GB2203256A

GB2203256A - Negative type silver halide photographic material

Info

Publication number: GB2203256A
Application number: GB08801670A
Authority: GB
Inventors: Yoshihiro Takagi; Kazunobu Katoh; Hisashi Okada; Toshinao Ukai; Morio Yagihara
Original assignee: Fuji Photo Film Co Ltd
Current assignee: Fujifilm Holdings Corp
Priority date: 1987-01-26
Filing date: 1988-01-26
Publication date: 1988-10-12
Also published as: JP2515115B2; GB8801670D0; GB2203256B; JPS63183438A

Abstract

A high contrast negative type silver halide photographic material has a support bearing at least one layer of silver chloride or silver chlorobromide of </= 10 mol% Br emulsion, of which the silver halide grains have a mean grain size of </= 0.15 mu m, preferably 0.04-0.13 mu m, and a rhodium salt is added during grain formation or physical ripening in amount of more than 10<-5> mol but less than 5 X 10<-4> mol per mole of silver, and optionally with a Cd, Pb, Th and/or Ir salt. The emulsion preferably also contains a hydrazine derivative, preferably also with an amine; an organic desensitizer may be included, and/or a filter dye. General formulae are given for additives and specific examples. The photographic material can be handled in a bright room, with a low sensitivity. Development is preferably with a developer containing a dihydroxybenzene compound and a 3-pyrazolidone or aminophenol compound, for forming prints for graphic arts use.

Description

NEGATIVE TYPE SILVER HALIDE PHOTOGRAPHIC MATERIAL The present invention relates to a silver halide photographic material and a method of forming a superhighcontrast negative image using the same, and in particular, this relates to a silver halide photographic material to be used in a photomechanical process, and more precisely, a superhigh-contrast negative-type silver halide photographic material which is suitable as a silver halide photographic material which can be handled in a bright room (hereinafter referred to as "a bright room-type silver halide photographic material").

In the field of graphic arts, an image formation system is required which may form an image with a superhigh-contrast photographic characteristic (especially having r value of 10 or more), so as to improve the reproduction of a dot image for forming a continuous gradation image and the reproduction of a line image.

Hitherto, a special developer, which is a socalled lith developer, has been utilized for such a purpose. The lith developer contains only hydroquinone as a developing agent, and additionally contains a sulfite, as a preservative, in the form of an adduct with formaldehyde so as not to damage the infectious developability thereof, in which the concentration of the free sulfite ion is made extremely low (generally, 0.1 mol/liter or less). Accordingly, such a lith developer is extremely easily oxidized with air and therefore has a serious defect in that it is unstable in storage for longer than 3 days.

As examples of a method of obtaining a high contrast photographic characteristic by the use of a stable developer, there may be mentioned the methods using a hydrazine derivative, described in U.S. Patents 4,224,401, 4,168,977, 4,166,742, 4,311,781, 4,272,606, 4,211,857, 4,243,739, etc. According to these methods, a superhigh-contrast and high sensitive photographic characteristic can be obtained, and in addition, since the developer can contain a sulfite of a high concentration, the stability of the developer against air-oxidation is remarkably improved over the lith developer.However, when a superhigh-contrast image is formed by the use of such a hydrazine compound, there are some problems including the variation of the pH value of the processing solution due to processing fatigue or aerial fatigue, and the lowering of the concentration of the processing solution due to the depletion of the developing agent or accumulation of an inhibitor, each of which results in lowering of the contrast of the gradation. Under the circumstances, a means is strongly desired which is capable of accelerating the image contrast when a hydrazine compound is used.In this connection, the use of a contrast-enhancing agent has been proposed example, Japanese Patent Application (OPI) No. 167939/86 (the term "OPI" as used herein means a "published unexamined Japanese patent application) illustrates the use of a phosphonium salt compound, Japanese Patent Application (OPI) No. 198147/86 illustrates the use of a disulfide compound, and Japanese Patent Application (OPI) No.

140340/85 illustrates the use of an amine series compund.

However, even though these compounds are used, it was still difficult to prevent the decrease of the image contrast of photographic materials during the photographic processing.

On the other hand, when a bright room-type silver halide photographic material having a low sensitiveity is to be obtained by the use of a hydrazine compound, for example, a water-soluble rhodium salt-containing silver halide photographic material is illustrated in Japanese Patent Applications (OPI) Nos. 83038/85 and 162246/85.

However, when a rhodium salt is added in an amount sufficient for lowering the sensitivity of the material, the contrast-enhancement by the hydrazine compound would be inhibited so that the desired, sufficiently high contrast image could not be obtained.

In addition, Japanese Patent Application (OPI) No.

157633/84 discloses a method for preparation of a silver halide photographic emulsion containing a water-soluble rhodium salt in an amount of from 10-8 to 10-5 mol per mol of the silver halide and an organic desensitizer when the sum of the anode potential and the cathode potential in polarography is positive. However, although the material obtained by the method can actually have a low sensitivity, the material is still impossible to form a high contrast image which would sufficiently be utilized in the industrial field as intended by the present invention.

Japanese Patent Application (OPI) No. 62245/81 discloses a method of forming a high contrast image, in which the development is effected in the presence of a tetrazolium compound so that the development of the toe part of the characteristic curve may be inhibited by the tetrazolium compound. However, the tetrazolium compoundcontaining silver halide photographic material has some problems in that this is deteriorated during storage so that only a soft image would be obtained and a reaction product of the tetrazolium compound formed during the development would in part remain in the film, often so as to cause unevenness in development.

As mentioned above, the conventional method of fonUng a high contrast image by the use of a hydrazine compound always involves the problem of softening the contrast when the photographic material is processed by running treatment or when a low sensitive image is to be obtained by the use of a rhodium salt or an organic desensitizer. In othex words, it was extremely difficult to lower the sensitivity of the hydrazine compoundcontaining photographic material while the superhic contrast of the image formed is maintained as such.

In some cases, a large amount of a hydrazine compound is often added so as to attain the high contrast of the image formed, and as a result, the strength of the emulsion film would be weakened or the storability of the material would be deteriorated, or as the case may be, a noticeable amount of the hydrazine compound incorporated into the material would be dissolved out into the developer during the running processing of the material, and in addition, the photographic material would norse or less be badly influenced by the excess amount of the hydrazine compound. Accordingly, a method of enhancing the contrast of the photographic image by the use of a small amount of a hydrazine compound has also been desired.

As mentioned above, it is extremely difficult to lower the sensitivity of the contrast-enhanced photographic material by the use of a hydrazine compound, while the thus-enhanced contrast of the material is maintained as such. This is because the hydrazine compound has an activity of participating in the development procedure to cause the nucleating infectious development because of the electron-donating effect thereof to the silver halide thereby to form a high contrast image, while an organic desensitizer or an inorganic desensitizer such as a rhodium salt is an acceptor for a photoelectron and therefore accepts the photoelectron during the image exposure so as to inhibit the latent image formation, whereby the sensitivity of the material is lowered. In addition, the desensitizer can accept the electron from the electron-donating material such as a hydrazine compound at the development processing so as to inhibit the nucleating infectious development, and accordingly, a high contrast image could not be formed. Under the circumstances, a method of lowering the sensitivity of a photographic material containing a hydrazine compound with maintaining the high contrast property of the hydrazine compound-containing material has heretofore been strongly desired in this technical field.

In the field of contact work in the graphic arts, photographic materials having a photographic characteristic of a gradation r of from 4 to 8 or so can be used in addition to superhigh-contrast photographic materials having a gradation r of 10 or more. The photographic mateLials having such lower gradation r may have a smaller amount of pin holes which would be caused by dust and the like in air or may have a smaller white background part which would be caused by adhesive tapes to be used for fixing the original onto the film in the contact reverse work, the white background part being called a tape-stuck trace, as compared with the superhighcontrast photographic materials, but on the other hand, the former materials have a defect in that these are poor in the letter or dot image sharpness.In practice, it is necessary to maintain the image sharpness in some degree, and for this, the r value is required to be from 3.5 to 8.

In addition, when the photographic materials are those for a bright room, the sensitivity of the materials is required to be lowered. The addition of a rhodium salt to the silver halide grains would be effective for lowering the sensitivity, which, however, causes some other problems in that the r value of the photographic material would be lowered and the image sharpness would be lost.

The use of dye for lowering the sensitivity would cause another problem in that the tone adjustment of dot images or the line width adjustment on the basis of the amount of the exposure would become difficult because of the anti-irradiation effect of the dye.

Accordingly, a method of lowering the sensitivity without lowering the r value has also been strongly desired.

The photographic materials for contact work are used in such state that the processed film, as an original, is subjected to contact printing with an Hg printer and then printed in a printing plate such as a PS plate by the use of ultraviolet light in the post-step, and therefore, these materials require the use of a high ultraviolet ray concentration. On the contrary, there is another demand that the amount of the silver to be coated on the photographic material is to be minimized as little as possible for economization of natural resources.

Accordingly, a method capable of obtaining a high ultraviolet ray concentration by the use of a small amount of silver to be coated has also been strongly desired.

One object of the present invention is to provide a means of enhancing the high contrast of a type of photographic material containing a rhodium salt or an organic desensitizer.

Another object of the present invention is to provide a means of enhancing the high contrast of a photographic material system containing a hydrazine compound.

Still another object of the present invention is to provide a bright room-type photographic material having a low sensitivity.

A further object of the present invention is to provide a silver halide photographic material having a high covering power.

The above-mentioned objects of the present invention can be attained by a negative type silver halide photographic material which comprises a support having thereon at least one silver halide emulsion layer comprising a silver chloride emulsion or a silver chlorobromide emulsion I containing 10 mol% or less bromide, wherein the silver halide emulsion layer comprises silver halide grains having a mean grain size of 0.15 pm or less and more than 10-5 mol but less than 5 x 10-4 mol of a rhodium salt, per mol of silver.

The mean grain size of the silver halide to be used in the present invention is 0.15 pm or less, and in particular, preferably from 0.04 to 0.13 pm. The grain size distribution is basically not limitative but is preferably to form a monodispersed emulsion. The term "monodispersed emulsion" as used herein means that the emulsion contains silver halide grains of which at least 95% hy weight or by number have a grain size falling within the range of the mean grain size i 40%.

For the preparation of the silver halides for use in the present invention, which have a mean grain size of 0.15 vm or less, various conventional methods which are well known by those skilled in the art can be used, including, for example, a method of lowering the temperature during the formation of the grains, a method of adequately controlling the concentration of the binder used, a method of adequately controlling the addition speed or concentration of the silver nitrate or halide compounds to be added, and a method of using a - mercapto compound, an azole compound, an imidazole compound, a triazole compound, a thiazole compound or an azaindene compound.

The silver halide grains in the photographic emulsion may have a regular crystal form such as a cubic or octahedral form, or an irregular crystal form such as a spherical or tabular form, or a composite crystal form comprising the different crystal forms.

The silver halide grains may have a uniform phase both in the inner part and in the surface layer part or may have different phases in these parts. Two or more silver halide emulsions which were prepared separately can be blended and used in the formation of the photographic materials of the present invention.

The halogen composition must be silver chloride or silver chlorobromide (having Br-content of 10 mol% or less).

In the practice of the present invention, if the mean grain size is more than 0.15 pm, the clearing of fine lines would become worsened, as mentioned in detail hereinlfter (see the Examples).

Especially in the case of the photographic material containing a hydrazine derivative, the larger mean grain size is inconvenient since the gradation would become softened, as mentioned in detail hereinafter, or the super-imposed letter image quality would become worsened.

The silver halide emulsion of the present invention may contain a rhodium salt in the formation of the silver halide grains or in the step of the physical ripening of the grains.

As the rhodium salt for the present invention, any rhodium salt which can be incorporated into silver halide grains can be used, for example, including rhodium monochloride, rhodium dichloride, rhodium trichloride or ammonium hexachlororhodate, and preferably, a water soluble trivalent rhodium halogeno-complex compound, for example, hexachlororhodate (III) or a salt thereof (e.g., ammonium salt, sodium salt .or potassium salt), is used.

The amount of the rhodium salt or complex salt thereof to be used in the present invention is more than 10-5 mol but less than 5 x 10-4 mol, and preferably is 1.1 x 10-5 to 4.0 x 10-4 mol, per mol of silver.

If a larger amount of the rhodium salt than 5 x 10-4 mol is used, the clearing of fine lines would become worsened, as mentioned in detail hereinafter. In particular, the use of the larger amount of the rhodium salt in a hydrazine-containing photographic material is disadvantageous, since the sensitivity of the material is too much lowered.

On the contrary, if a smaller amount of the rhodium salt than 10-5 mol is used, the edge trace of the image formed would undesirably become too visible.

In particular, in the case of the hydrazine-containing photographic material, the use of such smaller amount of the rhodium salt is disadvantageous since the sensitivity of the material could not be lowered to the desired value.

In the present invention, a cadium salt, a lead salt, a thallium salt and/or an iridium salt can be used together with the rhodium salt.

The present invention is characterized by the incorporation of the rhodium salt in an amount more than than 10-5 mol but less than 5 x 10-4 mol per mol of silver into the emulsion having the mean grain size of 0.15 lfm or less at any stage of silver halide emulsion-making, provided that the physical ripening is not yet finished, and the effect attainable by the present invention is especially remarkable when the present invention is applied to a superhigh-contrast photographic material containing a hydrazine derivative in the emulsion.

As hydrazine derivatives used in the invention, those represented by the general formula (I) as set forth below are preferred:

wherein A represents a substituted or unsubstituted aliphatic or aromatic group; B represents a formyl group, an acyl group, an alkylsulfonyl group,. an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a carbamoyl group; a sulfamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfinamoyl group, an alkoxysulfonyl group, a thioacyl group, a thiocarbamoyl group, or a heterocyclic group; and both X0 and Y0 represent hydrogen atoms or one of X0 and Y0 represents a hydrogen atom and the other represents a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.

However, B, Y0 and the nitrogen atom to which they are bonded may form the partial structure of of hydrazone.

Next, the general formula (I) will be described in detail.

In the.general formula (I), aliphatic groups represented by A are preferably the ones of 1 to 30 carbon atoms and, especially preferably, linear, branched, or cyclic alkyl groups of 1 to 20 carbon atoms. The branched alkyl group may be cyclized to form a saturated heterocyclic ring containing one or more hetero atoms. The alkyl groups may have a substituent group such as an aryl group, an alkoxy group, a sulfoxylic group, a sulfonamide group, a carboxylic acid amide group, or the like.

As the examples of the aliphatic group, there may be mentioned, a t-butyl group, an n-octyl group, a t-octyl group, a cyclohexyl group, a pyrrolidyl group, an imidazolidyl group, a tetrahydrofuryl group, a morpholino group, and the like.

The aromatic group represented by A in general formula (I) is preferably a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. The unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a heteroaryl group.

The aromatic group includes, for example, a benzene ring1 a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, a benzothiazole ring, and the like, and of these, the aromatic group containing a benzene ring is preferred.

The especially preferred aromatic groups as A are benzene and naphthalene.

Aryl groups or unsaturated heterocyclic groups represented by A may have a substituent group.

As representative substituent groups, there may be mentioned linear, branched or cyclic alkyl groups (preferably, with 1 to 20 carbon atoms), aralkyl groups (preferably, monocyclic or bicyclic groups whose alkyl moiety has a carbon atom number of 1 to 3), alkoxy groups (preferably, with 1 to 20 carbon atoms), substituted amino groups (preferably, substituted with an alkyl group of 1 to 20 carbonatoms), acylamino groups (preferably, with 2 to 30 carbon atoms), sulfonamide groups (preferably, with 1 to 30 carbon atoms), ureido groups (preferably, with 1 to 30 carbon atoms), and the like.

A in formula (I) may additionally have a ballast group incorporated into it which ballast group is commonly used to render a photographic additive such as a coupler or the like non-diffusible.

The ballast group is a group relatively inactive with respect to photographic properties and has a carbon atom number of 8 and over. The ballast group can be selected from among alkyl groups, alkoxy groups, a phenyl group, alkyl phenyl? groups, a phenoxy group, alkylphenoxy groups, and the like.

A in formula (I) may have a group incorporated into it which group strengthens adsorption to the surface of silver halide grains.

As such a group, there may be mentioned groups such as a thiourea group, heterocyclic thioamide groups, mercapto heterocyclic groups, triazole groups, and the like which are disclosed in U.S. Patents 4,385,108 and 4,459,347, in Japanese Patent Applications (OPI) Nos. 195233/84, 200231/84, 201045/84, 201046/84, 201047/84, 201048/84, 201049/84, 179734/85. and 170733/86, and U.S. Patent Application Serial No.826,153.

B represents preferably a formyl group, an acyl group (such as an acetyl group, a propionyl group, a trifluoroacetyl group, a chloroacetyl group, a benzoyl group, a 4-chlorobenzoyl group, a pyruvoyl group, a methoxalyl group, a methyloxamoyl group, or the like), an alkyl sulfonyl group (such as a methane sulfonyl group, a 2-chloroethane sulfonyl group, or the like), an aryl sulfonyl group (such as a benzene sulfonyl group, or the like), an alkyl sulfinyl group (such as a methane sulfinyl group or the like) an aryl sulfinyl group (such as a benzene sulfinyl group or the like), a carbamoyl group (such as a methylcarbamoyl group, a phenylcarbamoyl group, or the like), a sulfamoyl group (such as a dimethylsulfamoyl group, or the like), an alkoxycarbonyl group, such as anethoxycarkonyl group, a methoxyethoxycarbonyl group, or the like), an aryloxycarbonyl group (such as a phenoxycarbonyl group, or the like), a sulfinamoyl group (such as a methylsulfinamoyl group, or the like), an alkoxy sulfonyl group (such as a methoxy sulfonyl group, an ethoxy sulfonyl group, or the like), a thioacyl group (such as a methylthiocarbonyl group, or the like), a thiocarbamoyl group (such as a methylthiocarbamoyl group, or the like), or a heterocyclic ring group (such as a pyridine ring, or the like).

A formyl group or an acyl group as B is, in particular, preferred.

B in the general formula (I) together with Y0 and a nitrogen atom to which B and Yo are bonded may form the partial structure

of hydrazone.

In the above formula, Y' represents an alkyl group, an aryl group, or a heterocyclic ring group, and Y" represents a hydrogen atom or an alkyl group, an aryl group, or a heterocyclic ring group.

One of X0 and Y0 is a hydrogen atom, and the other is a hydrogen atom, an alkyl sulfonyl group having 20 carbon atoms or less, an aryl sulfonyl group having 20 carbon atoms or less (preferably, a phenyl sulfonyl group or a phenyl sulfonyl group substituted so that the sum of substituent constants of Hammett becomes -0.5 or more), an acyl group having 20 carbon atoms or less (preferably, a benzoyl group, a benzoyl group substituted so that the sum of substituent constants of Hammett becomes -0.5 or more, or an unsubstituted or substituted, linear, branched or cyclic aliphatic acyl group (wherein, as the substituent group, there may be mentioned, for example, halogen atoms, ether groups, sulfonamide groups, carboxylic acid amide groups, hydroxyl group, carboxylic group, sulfonic acid group, and the like).

It is most preferred that both X0 and Yo are hydrogen atoms.

Specific examples of compounds represented by formula (I) are the following.

However, the invention is not limited to these compounds.

As the hydrazine derivatives used in the present invention, there may further be mentioned, in addition to the above-mentioned examples, the compounds described in Research Disclosure, Item 23516 (November, 1983, page 346) and literature as referred to therein as well as in U.S.

Patents 4,080,207, 4,269,929, 4,276,364, 4,278,748, 4,385,108, 4,459,347, 4,560,638 and 4,478,928, British Patent 2,011,391B and Japanese Patent Application (OPI) No. 179734/85.

The compound of formula (I) is preferably contained in an amount of from 1 x 10-6 to 5 x 10-2 mol, especially preferably from 1 x 10-5 to 2 x 10-2 mol, per mol of silver halide in the silver halide emulsion layer.

In accordance with the present invention, a compound of formula (II) or (III) as shown below is preferably incorporated into the photographic material together with the hydrazine derivative represented by formula (I), so as to accelerate the high contrast degree and to prevent the lowering of the gradation resulting from the lowering of the sensitivity.

Y-[-(X)-A'-B']m (II) wherein Y represents a group capable of adsorbing on silver halide; X represents a divalent linking group comprising an atom or atoms selected from a hydrogen atom, a carbon atom, a nitrogen atom, an oxygen atom and,a sulfur atom, or an atomic group comprised of the atoms; A' represents a divalent linking group; B' repre sents a substituted or unsubstituted amino group, an ammonium group or a nitrogen-containing heterocyclic group; m represents 1, 2 or 3; and n represents 0 or 1.

When m is more than 1, -;AX;-nA'-B' ] may be the same or different.

The group capable of adsorbing to silver halide, as represented by Y, includes a residue of a nitrogen-containing heterocyclic compound.

When Y represents a residue of a nitrogencontaining heterocyclic compound, the compound of formula (z) is represented by formula (Il-a)

wherein Q represents 0 or 1; X, A', B', m and n have the same meaning as those defined in the above-mentioned formula (IL);Q represents an atomic group necessary for forming a 5- or 6-membered hetero ring which comprises at least one atom selected from a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom, and the hetero ring may optionally be condensed with a carbon-aromatic ring or a hetero-aromatic ring; and M represents a hydrogen atom, an alkali metal atom (such as a sodium atom, a potassium atom,), an ammonium group (such as a trimethylammonium group, a dimethylbenzylammonium group, ), or a group capable of being converted into H or an alkali metal atom under an alkali condition (such as an acetyl group, a cyanoethyl group, a methanesulfonylethyl group).

The hetero ring formed by Q includes, for example, substituted or unsubstituted imidazoles, benzimidazoles, benzotriazoles, benzoxazoles, benzothiazoles, imidazoles, thiazoles, oxazoles, triazoles, tetrazoles, azaindenes, pyrazoles, indoles, triazines, pyrimidines, pyridines and quinolines.

These hetero rings may optionally be substituted by one or more substituents selected from a nitro group, a halogen atom (e.g., a chlorine atom, a bromine atom, etc.), a mercapto group, a cyano group, a substituted or unsubstituted alkyl group (e.g., a methyl group, an ethyl group, a propyl group, a t-butyl group, a cyanoethyl group, a methoxyethyl group, a methylthioethyl group, etc.),a substituted or unsubstituted aryl group (e.g., a phenyl group, a 4-methanesulfonamidophenyl group, a 4-methylphenyl group, a 3,4-dichlorophenyl group, a naphthyl group, etc.), a substituted or unsubstituted alkenyl group (e.g., an allyl group, etc.), a substituted or unsubstituted aralkyl group (e.g., a benzyl group, a 4-methylbenzyl group, a phenethyl group, etc.), a substituted or unsubstituted alkoxy group (e.g., a methoxy group, an ethoxy group, etc.), a substituted or unsubstituted aryloxy group (e.g., a phenoxy group, a 4-methoxyphenoxy group, etc.), a substituted or unsubstituted alkylthio group (e.g., a methylthio group, an ethylthio group, a methoxyethylthio group, etc.), a substituted or unsubstituted arylthio group (e.g., a phenylthio group, etc.), a substituted or unsubstituted sulfonyl group (e.g., a methanesulfonyl group, an ethanesulfonyl group, a p-toluenesulfonyl group, etc.)-, a substituted or unsubstituted carbamoyl group (e.g., an unsubstituted carbamoyl group, a methylcarbamoyl group, a phenylcarbamoyl group, etc.), a substituted or unsubstituted sulfamoyl group (e.g., an unsubstituted sulfamoyl group, a methylsulfamoyl group, a phenylsulfamoyl group, etc.), a substituted or unsubstituted carbonamido group (e.g., an acetamido group, a benzamido group, etc.), a substituted or unsubstituted sulfonamido group (e.g., a methanesulfonamido group, a benzenesulfonamido group, a ptoluenesulfonamido group, etc.), a substituted or unsubstituted acyloxy group (e.g., an acetyloxy group, a benzoyloxy group, etc.), a substituted or unsubstituted sulfonyloxy group (e.g., a methanesulfonyloxy group, etc.), a substituted or unsubstituted ureido group (e.g., an unsubstituted ureido group, a methylureido group, an ethylureido group, a phenylureido group, etc.), a substituted or unsubstituted thioureido group (e.g., an unsubstituted thioureido group, a methylthioureido group, etc.), a substituted or unsubstituted acyl group (e.g., an acetyl group, a benzoyl group, etc.), a substituted or unsubstituted heterocyclic group (e.g., a 1-morpholino group, a 1-piperazino group, a 2-pyridyl group, a 4pyridyl group, a 2-thienyl group, a 1-pyrazolyl group, a 1-imidazolyl group, a 2-tetrahydrofuryl group, a tetrahydrothienyl group, etc.), a substituted or unsubstituted oxycarbonyl group (e.g., a methoxycarbonyl group, a phenoxycarbonyl group, etc.), a substituted or unsubstituted oxycarbonylamino group (e.g., a methoxycarbonylamino group, a phenoxycarbonylamino group, a 2-ethylhexyloxycarbonylamino group, etc.), a substituted or unsubstituted amino group (e.g., an unsubstituted amino group, a dimethylamino group, a methoxyethylamino group, an anilino group, etc.), a substituted or unsubstituted carboxylic acid or a salt thereof, a substituted or unsubstituted sulfonic acid or a salt thereof, a hydroxyl group, etc.

The diva lent linking group represented by X includes, for example,

etc.; and the linking group may be bonded to Q optionally via a linear or branched alkylene group (such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, a 1-methylethylene group, etc.).R1, R2, R3, R4, R5, R6, R7, R8, Rg and R10 each represents a hydrogen atom, a substituted or unsubstituted alkyl group (e.g., a methyl group, an ethyl group, a propyl group, an n-butyl group, etc.), a substituted or unsubstituted aryl group (e.g., a phenyl group, a 2-methylphenyl group, etc.), a substituted or unsubstituted alkenyl group (e.g., a propenyl group, a 1-methylvinyl group, etc.), or a substituted or unsubstituted aralkyl group (e.g., a benzyl group, a phenethyl group, etc.).

A1 represents a divalent linking group, which includes, for example, a linear or branched alkylene group (e.g., a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, a 1-methylethylene group, etc.), a linear or branched alkenylene group (e.g., a vinylene group, a 1-methylvinylene group, etc.), a linear or branchedaralkylene group (e.g., a benzylidene group, etc.), an arylene group (e.g., a phenylene group, a naphthylene group, etc.), etc. The above-mentioned group represented by A' may be further substituted, and X and A' can be bonded to each other in any desired combination. Substituents for A' may be selected from the group mentioned for the hetero ring of Y.

The substituted or unsubstituted amino group of B1 is represented by formula (II-b):

wherein R11 and R12 may be the same or different and each represents a hydrogen atom or a substituted or unsubstituted alkyl, alkenyl or aralkyl group having from 1 to 30 carbon atoms, and the group may be linear (for example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-octyl group, an allyl group, a 3-butenyl group, a benzyl group, a 1-naphthylmethyl group, etc.), or branched (for example, an iso propyl group, a t-octyl group, etc.), or cyclic (for example, a cyclohexyl group, etc.).

In addition, R11 and R12 may be linked together to form a ring or may be cyclized to form a saturated hetero ring containing one or more hetero atoms (such as an oxygen atom, a sulfur atom, a nitrogen atom, etc.) therein. As the cyclic group, there may be mentioned a pyrrolidyl group, a piperidyl group, a morpholino group, etc.As the substituents for R11 and R12, there may be mentioned, for example, a carboxyl group, a sulfo group, a cyano group, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom), a hydroxyl group, an alkoxycarbonyl group having 20 or less carbon atoms (e.g., a methoxycarbonyl group, an ethoxycarbonyl group, a benzyloxycarbonyl group, etc.), an aryloxycarbonyl group having 20 or less carbon atoms (e.g., a phenoxycarbonyl group, etc.), an alkoxy group having 20 or less carbon atoms (e.g., a methoxy group, an ethoxy group, a benzyloxy group, a phenethyloxy group, etc.), a monocyclic aryloxy group having 20 or less carbon atoms (e.g., a phenoxy group, a p-tolyloxy group, etc.), an acyloxy group having 20 or less carbon atoms (e.g., an acetyloxy group, a propionyloxy group, etc.), an acyl group having 20 or less carbon atoms (e.g., an acetyl group, a propionyl group, a benzoyl group, a mesyl group, etc.), a carbamoyl group (e.g., an unsubstituted carbamoyl group, an N,N-dimethylcarbamoyl group, a morpholinocarbonyl group, a piperidinocarbonyl group, etc.), a sulfamoyl group (e.g., an unsubstituted sulfamoyl group, an N,N-dimethylsulfamoyl group, a morpholinosulfonyl group, a piperidinosulfonyl group, etc.), an acylamino group having 20 or less carbon atoms (e.g., an acetylamino group, a propionylamino group, a benzoylamino group, a mesylamino group, etc.), a sulfonamido group (e.g., an ethylsulfonamido group, a p-toluenesulfonamido group, etc.), a carbonamido group having 20 or less carbon atoms (e.g., a methylcarbonamido group, a phenylcarbonamido group, etc.), a ureido group having 20 or less carbon atoms (e.g., a methylureido group, a phenylureido group, etc.), an amino group (having the same meaning as in formula (lib)), etc.

The ammonium group of B1 may be represented by formula (II-c):

wherein the substituents comprising R13, R14 and R15 are the same as those of R11 and R12 in the above-mentioned formula (VII); and Z- represents an anion, for example, a halide ion (e.g., Cl-, Br-, I-, etc.), a sulfonato ion (e.g., trifluoromethanesulfonato, paratoluenesulfonato, benzenesulfonato, parachlorobenzenesulfonato, etc.), a sulfato ion (e.g., ethylsulfato, methylsulfato, etc.), a perchlorato, a tetrafluoroborato, etc.; and p represents 0 or 1, provided that when the compound forms an inner salt, p is 0.

The nitrogen-containing heterocyclic group of B'is a 5- or 6-membered cyclic group containing at least one or more nitrogen atoms, and the ring may optionally have substituent(s) or may optionally be condensed with other ring(s) such as a benzene ring or a naphthalene ring. As the nitrogen-containing heterocyclic ring, there may, for example, be mentioned an imidazolyl group, a pyridyl group, a thiazolyl group, etc.

Among the compounds of formula (II), those represented by formulae (II-m), (II-n), (II-o) and (II-p) are preferred.

wherein X, A', B', M, m and n have the same meaning as those given in the above-mentioned formula (II); and Z1, Z2 and Z3 have the same meaning as XALB' in the abovementioned formula (II) or these may independently represent a halogen atom, an alkoxy group having 20 or less carbon atoms (e.g., a methoxy group), a hydroxyl group, a hydroxylamino group, or a substituted or unsubstituted amino group, and the substituents thereof can be selected from the same substituents listed for R11 and R12 in the above-mentioned formula (IL-b), provided that at least one of these Z1, Z2 and Z3 must have the same meaning as QXenA'-B ' .

In addition, these hetero rings may optionally be substituted by substituent(s) selected from the group which may be applied to the hetero ring of formula (II).

Specific examples of the compounds of formula (II) are shown below, which, however, are not intended to restrict the scope of the present invention.

wherein R21 and R22 each represents a hydrogen atom or an aliphatic residual group; R21 and R22 may be linked together to form a ring; R23 represents a divalent aliphatic group; X' represents a divalent hetero-ring residual group containing at least one of nitrogen, oxygen and sulfur atoms; n' represents 0 or 1; and M' represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, a quaternary ammonium group, a quaternary phosphonium group or an amidino group.

As the aliphatic residual group for R21 and R22 are preferred alkyl, alkenyl and alkynyl groups each having from 1 to 12 carbon atoms, which can optionally be substituted by pertinent substituent(s).

As the alkyl group, there may be mentioned, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a decyl group, a dodecyl group, an isopropyl group, a secbutyl group, a cyclohexyl group, etc.

As the alkenyl group, there may be mentioned, for example, an ally group, a 2-butenyl group, a 2-hexenyl group, a 2-octenyl group, etc.

As the alkynyl group, there may be mentioned, for example, a propargyl group, a 2-pentynyl group, etc.

As the substituents for these groups, there may be mentioned, for example, a phenyl group, a substituted phenyl group, an alkoxy group, an alkylthio group, a hydroxyl group, a carboxyl group, a sulfo group, an alkylamino group, an amido group, etc.

When R21 and R22 together form a ring, the ring may be a 5-membered or 6-membered carbon-ring or heteroring comprising carbon atoms or a combination of nitrogen and oxygen atoms and carbon atoms, and especially a saturated ring is preferred, for example, including the following groups:

R21 and R22 are especially preferably an alkyl group having from 1 to 3 carbon atom, and most preferably an ethyl group.

The divalent aliphatic group of R23 is preferably -R24- or -R24S- , wherein R24 represents a divalent aliphatic residual group, preferably a saturated or unsaturated divalent aliphatic residual group, for example, including -CH2-, -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CH2)6-, -CH2CH=CHCH2-, -CH2C=CCH2-, -CH2CH(CH3)CH2-, etc.

R24 preferably has from 2 to 4 carbon atoms, and more preferably R24 represents -CH2CH2- or -CH2CH2CH2-.

When n'of (X' )n represents 0, R23 is only the group -R24-.

The hetero-ring of X' may be a 5-membered or 6membered hetero-ring containing at least one of nitrogen, oxygen and sulfur atoms, which may optionally be condensed with benzene ring(s). The hetero-ring is preferably an aromatic hetero-ring, for example, including a tetrazole, a triazole, a thiadiazole, an oxadiazole, an imidazole, a thiazole, an oxazole, a benzimidazole, a benzothiazole, a benzoxazole, etc. In particular, tetrazole and thiazole rings are preferred among them.

As the alkali metal of M' may be mentioned, for example, Na, Ke, Lie, etc.

As the alkaline earth metal of M' may be mentioned, for example, Ca, Mg, etc.

The quaternary ammonium salt of M' may have from 4 to 30 carbon atoms, which includes, for example, (CH3)4Ne, (c2H5)Ne, (C4H9)4Ne, c6H5CH2Ne(cH3)3, C16H33Ne(CH3)3, etc.

As the quaternary phosphonium salt of M' may be mentioned, for example, (C4H9)4 P+, C16H33 P+(CH3)3, C6H5CH2P+(CH3)3 etc.

As counter salts of the compounds of formulae (II) and (III), there may be mentioned, for example, inorganic acid salts or organic acid salts.

As the inorganic acid salts, there may be mentioned, for example, hydrochlorides, sulfates, phosphates, etc.; and as the organic acid salts, there may be mentioned, for example, acetates, propionates, methanesulfonates, benzenesulfonates, p-toluenesulfonates, etc.

Examples of the compounds of the formula (III) are mentioned below.

The compound of the formula (II) is preferably contained in a silver halide emulsion layer in an amount of from 1 x 10-3 to 0.5 g/m2, and more preferably from 5 x 10-3 to 0.3 g/m2.

The compound of the formula (III) is preferably contained in a silver halide emulsion layer in an amount of from 1 x 10-3 to 0.5 g/zn2, and more preferably from 5 x 10-3 to 0.1 g/m2.

The present invention is especially effective in -a photographic system containing an organic desensitizer.

The organic desensitizer for use in the present invention preferably has at least one water-soluble group or alkali dissociating group. The present inventors are the first to find out that the incorporation of the organic desensitizer into a hydrazine compound-containing high contrast photographic material is effective for lowering the sensitivity of the material without interfering with the high contrast thereof.

The compounds represented by formulae (II) and (III) for use in the present invention can easily be synthesized by conventional methods, for example, as described in Berichte der Deutschen Chemischen Gesellschaft, 28, 77 (1985); Japanese Patent Applications (OPI) Nos. 37436/75 and 3231/76; U.S. Patents 3,295,976 and 3,376,310; Berichte der Deutschen Chemischen Gesellschaft, 22, 568 (1889), ibid., 29, 2483 (1896); J. Chem. Soc., 1932, 1806; J. Am. Chem. Soc., 71, 4000 (1949); U.S. Patents 2,585,388 and 2,541,924; Advances in Heterocyclic Chemistry, 9, 165 (1968); Organic Synthesis, IV, 569 (1963); J. Am. Chem. Soc., 45, 2390 (1923); Chemische Berichte, , 465 (1876); Japanese Patent Publication No.

28496/65; Japanese Patent Applications (OPI) No. 89034/75; U.S. Patents 3,106,467, 3,420,670, 2,271,229, 3,137,578, 3,148,066, 3,511,663, 3,060,028, 3,271,154, 3,251,691, 3,598,599 and 3,148,066; Japanese Patent Publication No.

4135/68; U.S. Patents 3,615,616, 3,420,664, 3,071,465, 2,444,605, 2,444,606, 2,444,607 and 2,935,404; Japanese Patent Applications (OPI) Nos. 202531/82, 167023/82, 164735/82, 80839/85, 152235/83, 14836/82, 162546/84, 130731/85, 138548/85, 83852/83, 159529/83, 159162/84, 217358/85 and 80238/86; Japanese Patent Publications Nos.

29390/85, 29391/85, 133061/85 and 1431/86.

Such organic desensitizer must contain at least one water-soluble group, which includes, for example, a sulfonic acid group, a carboxylic acid group and a phosphonic acid group.

These groups can be in the form of a salt, for example, with an organic base (e.g., ammonia, pyridine, triethylamine, piperidine, morpholine, etc.) or an alkali metal (e.g., sodium, potassium, etc.).

The term alkali dissociating group" means a substituent that causes a deprotonization reaction to become anionic at or below the pH of a developing solution (generally, a developing solution has a pH range of from 9 to 13, although the developing solution may have a pH outside this range), and specifically refers to a substituent having at least one hydrogen atom attached to a nitrogen atom such as a substituted or unsubstituted sulfamoyl group, a substituted or unsubstituted carbamoyl group, a sulfonamido group, an acylamino group and a substituted or unsubstituted ureido group and a hydroxyl group.

The alkali dissociating group also includes a nitrogen-containing heterocyclic ring group having a hydrogen atom on the nitrogen atom constituting the nitrogen-containing heterocyclic ring.

These water-soluble groups and alkali dissociating groups may be attached to any part of the organic desensitizer, and the organic desensitizer may have two or more such groups at the same time.

Preferable organic desensitizers used in the present invention include compounds represented by the following formulae (IV) to (VI):

wherein T represents an alkyl group (preferably having 1 to 18 carbon atoms), a cycloalkyl group (preferably having 3 to 18 carbon atoms), an alkenyl group (preferably having 2 to 18 carbon atoms), a halogen atom, a cyano group, a trifluoromethyl group, an alkoxy group (preferably having 1 to 18 carbon atoms), an aryloxy group (preferably having 6 to 12 carbon atoms), a hydroxy group, an alkoxycarbonyl group (preferably having 2 to 18 carbon atoms), a carboxyl group, a carbamoyl group, a sulfamoyl group, an aryl group (preferably having 6 to 12 carbon atoms), an acylamino group (preferably having 2 to 18 carbon atoms), a sulfonamido group (preferably having 1 to 18 carbon atoms), a sulfo group or a benzocondensed ring, which may or may not have one or more substituents; zil represents a group of nonmetal atoms required to complete a nitrogen-containing heterocyclic ring; q is 1, 2 or 3; and r is 0, 1 or 2;

wherein P and Q, which may be the same or different, each represents a cyano group, an acyl group (preferably having 2 to 18 carbon atoms), a thioacyl group (preferably having 2 to 18 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 18 carbon atoms), an alkylsulfonyl group (preferably having 1 to 18 carbon atoms), an arylsulfonyl group (preferably having 6 to 12 carbon atoms), a substituted or unsubstituted sulfamoyl group, a substituted or unsubstituted carbamoyl group, a nitro group, or a substituted or unsubstituted aryl group; n is 1, 2 or 3; and T, r and q have the same meaning as defined in formula (IV) above; and

wherein Z12 represents a group of nonmetal atoms required to complete a ketomethylene ring; m is 1, 2 or 3; and T, r and q have the same meaning as defined in formula (IV) above; with the proviso that substituents Z11' Z12' T, P and Q in formulae (IV) to (VI) have at least one water-soluble group or alkali dissociating group.

In formula (IV), the nonmetal atoms represented by Z11 may, for instance, be comprised of one or more nitrogen, oxygen, sulfur and carbon atoms, which may or may not be substituted with one or more substituents and which form a ring containing at least three members, which may be further fused to one or more additional rings. The substituents may, for instance, be oxygen atoms, sulfur atoms, and oxygen-, sulfur-, nitrogen-, and carbon-containing groups.

In formulae (IV) to (VI), the substituents for T include an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 18 carbon atoms, an aryl group having 6 to 12 carbon atoms, an acylamino group having 2 to 18 carbon atoms, a sulfonamido group having 1 to 18 carbon atoms, a halogen atom, a cyano group, a trifluoromethyl group, a hydroxy group, a carboxyl group, and a sulfo group.

In formula (V), the substituents of the substituted sulfamoyl, carbamoyl, and aryl groups for P and Q include the same groups as exemplified for the substituents for T in formulae (IV) to (VI).

Specific examples of nitrogen-containing heterocyclic rings completed through Z11 include a 1,2,4triazole ring, a 1,3,4-oxadiazole ring, a 1,3,4-thiadiazole ring, a tetraazaindene ring, a pentaazaindene ring, a triazaindene ring, a benzothiazole ring, a benzimidazole ring, a benzoxazole ring, a pyrimidine ring, a triazine ring, a pyridine ring, a quinoline ring, a quinazoline ring, a phthalazine ring, a quinoxaline ring, an imidazo[4,5-b]quinoxaline ring, a tetrazole ring and a 1,3-diazaazulene ring, which may or may not have one or more substituents or may be fused with one or more additional aromatic rings such as a benzene ring, a naphthalene ring, an anthracene ring, a pyridine ring, a pyrazine ring, and a pyrimidine ring.

In formula (VI), the nonmetal atoms represented by Z12 may, for instance, be comprised of one or more nitrogen, oxygen, sulfur and carbon atoms, which may or may not be substituted with one or more substituents and which form a 4- to 7-membered ring, which may be further fused to one or more additional rings. The substituents may, for example, be oxygen atoms, sulfur atoms, and oxygen-, sulfur- and nitrogen-containing groups.

Specific examples of ketomethylene rings completed through Z12 include a pyrazolone ring, an isoxazolone ring, an oxindol ring, a barbituric ring, a thiobarbituric ring, a rhodanine ring, an imidazo [1,2-a]pyridone ring, a 2-thio-2,4-oxazolidinedione ring, a 2-thio-2,5-thiazolidinedione ring, a thiazolidone ring, a 4-thiazolone ring, a 2-imino-2,4-oxazolinone ring, a 2,4-imidazolinedione ring (a hydantoin ring), a 2-thiohydantoin ring and a 5-imidazolone ring.

Specific examples of the compounds represented by formulae (IV) to (VI) are given below, but the present invention is not limited to these compounds:

The organic desensitizer is preferably present in a silver halide emulsion layer in an amount of from 1.0 x 10-8 to 1.0 x 10-4 mol/m2, and more preferably -7 -5 2 from 1.0 x 10 7 to 1.0 x 10 5 mol/m2.

The emulsion layers or other hydrophilic colloid layers of the photographic materials of the present invention can contain water-soluble dyes as safelight dyes or anti-irradiation dyes or for other various purposes. Water-soluble dyes suitable as safelight dyes are dyes for further reducing photographic sensitivity, and preferably ultraviolet absorbents having a spectral absorption maximum in an inherent sensitivity region of silver halide, and dyes for ensuring safety against safelight under which the bright room-type photographic materials are processed, and preferably those showing substantial light absorption in the region of from 380 nm to 600 nm.

These dyes are preferably incorporated into the emulsion layers or layers above the silver halide emulsion layers, i.e., light-insensitive hydrophilic colloid layers farther from a support than the silver halide emulsion layers according to the end use and fixed therein with the aid of a mordant.

The amount of the ultraviolet absorbent to be added, though varying depending on molar extinction coefficient, usually ranges from 10-2 to 1 g/m2, and preferably from 50 to 500 mg/m2.

Incorporation of the ultraviolet absorbent in a coating solution can be carried out by dissolving it in an appropriate solvent, such as water, alcohols (e.g., methanol, ethanol, propanol, etc.), acetone, methyl cellosolve, etc., and mixtures thereof, and dispersing the solution in a coating solution.

The ultraviolet absorbent which can be used in the present invention includes aryl-substituted benzotriazole compounds, 4-thiazolidone compounds, benzo phenone compounds, cinnamic ester compounds, butadiene compounds, benzoxazole compounds, and ultraviolet absorbing polymers. Specific examples of these ultraviolet absorbents are described in U.S. Patents 3,533,794, 3,314,794 and 3,352,681, Japanese Patent Application (OPI) No. 2784/71, U.S. Patents 3,705,805, 3,707,375, 4,045,229, 3,700,455 and 3,499,762, West German Patent Application (OLS) o. 1,547,863, etc.

Specific but nonlimiting examples of the ultraviolet absorbents usable in the present invention are shown below.

The safelight dyes which can be used in the present invention include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. From the standpoint of minimizing color retention after development processing, water-soluble dyes or dyes decolorizable with an alkali or a sulfite ion are preferred. Examples of such filter dyes are the pyrazoloneoxonol dyes disclosed in U.S. Patent 2,274,782; the diarylazo dyes disclosed in U.S. Patent 2,956,879; the styryl dyes or butadienyl dyes disclosed in U.S. Patents 3,423,207 and 3,384,487; the merocyanine dyes disclosed in U.S. Patent 2,527,583; the merocyanine dyes or oxonol dyes disclosed in U.S. Patents 3,486,897, 3,652,284 and 3,718,472; the enaminohemioxonol dyes disclosed in U.S.

Patent 3,976,661; and the dyes disclosed in British Patents 584,609 and 1,177,429, Japanese Patent Applica tionj (OPI) Nos. 85130/73, 99620/74 and 114420/74, U.S.

Patents 2,533,472, 3,148,187, 3,177,078, 3,247,127, 3,540,887, 3,575,704 and 3,653,905.

Specific examples of these filter dyes can be represented by the following formulae (VII) to (XII).

Formula (VII) is represented by

wherein Z' represents a nonmetal atomic group necessary for forming a benzothiazole ring, a naphthothiazole ring or a benzoxazole ring; R50 represents a substituted or unsubstituted alkyl group; R51 and R52, which may be the same or different, each represents a hydrogen atom, an alkoxy group, a dialkylamino group or a sulfo group; ' represents an anion; and m' represents 1 or 2.

In formula (VII) when m' is 1, the compound is in the form of an inner salt.

Substituents for the alkyl group which may be substituted of 250 include an alkoxy group (preferably having from 1 to 20 carbon atoms), an aryloxy group (preferably having from 6 to 10 carbon atoms), an alkoxycarbonyl group (preferably having from 2 to 20 carbon atoms), a carboxy group, a sulfo group, a halogen atom, a hydroxy group, an aryl group (preferably having from 6 to 10 carbon atoms), and a cyano group.

Specific examples of the anion of X' are a halogen anion (e.g., chloride, bromide and iodide), a perchlorate, a tetrafluoroborate, a hexafluorophosphate, a p-toluenesulfonate, a methanesulfonate, and an ethylsulfonate.

Formula (Vm) is represented by

wherein Q' represents an atomic group necessary for forming a pyrazolone ring, a barbituric acid ring, a thiobarbituric acid ring, an isoxazolone ring, a 3oxythionaphthene ring or a 1,3-indanedione ring; and R53 and R54, which may be the same or different, each represents a hydrogen atom, an alkoxy group, a dialkylamino group or a sulfo group.

Formula (IX) is represented by

wherein Z', Q' and R50 are as defined above; and n1 represents 1 or 2.

Formula (X) is represented by

wherein Q' is as defined above; R55 represents a hydrogen atom or a halogen atom; M' represents a hydrogen atom, a sodium atom or a potassium atom; and n2 represents 1 or 2.

Formula (XI) is represented by

wherein Y' represents an alkyl group or a carboxyl group; and R56, R57, R58, R59 and R60, which may be the same or different, each represents a hydrogen.atom, an alkyl group, a hydroxyl group, an amino group, an acylamino group, a carboxyl group or a sulfo group.

Formula (XII) is represented by

wherein R61, R62, R63r R64, R65, R66 and R67, which may be the same or different, each represents a hydrogen atom, an alkyl group, a hydroxyl group, an amino group, an acylamino group, a carboxyl group or a sulfo group, or R62 and R63 are taken together to form a benzene ring.

Among the dyes represented by formulae (VII) to (XII), preferred are acid dyes having an acid radical, e.s., a sulfo group, a carboxyl group, etc., in the molecule. Specific examples of the acid dyes are shown below.

These dyes can be used as a combination of two or more of them.

The dyes of the present invention are used in an amount necessary for the possibility of the treatment in a bright room of the photographic materials.

The amount of the dye to be used can be found within the range of, in general, from 10-3 g/m2 to 1 g/m2 especially from 10-3 g/m2 to 0.5 g/m2.

As the binder or protective colloid for the photographic emulsion of the present invention there is advantageously used a gelatin, and other hydrophilic colloids can of course be used. For instance, cellulose derivatives such as carboxymethyl cellulose, etc.; saccharide derivatives such as dextran, starch derivatives, etc.; and other various kinds of synthetic hydrophilic polymer substances such as homo- or copolymers, for example, polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polyacrylamide, etc., can be used As the gelatin there can be used a limeprocessed gelatin and an acid-processed gelatin.

The silver halide emulsion for use in the present invention may or may not be chemically sensitized. For the chemical sensitization of the silver halide emulsion there are known various methods of sulfur sensitization, reduction sensitization and noble metal sensitization, and the emulsion may be chemically sensitized by any of the methods singly or by combination of any of the methods.

As the noble metal sensitization method, a gold sensitization is typical, using a gold compound, mainly a gold complex. Compounds of noble metals other than gold, such as complexes of platinum, palladium, iridium, etc., can of course be used together without any problem.

As the sulfur sensitizer there can be used, for example, sulfur compounds contained in gelatin as well as various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines, etc.

As the reducing sensitizer there can be used, for example, stannous salts, amines, formamidinesulfinic acids, silane compounds, etc.

The photographic materials of the present invention can contain various compounds for the purpose of inhibiting fog during the manufacture step of the materials, storage thereof and photographic processing thereof, or of stabilizing the photographic property of the materials. For instance, various compounds which are known as an antifoggant or stabilizer can be added to the photographic materials of the present invention, including azoles, such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitrobenzotriazoles, etc.; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethiones; azaindenes, such as triazaindenes, tetraazaindenes (especially 4hydroxy-substituted (1 ,3,3a,7) tetraazaindenes) , penta azaindenes, etc.; benzenethiosulfonic acids, benzenesulfinic acids, benzenesulfonic acid amides, etc. Among these compounds, preferable are benzotriazoles (e.g., 5methylbenzotriazole) and nitroindazoles (e.g., 5-nitroindazole).- These compounds can be incorporated in the processing solutions for the materials of the present invention.

The photographic materials of the present invention may also contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer. For instance, chromium salts, aldehydes (e.g., formaldehyde, glutaraldehyde, etc.), N-methylol compounds, active vinyl compounds (e.g., 1,3,5triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2propanol, etc.), active halogen compounds (e.g., 2,4dichloro-6-hydroxy-s-triazine, etc.), mucohalogenic acids, epoxy compounds, etc., can be used singly or in combination, as the hardener.

Further, the photographic materials of the present invention may also contain various surfactants in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of coating assistance, impartation of antistatic property, improvement of sliding property, emulsification and dispersion, prevention of adhesion, and improvement of photographic charac teristics (including acceleration of developability, elevation of contrast and intensification of sensitization), etc.

For instance, nonionic surfactants, such as saponins (e.g., steroid type saponins), alkylene oxide derivatives (e.g.,-polyethylene glycol, polyethylene glycol/polypropylene glycol condensation product, polyethylene glycol alkyl ethers, polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, silicone-polyethylene oxide adducts), glycidol derivatives (e.g., alkenylsuccinic acid polyglyceride; alkylphenol polyglyceride), esters of polyhydric alcohols and fatty acids, alkyl esters of saccharides, etc.; anionic surfactants containing an acid group such as a carboxyl group, a sulfo group, a phospho group, a sulfate group or a phosphate group, for example, alkylcarboxylic acid salts, alkylsulfonic acid salts, alkylbenzenesulfonic acid salts, alkylnaphthalenesulfonic acid salts, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyltaurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc.; ampholytic surfactants such as amino acids, aminoalkylsulfonic acids, aminpalkyl sulfates or phosphates, alkylbetaines, amine oxides, etc.; and cationic surfactants such as alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts (e.g., pyridinium or imidazolium salts), aliphatic or heterocyclic phosphonium or sulfonium salts, etc., can be used.

The polyalkylene oxides having a molecular weight of 600 or more, described in Japanese Patent Publication No. 9412/83, are especially preferably used as the surfactant in the present invention. In addition, a polymer latex such as a polyalkyl acrylate can be incorporated into the photographic material of the present invention so as to ensure the dimensional stability.

In order to attain the superhigh contrast photographic characteristic of the silver halide photographic material of the present invention, it is unnecessary to use a conventional infectious developer or the high alkali developer having a pH value of near 13, such as is described in U.S. Patent 2,419,975, but a stable developer can be used.

For instance, the silver halide photographic material of the present invention can satisfactorily be developed with a developer containing a sulfite ion, as a preservative, in an amount of 0.15 mol/liter or more and having a pH value of from 10.5 to 12.3, especially from 11.0 to 12.0, whereby a sufficiently superhigh contrast negative image can be obtained.

The developing agent for use in the development of the photographic material of the present invention is not specifically limitative, but any of dihydroxybenzenes (e.g., hydroquinone, 3-pyrazolidones (e.g., 1-phenyl-3pyrazolidone, 4,4-dimethyl-1-phenyl-3-pyrazolidone), aminophenols (e.g., N-methyl-p-aminophenol), etc., can be used singly or in combination.

The silver halide photographic materials of the present invention are especially preferably developed with a developer containing a dihydroxybenzene compound as a developing agent and a 3-pyrazolidone or aminophenol compound as an auxiliary developing agent. Advantageously, the developer contains the dihydroxybenzene compound in an amount of from 0.05 to 0.5 mol/liter and the 3pyrazolidone or aminophenol compound in an amount of 0.06 mol/liter or less.

Further, an amine compound can be added to the developer, as described in U.S. Patent 4,269,929, so as to accelerate the development speed and to realize a shortening of the development time.

Further, the developer may also contain, in addition to the above-mentioned components, a pH buffer such as an alkali metal sulfite, carbonate, borate or phosphate, as well as a development inhibitor or antifoggant such as a bromide, an iodide, an organic antifoggant (especially preferably nitroindazoles or benzotriazoles), etc. Moreover, the developer may further contain, if desired, a hard water softener, a dissolution aid, a toning agent, a development accelerator, a surfactant (especially preferably the above-mentioned polyalkylene oxides), a defoaming agent, a hardener, a film silver stain inhibitor (such as 2-mercaptobenzimidazolesulfonic acids, etc.), etc.

As the fixing solution, any one having a conventional composition can be used. As the fixing agent there can be used thiosulfates and thiocyanates as well as other organic sulfur compounds which are known to have an effect as a fixing agent. The fixing solution can contain a water-soluble aluminum salt or the like as a hardener.

The processing temperature for the photographic materials of the present invention can be selected, in general, from the range of from 180C to 500C.

For the photographic processing of the materials of the present invention, an automatic developing machine is preferably used. The total processing time from the introduction of the photographic material of the present invention into the automatic developing machine to the taking out of the material processed therefrom can be set to fall within the range of from 90 seconds to 120 seconds, whereby an excellent photographic characteristic with a sufficiently superhigh contrast negative gradation can be obtained.

The developer for use in the processing of the material of the present invention can contain the compound described in Japanese Patent Application (OPI) No. 24347/81 as a silver stain inhibitor. As a dissolution aid to be added to the developer there can be used the compound described in Japanese Patent Application (OPI)-No. 267759/86. Further, the compound described in Japanese Patent Application (OPI) No. 93433/85 or the compound described in Japanese Patent Application (OPI) No. 28708/86 can be incorporated into the developer as a pH buffer.

Supports which can be used in the present invention include cellulose acetate film, polyetlylene terephthalate film, polystyrene film, polyethylene film or synthetic films thereof.

The following examples are intended to illustrate the present invention but not to limit it in any way.

In the examples, the developer having the following composition was used.

Developer: Hydroquinone 45.0 g N-methyl-p-aminophenol.l/2 sulfate 0.8 g Sodium Hydroxide 18.0 g Potassium Hydroxide 55.0 g 5-Sulfosalicylic Acid 45.0 g Boric Acid 25.0 g Potassium Sulfite 110.0 g Disodium Ethylenediamine-tetraacetate 1.0 g Potassium Bromide 6.0 g 5-Methylbenzotriazole 0.6 g n-Butyl-diethanolamine 15.0 g Water to make 1 liter (pH = 11.6) EXAMPLE 1 An aqueous silver nitrate solution and an aqueous sodium chloride solution were blended at a time in an aqueous gelatin solution kept at 30 C, in the presence of 1.1 x 10-5 mol, per mol of silver, of (NH4)3RhCl6, to form silver chloride grains, and the soluble salts were removed in a conventional manner which was well known in this technical field.Afterwards, gelatin was added, and without chemical ripening, 2-methyl-4-hydroxy-l,3,3a,7tetraazaindene was added as a stabilizer. The thus-formed emulsion was a monodispersed emulsion containing cubic crystals having a mean grain size of 0.08 pm. This emulsion was called Emulsion (A).

To this Emulsion (A) were added 70 mg/m2 of the hydrazine compound (I-30) and 50 mg/m2 of the nucleation accelerator (II-8), and then a polyethyl acrylate latex was further added thereto in an amount of 30% by weight of the solid content. Next, l,3-vinylsulfonyl-2-propanol was added thereto as a hardener, and the resulting emulsion was coated on a polyester support in an amount of 3.8 g/m2 as silver. The gelatin in the emulsion layer was 1.8 g/m2, and a protective layer comprising 1.0 g/m2 of gelatin was overcoated. The sample was called Sample (1 A).

The same process was repeated except that only the amount of the (NH4)3RhCl6 was varied, and Emulsions (B), (C) and (D) were prepared. Using each of these emulsions, Samples (l-B) to (l-D) were prepared in the same manner as the preparation of Sample (l-A).

(preparation of Comparative Samples) An aqueous silver nitrate solution and an aqueous sodium chloride solution were blended at a time in an aqueous gelatin solution kept at 450C, in the presence of 1.1 x 10-5 mol, per mol of silver, of (NH4)3RhCl6, to form silver chloride grains, and the soluble salts. were removed in a conventional manner which was well known in this technical field. Afterwards, gelatin was added and, without chemical-ripening, 2-methyl-4-hydroxy-l,3,3a,7tetraazaindene was added as a stabilizer. The thus-formed emulsion was a monodispersed emulsion containing cubic grains having a mean grain size of 0.16 pm. This emulsion was called Emulsion (a).

Using Emulsion (a), ' the process for the preparation of Sample (l-A) as above was repeated, to obtain Sample (l-a). In addition, other samples were also prepared in the same manner, using Emulsion (b), (c), (d), (e) or (g), which had been prepared in the sane manner as the preparation of Emulsion (a) except that the amount of (NH4)3RhCl6 was varied, and the thus-formed samples were called Samples (l-b) to (l-d) and (l-m) and (l-n), respectively, as shown in Table 1 below.

On the other hand, Emulsions (E), (G) and (H) were prepared in the same manner as the preparation of Emulsion (A) except that only the amount of (NH4)3RhCl6 was varied, and still other samples were further prepared also in the same manner as the preparation of Sample (1-A), using Emulsion (E), (G) or (H). The thus-formed samples were called Samples (l-M), (l-N) and (l-L), respectively, as shown in Table 1 below.

These samples were exposed with a printer for use in bright-room, P-607 (manufactured by Dainippon Screen Mfg. Co., Ltd.) through an optical wedge, developed with the above-mentioned developer at 380C for 30 seconds, fixed, rinsed with water and dried. The photographic results obtained are shown in Table 1. Next, using the samples, a positive original film having 6th grade Mingcho type letters was printed by contact print with P-607 Printer through two sheets of transparent PET base having a thickness of 100 pm under such exposure that the dot area by the contact exposure was a ratio of 1/1, and thereafter processed in the same manner as above. The super-imposed letter image quality of the negative film thus obtained was evaluated, and the results are shown in Table 1.For the evaluation, the mark "0" means that the grade letters were cleared; the mark "A" means that the clearing was somewhat insufficient but the negative could be put in practical use; and the mark "X" means that the clearing was bad and the negative could not be put in practical use.

Table 1 super-imposed Sample Sensi- letter image Mean Grain No. Rh tivity G quality Size Emulsion Remarks (mol/mol-Ag) (#logE) ( m) 1-L 0 Type 40 # 0.08 H Comparison 1-M 0.5 x 10-5 -0.7 35 # " E " 1-A 1.1 x 10-5 -1.1 30 # " A Invention 1-B 5 x 10-5 -1.7 25 # " B " 1-C 1 x 10-4 -1.9 20 # " C " 1-D 4.8 x 10-4 -2.1 12 # " D " 1-N 5.5 x 10-4 -2.15 8 X " G Comparison 1-m 0.5 x 10-5 -0.55 20 # 0.16 e Comparison 1-a 1.1 x 10-5 -1.0 10 X " a " 1-b 5 x 10-5 -1.6 8 X " b " 1-c 1 x 10-4 -1.8 6 X " c " 1-d 4.8 x 10-4 -2.0 5 X " d " 1-n 5.5 x 10-4 -2.05 4 X " g " The sensitivity was represented by the difference of the sensitiveity point in the density 1.5.

G is represented by the following formula: 3.0 - 0.3 G= Difference of Sensitivity Point Between Density 3.0 and Density 0.3 The above results indicate that the remarkable sensitivity lowering, the high G and the sufficient superimposed letter image quality could be attained at the same time in the samples of the present invention which satisfied both the claimed range of the mean grain size and the claimed range of the Rh-content.

EXAMPLE 2 In the same manner as in the preparation of Emulsion (A) of Example 1, which was prepared at 300C, other three kinds of Emulsion (I), Emulsion (J) and Emulsion (K) were prepared whereupon the temperature in the grain formation was varied to 350C, 400C and 450C, respectively. Using each of these emulsions, Sample (2-A), Sample (2-B) and Sample (2-C) were prepared in the same manner as the preparation of Sample (l-A) using the same hydrazine compound and the same nucleation accelerater.

In the same manner as the preparation of Samples (2-A), (2-B) and (2-C), except that the Rh-content in the emulsion was varied as shown in Table 2 below, other Sample (2-a), Sample (2-b) and Sample (2-c) were preapred.

These samples were processed in the same manner as Example 1 for sensitometry and for practical evaluation, and the results obtained are shown in Table 2 below. Table 2 --------- Super-imposed Sample Mean Grain Sensi- Letter Image No. Rh Size tivity(*) G Quality Emulsion Remarks ------ -------------- -------------- ----------- --- ------------ ----------- --------- (mol/mol-Ag) (um) 2-A 1.1 x 10-5 0.10 -1.08 25 # I Invention (35 C) 2-a 4.8 x 10-4 " -2.07 14 # I " 2-B 1.1 x 10-5 0.14 -1.04 18 # J (40 C) 2-b 4.8 x 10-4 " -2.04 10.5 # J " 2-c 1.1 x 10-5 0.16 -1.0 10 x k Comparison (45 C) 2-c 4.8 x 10-4 " -2.0 5 x k " (*) This is represented by the sensitivity difference from the sensitivity of Sample (1-L) of Example 1.

Table 2 apparently indicates that the remarkable sensitivity lowering, the high G value and the sufficient letter-clearing property could be attained in the samples of the present invention which satisfied both the claimed range of the mean grain size and the claimed range of the Rh-contnet.

EXAMPLE 3 An aqueous silver nitrate solution and an aqueous sodium chloride solution were blended at a time in an aqueous gelatin solution kept at 250C, in the presence of 5 x 10-5 mol, per mol of silver, of (NH4)3RhC16, to form silver chloride grains, and the soluble salts were removed in a conventional manner which was welll known in this technical field. Afterwards, gelatin was added, and without chemical ripening, 2-methyl-4-hydroxy-1,3,3a,7tetraazaindene was added as a stabilizer. The thus-formed emulsion was a monodispersed emulsion containing cubic grains having a mean grain size of 0.06 pm.

To this emulsion was added the compounds as mentioned in Table 3 below, which were selected from the hydrazine compounds of the formula (I) and the nucleation accelerators of the formulae (II) and (III). Next, in the same manner as the preparation of Sample (1-A), Samples (3-A) to (3-I) were prepared, and these samples were processed and evaluated in the same manner as Example 1.

The results obtained are shown in Table 3 below.

Table 3 Nucleating Agent Nucleation super Accelerator imposed Sample Amount Amount letter image No. Kind Added Kind Added G quality Remarks (mg/m) (mg/m) 3-A I-21 15 II-8 50 22 # Invention 3-B I-30 70 " " 27 # " 3-C I-19 15 " " 24 # " 3-D I-21 15 III-7 20 20 # " 3-E I-30 70 " " 25 # " 3-F I-19 15 " " 22 # " 3-G I-21 15 - - 12 # " 3-H I-30 70 - - 14 # " 3-I I-19 15 - - 13 # " The results of Table. 3 apparently indicate that the intended G value and super-imposed letter image quality could be attained by the use of the nucleating agents of the present invention and that the super-imposed letter image quality could be improved by the nucleation accelerator of the present invention.

EXAMPLE 4 An aqueous silver nitrate solution and an aqueous sodium chloride solution were blended at a time in an aqueous gelatin solution kept at 300C, in the presence of 5 x 10-5 mol, per mol of silver, of (NH4)3RhCl6, to form silver chloride grains, and the soluble salts were removed in a conventional manner which was well known in this techical field. Afterwards, gelatin was added and, without chemical ripening, 2-methyl-4-hydroxy-l,3,3a-7tetraazaindene was added as a stabilizer. The thus-formed emulsion was called Emulsion (N).

On the other hand, a mixed solution comprising sodium chloride and potassium bromide was used in place of the aqueous sodium chloride solution and the same procedure as above was repeated to obtain three kinds of silver chlorobromide emulsions each having a different halogen composition as shown in Table 4 below. These emulsions were called Emulsion (O), Emulsion (P) and Emulsion (Q), respectively.

All of these emulsions were monodispersed emulsions each containing cubic grains having a mean grain size of 0.08 pm.

Using these emulsions, the coated Samples (4-A), (4-B), (4-C) and (4-D) were prepared in the same manner as the preparation of Sample (l-A) of Example 1.

In order to test the safe light-stability of these samples, they were irradiated by a UV-cut fluorescent lamp NU/M (manufactured by Toshiba Corporation.) of 200 lux for 30 minutes and then processed with the same processing solution as Example 1. The fog value of each of the thusprocessed samples was measured, and the practical usability of the fog value was evaluated.

The results are shown in Table 4 below.

Table 4 Evaluation Sample Halogen of Fog Value No. Emulsion Composition Fog Value Practical Femarks 4-A N AgCl 0.03 Practical Invention 4-B O AgClBr 0.035 " " (Br : 5 mol%) 4-C P AgClBr 0.04 " " (Br : 10 mol%) 4-D Q AgClBr 0.10 Impractical Comparison (Br : 15 mol%) The results of Table 4 indicate that the samples having the halogen composition falling within the scope of the present invention are practical.

EXAMPLE 5 Sample (5-A) was prepared in the same manner as the preparation of Sample (4-A) of Example 4, provided that 3 mg/m2 of the compound (IV-2) was further added.

Also in the same manner, other four kinds of Samples (5 B), (5-C), (5-D) and (5-E) were prepared, provided that the Compound (IV-8), (IV-37), (V-l) and (VI-2) were added, respectively, each in an amount of 3 mg/m2.

The thus-formed samples were irradiated with a 400 lux UV-cut fluorescent lamp NU/M (manufactured by Thoshiba Corporation) for 1 hour, subjected to sensitometry exposure and then processed with the processing solution of Example 1, in the same manner as Example 1, for sensitometry and for testing the safe-light stability.

The fluctuation of the sensitivity of each sample was measured.

In addition, the super-imposed letter image quality was also tested in the same manner as Example 1.

The results obtained are shown in Table 5 below. Table 5 Super-imposed Sample Desensitizing agent Sensi- Letter Image Safe-light No. Kind Amount Added tivity G Quality Stability Remarks (mg/m) (#logE)* 4-A - - type 25 # +0.3 Invention 5-A IV-2 3 -0.06 23 # +0.15 " 5-B IV-8 " -0.08 20 # +0.15 " 5-C V-1 " -0.15 15 # +0.20 " 5-D IV-22 " -0.1 12 # +0.13 " 5-E VI-2 " -0.15 13 # +0.20 " (*) The value means the difference of sensitivity between after and before irradiation.

The results of Table 5 indicate that the sensitivity was lowered and the safe-light stability was improved by the addition of the compound of the present invention (as represented by the above-mentioned formula (IV), (V) or (VI)). In addition, the super-imposed letter image quality was also noted to be improved to practical level, while the safe-light stability was maintained.

EXAMPLE 6 Polyethyl acrylate latex, in an amount of 30% by weight to gelatin, and l,3-vinylsulfonyl-2-propanol, as a hardener, were added to each of Emulsions (A), (B), (C), (D), (E), (G) and (H) as prepared in Example 1 and Emulsions (I), (J) and (K) as prepared in Example 2, and each of the resulting emulsions was coated on a polyester support in an amount of 3.8 g/m2 as silver. The gelatin content in the emulsion layer was 1.8 g/m2, and a protective layer comprising 1.0 g/m2 of gelatin was overcoated. The thus-formed samples were called Samples (6-A), (6-B), (6-C), (6-D), (6-M), (6-N), and (6-L), and (6-a), (6-b) and (6-c), respectively.

These samples were exposed with a printer for use in a bright-room, P-607 (manufactured by Dainippon Screen Mfg. Co., Ltd.) through an optical wedge, developed with the above-mentioned developer at 380C for 30 seconds, fixed, rinsed with water and dried. The photographic results obtained are shown in Table 6 below.

Next, using these samples, an original formed by sticking a 100 um fine line positive film (100 um PET base) to a transparent sticking base was printed by contact print with P-607 Printer through two sheets of transparent PET base having a thickness of 100 pm under such exposure that the dot area by the contact exposure was a ratio of 1/1, and thereafter processed in the same manner as above. The degree of the broken fine lines in the negative film obtained and the edge trace of the original were evaluated. For evaluation, the mark "0" means that the fine lines were cleared; the mark "A" means that the clearing was somewhat insufficient; and the mark "X" means that the fine lines were not cleared.

Regarding the evaluation of the edge trace, the mark "0" means that no trace was found; the mark "A" means that the trace was somewhat found; and the mark "X" means that the trace was distinctly found (or that is, the trace was cleared white). The evaluation of the sensitivity and that of the value G were same as those in Example 1. Table 6 Mean Sample Grain Sensi- Clearing No. Emulsion Rh Size tivity of Fige Edge (mol/mol-Ag) ( m) (#logE) G Lines Trace Remarks 6-A A 1.1 x 10-5 0.08 -1.15 7.0 # # Invention 6-B B 5 x 10-5 " -1.8 6.0 # # " 6-C C 1 x 10-4 " -2.1 5.0 # # " 6-D D 4.8 x 10-4 " -2.3 4.0 # # " 6-M E 0.5 x 10-5 " -0.7 7.2 # X Comparison 6-N G 5.5 x 10-4 " -2.35 3.2 X # " 6-a I 1.1 x 10-5 0.10 -1.12 6.0 # # Invention 6-b J 1.1 x 10-5 0.14 -1.08 4.0 # # " 6-c K 1.1 x 10-5 0.16 -1.05 3.2 X # Comparison 6-L H - 0.08 Type 7.2 # X " The results of Table 6 indicate that both the clearing of fine lines and the edge trace were good in the samples having the claimed rhodium (Rh) content and the claimed mean grain size.

Claims

CLAIMS:

1. A negative type silver halide photographic material which comprises a support having thereon at least one layer of a silver halide photographic silver chloride or silver chlorobromide emulsion containing 10 mol% or less bromide, wherein the grains of said silver halide have a mean grain size of 0.15 um or less and the silver halide emulsion contains a rhodium salt in amount of more than 10 5 but less than 5 X 10 4 mol per mol of silver.

2. A negative type silver halide photographic material as in Claim 1, wherein the mean grain size of silver halide grains in said silver halide emulsion layer is from 0.04 vm to 0.13 um.

3. A negative type silver halide photographic material as in Claim 1 or 2, wherein the rhodium salt contained in aid silver halide emulsion layer is a water-soluble trivalent rhodium halogeno-complex compound.

4. A negative type silver halide photographic material as in Claim 1, 2 or 3, wherein the amount of the rhodium salt contained in said silver halide emulsion layer is 1.1 X 10 5 to 4.0 X 10 4 mol per mol of silver.

5. A negative type silver halide photographic material as in any of Claims 1 to 4, wherein said silver halide emulsion layer also contains a hydrazine derivative represented by the general formula (I):

wherein A represents a substituted or unsubstituted aliphatic or aromatic group;B represents a formyl group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfinamoyl group, an alkoxysulfonyl group, a thioacyl group, a thiocarbamoyl group, or a heterocyclic group; and both Xo and Yo represent hydrogen atoms, or one of X0 and Y0 represents a hydrogen atom and the other represents a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group; provided that B, Yo and the nitrogen atom to which they are bonded may form the partial structure -N=Cs of hydrazone.

6. A negative type silver halide photographic material as in Claim 5, wherein the compound represented by formula (I) is contained in an amount of from 1 x 10-6 to 5 x 10-2 mol per mol of silver halide in said emulsion layer.

7. A negative type silver halide photographic material as in Claim 6, wherein the compound represented by formula (I) is contained in an amount of from 1 x 10-5 to 2 x 10-2 mol per mol of silver halide in said emulsion layer.

8. A negative type silver halide photographic arterial as in Claim 5, 6 or 7, wherein the photographic material also contains;a compound represented by formula (II): Y*(X)n A'-B' 3 m (11) wherein Y represents a group capable of being absorbed in silver halide; X represents a divalent linking group comprising an atom or atoms selected from a hydrogen atom, a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom, or an atomic group comprised of the atoms; A' represents a divalent linking group;B' represents a substituted or unsubstituted amino group, an ammonium group or a nitrogen-containing heterocyclic group; m represents Ir 2 or 3; and n represents 0 or 1; or a compound represented by the formula (III):

wherein R21 and R22 each represents a hydrogen atom or an aliphatic residual group; R21 and R22 may be linked together to form a ring; R23 represents a divalent aliphatic group; X' represents a divalent hetero-ring residual group containing at least one of nitrogen, oxygen, and sulfur atoms; n' represents 0 or 1; and M' represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, a quaternary ammonium group, a quaternary phosphonium group or an amidino group.

9. A negative type silver halide photographic material as in Claim 8, wherein the compound represented by formula (II) or (III) is contained in the silver halide emulsion layer of the photographic material.

10. A negative type silver halide photographic material as in Claim 9, wherein the compound represented by formula (II) is contained in an amount of from 1 x 10-3 to 0.5 g/m2.

11. A negative type silver halide photographic material as in Claim 10, wherein the compound represented by formula (II) is contained in an amount of from 5 x 10-3 to 0.3 g/m2.

12. A negative type silver halide photographic material as in Claim 9, wherein the compound represented by formula (III) is contained in an amount of from 1 x 103 3 to 0.5 g/m2.

13. A negative type silver halide photographic material as in Claim 12, wherein the compound represented by formula (III) is contained in an amount of from 5 x 103 to 0.1 g/m2.

14. A negative type silver halide photographic material as in any preceding claim, wherein said silver halide emulsion layer further comprises an organic desensitizer.

15. A negative type silver halide photographic material as in Claim 14, wherein the organic desensitizer has at least one water-soluble group or alkali dissociating group.

16. A negative type silver halide photographic material as in Claim 14 or 15, wherein the organic desensitizer is contained in an amount of from 1.0 x 10-8 to 1.0 x 10-4 mol/m2.

17. A negative type silver halide photographic material as in Claim 16, wherein the organic desensitizer is contained in an amount of from 1.0 x 10-7 to 1.0 x 10-5 mol/m2.

18. A negative type silver halide photographic material as claimed in Claim 1, substantially as described with reference to any of the Examples according to the invention.

19. A method of photography which comprises imagewise exposing and developing a photographic material as claimed in any preceding claim.

20. A method as claimed in Claim 19, wherein the development is with a developer containing a dihydroxybenzene compound and a 3-pyrazolidone or aminophenol compound.

21. A photograph made by the method of Claim 19 or 20.