JPH07104443A - Image forming method - Google Patents

Abstract

PURPOSE:To obtain an image high in contrast by developer high in safety by processing photosensitive material which has a specified hydrazine compound contained in a silver halide emulsion layer spectrally sensitized by a specified compound, by specified developer. CONSTITUTION:Photosensitive material is equipped with a emulsion layer over a carrier, which is composed of silver halide emulsion whose content of silver chloride spectrally sensitized by a compound indicated by a formula I is equal to or more than 50mol%, and includes hydrazine compounds indicated by a formula II in the aforesaid emulsion layer or in another hydropholic colloid layer. In the formula I, R1 and R2 represent alxyl groups which may have respective substitutional groups, and V1 and V2 represent hydrogen atoms and the like respectively. Besides, in the formula II, R, represents aliphatic series groups and the like, G1 represents -CO- groups and the like, both of A1 and A2 represent hydrogen atoms and the like. The aforesaid photosensitive material is processed by developer which includes a developing main ingredient indicated by a formula III, but does not include a main ingredient in a dihydroxybenzen series. In the formula III, R1 and R2 represent amino groups and the like, P and Q represent hydroxy groups and the like, and Y represents =0 and the like.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming an image on a silver halide photographic light-sensitive material, and more particularly, it is possible to develop a highly sensitive and ultrahigh contrast image by exposure to Ar laser, without developing a dihydroxybenzene type developing agent. The present invention relates to an image forming method of developing with a liquid.

[0002]

2. Description of the Related Art As one of the exposure methods for a photographic light-sensitive material, an original image is scanned, and a silver halide photographic light-sensitive material is exposed on the basis of the image signal to expose a negative image or a positive image corresponding to the image of the original image. There is known an image forming method using a so-called scanner method for forming an image. Although there are various recording apparatuses that have practically used the image forming method by the scanner method, many so-called dot generator methods using a halftone dot generating base are currently used. Conventionally, glow lamps, xenon lamps, mercury lamps, tungsten lamps, light emitting diodes and the like have been used as recording light sources of these scanner type recording devices. However, each of these light sources has a practical drawback that the output is weak and the life is short. To compensate for these drawbacks, He-
There is a scanner that uses a coherent laser light source such as a Ne laser, an argon laser, a He-Cd laser, and a semiconductor laser as a light source of a scanner system.
Among them, many scanners using an argon laser as its light source are used because of the high output and the ability to narrow the laser beam. Furthermore, in recent years, the platemaking process has become brighter, and silver halide photographic light-sensitive materials that can be handled under white fluorescent lamps or yellow safety lamps have been widely used. In the process of using it, it is required that the light-sensitive material can be handled under a bright yellow safety light. In the plate-making process, a so-called half-shading process is required to convert the gradation of an original image having continuous tones into the area of halftone dots, but the original is screened during scanner exposure, or a so-called dot generator is used. It is common practice to directly obtain a halftone dot image. Therefore, as a light-sensitive material used for such a scanner, a silver halide photographic light-sensitive material having high photosensitivity to Ar laser light and having an extremely high contrast suitable for halftone dot formation is required.

As a method for obtaining high-contrast photographic characteristics, a lithographic development method utilizing a so-called "infectious development effect" has been used for a long time, but it has a drawback that the developing solution is unstable and difficult to use. . There is a demand for an image forming system which is developed with a processing solution having good storage stability and obtains ultra-high contrast photographic characteristics. One of them is US Pat. Nos. 4,166,742 and 4,168,977. , No. 4,221,857, No. 4,224,401,
No. 4,243,739, No. 4,269,922
Issue No. 4,272,606, No. 4,311,78
No. 1, No. 4,332, 878, No. 4,618, 5
No. 74, No. 4,634, 661, No. 4,681,
No. 836, No. 5,650,746 and the like are disclosed. These are surface latent image type silver halide photographic light-sensitive materials to which a hydrazine derivative is added, and have a pH of 11.0 to 12.3.
Is a system that obtains a super-high contrast negative image in which γ exceeds 10 by processing with a stable MQ or PQ developer. According to this method, super-high contrast and high-sensitivity photographic characteristics can be obtained, and Since the concentration of sulfite can be added, the stability of the developing solution against air oxidation is dramatically improved as compared with the conventional lith developer. Further, in a nucleating high contrast negative image system using a hydrazine derivative, one of the points that is desired to be improved is that it causes an undesired phenomenon called flat mesh unevenness, which is a problem in the photomechanical process.
Here, the flat halftone unevenness refers to unevenness caused by halftone dot images that are originally the same area due to differences in the size of individual halftone dots due to variations in the nip pressure of the developing roller during development processing. Therefore, since it greatly affects the halftone or highlight finish of printed matter, improvement is strongly desired.

On the other hand, from an ecological and toxicological point of view, a developing system using a dihydroxybenzene type developing agent such as PQ or MQ developing solution as a developing agent has some disadvantages. For example, hydroquinone is an undesired component because of its allergic effect, and 1-phenyl-3-pyrazolidones are poor biodegradable components. High concentrations of sulfite also show high COD (chemical oxygen demand). This system is also known from US Pat. No. 4,975,3.
Although the amines described in No. 54 are used together, they are not preferable in terms of toxicity and volatility.

It is widely known that enediols such as ascorbic acid function as a developing agent, and is attracting attention as a developing agent free from the above ecological or toxicological problems. For example, U.S. Pat. No. 2,668,549
No. 3,826,654, at least pH 12
It is said that image formation is possible under the above-mentioned highly alkaline conditions. However, it is impossible to obtain a high-contrast image by these image forming methods. Some attempts have been made to increase the contrast in a developing system using ascorbic acid. For example, Zwicky says that when ascorbic acid is used as the only developing agent, a kind of lith effect is exhibited (J.Phot.Sci. 27, 185 (1979)), but in the case of hydroquinone developing system. It was a system with much lower contrast than that of. Further, U.S. Pat. No. 896,022 and Japanese Patent Publication No. 49-46939 disclose a system in which a diquaternary ammonium salt and ascorbic acid are used in combination. I can't. In addition, JP-A-3-2
No. 49756 and No. 4-32838 describe the combined effect of ascorbic acid and a quaternary salt, but the contrast of the obtained image is not sufficient. Furthermore, JP-A-5-88
No. 306 ascorbic acid as the only developing agent, p
It is said that a high contrast can be obtained by keeping H at 12.0 or more, but there is a problem in the stability of the developer. Using a special developer mainly composed of ascorbic acid and a specific hydrazine derivative, high sensitivity, stain,
Example of developing a developer with low fog (US Pat. No. 3,
No. 730,727), but no mention is made of improvement in contrast. An example of developing a photosensitive material containing a hydrazine derivative in a developing system using ascorbic acid is disclosed in U.S. Pat. No. 5,236,816, but no mention is made of flat mesh unevenness.

[0006]

SUMMARY OF THE INVENTION The first object of the present invention is to obtain a high-contrast image required in the graphic arts field by using a developing solution that does not pose a problem to the ecosystem and working environment. Another object is to provide a simple image forming method. Secondly, using the above developer,
To provide a silver halide photographic light-sensitive material having high sensitivity and high contrast photographic performance with respect to r laser exposure, high safety of safelight under a yellow safety light, and less flat mesh unevenness. Is.

[0007]

The above object of the present invention is to provide a silver halide emulsion having a silver chloride content of 50 mol% or more, which is spectrally sensitized with a compound represented by the following general formula (I) on a support. A silver halide photograph having at least one silver halide emulsion layer consisting of, and containing a hydrazine compound represented by the general formula (II) in at least one of the emulsion layer and other hydrophilic colloid layers. After imagewise exposure of the light-sensitive material, image formation characterized by being subjected to development processing with a developer containing substantially no dihydroxybenzene-based developing agent as a developing agent and containing a developing agent represented by the following general formula (III) Achieved by the method. General formula (I)

[0008]

[Chemical 5]

In the formula, R ₁ and R ₂ each represent an alkyl group which may have a substituent, and at least one of R ₁ and R ₂ is an acetylaminoalkyl group or an N-alkylcarbamoylaminoalkyl group. is there. V ₁ and V ₂ each represent a hydrogen atom, an alkyl group, an alkoxy group or a trifluoromethyl group. General formula (II)

[0010]

[Chemical 6]

In the formula, R ₁ represents an aliphatic group or an aromatic group, R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an unsaturated heterocyclic group, an alkoxy group, an aryloxy group, an amino group, a hydrazino group, Represents a carbamoyl group or an oxycarbonyl group, and G ₁ represents a —CO— group, a —SO ₂ — group,
SO-group,

[0012]

[Chemical 7]

Represents a --CO--CO-- group, a thiocarbonyl group, or an iminomethylene group, wherein both A ₁ and A ₂ are hydrogen atoms, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted Alternatively, it represents an unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. The R ₃ is selected from the same range as radical as defined R _2, may be different from R _2. General formula (II
I)

[0014]

[Chemical 8]

In the formula, R ₁ and R ₂ each represent a hydroxy group, amino group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkoxycarbonylamino group, mercapto group or alkylthio group. P and Q are hydroxy group, carboxyl group, alkoxy group, hydroxyalkyl group, carboxyalkyl group, sulfo group, sulfoalkyl group, amino group,
An atom group which represents an aminoalkyl group, an alkyl group or an aryl group, or forms a 5- to 8-membered ring with two vinyl carbon atoms substituted by R ₁ and R ₂ and a carbon atom substituted by Y Represents Y represents = O or = N-R _3,. R ₃ is a hydrogen atom, a hydroxyl group, an alkyl group,
Acyl group, hydroxyalkyl group, sulfoalkyl group,
Represents a carboxyalkyl group. The compound of the general formula (I) will be described. In the formula, R ₁ and R ₂ each have 4 carbon atoms
The following alkyl groups (eg, methyl group, ethyl group, 3-propyl group, 3-butyl group, 4-butyl group, etc.), substituted alkyl groups having 4 or less carbon atoms in the alkyl moiety [eg, sulfoalkyl group (eg, sulfoethyl group) , 3-sulfopropyl group, 3-sulfobutyl group, etc.), carboxyalkyl group (for example, carboxymethyl group, carboxyethyl group,
3-carboxypropyl group etc.), hydroxyalkyl group (eg hydroxymethyl group, hydroxyethyl group etc.), aralkyl group (eg benzyl group, phenethyl group, sulfophenethyl group etc.), aryloxyalkyl group (eg phenoxyethyl group, phenoxy group) Propyl group, sulfophenoxypropyl group, etc.), acetylaminoalkyl group (eg 2-acetylaminoethyl group, 3-
Acetylaminopropyl group, etc.), alkylsulfonylaminoalkyl group (for example, 2-methylsulfonylaminoethyl group, 3-methylsulfonylaminopropyl group, etc.),
N-alkylcarbamoylaminoalkyl group (for example, 2
-(N-methylcarbamoyl) aminoethyl group, 2-
(N-ethylcarbamoyl) aminoethyl group, 3- (N
-Methylcarbamoyl) aminopropyl group],
At least one of R ₁ and R ₂ is an acetylaminoalkyl group or an N-alkylcarbamoylaminoalkyl group. V ₁ and V ₂ each represent a hydrogen atom, an alkyl group having 3 or less carbon atoms (eg, methyl group, ethyl group, etc.), an alkoxy group having 3 or less carbon atoms (eg, methoxy group, ethoxy group, etc.), and trifluoromethyl group. . Specific examples of the compound represented by formula (I) are shown below, but the invention is not limited thereto.

[0016]

[Chemical 9]

[0017]

[Chemical 10]

[0018]

[Chemical 11]

The effective addition amount of the compound of formula (I) is in the range of 1 × 10 ^-5 to 1 × 10 ^-2 mol per mol of silver.

Next, the hydrazine compound represented by the general formula (II) will be described in detail. In the general formula (II), the aliphatic group represented by R ₁ preferably has 1 to 1 carbon atoms.
30 is a straight chain, branched or cyclic alkyl group having 1 to 20 carbon atoms. This alkyl group may have a substituent. In the general formula (II), the aromatic group represented by R ₁ is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with an aryl group. Preferred as R ₁ is an aryl group, and particularly preferred is one containing a benzene ring. The aliphatic group or aromatic group of R ₁ may be substituted, and typical examples of the substituent include, for example, an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group and a ureido group. Group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkyl or arylthio group,
Alkyl or aryl sulfonyl group, alkyl or aryl sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, carbonamide group, sulfonamide group, carboxyl group, Phosphoric acid amide group, diacylamino group, imide group,
R ₄ —NHCON (R ₅ ) —CO— group (R ₄ and R ₅ are R
₂ may be selected from the same groups as defined in ₂ and may be different from each other. Preferred substituents are an alkyl group (preferably having a carbon number of 1 to 20) and an aralkyl group (preferably having a carbon number). 7 to 30), alkoxy group (preferably having 1 to 20 carbon atoms), substituted amino group (preferably amino group substituted with alkyl group having 1 to 20 carbon atoms), acylamino group (preferably having carbon number) 2-3
0), sulfonamide group (preferably having 1 to 30 carbon atoms), ureido group (preferably having 1 to 30 carbon atoms), phosphoric acid amide group (preferably having 1 to 30 carbon atoms) Things). These groups may be further substituted.

In the general formula (II), the alkyl group represented by R ₂ is preferably an alkyl group having 1 to 4 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group (for example, benzene). Including rings). G
_{When 1} is a —CO— group, preferred among the groups represented by R ₂ are a hydrogen atom and an alkyl group (eg, methyl group, trifluoromethyl group, 3-hydroxypropyl group, 3-methanesulfonamidopropyl group). , Phenylsulfonylmethyl groups, etc.), aralkyl groups (eg o-
A hydroxybenzyl group), an aryl group (eg, a phenyl group, a 3,5-dichlorophenyl group, an o-methanesulfonamidophenyl group, a 4-methanesulfonylphenyl group, a 2-hydroxymethylphenyl group, etc.), and particularly hydrogen. Atoms are preferred. R ₂ may be substituted, and as the substituent, the substituents listed for R ₁ can be applied.

Most preferably, G in the general formula (II) is a -CO- group. Further, R ₂ disrupts the portion of the G ₁ -R ₂ from the remainder molecule may be such as to rise to cyclization reaction to form a cyclic structure containing a -G ₁ -R ₂ moiety of atoms Examples thereof include those described in JP-A-63-29751. A hydrogen atom is most preferable as A ₁ and A ₂ .

R ₁ or R _{2 in} the general formula (II) may have a ballast group or a polymer incorporated therein which is commonly used in a non-moving photographic additive such as a coupler. The ballast group is a group having a carbon number of 8 or more and relatively inactive to photographic properties, and examples thereof include an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group,
It can be selected from phenoxy group, alkylphenoxy group and the like. Further, as a polymer, for example, JP-A-1
The thing described in No. 100530 is mentioned.

R ₁ or R _{2 in} the general formula (II) may be one in which a group for enhancing adsorption to the surface of silver halide grains is incorporated. Examples of the adsorptive group include U.S. Pat. No. 4,385,108 such as thiourea group, heterocyclic thioamide group, mercaptoheterocyclic group, and triazole group.
U.S. Pat. No. 4,459,347, JP-A-59-195233.
No. 59-202331, 59-201045
Issue 59-201046 Issue 59-201047
Issue 59-201048, Issue 59-201049.
No. 61-170733 and No. 61-270744.
No. 62-270948 and 63-234244.
No. 63-234245 and No. 63-234246.

Among the general formula (II), R₁Or R₂of
At least one has a ballast group or R₁Or R₂
At least one of them strongly adsorbs on the silver halide grain surface.
Have a radical or R₁Is a trialkylammonium group
Have or R₁Is an alkylthio group (cycloalkylthio group
Or containing an arylthio group, or R₂G in ₁
The carbon atom bonded to is an electron-withdrawing group (eg halogen
Atom, cyano group, nitro group, sulfonyl group, etc.)
Those that have been described are preferable.

Specific examples of the compound represented by the general formula (II) are listed below, but the present invention is not limited thereto.

[0027]

[Chemical 12]

[0028]

[Chemical 13]

[0029]

[Chemical 14]

[0030]

[Chemical 15]

[0031]

[Chemical 16]

[0032]

[Chemical 17]

[0033]

[Chemical 18]

[0034]

[Chemical 19]

[0035]

[Chemical 20]

[0036]

[Chemical 21]

[0037]

[Chemical formula 22]

[0038]

[Chemical formula 23]

[0039]

[Chemical formula 24]

[0040]

[Chemical 25]

[0041]

[Chemical formula 26]

[0042]

[Chemical 27]

[0043]

[Chemical 28]

[0044]

[Chemical 29]

[0045]

[Chemical 30]

[0046]

[Chemical 31]

As the hydrazine derivative used in the present invention, in addition to the above, RESEARCH DISCLOSURE Item 2
3516 (November 1983, p. 346) and references cited therein, as well as U.S. Pat. No. 4,080,20.
No. 7, No. 4,269,929, No. 4,276,364
Nos. 4,278,748, 4,385,108
Nos. 4,459,347 and 4,560,638
No. 4,478,928, British Patent No. 2,011,
391B, JP-A-60-179734, and JP-A 62-2.
70948, 63-29751, 61-170.
No. 733, No. 61-270744, and European Patent No. 21.
7,310, 356,898, U.S. Pat.
86,167, JP-A-62-178246, 63.
-32538, 63-104047, 63-1
21838, 63-129337, 63-22
No. 3744, No. 63-234244, No. 63-234
245, 63-234246, 63-2945.
No. 52, No. 63-306438, No. 64-10233
, JP-A-1-90439, 1-100530,
1-105941, 1-105943, 1-
276128, 1-280747, 1-283
No. 548, No. 1-283549, No. 1-285940
No. 2-2541, No. 2-77057, No. 2-1
39538, 2-196234, 2-1962.
No. 35, No. 2-198440, No. 2-198441,
No. 2-198442, No. 2-220042, No. 2-
221953, 2-221954, 2-302
Nos. 750 and 2-304550 can be used.

The addition amount of the hydrazine derivative in the present invention is preferably 1 × 10 ^-6 mol to 5 × 10 ^-2 mol per mol of silver halide, and particularly 1 × 1.
The preferable addition amount is in the range of 0 ^-5 mol to 2 × 10 ^-2 mol.

The hydrazine derivative 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, methylcell. It can be used by dissolving it in sorb or the like. Further, by a well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, glyceryl triacetate, or oil such as diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved to mechanically emulsify. It is also possible to prepare and use a dispersion. Alternatively, the hydrazine derivative powder may be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves according to a method known as a solid dispersion method.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention is silver chlorobromide or silver iodochlorobromide having a silver chloride content of 50 mol% or more as silver halide. The silver iodide content is 3 mol% or less, more preferably 0.
It is preferably 5 mol% or less. The shape of silver halide grains is
It may be a cube, a tetradecahedron, an octahedron, an irregular shape, or a plate shape, but a cube is preferable. The average grain size of silver halide is preferably 0.1 μm to 0.7 μm, more preferably 0.2 to 0.5 μm, and {(standard deviation of grain size) /
It is preferable that the coefficient of variation represented by (average particle size) × 100 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, Chimie et.
Physique Photographique (Paul Montel, 1967
,) By GFDufin, Photographic Emulsion Chemistry
(The Forcal Press, 1966), VLZelikman et al
By Making and Coating Photographic Emulsion (The F
Ocal 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 type of the simultaneous mixing method, a method of keeping pAg constant in a liquid phase where 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 Patent Publication No. 48-36890.
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. 4,242,44.
As described in JP-A-55-158124 and JP-A-55-158124, it is preferable to use the method of changing the concentration of the aqueous solution to grow it quickly within a range not exceeding the critical saturation.

The silver halide grains used in the silver halide photographic light-sensitive material of the present invention contain at least one metal selected from rhodium, ruthenium, rhenium, osmium and iridium in order to achieve high contrast and low fog. Preferably. This content is preferably in the range of 1 × 10 ⁻⁹ mol to 1 × 10 ⁻⁵ mol, and more preferably in the range of 1 × 10 ^{−8 to} 5 × 10 ⁻⁶ mol, per mol of silver. Two or more of these metals may be used in combination. These metals can be uniformly contained in the silver halide grains, and they are disclosed in JP-A-63-29603, JP-A-2-306236, JP-A-3-167545 and JP-A-4-167453.
No. 76534, Japanese Patent Application Nos. 4-68305 and 4-258.
No. 187, etc., it may be contained in the particles with a distribution.

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, amine, oxalate, etc. as a ligand, for example, hexachlororhodium (III)
Examples thereof include complex salts, hexabromorhodium (III) complex salts, hexaamminerhodium (III) complex salts, and trisalatrodium (III) complex salts. These rhodium compounds are used by being dissolved in water or a suitable solvent, and a method that is generally performed to stabilize the solution of the rhodium compound,
That is, a method of adding 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 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 addition of these compounds can be appropriately carried out at each stage during the production of silver halide emulsion grains and before the coating of the emulsion, but it is added especially at the time of emulsion formation and incorporated into the silver halide grains. It is preferable.

Rhenium, ruthenium and osmium used in the present invention are disclosed in JP-A-63-2042 and JP-A-1.
-2859451, 2-20852, 2-208
It is added in the form of a water-soluble complex salt described in No. 55, etc. Particularly preferred are hexacoordinated complexes represented by the following formulas. [ML ₆ ] ^-n Here, M represents Ru, Re, or Os, n is 0,
Represents 1, 2, 3 or 4. In this case, the counterion has no significance and ammonium or alkali metal ions are used. Examples of preferable ligands include halide ligands, cyanide ligands, cyan oxide ligands, nitrosyl ligands and thionitrosyl ligands. Examples of specific complexes used in the present invention are shown below, but the present invention is not limited thereto.

ReCl ₆ ^-3 ReBr ₆ ^-3
ReCl ₅ (NO) ^-2 Re (NS) Br ₅ ^-2 Re (NO) (CN) ₅ ^-2 Re
(O) ₂ (CN) ₄ ^-3 RuCl ₆ ^-3 RuCl ₄ (H ₂ O) ₂ ^-2 Ru
Cl ₅ (NO) ^-2 RuBr ₅ (NS) ^-2 Ru (CN) ₆ ^-4 Ru
(CO) ₃ Cl ₃ ^-2 Ru (CO) Cl ₅ ^-2 Ru (CO) Br ₅ ^-2 OsCl ₆ ^-3 OsCl ₅ (NO) ^-2 Os
(NO) (CN) ₅ ^-2 Os (NS) Br ₅ ^-2 Os (CN) ₆ ^-4 Os
(O) ₂ (CN) ₄ ^-4

The addition of these compounds can be appropriately carried out at each stage before the production of the silver halide emulsion grains and before the coating of the emulsion, but it is added especially at the time of forming the emulsion and incorporated into the silver halide grains. It is preferable. In order to add these compounds to the silver halide grains by adding them during grain formation of silver halide, a powder of a metal complex or an aqueous solution dissolved with NaCl or KCl is used to form a water-soluble salt or a water-soluble salt during grain formation. Method in which it is added to the basic halide solution, or when a silver salt and a halide solution are simultaneously mixed, and added as a third solution to prepare silver halide grains by a three-liquid simultaneous mixing method, or grain formation There is a method in which a water-soluble amount of a required amount of the metal complex is charged into the reaction vessel. Particularly preferred is a method of adding powder or an aqueous solution dissolved together with NaCl and KCl to the water-soluble halide solution. To add to the surface of the particles, a necessary amount of an aqueous solution of the metal complex may be added to the reaction vessel immediately after the particles are formed, during or during physical ripening, or at the time of chemical ripening.

As the iridium compound used in the present invention, various compounds can be used, and examples thereof include hexachloroiridium, hexaammineiridium, trioxalatoiridium and hexacyanoiridium.
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 (eg 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 silver halide grains in the present invention may be doped with another heavy metal salt. Especially K ₄ [Fe (C
N) ₆ ] is preferably used to dope the Fe salt. Further silver halide grains used in the present invention, cobalt, nickel, palladium, platinum, gold, thallium, copper,
It may contain a metal atom such as lead. 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.

The silver halide emulsion of the present invention is preferably chemically sensitized, and sulfur sensitization, selenium sensitization, tellurium sensitization,
Known methods such as reduction sensitization and noble metal sensitization can be used, and they can be used alone or in combination. When used in combination, for example, sulfur sensitization and gold sensitization, sulfur sensitization and selenium sensitization and gold sensitization, sulfur sensitization and tellurium sensitization and gold sensitization, etc. Is preferred.

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, for example, thiosulfates, thioureas, thiazoles, rhodanins and the like can be used. Can be used. 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.

Known selenium compounds can be used as the selenium sensitizer used in the present invention. 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.
No. 3489, Japanese Patent Application Nos. 2-130976 and 2-229.
The compounds described in No. 300, No. 3-121798 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 capable of producing silver telluride, which is presumed to serve as a sensitizing nucleus, on the surface or inside of silver halide grains. 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 Application No. 2-33
No. 3819, No. 3-53693, No. 3-131598.
No. 4-129787, J. Chem. Soc. Chem. Commun.,
635 (1980), 1102 (1979), 645 (1979), J. Chem. So
c.Perkin.Trans., 1,2191 (1980), edited by S. Patai, The Che
mistry of Organic Serenium and Tellurium Compound
s, Vol. 1 (1986) and the same Vol. 2 (1987) can be used. Particularly preferred are compounds represented by formulas (II), (III) and (1V) 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, etc., but generally 10 ^-8 to 10 ^-2 mol per mol of silver halide. , Preferably 10 ⁻⁷ to 10 ⁻³
Use molar amounts. 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 chloroaurate, potassium auritin cyanate, gold sulfide, etc., and 10 ^-7 to 10 ^-2 per mol of silver halide. Molar amounts 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 and the like may coexist in the process of formation of silver halide grains or physical ripening. 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 (EP) -293,917. The silver halide emulsion in the light-sensitive material used in the present invention may be one kind or two or more kinds (for example, those having different average grain sizes, different halogen compositions, different crystal habits, chemically sensitized ones). Different conditions) may be used together.

The silver halide photographic light-sensitive material of the present invention comprises
Nucleation accelerators such as amine derivatives, onium salts, disulfide derivatives, and hydroxylamine derivatives are preferably added to the silver halide emulsion layer or other hydrophilic colloid layers.

The nucleation accelerator used in the present invention includes
Examples thereof include amine derivatives, onium salts, disulfide derivatives, and hydroxymethyl derivatives. As the amine derivative, for example, JP-A-60-140,340, JP-A-62-50,829, JP-A-62-222,241, JP-A-62-250,439, JP-A-62-280,733,
63-124,045, 63-133,145.
No. 63-286,840 and the like. More preferably as an amine derivative,
Compounds having a group capable of adsorbing to silver halide described in JP-A-63-124,045, 63-133,145, 63-286,840 and the like, or described in JP-A-62-222,241 and the like. Compounds with 20 or more carbon atoms in total, US 4,97
No. 5,354, EP 458 P706A, etc., amine compounds having an ethylene group, JP-A-62-50.
The compounds described in No. 829 and the like can be mentioned. The onium salt is preferably a pyridinium salt, an ammonium salt or a phosphonium salt. Examples of preferable pyridinium salts include the compounds described in Japanese Patent Application No. 5-97866. Further, examples of preferable ammonium salts include JP-A Nos. 62-250,439 and 62-62.
-280,733 etc. can be mentioned. Further, examples of preferable phosphonium salts include JP-A-61-167,939 and JP-A-62-280.
The compound described in No. 733 etc. can be mentioned. Examples of the disulfide derivative include, for example, JP-A-61-19
The compounds described in No. 8,147 can be mentioned. As the hydroxymethyl derivative, for example, U.S. Pat. No. 4,698,956
No. 4,777,118, EP 231,850, JP-A-6
2-50,829 etc. can be mentioned, More preferably, it is a diarylmethanol derivative. As the acetylene derivative, for example, Japanese Patent Application Laid-Open No. 3-1
68735, the compound of Unexamined-Japanese-Patent No. 2-271351, etc. can be mentioned. Examples of the urea derivative include compounds described in JP-A-3-168736.

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

[0070]

[Chemical 32]

[0071]

[Chemical 33]

[0072]

[Chemical 34]

[0073]

[Chemical 35]

[0074]

[Chemical 36]

[0075]

[Chemical 37]

[0076]

[Chemical 38]

[0077]

[Chemical Formula 39]

[0078]

[Chemical 40]

[0079]

[Chemical 41]

[0080]

[Chemical 42]

The optimum addition amount of these compounds varies depending on the kind thereof, but is 1.0 × 1 per mol of the hydrazine compound.
0 ⁻² mol to 1.0 × 10 ² mol, preferably 1.0 ×
It is preferably used in the range of 10 ^-1 mol to 5.0 x 10 mol. These compounds are suitable water-miscible organic solvents such as alcohols (methanol, ethanol, propanol, fluorinated alcohols), ketones (acetone,
Methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl cellosolve, etc. can be used after dissolving. 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. It is also possible to create and use things. Alternatively, powders of these compounds may be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method, and then used.

As the binder or protective colloid of the photographic emulsion, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfate, sodium alginate, sugar derivatives such as starch derivatives, polyvinyl alcohol, poly A variety of synthetic hydrophilic polymer substances such as a single or copolymer such as acrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinyl butyral and the like can be used.

The support used in the light-sensitive material of the present invention is a flexible support of paper or synthetic paper laminated with α-olefin polymer (eg polyethylene, polypropylene, ethylene / butene copolymer). , Metal, etc. are included. Among them, polyethylene terephthalate is particularly preferable. As the undercoat layer to be used in the present invention, the undercoat layer described in JP-A-9-3972 in an organic solvent system containing polyhydroxybenzenes, JP-A-49-1111.
No. 8, No. 52-10491, etc., and the aqueous latex undercoating layer. The surface of the undercoat layer can be chemically or physically treated. Examples of the treatment include chemical treatment, mechanical treatment, corona discharge treatment, and other surface activation treatments.

Next, the developing solution used in the present invention will be described. As described above, the developer of the present invention contains substantially no dihydroxybenzene-based developing agent, and the main developing agent is the compound represented by the general formula (II). The developer of the present invention preferably contains a 1-phenyl-3-pyrazolidone type auxiliary developing agent and / or a p-aminophenol type auxiliary developing agent as an auxiliary developing agent.

Next, the compound represented by the general formula (III) used in the present invention will be described in detail. General formula (III)
In the formula, R ₁ and R ₂ are each a hydroxy group, an amino group (having a substituent having an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-butyl group, or a hydroxyethyl group as a substituent). ,), Acylamino group (acetylamino group, benzoylamino group, etc.), alkylsulfonylamino group (methanesulfonylamino group, etc.), arylsulfonylamino group (benzenesulfonylamino group, p-toluenesulfonylamino group, etc.), alkoxy It represents a sulfonylamino group (such as a methoxycarbonylamino group), a mercapto group, and an alkylthio group (such as a methylthio group and an ethylthio group). R ₁ ,
Preferred examples of 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,
Alternatively, P and Q represent a group of atoms necessary for bonding to form a 5- to 8-membered ring with two vinyl carbon atoms substituted by R ₁ and R ₂ and a carbon atom substituted by Y. . Specific examples of the ring structure, -O -, - C (R 4) (R 5) -, - C
(R ₆ ) =, -C (= O)-, -N (R ₇ )-, -N =. However, R ₄ , R ₅ , R ₆ , R
₇ is 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 may be mentioned as a substituent), and an aryl group having 6 to 15 carbon atoms which may be substituted ( Examples of the substituent include an alkyl group, a halogen atom, a hydroxy group, a carboxy group and a sulfo group), a hydroxy group and a carboxyl group. Further, a saturated or unsaturated condensed ring may be formed on the 5- to 7-membered ring.

Examples of the 5- to 8-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 8-membered ring are:
Dihydrofuranone ring, cyclopentenone ring, cyclohexenone ring, pyrazolinone ring, azacyclohexenone ring,
The uracil ring can be mentioned.

Y is composed of = 0 or = N-R ₃ . Here, R ₃ is a hydrogen atom, a hydroxyl group, an alkyl group (eg, methyl group, ethyl group), an acyl group (eg, acetyl group), a hydroxyalkyl group (eg, hydroxymethyl group, hydroxyethyl group), a sulfoalkyl group (eg, sulfomethyl group). Group, sulfoethyl group) and carboxyalkyl group (eg carboxymethyl group, carboxyethyl group).

Specific examples of the compound of the present invention are shown below, but the present invention is not limited thereto.

[0090]

[Chemical 43]

[0091]

[Chemical 44]

[0092]

[Chemical formula 45]

[0093]

[Chemical formula 46]

[0094]

[Chemical 47]

[0095]

[Chemical 48]

Of these, ascorbic acid or erythorbic acid (stereoisomer) (III-1) is preferable. A general range of the amount of the compound of the general formula (III) to be used is 5 × 10 ⁻³ mol to 1 mol, particularly preferably 10 ⁻² mol to 0.5 mol, per liter of the developing solution.

1-Phenyl-3 as an auxiliary developing agent
Examples of pyrazolidone or a derivative thereof include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone and 1-phenyl-4-methyl-4.
-Hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxylmethyl-3-pyrazolidone,
1-phenyl-5-methyl-3-pyrazolidone, 1-p
-Aminophenyl-4,4 dimethyl-3-pyrazolidone, 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone and the like. As the p-aminophenol-based auxiliary developing agent, N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine, 2- There are methyl-p-aminophenol, p-benzylaminophenol and the like, and among them, N-methyl-p-aminophenol is preferable.
When the combination of the compound represented by the general formula (II) of the present invention and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the latter is usually added in an amount of 10 ⁻³ mol / liter to 0.1. It is preferably used in an amount of mol / liter, more preferably 10 ⁻³ mol / liter to 0.06 mol / liter.

In the present invention, the term "substantially free of dihydroxybenzenes" means that the concentration of dihydroxybenzenes in the developing solution is determined relative to the amount of the compound of the general formula (II) or the above-mentioned auxiliary developing agent. Not enough (eg 5 × 1
^0-4 mol / liter or less). The developer of the present invention preferably contains no dihydroxybenzenes.

Sulfites such as sodium sulfite, potassium sulfite, lithium sulfite, sodium bisulfite, potassium metabisulfite and formaldehyde sodium bisulfite may be added to the developer of the present invention as preservatives.
The sulfite is used at 0.01 mol / l or more. If used in a large amount, it will dissolve silver halide emulsion grains and cause silver stains. Moreover, since it also causes an increase in COD (chemical oxygen demand), the amount added should be minimized.

The pH of the developer used in the developing treatment of the present invention is preferably in the range of 10.0 to 12.0. More preferably, it is in the range of 10.4 to 12. pH is 12.
When it is 0 or more, stains and black spots in the non-image area sharply increase, which is not preferable. Further, if the pH is 10.0 or less, sufficient contrast cannot be obtained. Alkali agents used to set the pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like. The developer of the present invention includes saccharides (for example, saccharose), oximes (for example, acetoxime) described in JP-A-60-93433,
A pH buffering agent such as phenols (for example, 5-sulfosalicylic acid), silicates, sodium triphosphate and potassium triphosphate can be used. The concentration of the buffer is 0.
It is preferably 3 mol / liter or more. Boron compounds such as boric acid and sodium metaborate are not preferable because they may react with the compound of the present invention represented by the general formula (II) to inactivate them.

Development inhibitors such as potassium bromide and potassium iodide, organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol and methanol, and indazoles such as 5-nitroindazole. Compounds, benzimidazole compounds such as 2-mercaptobenzimidazole-5-sodium sulfonate, and antifoggants such as benztriazole compounds such as 5-methylbenztriazole, Research Disclosure Vol. 176 No. 17643, Item XXI (December issue, 1978). It may also contain amine compounds described in U.S. Pat. No. 4,269,929, JP-A-61-267759 and Japanese Patent Application No. 1-291818. Further, a color tone agent, a surface active agent, a hardener, etc. may be contained if necessary. The developer of the present invention includes European Patent Publication 13
6582, British Patent No. 958678, US Patent No. 3
Amino compounds such as alkanolamines described in JP-A No. 232761 and JP-A No. 56-106244 can be used for the purpose of promoting development and increasing contrast.

The fixing solution used in the present invention is an aqueous solution containing thiosulfate, and has a pH of 3.8 or higher, preferably 4.2 to 4.2.
Has 7.0. Sodium thiosulfate as a fixing agent,
There are ammonium thiosulfate and the like, but ammonium thiosulfate is particularly preferable from the viewpoint of fixing speed. The amount of the fixing agent used can be appropriately changed and is generally about 0.1 to about 6 mol / liter. The fixing solution may contain a water-soluble aluminum salt which acts as a hardening agent, and they include, for example, aluminum chloride, aluminum sulfate and potassium alum. Tartaric acid, citric acid, gluconic acid or their derivatives can be used alone or in combination of two or more in the fixing solution. It is effective that these compounds contain 0.005 mol / liter or more per liter of the fixing solution, and particularly 0.01 mol / liter to 0.03 mol / liter is particularly effective. Preservatives (eg, sulfite, bisulfite), pH buffers (eg, acetic acid, boric acid) pH adjusters (eg, sulfuric acid, ammonia), chelating agents having a water softening ability may be included in the fixer, if desired. Surfactants, wetting agents, fixing accelerators, and compounds described in JP-A-62-78551 may be included. Examples of the fixing accelerator include thiourea derivatives described in JP-A-45-35754, JP-A-58-122535, and JP-A-58-122536, alcohol having a triple bond in the molecule, and US Pat.
Examples thereof include thioether compounds described in JP-A No. 59, and compounds described in JP-A-2-44355 may be used.
Further, as the dye elution accelerator, the compounds described in JP-A 64-4739 can be used.

In the development processing method of the present invention, development,
After the fixing step, it is treated with washing water or a stabilizing solution and then dried. It is also possible to process with a rinsing water or a stabilizing solution of a replenishing amount of 3 liters or less (zero, that is, including rinsing with water) per 1 m ^{2 of the} silver halide photographic material.
That is, not only water saving processing becomes possible, 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 processed in a gradually cleaning direction, that is, the processing solution which is not contaminated with the fixing solution is sequentially processed, so that the efficiency is further improved. Washed with water. When washing with a small amount of water, the method described in JP-A-63-1 is used.
It is preferable to provide a washing tank for a squeeze roller and a cross over roller as described in Nos. 8350 and 62-287252. Further, various oxidizers may be added or filter-filtration may be combined in order to reduce the pollution load which becomes a problem when washing with a small amount of water. In the above water-saving treatment or pipe-less treatment, it is preferable to apply antifouling means to the washing water or the stabilizing solution.

As an anti-fungus means, Japanese Patent Laid-Open No. 60-263
UV irradiation method described in No. 939, 60-26394
Method using magnetic field described in No. 0, Ibid.
A method for producing pure water using the ion exchange resin described in JP-A No. 62-115154 and JP-A No. 62-15395.
No. 2, No. 62-220951, No. 62-209532
It is possible to use the method using the antibacterial agent described in No.
Furthermore, LFWest, "Water Quality Criteria" Photo.
Sci. & Eng., Vol.9 No.6 (1965), MWReach, "Microbi
ological Growths in Motion- picture Processing ", SM
PTE Journal Vol.85 (1976), RODeegan, "Photo Proces
sing Wash Water Biocides ", J. Imaging Tech., Vol.10,
No. 6 (1984), and JP-A-57-8542 and 57-
56143, 58-105145, 57-13.
No. 2146, No. 58-18631, No. 57-9753
No. 0, No. 57-157244 and the like can be used in combination with antibacterial agents, antifungal agents, surfactants and the like. In addition, RTKreiman can be used as a washing bath or stabilizing bath.
Research Disclosure No. 2, isothiazolidine compounds described in J. Imaging Tech., 10 (6) p.242 (1984).
The compounds described in Vol. 05, No. 20526 (1981, No. 4) and the like can be used together as a bacteriostatic agent (Microbiocide).
In addition, compounds such as those described in "The Chemistry of Antibacterial and Antifungal" by Hiroshi Horiguchi, Sankyo Publishing (Showa 57), "Handbook of Antibacterial and Antifungal Technology", Japan Society of Antibacterial and Antifungal, Hakuhodo (Showa 61) May be included.

When washing with a small amount of washing water in the method of the present invention, it is also preferable to adopt a constitution of a washing step as described in JP-A-63-143548. Furthermore, some or all of the overflow from the washing or stabilizing bath caused by supplementing the washing or stabilizing bath with antifungal means by the method of the present invention depending on the treatment is disclosed in JP-A-60-
As described in No. 235133, it can also be used for a processing liquid having a fixing ability which is a processing step before that. In the development processing of the present invention, the development time is 5 seconds to 3 seconds.
Min, preferably 8 seconds to 2 minutes, and the developing temperature is 18 ° C to
50 degreeC is preferable and 24 degreeC-40 degreeC is more preferable.

The fixing temperature and time are about 18 ° C to about 50 ° C.
5 seconds to 3 minutes is preferable, and 24 seconds to 40 degrees Celsius is 6 seconds to 2
Minutes are more preferred. Within this range, sufficient fixing can be carried out, and the sensitizing dye can be eluted to the extent that no residual color is generated.
0 ° C., 6 seconds to 3 minutes are preferable, 15 to 40 ° C., 8 seconds to 2
Minutes are more preferred. The light-sensitive material which has been developed, fixed and washed (or stabilized) is squeezed out of washing water, that is, dried through a squeeze roller. Drying is about 40 ℃ -1
The drying is carried out at 00 ° C., and the drying time may be appropriately changed depending on the ambient conditions, but is usually about 4 seconds to 3 minutes, particularly preferably 40 ° C. to 80 ° C. for about 5 seconds to 1 minute. Dry to
When developing with a dry process for 100 seconds or less, in order to prevent development unevenness peculiar to rapid processing, JP-A-63-1 is used.
A roller made of a rubber material as described in Japanese Patent No. 51943 is applied to the roller at the outlet of the developing tank, and a discharge for stirring the developing solution in the developing tank as described in JP-A-63-151944. It is more preferable to set the flow velocity to 10 m / min or more, and further, as described in JP-A-63-264758, vigorously stirrer during standby at least during development processing. For further rapid processing, it is more preferable that the rollers of the fixing tank are opposed rollers in order to increase the fixing speed. By configuring with opposed rollers, it is possible to reduce the number of rollers and the processing tank. That is, the automatic processing machine can be made more compact.

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 1) Nucleation accelerator JP-A-2-103536, page 9, upper right column, line 13 to page 16, upper left column, line 10 General formula (II-m) to (II-p) ) And Compound Examples II-1 to II-22, and the compounds described in JP-A-1-179939. 2) Surfactant JP-A-2-122363, page 9, upper right column, line 7 to right, lower column, line 7, and JP-A-2-185424, page 2, lower left column, line 13 to page 4, right. Bottom line, line 18. 3) Antifoggant 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; JP-A 1-237538 A thiosulfinic acid compound described in the official gazette. 4) Polymer latex JP-A-2-103536, page 18, lower left column, lines 12 to 20. 5) Compounds having an acid group JP-A-2-103536, page 18, lower left column, line 6 to page 19, upper left column, line 1 6) Matting agent, slipping agent, JP-A-2-103536, page 19, upper left column, line 15 to plasticizer, page 19 upper right column, line 15 7) Hardener JP-A-2-103536, page 18, upper right column, line 5 to page 17, line 17 of the same. 8) Dyes Dyes in JP-A-2-103536, page 17, lower right column, lines 1 to 18; solid dyes described in JP-A 2-294638 and Japanese Patent Application No. 3-185773. 9) Binder JP-A-2-18542, page 3, lower right column, lines 1 to 20. 10) Black spot preventing agent Compounds described in US Pat. No. 4,956,257 and JP-A No. 1-118832. 11) Redox compound A compound represented by formula (I) in JP-A-2-301743 (particularly compounds 1 to 50), a compound represented by formula (I) in pages 3 to 20 of JP-A 3-174143. R-1), (R-2), (R-3), compound examples 1 to 75, and compounds 12) monomethine compounds described in Japanese Patent Application Nos. 3-69466 and 3-15648. Compounds of the general formula (II) disclosed in Japanese Patent No. 287532 (in particular, Compound Examples II-1 to II-26). 13) Dihydroxybenzes Compounds described in JP-A-3-39948, page 11, upper left column to page 12, lower left column, and EP452772A. 14) 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 by way of examples, but the present invention is not limited thereto.

[0109]

【Example】

Example 1 <Preparation of developing solution>
A developer containing the compound of the present invention represented by I) was prepared. As a comparative example, a developer containing hydroquinone as a main component was also prepared.

[0110]

[Table 1]

<Measurement of COD> According to 18 of JIS K 0102, the COD (chemical oxygen demand) of the developer prepared in Table 1 was measured. The results are also shown in Table 1. As can be seen from the table, the developer of the present invention has a very low COD value as compared with the developer using the conventional hydroquinone type developing agent. This developer itself is ecological,
Not only is it less dangerous from a toxicological point of view, but when it is developed using a well-known automatic processor that undergoes the steps of developing, fixing, washing and drying with this developer, it mixes into the overflow of the washing tank. It indicates that the degree of pollution to the environment due to the developing solution components coming in is low. <Preparation of silver halide light-sensitive material> Emulsion preparation An emulsion 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 (H ₂ O) Cl ₅ equivalent to 2.0 × 10 ⁻⁷ mol
Halogen salt solution containing
-Adding to a gelatin aqueous solution containing dimethyl-2-imidazolidinethione by a double jet method with stirring, an average particle size of 0.25 µm and a silver chloride content of 70
Mol% silver chlorobromide grains were prepared.

Then, 1 × 10 ⁻³ mol of KI solution was added to 1 mol of silver for conversion, followed by washing with water by a flocculation method according to a conventional method, and 40 g of gelatin was added per mol of silver. 7 mg sodium benzenethiosulfonate and 2 benzenesulfinic acid
After adding mg, the pH was adjusted to 6.0 and pAg was 7.8, 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. Then, 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 0.25 μm,
The silver iodochlorobromide cubic grains had a silver chloride content of 69.9 mol%. (Variation coefficient 10%)

Preparation of Coating Sample To the above emulsion, as shown in Table 2, a sensitizing dye was added at 5 × 10 ⁻⁴ mol per mol of silver, and further 3 × 10 per mol of silver was added.
^-4 mol of mercapto compound represented by the following (a), 4x
10 ⁻⁴ mol of the mercapto compound represented by (b), 4 ×
10 ⁻⁴ mol of the triazine compound represented by (c), 2 ×
10 ⁻³ mol of 5-chloro-8-hydroxyquinoline was added, and as shown in Table 2, the hydrazine derivative and the nucleation accelerator were added. Furthermore, hydroquinone 100mg, was added N- oleyl -N- methyl taurine sodium salt as 30 mg / m ² coating, a dispersion of a water-soluble latex 200 mg / m ^2, polyethyl acrylate represented by (d) 200 mg / m ² , methyl acrylate and 2-acrylamido-2-methylpropanesulfonic acid sodium salt and 2
- Latex copolymers of acetoacetoxyethyl methacrylate (weight ratio 88: 5: 7) to 200 mg / m ^2, a further 1,3-vinylsulfonyl-2-propanol as a hardening agent were added 200 mg / m ^2. The pH of the solution is 6.0
Was prepared. They were coated on a polyethylene terephthalate film having a moistureproof layer undercoating containing vinylidene chloride on both sides so that the coating silver amount was 3.0 g / m ² .

On these emulsion layers, as a protective layer, 1.0 g / m ² of gelatin, 40 mg / m ^{2 of} amorphous SiO ₂ matting agent having an average particle size of about 3.5 μm, methanol silica of 0.1.
1 g / m ² , polyacrylamide 100 mg / m ² , sodium ethylsulfonate 5 mg / m ² and silicone oil 20 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.

[0115]

[Chemical 49]

[0116]

[Table 2]

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 Polyethylene acrylate 2 g / m ² Surfactant sodium p-dodecylbenzenesulfonate 40 mg / m ²

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

[0119]

[Chemical 50]

[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

<Exposure and development> (1) Evaluation of photographic performance The above sample was exposed with a xenon flash light having an emission time of 10 ^-5 sec through a step wedge through an interference filter having a peak at 488 nm to obtain a developing solution. After developing with D-3, D-4, D-5, and D-6 of the above-mentioned composition for 30 seconds at 35 ° C., fixing, washing and drying treatments were carried out. GR-F1 (manufactured by Fuji Photo Film Co., Ltd.) was used as a fixing solution, and FG-68 was used for this development processing.
An OA automatic processor (manufactured by Fuji Photo Film Co., Ltd.) was used. The sensitivity is indicated by the relative value of the reciprocal of the exposure amount that gives a density of 1.5, and the higher the value, the higher the sensitivity. As an index (γ) representing the contrast of the image, f of the characteristic curve is used.
A point from the og + concentration of 0.3 to a point from the fog + concentration of 3.0 was connected by a straight line, and the slope of this straight line was expressed as a γ value. That is, γ = (3.0-0.3) / [log (exposure amount giving a density of 3.0) -log (exposure amount giving a density of 0.3)], and the higher the γ value, the harder the image. It shows that it is a characteristic.

(2) Evaluation of safety of safe light: SLF-1B (safe light for yellow light) manufactured by Fuji Photo Film Co., Ltd. was applied with 20 lux of light, and the time until the fogging increased was measured. The higher the value, the better the safelight safety. (3) Evaluation of flat mesh unevenness Using the above-mentioned sample, Magnascan M-656 (manufactured by Crossfield) was used to expose a flat mesh having a mesh% of 93%, and the developing rollers were each decentered by 0.3 mm. -680A
After developing with an automatic processor, the level of flat mesh unevenness of the sample after processing was evaluated, "5" represents a good level without flat mesh unevenness at all, and "1" generated flat mesh unevenness. Indicates significantly worse quality. "3" is a level at which the occurrence of flat mesh unevenness is substantially allowable.

<Results> As shown in Table 3, according to the image forming method using the compound of the present invention, high safelight safety, high sensitivity, high contrast (γ), and good flat screen level of pH 10 were obtained. It can be seen that it can be obtained with the developer of 12 or less. In particular, when a nucleation accelerator was used in combination, a high-contrast image was obtained at a lower pH. When the pH became 12.5, the flat mesh unevenness increased and exceeded the permissible level, the fog level increased and the contrast decreased.

[0124]

[Table 3]

[0125]

[Table 4]

Example 2 Except that a silver halide emulsion having a halogen composition as shown in Table 5 was prepared by changing the ratio of potassium bromide to sodium chloride in an aqueous halogen solution added during grain formation in the emulsion preparation. An emulsion and a coated sample were prepared in the same manner as the emulsion A of Example 1, and exposed and developed. <Results> The results are also shown in Table 5. It can be seen that particularly good performance can be obtained with the sample of the present invention having a silver chloride content of 50 mol% or more.

[0127]

[Table 5]

Example 3 An emulsion and a coating sample were prepared in the same manner as in the emulsion A of Example 2 except that the metal complex salt contained in the aqueous halogen solution added during grain formation in the emulsion preparation was changed as shown in Table 6. Was prepared and exposed and developed. <Results> The results are also shown in Table 6. It is understood that particularly good performance is obtained with samples containing rhodium, ruthenium, osmium, iridium.

[0129]

[Table 6]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location G03C 1/295 5/30

Claims (4)

[Claims] 1. A silver chloride content of 50 mol% spectrally sensitized with a compound represented by the following general formula (I) on a support.
It has at least one silver halide emulsion layer consisting of the above silver halide emulsion, and contains the hydrazine compound represented by the general formula (II) in at least one of the emulsion layer and other hydrophilic colloid layers. After imagewise exposing the silver halide photographic light-sensitive material consisting of the following, developing treatment with a developer containing substantially no dihydroxybenzene-based developing agent as a developing agent and containing a developing agent represented by the following general formula (III) And an image forming method. General formula (I) In the formula, R ₁ and R ₂ each represent an alkyl group which may have a substituent, and at least one of R ₁ and R ₂ is an acetylaminoalkyl group or an N-alkylcarbamoylaminoalkyl group. V ₁ and V ₂ each represent a hydrogen atom, an alkyl group, an alkoxy group or a trifluoromethyl group. General formula (II) In the formula, R ₁ represents an aliphatic group or an aromatic group, R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an unsaturated heterocyclic group,
Represents an alkoxy group, an aryloxy group, an amino group, a hydrazino group, a carbamoyl group, or an oxycarbonyl group, and G ₁ is a —CO— group, a —SO ₂ — group, a —SO— group, or Represents a —CO—CO— group, a thiocarbonyl group, or an iminomethylene group, and A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted Represents an arylsulfonyl group or a substituted or unsubstituted acyl group. The R ₃ is selected from the same range as radical as defined R _2, may be different from R _2. General formula (III): In the formula, R ₁ and R ₂ are each a hydroxy group, an amino group,
It represents an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group or an alkylthio group. P, Q
Each represents a hydroxy group, a carboxyl group, an alkoxy group, a hydroxyalkyl group, a carboxyalkyl group, a sulfo group, a sulfoalkyl group, an amino group, an aminoalkyl group, an alkyl group or an aryl group, or R
₁ and ₂ represent an atomic group forming a 5- to 8-membered ring together with two vinyl carbon atoms substituted with R ₂ and a carbon atom substituted with Y. Y represents = O or = N-R _3,. R ₃ represents a hydrogen atom, a hydroxyl group, an alkyl group, an acyl group, a hydroxyalkyl group, a sulfoalkyl group or a carboxyalkyl group. 2. The silver halide emulsion per mol of silver,
2. The image forming method according to claim 1, which contains 1 × 10 ⁻⁸ to 5 × 10 ⁻⁶ mol of at least one kind of rhodium, ruthenium, rhenium, osmium or iridium compound. 3. The silver halide emulsion layer or other hydrophilic colloid layer contains at least one amine derivative, onium salt, disulfide derivative or hydroxymethyl derivative as a nucleation accelerator. Item 1. The image forming method according to Item 1. 4. The pH of the developer is 10.0 or more, 12.
The image forming method according to claim 1, wherein the image forming method is 0 or less.