JPH08211572A - Image forming method - Google Patents

Abstract

PURPOSE: To provide a silver halide photographic image forming method by which photographic performance with such very contrasty negative gradation as gamma of >10 can be ensured using a stable developer. CONSTITUTION: A silver halide photographic sensitive material having at least one silver halide emulsion layer on the substrate and contg. a hydrazine nucleus forming agent having an anionic group close to a hydrazino group or a nonionic group forming an intra-molecular hydrogen bond with a hydrogen atom of hydrazine in the emulsion layer or other hydrophilic colloidal layer is developed with a developer of pH8.5-11.0 contg. ascorbic acid or its deriv. and <=0.5mol/l sulfite.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an image forming method using a silver halide photographic light-sensitive material for plate making.

[0002]

2. Description of the Related Art A method of producing a high contrast image using a hydrazine derivative is well known and widely used for photolithography. However, since a high pH is generally required, the developer is easily oxidized by air and is unstable.

Attempts have been made to develop a high-contrast image by developing a silver halide light-sensitive material containing a hydrazine compound with a developer having a lower pH. Japanese Patent Laid-Open No. 1-19993
No. 9 and JP-A-1-179940, a photosensitive material containing a nucleation development accelerator having an adsorbing group for silver halide emulsion grains and a nucleating agent also having an adsorbing group was used to obtain a pH of 11.0. The processing method of developing with the following developing solution is described. U.S. Pat. Nos. 4,998,604 and 4,994,365 disclose hydrazine compounds having a repeating unit of ethylene oxide and hydrazine compounds having a pyridinium group. However, as is clear from these examples, the high contrast is not sufficient, and the high contrast and the required D
Getting max is difficult.

Further, the pH of the developing solution is increased by the concentration of the developing agent due to air oxidation and evaporation of water, or is lowered by the absorption of CO ₂ gas in the air and the development processing of the exposed photosensitive material. It is not always kept constant. If the pH of the developer changes, the photographic performance also changes, and especially the contrast adjustment performance changes, so it was necessary to add a large amount of replenisher.

As described above, there has been a demand for an image forming method in which the development pH is further lowered and the change in photographic performance due to the pH change is small, but the conventional technique cannot satisfy the demand.

[0006]

SUMMARY OF THE INVENTION Therefore, firstly, the object of the present invention is to obtain a silver halide photograph capable of obtaining a very hard negative tone photographic property with a gamma of more than 10 using a stable developing solution. An image forming method is provided. A second object of the present invention is a substantially hydroquinone-free ascorbic acid developer having a pH of 11.0 or less,
An object of the present invention is to provide an image forming method capable of obtaining a super-high contrast image.

[0007]

The above object of the present invention is to provide at least one silver halide emulsion layer on a support, which emulsion layer, or another hydrophilic colloid layer, is provided in the vicinity of a hydrazine group. A silver halide photographic light-sensitive material containing a hydrazine nucleating agent having an anionic group or a nonionic group forming an intramolecular hydrogen bond with a hydrogen atom of hydrazine, ascorbic acid, or a derivative thereof, and a sulfite of 0. It was achieved by an image forming method characterized in that development processing was carried out with a developing solution containing an amount of 5 mol / liter or less and having a pH of 8.5 to 11.0. A hydrazine-based nucleating agent having an anionic group or a nonionic group that forms an intramolecular hydrogen bond with a hydrogen atom of hydrazine in the vicinity of the hydrazine group of the present invention will be described.

Examples of the anionic group include carboxylic acid, sulfonic acid, sulfinic acid, phosphoric acid, phosphonic acid and salts thereof. Here, the vicinity of the hydrazine group is formed by 2 to 5 atoms selected from at least one kind of carbon atom, nitrogen atom, oxygen atom and sulfur atom between the nitrogen atom close to the anionic group of hydrazine and the anionic group. Means that the binding chain is intervened. More preferably as a neighborhood, there is an intervening bond chain formed of 2 to 5 atoms selected from at least one of carbon and nitrogen atoms, and even more preferably a bond chain formed of 2 to 3 carbon atoms. This is when intervening. A lone electron pair is 5 as a nonionic group that forms an intramolecular hydrogen bond with hydrazine hydrogen.
To a 7-membered ring to form a hydrogen bond with hydrazine hydrogen, and a group having at least one of an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom. Examples of the nonionic group include an alkoxy group, an amino group, an alkylthio group, a carbonyl group, a carbamoyl group, an alkoxycarbonyl group, a urethane group, a ureido group, an acyloxy group and an acylamino group. Of these, anionic groups are preferred, and carboxylic acids and salts thereof are most preferred. Preferred nucleating agents used in the present invention are those represented by the following general formulas (H-1) to (H-3). General formula (H-1)

[0009]

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(Wherein R ¹ represents an alkyl group, an aryl group or a heterocyclic group, L ¹ represents a divalent linking group having an electron-withdrawing group, Y ¹ represents an anionic group or a hydrogen atom of hydrazine). It represents a nonionic group forming an intramolecular hydrogen bond.) General formula (H-2)

[0011]

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(Wherein R ² represents an alkyl group, an aryl group or a heterocyclic group, L ² represents a divalent linking group, and Y
² represents an anionic group or a nonionic group that forms an intramolecular hydrogen bond with a hydrogen atom of hydrazine. ) General formula (H-3)

[0013]

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(In the formula, X ³ represents a group capable of substituting on a benzene ring, R ³ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group or an amino group, and Y ³ represents An anionic group or a nonionic group that forms an intramolecular hydrogen bond with a hydrogen atom of hydrazine, m ³ is an integer of 0 to 4, n ³ is 1 or 2. When n ³ is 1, R ³ is It has an electron-withdrawing group.)

The general formulas (H-1) to (H-3) will be described in more detail. The alkyl group of R ¹ and R ^{2 has 1 to} 16 carbon atoms, preferably a straight chain having 1 to 12 carbon atoms,
A branched or cyclic alkyl group, such as methyl,
Ethyl, propyl, isopropyl, t-butyl, allyl, propargyl, 2-butenyl, 2-hydroxyethyl, benzyl, benzhydryl, trityl, 4-methylbenzyl, 2-methoxyethyl, cyclopentyl, 2-
Acetamidoethyl.

The aryl group is an aryl group having 6 to 24 carbon atoms, preferably 6 to 12 carbon atoms, for example, phenyl, naphthyl, p-alkoxyphenyl, p-sulfonamidophenyl, p-ureidophenyl, p-amidophenyl. Is. The heterocyclic group is a 5-membered or 6-membered saturated or unsaturated heterocycle containing at least one oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms, and the number of heteroatoms constituting the ring. The type of the element may be one or plural, and examples thereof include 2-furyl, 2-thienyl, and 4-pyridyl.

An aryl group is preferred as R ¹ and R ² .
An aromatic heterocyclic group or an aryl-substituted methyl group,
More preferably, it is an aryl group (eg phenyl, naphthyl). R ¹ and R ² may be substituted with a substituent, and examples of the substituent include an alkyl group, an aralkyl group,
An alkoxy group, an alkyl- or aryl-substituted amino group,
Amido group, sulfonamide group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, aryl group, alkylthio group, arylthio group,
A sulfonyl group, a sulfinyl group, a hydroxy group, a halogen atom, a cyano group, a sulfo group, a carboxyl group, and a phosphorus amide group. These groups may be further substituted. Of these, a sulfonamide group, a ureido group, an amide group, an alkoxy group and a urethane group are preferable, and a sulfonamide group and a ureido group are more preferable. When possible, these groups may be linked to each other to form a ring.

Alkyl groups R ^3, aryl group, heterocyclic group include those described in R ^1. The alkenyl group has 2 to 18 carbon atoms, preferably 2 to 10 carbon atoms, and examples thereof include vinyl and 2-styryl. The alkynyl group has 2 to 18 carbon atoms, preferably 2 to 10 carbon atoms, and examples thereof include ethynyl and phenylethynyl. The alkoxy group is a linear, branched or cyclic alkoxy group having 1 to 16 carbon atoms, preferably 1 to 10 carbon atoms, and examples thereof include methoxy, isopropoxy and benzyloxy. The amino group has 0 to 16 carbon atoms, preferably 1 to 1 carbon atoms.
10 of them are ethylamino, benzylamino and phenylamino. When n ³ = 1, R ³ is preferably an alkyl group, an alkenyl group or an alkynyl group. n ³ = 2
At this time, R ³ is preferably an amino group or an alkoxy group.

The electron-withdrawing group contained in R ³ has a Hammett σ _m value of 0.2 or more, preferably 0.3.
Examples of the above include halogen atoms (fluorine, chlorine, bromine), cyano groups, sulfonyl groups (methanesulfonyl, benzenesulfonyl), sulfinyl groups (methanesulfinyl), acyl groups (acetyl, benzoyl), oxycarbonyl groups (methoxycarbonyl). ), Carbamoyl group (N-methylcarbamoyl), sulfamoyl group (methylsulfamoyl), halogen-substituted alkyl group (trifluoromethyl), heterocyclic group (2-benzoxazolyl, pyrrolo), quaternary onium group (tri Phenylphosphonium, trialkylammonium, pyridinium). Examples of R ³ having an electron-withdrawing group include trifluoromethyl, difluoromethyl, pentafluoroethyl, cyanomethyl, methanesulfonylmethyl, acetylethyl, trifluoromethylethynyl and ethoxycarbonylmethyl.

L ¹ and L ² represent a divalent linking group, and include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, a divalent heterocyclic group and their -O-, -S-,
It is a group in which groups such as —NH—, —CO—, and —SO ₂ — are used alone or in combination. L ¹ and L ² are R
^It may be substituted with the group described as the substituent of ¹ . Examples of the alkylene group include methylene, ethylene, trimethylene, propylene, 2-butene-1,4-yl, 2
-Butyn-1,4-yl. The alkenylene group is, for example, vinylene. The alkynylene group is ethynylene. The arylene group is, for example, phenylene. The divalent heterocyclic group is, for example, furan-1,4-diyl. L ¹ is an alkylene group,
An alkenylene group, an alkynylene group and an arylene group are preferable, and an alkylene group is more preferable. Further, an alkylene group having a chain length of 2 to 3 carbon atoms is most preferable. L ² is an alkylene group, an arylene group, —NH-alkylene-,
-O-alkylene- and -NH-arylene- are preferable, and -NH-alkylene- and -O-alkylene- are more preferable.

The electron-withdrawing group of L ¹ is R ³
Examples of the electron-withdrawing group of the above include.
Examples of L ¹ include tetrafluoroethylene, fluoromethylene, hexafluorotrimethylene, perfluorophenylene, difluorovinylene, cyanomethylene, and methanesulfonylethylene.

Y ¹ to Y ^{3 are} as described above, and are anionic groups or nonionic groups in which a lone pair of electrons forms a hydrogen bond with hydrazine hydrogen in a 5- to 7-membered ring. More specifically, examples of the anionic group include carboxylic acid, sulfonic acid, sulfinic acid, phosphoric acid, phosphonic acid and salts thereof. Examples of the salt include alkali metal ions (sodium and potassium), alkaline earth metal ions (calcium and magnesium), ammonium (ammonium, triethylammonium, tetrabutylammonium, pyridinium) and phosphonium (tetraphenylphosphonium). The nonionic group is a group having at least one of an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom, an alkoxy group, an amino group, an alkylthio group, a carbonyl group, a carbamoyl group,
Examples thereof include an alkoxycarbonyl group, a urethane group, a ureido group, an acyloxy group and an acylamino group. As Y ¹ to Y ³ , an anionic group is preferable, and a carboxylic acid and its salt are more preferable.

Examples of the group capable of substituting on the benzene ring of X ³ and its preferable groups include those mentioned as the substituents of R ^{1 in the} general formula (1). When m ³ is 2 or more, they may be the same or different.

R ¹ to R ³ or X ³ may have a diffusion resistant group used in a photographic coupler, or may have an adsorption promoting group to silver halide. The diffusion resistant group has 8 to 30 carbon atoms, preferably 12 to 25 carbon atoms. The adsorption promoting group for silver halide is preferably a thioamide (eg thiourethane,
Thioureido, thioamide), mercaptos (eg 5
-Mercaptotetrazole, 3-mercapto-1,2,
Heterocyclic mercapto such as 4-triazole, 2-mercapto-1,3,4-thiadiazole, and 2-mercapto-1,3,4-oxadiazole, alkylmercapto,
Aryl mercapto) and a 5- or 6-membered nitrogen-containing heterocycle (eg benzotriazole) which produces silver imino
Is. Examples of those having a silver halide adsorption promoting group include those having a structure in which the adsorbing group is protected and the protecting group is removed during the development processing to enhance the adsorptivity to silver halide.

In the general formulas (H-1) to (H-3), radicals from which hydrogen atoms of two compounds are removed may combine with each other to form a bis type. In the general formulas (H-1) to (H-3), the general formula (H-
1) and (H-2) are preferable, and general formula (H-1) is more preferable. Furthermore, general formulas (H-1) to (H-
3), the following general formulas (H-4) to (H-
6) is more preferable, and general formula (H-4) is most preferable. General formula (H-4)

[0026]

[Chemical 4]

(In the formula, R ⁴ , X ⁴ and m ⁴ are respectively synonymous with R ³ , X ³ and m ^{3 of the} general formula (H-3), and L ⁴ ,
Y ⁴ has the same meaning as L ¹ and Y ^{1 in} formula (H-1). ) General formula (H-5)

[0028]

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(In the formula, R ⁵ , X ⁵ and m ⁵ are respectively synonymous with R ³ , X ³ and m ^{3 in the} general formula (H-3), and L ⁵ ,
Y ⁵ has the same meaning as L ² and Y ^{2 in} formula (H-2). ) General formula (H-6)

[0030]

[Chemical 6]

(Wherein R ⁶¹ , R ⁶² , X ⁶ , m ⁶ , n ⁶ ,
Y is R ³ , R ³ , X ³ , m ³ of the general formula (H-3),
n ^3, Y ³ as synonymous. )

Specific examples of the nucleating agent used in the present invention are shown below, but the present invention is not limited thereto.

[0033]

[Chemical 7]

[0034]

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[0035]

[Chemical 9]

[0036]

[Chemical 10]

[0037]

[Chemical 11]

[0038]

[Chemical 12]

[0039]

[Chemical 13]

The hydrazine nucleating agent of the present invention is a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, It can be used by dissolving it in methyl cellosolve or the like. Further, by a well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as 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 produced and used. Alternatively, the hydrazine derivative powder can be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves according to a method known as a solid dispersion method, and then used.

The hydrazine nucleating agent of the present invention may be added to any of the silver halide emulsion layer on the silver halide emulsion layer side of the support or any other hydrophilic colloid layer. 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 1 × 10 ⁻⁶ to 1 × with ^respect to 1 mol of silver halide.
10 ⁻² mol is preferable, 1 × 10 ^{−5 to} 5 × 10 ⁻³ mol is more preferable, and 5 × 10 ⁻⁵ to 1 × 10 ⁻³ mol is most preferable.

The silver halide photographic light-sensitive material of the present invention comprises a silver halide emulsion layer or at least one other hydrophilic colloid layer, which is selected from amine derivatives, onium salts, disulfide derivatives and hydroxymethyl derivatives. It is preferable to contain a nuclear promoter. These nucleation accelerators may be used alone or in combination of two or more. Examples of amine derivatives include those disclosed in JP-A-60-14.
0,340, 62-50,829, 62-22
2,241, 62-250,439, 62-2
80,733, 63-124,045, 63-
Examples thereof include compounds described in Nos. 133,145 and 63-286,840. More preferred as amine derivatives are JP-A Nos. 63-124,045 and 63.
-133, 145, 63-286, 840 and the like having a group having a group capable of adsorbing to silver halide, or the sum of carbon numbers described in JP-A-62-222, 241 and the like. Is 20 or more compounds. The onium salt is preferably an ammonium salt or a phosphonium salt. Examples of preferable ammonium salts include the compounds described in JP-A Nos. 62-250,439 and 62-280,733. Also,
Examples of preferable phosphonium salts include JP-A-61-116
The compounds described in No. 7,939, No. 62-280,733, etc. can be mentioned. Examples of the disulfide derivative include the compounds described in JP-A No. 61-198,147. As the hydroxymethyl derivative, for example, US Pat. No. 4,693,956,
Examples thereof include compounds described in JP-A No. 4,777,118, EP231,850, JP-A-62-50,829, and the like, and a diarylmethanol derivative is more preferable.

Specific examples of the nucleation accelerator are shown below. However, the present invention is not limited to the following compounds.

[0044]

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[0045]

[Chemical 15]

[0046]

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[0047]

[Chemical 17]

[0048]

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[0049]

[Chemical 19]

[0050]

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[0051]

[Chemical 21]

[0052]

[Chemical formula 22]

[0053]

[Chemical formula 23]

[0054]

[Chemical formula 24]

The optimum addition amount of these compounds varies depending on the kind thereof, but 1.0 × 1 per mol of the hydrazine compound.
0 ⁻² mol to 1.0 × 10 ² mol, preferably 1.0 ×
It is desirable to use it in the range of 10 ⁻¹ mol to 1.0 × 10 mol. These compounds are dissolved in a suitable solvent (H ₂ O) alcohols such as methanol and ethanol, acetone, dimethylformamide, methylcellosolve, etc.) and added to the coating solution.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention includes silver chloride, silver bromide, and mixed silver halides such as silver chlorobromide, silver iodobromide and salts. Silver iodobromide or the like can be used. Silver chlorobromide and silver iodochlorobromide having a silver chloride content of 50 mol% or more are preferable. The silver iodide content is preferably 3 mol% or less, more preferably 0.5 mol or less. The shape of the silver halide grains may be any of a cube, a tetradecahedron, an octahedron, an irregular shape and a plate shape, but a cube is preferable. The average grain size of silver halide is preferably 0.01 μm to 0.7 μm, more preferably 0.05 to 0.5 μm, and {(standard deviation of grain size) / (average grain size)} × 100 It is preferable that the variation coefficient is 15% or less, more preferably 10% or less and the particle size distribution is narrow. The silver halide grains may have a uniform inner layer and a surface layer, or may have different layers. The photographic emulsion used in the present invention is described by P. Glafkides C
himie et Physique Photographique (Paul Montel, 1967), GFDufin, Photographic Emulsi
on Chemistry (The Focal Press, 1966), V.
Making and Coating Photographi by L. Zelikman et al
c Emulsion (The Focal Press, 1964) and the like.

As the method for reacting the soluble silver salt and the soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. Method of forming grains in the presence of excess silver ion (so-called reverse mixing method)
Can also be used. As one form of the simultaneous mixing method, a method of keeping pAg constant in the liquid phase in which silver halide is produced, that is, a so-called controlled double jet method can be used. Further, it is preferable to form grains using a so-called silver halide solvent such as ammonia, thioether, or tetra-substituted thiourea. More preferably, it is a tetra-substituted thiourea compound and is disclosed in JP-A-53-824.
08, 55-77737. Preferred thiourea compounds are tetramethylthiourea, 1,3-
Dimethyl-2-imidazolidinethione. In the controlled double jet method and the grain forming method using a silver halide solvent, it is easy to prepare a silver halide emulsion having a regular crystal form and a narrow grain size distribution. It is a useful tool for making emulsions. Further, in order to make the particle size uniform, British Patent No. 1,535,016 and Japanese Examined Patent Publication No. 48-3689.
As described in No. 0 and No. 52-16364,
A method of changing the addition rate of silver nitrate or an alkali halide according to the grain growth rate, and British Patent No. 4,242,4
It is preferable to use the method of changing the concentration of the aqueous solution as described in JP-A-45-58-158124, and to grow it quickly within a range not exceeding the critical saturation.

The silver halide emulsion of the present invention is preferably chemically sensitized. As the chemical sensitization method, 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 they can be used alone or in combination. When used in combination,
For example, the sulfur sensitizing method and gold sensitizing method, the sulfur sensitizing method, selenium sensitizing method and gold sensitizing method, the sulfur sensitizing method, tellurium sensitizing method and gold sensitizing 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 period of time. As the sulfur sensitizer, known compounds can be used. For example, in addition to the sulfur compound contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, and rhodanines are used. be able to. Preferred sulfur compounds are
Thiosulfate and thiourea compounds. The addition amount of the sulfur sensitizer changes under various conditions such as pH, temperature and size of silver halide grains during chemical ripening, but it is 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, it is usually carried out by adding an unstable and / or unstable selenium compound and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. Unstable selenium compounds are disclosed in JP-B-44-15748 and JP-B-43-1.
3489, JP-A-4-25832, and 4-1092.
No. 40, No. 4-324855, etc. can be used. It is particularly preferable to use the compounds represented by the general formulas (VIII) and (IX) in JP-A-4-324855.

The tellurium sensitizer used in the present invention is a compound capable of producing silver telluride which is presumed to serve as a sensitizing nucleus on the surface or inside of the silver halide grain. Regarding the rate of silver telluride formation in a silver halide emulsion, Japanese Patent Application No. 4-
It can be tested by the method described in 146739.
Specifically, U.S. Patent Nos. 1,623,499, 3,320,069, 3,772,031, British Patent 235,211 and 1,121,496.
No. 1, No. 1,295,462, No. 1,396,69
6, Canadian Patent No. 800,958, Japanese Patent Laid-Open No. 4-20
No. 4640, No. 4-271341, No. 4-33304
No. 3, No. 4-129787, J. Chem. Soc. Chem. Commu
n., 635 (1980), ibid. 1102 (1979), ibid. 645 (1979), J. Chem. Soc. Perkin. Trans., 1,
2191 (1980), edited by S. Patai, The Chemistry of
OrganicSerenium and Tellurium Compounds, Vol1
(1986) and Vol 2 (1987) can be used. Particularly preferred are the compounds represented by the general formulas (II) (III) (IV) in Japanese Patent Application No. 4-146739.

The amounts of the selenium and tellurium sensitizers used in the present invention vary depending on the silver halide grains used, the chemical ripening conditions and the like, but 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. It is 85 ° C.

Examples of the noble metal sensitizer used in the present invention include gold, platinum and palladium, with gold sensitization being particularly preferred. 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 of silver halide is used. Can be used.

In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite salt, a lead salt, a thallium salt or the like may coexist in the process of forming silver halide grains or physically ripening them. Reduction sensitization can be used in the present invention. As the reduction sensitizer, stannous salt, amines, formamidinesulfinic acid, silane compound and the like can be used. A thiosulfonic acid compound may be added to the silver halide emulsion of the present invention by the method shown in European Patent 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, those having different crystal habits, those having chemical sensitization, Those with different conditions) may be used in combination.

The silver halide photographic light-sensitive material of the present invention preferably contains a rhodium compound in order 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 halogen, an amine, oxalate, etc. as a ligand, such as a hexachlororhodium (III) complex salt, a hexabromorhodium (III) complex salt, a hexaamminerhodium ( Examples thereof include III) complex salts and trizalatrodium (III) complex salts. These rhodium compounds are used by dissolving them in water or a suitable solvent, and they are generally used to stabilize the solution of the rhodium compound, that is, an aqueous solution of hydrogen halide (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid). Etc.) or an alkali halide (eg, KCl, NaCl: KBr, Na
A method of adding Br or the like) can be used. Instead of using water-soluble rhodium, it is also possible to add and dissolve another silver halide grain which has been previously doped with rhodium when preparing the silver halide.

The total addition amount of the rhodium compound is 1 × 10 ^{-8 to} 5 × 1 per mol of the finally formed silver halide.
0 ^-6 mol is suitable, and preferably 5 x 10 ^-8 to 1 x 1
It is 0 ^-6 mol. The addition of these compounds can be appropriately carried out at the time of producing 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 be incorporated in the silver halide grains. preferable.

The silver halide photographic light-sensitive material of the present invention preferably contains an iridium compound in order to achieve high sensitivity and high contrast. Although various compounds can be used as the iridium compound used in the present invention,
For example, hexachloroiridium, hexaammineiridium, trioxalatoiridium, hexacyanoiridium and the like can be mentioned. These iridium compounds are used by dissolving them in water or a suitable solvent, and they are generally used to stabilize the solution of the iridium compound, that is, an aqueous solution of hydrogen halide (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid). Etc.) or an alkali halide (for example, KCl, NaCl, KBr, NaBr, etc.) can be used. Instead of using water-soluble iridium, it is also possible to add and dissolve another silver halide grain which has been previously doped with iridium when preparing the silver halide.

The total amount of the iridium compound added is 1 × 10 ^{-8 to} 5 × per mol of the finally formed silver halide.
10 ^-6 mol is suitable, and preferably 5 × 10 ^-8 to 1 ×.
It is 10 ^-6 mol. The addition of these compounds can be appropriately carried out during the production of silver halide emulsion grains and before each step of coating the emulsion, but it is particularly preferable to add these compounds at the time of emulsion formation and to incorporate them into the silver halide grains. .

The silver halide grains used in the present invention include
It may contain metal atoms such as iron, cobalt, nickel, ruthenium, palladium, platinum, gold, thallium, copper, lead and osmium. The metal is preferably 1 × 10 ⁻⁹ to 1 × 10 ⁻⁴ mol per mol of silver halide. Further, in order to contain the above metal, a metal salt in the form of a single salt, a double salt or a complex salt can be added and added at the time of preparation of particles.

Further, contact films and contact papers that can be handled in a bright room are generally called bright room return sensitive materials, and silver chloride emulsions are preferred for such sensitive materials.

The developing solution used in the present invention will be described. At least one ascorbic acid or its derivative is contained as a developing agent. Preferred ascorbic acid or its derivative is a compound represented by the general formula (II).

[0072]

[Chemical 25]

In the general formula (II), R ₁ and R ₂ are respectively a hydroxy group and an amino group (having 1 carbon as a substituent).
-10 alkyl groups such as methyl, ethyl, n-
Those having a butyl group, a hydroxyethyl group or the like as a substituent are included. ), An acylamino group (acetylamino group, benzoylamino group, etc.), an alkylsulfonylamino group (methanesulfonylamino group, etc.), an arylsulfonylamino group (benzenesulfonylamino group, p-
It represents a toluenesulfonylamino group), an alkoxycarbonylamino group (a methoxycarbonylamino group, etc.), a mercapto group, an alkylthio group (a methylthio group, an ethylthio group, etc.). Preferred examples of R ₁ and R ₂ include a hydroxy group, an amino group, an alkylsulfonylamino group and an arylsulfonylamino group.

P and Q are hydroxy group, hydroxyalkyl group, carboxyl group, carboxyalkyl group, sulfo group, sulfoalkyl group, amino group, aminoalkyl group,
Represents an alkyl group, an alkoxy group, a mercapto group, or P and Q are bonded to each other, together with two vinyl carbon atoms substituted by R ₁ and R ₂ and a carbon atom substituted by Y; It represents an atomic group necessary for forming a 7-membered ring. Specific examples of the ring structure, -O -, - C (R 4) (R 5) -, -
_{C (R 6) =, -} C (= O) -, - N (R 7) -, - N =,
It is configured by combining. However, R ₄ , R ₅ , R ₆ ,
R ₇ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be substituted (a hydroxy group, a carboxy group or a sulfo group can be mentioned as the substituent), a hydroxy group or a carboxy group. Further, a saturated or unsaturated condensed ring may be formed on the 5- to 7-membered ring.

Examples of the 5- to 7-membered ring include dihydrofuranone ring, dihydropyrone ring, pyranone ring, cyclopentenone ring, cyclohexenone ring, pyrrolinone ring, pyrazolinone ring, pyridone ring, azacyclohexenone ring, uracil ring and the like. And preferred examples of the 5- to 7-membered ring are:
Dihydrofuranone ring, cyclopentenone ring, cyclohexenone ring, pyrazolinone ring, azacyclohexenone ring,
The uracil ring can be mentioned.

Y is a group composed of ═O or ═N—R ₃ . Here, R ₃ is a hydrogen atom, a hydroxyl group, an alkyl group (eg methyl, ethyl), an acyl group (eg acetyl), a hydroxyalkyl group (eg hydroxymethyl, hydroxyethyl), a sulfoalkyl group (eg sulfomethyl, sulfoethyl), carboxy. Represents an alkyl group (eg carboxymethyl, carboxyethyl). Specific examples of the compound represented by formula (II) are shown below, but the invention is not limited thereto.

[0077]

[Chemical formula 26]

[0078]

[Chemical 27]

[0079]

[Chemical 28]

[0080]

[Chemical 29]

Of these, ascorbic acid and erythorbic acid (diastereomers of ascorbic acid) are preferred. The general range of the amount of the compound of the general formula (II) used is 5 × 10 ⁻³ per liter of the developing solution.
The amount is 1 to 1 mol, particularly preferably 10 ^{-2 to} 0.5 mol. The developer of the present invention preferably contains an auxiliary developing agent.

As the auxiliary developing agent, 3-pyrazolidones, phenylenediamines, and aminophenols can be used. As 3-pyrazolidones,
For example, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-5
-Methyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4
-Hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone,
1,5-diphenyl-3-pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1-phenyl-2-acetyl-
4,4-dimethyl-3-pyrazolidone, 1-p-hydroxyphenyl-4,4-dimethyl-3-pyrazolidone,
1- (2-benzothiazolyl) -3-pyrazolidone, 3
-Acetoxy-1-phenyl-3-pyrazolidone, etc.), 3-aminopyrazolines (eg, 1- (p-hydroxyphenyl) -3-aminopyrazoline, 1- (p
-Methylaminophenyl) -3-aminopyrazoline, 1
-(P-amino-m-methylphenyl) -3-aminopyrazoline and the like are used. Examples of the phenylenediamines include 4-amino-N, N-diethylaniline,
3-methyl-4-amino-N, N-diethylaniline,
4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β
-Hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β
-Methoxyethylaniline, etc.) and the like can be added.

As aminophenones, 4-aminophenol, 4-amino-3-methylphenol, 4- (N
-Methyl) aminophenol, 2,4-diaminophenol, N- (4-hydroxyphenyl) glycine, N-
(2'-hydroxyethyl) -2-aminophenol,
Examples thereof include 2-hydroxymethyl-4-aminophenol, 2-hydroxymethyl-4- (N-methyl) aminophenol, and hydrochlorides and sulfates of these compounds.

The amount of these auxiliary developing agents used is generally in the range of 5 × 10 ^-4 mol to 0.5 mol, preferably 10 ^-3 mol to 0.1 mol, per liter of the developing solution.

The developer of the present invention preferably contains hydroquinone monosulfonic acid or its derivative. In that case, the ascorbic acid, the hydroquinone monosulfonic acid, and the auxiliary developing agent are contained.

The developer of the present invention preferably contains a preservative and an alkali in addition to the above essential components. Sulfite can be used as a preservative. Examples of sulfites include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium bisulfite, and potassium metabisulfite. The larger the amount of preservative added, the better the preservability of the developer, but on the other hand, the amount of silver ions dissolved from the photosensitive material into the developer increases, so silver sludge gradually accumulates in the developer. It has an adverse effect. Since the developer of the present invention has high stability, it is possible to obtain sufficient preservability by reducing the amount of sulfite added. Therefore, the amount of sulfite added is preferably 0.5 mol or less per liter of the developing solution. More preferably 0.0
3 to 0.3 mol / liter is preferable.

The pH of the developing solution of the present invention is 8.5 to 11.0.
Is. It is preferably used in the range of 9.0 to 10.5. p
As the alkali agent used for setting H, a usual water-soluble inorganic alkali metal salt (for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate) can be used. As additives used other than the above, development inhibitors such as sodium bromide and potassium bromide; organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol and dimethylformamide; alkanolamines such as diethanolamine and triethanolamine, Development accelerators such as imidazole and its derivatives; mercapto compounds, indazole compounds, benzotriazole compounds, benzimidazole compounds as antifoggants or black pep
per) inhibitor may be included. 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-mercapto-1,3,4-
Thiadiazol-2-yl) thio] butanesulfonate sodium, 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 0.01 to 10 mmol, and more preferably 0.05 to 2 mmol, per liter of the developing solution.

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

Examples of aminopolycarboxylic acids include iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediaminemonohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, glycol ether tetraacetic acid, 1,2-diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid. Acetic acid,
Triethylene tetramine hexaacetic acid, 1,3-diamino-2
-Propanol tetraacetic acid, glycol ether diamine tetraacetic acid, etc. JP-A-52-25632, 55-67
No. 747, No. 57-102624, and Japanese Patent Publication No. 53-53
The compounds described in the specification of No. 40900 and the like can be mentioned.

As the organic phosphonic acid, US Pat.
4454, 3794591, and West German Patent Publication 2
227639 and the like, hydroxyalkylidene-diphosphonic acid and Research Disclosure (Research
Disclosure) Volume 181, Item 18170 (1979)
May issue) and the like. Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, and aminotrimethylenephosphonic acid. In addition, the above Research Disclosure 18170, JP-A-57-208554 and 54- 61125, 5
Examples thereof include compounds described in JP-A Nos. 5-29883 and 56-97347.

Examples of the organic phosphonocarboxylic acid include JP-A Nos. 52-102726, 53-42730, and 54.
-112127, 55-4024, 55-40
No. 25, No. 55-126241, No. 55-65955.
No. 55-69556, and the above-mentioned Research Disclosure 18170. These chelating agents may be used in the form of alkali metal salts or ammonium salts. The addition amount of these chelating agents is preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻¹ mol, more preferably 1 ×, per 1 liter of the developing solution.
It is 10 ⁻³ to 1 × 10 ⁻² mol.

Further, if necessary, a toning agent, a surfactant,
You may also contain a defoaming agent, a hardening agent, etc.

For the developer used in the present invention, carbonate, boric acid and borate as a buffer (for example, boric acid, borax, sodium metaborate, potassium borate) are disclosed in Japanese Patent Laid-Open Publication No.
0-93433 sugars (eg saccharose), oximes (eg acetoxime), phenols (eg 5-sulfosalicylic acid), tertiary phosphates (eg sodium salt, potassium salt), aluminates (eg sodium). Etc. are used, and preferably carbonates and borates are used. The developing temperature and time are interrelated and are determined in relation to the total processing time. Generally, the developing temperature is about 20 ° C to about 50 ° C, preferably 25 to 45 ° C, and the developing time is 5 seconds to 2 seconds. Minutes, preferably 7
Second to 1 minute and 30 seconds. When processing 1 square meter of silver halide black and white photographic light-sensitive material, the replenisher amount of the developer is 5
The amount is 00 ml or less, preferably 400 ml or less. It is preferable to concentrate the treatment liquid and dilute it at the time of use for the purpose of transportation cost of the treatment liquid, packaging material cost, space saving and the like. In order to concentrate the developer, it is effective to potassium salt the salt component contained in the developer.

The fixing solution used in the fixing step of the present invention is sodium thiosulfate, ammonium thiosulfate, if necessary tartaric acid, citric acid, gluconic acid, boric acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanoic acid, tyron, ethylenediamine. Tetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid are aqueous solutions containing these salts.
From the viewpoint of recent environmental protection, it is preferable that boric acid is not contained. As the fixing agent of the fixing solution used in the present invention, sodium thiosulfate, ammonium thiosulfate and the like are used, and ammonium thiosulfate is preferable from the viewpoint of the fixing speed, but sodium thiosulfate may be used from the viewpoint of recent environmental protection. . The use amount of these known fixing agents can be appropriately changed and is generally about 0.1 to about 2 mol / liter. Particularly preferably, it is 0.2 to 1.5 mol / liter. If desired, the fixer may include a hardening agent (eg, water-soluble aluminum compound), preservative (eg, sulfite, bisulfite), pH buffer (eg, acetic acid), 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. Further, a known antifoaming agent may be added. Examples of the wetting agent include alkanolamine and alkylene glycol. Examples of fixing accelerators include JP-B-45-35754 and JP-A-58-122535.
No. 58-122536, thiourea derivatives, alcohol having triple bond in the molecule, US Pat.
A thioether compound described in JP-A-126459, JP-A-4-
The mesoionic compounds described in JP-A No. 229860 and the like may be mentioned, and the compounds described in JP-A-2-44355 may be used. Examples of the pH buffering agent 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. A buffer can be used. Acetic acid, tartaric acid, and sulfite are preferably used. The pH buffer agent is used for the purpose of preventing the pH of the fixing agent from rising due to the carry-in of the developing solution, and is 0.01 to 1.0.
Mol / l, more preferably about 0.02-0.6 mol / l. The pH of the fixing solution is preferably 4.0 to 6.5, and particularly preferably 4.5 to 6.0. Further, as a dye elution accelerator, JP-A 64-473
The compounds described in No. 9 can also be used.

As the hardening agent in the fixing solution of the present invention, there are water-soluble aluminum salts and chromium salts. A preferred compound is a water-soluble aluminum salt, such as aluminum chloride, aluminum sulfate, potassium alum. The preferable addition amount is 0.01 to 0.2 mol / liter, more preferably 0.03 to 0.08 mol / liter. The fixing temperature is
The fixing time is 5 seconds to 1 minute, preferably 7 seconds to 50 seconds at about 20 ° C to about 50 ° C, preferably 25 to 45 ° C. The replenishing amount of the fixing solution is 600 ml / per processing amount of the light-sensitive material.
m ² or less, particularly preferably 500 ml / m ² or less.

The photosensitive material which has been developed and fixed is then washed with water or stabilized. For washing or stabilizing treatment, the amount of washing water is usually ² per 1 m ^{2 of} silver halide light-sensitive material.
It is performed at 0 liters or less, and a replenishment amount (0 liters or less
It can also be carried out by including, that is, 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 of reducing the replenishment amount of flush water, a multistage countercurrent method (for example, 2
Stages, 3 stages, etc.) are known. When 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 contaminated with the fixing solution is sequentially processed. Washed with water. When the washing with water is carried out with a small amount of water, JP-A-63-18
It is more preferable to provide washing tanks for squeeze rollers and crossover rollers described in No. 350 and No. 62-287252. Alternatively, addition of various oxidizing agents and filter filtration may be combined in order to reduce the pollution load which is a problem when washing with a small amount of water. Furthermore, a part or all of the overflow liquid from the washing or stabilizing bath produced by supplementing the washing or stabilizing bath with antifungal means according to the method according to the present invention is disclosed in JP-A-60- 23
As described in No. 5133, it can also be used for a processing solution having a fixing ability, which is a processing step before that. Further, a water-soluble surfactant or an antifoaming agent may be added in order to prevent water bubble unevenness that tends to occur when washing with a small amount of water and / or to prevent the processing agent component attached to the squeeze roller from being transferred to the processed film. Good. Further, in order to prevent contamination by dyes eluted from the light-sensitive material, JP-A-63-16345
The dye adsorbent described in No. 6 may be installed in the washing tank. In addition, in some cases, stabilization treatment may be performed following the water washing treatment,
As examples thereof, JP-A-2-201357 and JP-A-2-132
No. 435, No. 1-102553, JP-A-46-444.
A bath containing the compound described in No. 46 may be used as the final bath of the light-sensitive material. Also in this stabilizing bath, if necessary, ammonium compounds, metal compounds such as Bi and Al, optical brighteners, various chelating agents, film pH adjusting agents, film hardening agents, bactericides, fungicides, alkanolamines and surface active agents. Agents can also be added. Water used in the washing or stabilization process includes tap water, deionized water, halogen, water sterilized with ultraviolet germicidal lamps and various oxidizers (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 is 0-5
0 ° C. and 5 seconds to 2 minutes are preferable.

The treatment liquid used in the present invention is disclosed in JP-A-61-161.
It is preferable to store the packaging material having low oxygen permeability described in No. 73147. The treatment liquid used in the present invention may be powdered or solidified. As the method, 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 rate 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-conveying type automatic developing machine is described in U.S. Pat. Nos. 3,025,779 and 3,545,971, and is referred to simply as a roller-conveying type processor in this specification. The roller conveyance type processor comprises four steps of developing, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, stopping step), but it is most preferable to follow these four steps. . Instead of the water washing step, four stable steps may be used.

There are no particular restrictions on various additives and development processing methods used in the light-sensitive material of the present invention. For example, those described in the following sections can be preferably used. Item This section 1) Nucleating agent accelerator JP-A-2-103536, page 9, upper right column, line 13 to page 16, upper left column, line 10 General formulas (II-m) to (II- p) and compound examples II-1 to II-22, and compounds described in JP-A No. 1-179939. 2) Silver halide emulsion JP-A-2-97937, page 20, lower right column, line 12 and its manufacturing method to page 21, left lower column, line 14; JP-A-2-122336, page 7, upper right column 19 The selenium sensitization method described in the second to the lower left column 1 and 2 of the same page and Japanese Patent Application No. 2-189532. 3) Spectral sensitizing dye JP-A-2-12236, page 8, lower left column, line 13 to lower right column, line 4; JP-A-2-103536, page 16, lower right column, line 3 to page 17 Lower left column, line 20, and further described in JP-A Nos. 1-112235, 2-124560, 3-79928, Japanese Patent Application Nos. 3-189532, 3-411064 and 6-103272. Sensitizing dye. 4) Surfactant JP-A-2-12236, page 9, upper right column, line 7 to lower right column, line 7 and JP-A-2-18542, page 2, lower left column, line 13 to page 4, right Lower column, line 18, Japanese Patent Application No. 5-204325. 5) 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; further JP-A 1-237538 The thiosulfinic acid compounds described in Japanese Patent Publication No. 6) Polymer latex JP-A-2-103536, page 18, lower left column, lines 12 to 20. 7) Compound having an acid group JP-A-2-103536, page 18, lower right column, line 6 to page 19, upper left column, line 1 8) Matting agent, slip agent JP-A-2-103536, page 19, upper left column, line 15 Plasticizer to page 19, upper right column, line 15 9) Hardeners, JP-A-2-103536, page 18, upper right column, line 5 to line 17 thereof. 10) Dyes Dyes from the lower right column, lines 1 to 18 of page 17, JP-A-2-103536, solid dyes described in JP-A-2-294638 and JP-A-3-185773. 11) Binder JP-A-2-18542, page 3, lower right column, lines 1 to 20. 12) Black spot preventing agent Compounds described in U.S. Pat. No. 4,956,257 and JP-A No. 1-118832. 13) Monomethine compound A compound of the general formula (II) described in JP-A-2-287532 (particularly compound examples II-1 to II-26). 14) Dihydroxy Compounds described in JP-A-3-39948, page 11, upper left column to first benzene, page 2, lower left column, and EP452772A. 15) Developer and developing method JP-A-2-103536, page 19, upper right column, line 16 to page 21, upper left column, line 8

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

[0100]

【Example】

Example 1 <Preparation of silver halide photographic light-sensitive material> Emulsion preparation Emulsion A was prepared by the following method. [Emulsion A] Aqueous silver nitrate solution, potassium bromide, sodium chloride and K corresponding to 3.5 × 10 ^-7 mol per mol of silver
₃ IrCl ₆ and K ₂ Rh equivalent to 2.0 × 10 ⁻⁷ mol
An aqueous solution of halogen salt containing (H ₂ O) Cl ₅ , sodium chloride, and an aqueous solution of gelatin containing 1,3-dimethyl-2-imidazolidinethione were added by a double jet method with stirring to obtain an average particle size of 0.25 μm. Silver chlorobromide grains having a silver chloride content of 70 mol% were prepared.

Thereafter, the product was washed with flocculation according to a conventional method, 40 g of gelatin was added per 1 mol of silver, 7 mg of sodium benzenethiosulfonate and 2 mg of benzenesulfinic acid were added per 1 mol of silver, and the pH was adjusted to 6.0. The pAg was adjusted to 7.5, and 2 mg of sodium thiosulfate and 4 mg of chloroauric acid were added per 1 mol of silver, and chemical sensitization was performed at 60 ° C. to obtain optimum sensitivity. Thereafter, 150 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added as a stabilizer, and 100 mg of proxel was added as a preservative. The obtained particles each have an average particle size of 0.25μ.
m and a silver chlorobromide cubic grain having a silver chloride content of 70 mol%. (Variation coefficient 10%)

Preparation of Coating Sample On a polyethylene terephthalate film support having a moistureproof layer undercoat containing vinylidene chloride, from the support side,
A UL layer, an EM layer, a PC layer, and an OC layer were applied in this order to form a sample, and a sample was prepared. The preparation method and coating amount of each layer are shown below.

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

[0104] 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), 4 × 10 ^-4 mol of mercapto compound represented by (b), and 4 × 10 ^-4 mol of (c) per 1 mol of silver Triazine compound, 2 × 10 ⁻³ mol of 5-chloro-8-hydroxyquinoline, 5 × 10 ⁻⁴ mol of the following compound (p), and 4 × 10 ⁻⁴ mol of the following compound (A) as a nucleation accelerator. Was added. Furthermore, hydroquinone 100 mg and N-oleyl-N-methyltaurine sodium salt 30 mg / m ²
Added as applied. Next, 1 × 10 ⁻⁵ mol of the nucleating agent (hydrazine derivative) of the present invention and the comparative one shown in Table 1
/ M ² , 200 mg of the water-soluble latex represented by (d)
/ M ² , 200 mg of polyethyl acrylate dispersion
/ M ² , methyl acrylate and 2-acrylamide-2
- Latex copolymers of methylpropane sulfonic acid sodium salt and 2-acetoacetoxyethyl methacrylate (weight ratio 88: 5: 7) to 200 mg / m ^2, colloidal silica having an average particle size of 0.02μm 200mg / m ^2,
Sodium dodecylbenzenesulfonate (30 mg / m ²⁾ and 1,3-divinylsulfonyl-2-propanol (200 mg / m ² ) as a hardening agent were added. The pH of the solution was adjusted to 5.65 with acetic acid. They were coated such that the coated silver amount was 3.5 g / m ² .

[0105]

[Table 1]

(PC layer) A dispersion of 50 wt% ethyl acrylate in gelatin aqueous solution, and
The following surfactant (w) was added at 5 mg / m ² , 1,5-dihydroxy-2-benzaldoxime was added at 10 mg / m ² so as to be coated, and gelatin was coated at 0.5 g / m ² . .

(OC layer) Gelatin 0.5 g / m ² , amorphous SiO ₂ matting agent 4 having an average particle size of about 3.5 μm 4
0 mg / m ² , methanol silica 0.1 g / m ² , polyacrylamide 100 mg / m ² and silicone oil 2
0 mg / m ² and 5 mg / m ^{2 of} a fluorosurfactant represented by the following structural formula (e) as a coating aid and 100 mg / m ² of sodium dodecylbenzenesulfonate were coated.

[0108]

Embedded image

[0109]

[Chemical 31]

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

[0111]

Embedded image

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

[0113]

[Chemical 33]

[Back protective layer] Gelatin 0.8 mg / m ² polymethylmethacrylate fine particles (average particle size 4.5 μm) 30 mg / m ² Dihexyl-α-sulfosuccinate sodium salt 15 mg / m ² p-dodecylbenzenesulfonic acid Sodium 15 mg / m ² Sodium acetate 40 mg / m ²

<Evaluation of Photographic Performance> (1) Exposure and Development Treatment The above sample was passed through an interference filter having a peak at 488 nm and passed through a step wedge to emit light for 10 ⁻⁵ se.
After being exposed to the xenon flash light of c and developed with developers A to D shown in Table 2 at 35 ° C. for 30 seconds, fixing, washing and drying treatments were performed. The amount of sodium metabisulfite in Table 2 is 0.105 mol / liter.

[0116]

[Table 2]

The fixing solution used had the following formulation. (Fixer formulation) Ammonium thiosulfate 359.1 g Ethylenediaminetetraacetic acid 2Na dihydrate 0.09 g Sodium thiosulfate pentahydrate 32.8 g Sodium sulfite 64.8 g NaOH 37.2 g Glacial acetic acid 87.3 g Tartaric acid 8.76 g Sodium gluconate 6.6g Aluminum sulphate 25.3g pH (adjusted with sulfuric acid or sodium hydroxide) 4.85 Add 3 liters of water

(2) Evaluation of Image Contrast As an index (gamma) indicating the contrast of an image, fog + density of 3.
The point of 0 was connected by a straight line, and the slope of this straight line was expressed as a gamma value. That is, gamma = (3.0-0.1) / [l
og (exposure amount that gives a density of 3.0)-(exposure amount that gives a density of 0.1)], and the larger the gamma value, the harder the photographic characteristics are. The gamma of the light-sensitive material for graphic arts is preferably 10 or more, more preferably 15 or more. (3) Evaluation of halftone dot quality (DQ) The halftone dots of the light-sensitive material exposed through the contact screen were observed with a magnifying glass, and the sharpness and smoothness were evaluated on a 5-point scale.
[5] represents the best level for both sharpness and smoothness, and [1] represents the lowest level. When the level is [3] or higher, the sharpness and smoothness of the on / off portions of the image when the scanner exposure is actually performed can be practically allowed. (4) Evaluation of Developer pH Dependency With respect to the sample showing a high contrast of gamma of 10 or more in the developer A, the developer pH dependency was evaluated. With respect to the developer A, the developer A-II whose pH is lowered by 0.2 and the pH is 0.2
Elevated Developer A-III was prepared. Difference in sensitivity between developer A and solutions A-II and A-III (Δ
The pH dependence was evaluated by S). The smaller this difference, the smaller the pH dependency, which is preferable. <Results> The results are shown in Tables 3 and 4.

[0119]

[Table 3]

[0120]

[Table 4]

From the data in Table 3, samples 1-3 to 1-
It can be seen that a super-high contrast image having a gamma of 10 or more is obtained and a high Dmax and a good halftone dot quality are obtained when the development processing is performed with Developers A and B using No. 7. In addition, it can be seen from Table 4 that Samples 1-4 to 1-7 of the present invention have a particularly small pH dependency on the developer and are preferable.

Example 2 Developers A-a to A-f having the same formulation as developer A but having different amounts of sodium metabisulfite were prepared as follows. The value in parentheses is the amount of sodium metabisulfite added (mol /
Liter). A-a (0.01), A-b (0.03), A-c
(0.10, same as developer A), Ad (0.3), A
-E (0.5), Af (1.0). Table 5 shows the results of processing Samples 1-5 of Example 1 using these developers. The residual color was determined by visually evaluating the tint of the film when the temperature of the fixing solution was cooled to 5 ° C. and processed. The case where the tint of the dye remained clearly was evaluated as 1, the case where it was slightly recognized was evaluated as 2, and the case where it was not recognized enough was evaluated as 3 levels. The silver sludge of the developing solution was evaluated by visual evaluation of the developing solution after treating the photosensitive material with 16 m ² using 2 liter of the developing solution without replenishing the solution. Rank 1 is such a degree that the developer is turbid and turbid, and a deposit is observed at the bottom of the developing tank, Rank 2 is a case where the developer is slightly turbid, and Rank 3 is not turbid at all. Represents a case.

[0123]

[Table 5]

From the data in Table 5, the sulfite concentration was 0.5.
It is not more than mol / l, preferably 0.03 to 0.3 mol / l, and the residual color and silver sludge are good.

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

[0126]

Embedded image

Preparation of Coating Sample Instead of the sensitizing dye of the EM layer of Example 1, 2.1 × 10 ⁻⁴ mol of the following compound (S-3) was added per 1 mol of silver to prepare an emulsion for the EM layer. A sample was prepared in the same manner as in Example 1 except that Emulsion B was used.

[0128]

Embedded image

<Evaluation of Photographic Performance> (1) Exposure and Development Treatment The above sample was passed through an interference filter having a peak at 633 nm and a step wedge to emit light at a light emission time of 10 ⁻⁶ se.
Exposed to xenon flash of c. After developing with the developer A described in Example 1 at 35 ° C. for 30 seconds,
Fixing (same as in Example 1), washing with water and drying were performed.

Example 4 <Preparation of silver halide photographic light-sensitive material> A sample was prepared in the same manner as in Example 1 except that the sensitizing dye in the EM layer of Example 1 was changed to the following compound (S-4). Created.

[0131]

Embedded image

<Evaluation of Photographic Performance> 780 n
Through an interference filter having a peak at m, it was exposed with a xenon flash light having an emission time of 10 ⁻⁶ sec through a step wedge. After developing with the developer A described in Example 1 for 30 seconds at 35 ° C., fixing (the same as in Example 1), washing with water, and drying were performed. Evaluation of various performances was performed in the same manner as in Examples 1 and 2. <Results> By using the light-sensitive material of the present invention and the developer, a good light-sensitive material for a semiconductor laser scanner having a high image quality and a small pH dependency of the developer can be obtained.

Example 5 <Preparation of silver halide photographic light-sensitive material> A sample was prepared in the same manner as in Example 1 except that the sensitizing dye in the EM layer of Example 1 was changed to the following compound (S-5). Created.

[0134]

Embedded image

<Evaluation of Photographic Performance> The above sample was exposed to tungsten light at 3200 ° K through a step wedge. The developer A described in Example 1 was used for 30 at 35 ° C.
After developing for a second, fixing, washing with water and drying were performed. GR-F1 (manufactured by Fuji Photo Film Co., Ltd.) as the fixer
Was used. Various performances were evaluated in the same manner as in Examples 1 and 2.

<Results> As in Example 1, by using the light-sensitive material of the present invention and the developer, a good image-sensitive light-sensitive material having high image quality and small pH dependency of the developer could be obtained.

Example 6 A coating sample containing the hydrazine derivative of the present invention was prepared on the basis of the photosensitive material formulation of Example 5 of Japanese Patent Application No. 5-202547, and a development treatment was conducted in the same manner as in Examples 1 and 2. , Evaluated. As in Example 1 of the present specification, a good photographic light-sensitive material could be obtained.

Example 7 <Emulsion preparation> Emulsion C: 3 × 10 ⁻⁵ mol of the following compound (f) per mol of sodium chloride and silver kept at 40 ° C.
Containing 1.5% gelatin aqueous solution of pH = 2.0 containing silver nitrate solution and 3.5 × 10 ⁻⁵ mol of (NH ₄ ) ₂ Rh per 1 mol of silver.
An aqueous sodium chloride solution containing (H ₂ O) Cl ₅ was simultaneously added by a double jet method at a potential of 95 mV for 3 minutes and 30 seconds to prepare core particles of 0.12 μm. Then, 10.5 × 10 ⁻⁵ mol of (NH ₄ ) ₂ per mol of gold and an aqueous solution of silver nitrate were used.
A sodium chloride aqueous solution containing Rh (H ₂ O) Cl ₅ was added in the same manner as above for 7 minutes to prepare silver chloride cubic particles having an average particle size of 0.15 μm. (Coefficient of variation 12%) After that, 4-hydroxy-6-methyl-1,3,3a,
1.5 × 10 ^{−3 of} 7-tetrazaindene per 1 mol of silver
Mole was added. Further, after this, the product is washed with water by a flocculation method well known in the art to remove soluble salts, and then gelatin is added. 50 mg, 4-hydroxy-6-methyl- as stabilizer
1,3,3a, 7-Tetrazaindene was added at 3 × 10 ⁻³ mol per mol of silver (pH = 5.7, pAg = 7.
5, Rh = 6 × 10 ⁻⁵ mol / Ag mol).

<Preparation of Emulsion Layer Coating Solution and Its Coating> Emulsion C
The following compound was added to the gelatin coating amount of 1.1 g /
m ^2, the coating amount of silver coated with silver halide emulsion layers so that 2.5 g / m ^2. 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 10 mg / m ² N-oleyl-N-methyltaurine sodium salt 35 mg / m ² compound (h) 10 mg / m ² compound (i) 20 mg / M ² n-butyl acrylate / 2-acetoacetoxyethyl methacrylate / acrylic acid copolymer (89/8/3) 900 mg / m ² compound (j) (hardener) 150 mg / m ² Further nucleation accelerator ( k) was added at 20 mg / m ² , and a nucleating agent was added so as to be coated as shown in Table 3.

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

<Preparation and Coating of Emulsion Protecting Lower Layer Coating Liquid>
The following compounds were added to a gelatin aqueous solution and coated so that the gelatin coating amount would be 0.7 g / m ² . Gelatin (Ca ⁺⁺ content 2700 ppm) 0.7 g / m ² sodium p-dodecylbenzenesulfonate 15 mg / m ² compound (g) 5 mg / m ² compound (l) 10 mg / m ² compound (m) 20 mg / m ²

<Preparation of Emulsion Protection Upper Layer Coating Liquid and Its Coating>
The following compounds were added to an aqueous gelatin solution and coated so that the coating amount of gelatin was 0.8 g / m ² . Gelatin (Ca ⁺⁺ content 2700ppm) 0.8g / m ² amorphous silica matting agent 40 mg / m ² (average particle size 3.5 [mu], pore diameter 25 Å, surface area 700m ² / g) amorphous silica matting agent 10mg / m ² (average particle size 2.5 μ, pore diameter 170 Å, surface area 300 m ² / g) N-perfluorooctanesulfonyl-N-propylglycine sympottadium 5 mg / m ² sodium dodecylbenzenesulfonate 30 mg / m ² compound (g) 5 mg / m ² solid disperse dye-G ₁ 100 mg / m ² solid disperse dye-G ₂ 50 mg / m ²

Then, a conductive layer and a back layer shown below were simultaneously coated on the opposite surface of the support.

<Preparation of Coating Solution for Conductive Layer and Coating> The following compounds were added to a gelatin aqueous solution to give a gelatin coating amount of 77
It was applied so as to be mg / m ² . SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25μ) 200 mg / m ² Gelatin (Ca ⁺⁺ content 3000 ppm) 77 〃 Sodium dodecylbenzene sulfonate 10 〃 Sodium dihexyl-α-sulfosuccinate 40 〃 Polystyrene Sodium sulfonate 9〃 Compound (g) 7〃

<Preparation of Back Layer Coating Liquid and Its Coating> The following compounds were added to a gelatin aqueous solution and coated so that the gelatin coating amount would be 2.92 g / m ² . Gelatin (Ca ⁺⁺ content 30 ppm) 2.92 g / m ² Polymethylmethacrylate fine particles (average particle size 3.4 μ) 54 mg / m ² Compound (h) 140 〃 Compound (r) 140 〃 Compound (s) 40 〃 Dodecyl Sodium benzene sulfonate 75 〃 Dihexyl-α-sulfosuccinate sodium 20 〃 Compound (t) 5 〃 N-perfluorooctane sulfonyl-N-propyl glycine potassium 5 〃 Sodium sulfate 50 〃 Sodium acetate 85 〃

(Support, Undercoat Layer) A biaxially stretched polyethylene terephthalate support (thickness: 100 μm) was coated on both sides with the first and second undercoat layers having the following compositions. <Undercoat layer 1 layer> Core-shell type vinylidene chloride copolymer 15 g 2,4-dichloro-6-hydroxy-s-triazine 0.25 〃 Polystyrene fine particles (average particle size 3 µ) 0.05 〃 Compound (u) 0. 20〃 colloidal silica (Snowtex ZL: particle size 70-100 μm, manufactured by Nissan Chemical Co., Ltd.) 0.12〃 Water added 100〃 Furthermore, 10 wt% KOH was added to adjust the coating solution to pH = 6. When the drying temperature is 180 ° C. for 2 minutes, the dry film thickness is 0.
It was applied so as to be 9μ.

<Undercoat Second Layer> Gelatin 1 Methylcellulose 0.05 〃 Compound (v) 0.02 〃 C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H 0.03 〃 Compound (g) 3. 5 × 10 ⁻³ 〃 acetic acid 0.2 〃 water was added and 100 〃 This coating solution was applied at a drying temperature of 170 ° C. for 2 minutes so that the dry film thickness was 0.1 μm.

[0148]

[Chemical 38]

[0149]

[Chemical Formula 39]

[0150]

[Chemical 40]

<Evaluation of Photographic Performance> (1) Exposure and Development Treatment The sample thus obtained was exposed by an optical wedge to a P-627FM printer manufactured by Dainippon Screen Co., Ltd., and automatically developed by Fuji Photo Film Co., Ltd. Machine FG-680AG and Developer A of Example 1 were treated at 38 ° C. for 20 seconds, fixed, washed with water, and dried. The same fixing solution as in Example 1 was used. <Results> As in Examples 1 and 2, various performances were evaluated. As a result, high image quality was obtained by the image forming method of the present invention, and development pH dependency was also good.

Evaluation of various performances was performed in the same manner as in Examples 1 and 2. <Results> By using the nucleating agent of the present invention, it was possible to obtain a good bright room return photographic material having a high gamma and a small development pH dependency.

Example 8 Developer A of Example 1 was prepared from a pack stored in the solid state. In the method for manufacturing the pack of the solid processing agent, the components of the developing solution are solidly laminated and packed in a bag made of an aluminum foil coated with a plastic material. The order of stacking is from the top, the first layer is sodium erythorbate, the second layer and other components, the third layer is sodium bisulfite, the fourth layer is potassium carbonate, the fifth layer is potassium hydroxide, and the mixture is evacuated in a conventional manner and the system is vacuumed. And sealed.

<Results> Even if a developing solution prepared from this solid processing agent was used in the development processing of Examples 1 to 7, Example 1 was used.
Similar results to ~ 7 were obtained.

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[Procedure amendment]

[Submission date] June 5, 1995

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<Evaluation of Photographic Performance> (1) Exposure and Development Treatment The above sample was passed through an interference filter having a peak at 633 nm and a step wedge to issue time 10 ⁻⁶ se.
Exposed to xenon flash of c. After developing with the developing solution A described in Example 1 for 30 seconds at 35 ° C., fixing (same as in Example 1), washing with water, and drying were performed. Evaluation of various performances was performed in the same manner as in Examples 1 and 2. <Results> By using the light-sensitive material of the present invention and the developer, it was possible to obtain a light-sensitive material for a He—Ne laser scanner having a high image quality and a small pH dependency of the developer.

[Procedure Amendment 9]

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[Correction method] Change

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<Evaluation of Photographic Performance> (1) Exposure and Development Treatment The sample thus obtained was exposed by an optical wedge to a P-627FM printer manufactured by Dainippon Screen Co., Ltd., and automatically developed by Fuji Photo Film Co., Ltd. Machine FG-680AG and Developer A of Example 1 were treated at 38 ° C. for 20 seconds, fixed, washed with water, and dried. The same fixing solution as in Example 1 was used.

Claims (6)

[Claims] 1. A support having at least one silver halide emulsion layer, the emulsion layer or another hydrophilic colloid layer having an anionic group in the vicinity of a hydrazine group, or a hydrogen atom and a molecule of hydrazine. A silver halide photographic material containing a hydrazine nucleating agent having a nonionic group forming an internal hydrogen bond, ascorbic acid, or a derivative thereof, containing sulfite in an amount of 0.5 mol / liter or less, and a pH The image forming method is characterized in that development processing is performed with a developing solution of 8.5 to 11.0. 2. The image forming method according to claim 1, wherein a developing solution containing hydroquinone monosulfonic acid or a derivative thereof is used. 3. The image forming method according to claim 1, wherein a silver halide photographic light-sensitive material containing an onium salt is used. 4. The image forming method according to claim 1, wherein a silver halide photographic light-sensitive material containing amines is used. 5. The image forming method according to claim 1, wherein the anionic group is selected from carboxylic acid, sulfonic acid, sulfinic acid, phosphoric acid, phosphonic acid and salts thereof. 6. The nonionic group forming an intramolecular hydrogen bond with hydrazine hydrogen is a group in which a lone electron pair forms a hydrogen bond with hydrazine hydrogen in a 5- to 7-membered ring, and is an oxygen atom, a nitrogen atom or a sulfur atom. The image forming method according to claim 1, which is a group having at least one phosphorus atom.