alkyl group (preferably a group having 1 to 20 carbon atoms, for example a methyl group, ethyl group, isopropyl group, and n-dodecyl group); alkoxy group (preferably a group having 1 to 20 carbon atoms, for example a methoxy group, and ethoxy group); aliphatic acylamino group (preferably a group having 2 to 21 carbon atoms and an alkyl group, for example an acetylamino group, or a heptylamino group); or an aromatic acylamino group; and, additionally, the substituted or unsubstituted aromatic ring may be bonded via a bonding group such as -CONH, -S-, -O-, -SO₂NH-, -NHCONH-, and -CH₂ CHN-. The hydrazine compounds can be synthesized by referring to the description in U.S. Patent No. 4,269,929. The hydrazine compound can be incorporated into an emulsion layer; or a hydrophilic colloid layer adjacent to the emulsion layer; or another hydrophilic colloid layer. Preferably, it is incorporated into the emulsion layer of a layer adjacent to the emulsion layer. The hydrazine compound can be incorporated into the layers by first dissolving in an alcohol, for example methanol, or ethanol; or a glycol for example ethylene glycol, or diethylene glycol; or an ether; or ketone. The amount of compound added is preferably 10⁻⁶ to 10⁻¹, more preferably 10⁻⁴ to 10⁻² mol per mol silver halide. The examples of particularly preferred hydrazine compounds are as follows. The silver halide emulsions used in embodying the invention may be stabilized by using the compounds described for example in U.S. Patent Nos. 2,444,607, 2,716,062, and 3,512,982; West German DAS Patent Nos. 1,189,380, 2,058,626, and 2,118,411; Japanese Patent Examined Publication No. 4133/1968; U.S. Patent No. 3,342,596; Japanese Patent Examined Publication No. 4417/1972; West German DAS Patent No. 2,149,789; Japanese Patent Examined Publication Nos. 2825/1964, 13566/1974, and 40665/1975; Japanese Patent O.P.I. Publication No. 198147/1986. Those particularly preferred among these compounds are 5,6-trimethylene-7-hydroxy-S-triazolo(1,5-a)pyridine, 5,6-trimethylene-7-hydroxy-S-triazolo(1,5-a)pyrimidine, 5-methyl-7-hydroxy-S-triazolo(1,5-a)pyrimidine, 7-hydroxy-S-triazolo(1,5-a)pyrimidine, 5-methyl-6-bromo-hydroxy-S-tria-zolo(1,5-a)pyrimidine, gallate esters (such as isoamyl gallate, dodecyl gallate, propyl gallate, and sodium gallate), mercaptans (such as 1-phenyl-5-mercaptotetrazole, and 2-mercaptobenzothiazole), benzotriazoles (such as 5-bromo-benzotriazole, and 5-methylbenzotriazole), benzimidazoles (such as 6-nitrobenzimidazole), and quaternary chloride compounds of disulfides. The developing agents which are advantageously used with the materials of the invention are those such that described in The Theory of the Photographic Process, 4th edition, by T.H. James, pp. 291-334; and in Journal of the American Chemical Society, Vol. 73, pp. 3100 (1951). These developing agents are used either singly or in combination of more than two. When more than two types combinedly used, more favorable results will be attained. Developer solutions used for developing the light-sensitive material of the invention may contain as a preservative sulfite such as sodium sulfite, and potassium sulfite. Such a preservative does not hinder the effects of the invention. [Example] The present invention is hereunder described in detail. It should be understood that the scope of the invention is not limited only to the example. Example 1 Preparation of samples The [Solution B] specified below was added to the [Solution A] specified below at an adding velocity specified in the following Table 5, in the acid environment of pH 3.0 controlled with nitric acid. While the silver potential EAg was being maintained at 170 mV, both solutions were blended together in compliance with a controlled double-jet process. Then while the EAg was being controlled using one normal NaCl, the [Solution C] was added for 2 minutes at a reaction temperature and adding velocity identical with those for [Solution B], and then, more was added at a velocity 0.99 times that of the listed velocity while the EAg of [Solution B] being controlled with one normal NaCl. Thus, the silver halide emulsions a, b, c, d, and e according to the invention, listed in Table 5 were obtained. [Solution A] [Solution B] [Solution C] [Solution D] The average grains sizes of the respective obtained silver halide emulsions are listed in Table 5. Additionally, a silver chloride content of silver halide grains in the respective emulsion was 90 mol%; a rhodium content was 2 x 10⁻⁶ mol per mol silver halide; and mono-dispersity ranged from 8 to 15%. In measuring the EAg level, a metal silver electrode as well as a double-junction type saturated Ag/AgCℓ reference electrode were used (the constitution of the latter electrode used was a double junction type disclosed in Japanese Patent O.P.I. Publication No. 197534/1982). In the addition of [Solution B] and [Solution C], a variable flow rate, roller tube quantity determination pump was used. Additionally, in the course of addition it was confirmed by observing a sampled emulsion using an electron microscope that no further grains were generated, and that the addition rate did not exceed the critical growth rate in an emulsion system. To each of the emulsions a through e thus prepared, 6-methyl-4-hydroxy-1,3,3a,7-tetraazaindene was added at a rate of 200 mg per mol silver halide, and the pH level of each emulsion was adjusted to 5.7 using sodium carbonate. Then [Solution 0] was added to each emulsion. Next, each silver halide emulsion was subjected to washing and desalination using a conventional method. Then 58 mg of 6-methyl-4-hydroxy-1,3,3a,7-tetraazaindene and 150 mg of potassium bromide per mol silver halide were added to each emulsion, and each emulsion was subjected to sulfur sensitization. Once the sulfur sensitization was complete, 570 mg of 6-methyl-4-hydroxy-1,3,3a,7-tetraazaindene as a stabilizer and 25 g of gelatin per mol silver halide were added. Then the following additives were further added, and, thus each coating solution for emulsion layer was prepared. Each coating solution was applied to and dried on a 100 µm thick polyethylene terephthalate film which has been subjected to latex subbing and provided with a lamination comprising the backing layer and backing-protecting layer specified below. Thus sample Nos. 1 through 21 listed in Table 6 were obtained. The coating silver weight of the respective samples was commonly 3.5 g/m². The samples thus obtained were exposed, through an optical wedge, with an "illuminated room" printer that has a light source having the spectra shown in Fig. 1 and comprising an electrodeless discharge tube manufactured by Fusion Co. in U.S.. Then the samples were developed using the following developer and fixer solutions. The sensitivity is represented by a value relative to an inverse number of an exposure that is required for attaining density of 3.0. The sensitivity of sample No. 2 was assumed to be 100. Table 6 lists the results. [Evaluation of safelight insensitivity] 1) Fog: each sample was irradiated at approx. 300 luxes for 60 minutes with an anti-fading fluorescent lamp (Toshiba Corporation, FL40SW-NU) wrapped with a UV filtering tube (Mitsubishi Plastics Industries, Ltd.), thereby the sample was subjected to developing in a manner identical with that for the sensitivity evaluation, in order to evaluate fogging. Incidentally, irradiation with the safelight was performed independently on the Em face and BC face. Table 6 lists the results. 2) Dot % change: a color transparency having 50% dot percentage was tightly placed on each sample, and each sample was exposed using an "illuminated room" printer used in sensitivity evaluation. They were then, irradiated at approx. 300 luxes for 30 minutes with a safelight used in safelight fogging evaluation, and developed in a manner identical with that used for the sensitivity evaluation. The exposure was controlled so that the 50% dot percentage was obtained by developing immediately after exposing with the illuminated room printer, whereby the change in dot percentage due to irradiation with the safelight was measured. Incidentally, irradiation with the safelight was performed independently on the Em face and BC face. Table 6 lists the results. [Developer solution compositions] Before the use of a developer solution, the above composition A and composition B were sequentially dissolved in 500 mℓ of water, and the volume of the solution was adjusted to one liter. (Fixer compositions) Before the use of a fixer solution, the above composition A and composition B were sequentially dissolved in 500 mℓ of water, and the solution was adjusted to one liter. The pH level of this fixer was approx. 4.3. [Developing conditions] As can be understood from the results in Table 6, every comparative example exhibits significant loss in dot percentage relative to the safelight insensitivity on the BC face. In contrast, each sample according to the invention exhibits smaller change in dot percentage relative to the safelight illuminating both the emulsion face and the BC face. In particular, samples incorporating a tetrazolium compound or hydrazine compound demonstrate further improved safelight insensitivity on the emulsion face. Additionally, in terms of difference in average grain size, it is apparent that , both grains having the preferred average grain size of 0.2µ, which are used in the usual photosensitive material for photo-lithography, and those having the more preferred average grain size of less than 0.1 µ, which is called as "Lippmann emulsion" have technical advantages.

Claims: A negative-type silver halide light-sensitive photographic material comprising a support; at least one silver halide emulsion layer being provided on one side of the support and containing silver halide grains containing at least 50 mol % of silver chloride, 10⁻⁴ to 10⁻⁸ mol per 1 mol of silver halide of a rhodium salt and a desensitizing dye; and at least one hydrophilic colloidal layer being provided on the other side of the support and containing at least one dye so that the absorbancy of the dye at the maximum spectral sensitivity wavelength (λ max) of the desensitizing dye is not less than 0.3, and the ratio of the absorbancy of the dye at the maximum spectral sensitivity wavelength of the desensitizing dye to the absorbancy of the same dye at 450 nm is not less than 0.2:1. The silver halide light-sensitive photographic material of claim 1, wherein the photographic material comprises a hydrophilic colloidal layer being provided contiguous to said silver halide emulsion layer, and either said silver halide emulsion layer or said hydrophilic colloidal layer contains a tetrazolium compound. The silver halide light-sensitive photographic material of claim 1, wherein the photographic material comprises a hydrophilic colloidal layer being provided contiguous to said silver halide emulsion layer, and either said silver halide emulsion layer or said hydrophilic colloidal layer contains a hydrazine compound. the silver halide light-sensitive photographic material of claim 1, 2 or 3, wherein said silver halide is silver chloride or silver chlorobromide. The silver halide light-sensitive photographic material of any one of the preceding claims, wherein said silver halide emulsion layer contains silver halide grains having an average grain size of not more than 0.5 µm. The silver halide light-sensitive photographic material of claim 5, wherein said silver halide emulsion layer contains silver halide grains having an average grain size of not more than 0.3 µm. The silver halide light-sensitive photographic material of claim 6, wherein said silver halide emulsion layer contains silver halide grains having an average grain size of not more than 0.1 µm. The silver halide light-sensitive photographic material of any one of the preceding claims, wherein the rhodium salt is [Na₃RhCl₆], [K₃RhBr₆], a rhodium chloride-amine complex or rhodium trichloride. The silver halide light-sensitive photographic material of any one of the preceding claims, wherein the desensitizing dye is a compound whose anode potential and cathode potential sum is positive when analyzed by polarography. The silver halide light-sensitive photographic material of any one of the preceding claims, wherein the desensitizing dye is a compound represented by formulas [I] through [V]; (in formulas [I] or [II], R₁ and R₂ are independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group or together represent a group necessary to complete a fused aromatic ring; R₃ and R₄ are independently an alkyl group, an alkenyl group, phenyl group or a hydroxylalkyl group provided that when neither R₁ nor R₂ is a hydrogen atom, at least one of R₃ and R₄ may be an aryl group; n is a positive integer of from 1 to 4; R₅ is an alkyl group having 1 to 5 carbon atoms or a sulfonated alkyl group having 1 to 5 carbon atoms; and X represents an anion; (in formula [III], R₁ and R₂ are independently a hydrogen atom or a nitro group; R₃ and R₄ are independently an alkyl group, an allyl group or a phenyl group, Z is a group of atoms necessary to complete a nitrobenzothiazole nucleus, a nitrobenzoxazole nucleus, a nitrobenzoselenazole nucleus, an imidazo[4,5-b] quinoxaline, a 3,3-dimethyl-3H-pyrrolo[2,3-b]pyridine nucleus, a 3,3-dialkyl-3H-nitroindole nucleus, a thiazolo[4,5-b]quinoline nucleus, a nitroquinoline nucleus, a nitrothiazole nucleus, a nitronaphthothiazole nucleus, a nitroxazole nucleus, nitronaphthoxazole nucleus, or a nitroselenazole nucleus, a nitronaphthoselenazole nucleus, or a nitropyridine nucleus; X represents an anion; m and n independently are an integer of 1 or 2 provided that when the compound forms an inner salt n is 1; (in formula [IV], R₁, R₂, R₃ and R₄ are independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group or a nitro group; R₅ is a hydrogen atom, an alkyl group or a nitro group; Z is a group of atoms necessary to complete a heterocyclic nucleus selected from a thiazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, an oxazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a selenazole nucleus, a benzoselenazole nucleus, a naphthoselenazole nucleus, thiazoline nucleus, a pyridine nucleus, a quinoline nucleus, an iso-quinoline nucleus, a 3,3-dialkyl-3H-indole nucleus, an imidazole nucleus, a benzoimidazole nucleus, and a naphthoimidazole nucleus, provided that these heterocyclic rings may have a substituent; L₁ and L₂ independently are either an unsubstituted methine group or a methine group substituted by an alkyl group having 1 to 5 carbon atoms or an aryl group; R₆ and R₇ are independently an alkyl group, an alkenyl group, an aryl group, a sulfoalkyl group, or an aralkyl group; X is an anion; and m and n are independently an integer of 1 or 2, provided that when the compound forms an inner salt, n is 1); (in formula [V], R₁ is an alkyl group; R₂ is an aryl group; R₃ is an alkyl group; L₁ and L₂ are independently an unsubstituted methine group or a methine group substituted by an alkyl group having 1 to 5 carbon atoms or an aryl group; Z is a group of atoms necessary to complete a heterocyclic nucleus selected from a thiazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, an oxazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a selenazole nucleus, a benzoselenazole nucleus, a naphthoselenazole nucleus, thiazoline nucleus, a pyridine nucleus, a quinoline nucleus, a 3,3-dialkylindolenine nucleus, an imidazole nucleus, and an imidazo[4,5-b] quinoxaline nucleus; X is an anion; m is an integer of 1 to 3; and n is an integer of 1 or 2. The silver halide light-sensitive photographic material of any one of the preceding claims, wherein the absorbancy of the dye at the maximum spectral sensitivity wavelength (λ max) of the desensitizing dye is not less than 0.5.

Inventors: ARAI TAKEO, NAGASHIMA TOSHIHARU, ARAI, TAKEO, NAGASHIMA, TOSHIHARU
Applicants: KONISHIROKU PHOTO IND, KONICA CORPORATION
Application year: 1988
Main classification: G03C1
IPC codes: G03C1