JPH1195360A - Silver halide photographic sensitive material and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To stabilize a processing stage, while reducing occurrence of fog and to enhance precision stability of the whole process by controlling a coating amount of silver in the photosensitive material and a coating amount of gelatin in an emulsion layer each in a specified range and incorporating a specified amount of a specified mercaptoazole compound in at least one of the emulsion layers and the other hydrophilic colloidal layers. SOLUTION: The silver halide emulsion layer formed on a support contains silver in a coating amount of 0.6-2.0 g/m<2> of the photosensitive material and this emulsion layer contains the gelatin in an amount of 0.3-0.8 g of 1 g of silver, and at least one of the emulsion layer and the other hydrophilic colloidal layers in 0.3-5.0 mmol per 1 mol of silver halide of the mercaptoazole compound represented by formula in which Z is a =N- or =C(x)- group; X is an alkyl or aryl group; M is an H or metal atom or an ammonium group; and Y is an alkyl or aryl group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material for forming a silver image as a final image, and more particularly to a silver halide photographic material which can be handled in an environment which can be substantially called a bright room. The present invention relates to a return silver halide black-and-white photographic light-sensitive material suitable for use in the field of photolithography and capable of forming a high contrast negative silver image, and an image forming method.

[0002]

2. Description of the Related Art Among photoengraving processes in the field of print duplication, in particular, in a work process of collecting and returning a plate, work is performed in a brighter environment to improve work efficiency and work environment. Thus, a silver halide photographic light-sensitive material for plate making that can be handled in an environment that can be substantially called a bright room is provided. As a method of producing a light-sensitive material that can be handled in a bright room by lowering the sensitivity to visible light, a silver halide emulsion mainly composed of silver chloride is added to an inorganic material such as a rhodium salt, an iridium salt, a pinacryptol yellow, or a phenosafranine. And a method using an emulsion to which an organic desensitizer is added is well known. Especially without chemical sensitization 0.05
A method in which a rhodium salt and / or an organic desensitizer is used in a fine grain silver chloride or fine grain silver chlorobromide emulsion of .about.0.5 .mu.m is preferably used.

On the other hand, a plate-making film for printing is treated with a developing solution having a small pH fluctuation to stabilize the developing process, thereby improving the accuracy of the entire plate-making process.
There is a method for reducing the work load by reducing the replenishing amount of the developer. Japanese Patent Publication No. 3-5730 discloses that a change in the pH value of a developing solution is reduced by increasing the pH buffer capacity of the developing solution to stabilize photographic performance. However, when a silver halide photosensitive material mainly composed of silver chloride having a high solubility as a silver halide composition is processed with an automatic developing machine using a developing solution having a high pH buffering property, physical development fog occurs during fixing processing. There is. Immediately after the photosensitive material is conveyed to the fixing tank, it is considered that the developer and the fixing solution are mixed and exist on the surface of the photosensitive material. Therefore, the dissolution of the silver halide particles by the fixing agent and the reduction of Ag ions by the developing agent occur simultaneously, resulting in dissolved physical development fog.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide photographic light-sensitive material which achieves both the stabilization of the processing step and the reduction of fogging in the entire plate-making step, thereby improving the accuracy stability of the entire step. An object of the present invention is to provide an image forming method for a material.

[0005]

The present invention has been attained by the following. (1) In a silver halide photographic material having at least one silver halide emulsion layer on a support, the amount of silver applied to the photographic material is from 0.6 g to 2 g per square meter of the silver halide photographic material. And the amount of gelatin in the emulsion layer is in the range of 0.3 g to 0.8 g per 1 g of silver. The emulsion layer and at least one other hydrophilic colloid layer are represented by the following general formula. A silver halide photographic light-sensitive material containing a mercaptoazole compound in an amount of 0.3 to 5.0 mmol or more per mole of silver. General formula (1)

[0006]

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Wherein Z is ＮN- or −C (X)-(X
Represents an alkyl group or an aryl group), M represents a hydrogen atom, a metal atom or ammonium, and Y represents an alkyl group or an aryl group. (2) In the above (1), the silver halide in the emulsion layer is I
A heavy metal selected from r, Ru, Rh, Cr and Re is added in an amount of 1 × 10 ⁻⁷ mol to 1 × 10 ⁷ mol per mol of silver halide.
^A silver halide photographic light-sensitive material, characterized in that it is contained in an amount of ^-5 mol. (3) A silver halide photographic light-sensitive material according to (1) or (2), wherein the emulsion layer or another hydrophilic colloid layer contains a hydrazine derivative and a nucleation accelerator. (4) A silver halide photographic light-sensitive material according to the above (1) to (3), wherein the support is a paper support. (5) In the method of (1) to (4), wherein the silver halide photographic light-sensitive material is exposed and then developed with a developing solution, the developing solution contains a dihydroxybenzene-based developing agent and a super-additive auxiliary developing agent. PH rise when adding 0.1 mol of sodium hydroxide to 1 liter of the developer is not more than 0.3, and the initial pH of the developer is from 9.5 to 11.0. For forming an image of a silver halide photosensitive material. (6) The method for forming an image of a silver halide photographic material according to the above (5), wherein the replenishing amount of the developing solution is 225 ml or less per square meter of the silver halide photographic material.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the mercaptoazoles represented by the general formula (1) used in the present invention will be described. General formula (1)

[0009]

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Wherein Z is ＮN- or ＣC (X)-(X
Represents an alkyl group or an aryl group), M represents a hydrogen atom, a metal atom or ammonium, and Y represents an alkyl group or an aryl group having a hydrophilic group. The alkyl group, aryl group and ammonium group represented by X, Y and M include those having a substituent. Among the groups represented by X, preferred are an alkyl group having 1 to 30 carbon atoms, a phenyl group having 6 to 30 carbon atoms, or a group having 10 carbon atoms.
To 30 naphthyl groups. These also include those having a substituent. Among the groups represented by Y, preferred are an alkyl group having 1 to 30 carbon atoms and an aryl group having 6 to 30 carbon atoms, particularly preferably a phenyl group having 6 to 30 carbon atoms, or a carbon atom having 6 to 30 carbon atoms. 10 to 30 naphthyl groups. These also include those having a substituent. In the above, the substituent is not particularly limited, and examples thereof include a hydroxy group, a carboxyl group, a sulfo group, an alkoxy group, an aminocarbonyl group, an acylamino group, and a ureido group. M represents a hydrogen atom, an alkali metal, a quaternary ammonium, or a quaternary phosphonium.
Hereinafter, specific examples of the compound represented by Formula (1) used in the present invention are shown, but the scope of the present invention is not limited to these compound examples.

[0011]

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[0012]

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[0013]

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[0014]

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[0015]

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[0016]

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The compound represented by the general formula (1) can be easily synthesized by using isothiocyanate as a starting material, as is generally well known. The patents and literature examples in which reference synthesis methods are described are shown below. U.S. Pat. No. 2,585,388
No. 2,541,924, Japanese Patent Publication No. 42-21842
JP-A-53-50169; British Patent No. 1,
275,701; DABerges et all, "Journa
l of Heterocyclic Chemistry "Vol. 15, p. 981 (1978
Year); "The Chemistry of Heterocyclic Chemistry" Im
idazole and Derivatives part I. pp. 336-339 Chemic
al Abstract 58, 7921 (1963), p. 394; E. Hoggarth
"Journal of Chemical Society" 1949 1160-1167
And SRSandler, W. Karo, "Organic Functional
Group Preparations ", Academic Press, 1968, pp. 312-315.

These compounds are used as an aqueous solution, a hydrochloric acid aqueous solution or a methanol solution as a photographic emulsion or a constituent layer other than the emulsion layer (for example, an overcoat layer, a filter layer, an intermediate layer, etc., and a layer adjacent to the emulsion layer is preferred). ) Is added to the hydrophilic colloid solution. The timing of addition is not particularly limited, but when it is added to a photographic emulsion, it is convenient to add it during the second ripening and immediately before coating. These compounds are used in an amount of 0.3 to 5 mmol, preferably 0.5 to 2 mmol, per 1 mol of silver.

The silver halide emulsion of the present invention comprises Ir, R
It is preferable to contain at least one heavy metal selected from u, Rh, Cr and Re. Preferred as these heavy metals are metal coordination complexes, and hexacoordinate complexes represented by the following general formula. [M (NY) _m L _6-m ] ⁿ (where M is a heavy metal selected from Ir, Ru, Rh, Cr and Re. L is a bridging ligand. Y is oxygen or sulfur. M = 0, 1, 2 and n = 0, −1, −
2, -3. Preferable examples of L include halide ligands (fluoride, chloride, bromide and iodide), cyanide ligand, cyanate ligand, thiocyanate ligand, selenocyanate ligand, tellurocyanate Nate, acid and aquo ligands. If an aquo ligand is present, it preferably occupies one or two of the ligands. Specific examples of the metal coordination complex are shown below. M-1. [Rh (H ₂ O) Cl _5] ^-2 M-2. [RhCl ₆ ] ^-3 M-3. [Ru (NO) Cl _5] ^-2 M-4. [RhCl ₆ ] ^-3 M-5. [Rh (H ₂ O) Cl _5] ^-2 M-6. _{[Ru (NO) (H 2 O} ) Cl 4 ] ^-1 M-7. [Re (NO) Cl _5] ^-2 M-8. [Ir (NO) Cl _5] ^-2 M-9. [Ir (H ₂ O) Cl _5] ^-2 M-10. _{[Re (H 2 O) 5 Cl} 5 ] ^-2 M-11. [RhBr _6] ^-3 M-12. [ReCl _6] ^-3 M -13. [IrCl ₆ ] ^-3 M-14. [Re (NS) Cl ₄ (SeCN)] ^-2 M-15. [Cr (CN) ₆ ] ^-3

The above metal complex can be added to silver halide at the time of grain preparation. The content of the heavy metal in the silver halide grains of the present invention is from 1 × 10 ^-7 mol to 1 × 10 ^-4 mol per mol of silver halide. Preferably it is 5 × 10 ^{-7 to} 5 × 10 ^-5 mol.
The above heavy metals may be used in combination. The distribution of the heavy metal in the silver halide grains is not particularly limited, but is preferably present outside the grains.

The silver halide emulsion preferably used in the present invention is silver chlorobromide, silver chloroiodobromide or silver chloride in which 95 mol% or more, particularly 99 mol% or more, consists of silver chloride. An increase in the ratio of silver bromide or silver iodide is not preferable because the safelight safety in a bright room deteriorates or γ decreases.

The silver halide emulsion of the silver halide photographic light-sensitive material used in the present invention has an average grain size of 0.23.
μm or less, particularly preferably 0.08 to 0.20 μm. If the particle size exceeds 0.25 μ, γ will decrease, and Dmax of the practical technique will decrease. In the present invention, in order to adjust silver halide grains, the reaction temperature is set to 50 as a mixing condition.
C. or lower, preferably 40.degree. C. or lower, and a silver potential of 70 mV or higher, preferably 300 mV to 400 mV, or 6-methyl-4-hydroxy-1,3,3a, 7 under a condition of sufficiently high stirring speed for uniform mixing. Good results can be obtained by adjusting at 80 mV to 120 mV in the presence of a stabilizer such as tetrazaindene. The particle size distribution is basically not limited, but is preferably monodispersed. The term “monodispersion” as used herein means at least 9 parts by weight or number of particles.
5% is composed of particles having a size within ± 40% of the average particle size, more preferably within ± 20%. The silver halide grains of the present invention preferably have regular crystals such as cubes and octahedrons, and particularly preferably cubes.

In the present invention, the grain formation of the silver halide emulsion is preferably carried out under acidic conditions. This is effective for minimizing fog in the subsequent chemical sensitization. The acidic condition is pH 4.0 or less, preferably pH 3.0 to pH 1.5.

The silver halide emulsion of the silver halide photographic material used in the present invention may or may not be chemically sensitized after grain formation. In the case of chemical sensitization, known sensitizers can be used, but gold-sulfur sensitization by a gold sensitizer and a sulfur sensitizer, gold-sulfur selenium sensitization by combining them with a selenium sensitizer, and gold selenium sensitization Is preferable, and gold-sulfur selenium sensitization is particularly preferable. In the present invention, a known hydrazine nucleating agent may be used to further increase the contrast. The hydrazine nucleating agent used will be described. In the present invention, the compound of the general formula (I) described in JP-A-7-287335 is used. Specifically, I-
Compounds represented by 1 to I-53 are used.

The following hydrazine nucleating agents are also preferably used. Compounds represented by (Chemical Formula 1) described in JP-B-6-77138, specifically, compounds described on pages 3 and 4 of the same publication. A compound represented by the general formula (I) described in JP-B-6-93082, specifically, pages 8 to 1 of the publication
The compound of 1-38 on page 8. JP-A-6-23049
General formulas (4), (5) and (6) described in No. 7
And specifically, compounds 4-1 to 4-10 and pages 28 to 36 described in pages 25 and 26 of the same publication.
Compounds 5-1 to 5-42 described on page 39 and page 39, 4
Compounds 6-1 to 6-7 described on page 0. JP-A-6
Compounds represented by general formulas (1) and (2) described in JP-A-289520, specifically, compounds 1-1) to 1-17) and 2- 1). Compounds represented by (Chemical Formula 2) and (Chemical Formula 3) described in JP-A-6-313936, specifically, compounds described on pages 6 to 19 of the same. Compounds represented by (Chemical Formula 1) described in JP-A-6-313951, specifically, compounds described on pages 3 to 5 of the same. Compounds represented by general formula (I) described in JP-A-7-5610, specifically, pages 5 to 1 of the same.
Compounds I-1 to I-38 described on page 0. JP-A-7-77
No. 783, represented by the general formula (II), specifically, compounds II-1 to
II-102, compounds represented by formulas (H) and (Ha) described in JP-A-7-104426, specifically, compounds H-1 to -8 described on pages 8 to 15 of the same publication. H-
44.

The hydrazine-based nucleating agent of the present invention includes a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethylsulfoxide, It can be used as a solution in methylcellosolve or the like. In addition, dibutyl phthalate,
Oils such as tricresyl phosphate, glyceryl triacetate or diethyl phthalate, dissolved using an auxiliary solvent such as ethyl acetate or cyclohexanone,
An emulsified dispersion can be prepared and used mechanically. Alternatively, a powder of a hydrazine derivative can be dispersed in water by a ball mill, a colloid mill, or an ultrasonic wave by a method known as a solid dispersion method and used.

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

In the present invention, a nucleation accelerator may be used in addition to the nucleating agent. Examples of the nucleation accelerator used include an amine derivative, an onium salt, a disulfide derivative, and a hydroxymethyl derivative. Examples are listed below. Compounds A-1) to A-73) described in JP-A-7-77783, pages 49 to 58. JP-A-7-843
(Chemical Formula 21), (Chemical Formula 22) and (Chemical Formula 2)
The compounds represented by 3), specifically, the compounds described on pages 6 to 8 of the same publication. Compounds represented by general formula [Na] and general formula [Nb] described in JP-A-7-104426, specifically, Na-1 described on pages 16 to 20 of the same publication.
To Nb-12 and compounds of Nb-1 to Nb-12. General formula (1) described in JP-A-8-272231
, General formula (2), general formula (3), general formula (4), general formula (5),
Compounds represented by the general formula (6) and the general formula (7), specifically, the compounds of 1-1 to 1-19 and 2-
1-2-2, 3-1-3-36, 4
Compounds of -1 to 4-5, compounds of 5-1 to 5-41, 6
-1 to 6-58 and 7-1 to 7-38.

[0029] The nucleation accelerator is a suitable water-miscible organic solvent,
For example, alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone,
Methyl ethyl ketone), dimethylformamide, dimethylsulfoxide, methylcellosolve and the like can be used. Also, by an already well-known emulsification dispersion method, dissolution is performed using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. An object can be prepared and used. Alternatively, a powder of a nucleation accelerator can be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method, and used.

The nucleation accelerator is halogenated on the support.
The silver halide emulsion layer on the side of the silver emulsion layer or other hydrophilicity
It may be added to any of the colloid layers.
Add to silver emulsion layer or adjacent hydrophilic colloid layer
Is preferably added. The amount of nucleation accelerator added is halogenated
1 × 10 per mole of silver^-6~ 2 × 10^-2Mol is preferred
1 × 10^-Five~ 2 × 10^-2More preferably 2 ×
10^-Five~ 1 × 10 ^-2Molar is most preferred.

In the present invention, the emulsion layer or other hydrophilic colloid layer may have a thickness of 400 to 470 nm in order to prevent irradiation, improve safelight safety, and various other purposes.
It is preferable to contain at least one or more light-absorbing substances having an absorption peak in the vicinity. A water-soluble dye or a solid dispersion dye is used as the light absorbing substance. Also,
In the present invention, it is preferable to include at least one light absorbing compound having an absorption peak at 330 to 370 nm among the above light absorbing compounds for the purpose of improving the safelight property by ultraviolet light. A water-soluble dye or a solid dispersion dye is used as the light absorbing substance. Varies by the molar extinction coefficient of the light absorbing substance is added in an amount of usually ^{10 -2 g / m 2 ~1g /} m 2. Preferably it is 30 to 300 mg / m ² . As the dye used in the present invention, known dyes or pigments,
For example, "Dye Handbook" (pages 315 to 1109, edited by The Society of Synthetic Organic Chemistry, 1970) and "Handbook of Color Material Engineering" (pages 225 to 417, edited by The Color Material Association, 1989)
Annual Publication), US Patent Nos. 3,533,794 and 3,3
14,794, 3,707,375, 4,04
No. 5,229, No. 3,700,455, No. 3,3
52,681, JP-A-46-2784, U.S. Pat. Nos. 3,705,805 and 3,499,762, and West German Patent Application Publication No. 1,547,863.
Or pyrazolone oxonol dyes described in U.S. Pat. No. 2,274,782, diarylazo dyes described in U.S. Pat. No. 2,956,879, and 3,423,207
And styryl dyes and butadienyl dyes described in JP-A Nos. 3,384,487 and 2,527,58.
No. 3, the merocyanine dye described in No. 3,486,89
No. 7, No. 3,652,284, No. 3,718,4
No. 72 merocyanine dyes and oxonol dyes,
No. 3,976,661, enaminohemioxonol dyes described in British Patent Nos. 584,609 and 1,177,429, JP-A-48-85130, JP-A-49-99620, No. 49-114420, U.S. Pat. Nos. 2,533,472 and 3,148,187.
No. 3,177,078, No. 3,247,12
No. 7, No. 3,540,887, No. 3,575,7
Nos. 04 and 3,653,905 may be used. Preferred compounds include oxonol dyes, merocyanine dyes, cyanine dyes, arylidene dyes, azomethine dyes, triphenylmethane dyes, azo dyes, anthraquinone dyes, and indoaniline dyes.

Gelatin is used as a binder for the silver halide emulsion layer and other hydrophilic colloid layers of the present invention, but other hydrophilic colloids may be used in combination. For example, gelatin derivatives, graft polymers of gelatin and other macromolecules, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl Uses various kinds of synthetic hydrophilic polymer substances such as alcohols, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole and the like, or a single or copolymer. be able to. As gelatin, acid-processed gelatin may be used in addition to lime-processed gelatin, and gelatin hydrolyzate and gelatin enzyme hydrolyzate can also be used. In the present invention, for the purpose of preventing softening of gradation due to the addition of a light absorbing substance, the amount of gelatin applied as a binder is preferably the amount of gelatin in the entire hydrophilic colloid layer on the side having the silver halide emulsion layer. 0.0 g / m ² or less;
In particular, it is 1.0 to 2.3 g / m ² . The amount of gelatin in the emulsion layer ranges from 0.8 g to 0.3 g per 1 g of silver.

As the support used in the present invention, a transmission type support or a reflection type support can be used. As the transmission type support, a transmission film such as cellulose triacetate film, polyethylene terephthalate, or syndiotactic polystyrene is preferably used.
As the reflective support, a reflective support laminated with a plurality of polyethylene layers or polyester layers, and containing a white pigment such as titanium oxide in at least one of such water-resistant resin layers (laminated layers) is preferable.

Further, when the above-mentioned reflective support is used, it is preferable to contain a fluorescent whitening agent. The optical brightener may be either water-soluble or oil-soluble. Further, these fluorescent whitening agents may be contained in the water-resistant resin layer,
It may be dispersed in an emulsion layer or a hydrophilic colloid layer in the light-sensitive material. Water-soluble stilbene compounds are known as water-soluble fluorescent whitening agents. Specifically, Japanese Patent Application Laid-Open No. 55-135833
May be used. Benzoxazoles, coumarins, and pyrazolines can be used as oil-soluble fluorescent whitening agents. Specifically, Japanese Patent Application Laid-Open
Compounds disclosed in JP-A-154251 and JP-A-5-165137 may be used.

Although there is no particular limitation on development and fixing in the present invention, it is preferable to use a dihydroxybenzene compound or reductone as a developing agent as a developing solution. Among these, a preferred developer in the case of using a dihydroxybenzene-based developing agent has the following composition. (1) 0.2 to 0.75 mol / l dihydroxybenzene developing agent, (2) 0.001 to 0.06 mol / l 1-phenyl-3-pyrazolidone or p-aminophenol type auxiliary agent A developing agent, (3) 0.15 to 1.2 mol / l free sulfite ion, (4) a compound represented by the general formula (14), and a compound represented by the general formula (14) and dihydroxybenzene When the concentration ratio of the system developing agent is 0.03 to 0.
12, and a developer having a pH of 9.0 to 11.0, particularly preferably 9.5 to 10.7. General formula (14)

[0036]

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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 represent 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 P and Q represent It represents an atomic group which forms a 5- to 8-membered ring together with the two vinyl carbon atoms substituted by R ₁ and R ₂ and the carbon atom substituted by Y when bonded to each other. Y represents ＝ O or ＮN—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.

A detailed description of the general formula (14) and specific compounds are described in JP-A-7-168324. Among them, ascorbic acid or erythorbic acid (stereoisomer) is preferable. The amount of the compound represented by the general formula (14) is determined by the concentration ratio of the compound represented by the general formula (14) / the hydroquinone-based developing agent (the concentration of the compound represented by the general formula (14) is determined by the concentration of the dihydroxybenzene-based developing agent). (Value divided by the concentration) is in the range of 0.03 to 0.12. A preferred concentration ratio is from 0.03 to 0.10, and a particularly preferred concentration ratio is from 0.05 to 0.09.

The dihydroxybenzene-based developing agents used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dibromohydroquinone, and 2,5-dimethylhydroquinone. preferable. The concentration of the hydroquinone derivative in the developer is from 0.2 to 0.75 mol / l, preferably from 0.2 to 0.5 mol / l, particularly preferably from 0.2 to 0.4 mol / l. is there.

The 1-phenyl-3-pyrazolidone derivative developing agents used in the present invention include 1-phenyl-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-phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-p-
Tolyl-4,4-dimethyl-3-pyrazolidone, 1-p
-Tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone and the like, preferably 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone and the like.

The p-aminophenol-based developing agents used in the present invention include N-methyl-p-aminophenol and p-aminophenol.
-Aminophenol, N- (β-hydroxyethyl)-
There are p-aminophenol and N- (4-hydroxyphenyl) glycine, among which N-methyl-p-aminophenol is preferable. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is 0.05
Mol / l to 0.5 mol / l, the latter being 0.06 mol / l
It is preferably used in an amount of less than 1 liter.

When reductones are used as a developing agent, it is preferable to use the compounds of the above-mentioned general formula (14) as reductones, and ascorbic acid or erythorbic acid (stereoisomer) is particularly preferable. As the auxiliary developing agent in this case, the same as the dihydroxybenzene-based developing agent can be used, and a p-aminophenol-based and / or 1-phenol-3-pyrazolidone-based auxiliary developing agent is preferable. When the compound of the general formula (14) is used as a developing agent, a general range of the amount used is 5 × 10 ⁻³ mol to 1 mol per liter of the developer,
It is particularly preferably from 10 ^-2 mol to 0.5 mol.

The preservative used in the developer preferred in the present invention is free sulfite ion, and the form of addition to the developer includes sodium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite and the like. The free sulfite ion concentration is 0.15 to 1.2 mol / l, preferably 0.3 to 1.0 mol / l, particularly preferably 0.1 to 1.0 mol / l.
It is 3 to 0.8 mol / liter. The pH of the developer used in the development processing of the present invention is in the range of 9.0 to 11.0, preferably 9.5 to 10.7. The alkaline agent used for setting the pH includes a pH adjusting agent such as sodium hydroxide, sodium carbonate, tribasic sodium phosphate, potassium hydroxide, potassium carbonate, boric acid and the like.

In the developer used in the method of the present invention, a dialdehyde hardener or a bisulfite adduct thereof may be used. Specific examples thereof include glutaraldehyde, α-methylglutaraldehyde, β-methylglutaraldehyde, maledialdehyde, succindialdehyde, methoxysuccindialdehyde, methylsuccindialdehyde, α-methoxy-β-ethoxyglutaraldehyde, α -N-butoxyglutaraldehyde, α, α-diethylsuccindialdehyde, butylmaledialdehyde, or bisulfite adduct thereof. Among them, glutaraldehyde or its bisulfite adduct is most commonly used. The dialdehyde compound is used in such an amount that the sensitivity of the photographic layer to be processed is not suppressed and the drying time does not significantly increase. Specifically, the amount is 1 to 50 g, preferably 3 to 10 g per liter of the developer.

The developer used in the method of the present invention uses an antifoggant, and examples thereof include indazole, benzimidazole and benztriazole. 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] butane Sodium sulfonate, 5-amino-1,
3,4-thiadiazole-2-thiol and the like can be mentioned. The amount of these antifoggants is usually 0.01 to 10 mmol, more preferably 0.1 to 2 mmol, per liter of developer. In addition to these organic antifoggants, for example, halides such as potassium bromide and sodium bromide can be used.

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

Examples of aminopolycarboxylic acids include iminodiacetic acid, nitriloacetic acid, nitrilic acid propionic acid, ethylenediaminomonohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, glycol ether tetraacetic acid, 1,2-diaminopropanetetraacetic acid, diethylenetriamine Pentaacetic acid,
Triethylenetetramine hexaacetic acid, 1,3-diamino-2
-Propanol tetraacetic acid, glycol ether diaminotetraacetic acid, and others as described in JP-A-52-25632 and 55-67.
Nos. 747, 57-102624, and JP-B-53-
Compounds described in, for example, Japanese Patent No. 40900 can be exemplified.

As the organic phosphonic acid, US Pat.
Nos. 214,454 and 3,794,591, and West German Patent Publication 2,227,639, etc., hydroxyalkylidene-diphosphonic acid and Research Disclosure Vol. 181, Item 18170 (1
May 979) and the like. Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminotetramethylenephosphonic acid, aminotrimethylenephosphonic acid, and the like. Other examples include Research Disclosure No. 18170, JP-A-57-208554, and JP-A-57-208554. -61125, 5
Compounds described in JP-A-5-29883 and JP-A-56-97347 can be exemplified.

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

In the developer used in the method of the present invention, in addition to the above-mentioned composition, a buffer (eg, carbonate, alkanolamine), an alkaline agent (eg, hydroxide, carbonate), and a dissolution aid may be used, if necessary. (For example, polyethylene glycols,
These esters), pH adjusters (eg, organic acids such as acetic acid), development accelerators (eg, US Pat. No. 2,648,
No. 604, Japanese Patent Publication No. 44-9503, U.S. Pat.
No. 71,247, various pyridinium compounds and other cationic compounds, cationic dyes such as phenosafranine, neutral salts such as thallium nitrate and potassium nitrate, JP-B-44-9304, U.S. Pat.
No. 3,990, No. 2,531,832, No. 2,95
Nos. 0,970 and 2,577,127, nonionic compounds such as polyethylene glycol and derivatives thereof, polythioethers, organic solvents described in JP-B-44-9509, Belgian Patent 682,862, and U.S. Pat. Thioether compounds described in U.S. Pat. No. 3,201,242, especially thioether compounds), and a surfactant.

The development processing temperature and time are interrelated and are determined in relation to the total processing time. Generally, the processing temperature is about 20 ° C. to about 50 ° C. and the processing time is 10 seconds to 2 minutes. When processing 1 square meter of a silver halide black-and-white photographic light-sensitive material, the replenisher amount of the developing solution is 400 ml or less, preferably 200 ml or less.

The fixing solution used in the fixing step of the present invention includes sodium thiosulfate, ammonium thiosulfate, and, if necessary, tartaric acid, citric acid, gluconic acid, boric acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptane, tiron and ethylenediamine It is an aqueous solution containing acetic acid, diethylenetriaminepentaacetic acid, and nitrilotriacetic acid salts thereof.
From the viewpoint of environmental protection in recent years, it is preferable that boric acid is not contained. The fixing agent of the fixing solution used in the present invention is sodium thiosulfate, ammonium thiosulfate or the like, and ammonium thiosulfate is preferred from the viewpoint of fixing speed, but sodium thiosulfate may be used from the viewpoint of environmental protection in recent years. . The amount of these known fixing agents can be varied as appropriate, and is generally about 0.1 to about 2 mol / l. Particularly preferably, it is 0.2 to 1.5 mol / liter. The fixing solution may optionally contain a hardener (eg, a water-soluble aluminum compound), a preservative (eg, sulfite, bisulfite), a pH buffer (eg, acetic acid), and a pH adjuster (eg, ammonia, sulfuric acid). ), Chelating agents, surfactants,
It may contain a wetting agent and a fixing accelerator. Examples of the surfactant include anionic surfactants such as sulfates and sulfonates, polyethylene-based surfactants,
And amphoteric surfactants described in JP-A-6740. In addition, a known antifoaming agent may be added. Examples of the wetting agent include alkanolamine and alkylene glycol. Examples of the fixing accelerator include, for example, JP-B Nos. 45-35754, 58-122535, and 5
No. 8-122536, thiourea derivatives, alcohols having a triple bond in the molecule, U.S. Pat.
Thioether compound described in JP-A-6-459
No. 29860, and the like.
Further, compounds described in JP-A-2-44355 may be used. The pH of the fixing solution is preferably from 4.0 to 6.5, and particularly preferably from 4.5 to 6.0. Further, compounds described in JP-A-64-4739 can be used as the dye elution accelerator.

The hardener in the fixing solution of the present invention includes a water-soluble aluminum salt and a chromium salt. Preferred compounds are water-soluble aluminum salts, such as aluminum chloride, aluminum sulfate and potassium alum. A preferable addition amount is 0.01 mol to 0.2 mol / l, and more preferably 0.03 to 0.08 mol / l. The fixing temperature is about 20 ° C to about 50 ° C, preferably 25 to 45 ° C.
The fixing time is 5 seconds to 1 minute, preferably 7 seconds to 50 seconds. The replenishment rate of the fixing solution is 6
100 ml / m ² or less, particularly 300 ml / m ² or less.

The photosensitive material which has been subjected to development and fixing is then washed or stabilized. The washing or stabilizing treatment can be carried out with a replenishment amount of 3 liters or less (including 0, that is, washing with water) per 1 m ^{2 of the} silver halide light-sensitive material. That is, not only water saving processing can be performed, but also piping for installing the automatic processing machine can be eliminated. When washing with a small amount of water, JP-A-63-18350 and JP-A-63-18350
It is more preferable to provide a septic tank for a squeeze roller described in -287252. In addition, various oxidizing agents may be added or a filter may be combined to reduce the pollution load which is a problem when washing with a small amount of water. Further, part or all of the overflow liquid from the washing or stabilizing bath produced by replenishing the water subjected to the anti-bubbling means to the washing or stabilizing bath by the method of the present invention in accordance with the treatment is disclosed in 2
As described in JP-A-35133, it can also be used for a processing solution having a fixing ability, which is the preceding processing step.
Further, a water-soluble surfactant or an antifoaming agent may be added in order to prevent unevenness of water bubbles which are easily generated at the time of washing with a small amount of water and / or to prevent a treatment agent component adhering to a squeeze roller from being transferred to a treated film. Good. Further, in order to prevent contamination by a dye eluted from a light-sensitive material, JP-A-63-1634 has been proposed.
The dye adsorbent described in No. 56 may be installed in a washing tank.

In some cases, a stabilization treatment may be performed after the water washing treatment.
Baths containing the compounds described in JP-A Nos. 2-132435 and 1-125553 and JP-A-46-44446 may be used as the final bath of the photosensitive material. If necessary, metal compounds such as ammonium compounds, Bi and Al, fluorescent brighteners, various chelating agents, membrane pH buffers, hardeners, bactericides, fungicides, alkanolamines and surfactants Water used for the agent is tap water, deionized water, halogen, ultraviolet germicidal lamps and various oxidizing agents (ozone,
It is preferable to use water sterilized by hydrogen peroxide, chlorate, or the like.

The processing solution preferably used in the present invention is preferably stored in a packaging material having low oxygen permeability described in JP-A-61-73147. On the other hand, when the replenishment amount is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. Roller transport type automatic developing machines are described in U.S. Pat. Nos. 3,025,779 and 3,545,971.
It is described in the specification and the like, and a roller transport type automatic developing machine comprising four steps of development, fixing, washing and drying can be preferably used. Further, the above treatment liquid may be used as a solid treatment agent. The solid processing agent preferably used in the present invention is in the form of powder, tablet, granule, powder, block or paste.
No. 259921 or a tablet. The method for producing tablets is described, for example, in JP-A-51-61837, 54
Nos. 155038 and 52-88025, and British Patent No. 1,213,808, and the like.
No. 42, No. 2-109043, No. 3-39735, No. 3-39939 and the like. Furthermore, powder processing agents are described in, for example,
No. 133332, British Patent Nos. 725,892 and 72
No. 9,862 and German Patent No. 3,733,861 and the like.

The bulk density of the solid processing agent preferably used in the present invention is preferably 0.5 to 6.0 g / cm ³ from the viewpoint of its solubility and the effect of the object of the present invention. Those having 1.0 to 5.0 g / cm ³ are preferred.

There are no particular restrictions on the various additives and the like used in the light-sensitive material of the present invention, and for example, those described in the following corresponding places can be preferably used. Item This section 1) 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 spectral sensitization described in JP-A-1-112235, JP-A-3-124560, JP-A-3-7928, JP-A-5-11389 and JP-A-4-330434. Pigment. 2) Surfactant, antistatic From page 7, upper right column, line 7 of JP-A-2-12236 or from the lower right column, line 7 of the stopping agent and from page 13, lower left column, line 13 of JP-A-2-18542. Page 4, lower right column, line 18. 3) Antifoggant, stable JP-A-2-103536, page 17, lower right column, line 19 to line 18, page 18, upper right column, line 4 and lower right column, line 1 to line 5. Further, thiosulfinic acid compounds described in JP-A-1-237538. 4) Compound having an acid group From JP-A-2-103536, page 8, lower right column, line 5 to page 19, upper left column, line 1 and JP-A-2-55349, page 8, lower right column, line 13 Page 11, upper left column, line 8. 5) Matting agent, slip agent JP-A-2-103536, page 19, upper left column, line 15 to page 19, upper right column, line 15; 6) Hardener JP-A-2-103536, page 18, upper right column, 5th line to 17th line. 7) Dyes JP-A-2-103536, page 17, lower right column, line 1 to line 18, JP-A-2-39042, page 4, upper right column, line 1 to page 6, upper right column, line 5, Dyes described in JP-A-2-294638 and JP-A-63-296039. Further, solid disperse dyes described in publications or specifications such as WO 88/04794, EP 456148, JP-A-5-11382, and JP-A-7-301878. 8) Binder JP-A-2-18542, page 3, lower right column, line 1 to line 20. 9) Black spot inhibitors Compounds described in U.S. Pat. No. 4,957,257 and JP-A-1-18832. 10) Redox compounds The compounds represented by the general formula (I) in JP-A-2-301743 (especially compound examples 1 to 50), and the compounds described in pages 3 to 20 of JP-A-3-174143. Formulas (R-1), (R-2), and (R-3), Compound Examples 1 to 75, and compounds described in JP-A-5-257239 and JP-A-4-278939. 11) Monomethine compounds Compounds of the general formula (II) described in JP-A-2-287532 (especially compound examples II-1 to II-26). 12) Dihydroxybenze Compounds described in JP-A-3-39948, from page 11, upper left column to class II, page 12, lower left column, and European Patent No. 452,772A. 13) Polymer latex JP-A-2-103536, page 18, lower left column, lines 12 to 20. Furthermore, JP-B-46-22507, JP-A-50-73625, U.S. Pat. Nos. 3,488,708, 3,939,130, 3,92,482, and JP-A-7-152112 disclose in the publications or the specification. Polymer latex containing active methylene groups. 14) Organic desensitizers Compounds described in publications or specifications such as JP-B-3-76450, JP-A-63-64039 and JP-A-7-301878. 15) Amino group, ammonia From page 8, line 5 of JP-A-63-133145, and nitrogen-containing, page 40, line 5. Compounds having a heterocyclic ring

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

[0060]

【Example】

 Example 1 <Emulsion preparation> Emulsion A: 1 mol equivalent of sodium chloride and silver kept at 40 ° C
3 × 10^-FiveMole sodium benzenethiosulfonate
5 × 10^-3Mole of 4-hydroxy-6-methyl-
PH containing 1,3,3a, 7-tetrazaindene = 2.
Silver nitrate aqueous solution and silver
3.0 × 10 per le^-6Mole k_TwoRu (NO) Cl _FiveContaining chloride
Potential 95mV by sodium jet solution with double jet method
In 3 minutes 30 seconds, add half of the silver content of the final grain
To adjust the core particles to 0.12 μm. Then,
6 × 10 per silver salt aqueous solution and silver mole^-7Mole k_TwoRu (NO)
Cl_FiveFor 7 minutes as above
Silver chloride cubic grains having an average grain size of 0.16 μm.
It was adjusted. (Coefficient of variation 12%) Then, the flocculation method well known in the industry
After washing with water and removing soluble salts, gelatin was added,
Compound A and phenoxyeta as preservatives without chemical aging
60 mg each per mole of silver, 4-H
Droxy-6-methyl-1,3,3a, 7-tetrazai
1 × 10 per mole of silver^-3Mole was added. (Most
As final particles, pH = 5.7, pAg = 7.5, Ru =
3 × 10 ^-6Mol / Ag mol. )

Emulsion B: Adjusted in exactly the same manner as Emulsion A except that the grains were formed in the presence of 2 × 10 ^-4 mol of 1,3-dimethyl-2-imidazolithion per mol of silver while keeping the temperature at 45 ° C. Thus, silver chloride cubic grains having an average grain size of 0.20 μm were obtained.

Emulsion C: Preparation was performed in the same manner as in Emulsion A except that the metal species doped in grain formation was (NH ₄ ) ₂ Rh (H ₂ O) Cl ₅ .

<Preparation of Emulsion Layer Coating Solution and Its Coating> Emulsion A
The following compounds were added to Nos. To C, and a silver halide emulsion layer was coated on a polyethylene-laminated paper support having a thickness of 110 .mu.m as shown by a gelatin coating amount, a coating silver amount and the general formula (1). Emulsion layer coating solution 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 3 mg / m ² Compound-B (desensitizer) 0.1 mg / m ² Compound-C (oil-soluble fluorescent whitening) 6 mg / m ² Compound-D (dye, peak wavelength 435 nm) 220 mg / m ² Compound-E (dye, peak wavelength 350 nm) 26 mg / m ² Compound-F (hardener) 105 mg / m ² p-dodecylbenzene Sodium sulfonate 30mg / m ² (adjusted to pH = 6.5)

<Preparation of Emulsion Protection Lower Layer Coating Solution and Its Coating Solution> The following compounds were added to an aqueous gelatin solution, and coated so that the coated amount of gelatin was 0.5 g / m ² . Gelatin (Ca ²⁺ content 2700 ppm) 0.5 g / m ² Sodium p-dodecylbenzenesulfonate 26 mg / m ² Sodium polystyrene sulfonate 230 mg / m ²

<Preparation of Emulsion Protection Upper Layer Coating Solution and Its Coating Solution> The following compound was added to an aqueous gelatin solution, and coated so that the coated amount of gelatin was 0.5 g / m ² . Gelatin (Ca ²⁺ content 2700 ppm) 0.5 g / m ² Polymethyl methacrylate fine particles (average particle size 2.5 μ) 40 mg / m ² N-perfluorooctanesulfonyl-N-propylglycine potadium 5 mg / m ² p-dodecyl Sodium benzenesulfonate 30mg / m ²

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

<Preparation of Coating Solution for Back Layer Lower Layer and Its Coating Solution> The following compounds were added to an aqueous gelatin solution, and coated so that the coated amount of gelatin was 1.2 g / m ² . Gelatin (Ca ²⁺ content 2700 ppm) 1.2 g / m ² Sodium p-dodecylbenzenesulfonate 14 mg / m ² Sodium polystyrene sulfonate 27 mg / m ² Compound-G (dye, peak wavelength 630 nm) 10 mg / m ² Compound- H (hardener) 49mg / m ²

<Preparation of Coating Solution for Back Layer Protective Layer and Its Coating Solution> The following compound was added to an aqueous gelatin solution and coated so that the coated amount of gelatin was 1.94 g / m ² . Gelatin (Ca ²⁺ content: 2700 ppm) 0.9 g / m ² Polymethyl methacrylate fine particles (average particle size: 3.4 μ) 6 mg / m ² rice starch 10 mg / m ² Sodium p-dodecylbenzenesulfonate 9 mg / m ² N- Perfluorooctanesulfonyl-N-propylglycine potadium 5 mg / m ² Compound-H (hardener) 20 mg / m ²

The coating solution was dried at 170 ° C. for 2 minutes,
Coating was performed so that the dry film thickness was 0.1 μm. Thus, samples 1-1 to 1-20 were prepared.

[0070]

Embedded image

<Evaluation method> Evaluation of photographic characteristics The obtained sample was exposed through an optical wedge to a P-627FM printer manufactured by Dainippon Screen Co., Ltd., and developed using an automatic developing machine FG-680AG manufactured by Fuji Photo Film Co., Ltd. The solution 1 was treated at 38 ° C. for 20 seconds, fixed, washed with water and dried. Fixer 1 was used as the fixer. In addition, between the light source at the time of exposure and the sample, Mitsubishi Rayon Co., Ltd. Dialite P-1003mm
Exposure was performed with a thickness (a filter having a transmittance of 393 nm of 50%, which absorbs light on the shorter wavelength side and transmits light on the longer wavelength side). These samples were evaluated for sensitivity as follows. Sensitivity (S _1.0 ); reciprocal of the exposure amount giving a density of 1.0 (the larger the numerical value, the higher the sensitivity)

Evaluation of fixation loss Samples No. 1 to No. 1 were processed in the same manner as in the photographic test described above except that the development and fixing times were set to 10 seconds.
19 was exposed, fixed, washed with water and dried. Then, P-
Exposure was performed for 3 minutes with a 627FM printer to visualize the remaining silver halide emulsion which was not fixed. The degree of fog at this time was visually evaluated on a five-point scale. "5" is the best,
"1" is the worst. "5" and "4" are practical,
"3" is bad but at a practically usable level.
"2" and "1" are levels that do not endure practical use.

Evaluation of Physical Development Unevenness In the photographic test described above, Samples Nos. 1 to 19 were unexamined in exactly the same manner except that a fatigue solution of the developer 1 and a fatigue solution of the fixer 1 were used as the developer and the fixer. It was developed, fixed, washed with water and dried by exposure. At this time, physical development fog generated at the rear end of the sample was visually evaluated on a five-point scale. "5" is the best,
"1" is the worst. "5" and "4" are practical,
"3" is bad but at a practically usable level.
"2" and "1" are levels that do not endure practical use. However,
The developer and fixer fatigue fluids should be used in a large amount (0.3%).
1 m ² ) Sample 1-12 was processed while replenishing 50 cc per sheet and 64 cc of fixing solution per sheet, and processed for 5 m ² per day for 4 weeks. (The processing conditions are 3
8 ° C for 20 seconds, blackening rate is 20%)

Evaluation of pressure property Under a condition of 25 ° C. and 60% RH, the surface of the sample was rubbed with a continuous load of 0 to 100 g with a sapphire needle having a diameter of 0.1 mm. The load at which fogging occurred was determined. Practically, it is preferable that fog does not occur with a load of 70 g or more. Samples 1-1 to 1-
For No. 20, evaluation of photographic characteristics, fixation loss, physical development unevenness, and pressure property were performed, and Table 1 summarizes the results. Samples 1-9 to 1-14 and 1-17 to 1-20 of the present invention have appropriate sensitivity and good performance without occurrence of fixing loss, physical development unevenness, and pressure fog.

[0075]

[Table 1]

Example 2 K doped in Emulsion A prepared in Example 1_TwoRu (NO) Cl_Five
Instead of K_TwoIr (NO) Cl _Five, K_ThreeCr (CN)₆, K_ThreeReCl₆Using
The emulsion was adjusted in the same manner as in Sample 1-12 of Example 1.
Was prepared and evaluated in the same manner as in Example 1. Results are in the example
Good performance was obtained as in Sample 1-12 of Example 1.

Example 3 In the formulation of the emulsion layer coating solution of Example 1, compound I was used as a nucleating agent at 10 mg / m ² , and compound J was used as a nucleating accelerator at a concentration of ² mg / m ² .
A sample was prepared in the same manner as in 1-12 of Example 1 by adding 0 mg / m ² , and evaluated in the same manner as in Example 1. As a result, good performance was obtained as in the case of Sample 1-12 of Example 1.

[0078]

Embedded image

Example 4 Samples 1-1 to 1-20 prepared in Example 1 were used in place of the above-mentioned developer 1 and fixer 1 in the form of a developer 2 having a solid processing agent of the following manufacturing method and storage form. Then, processing was performed using Fixer 2, and evaluation was performed in the same manner as in Example 1. As a result, the same result as that of the samples 1-1 to 1-12 of the example 1 was obtained.

The formulas of the developing solutions 1 and 2 and the fixing solution 1 used in the above embodiment are shown below. Developer 1 <Preparation of Developer 1> Potassium hydroxide 40.0 g Diethylenetriamine-5-acetic acid 2.0 g Potassium carbonate 60.0 g Sodium metabisulfite 70.0 g Potassium bromide 7.0 g Hydroquinone 40.0 g 5-methylbenzotriazole 0 0.35 g 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1.50 g 2-mercaptobenzimidazole-5-sulfonic acid sodium 0.30 g 3- (5-mercaptotetrazole) benzenesulfonic acid 0.10 g Sodium erythorbate 6.0 g Diethylene glycol 5.0 g Potassium hydroxide is added, water is added to make up to 1 liter, and the pH is adjusted to 10.65. (The increase in pH when 0.1 mol of sodium hydroxide was added to Developer 1 was 0.25.)

Fixing Solution 1 <Fixing Solution 1> Ammonium thiosulfate 119.7 g Ethylenediaminetetraacetic acid / 2Na dihydrate 0.03 g Sodium thiosulfate pentahydrate 10.9 g Sodium sulfite 25.0 g NaOH (as pure) 12 0.4 g Glacial acetic acid 29.1 g Tartaric acid 2.92 g Sodium gluconate 1.74 g Aluminum sulfate 8.4 g pH (adjusted with sulfuric acid or sodium hydroxide) 4.8 Add water to 1 liter

Developer 2 Developer 2 is produced as a solid developer. In the production method, a container made of high-density polyethylene (thickness average = 500 μm, width: 200-1000 μm) was filled with a developing solution corresponding to 10 liters of a used liquid as a solid. At this time, each component was mixed and then charged into a container. <Formulation of developer 2> Raw material name Raw material form Content sodium hydroxide (99.5%) beads 40.0 g Potassium sulfite bulk powder 71.8 g Sodium sulfite bulk powder 35.0 g diethylenetriaminepentaacetic acid * 1 2.0 g 5-methyl Benzotriazole * 1 0.35 g 2-mercaptobenzimidazole-5-sodium sulfonate * 1 0.30 g 2-mercaptotetrazole-1-phenyl-3-sulfonate sodium * 1 0.10 g Potassium bromide * 1 6.6 g Hydroquinone * 1 40.0 g 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone * 1 1.50 g Sodium erythorbate * 1 6.0 g Potassium carbonate bulk powder 62.0 g Hydroquinone briquette 40.0 g Total weight 233 2.6g Alkali weight% 4.9% H 10.6 Here, in raw material form, bulk powder were used as is general industrial products, was a commercially available product to the beads, pellets both alkali metal salts. However, * 1 was made into briquettes.
The briquette was pressurized and compressed using a briquetting machine to form a rugby ball type shape having an irregular length of about 4 to 6 mm, which was then crushed and used. For minor components, each component was blended before briquetting.

Fixer 2 Fixer 2 was prepared by filling the following formulation in a container made of high-density polyethylene (thickness average = 500 μm, width 200-1000 μm) for both the solid part and the liquid part. The solution volume after dissolution was 10 liters, and the pH was 4.85. <Prescription of Fixer 2> Solid agent part ammonium thiosulfate 1200 g sodium thiosulfate 150 g sodium acetate 400 g sodium metabisulfite 200 g liquid agent part aluminum sulfate (27%) 8.4 g sulfuric acid (75%) 30 g sodium gluconate 20 g ethylenediaminetetraacetic acid 2Na dihydrate 0.3 g citric acid 40 g The solid part is mixed and filled.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03C 1/74 G03C 1/74 1/775 1/775 5/29 501 5/29 501 5/30 5/30 5/31 5/31

Claims (6)

[Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support,
The amount of silver applied to the photographic material is equal to the silver halide photographic material 1
The amount of gelatin in the emulsion layer ranges from 0.6 g to 2.0 g per square meter, and the amount of gelatin in the emulsion layer ranges from 0.3 g to 0.8 g per silver gram; and at least one layer of the emulsion layer and another hydrophilic colloid layer. And a mercaptoazole compound represented by the following general formula:
A silver halide photographic material characterized by containing 0 mmol or more. General formula (1) In the formula, Z represents ＝ N— or ＣC (X) — (X represents an alkyl group or an aryl group), M represents a hydrogen atom, a metal atom or ammonium, and Y represents an alkyl group or an aryl group. 2. The emulsion according to claim 1, wherein the silver halide in the emulsion layer is a heavy metal selected from Ir, Ru, Rh, Cr and Re in an amount of 1 × 10 ⁻⁷ mol to 1 mol per mol of silver halide.
A silver halide photographic light-sensitive material characterized in that it is contained in an amount of from × 10 ^-4 mol. 3. A silver halide photographic light-sensitive material according to claim 1, wherein said emulsion layer or another hydrophilic colloid layer contains a hydrazine derivative and a nucleation accelerator. 4. A silver halide photographic light-sensitive material according to claim 1, wherein the support is a paper support. 5. A method of developing a silver halide photographic light-sensitive material according to claim 1, wherein said light-sensitive material is exposed to a dihydroxybenzene-based developing agent. It contains a main agent, and when 0.1 mol of sodium hydroxide is added to 1 liter of the developing solution, the pH rise is 0.3 or less, and the initial pH of the developing solution is from 9.5 to 11.
0. The image forming method according to claim 1, wherein 6. The method for forming an image of a silver halide photographic light-sensitive material according to claim 5, wherein the replenishing amount of the developing solution is 225 ml or less per square meter of the silver halide photographic light-sensitive material.