JPH09281628A - Silver halide photographic sensitive material and processing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material high in sensitivity, low in fog, small in black pots, and high in contrast and to provide the processing method therefor. SOLUTION: This silver halide photosensitive material having a silver halide emulsion layer is processed with a developing solution containing ascorbic acid or one of its derivatives in the presence of at least one of 3-indazolinones, urazoles, 2,3-pyrazolin-5-ones, and pyrimidones, and the photosensitive material containing a hydrazine derivative in the silver halide emulsion layer or its adjacent layer is processed with the developing solution in the presence of one of the compounds.

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 light-sensitive material and a processing method, and in particular, a silver halide photographic with high sensitivity, low fog, little black spots and high contrast, using a developing solution which does not deteriorate the environment. The present invention relates to a photosensitive material and a processing method.

[0002]

2. Description of the Related Art In recent years, environmental problems have become serious around the world, and from the standpoint of environmental protection, the research and development of products and systems with excellent environmental suitability are being actively pursued in each industry. is there. The printing industry is no exception, for example, with regard to developing waste liquid for obtaining printed manuscripts,
Since the dumping of waste liquid into the ocean is also prohibited from January 1996,
There is an urgent need for improvement.

Heretofore, there has been disclosed a method of using ascorbic acid as a developing agent excellent in environmental suitability. However, when ascorbic acid is used as a developing agent, the developing property becomes inactive and high sensitivity cannot be obtained as compared with the conventional developing agents. Means such as increasing the amount of ascorbic acid developing agent and auxiliary developer and decreasing the amount of inhibitor can be considered for the purpose of increasing the sensitivity, but an effective means for obtaining a satisfactory developing performance has not been proposed yet.

Further, when the hydrazine derivative is used in a silver halide photographic light-sensitive material, there is a problem that sandy spot-like fog called black spot occurs.

[0005]

In contrast to the above problems, an object of the present invention is to use a developer which does not deteriorate the environment, and which has high sensitivity, low fog, few black spots, and a high contrast image. To provide a silver halide photographic light-sensitive material and a processing method capable of obtaining high quality.

[0006]

The above object of the present invention is to provide a processing method in which a silver halide photographic light-sensitive material having a silver halide emulsion layer is processed with a developing solution containing ascorbic acid or an ascorbic acid derivative. A method for processing a silver halide photographic light-sensitive material, characterized in that the processing is carried out in the presence of at least one of indazolinones, urazoles, 2-, 3-pyrazolin-5-ones and pyrimidones, and the processing. The silver halide photographic light-sensitive material used in the method is achieved by a silver halide photographic light-sensitive material characterized by containing a hydrazine derivative in its silver halide emulsion layer or its adjacent layer.

The present invention will be specifically described below.

In the present invention, processing in the presence means that
It may be present in the silver halide photographic light-sensitive material (hereinafter referred to as "light-sensitive material") or may be present in the processing liquid, as long as it is present during processing.

In the processing method of the present invention, processing is carried out using an automatic processor in order to shorten the processing time. On this occasion,
The processing is carried out while replenishing with a constant developing solution proportional to the area of the silver halide photographic light-sensitive material to be processed. The developing replenishment amount is 300 ml or less per 1 m ² in order to reduce the amount of waste liquid, and preferably 75 to 200 ml per 1 m ² .

In the processing method of the present invention, the total processing time (Dry to Dry) from the start of dipping the processed silver halide photographic material in the developing solution to the end of drying is 1
It is preferably 0 to 45 seconds.

The total processing time mentioned here includes the total process time required for processing a black and white silver halide photographic light-sensitive material, and specifically, for example, development, fixing and bleaching (reduction) required for processing. The time including all the steps of the stabilization treatment, the drying, etc., that is, the time of Dry to Dry.
In this case, the line speed of the automatic processor is 1500m /
It is more than min.

Further, in the processing method of the present invention, a heat transfer body having a temperature of 90 ° C. or higher (for example, a heat roller having a temperature of 90 ° C. to 130 ° C.) or a radiant object having a temperature of 150 ° C. or higher (for example, tungsten, carbon, Ni) is used in the automatic developing machine. -Cr, a mixture of zirconium oxide / yttrium oxide / thorium oxide, silicon carbide, etc. generate heat directly and radiate heat, or heat energy is transferred from a resistance heating element to radiators such as copper, stainless steel, nickel and various ceramics to generate heat. Those that emit infrared radiation) and those that have a drying zone are included.

The silver halide photographic light-sensitive material according to the present invention is preferably subjected to photographic processing after exposure by an automatic processor having at least four processes of development, fixing, washing (or stabilizing bath) and drying.

One of the preferred embodiments of the developing solution used in the present invention contains ascorbic acid and its derivative, and also contains a compound represented by the following general formula (1).

The general formula (1) R- (B) _n -CH ₂ R'ascorbic acid and its derivatives are known as developing agents, for example, US Pat. Nos. 2,688,548 and 2,688,549. Nos. 3,022,168, 3,512,981, 4,975,354 and 5,326,816 can be used. In the present invention, as R of the compound represented by the general formula (1) contained together with ascorbic acid and its derivative, R is at least one substituent selected from a hydroxyl group, an amino group, a sulfonic acid group, a nitro group and a halogen atom. An alkyl group substituted with (for example, methyl, ethyl,
Propyl, isopropyl, etc.) and aryl groups (eg, phenyl, naphthyl, etc.). More preferably, R is represented by a hydroxyl group and an amino group. R'represents at least one group selected from a carboxyl group and a sulfonic acid group. Each of these groups can take the form of an alkali metal salt such as sodium salt or potassium salt. R'is more preferably a carboxyl group or a salt thereof. B represents an ester, an amide, an ether or a thioether. In the above general formula (1), R is a hydroxyl group, an amino group, a sulfonic acid group,
The alkyl group substituted with a halogen atom preferably has 5 or less carbon atoms, and preferably n = 0.

Examples of the compound represented by the general formula (1) are shown below, but the invention is not limited thereto.

1 HOCH ₂ CH ₂ COOH 2 HOCH ₂ CH ₂ CH ₂ COOH 3 HOCH ₂ CH ₂ CH ₂ CH ₂ COOH 4 CH ₃ CH (OH) CH ₂ COOH 5 CH ₃ CH (OH) CH ₂ CH ₂ COOH 6 _{H 2 N-CH 2 CH 2} COOH 7 H 2 N-CH 2 CH 2 CH 2 COONa 8 H 2 N-CH 2 CH 2 CH 2 CH 2 COOH 9 HO 3 S-CH 2 CH 2 COOH 10 HO 3 S- _{CH 2 CH 2 CH 2 COOH 11} HO 3 S-CH 2 CH 2 CH 2 CH 2 COOH 12 O 2 N-CH 2 CH 2 COOH 13 O 2 N-CH 2 CH 2 CH 2 COOH 14 O 2 N-CH 2 _{CH 2 CH 2 CH 2 COOH 15} Cl-CH 2 CH 2 COOH 16 Cl-CH 2 CH 2 CH 2 COOH 17 Cl-CH 2 CH 2 CH 2 CH 2 COOH 18 Br- _{H 2 CH 2 COOH 19 BrCH 2} CH 2 CH 2 COOH 20 CH 3 CHBrCH 2 COOH 21 BrCH 2 CH 2 CH 2 CH 2 COOH 22 ICH 2 CH 2 COOH 23 H 2 N-CH 2 CH (OH) CH 2 _{CH 2 COOH 24 HOCH 2 C (} CH 3) 2 CH (OH) CONH-
_{CH 2 COOH 25 H 2 NCH (} OH) CH 2 CH 2 CH 2 COOH 26 H 2 NCH 2 CH 2 SO 3 K 27 H 2 NCH 2 CH 2 CH 2 SO 3 Na 28 H 2 NCH 2 CH ₂ CH ₂ CH ₂ SO ₃ H 29 p-ClC ₆ H ₄ SO ₃ Na The above compound can be easily synthesized by, for example, the method described in Shin Jikken Kagaku Koza (Maruzen) or a method analogous thereto.

The amount of the compound represented by the general formula (1) added to the developer is preferably 0.05 to 3 mol / l,
0.1 to 2 mol / l is more preferable. The compound represented by the general formula (1) may be used alone or in combination with a plurality of compounds. Moreover, you may use together with acetic acid. These compounds may be added as salts such as sodium and potassium.

In the present invention, examples of sulfites and metabisulfites used as preservatives include sodium sulfite, potassium sulfite, ammonium sulfite, and sodium metabisulfite. The sulfite is preferably at least 0.25 mol / l. Particularly preferably, it is at least 0.4 mol / l.

In the developer, if necessary, an alkali agent (sodium hydroxide, potassium hydroxide, etc.) and a silver sludge inhibitor (for example, JP-B-62-4702, JP-A-3).
-51844, 4-26838, 4-3629.
Nos. 42 and 1-319031, etc.),
pH buffers (eg, carbonates, phosphates, borates,
Boric acid, acetic acid, citric acid, alkanolamine, etc.),
Dissolution aids (eg, polyethylene glycols, their esters, alkanolamines, etc.), sensitizers (eg, nonionic surfactants including polyoxyethylenes,
Quaternary ammonium compounds), surfactants, defoamers,
Antifoggants (eg, halogens such as potassium bromide and sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (eg, ethylenediaminetetraacetic acid or alkali Metal salts, nitrilotriacetates, polyphosphates, and the like, development accelerators (eg, US Pat. No. 2,304,0)
No. 25, JP-B-47-45541, etc.), a hardening agent (for example, glutaraldehyde or a bisulfite adduct thereof) or an antifoaming agent can be added. The pH of the developer is less than 11.0 and is preferably adjusted to 9.5 to 10.5.

In the present invention, an activator processing solution containing a developing agent in a light-sensitive material, for example, an emulsion layer, and processing the light-sensitive material in an alkaline aqueous solution to perform development may be used as a special form of the development processing. . Such a development process, in combination with a thiocyanate silver salt stabilization treatment,
It is often used as one of the methods for rapid processing of a light-sensitive material, and the effects of the present invention can be obtained even when rapid processing is performed with such a processing solution.

As the fixing liquid, those having a generally used composition can be used. The fixing solution is generally an aqueous solution comprising a fixing agent and other components, and has a pH of usually 3.8 to 5.8. As a fixing agent, thiosulfates such as sodium thiosulfate, potassium thiosulfate, and ammonium thiosulfate; thiocyanates such as sodium thiocyanate, potassium thiocyanate, and ammonium thiocyanate; and organic sulfur compounds capable of forming a soluble stable silver complex salt And those known as fixing agents can be used.

A water-soluble aluminum salt acting as a hardening agent, for example, aluminum chloride, aluminum sulfate, potassium alum or the like can be added to the fixing solution.

If desired, the fixer contains a preservative (eg, sulfite, bisulfite), a pH buffer (eg, acetic acid), a pH adjuster (eg, sulfuric acid), and a chelating agent capable of softening water. And the like.

The developing solution may be a mixture of fixed components, an organic aqueous solution containing glycol or amine, or a viscous liquid having a high viscosity in a semi-kneaded state. Further, it may be used after being diluted at the time of use, or may be used as it is.

In the development processing of the present invention, the development temperature can be set in the usual temperature range of 20 to 30 ° C. or in the high temperature processing range of 30 to 40 ° C.

In the present invention, the hydrazine derivative contained in at least one layer on the silver halide emulsion layer side of the silver halide photographic light-sensitive material is preferably a compound represented by the following general formula (H).

[0028]

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In the formula, A represents an aryl group, a heterocycle containing at least one sulfur atom or oxygen atom, and G represents-(C
O) n-group, sulfonyl group, sulfoxy group, -P (=
O) represents an R ₂ — group or an iminomethylene group, and n is 1
Or an integer of ₂ , both A ₁ and A ₂ represent a hydrogen atom or one represents a hydrogen atom and the other represents a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted acyl group, and R represents a hydrogen atom, respectively. Represents a substituted or unsubstituted alkyl group, alkenyl group, aryl group, alkoxy group, alkenyloxy group, aryloxy group, heterocyclic oxy group, amino group, carbamoyl group, or oxycarbonyl group. R ₂ represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group, alkoxy group, alkenyloxy group, alkynyloxy group, aryloxy group or amino group.

Of the compounds represented by the general formula (H), the compounds represented by the following general formula (Ha) are more preferred.

[0031]

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In the formula, R ¹ is an aliphatic group (eg, octyl group, decyl group), aromatic group (eg, phenyl group, 2-hydroxyphenyl group, chlorophenyl group) or heterocyclic group (eg, pyridyl group, thienyl group, Represents a furyl group),
As these groups, those further substituted with a suitable substituent are preferably used. Further, R ¹ preferably contains at least one diffusion resistant group or silver halide adsorption promoting group.

The diffusion resistant group is preferably a ballast group commonly used in non-moving photographic additives such as couplers, and the ballast group having 8 or more carbon atoms is relatively inert to photographic properties, for example, an alkyl group. , Alkenyl group, alkynyl group, alkoxy group, phenyl group, phenoxy group, alkylphenoxy group and the like.

As the silver halide adsorption promoting group, thiourea, thiourethane group, mercapto group, thioether group,
Examples thereof include a thione group, a heterocyclic group, a thioamide heterocyclic group, a mercapto heterocyclic group, and an adsorptive group described in JP-A-64-90439.

In the general formula (Ha), X represents a group capable of substituting for a phenyl group, m represents an integer of 0 to 4, and when m is 2 or more, X may be the same or different.
A ₃ and A ₄ have the same meanings as A ₁ and A _2, and it is preferable that both are hydrogen atoms. G represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group or an iminomethylene group, and G is preferably a carbonyl group.

In the general formula (Ha), R ² is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an allyl group, a heterocyclic group, an alkoxy group, a hydroxyl group, an amino group,
Represents a carbamoyl group or an oxycarbonyl group. Most preferred R ² includes a —COOR ³ group and —CON (R ⁴ )
(R ⁵⁾ groups (R ³ represents an alkynyl group or a saturated heterocyclic group, R ⁴ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, R ⁵ is alkenyl A alkynyl group, a saturated heterocyclic group, a hydroxy group or an alkoxy group).

Specific examples of the compound represented by formula (H) are shown below, but the invention is not limited thereto.

[0038]

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[0039]

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[0040]

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[0041]

[Chemical 6]

[0042]

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Specific examples of other preferable hydrazine derivatives are (1) to (252) described in US Pat. No. 5,229,248, columns 4 to 60.

The hydrazine derivative according to the present invention can be synthesized by a known method. For example, US Pat.
It can be synthesized by a method as described in columns 59 to 80 of No. 29,248.

The addition amount may be any amount as long as it gives a high contrast (amount of high contrast), and the grain size of the silver halide grains, the halogen composition,
Although the optimum amount varies depending on the degree of chemical sensitization and the type of the inhibitor, it is generally 10 ^-6 to 10 per mol of silver halide.
It is in the range of ^-1 mol, preferably in the range of ^10-5 to ^10-2 mol. The hydrazine derivative used in the present invention is
It is added to at least one layer on the silver halide emulsion layer side.

The present invention is characterized in that the treatment is carried out in the presence of at least one of 3-indazolinones, urazoles, 2-, 3-pyrazolin-5-ones and pyrimidones. Include the following compounds.

[0047]

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[0048]

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The amount of the above compound added is 1.0 × 10 ^{-5 to} 1.0 × 10 ^-2 mol / l when it is added to the light-sensitive material.
molAg, preferably 1.0 × 10 ^{−4 to} 1.0
× 10 ⁻³ mol / molAg. When it is added to the developer, 1.0 × 10 ⁻³ to 10 ⁻¹ mol / mol
Ag, preferably 1.0 × 10 ^{-2 to} 1.0 mol
/ MolAg.

In the present invention, the halogen composition of silver halide in the silver halide emulsion is not particularly limited, but silver chloride, silver chlorobromide or silver chloroiodobromide is preferable.

The average grain size of silver halide is 0.7 μm.
m, particularly 0.5 to 0.1 μm
Is preferred. The average particle size is a term that is commonly used by experts in the field of photographic science and is easily understood. The particle size means a particle diameter when the particles are spherical or spherical particles. If the particles are cubic, they are converted into spheres, and the diameter of the sphere is defined as the particle size. For details of the method for determining the average particle size, see Mies, James: The Theory of the Photographic Process (CE.
Mees & T. H. By James: The theor
y of the photographic pro
ccs), 3rd edition, pp. 36-43 (1966 (published by Macmillan "Mcmilllan")).

The shape of the silver halide grains is not limited,
The shape may be flat, spherical, cubic, tetrahedral, octahedral, or any other shape. Further, it is preferable that the particle size distribution is narrower, and in particular, a so-called monodisperse emulsion in which 90%, preferably 95% of the total number of particles falls within a particle size range of ± 40% of the average particle size is preferable.

As the method of reacting the soluble silver salt and the soluble halogen salt in the present invention, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used.

A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one form of the simultaneous mixing method, a method of keeping pAg constant in a liquid phase in which silver halide is produced, that is, a so-called controlled double jet method can be used. According to this method, the crystal form is regular. Gives a silver halide emulsion having a substantially uniform grain size.

The silver halide grains used in the silver halide emulsion are cadmium salt, zinc salt, lead salt, thallium salt, iridium salt, rhodium salt, or at least one of them during the grain forming process or the growing process. It is preferable to add a complex salt containing the element.

For details of the silver halide emulsion and its preparation method, see Research Disclosure (Res).
(Earth Disclosure) 176 No. 1764
3, pages 22 to 23 (December 1978).

The silver halide emulsion may or may not be chemically sensitized. As methods for chemical sensitization, sulfur sensitization, reduction sensitization and noble metal sensitization are known, and any of these methods may be used alone or in combination. A preferred chemical sensitization method is sulfur sensitization. Examples of the sulfur sensitizer include, in addition to a sulfur compound contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, rhodanines, and polysulfide compounds. Can be used.

The gold sensitization method is a typical one of the noble metal sensitization methods, and a gold compound, mainly a gold complex salt is used. Noble metals other than gold, for example, complex salts such as platinum, palladium, and rhodium may be contained.

Examples of the reduction sensitizer include stannous salt, amines,
Formamidinesulfinic acid, silane compounds and the like can be used.

The light-sensitive material used in the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. . That is, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1
-Phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines and mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as triazaindenes and tetrazaindenes (especially 4-hydroxy-substituted-1,3 , 3a, 7-tetrazaindenes), pentazaindenes and the like; adding many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide and the like. Can be.

The photographic emulsion and the non-photosensitive hydrophilic colloid of the present invention may contain an inorganic or organic hardener. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), Active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis- [β- (vinylsulfonyl) propionamide], etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine etc.), mucohalogen acids (mucochloric acid, phenoxymucochloric acid etc.) isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin. Etc. alone It can be used in combination.

The photosensitive emulsion layer and / or the non-photosensitive hydrophilic colloid layer of the present invention may be used for various purposes such as coating aid, antistatic property, slipperiness improvement, emulsion dispersion, adhesion prevention and photographic property improvement. Known surfactants may be used.

Gelatin is advantageously used as the binder or protective colloid of the photographic emulsion, 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 hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol , Polyvinyl alcohol partial acetal, poly-N-
Various kinds of synthetic hydrophilic polymer substances such as a single or copolymer such as vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole can be used.

As gelatin, in addition to lime-processed gelatin,
Acid-treated gelatin may be used, gelatin hydrolyzate,
Enzymatic degradation products of gelatin can also be used.

The photographic emulsion of the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. For example, alkyl (meth) acrylate, alkoxyacryl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide,
Vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene or the like alone or in combination;
Alternatively, it is possible to use a polymer having a monomer component of a combination of these with acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid, or the like. it can.

The silver halide emulsion of the present invention is preferably spectrally sensitized with various sensitizing dyes. Research Disclosure 176 is a preferred sensitizing dye.
Volume 1978 (17643) pages 23-24 and 3
Vol. 46, published in 1993 (34685) can be used.

Various other additives are used in the light-sensitive material used in the present invention. For example, desensitizers, plasticizers, slip agents, development accelerators, oils, dyes, etc.

Regarding these additives and the above-mentioned additives, specifically, Research Disclosure 176
Nos. (Ibid.), Pages 22-31, etc. can be used.

In the light-sensitive material used in the present invention, the emulsion layer and the protective layer may be a single layer or a multi-layer composed of two or more layers. In the case of a multilayer, an intermediate layer or the like may be provided therebetween.

[0070]

EXAMPLES The effects of the present invention will now be illustrated by examples.

Example 1 (Preparation of silver halide emulsion) Aqueous silver nitrate solution and NaCl
70 mL of silver chloride was prepared by using a simultaneous mixing method of a mixed aqueous solution of KBr and KBr.
Silver halide grains consisting of mol% and the rest silver bromide were grown. At this time, mixing was carried out at 40 ° C., pAg 8.0, pH 3.
5. Water-soluble rhodium salt (1.8 × 10 ⁻⁷ mol per 1 mol of silver) and water-soluble iridium salt (3.25 × 10 ⁻⁶ mol per 1 mol of silver) were added during grain formation. did. Then, it was washed with demineralized water by the flocculation method.
The EAg after redispersion was 220 mV. The obtained emulsion was cubic grains having an average grain size of 0.33 μm and a coefficient of variation of 12%. The pH of the emulsion thus obtained was adjusted with citric acid, the pAg was adjusted to 8.0 at 40 ° C. with NaCl, and then 8.5 mg of chloroauric acid and 1.9 mg of silver per mol of silver were adjusted.
Was added and chemically aged at 63 ° C. for 130 minutes.
After aging, 4-hydroxy-6-methyl-1,3,3
2.7 g of a, 7-tetrazaindene was added per mol of silver.

(Preparation of silver halide photographic light-sensitive material 1) An undercoat layer having a thickness of 0.1 .mu.m on both sides (JP-A-59-19941).
Example 1) in which a silver halide emulsion layer having the following formulation (1) is applied on one undercoat layer having a thickness of 100 μm and a gelatin amount of 1.4.
g / m ^{2 The} amount of silver was coated so that the amount of silver would be 3.9 g / m ^2, and a protective layer of the following formulation (2) was further applied thereon to give a gelatin amount of 0.6.
by coating so as to g / m ^2, also a backing layer was coated so that the amount of gelatin is 1.6 g / m ² according to the following formulation (3) on the opposite side of the other subbing layer , And a protective layer of the following formulation (4) with a gelatin content of 0.7
A sample was obtained by coating so as to have g / m ² .

Formulation (1) (Silver halide emulsion layer composition) Gelatin 1.4 g / m ² Silver halide emulsion Silver amount 3.9 g / m ² Sensitizing dye d-1 0.5 mg / m ² Sensitizing dye d -2 0.5 mg / m ² hydrazine derivative: Exemplified compound (shown in Table 1) 30 mg / m ² Nucleation accelerator: Exemplified compound (shown in Table 1) 40 mg / m ² Compound e 100 mg / m ² Latex polymer f 300 mg / M ² hydroquinone 1-phenyl-4-hydroxymethyl-4′-methyl-3-pyrazolidone 5 mg / m ² hardener g 5 mg / m ² formulation (2) (silver halide emulsion protective layer composition) gelatin 0.7 g / M ² matting agent: silica having an average particle size of 3.5 μm 20 mg / m ² surfactant: sodium sulfosuccinate di (2-ethylhexyl) ester 10 mg / m ² surfactant: I 2 mg / m ² Hardener: Formalin 30 mg / m ² formulation (3) (Backing layer composition) Gelatin 1.6 mg / m ² Dye: J-1 18.9 mg / m ² Dye: J-2 67.2 mg / m ² Saponin: 54 mg / m ² latex polymer f 350 mg / m ² hardener K: 110 mg / m ² hardener L: 110 mg / m ² formulation (4) (backing protective layer composition) gelatin 0.7 mg / m ² matting agent: average Polymethylmethacrylate having a particle size of 4.0 μm 50 mg / m ² Surfactant: sodium sulfosuccinate di (2-ethylhexyl) ester 10 mg / m ² Hardener g 23 mg / m ²

[0074]

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[0075]

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Sample No. obtained as described above. 1 to
Regarding No. 8, the following developer and fixer CFL-881 (manufactured by Konica Corporation) were used as an automatic processor GX-680 (Konica Corporation).
Was used for the development process.

(Developer Formulation 1) Diethylenetriamine pentaacetic acid 40% aqueous solution 3.63 g Sodium sulfite 31.52 g Potassium bromide 6.94 g Potassium carbonate 149.7 g Potassium hydrogencarbonate 21.69 g 8-Mercaptoadenine 0.1 liter per 1 l of the used liquid. 06 g Diethylene glycol 50 g Compound p 0.25 g 1-Phenyl-5-mercaptotetrazole 0.025 g Sodium erythorbate (sodium isoascorbate) 45 g Diethylaminopropanediol 20 g 1-Phenyl-4-hydroxymethyl-3-pyrazolidone 1.5 g

[0078]

[Chemical 12]

Water and potassium hydroxide are added to make 1 liter, and the pH is adjusted to 10.4.

(Developer formulation 2) Diethylenetriamine pentaacetic acid 40% aqueous solution per 1 l of the used solution 3.63 g Sodium sulfite 31.52 g Potassium bromide 6.94 g Potassium carbonate 149.7 g Potassium hydrogen carbonate 21.69 g 8-Mercaptoadenine 0.1. 06 g Diethylene glycol 50 g Compound p 0.25 g 1-Phenyl-5-mercaptotetrazole 0.025 g Hydroquinone 20 g Diethylaminopropanediol 20 g 1-Phenyl-4-hydroxymethyl-3-pyrazolidone 1.5 g Water and potassium hydroxide were added to 1 l. Finish to pH 10.4.

(Developer formulation 3) Diethylenetriamine pentaacetic acid 40% aqueous solution 3.61 g per 1 liter of working solution 3.63 g Sodium sulfite 31.52 g Potassium bromide 6.94 g Potassium carbonate 149.7 g Potassium hydrogen carbonate 21.69 g 8-Mercaptoadenine 0.1. 06 g Diethylene glycol 50 g Compound p 0.25 g 1-Phenyl-5-mercaptotetrazole 0.025 g Sodium erythorbate (sodium iso-ascorbate) 45 g Nucleation accelerator 2 g Diethylaminopropanediol 20 g 1-Phenyl-4-hydroxy Methyl-3-pyrazolidone 1.5 g Water and potassium hydroxide are added to make 1 L, and the pH is adjusted to 10.4.

(Treatment Conditions) Process Temperature (° C.) Time (sec) Replenishment amount (ml / m ² ) Development 35 15 250 Fixing 35 10 250 Washing with water Room temperature 8-Drying 40 11 The following evaluation was performed.

(Sensitivity and gamma) The obtained sample was exposed to light having passed through an interference filter of 780 nm through an optical wedge for 10 ^-6 seconds and developed with a developing solution having the following formulation. Note that the sensitivity is the reciprocal of the exposure amount that gives a transmission density of fog density + 3.0, and was determined as a relative value under each condition with the sensitivity of Sample 1 being 100.

Further, gamma was obtained from the slope of the characteristic curve at transmission densities of 1.0 to 3.0. A gamma of 10 or more is necessary for practical use.

(Evaluation of black spots) The black spots in the unexposed area are set to 40.
It was observed with a double magnifying glass, and a grade having no black spots was set to 5 and a 5-grade evaluation was performed. Ranks 1 and 2 are levels that are not practically desirable.

[0086]

[Table 1]

From the results shown in Table 1, it can be seen that by using the nucleation accelerator of the present invention and the developer, high sensitivity, low fog, few black spots and high contrast are achieved.

Example 2 (Preparation of silver halide photographic light-sensitive material 2) Silver halide photographic light-sensitive material 1 except that the nucleation accelerator in (formulation 1) of silver halide photographic light-sensitive material 1 in Example 1 was removed. A silver halide photographic light-sensitive material 2 was prepared in the same manner as in, and the same processing and evaluation as in Example 1 were performed. Table 2 shows the results.

[0089]

[Table 2]

From the results shown in Table 2, it is possible to obtain a silver halide photographic light-sensitive material having high sensitivity, low fog, little black spots, and high contrast even when the nucleation accelerator of the present invention is contained in the developer. I understand.

[0091]

According to the present invention, a silver halide photographic light-sensitive material and a processing method which have high sensitivity, low fog, few black spots and high contrast can be obtained.

Claims (2)

[Claims] 1. A processing method for processing a silver halide photographic light-sensitive material having a silver halide emulsion layer with a developing solution containing ascorbic acid or an ascorbic acid derivative,
A method for processing a silver halide photographic light-sensitive material, which comprises processing in the presence of at least one of 3-indazolinones, urazoles, 2-, 3-pyrazolin-5-ones, and pyrimidones. 2. A silver halide photographic light-sensitive material having a silver halide emulsion layer and processed with a developing solution containing ascorbic acid or an ascorbic acid derivative, wherein 3-indazolinones, urazoles, 2, 3 are used. -A silver halide photographic light-sensitive material processed in the presence of at least one of pyrazolin-5-ones and pyrimidones, characterized in that the silver halide emulsion layer or its adjacent layer contains a hydrazine derivative. And a silver halide photographic light-sensitive material.