JP3339666B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material containing a hydrazide compound having a specific structure.

[0002]

2. Description of the Related Art In the field of graphic arts, an image forming system exhibiting photographic characteristics of ultra-high contrast (especially γ is 10 or more) in order to improve reproduction of continuous tone images or line images by halftone images. is necessary.
There has been a demand for an image forming system which can develop with a processing solution having good storage stability and obtain ultra-hard photographic characteristics. One of them is U.S. Pat. Nos. 4,166,742 and 4,16.
8,977, 4,221,857, 4,22
4,401, 4,243,739, 4,27
As can be seen in JP-A Nos. 2,606 and 4,311,781, a surface latent image type silver halide photographic material to which a specific acylhydrazine compound has been added is used.
A system has been proposed which forms a negative image having a super-high contrast of more than 10 by processing with a developer having a pH of 11.0 to 12.3 containing 5 mol / l or more. This new image forming system can use only silver chlorobromide having a high silver chloride content in conventional ultra-high contrast image formation, but can also use silver iodobromide and silver chloroiodobromide. There is. Another characteristic is that the conventional squirrel developer can contain only a trace amount of the sulfite preservative, whereas it can contain a large amount of the sulfite preservative, so that the storage stability is relatively good. . However, a developer having a pH of 11 or more is easily oxidized by air, is unstable, and cannot withstand long-term storage or use. There have been attempts to develop a silver halide photosensitive material containing a hydrazine compound with a developer having a lower pH to form a high contrast image. JP-A-1-179939 and JP-A-1-179940 disclose a photographic material containing a nucleation development accelerator having an adsorptive group for silver halide emulsion grains and a nucleator having the same adsorptive group, and a pH of 11 or more. A processing method of developing with a developer of 0.0 or less is described. However, the emulsions used in these inventions are silver bromide and silver iodobromide emulsions, and the photographic performance varies greatly with the development progress or the composition fluctuation of the processing solution, and is not sufficient in terms of stability. I can't say.

[0003] US Patent No. 4,998,604,
994,365 and 4,975,354 disclose a hydrazine compound having a repeating unit of ethylene oxide and a hydrazine compound having a pyridinium group. However, from the description of the examples, in these inventions, high contrast is not sufficient, and it is difficult to obtain high contrast and necessary Dmax under practical development processing conditions. A nucleation-sensitive material using a hydrazine derivative has a large change in photographic properties due to a change in the pH of a developer. The pH of the developing solution fluctuates greatly due to an increase due to air oxidation of the developing solution and concentration due to evaporation of water, or a decrease due to absorption of carbon dioxide in the air. Accordingly, attempts have been made to reduce the dependence of photographic performance on the developer pH.

[0004] By the way, the returned photographic material generally handled in the light room is one of the photographic materials for plate making, which covers a large field. In this field, there is a demand for a high blank character quality that can reproduce thin Mincho characters. I have. Therefore, development of a nucleating agent having higher activity has been desired. In particular, in a low-sensitivity light-sensitive material that can be handled in a light room, the nucleating agent is unlikely to harden, and the development of a highly active nucleating agent is desired.

In order to achieve such an object, highly active hydrazine-based nucleating agents disclosed in, for example, JP-A-6-148828, JP-A-6-180477, JP-A-6-194774 and the like have been developed. In particular, a nucleating agent having a substituted alkyl group substituted with at least one electron-withdrawing group as an acyl group can obtain extremely hard photographic properties even in a developing solution having a pH of 11 or less, and can provide photographic performance due to fatigue of the developing solution. However, the nucleating agent itself was easily oxidized, and some of the nucleating agents needed to be improved in terms of storage stability.

JP-A-64-86134, JP-A-4-1
No. 6,938, and JP-A-5-197091 disclose compounds in which two hydrazino groups are incorporated in a molecule. In particular, Japanese Unexamined Patent Publication (Kokai) No. 5-197091 discloses some compounds which are superior in terms of contrast enhancement performance as compared with conventional acylhydrazine compounds having the same acyl group, but these compounds have a pH of 11 or less. They were not sufficiently satisfactory in terms of high contrast in the developer, stability against fluctuation factors of the processing solution, storage stability, and the like.

On the other hand, a method of directly obtaining a positive image by developing a surface of an internal latent image type silver halide photographic emulsion in the presence of a nucleating agent and a photographic emulsion or a light-sensitive material used in such a method are described in, for example, US Pat. 2,456,953, 2,497,875, 2,497,876, 2,588,982, 2,592,250, 2,675,318, 3, 227,552 and 3,317,322, British Patent 1,011,062
Nos. 1,151,363 and 1,269,640
No. 2,011,391, JP-B-43-29405
No. 49-38164, JP-A-53-16623.
No. 53-137133, No. 54-37732.
No. 54-40629, No. 54-74536, No. 54
-74729, 55-52055 and 55-90
940 and the like. In the above method for obtaining a direct positive image, a nucleating agent may be added to a developer, but a more general method is to add the nucleating agent to a photographic emulsion layer or another appropriate layer of a light-sensitive material.

As the nucleating agent to be added to the direct positive silver halide light-sensitive material, a hydrazine compound is best known, specifically, Research Disclosure No. 23510 (November 1953), 15162. (1
November 976, Volume 151) and 17626 (1
Vol. 176, December 978). Generally, the maximum concentration of hydrazine nucleating agent (Dmax)
And the minimum concentration (Dmin) are large, and are the best in terms of discrimination.
(PH 11 or more), and there is a demand for improvement.

[0009]

Accordingly, an object of the present invention is to firstly provide a silver halide photographic light-sensitive material capable of obtaining extremely hard photographic properties having a gamma exceeding 10 using a stable developing solution. It is in. A second object of the present invention is to provide a silver halide photographic light-sensitive material for plate making having high processing stability and excellent storage stability. A third object of the present invention is to provide a direct positive photosensitive material which shows sufficient reversibility even with a low pH processing solution when added in a small amount.

[0010]

These objects of the present invention have been attained by a silver halide photographic material characterized by containing a hydrazine compound represented by the following general formula (I) or (II). . General formula (I) A _1- (B) b ₁ General formula (II) L _0- {A _2- (B) b ₂ } m _{1 In the} formula, A ₁ represents a substituted or unsubstituted benzene ring;
₂ represents an arylene group, B represents a group represented by the following general formula (III), and b ₁ represents an integer of 3 to 6. L ₀ is 2
Represents a hexavalent linking group from the valence, b ₂ represents an integer of from 1 5, m ₁ represents an integer of 2 to 6. However, when b ₂ is 1,
m ₁ represents an integer of 3 to 6. Formula (III) -L ₁ -Ar ₁ -NHNH-G ₁ -R _{1 In the} formula, G ₁ represents a carbonyl group, an oxalyl group, a sulfonyl group, or a phosphoryl group, and R ₁ represents a hydrogen atom or a block group. Ar ₁ represents an aromatic group, and L ₁ represents a linking group.

[0011]

Next, the compounds of the present invention will be described in detail. In the general formula (I), A ₁ represents a substituted or unsubstituted benzene ring.

In the present invention, the substituent means a halogen atom or a substituent bonded to a ring or a main chain by a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom. As those bonded by carbon atoms, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, carbamoyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, acyl groups,
Acyl carbamoyl group, sulfonyl carbamoyl group, carboxyl group or a salt thereof, cyano group, heterocyclic group,
As a group bonded with an oxygen atom, a hydroxy group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, a sulfonyloxy group is a group bonded with a nitrogen atom, an acylamino group,
Amino group, alkylamino group, arylamino group, heterocyclic amino group, ureido group, sulfamoylamino group,
Alkoxycarbonylamino groups, aryloxycarbonylamino groups, sulfonamide groups, imide groups, and heterocyclic groups, which are bonded by a sulfur atom, include an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfamoyl group, and an acylsulfamoyl group. , An alkoxysulfonyl group, an aryloxysulfonyl group, a sulfonyl group, a sulfo group or a salt thereof, and a sulfinyl group. These may be further substituted with a substituent.

The substituent will be described in more detail. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. The alkyl group is a linear, branched or cyclic alkyl group having 1 to 16 carbon atoms, preferably 1 to 10 carbon atoms, such as methyl, ethyl, isopropyl, t
-Butyl, benzyl, cyclopentyl. The alkenyl group has 2 to 16 carbon atoms, for example, vinyl,
Examples include 1-propenyl, 1-hexenyl, styryl and the like. The alkynyl group has 2 to 16 carbon atoms,
For example, ethynyl, 1-butynyl, 1-dodecenyl, phenylethynyl and the like can be mentioned. The aryl group is an aryl group having 6 to 24 carbon atoms, for example, phenyl, naphthyl and p-methoxyphenyl.

The carbamoyl group has 1 to 18 carbon atoms, for example, carbamoyl, N-ethylcarbamoyl, N-octylcarbamoyl and N-phenylcarbamoyl. The alkoxycarbonyl group has 2 carbon atoms.
~ 18, for example, methoxycarbonyl and benzyloxycarbonyl. The aryloxycarbonyl group has 7 to 18 carbon atoms and is, for example, phenoxycarbonyl. The acyl group has 1 to 18 carbon atoms, such as acetyl and benzoyl. The heterocyclic group linked by a carbon atom on the ring is a 5- or 6-membered saturated or unsaturated heterocyclic ring having at least one oxygen atom, nitrogen atom or sulfur atom having 1 to 5 carbon atoms. The number of heteroatoms constituting the ring and the types of elements may be one or more, for example, 2-furyl, 2-thienyl,
2-pyridyl and 2-imidazolyl. The acylcarbamoyl group has 1 to 18 carbon atoms, for example, N-
Acetylcarbamoyl and N-benzoylcarbamoyl. Examples of the sulfonylcarbamoyl group include those having 1 to 1 carbon atoms.
18, for example, N-methanesulfonylcarbamoyl and N-benzenesulfonylcarbamoyl.

The alkoxy group has 1 to 16 carbon atoms, preferably 1 to 10 carbon atoms, for example, methoxy, 2
-Methoxyethoxy, 2-methanesulfonylethoxy. The aryloxy group has 6 to 24 carbon atoms and includes, for example, phenoxy, p-methoxyphenoxy, m-
(3-hydroxypropionamide) phenoxy. The heterocyclic oxy group is a 5- or 6-membered saturated or unsaturated heterocyclic oxy group containing at least one oxygen atom, nitrogen atom or sulfur atom having 1 to 5 carbon atoms, which forms a ring. The number of atoms and the type of element may be one or more, for example, 1-phenyltetrazolyl-5-oxy, 2-tetrahydropyranyloxy,
2-pyridyloxy. The acyloxy group has 1 to 16 carbon atoms, preferably 1 to 10 carbon atoms, and includes, for example, acetoxy, benzoyloxy and 4-hydroxybutanoyloxy. The carbamoyloxy group has 1 to 16 carbon atoms, preferably 1 to 10 carbon atoms, and examples thereof include N, N-dimethylcarbamoyloxy, N-hexylcarbamoyloxy and N-phenylcarbamoyloxy. The sulfonyloxy group has 1 to 1 carbon atoms.
6, for example, methanesulfonyloxy and benzenesulfonyloxy.

The acylamino group has 1 to 16 carbon atoms;
It preferably has 1 to 10 carbon atoms, such as acetamide and p-chlorobenzoylamide. The alkylamino group has 1 to 16 carbon atoms, preferably 1 to 1 carbon atoms.
0, for example, N, N-dimethylamino, N- (2
-Hydroxyethyl) amino. As the arylamino group, one having 6 to 24 carbon atoms such as anilino, N-
It is methylanilino. As the heterocyclic amino group, an oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms
The number of heteroatoms and the type of element may be one or more, which is a saturated or unsaturated heterocyclic amino group of a 5- or 6-membered ring containing at least one, and may be, for example, 2-
Oxazolylamino, 2-tetrahydropyranylamino and 4-pyridylamino. The ureide group has 1 to 16 carbon atoms, preferably 1 to 10 carbon atoms, and includes, for example, ureide, methyl ureide, N, N-diethyl ureide, and 2-methanesulfonamidoethyl ureide.

The sulfamoylamino group has 0 carbon atoms.
To 16, preferably 0 to 10 carbon atoms, such as methylsulfamoylamino and 2-methoxyethylsulfamoylamino. The alkoxycarbonylamino group has 2 to 16 carbon atoms, preferably 2 to 10 carbon atoms, and is, for example, methoxycarbonylamino. The aryloxycarbonylamino group has 7 to 24 carbon atoms.
For example, phenoxycarbonylamino, 2,6
-Dimethoxyphenoxycarbonylamino. The sulfonamide group has 1 to 16 carbon atoms, preferably 1 to 10 carbon atoms, such as methanesulfonamide, p
-Toluenesulfonamide. The imide group has 4 to 16 carbon atoms, such as N-succinimide, N
-Phthalimide. The oxamoylamino group has 2 to 16 carbon atoms, preferably 2 to 10 carbon atoms, and is, for example, N-ethyloxamoylamino. The heterocyclic group linked by a nitrogen atom of the ring includes a carbon atom, an oxygen atom or a sulfur atom and
6-membered heterocycle, for example, pyrrolidino, morpholino, imidazolino.

The alkylthio group has 1 to 16 carbon atoms,
It preferably has 1 to 10 carbon atoms, such as methylthio and 2-phenoxyethylthio. The arylthio group has 6 to 24 carbon atoms, such as phenylthio and 2-carboxyphenylthio. The heterocyclic thio group is a 5- or 6-membered saturated or unsaturated heterocyclic thio group having at least one oxygen atom, nitrogen atom or sulfur atom having 1 to 5 carbon atoms, which forms a ring. The number of atoms and the type of element may be one or more, and examples include 2-benzothiazolylthio and 2-pyridylthio.

The sulfamoyl group has 0 to 1 carbon atoms.
6, preferably having 0 to 10 carbon atoms, such as sulfamoyl, methylsulfamoyl and phenylsulfamoyl. The alkoxysulfonyl group has 1 carbon atom
-16, preferably 1-10 carbon atoms, such as methoxysulfonyl. The aryloxysulfonyl group has 6 to 24 carbon atoms, preferably 6 to 12 carbon atoms, and is, for example, phenoxysulfonyl. The sulfonyl group has 1 to 16 carbon atoms, preferably 1 to 1 carbon atom.
0, for example, methanesulfonyl and benzenesulfonyl. The sulfinyl group has 1 to 16 carbon atoms,
It preferably has 1 to 10 carbon atoms, such as methanesulfinyl and benzenesulfinyl. The acylsulfamoyl group has 1 to 18 carbon atoms, preferably 1 to 16 carbon atoms, and includes N-acetylsulfamoyl,
-Benzoylsulfamoyl.

In the formula (I), the substituent on the benzene ring represented by A ₁ is preferably a hydroxy group, a halogen atom, an alkyl group, an aryl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group. An acyl group, a cyano group, an alkoxy group, an aryloxy group, a carbamoyloxy group, an acylamino group,
A ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, a sulfonamide group, a sulfamoyl group, and a sulfonyl group, and more preferably a halogen atom, an alkyl group, an aryl group, a carbamoyl group, an alkoxy group, an aryloxy group, and an acylamino group. , Ureido group, sulfonamide group, sulfamoyl group and the like.

The compound represented by formula (I) may have, as a substituent, a group which promotes adsorption to silver halide. Examples of the group for promoting adsorption to silver halide include thiourea group, heterocyclic thioamide group, mercaptoheterocyclic group, and triazole group.
No. 47, JP-A-59-195233 and JP-A-59-200.
No. 231, 59-201045, 59-2010
No. 46, No. 59-201047, No. 59-20104
No. 8, No. 59-201049, No. 61-170733
No. 61-270744, No. 62-948, No. 6
No. 3-234244, No. 63-234245, No. 63
-234246. Specific examples of preferred examples of the adsorption promoting group for silver halide include thioureido, thioamide, thiourethane, 5-
Mercaptotetrazole, 3-mercapto-1,2,4
-Triazole, 2-mercapto-1,3,4-thiadiazole, 2-mercapto-1,3,4-oxadiazole, alkylmercapto, arylmercapto, benzotriazole and the like.

In the general formula (II), A ₂ represents an arylene group. The arylene group is a monocyclic or condensed-ring arylene group, specifically, a substituted or unsubstituted phenylene group or naphthylene group. When A ₂ has a substituent, examples of the substituent include the same substituents as A _{1 in} formula (I), and the preferred range is also the same. In the general formula (II), A ₂ is preferably a substituted or unsubstituted phenylene group.

In the formula (II), the divalent to hexavalent linking group represented by L ₀ is a divalent to hexavalent alkylene group,
Cycloalkylene group, alkenylene group, alkynylene group, phenylene group, -O-, -S-, -N ( _RN )-
( _RN represents a single bond, a hydrogen atom, an alkyl group, or an aryl group.), -CO-, -C (= S)-, -C (=
_{N-R N) -, -} SO 2 -, - SO -, - P (= O)
_{-, - N (R N)} N (R N) - which is of a combination of group group. Here, the alkylene group is a linear or branched, substituted or unsubstituted alkylene group, and specific examples include a methylene group, an ethylene group, a propylene group, a hexafluoropropylene group, and an α-ethylmethylene group. The cycloalkylene group is a monocyclic, bicyclic or tricyclic, substituted or unsubstituted cycloalkylene group, specifically, a cyclohexylene group, a bicyclohexylene group, an adamantylene group, a norbornylene group, a decalin-2, 6
-Diyl group and the like. The alkenylene group is a substituted or unsubstituted alkenylene group, and specific examples thereof include a vinylene group, a 1,3-butadiene-1,4-diyl group, and a tetrafluorovinylene group. The alkynylene group is a substituted or unsubstituted alkynylene group, and specific examples include an ethynylene group. A phenylene group is a substituted or unsubstituted phenylene group. However, when the compound represented by the general formula (I) or (II) is biphenyl, diphenylmethane (including bisphenol), triphenylmethane,
It has no partial structure of benzophenone, triphenylamine, diphenyl ether, diphenyl sulfide, diphenyl sulfone, stilbene, fluorenone, anthraquinone, binaphthyl, or dinaphthyl ether. When the nitrogen atom is not directly or indirectly linked to the group represented by B in the general formula (I) or (II), the diphenylamino group may have a partial structure of the diphenylamino group. Absent. When the group represented by L ₀ has a substituent, examples of the substituent include the same substituents that A ₁ may have in general formula (I), and the preferred range is also the same. It is. Specific examples of the divalent to hexavalent linking group represented by L ₀ in formula (II) are shown below.

[0024]

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[0025]

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In the general formula (III), the linking group represented by L ₁ is -O-, -S-, -N ( _RN )-( _RN is a hydrogen atom, an alkyl group or an aryl group. ), -C
O -, - C (= S ) -, - SO 2 -, - SO -, - P
It is a group consisting of a combination of (＝ O)-groups. Here, when the group consisting of the combination is specifically shown, -CON
_{(R N) -, - SO} 2 N (R N) -, - COO -, - N
_{(R N) CON (R N} ) -, - N (R N) CSN
_{(R N) -, - N} (R N) SO 2 N (R N) -, - SO
_{2 N (R N) CO -} , - SO 2 N (R N) CON
(R _N )-, -N (R _N ) COCON (R _N )-, -C
ON include groups of (R _N) CO-, or the like. In addition, these groups may be connected from either side. General formula (II
Linking group at the I) represented by L ₁ is, when containing trivalent or more groups, L ₁ is -Ar ₁ -NH In formula (III)
Two or more groups represented by NH-G ₁ -R ₁ may be linked. In this case, the trivalent or higher linking group contained in L ₁ is specifically an amino group. In the general formula (III), L ₁ is preferably -SO ₂ NH-, -NHCONH
—, —O—, —S—, and —N (R _N ) —, and particularly preferably a —SO ₂ NH— group.

The aromatic group represented by Ar ₁ in the general formula (III) is a monocyclic or bicyclic arylene group,
Specific examples include a substituted or unsubstituted phenylene group and a naphthylene group. In the general formula (III), Ar ₁ is
Preferably it is a phenylene group. The group represented by Ar ₁ may have a substituent, and examples of the substituent include the same substituents as A ₁ in General Formula (I) may have. Preferred examples of the substituent of the group represented by Ar ₁ include a carboxyl group, a sulfo group, an alkyl group, an amino group, an alkylamino group, a hydroxy group,
Examples thereof include an alkoxy group, a halogen atom, an acylamino group, a sulfonamide group, and a ureido group, and the total number of carbon atoms is preferably 1 to 12, particularly preferably 1 to 8. In the general formula (III), Ar ₁ is preferably an unsubstituted phenylene group.

In the general formula (III), G ₁ represents a carbonyl group, an oxalyl group, a sulfonyl group or a phosphoryl group, preferably when these represent a carbonyl group or an oxalyl group, more preferably a carbonyl group. It is time to represent.

In the general formula (III), R ₁ represents a hydrogen atom or a block group. The block group specifically represents an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group, or a hydrazino group. It may be substituted. Examples of the alkyl group include a methyl group, a trifluoromethyl group, a difluoromethyl group, a 2-carboxytetrafluoroethyl group, a methoxyethyl group, a phenoxymethyl group, a pyridiniomethyl group,
3-hydroxypropyl group, 3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, and the like,
The aralkyl group is, for example, an o-hydroxybenzyl group,
o-aminobenzyl group and the like, an alkenyl group is, for example, a vinyl group, a 2-ethoxycarbonylvinyl group, and the like, and an alkynyl group is, for example, an ethynyl group, a 2-methoxycarbonylethynyl group, and an aryl group. Is, for example, a 3,5-dichlorophenyl group, a 2-hydroxymethylphenyl group, a 2-carbamoylphenyl group, a 3,5-
Dichloro-2-hydroxymethylphenyl group, 2-methanesulfonamidophenyl group, 4-cyanophenyl group,
3,4-dinitrophenyl group and the like, and the heterocyclic group is, for example, 4-pyridyl group, benzotriazol-5-yl group, 3- (2-mercaptotetrazolyl) phenyl group, N-methyl-4-group. A pyridinio group and the like, an alkoxy group is, for example, a methoxy group, a propoxy group, a 2-hydroxyethyl group and the like, an aryloxy group is, for example, a phenoxy group, a 1-naphthyloxy group and the like, and an amino group is For example, amino group, propylamino group, dimethylamino group, 2,2,6,6-tetramethylpiperidin-4-yl group, anilino group, 2-hydroxyanilino group, 5-benzotriazolylamino group, -Benzyl-
A hydrazino group; for example, a hydrazino group, a 2-phenylhydrazino group, a 4-hydridino group;
And a benzenesulfonamidophenylhydrazino group. When these groups have a substituent, examples of the substituent include the same substituents that A ₁ may have in general formula (I), and the total carbon number of the substituent is from 0 to 12
And more preferably 0 to 8.

When G ₁ and G _{2 in the} general formula (III) represent a carbonyl group, R ₁ and R ₂ are preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group,
It is a heterocyclic group, more preferably a hydrogen atom, an alkyl group or an aryl group, and most preferably an alkyl group. When G ₁ and G _{2 in the} general formula (III) represent an oxalyl group, R ₁ and R ₂ are preferably an alkoxy group, an aryloxy group or an amino group, and more preferably an amino group.

Among the compounds represented by the general formula (III), more preferable ones are represented by the following general formula (IV). General formula (IV)

[0032]

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In the general formula (IV), G ₂ and R ₂ are the same groups as G ₁ and R _{1 in the} general formula (III), X ₁ is a substituent, and m ₁ is Represents an integer of 0 to 4. The substituent represented by X ₁ in the general formula (IV) is
In the general formula (III), they are the same as the substituents which the group represented by Ar ₁ may have, and the preferred range is also the same. m ₁ represents an integer of 0 to 4, preferably m ₁ is 0 or 1, and particularly preferably 0.

In the general formula (I) or (II), b ₁ represents an integer of 3 to 6, preferably b ₁ is 3 or 4
And particularly preferably 3. In the general formula (II), b ₁ represents an integer of 1 to 5, preferably 1 or 2, and particularly preferably 1. m ₁ represents an integer of 3 to 6, and when b ₁ is 1, it is preferably 3 or 4, and when b ₁ is 2, it is preferably 2.

In the general formula (I), three to six groups represented by B may be the same or different. In addition, two to six ΔA ₂ − (B) in the general formula (II)
The group represented by b ₂ } and the group represented by 1 to 5 B may be the same or different.

The following are examples of compounds of the present invention, but the present invention is not limited thereto.

[0037]

[Table 1]

[0038]

[Table 2]

[0039]

[Table 3]

[0040]

[Table 4]

[0041]

[Table 5]

[0042]

[Table 6]

Synthesis Example 1 (Synthesis of Exemplified Compound 19c) Exemplified Compound 19c was synthesized according to Scheme 1.

[0044]

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(Synthesis of Synthetic Intermediate A) To a solution of 1.4 g of phloroglucinol in 100 ml of acetonitrile was added 9.3 ml of triethylamine, and the mixture was ice-cooled. Then, 16.1 g of p-chlorosulfonylbenzoyl chloride in acetonitrile 8
0 ml solution was added dropwise. After stirring at room temperature for 1 hour, ethyl acetate and dilute hydrochloric acid were added to extract the product, which was dried and concentrated to obtain 12.6 g of Synthetic Intermediate A. (Synthesis of Exemplified Compound 19c) Np-Nitrophenyl-
4.1 ml of pyridine was added to 80 ml of an isopropyl alcohol solution containing 10.3 g of Np-aminophenyl-N'-difluoroacetylhydrazine obtained by iron reduction of N'-difluoroacetylhydrazine.
12.6 g of a mixed solution of acetonitrile and dimethylacetamide (50 ml) was added, and the mixture was stirred for 1 hour. Ethyl acetate and diluted hydrochloric acid were added to extract the product, which was dried and concentrated, and then subjected to silica gel column chromatography to obtain 15.5 g of Exemplified Compound 19c.

Synthesis Example 2 (Synthesis of Exemplified Compounds 19a and 19d) Exemplified Compound 19
a and 19d were synthesized according to Scheme 2.

[0047]

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(Synthesis of Exemplified Compound 19a) A solution of 4.5 g of Np-aminophenyl-N'-formylhydrazine in 40 ml of dimethylacetamide was cooled with ice under a nitrogen atmosphere, 2.4 ml of pyridine and intermediate A7. 31 g was added slowly. After stirring for 2 hours, ethyl acetate and diluted hydrochloric acid were added to extract the product, which was dried and concentrated. After dimethylacetamide was added and dissolved, dilute hydrochloric acid was added to crystallize the product, thereby obtaining 7.71 g of Exemplified Compound 19a. (Synthesis of Synthetic Intermediate B) Exemplified Compound 19a 7.71 g
And 100 ml of a mixed solution of 3.8 g of 1,5-naphthalenedisulfonic acid in methanol and acetonitrile was stirred at 50 ° C. for 2 hours. The insolubles were collected by filtration to obtain 9.37 g of a synthetic intermediate B. (Synthesis of Exemplified Compound 19d) Intermediate B 9.37 g mixed solution of acetonitrile and dimethylacetamide 10
After cooling 0 ml of the mixture under ice-cooling in a nitrogen atmosphere, triethylamine 2.
7 ml and 3.4 g of tetrafluorosuccinic anhydride were added. After stirring at room temperature for 1 hour, ethyl acetate and diluted hydrochloric acid were added to extract the product, which was dried and concentrated, and then subjected to silica gel column chromatography to give Exemplified Compound 19d.
4.32 g were obtained. Synthesis Example 3 (Synthesis of Exemplified Compound 20c) Exemplified Compound 20c was synthesized according to Scheme 3.

[0049]

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(Synthesis of Synthetic Intermediate C) 1,2,4,5-
A solution of 3.5 g of benzenetetramine in acetonitrile 50
After adding 14 ml of triethylamine to the mixture and cooling with ice, p-
24 g of phenyl nitrochloroformate acetonitrile 80
ml solution was applied. After stirring at room temperature for 1 hour, the insoluble matter was filtered off, ethyl acetate and dilute hydrochloric acid were added to extract the product, which was dried and concentrated to obtain 21.6 g of synthetic intermediate C.
I got (Synthesis of Exemplified Compound 20c) Synthetic intermediate D 2 prepared from p-nitrobenzenesulfonyl chloride and Np-aminophenyl-N′-difluoroacetylhydrazine
1 g of ammonium chloride and 10 ml of water were added to 100 ml of a 0 g isopropyl alcohol solution, and the mixture was heated under reflux. After adding iron powder, the mixture was stirred for 1 hour. The insoluble matter was removed by celite filtration, 4.0 ml of pyridine was added to the obtained filtrate, 30 ml of a mixed solution of 12 g of synthetic intermediate C in acetonitrile and dimethylacetamide was added, and the mixture was stirred for 1 hour. Ethyl acetate and diluted hydrochloric acid were added to extract the product, which was dried and concentrated, and then subjected to silica gel column chromatography to obtain 11.3 g of Exemplified Compound 20c. Synthesis Example 4 Exemplified compound 12a was synthesized according to Scheme 4.

[0051]

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(Synthesis of Synthetic Intermediate F) 11 ml of triethylamine and 8.4 g of iminodipropionic acid were added to 70 ml of acetonitrile solution of 6.22 g of succinic dichloride under ice-cooling.
50 ml of acetonitrile solution was added dropwise. After stirring at room temperature for 1 hour, ethyl acetate and dilute hydrochloric acid were added to extract the product, which was dried and concentrated to obtain 12.4 g of a synthetic intermediate E.
I got (Synthesis of Synthetic Intermediate F) To 50 ml of a methylene chloride solution containing 12.4 g of Intermediate E, 1 ml of dimethylformamide was added.
At room temperature, 30 ml of thionyl chloride was added dropwise. After heating the reaction solution to reflux for 2 hours, excess thionyl chloride was distilled off under reduced pressure to obtain 4.1 g of synthetic intermediate F. (Synthesis of Exemplified Compound 12a) 1 g of ammonium salt and 10 ml of water were added to 100 ml of an isopropyl alcohol solution of 16.7 g of synthetic intermediate G prepared from p-nitrobenzenesulfonyl chloride and Np-aminophenyl-N'-formylhydrazine. After heating to reflux, iron powder was added and stirred for 1 hour. The insoluble matter was removed by celite filtration, and 4 ml of pyridine was added to the obtained filtrate to obtain a synthetic intermediate F4.
1 g of a mixed solution of acetonitrile and 30 ml of dimethylacetamide was added and stirred for 1 hour. The product was extracted by adding ethyl acetate and dilute hydrochloric acid, dried, concentrated, and then subjected to silica gel column chromatography to give Exemplified Compound 12
a 8.6 g were obtained.

Synthesis Example 5 The exemplified compound 12b was synthesized according to Scheme 5.

[0054]

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(Synthesis of Synthetic Intermediate H) Exemplary Compound 12a
100 ml of a mixed solution of 5.84 g and 6.0 g of 1,5-naphthalenedisulfonic acid in methanol and acetonitrile was stirred at 50 ° C. for 2 hours. The insolubles were collected by filtration to obtain 11.66 g of a synthetic intermediate H. (Synthesis of Exemplified Compound 12b) Intermediate H 4.74 g mixed solution of acetonitrile and dimethylacetamide 10
0 ml was cooled with ice in a nitrogen atmosphere, and then 3 ml of triethylamine was added.
And 3.3 g of trifluoroacetic anhydride. After stirring at room temperature for 1 hour, ethyl acetate and diluted hydrochloric acid were added to extract the product, dried and concentrated, and then 5.68 g of Exemplified Compound 12b by silica gel column chromatography.
I got

Synthesis Example 6 The exemplified compound 12b was synthesized according to Scheme 6.

[0057]

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7.44 g of intermediate H and difluoroacetic acid 3
3. triethylamine in 60 ml of acetonitrile solution.
6 ml was added, and a solution of 6.2 g of dicyclohexylcarbodiimide in 20 ml of acetonitrile was added dropwise under ice cooling. After stirring at room temperature for 2 hours, the insolubles were filtered off, ethyl acetate and dilute hydrochloric acid were added to extract the product, which was dried and concentrated, followed by silica gel column chromatography to give Exemplified Compound 1
6.3 g of 2c were obtained.

Synthetic Example 7 Exemplified Compound 4a was synthesized according to Scheme 7.

[0060]

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(Synthesis of Synthetic Intermediate J) To a solution of 6.22 g of succinic chloride in 80 ml of acetonitrile were added dropwise 15 ml of triethylamine and 8.4 g of diethanolamine in 60 ml of acetonitrile under ice cooling. After stirring at room temperature for 1 hour, ethyl acetate and dilute hydrochloric acid were added to extract the product, which was dried and concentrated to obtain 13.7 g of synthetic intermediate I. (Synthesis of Synthetic Intermediate J) To a solution of 3.4 g of Intermediate I in 100 ml of acetonitrile was added 7 ml of triethylamine and the mixture was ice-cooled. Then, m-chlorosulfonylbenzoyl chloride 1 was added.
1 g of a 40 ml solution of acetonitrile was acted upon. After stirring at room temperature for 1 hour, ethyl acetate and dilute hydrochloric acid were added to extract the product, which was dried and concentrated to obtain a synthetic intermediate J 1
0.6 g was obtained. (Synthesis of Exemplified Compound 4a) Np-aminophenyl-
A solution of 6 g of N'-formylhydrazine in 40 ml of a dimethylacetamide solution was ice-cooled under a nitrogen atmosphere to give intermediate J1.
0.6 g was gradually added. After stirring for 2 hours, ethyl acetate and diluted hydrochloric acid were added to extract the product, which was dried and concentrated. After adding and dissolving dimethylacetamide, the product was crystallized by adding dilute hydrochloric acid, and Exemplified Compound 4a 12.1
g was obtained.

SYNTHESIS EXAMPLE 8 Exemplified compound 4a was synthesized in exactly the same manner as in Example 4a except that Np-aminophenyl-N'-difluoroacetylhydrazine was used instead of Np-aminophenyl-N'-formylhydrazine. 4c could be synthesized.

Synthesis Example 9 The exemplified compound 4d was synthesized according to Scheme 8.

[0064]

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(Synthesis of Synthetic Intermediate K) Exemplary Compound 4a
12.7 g and 1,5-naphthalenedisulfonic acid 6 g
A liquid mixture of methanol and acetonitrile 10
0 ml was stirred at 50 ° C. for 2 hours. The insolubles were collected by filtration to obtain 15.1 g of a synthetic intermediate K. (Synthesis of Exemplified Compound 4d) Mixed solution of 5.44 g of intermediate K in acetonitrile and dimethylacetamide 100
After cooling ice-cooling under nitrogen atmosphere, triethylamine 1.5
Then, 1.8 g of tetrafluorosuccinic anhydride was added. After stirring at room temperature for 1 hour, ethyl acetate and dilute hydrochloric acid were added to extract the product, which was dried and concentrated, and then subjected to silica gel column chromatography to give Exemplified Compound 4d 6.
23 g were obtained.

The hydrazide compound of the present invention (hereinafter referred to as hydrazine nucleating agent) can be prepared by using a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethyl It can be used by dissolving it in formamide, dimethyl sulfoxide, methylcellosolve and the like. Also, by an already well-known emulsification dispersion method, an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified and dispersed. An object can be prepared and used. Alternatively, a powder of a hydrazine derivative can be dispersed in water by a ball mill, a colloid mill, or an ultrasonic wave by a method known as a solid dispersion method and used.

The hydrazine nucleating agent of the present invention is preferably used as a solid dispersion of fine powder (fine crystal particles). The fine (crystalline) particle solid dispersion of the hydrazine-based nucleating agent can be prepared by using a suitable solvent (water, alcohol, or the like) if necessary in the presence of a dispersant in the presence of a known micronizing means (for example, ball mill, vibrating ball mill, planetary Ball mill, sand mill, colloid mill, jet mill, roller mill). The fine (crystal) particles of the hydrazine-based nucleating agent are added to the poor solvent of the hydrazine-based nucleating agent after dissolving the hydrazine-based nucleating agent in an appropriate solvent using a dispersing surfactant. Then, the hydrazine-based nucleating agent is first dissolved by controlling the pH, and then the pH is changed to perform microcrystallization to control the pH. The layer containing the fine powder of the hydrazine-based nucleating agent is formed by dispersing the fine (crystal) particles of the hydrazine-based nucleating agent in an appropriate binder to obtain a solid dispersion of substantially uniform particles. After being prepared as a product, it can be provided by coating it on a desired support. Alternatively, it can be provided by a method in which a dissociated hydrazine-based nucleating agent is applied in the form of a salt, followed by overcoating with acidic gelatin to obtain dispersion fixation at the time of application.

As the binder, the above-mentioned polymer having an active methylene group and a hydrophilic colloid or a synthetic polymer which can be used for a photosensitive emulsion layer or a non-photosensitive layer are used. Although there is no particular limitation on the hydrophilic colloid, gelatin is usually preferred.

As the surfactant for dispersion, known surfactants can be used, and anionic, nonionic and amphoteric surfactants are preferred. In particular, use of an anionic and / or nonionic surfactant is preferred.

The fine particles of the hydrazine-based nucleating agent in the solid dispersion have an average particle diameter of 0.005 μm to 10 μm, preferably 0.01 μm to 1 μm, more preferably 0.01 μm to 1 μm.
μm to 0.5 μm.

The hydrazine nucleating agent of the present invention may be added to any layer of the silver halide emulsion layer or another hydrophilic colloid layer on the side of the silver halide emulsion layer with respect to the support. It is preferably added to the silver halide emulsion layer or the hydrophilic colloid layer adjacent thereto.

The addition amount of the nucleating agent of the present invention is preferably 1 × 10 ⁻⁶ to 1 × 10 ⁻² mol per mol of silver halide, and is preferably 1 × 10 ⁻⁶ mol to 1 × 10 ⁻² mol.
10 ^-5 to 1 × 10 ^-3 mol is more preferable, and 5 × 10 ^-5 to 5 × 10 ^-5
1 × 10 ^-3 mol is most preferred.

In particular, in the case of processing with the developer of the present invention having a pH of less than 11, the silver halide photographic light-sensitive material contains an amine derivative, an onium salt, a disulfide, a silver halide emulsion layer or another hydrophilic colloid layer. It is preferable to add a derivative and a nucleation enhancing accelerator such as a benzyl alcohol derivative.

The nucleation accelerator used in the present invention includes
Examples include an amine derivative, an onium salt, a disulfide derivative, and a hydroxymethyl derivative. Examples are listed below. Compounds described on page 48, lines 2 to 37 of JP-A-7-77783, specifically, compounds A-1) to A-73) described on pages 49 to 58. JP-A-7-84
No. 331, (Chem. 21), (Chem. 22) and (Chem. 2)
The compounds represented by 3), specifically, the compounds described on pages 6 to 8 of the same publication. Compounds represented by general formula [Na] and general formula [Nb] described in JP-A-7-104426, specifically, Na-1 described on pages 16 to 20 of the same publication.
To Nb-12 and compounds of Nb-1 to Nb-12. General formula (1) described in Japanese Patent Application No. 7-37817,
Compounds represented by the general formula (2), the general formula (3), the general formula (4), the general formula (5), the general formula (6) and the general formula (7). 1-1 to 1-19 described
2-1 to 2-22, 3-1 to 3-3
6, compound 4-1 to 4-5, 5-1 to 5-4
1 compound, 6-1 to 6-58 compound and 7-1 to
Compounds 7-38.

The nucleation accelerator of the present invention may be any suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl It can be used by dissolving it in Cellsolve or the like. Also, by an already well-known emulsification dispersion method, dissolution is performed using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. An object can be prepared and used. Alternatively, a powder of a nucleation accelerator can be dispersed in water by a ball mill, a colloid mill, or an ultrasonic wave and used by a method known as a solid dispersion method.

The nucleation promoting agent of the present invention is applied to a support.
The silver halide emulsion layer on the silver halide emulsion layer side or other
May be added to any of the hydrophilic colloid layers of
Silver colloid emulsion layer or hydrophilic colloid adjacent to it
It is preferably added to the metal layer. Nucleation accelerator of the present invention
The addition amount was 1 × 10 5 per mol of silver halide.^-6~ 2 × 10
^-2Mole is preferred and 1 × 10^-Five~ 2 × 10^-2Mole more
Preferably 2 × 10^-Five~ 1 × 10^-2Mole is most preferred
No.

There is no particular limitation on the halogen composition of the silver halide emulsion used in the present invention. However, in order to more effectively achieve the object of the present invention, silver chloride and salt having a silver chloride content of 50 mol% or more are used. Silver bromide and silver chloroiodobromide are preferred. The content of silver iodide is preferably less than 5 mol%, particularly preferably less than 2 mol%.

In the present invention, a photosensitive material suitable for high illuminance exposure such as scanner exposure and a photosensitive material for line drawing are
Contains rhodium compound to achieve high contrast and low fog. As the rhodium compound used in the present invention, a water-soluble rhodium compound can be used. For example, a rhodium (III) halide compound or a rhodium complex salt having a ligand such as halogen, amines, oxalato, etc., for example, hexachlororhodium (III) complex salt, hexabromorhodium (III) complex salt, hexaamine rhodium ( III) Complex salt, trizalatrodium (II
I) Complex salts and the like. These rhodium compounds are
It is used by dissolving it in water or a suitable solvent, but it is a commonly used method for stabilizing a solution of a rhodium compound, that is, an aqueous solution of hydrogen halide (eg, hydrochloric acid, bromic acid, hydrofluoric acid, etc.) A method of adding an alkali (for example, KCl, NaCl, KBr, NaBr, or the like) can be used. Instead of using water-soluble rhodium, it is also possible to add and dissolve other silver halide grains doped with rhodium during the preparation of silver halide. The addition amount is 1 × 10 ^{-8 to} 5 × 10 ^-6 mol, preferably 5 × 10 ^-8 to 1 × 10 ^-6 mol, per mol of silver of the silver halide emulsion. These compounds can be appropriately added at the time of production of silver halide emulsion grains and at each stage before coating the emulsion, but it is particularly preferable to add them at the time of emulsion formation and to incorporate them into silver halide grains. . The photographic emulsion used in the present invention is Chimie et Physique Photograp by P. Glafkides.
hique (Paul Montel, 1967), by GFDufin
Photographic Emulsion Chemistry (The Focal Press
Publishing, 1966), Making and Writing by VLZelikman et al
Coating Photographic Emulsion (The Focal Press
Ed., 1964) and the like.

As a method of reacting the soluble silver salt with the soluble halogen salt, any of a one-side mixing method, a simultaneous mixing method, a combination thereof and the like may be used. Method of forming grains in excess of silver ions (so-called reverse mixing method)
Can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used. Further, it is preferable to form grains by using a so-called silver halide solvent such as ammonia, thioether and tetra-substituted thiourea. More preferred are tetra-substituted thiourea compounds.
No. 08, 55-77737. Preferred thiourea compounds are tetramethylthiourea, 1,3-
Dimethyl-2-imidazolidinthione. According to the controlled double jet method and the grain forming method using a silver halide solvent, it is easy to produce a silver halide emulsion having a regular crystal form and a narrow grain size distribution, and the silver halide used in the present invention is easy to produce. It is a useful tool for making emulsions. Further, in order to make the particle size uniform, British Patent No. 1,535,016, JP-B-48-3689.
No. 0 and No. 52-16364,
A method of changing the addition rate of silver nitrate or alkali halide in accordance with the grain growth rate, and a method disclosed in British Patent No. 4,242,4
No. 45, and JP-A-55-158124, it is preferable to use a method of changing the concentration of the aqueous solution and to grow the solution quickly within a range not exceeding the critical saturation. The emulsion of the present invention is preferably a monodisperse emulsion, and the coefficient of variation is preferably 20% or less, particularly preferably 15% or less. The average grain size of the grains in the monodispersed silver halide emulsion is 0.5 μm.
m, particularly preferably 0.1 μm to 0.4 μm
It is.

The silver halide emulsion of the present invention is preferably subjected to chemical sensitization. As the method of chemical sensitization, known methods such as a sulfur sensitization method, a selenium sensitization method, a tellurium sensitization method, and a noble metal sensitization method can be used, and these are used alone or in combination. When used in combination,
For example, a sulfur sensitization method and a gold sensitization method, a sulfur sensitization method, a selenium sensitization method and a gold sensitization method, a sulfur sensitization method, a tellurium sensitization method, and a gold sensitization method are preferable.

The sulfur sensitization used in the present invention is usually carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain time. Known compounds can be used as the sulfur sensitizer. For example, in addition to sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines and the like are used. be able to. Preferred sulfur compounds are
Thiosulfate and thiourea compounds. The amount of the sulfur sensitizer to be added varies under various conditions such as pH during chemical ripening, temperature, and the size of silver halide grains, but is preferably 10 ^-7 to 10 ^-2 mol per mol of silver halide. And more preferably 10 ^-5 to 10 ^-3 mol.

As the selenium sensitizer used in the present invention, known selenium compounds can be used. That is, usually, an unstable and / or non-unstable selenium compound is added, and the emulsion is stirred at a high temperature of 40 ° C. or higher for a certain period of time. Examples of unstable selenium compounds include JP-B-44-15748, JP-B-43-13489, JP-A-2-13097, JP-A-2-229300, and JP-A-3-229300.
Compounds described in JP 121798 and the like can be used. In particular, it is preferable to use the compounds represented by formulas (VIII) and (IX) in Japanese Patent Application No. 3-121798.

The tellurium sensitizer used in the present invention is a compound which forms silver telluride which is presumed to be a sensitizing nucleus on the surface or inside of silver halide grains. Regarding the formation rate of silver telluride in a silver halide emulsion, see Japanese Patent Application No.
It can be tested by the method described in No. 146739.
Specifically, U.S. Pat. Nos. 1,623,499, 3,320,069, 3,772,031, British Patent 235,211 and 1,121,496
No. 1,295,462, No. 1,396,69
6, Canadian Patent No. 800,958, Japanese Patent Application No. 2-33.
No. 3819, No. 3-53693, No. 3-131598
No. 4-129787, Journal of Chemical Society Chemical Communication (J. Chem. Soc. Chem. Commun.) 635 (1980), ibid
1102 (1979), ibid 645 (1979),
Journal of Chemical Society Perkin Transaction (J.Chem.Soc.Perkin.Trans.)
1, 191 (1980); Patai (S.Patai)
Hen, The Chemistr of Organic Selenium and Tellurium Campounds
y of Organic Serenium and Tellunium Compounds),
The compounds described in Vol. 1 (1986) and Vol. 2 (1987) can be used. In particular, Japanese Patent Application No. 4-14673.
Compounds represented by general formulas (II), (III) and (IV) in No. 9 are preferred.

The amount of the selenium and tellurium sensitizers used in the present invention varies depending on the silver halide grains to be used, the conditions of chemical ripening, etc., but is generally 10 ^-8 to 10 ^-2 mol per mol of silver halide. Preferably about 10 ^-7 to 10 ^-3 mol is used. The conditions of the chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to 45 ° C. 85 ° C. Examples of the noble metal sensitizer used in the present invention include gold, platinum, palladium, and iridium, and gold sensitization is particularly preferable. Specific examples of the gold sensitizer used in the present invention include chloroauric acid, potassium chlorate, potassium aurithiocyanate, and gold sulfide.
About 10 ^-7 to 10 ^-2 mol per mol can be used. In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite, a lead salt, a thallium salt, and the like may coexist in the process of forming silver halide grains or physical ripening. In the present invention, reduction sensitization can be used. Stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used as the reduction sensitizer. A thiosulfonic acid compound may be added to the silver halide emulsion of the present invention by the method described in European Patent Application (EP) -293,917. The silver halide emulsion in the light-sensitive material used in the present invention may be only one kind, or two or more kinds (for example, those having different average grain sizes,
Those having different halogen compositions, different crystal habits, and different chemical sensitization conditions) may be used in combination.

In the present invention, a silver halide emulsion particularly suitable as a return photosensitive material is a silver halide comprising 90 mol% or more, more preferably 95 mol% or more, of silver chloride. Silver chlorobromide or silver chloroiodobromide containing 1 mol%. When the ratio of silver bromide or silver iodide increases, the safety of safelight under bright room deteriorates, or γ
Is undesirably reduced.

The silver halide emulsion used in the return photographic material of the present invention preferably contains a transition metal complex. As transition metals, Rh, Ru, Re, Os, I
r, Cr, and the like. Examples of ligands include nitrosyl and thionitrosyl bridging ligands, halide ligands (fluoride, chloride, bromide and iodide), cyanide ligand, cyanate ligand, thiocyanate ligand, selenoate ligand Cyanate, tellurocyanate, acid and aquo ligands. If an aquo ligand is present, it preferably occupies one or two of the ligands.

Specifically, in order to contain a rhodium atom, a metal salt of any form such as a single salt or a complex salt can be added at the time of preparing particles. Examples of the rhodium salt include rhodium monochloride, rhodium dichloride, rhodium trichloride, ammonium hexachlororhodate, and the like. Preferably, a water-soluble trivalent rhodium halide complex such as hexachlororhodium (III) acid or a salt thereof ( Ammonium salt, sodium salt, potassium salt, etc.). The addition amount of these water-soluble rhodium salts is in the range of 1.0 × 10 ^-6 mol to 1.0 × 10 ^-3 mol per mol of silver halide. Preferably, 1.0 × 10 ⁻⁵ mol to 1.0
× 10 ⁻³ mol, particularly preferably 5.0 × 10 ⁻⁵ mol
5.0 × 10 ^-4 mol.

The following transition metal complexes are also preferred. 1 [Ru (NO) Cl ₅ ] ^-22 [Ru (NO) ₂ Cl ₄ ] ^-13 [Ru (NO) (H ₂ O) Cl ₄ ] ^-14 [Ru (NO) Cl ₅ ] ^-2 5 [Rh (NO) Cl _5] ^-2 6 [Re (NO) CN _5] ^-2 7 [Re (NO) ClCN _4] ^-2 8 [Rh (NO) ₂ Cl _4] ^-1 9 [Rh (NO ) (H ₂ O) Cl _4] ^-1 10 [Ru (NO) CN _5] ^-2 11 [Ru (NO) Br _5] ^-2 12 [Rh (NS) Cl _5] ^-2 13 [Os (NO) Cl _5] ^-2 14 [Cr (NO) Cl _5] ^-3 15 [Re (NO) Cl _5] ^-1 16 _{[Os (NS) Cl 4 (TeCN} ) ] ^-2 17 [Ru (NS) I _5] ^-2 18 [Re (NS) Cl ₄ (SeCN)] ^-2 19 [Os (NS) Cl (SCN) ₄ ] ^-2 20 [Ir (NO) Cl ₅ ] ^-2

The spectral sensitizing dye used in the present invention is not particularly limited. The amount of the sensitizing dye used in the present invention varies depending on the shape and size of the silver halide grains, but is used in the range of 4 × 10 ^-6 to 8 × 10 ^-3 mol per mol of silver halide. For example, when the silver halide grain size is 0.2 to 1.3 μm, the addition amount is preferably 2 × 10 ^{−7 to} 3.5 × 10 ⁻⁶ mol per 1 m ² of the surface area of the silver halide grains. , Especially 6.5 × 10 ^{-7 to} 2.0 ×
An addition amount range of 10 ^-6 mol is preferred.

The photosensitive silver halide emulsion of the present invention may be spectrally sensitized to blue light, green light, red light or infrared light having a relatively long wavelength by a sensitizing dye. As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holo-holerocyanine dye, a styryl dye, a hemicyanine dye, an oxonol dye, a hemioxonol dye, and the like can be used. Useful sensitizing dyes for use in the present invention include, for example, RESEARCH DISCLOSURE ITEM 17643 IV-
Item A (p.23, December 1978), Item 183
It is described in the literature described or cited in section 1X (p. 437, August 1978). In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected. For example, A) For an argon laser light source,
No. 62247, JP-A-2-48653, U.S. Pat.
No. 161,331, West German Patent 936,071, Simple Merocyanines described in Japanese Patent Application No. 3-189532,
B) For a helium-neon laser light source, see JP-A-50-62425, JP-A-54-18726, and JP-A-59-62426.
No. 102229, trinuclear cyanine dyes, C) L
No.48 for ED light source and red semiconductor laser
-42172, 51-9609, 55-398
No. 18, JP-A-62-284343, JP-A-2-10
No. 5135, and D) an infrared semiconductor laser light source disclosed in JP-A-59-1910.
No. 32, tricarbocyanines described in JP-A-60-80841, and JP-A-59-192242 and JP-A-3-67242 disclose the compounds represented by the general formulas (IIIa) and (IIIb). Dicarbocyanines containing a quinoline nucleus are advantageously selected. These sensitizing dyes may be used alone or in combination, and a combination of sensitizing dyes is often used particularly for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are described in Research Disclosure (Resear
ch Disclosure), vol. 176, 17643 (published in December 1978), page 23, IV, section J.

For the argon laser light source, specifically, S1-1 to S1 described in Japanese Patent Application No. 7-151194.
The dye of -13 is particularly preferably used.

The helium-neon light source is represented by the general formula (I) described in Japanese Patent Application No. 4-228745, from the bottom line on page 8 to the top line on page 13 of page 8. Sensitizing dyes are particularly preferred. In addition, Japanese Patent Application No. 4-2287
Those described in No. 45 of the general formula (I) are also preferably used. Specifically, S2 described in Japanese Patent Application No. 7-151194 is disclosed.
Pigments -1 to S2-10 are particularly preferably used.

The LED light source and the infrared semiconductor laser are described in detail in Japanese Patent Application No. 7-151194.
The dyes of 3-1 to S3-8 are particularly preferably used.

For the infrared semiconductor laser light source, specifically, S4-1 to S4-1 described in Japanese Patent Application No. 7-151194 are used.
The dyes 4-9 are particularly preferably used.

For a white light source such as a camera image, a sensitizing dye represented by formula (IV) described in Japanese Patent Application No. 5-201254 (page 20, line 14 to page 22, line 23) is preferably used. . Specifically, the dyes S5-1 to S5-20 described in Japanese Patent Application No. 7-151194 are particularly preferably used.

The developer for developing the light-sensitive material in the present invention may contain commonly used additives (for example, a developing agent, an alkaline agent, a pH buffer, a preservative, a chelating agent). . In the development processing of the present invention, any of known methods can be used, and a known processing solution can be used. The developing agent used in the developer used in the present invention is not particularly limited, but preferably contains dihydroxybenzenes or ascorbic acid derivatives, and furthermore, from the viewpoint of developing ability, dihydroxybenzenes and 1-phenyl-3-amine. Combinations of pyrazolidones, combinations of dihydroxybenzenes and p-aminophenols, combinations of ascorbic acid derivatives and 1-phenyl-3-pyrazolidones, or combinations of ascorbic acid derivatives and p-
Combinations of aminophenols are preferred.

As the dihydroxybenzene developing agent used in the present invention, hydroquinone, chlorohydroquinone,
Isopropyl hydroquinone, methyl hydroquinone,
Hydroquinone monosulfonate and the like are preferred, and hydroquinone is particularly preferred. Ascorbic acid derivative developing agents used in the present invention include ascorbic acid, its stereoisomer erythorbic acid, and its alkali metal salts (sodium and potassium salts). 1- used in the present invention
As developing agents for phenyl-3-pyrazolidone or its derivatives, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3- And pyrazolidone. Examples of the p-aminophenol-based developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, and N- (4-hydroxyphenyl) glycine. And N-methyl-p
-Aminophenol is preferred. The dihydroxybenzene-based developing agent is preferably used usually in an amount of 0.05 to 0.8 mol / liter. Particularly preferably, 0.2 to
It is in the range of 0.6 mol / liter. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is used in an amount of 0.05 to 0.6 mol / liter, more preferably 0.2 to 0.5 mol. / L, and the latter is preferably used in an amount of 0.06 mol / l or less, more preferably 0.03 mol / l or less. The ascorbic acid derivative developing agent is preferably used usually in an amount of 0.05 to 0.8 mol / l. Particularly preferably, 0.2
０．６0.6 mol / liter. When a combination of an ascorbic acid derivative and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is used in an amount of 0.05 to 0.6 mol / liter, more preferably 0.2 to 0.5 mol. / L, and the latter is preferably used in an amount of 0.06 mol / l or less, more preferably 0.03 mol / l or less.

Examples of the preservative used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite.
Sulfite is used in an amount of 0.20 mol / l or more, particularly 0.3 mol / l or more. However, if added in an excessively large amount, it causes silver contamination in the developing solution. Is desirable. Particularly preferably, it is 0.
It is 35 to 0.7 mol / liter. As a preservative of the dihydroxybenzene-based developing agent, a small amount of an ascorbic acid derivative may be used in combination with a sulfite. Examples of the ascorbic acid derivative include ascorbic acid, its stereoisomer erythorbic acid and its alkali metal salts (sodium and potassium salts), and the use of sodium erythorbic acid is preferable in terms of material cost. The amount added is preferably in the range of 0.03 to 0.12, more preferably 0.05 to 0.10. In molar ratio to the dihydroxybenzene-based developing agent. When an ascorbic acid derivative is used as a preservative, it is preferable that the developer contains no boron compound.

As the alkali agent used for setting the pH, ordinary water-soluble inorganic alkali metal salts (eg, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate) can be used. The pH of the developer is 9.0-1.
It is preferably 2.0, and more preferably a stable processing system can be constructed by setting the pH to 9.0 to 11.0.

The additives used other than those described above include
Development inhibitors such as sodium bromide and potassium bromide; organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol and dimethylformamide; development accelerators such as alkanolamines such as diethanolamine and triethanolamine, imidazole and derivatives thereof; mercapto A compound, an indazole compound, a benzotriazole compound, or a benzimidazole compound may be contained as an antifoggant or a black pepper inhibitor. Specifically, 5-nitroindazole, 5-p-nitrobenzoylaminoindazole, 1
-Methyl-5-nitroindazole, 6-nitroindazole, 3-methyl-5-nitroindazole, 5-nitrobenzimidazole, 2-isopropyl-5-nitrobenzimidazole, 5-nitrobenztriazole, 4-[(2- Sodium mercapto-1,3,4-thiadiazol-2-yl) thio] butanesulfonate,
5-amino-1,3,4-thiadiazole-2-thiol, methylbenzotriazole, 5-methylbenzotriazole, 2-mercaptobenzotriazole and the like can be mentioned. The amount of these antifoggants is usually
The amount is 0.01 to 10 mmol, more preferably 0.1 to 2 mmol, per liter of the developer.

Further, various organic and inorganic chelating agents can be used in combination in the developer of the present invention. As the inorganic chelating agent, sodium tetrapolyphosphate, sodium hexametaphosphate and the like can be used. On the other hand, as organic chelating agents, mainly organic carboxylic acids, aminopolycarboxylic acids, organic phosphonic acids, aminophosphonic acids and organic phosphonocarboxylic acids can be used. Examples of organic carboxylic acids include acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, succinic acid, acelineic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, and maleic acid. , Itaconic acid, malic acid, citric acid, tartaric acid and the like, but are not limited thereto.

Examples of the aminopolycarboxylic acid include iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediaminemonohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, glycol ether tetraacetic acid, 1,2-diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid. Acetic acid,
Triethylenetetramine hexaacetic acid, 1,3-diamino-2
-Propanol tetraacetic acid, glycol ether diamine tetraacetic acid and others
Nos. 747, 57-102624, and JP-B-53-
Compounds described in, for example, Japanese Patent No. 40900 can be exemplified.

As the organic phosphonic acid, US Pat.
Nos. 4454 and 3794591, and West German Patent Publication 2
Hydroxyalkylidene-diphosphonic acid and Research Disclosure (Research Disclosure) described in US Pat.
Disclosure) Volume 181, Item 18170 (197
May, 1997) and the like. Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, aminotrimethylenephosphonic acid, and the like. No. 61125, 5
Compounds described in JP-A-5-29883 and JP-A-56-97347 can be exemplified.

Examples of the organic phosphonocarboxylic acid include JP-A-52-102726, JP-A-53-42730 and JP-A-54-42730.
No. 121127, No. 55-4024, No. 55-40
No. 25, No. 55-126241, No. 55-65555
And the compounds described in Research Disclosure No. 55-65556, and Research Disclosure No. 18170 described above. These chelating agents may be used in the form of an alkali metal salt or an ammonium salt. The amount of the chelating agent to be added is preferably 1 × 10 ^-4 to 1 × 10 ^-1 mol, more preferably 1 × 10 ^-1 mol per liter of the developer.
It is 10 ^-3 to 1 × 10 ^-2 mol.

Further, as a silver stain inhibitor in a developer, JP-A-56-24347, JP-B-56-46585,
The compounds described in JP-B-62-2849 and JP-A-4-362942 can be used. Further, a compound described in JP-A-62-212651 can be used as a development unevenness inhibitor, and a compound described in JP-A-61-267759 can be used as a dissolution aid. Further, if necessary, a color tone agent, a surfactant, an antifoaming agent, a hardening agent and the like may be contained.

In the developer used in the present invention, carbonate may be used as a buffer, boric acid described in JP-A-62-186259, saccharides (eg, saccharose) described in JP-A-60-93433, oximes (Eg acetoxime),
Phenols (eg, 5-sulfosalicylic acid), tertiary phosphates (eg, sodium salt, potassium salt), and the like are used, and preferably, carbonate and boric acid are used. Although the development processing temperature and time are interrelated and determined in relation to the total processing time, generally the development temperature is from about 20 ° C to about 5 ° C.
0 ° C., preferably 25 to 45 ° C., and the development time is 5 seconds to 2 seconds.
Minutes, preferably 7 seconds / 1 minute 30 seconds. When processing 1 square meter of a silver halide black-and-white photographic light-sensitive material, the replenisher of the developing solution is 500 ml or less, preferably 4 ml or less.
Not more than 00 milliliters. It is preferable to concentrate the processing liquid and dilute it at the time of use for the purpose of transporting the processing liquid, packaging material cost, saving space, and the like. For concentration of the developer, it is effective to convert a salt component contained in the developer into potassium salt.

The fixing solution used in the fixing step of the present invention comprises sodium thiosulfate, ammonium thiosulfate, and, if necessary, tartaric acid, citric acid, gluconic acid, boric acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanoic acid, tiron and ethylenediamine. It is an aqueous solution containing salts of tetraacetic acid, diethylenetriaminepentaacetic acid, and nitrilotriacetic acid.
From the viewpoint of environmental protection in recent years, it is preferable that boric acid is not contained. As a fixing agent of the fixing solution used in the present invention, sodium thiosulfate, ammonium thiosulfate and the like are used. From the viewpoint of fixing speed, ammonium thiosulfate is preferable, but sodium thiosulfate may be used from the viewpoint of environmental protection in recent years. . The amount of these known fixing agents can be varied as appropriate, and is generally about 0.1 to about 2 mol / l. Particularly preferably, it is 0.2 to 1.5 mol / liter. The fixing solution may optionally contain a hardening agent (eg, a water-soluble aluminum compound), a preservative (eg, a sulfite,
Bisulfite), a pH buffer (eg, acetic acid), a pH adjuster (eg, ammonia, sulfuric acid), a chelating agent, a surfactant, a wetting agent, and a fixing accelerator. Examples of the surfactant include anionic surfactants such as sulfates and sulfonates, polyethylene surfactants, and amphoteric surfactants described in JP-A-57-6740. In addition, a known antifoaming agent may be added. Examples of the wetting agent include alkanolamine and alkylene glycol. Examples of the fixing accelerator include, for example, JP-B Nos. 45-35754 and 58-122535.
Nos. 58-122536, alcohols having a triple bond in the molecule, U.S. Pat.
A thioether compound described in JP-A-126449;
And the like, and the compounds described in JP-A-2-44355 may be used. Examples of the pH buffer include organic acids such as acetic acid, malic acid, succinic acid, tartaric acid, citric acid, oxalic acid, maleic acid, glycolic acid, and adipic acid; and inorganic acids such as boric acid, phosphate, and sulfite. Buffers can be used. Acetic acid, tartaric acid, and sulfite are preferably used. Here, the pH buffering agent is used for the purpose of preventing the pH of the fixing agent from increasing due to carry-in of the developing solution, and 0.01 to
1.0 mol / liter, more preferably 0.02 to 0.1.
Use about 6 mol / l. Further, compounds described in JP-A-64-4739 can be used as the dye elution accelerator.

The hardener in the fixing solution of the present invention includes a water-soluble aluminum salt and a chromium salt. Preferred compounds are water-soluble aluminum salts, such as aluminum chloride, aluminum sulfate and potassium alum. The preferred addition amount is 0.01 mol to 0.2 mol / l, and more preferably 0.03 to 0.08 mol / l. The fixing temperature is about 20 ° C. to about 50 ° C., preferably 25 ° C.
At ~ 45 ° C, the fixing time is 5 seconds to 1 minute, preferably 7 seconds to
50 seconds. The replenishing amount of the fixing solution is not more than 600 ml / m ² , particularly preferably not more than 500 ml / m ² , based on the processing amount of the photosensitive material.

The photosensitive material which has been developed and fixed is then subjected to washing or stabilization. In the washing or stabilizing treatment, the washing water amount is usually ² m ² per m ^{2 of the} silver halide photosensitive material.
It is carried out at 0 liters or less, and the replenishment amount (3 liters or less)
In other words, it can also be carried out by washing with water. That is, not only water saving processing can be performed, but also piping for installing the automatic processing machine can be eliminated. As a method for reducing the replenishing amount of washing water, a multi-stage countercurrent method (for example, 2
Stage, three stage, etc.) are known. If this multi-stage countercurrent method is applied to the present invention, the photosensitive material after fixing is gradually processed in the normal direction, that is, the processing solution which is not stained with the fixing solution is sequentially contacted, so that the efficiency is further improved. Washing is performed. When washing with a small amount of water, see JP-A-63-18 / 1988.
It is more preferable to provide a washing tank for a squeeze roller and a crossover roller described in JP-A Nos. 350 and 62-28725. Alternatively, various oxidizing agents may be added or a filter may be combined to reduce the pollution load which is a problem when washing with a small amount of water. Further, part or all of the overflow liquid from the washing or stabilizing bath produced by replenishing the water subjected to the antifungal means to the washing or stabilizing bath by the method of the present invention according to the treatment is disclosed in 235
As described in JP-A-133, it can also be used for a processing solution having a fixing ability, which is the preceding processing step. Further, a water-soluble surfactant or an antifoaming agent may be added in order to prevent water bubble unevenness which is likely to be generated when washing with a small amount of water and / or to prevent a processing agent component adhering to a squeeze roller from being transferred to a processed film. Good. Further, in order to prevent contamination by the dye eluted from the photosensitive material, JP-A-63-16345
The dye adsorbent described in No. 6 may be installed in a washing tank. In addition, a stabilization process may be performed following the water washing process,
Examples thereof include JP-A-2-201357 and JP-A-2-132.
No. 435, No. 1-125553, JP-A-46-444.
A bath containing the compound described in No. 46 may be used as a final bath of the light-sensitive material. If necessary, a metal compound such as an ammonium compound, Bi, or Al, a fluorescent brightener, various chelating agents, a film pH regulator, a hardening agent, a bactericide, a fungicide, an alkanolamine or a surfactant may be used in this stabilizing bath. Agents can also be added. The water used in the washing step or the stabilization step includes tap water, deionized water, halogen, ultraviolet sterilizing lamp, and water sterilized by various oxidizing agents (ozone, hydrogen peroxide, chlorate, etc.). It is preferable to use, and washing water containing the compounds described in JP-A-4-39652 and JP-A-5-241309 may be used. Washing or stabilizing bath temperature and time are 0-5
0 ° C. and 5 seconds to 2 minutes are preferred.

The processing solution used in the present invention is disclosed in
It is preferable to store in a packaging material having low oxygen permeability described in No. 73147. The treatment liquid used in the present invention may be in the form of a powder and solidified. Known methods can be used, but it is preferable to use the methods described in JP-A-61-259921, JP-A-4-85533, and JP-A-4-16841. Particularly preferred is the method described in JP-A-61-259921. When the replenishment amount is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. The roller transport type automatic developing machine is described in U.S. Pat. Nos. 3,025,779 and 3,545,971 and the like, and is simply referred to as a roller transport type processor in this specification. The roller transport type processor has four steps of development, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, a stop step), but most preferably follows these four steps. . Four steps of a stabilization step may be used instead of the water washing step.

The hydrazine nucleating agent of the present invention comprises a method for directly obtaining a positive image by surface developing an internal latent image type silver halide photographic emulsion in the presence of a nucleating agent, and a photographic emulsion used in such a method. Or photosensitive materials (for example, U.S. Pat. Nos. 2,456,953, 2,497,875, 2,497,876, 2,588,982, 2,592,250, and 2,675). Nos. 3,318, 3,227,552, 3,317,322, British Patents 1,011,062, 1,151,363.
Nos. 1,269,640 and 2,011,391, JP-B-43-29405, JP-A-49-38164, JP-A-53-16623, JP-A-53-137133, and JP-A-5-137133.
No. 4-37732, No. 54-40629, No. 54-7
No. 4536, No. 54-74729, No. 55-5205
No. 5, No. 55-90940, etc.). In the above method for obtaining a direct positive image, a nucleating agent may be added to a developer, but a more general method is to add the nucleating agent to a photographic emulsion layer or another appropriate layer of a light-sensitive material. There are no particular restrictions on the various additives, development processing methods, and the like used in the light-sensitive material of the present invention, and for example, those described in the following places can be preferably used. Item The relevant section 1) Surfactant JP-A-2-12236, page 9, right upper column, line 7 to lower right column, line 7, and JP-A-2-18542, page 2, lower left column, page 13 From line 4 to line 18, lower right column, page 4. 2) Antifoggants JP-A-2-103536, page 17, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, lines 1 to 5, furthermore, JP-A-1-237538 Thiosulfinic acid compounds described in the official bulletin. 3) Polymer latex, page 12, lower left column, lines 12 to 20 of JP-A-2-103536. 4) Compound having an acid group From page 6, lower right column, line 6 to page 19, upper left column, line 1 of JP-A-2-103536. 5) Matting agent, slip agent JP-A-2-103536, page 19, upper left column, 15 plasticizer line to page 19, upper right column, line 15 line. 6) Hardener From page 5, right upper column, line 5 to line 17, JP-A-2-103536. 7) Dyes Dyes on page 17, lower right column, lines 1 to 18 of JP-A-2-103536, solid dyes described in JP-A-2-29438 and JP-A-3-185773. 8) Binder JP-A-2-18542, page 3, lower right column, line 1 to line 20. 9) Black spot inhibitors Compounds described in U.S. Pat. No. 4,956,257 and JP-A-1-118832. 10) Redox compound The compound represented by the general formula (I) of JP-A-2-301743 (especially compound examples 1 to 50) and the general formula (3) described in the publication of JP-A-3-174143, pp. 3 to 20. (R-1), (R-2), (R-3), compounds described in Compound Examples 1 to 75, and further described in Japanese Patent Application Nos. 3-69466 and 3-15648. 11) Monomethine compounds Compounds of the general formula (II) described in JP-A-2-287532 (especially compound examples II-1 to II-26). 12) Dihydroxybenze A compound described in the upper left column of page 11 of JP-A-3-39948 to the lower left column of page 12 of JP-A No. 3-39948, and in the publication of EP 452772A.

[0112]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.

Example 1 <Adjustment of solid dispersion of hydrazide compound> Demol SNB
A 25% aqueous solution of (Kao Corporation) was prepared. Next, Table 6
To 0.5 g of the hydrazide compound shown in (1), 0.6 g of the Demol SNB aqueous solution and 59 g of water were added and mixed to form a slurry. This slurry is dispersed in a disperser (1/16 gallon, sand grinder mill (manufactured by Imex Co., Ltd.))
And 170 g of glass beads having a diameter of 0.8 to 1.2 mm were used as a medium and dispersed for 15 hours. Next, an aqueous gelatin solution was added and mixed so that the hydrazide compound concentration was 0.5% and the gelatin concentration was 5%, and 2000 ppm of proxel was added to gelatin as a preservative. Finally, the pH was adjusted to 5.0 by adding ascorbic acid. Table 6 shows the average particle size of the solid dispersion of the hydrazide compound. As a comparative example of the hydrazide compound of the present invention, the following hydrazide compound was used.

[0114]

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[0115]

[Table 7]

Example 2 <Preparation of silver halide photographic light-sensitive material> Preparation of emulsion A Silver nitrate aqueous solution, potassium bromide, sodium chloride and silver 1
An aqueous solution of a halogen salt containing K ₃ IrCl ₆ corresponding to 3.5 × 10 ⁻⁷ mol and K ₂ Rh (H ₂ O) Cl ₅ corresponding to 2.0 × 10 ⁻⁷ mol per mol, sodium chloride, and 1 mol The mixture was added to a gelatin aqueous solution containing 2,3-dimethyl-2-imidazolidinthione by stirring by a double jet method to prepare silver chlorobromide particles having an average particle size of 0.25 µm and a silver chloride content of 70 mol%.

Thereafter, the resultant was washed with water by a flocculation method according to a conventional method, 40 g of gelatin was added per 1 mol of silver, and 7 mg of sodium benzenethiosulfonate and 2 mg of benzenesulfinic acid were added per 1 mol of silver.
H6.0, adjusted to pAg7.5, 2 mg per mole of silver
Of sodium thiosulfate and 4 mg of chloroauric acid
Chemical sensitization was carried out at 0 ° C. to obtain the optimum sensitivity. Thereafter, 4-hydroxy-6-methyl-1,3,3 is used as a stabilizer.
150 mg of a, 7-tetrazaindene was added, and 100 mg of proxel was further added as a preservative. The obtained grains had an average grain size of 0.25 μm and a silver chloride content of 7, respectively.
It was 0 mol% silver chlorobromide cubic grains. (Coefficient of variation 1
0%)

Preparation of Coated Sample On a polyethylene terephthalate film support having an undercoat of a moisture-proof layer containing vinylidene chloride, from the support side,
Samples were prepared by applying the layers sequentially to form a UL layer, an EM layer, a PC layer, and an OC layer. The preparation method and application amount of each layer are shown below.

(UL layer) A dispersion of polyethyl acrylate in an amount of 30 wt% based on gelatin was added to an aqueous gelatin solution, and the mixture was coated so as to have a gelatin content of 0.5 g / m ² .

[0120] in (EM layer) above emulsions A, the following compound as a sensitizing dye (S-1) per mole of silver 5 × 10 ^-4 mol, the 5 × 10 ^-4 mol was added (S-2), further 3 × 10 ⁻⁴ mol of mercapto compound represented by the following (a) per mol of silver, 4 × 10 ⁻⁴ mol of mercapto compound represented by (b), represented by 4 × 10 ⁻⁴ mol of (c) Triazine compound, 2 × 10 ⁻³ mol of 5-chloro-8-hydroxyquinoline, 5 × 10 ⁻⁴ mol of nucleation accelerator represented by (A), 5 × 10 ⁻⁴ mol of (p) Surfactant was added. Further, hydroquinone was added at 100 mg / m ² ,
-Oleyl-N-methyltaurine sodium salt 30 mg
/ M ² . Next, a solid dispersion of the hydrazide compound prepared in Example 1 as a nucleating agent was added as a hydrazide compound in an amount of 5 × 10 ⁻⁴ mol / Agmol as shown in Table 7. Further, the water-soluble latex shown in (d) was 200 mg / m ² , the dispersion of polyethyl acrylate was 200 mg / m ² , methyl acrylate, sodium 2-acrylamido-2-methylpropanesulfonic acid sodium salt and 2-acetoacetoxyethyl 200 mg / latex copolymer of methacrylate (88: 5: 7 by weight)
m ² , colloidal silica having an average particle size of 0.02 μm
mg / m ² , 200 mg / m ² of 1,3-divinylsulfonyl-2-propanol as a hardener, and 30 mg / m ^{2 of} sodium polystyrene sulfonate as a thickener.
The pH of the solution was adjusted to 5.65 using acetic acid. They were applied so that the applied silver amount was 2.8 g / m ² .

(PC layer) Ethyl acrylate dispersion of 50 wt% based on gelatin in aqueous gelatin solution;
The following surfactant (w) was added at 5 mg / m ² , and 1,5-dihydroxy-2-benzaldoxime was added at 10 mg / m ² , and gelatin was applied at 0.5 g / m ² . .

(OC layer) An amorphous SiO ₂ matting agent 40 having a gelatin of 0.5 g / m ² and an average particle size of about 3.5 μm.
mg / m ^2, methanol silica 0.1 g / m ^2, and polyacrylamide 100 mg / m ² and the silicone oil 20 mg / m fluorosurfactant 5 mg / m ^2, shown as ^2, and coating aids by the following structural formula (e) 100 mg / m ² of sodium dodecylbenzenesulfonate was applied.

[0123]

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These coated samples have a back layer and a back protective layer having the following compositions. [Back layer formulation] Gelatin 3 g / m ² latex Polyethyl acrylate 2 g / m ² Surfactant Sodium p-dodecylbenzenesulfonate 40 mg / m ²

[0125]

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SnO ₂ / Sb (weight ratio 90/10, average particle size 0.20 μm) 200 mg / m ² Dye Mixture of dye [a], dye [b] and dye [c] Dye [a] 70 mg / m ² Dye [b] 70 mg / m ² Dye [c] 90 mg / m ²

[0127]

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[Back protective layer] Gelatin 0.8 mg / m ² polymethyl methacrylate fine particles (average particle size 4.5 μm) 30 mg / m ² dihexyl-α-sulfosuccinate sodium salt 15 mg / m ² p-dodecylbenzene sulfone Sodium acetate 15 mg / m ² Sodium acetate 40 mg / m ²

As described above, the samples shown in Table 7 were prepared.

[0130]

[Table 8]

<Adjustment of Developer> A developer A having the following composition was prepared.

<Developer A> Sodium hydroxide 1.71 g Diethylenetriamine-5-acetic acid 4 g Potassium carbonate 27.5 g Sodium carbonate 25.5 g Sodium erythorbate 30 g N-methyl-p-aminophenol 7.5 g KBr 2 g 5-methylbenzotriazole 0.1 g 1-phenyl-5-mercaptotetrazole 0.02 g sodium sulfite 5 g glacial acetic acid 9 g Add water to 1 liter, and adjust the pH to 9.7.

Further, a developer B was adjusted to pH 9.4 by adding acetic acid to the developer A, and a developer C was adjusted to pH 10.0 by adding sodium hydroxide to the developer A. did.

<Evaluation> (1) Exposure and development treatment The above samples were exposed to xenon flash light with a light emission time of 10 ^-5 sec through a step wedge through an interference filter having a peak at 488 nm, and the developing solutions A, B, C was used to develop at 35 ° C. for 20 seconds with an automatic developing machine FG-680AG manufactured by Fuji Photo Film Co., Ltd., followed by fixing, washing and drying. The replenisher amounts of the developing solution and the fixing solution during processing were 100 ml and 150 ml, respectively, per 1 m ² of the sample.

As the fixing solution, a fixing solution A having the following formulation was used. <Fixing solution A> Ammonium thiosulfate 119.7 g Ethylenediaminetetraacetic acid 2Na dihydrate 0.03 g Sodium thiosulfate pentahydrate 10.9 g Sodium sulfite 25.0 g NaOH (in pure) 12.4 g Glacial acetic acid 29.1 g Tartaric acid 2.92 g Sodium gluconate 1.74 g Aluminum sulfate 8.4 g pH (adjusted with sulfuric acid or sodium hydroxide) 4.8 Add water to 1 liter

(2) High contrast The high contrast when developed with the developing solution A was expressed as follows. As an index (gamma) indicating the contrast of the image, a point between fog + density of 0.1 and a point of fog + density of 3.0 on the characteristic curve is connected by a straight line, and the slope of the straight line is represented as a gamma value. That is, gamma = (3.0−0.1) / [lo
g (exposure amount giving a density of 3.0)-(exposure amount giving a density of 0.1)], and the larger the gamma value, the harder the photographic characteristics. (3) Photosensitivity The sensitivity is represented by the reciprocal of the exposure amount that gives a density of 1.5,
The relative value of the sensitivity of each sample when the comparative sample was set to 100 was calculated. The higher the value, the higher the sensitivity. (4) Dependence of photographic properties on developer pH Using the sensitivity values at the time of development with developers B and C, the dependence of sensitivity on developer pH was calculated by the following equation. PH dependence of sensitivity (ΔS _1.5 ) = S _1.5 (Developer C) −
S _1.5 (Developer B) The smaller the value, the smaller the pH dependence of the developer, that is, the higher the processing stability. (5) Stability over time of photosensitive material A sample stored at 60 ° C. and 65% humidity for 3 days was subjected to a developing treatment with a developing solution A according to the method described above, and the sensitivity was measured. The change in photographic properties with a sample stored at room temperature and humidity for 3 days was expressed by the following equation. Sensitivity variation with time (ΔS _1.5 ) = S _1.5 (Temperature 60
(Sample stored at 65 ° C. and humidity of 65% for 3 days) −S _1.5 (Sample stored at normal temperature and normal humidity for 3 days) The closer the value is to 0, the higher the temporal stability of the light-sensitive material is.

Table 8 shows the results.

[0138]

[Table 9]

<Results> Only when the hydrazide compound of the present invention was used as a nucleating agent, an argon laser scanner having a high processing stability with a low pH developer and a high processing stability and excellent storage stability of a light-sensitive material was used. Sensitive material was obtained.

Example 3 <Preparation of a silver halide photographic light-sensitive material> Emulsion preparation Emulsion B was prepared by the following method. Same as Emulsion A except that 1 mg of selenium sensitizer of the following structural formula per mole of silver, 1 mg of sodium thiosulfate and 4 mg of chloroauric acid are added and chemically sensitized at 60 ° C. to obtain an optimum sensitivity. It was adjusted.

[0141]

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Preparation of Coated Sample The following compound (S-3) was added in place of the sensitizing dye of the EM layer of Example 2 in an amount of 2.1 × 10 ^-4 mol per mol of silver. A sample was prepared in the same manner as in Example 2 except that Emulsion B was used.

[0143]

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<Evaluation> (1) Exposure and development treatment The above sample was exposed to xenon flash light having an emission time of 10 ^-6 sec through a step wedge through an interference filter having a peak at 633 nm. Using the developer A described in Example 2, FG-680AG manufactured by Fuji Photo Film Co., Ltd.
After developing at 35 ° C. for 20 seconds with an automatic developing machine, fixing (same as in Example 2), washing with water and drying were performed. The replenisher amounts of the developing solution and the fixing solution at the time of processing were each 100 ml per 1 m ² of the sample.

The evaluation of the high contrast property, the dependence of the sensitivity on the developer pH, and the stability over time of the light-sensitive material were carried out in the same manner as in Example 2.

<Results> As in Example 2, only when the hydrazide compound of the present invention was used as a nucleating agent, the processing stability was high, the processing stability was high, and the storage stability of the photographic material was low in a low pH developer. An excellent photosensitive material for a helium neon laser scanner was obtained.

Example 4 <Preparation of a silver halide photographic light-sensitive material> A sample was prepared in the same manner as in Example 2 except that the sensitizing dye of the EM layer in Example 2 was changed to the following compound (S-4). Created.

[0148]

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<Evaluation> The above sample was exposed to xenon flash light having an emission time of 10 ⁻⁶ sec through a step wedge through an interference filter having a peak at 780 nm. The developer A described in Example 2 was used for development at 35 ° C. for 20 seconds using a FG-680AG automatic developing machine manufactured by Fuji Photo Film Co., Ltd., followed by fixing (same as in Example 2), washing with water and drying. . The replenisher amounts of the developing solution and the fixing solution at the time of processing were each 100 ml per 1 m ² of the sample.

The evaluation of the dependence of the high contrast, the sensitivity on the developer pH, and the stability over time of the light-sensitive material were carried out in the same manner as in Example 2.

<Results> As in Example 2, only when the hydrazide compound of the present invention was used as a nucleating agent, the processing stability was high, the processing stability was high, and the storage stability of the photosensitive material was low. An excellent photosensitive material for a semiconductor laser scanner was obtained.

Example 5 <Preparation of silver halide photographic material> A sample was prepared in the same manner as in Example 2 except that the sensitizing dye of the EM layer in Example 2 was changed to the following compound (S-5). Created.

[0153]

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<Evaluation> The above sample was exposed to tungsten light at 3200 ° K through a step wedge. Using the developer A described in Example 2, F photo by Fuji Photo Film Co., Ltd.
After developing at 35 ° C. for 20 seconds with a G-680AG automatic developing machine, fixing (same as in Example 2), washing with water and drying were performed. The amount of replenisher for the developer and fixer during processing was 1 m ²
100ml each.

The evaluation of the dependence of high contrast and sensitivity on the pH of the developer and the stability over time of the light-sensitive material were carried out in the same manner as in Example 2.

<Results> As in Example 2, only when the hydrazide compound of the present invention was used as a nucleating agent, the processing stability was high, the processing stability was high, and the storage stability of the photographic material was low in a low pH developer. Excellent photographic material was obtained.

Example 6 <Preparation of silver halide photographic light-sensitive material> Preparation of emulsion C: 3 × / mol of silver and sodium chloride kept at 38 ° C.
1.5% gelatin aqueous solution at pH = 2.0 containing 10 ^-5 mol of the following compound-Z, 5 × 10 ^-3 mol of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene Silver nitrate and 5 × 10 ^-5 mol of K ₂ Ru (NO) Cl per mol of silver
_An aqueous sodium chloride solution containing ₅ was added simultaneously by a double jet method at a potential of 95 mV for 3 minutes and 30 seconds to obtain half of the silver content of the final particles to prepare 0.12 μm of core particles. Thereafter, an aqueous solution of silver nitrate and an aqueous solution of sodium chloride containing 5 × 10 ⁻⁵ mol of K ₂ Ru (NO) Cl ₅ per mol of silver were added in the same manner as above for 7 minutes, and a silver chloride cube having an average grain size of 0.13 μm was added. Particles were prepared. (Coefficient of variation 12%). Thereafter, the resultant was washed with water by a flocculation method well-known in the art to remove soluble salts, and gelatin was added. Compounds -F and phenoxyethanol were added as preservatives at a concentration of 60 mg / mol of silver. pAg = 7.
5, 4 × 10 ⁻⁵ mol of chloroauric acid, 1 × 10 ⁻⁵ mol of the selenium sensitizer and 1
× 10 ^-5 mol of sodium thiosulfate was added at 60 ° C.
After heating for 0 minutes and performing chemical sensitization, 4-
Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added at 1 × 10 ⁻³ mol per mol of silver (final particles: pH = 5.7, pAg = 7.5, Ru =
Silver chloride containing 5.times.10.sup.- ⁵ mol / Ag mol).

[0158]

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Preparation of Coated Sample (Silver Halide Emulsion Layer) The following compound was added to Emulsion C, and a gelatin coating amount of 0.9 g was coated on a support described below including an undercoat layer.
/ M ^2, the coating amount of silver coated with silver halide emulsion layer as a 2.75 g / m ^2. N-oleyl-N-methyltaurine sodium salt 19 mg / m ² Solid dispersion of hydrazide compound prepared in Example 1 shown in Table 9 15 mg / m ² (as hydrazide compound) Nucleation promoter Z 20 mg / m ² Sodium 3- (5-mercaptotetrazole) -benzenesulfonate 11 mg / m ² Compound A 13 mg / m ² Ascorbic acid 1 mg / m ² Compound B 15 mg / m ² Compound C 70 mg / m ² Acetic acid the amount pH 5.2 the amount compound D 950 mg / m ² Riboran -1400 that (manufactured by Lion Yushi) to be ~6.0 47 mg / m ² compound E (hardening agent) swelling rate in water is 80%

An emulsion protective lower layer and upper layer were coated on the above emulsion layer.

(Emulsion Protection Lower Layer) The following compounds were added to an aqueous gelatin solution, and the mixture was coated so that the coated amount of gelatin was 0.8 g / m ² . Gelatin (Ca ⁺⁺ content 2700ppm) 0.8 g / m ² Compound F 1 mg / m ² 1,5- dihydroxy-2-benzaldoxime _{^{14 mg / m 2 C 2 H}} 5 SO 2 SNa 3 mg / m 2 Compound C 3 mg / m ² Sodium p-dodecylbenzenesulfonate 7 mg / m ² Water-soluble dye Y 25 mg / m ²

(Preparation of Emulsion Protection Upper Layer Coating Solution and Its Coating)
The following compound was added to the aqueous gelatin solution, and the mixture was coated so that the coated amount of gelatin was 0.45 g / m ² . Gelatin (Ca ⁺⁺ content 2700 ppm) 0.45 g / m ² amorphous silica matting agent (average particle size 4.4 μm) 40 mg / m ² amorphous silica matting agent (average particle size 3.6 μm) 10 mg / m ² Compound F 1 mg / m ² Compound C 8 mg / m ² Solid disperse dye-G ₁ 68 mg / m ² Liquid paraffin 21 mg / m ² N-Perfluorooctanesulfonyl-N-propylglycine potadium 5 mg / m ² p-dodecyl Sodium benzenesulfonate 29mg / m ²

Then, the following conductive layer and back layer were simultaneously coated on the opposite side of the support.

(Conductive layer) The following compounds were added to an aqueous gelatin solution, and the mixture was coated so that the coated amount of gelatin was 0.06 g / m ² . SnO ₂ / Sb (weight ratio 9/1, average particle size 0.25 μm) 186 mg / m ² gelatin (Ca ⁺⁺ content 2700 ppm) 0.06 mg / m ² sodium p-dodecylbenzenesulfonate 13 mg / m ² dihexyl α-Sulfosuccinate sodium 12 mg / m ² Compound C 12 mg / m ² Compound F 1 mg / m ²

(Back layer) The following compound was added to an aqueous gelatin solution, and the mixture was coated so that the coated amount of gelatin was 1.94 g / m ² . Gelatin (Ca ⁺⁺ content: 30 ppm) 1.94 g / m ² polymethyl methacrylate fine particles (average particle size: 4.7 μ) 7 mg / m ² compound-H 233 mg / m ² compound-I 21 mg / m ² compound-G 146 mg / m ² Compound-F 3 mg / m ² Sodium p-dodecylbenzenesulfonate 68 mg / m ² Sodium dihexyl-α-sulfosuccinate 21 mg / m ² C ₈ F ₁₇ SO ₃ Li 4 mg / m ² N-perfluorooctanesulfonyl-N-propyl glycine potadium 6 mg / m ² sodium sulfate 177 mg / m ² Compound-E (hardener) The amount of swelling ratio in water at 90%

(Support, Undercoat Layer) The first and second undercoat layers having the following composition on both sides of a biaxially stretched polyethylene terephthalate support (thickness: 100 μm) were applied. (One undercoat layer) Core shell type vinylidene chloride copolymer 15 g 2,4-dichloro-6-hydroxy-s-triazine 0.25 g Polystyrene fine particles (average particle size 3 μ) 0.05 g Compound-M 0.20 g Colloidal silica (Snow TEX ZL: particle size 70-100 μm, manufactured by Nissan Chemical Co., Ltd. 0.12 g 100 g by adding water Further, 10% by weight of KOH is added, and the coating solution adjusted to pH = 6 is dried at a drying temperature of 180 ° C. for 2 minutes. The film thickness is 0.
It was applied to 9 μm.

(Second layer of undercoat layer) Gelatin 1 g Methylcellulose 0.05 g Compound-J 0.02 g C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H 0.03 g Compound-F 3.5 × 10 ^-3 g Acetic acid 0.2 g 100 g of water was added, and this coating solution was applied at a drying temperature of 170 ° C. for 2 minutes to a dry film thickness of 0.1 μm to prepare a support having an undercoat layer.

[0168]

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[0169]

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[0170]

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The coating method, drying conditions, etc., were as follows. <Coating method> On the support on which the above-mentioned undercoat layer has been formed, the emulsion layer, the lower layer of the emulsion protective layer, and the upper layer of the emulsion protective layer are arranged in this order from the side closer to the support as the emulsion surface side by a slide hopper method while maintaining the temperature at 35 ° C. Coating is applied simultaneously while adding a hardener solution, and after passing through a cold air setting zone (5 ° C.), the conductive layer and the back layer are arranged in the order of the conductive layer and the back layer from the side closer to the support on the side opposite to the emulsion surface. Coating was applied simultaneously while adding a hardener solution by a system, and a cold air set zone (5 ° C.) was set. At the time of passing through each set zone, the coating liquid showed sufficient setting properties. Subsequently, both surfaces were simultaneously dried in the drying zone under the following drying conditions. In addition, after coating the back surface side, it was conveyed in a non-contact state with a roller and other parts until winding up. The coating speed at this time is 120
m / min.

<Drying Conditions> After setting, the mixture was dried with a drying air at 30 ° C. until the weight ratio of water / gelatin became 800%.
Dry 200 to 200% with dry air at 35 ° C and 30%, apply air as it is, and after 30 seconds from when the surface temperature reaches 34 ° C (assuming the end of drying), dry for 1 minute at 48 ° C and 2% air. did. At this time, the drying time is 50 seconds from the start of drying to a water / gelatin ratio of 800% and 35 from 800 to 200%.
Seconds, 5% from 200% to the end of drying.

This photosensitive material was wound up at 23 ° C. and 40%, then cut under the same environment, and placed in a barrier bag conditioned for 6 hours.
After humidifying at 0 ° C. 10% for 8 hours, the sample was sealed with cardboard conditioned at 23 ° C. 40% for 2 hours to prepare a sample. When the humidity inside the barrier bag was measured, it was 40%.

In the manner described above, the samples shown in Table 9 were produced.

[0175]

[Table 10]

<Evaluation> The above sample was exposed through a step wedge using a Dainippon Screen P-627FM printer. Using the developer A described in Example 2, a FG-680AG automatic developing machine manufactured by Fuji Photo Film Co., Ltd. at 35 ° C.
After development for 20 seconds, fixing (same as in Example 2), washing with water and drying were performed. The replenisher amounts of the developing solution and the fixing solution at the time of processing were each 100 ml per 1 m ² of the sample.

The evaluation of the high contrast property, the dependency of the sensitivity on the developer pH, and the stability over time of the light-sensitive material were carried out in the same manner as in Example 2.

Table 10 shows the results.

[0179]

[Table 11]

<Results> Only when the hydrazide compound of the present invention was used as a nucleating agent, a bright room return feeling was obtained in which the processing stability was high, the processing stability was high, and the storage stability of the photographic material was excellent, with a low pH developer. Wood was obtained.

Example 7 In Examples 2, 3, 4, 5, and 6, a developing solution D or a developing solution E having the following composition was used in place of the developing solution A, and a fixing solution having the following composition was used instead of the fixing solution A. Even when B is used, as in Examples 2, 3, 4, 5, and 6, only when the hydrazide compound of the present invention is used as a nucleating agent, the processing stability is high due to ultra-high contrast in a low pH developer. In addition, a light-sensitive material excellent in storage stability of the light-sensitive material could be obtained. In order to examine the pH dependence of the photographic properties of the developer, the pH of each developer was adjusted with acetic acid.
Was used, and a solution whose pH was increased by 0.3 with sodium hydroxide was used.

<Developer D> Potassium hydroxide 40.0 g Diethylenetriamine-pentaacetic acid 2.0 g Potassium carbonate 60.0 g Sodium metabisulfite 70.0 g Potassium bromide 7.0 g Hydroquinone 40.0 g 5-methylbenzotriazole 0.35 g 4-hydroxymethyl-4 -Methyl-1-phenyl-3-pyrazolidone 1.50 g 2-Sodium 2-mercaptobenzimidazole-5-sulfonate 0.30 g Sodium 3- (5-mercaptotetrazol-1-yl) benzenesulfonate 0.10 g Sodium erythorbate 6.0 g Diethylene glycol 5.0 g. Add potassium hydroxide, add water to make 1 liter and adjust pH to 10.65. 1 liter

<Developing solution E> A working solution was prepared in the following storage form by adding water to a solid developer to make 10 liters. The method for producing the solid developer is that the material is a high-density polyethylene (average thickness = 500 μm,
(00 to 1000 μm) A developing component corresponding to 10 liters of a working solution was packed as a solid in a container. At this time, each component was mixed and then charged into a container. Working solution of developer 10
Table 11 shows the composition of the liter and the form of the raw material.

[0184]

[Table 12]

As for the raw material form, the raw powder is used as a general industrial product, and beads of alkali metal salts,
Commercial products were used for both pellets. When the raw material was in the form of briquettes, it was pressurized and compressed using a briquetting machine to form an irregular shaped rugby ball type having a length of about 4 to 6 mm, which was then crushed and used. For minor components, each component was blended before briquetting.

<Fixing solution B> The following solid agent and liquid agent were added to water to make 10 liters, and the solution was used. The fixing solution was made of high density polyethylene (thickness average = 500 μm, width 200-
(1000 μm) was used. The solution volume after dissolution was 10 liters, and the pH was 4.85.

<Solid agent part> Ammonium thiosulfate 1200 g Sodium thiosulfate 150 g Sodium acetate 400 g Sodium metabisulfite 200 g <Liquid agent part> Aluminum sulfate (27%) 300 g Sulfuric acid (75%) 30 g Sodium gluconate 20 g EDTA 0.3 g Citric acid 40 g The solid part is mixed and filled.

Example 8 A photographic material was prepared in the same manner as in Example 2 except that the powder of the hydrazide compound shown in Table 12 was dissolved in methanol and added to the coating solution, and developed in the same manner as in Example 2. Processing was performed, and the dependence of high contrast and sensitivity on developer pH was evaluated.

Table 12 shows the results.

[0190]

[Table 13]

<Results> As in Example 2, only when the hydrazide compound of the present invention was used as a nucleating agent, a light-sensitive material having ultra-high contrast and high processing stability could be obtained with a low pH developer. .

────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-7-244348 (JP, A) JP-A-6-161011 (JP, A) JP-A-6-148777 (JP, A) JP-A-5-148777 197091 (JP, A) JP-A-5-142688 (JP, A) JP-A-3-123344 (JP, A) JP-A-2-139538 (JP, A) (58) Fields investigated (Int. ⁷ , DB name) G03C 1/06 501

Claims (1)

(57) [Claims] 1. A silver halide photographic material comprising a hydrazide compound represented by the following general formula (I) or (II). General formula (I) A _1- (B) b ₁ General formula (II) L _0- {A _2- (B) b ₂ } m _{1 In the} formula, A ₁ represents a substituted or unsubstituted benzene ring;
₂ represents an arylene group, B represents a group represented by the following general formula (III), and b ₁ represents an integer of 3 to 6. L ₀ is 2
Represents a hexavalent linking group from the valence, b ₂ represents an integer of from 1 5, m ₁ represents an integer of 2 to 6. However, when b ₂ is 1,
m ₁ represents an integer of 3 to 6. Formula (III) -L ₁ -Ar ₁ -NHNH-G ₁ -R _{1 In the} formula, G ₁ represents a carbonyl group, an oxalyl group, a sulfonyl group, or a phosphoryl group, and R ₁ represents a hydrogen atom or a block group. Ar ₁ represents an aromatic group, and L ₁ represents a linking group.