JPH09319020A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain photographic properties of extremely high contrast and high gamma with using a stable developer by incorporating a specified compd. into a photographic material. SOLUTION: This photographing material contains at least one compd. expressed by the formula. In the formula, A is an aryl group or unsatd. heterocyclic group, R1 , R2 , R3 are each hydrogen, a halogen, an alkyl, an alkenyl, an aryl, an alkoxy, an aryloxy, an acyl, cyano, carbamoyl, an alkoxycarbonyl or an aryloxycarbonyl. Therefore, photographic properties of extremely high contrast with >10 gamma can be obtd. by using a stable developer, and the obtd. direct positive photosensitive material has excellent high process stability and storage property and shows enough reversing property even with a low pH treating liquid in a small amt. of addition.

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 superhigh contrast negative image forming method using the same, and more particularly to a silver halide photographic light-sensitive material used in a photomechanical process.

[0002]

2. Description of the Related Art In the field of graphic arts, ultra-high contrast (especially when gamma is 1
An image forming system showing a photographic characteristic of 0 or more) is required. As a method of obtaining a photographic characteristic of high contrast using a stable developing solution, US Pat. Nos. 4,224,401, 4,168,977, and 4,166,742 are disclosed.
No. 4,311,781, No. 4,272,606
No. 4,211,857, No. 4,912,01
No. 6, No. 4,994, 365, No. 4,998, 6
04, JP-A-3-259240, JP-A-5-457.
No. 61, JP-A-5-150392 and the like are known methods using a hydrazine derivative. According to this method, photographic characteristics with high contrast and high sensitivity can be obtained, and since it is permissible to add a high concentration of sulfite to the developing solution, the stability of the developing solution against air oxidation is not improved in the lith developer. Greatly improved compared to. However, hitherto, it has been found that the known hydrazine compounds have some drawbacks. That is, it has been attempted to make the structure of the hydrazine compound a diffusion-resistant structure with a conventionally known hydrazine compound for the purpose of reducing the adverse effect on other photographic light-sensitive materials caused by flowing out into the developing solution. These diffusion-resistant hydrazine compounds are required in a large amount for sensitized contrast enhancement,
There are problems that the physical strength of the obtained photosensitive layer is deteriorated and that a hydrazine compound is precipitated in the coating solution. Further, it was also found that a sufficient hardness could not be obtained when a large amount of a light-sensitive material was treated with a fatigue developing solution. Also,
In general, the return sensitive material handled in a bright room is one of the sensitive materials for plate making and has a large field. In this field, high quality of blank characters for reproducing thin Mincho characters is required. Therefore, the development of a more active nucleating agent has been desired. In particular, in a low-sensitivity bright room light-sensitive material that can be handled even in a bright room, it is difficult for the nucleating agent to produce a high contrast, and there is a demand for the development of a highly active nucleating agent.

On the other hand, a method of directly obtaining a positive image by surface-developing an internal latent image type silver halide photographic emulsion in the presence of a nucleating agent, and a photographic emulsion or a light-sensitive material used in such a method are described in US Patent 2,456,953
No. 2,497,875 No. 2,497,876
No. 2,58,982, 2,592,250
Issue 2, Issue 2,675,318, Issue 3,227,552
No. 3,317,322, British Patent 1,011,0
No. 62, No. 1,151,363, No. 1,269,64
No. 0, No. 2,011,391, Japanese Patent Publication No. 43-2940
5, JP-A-49-38164, JP-A-53-16623.
No. 53-137133, No. 54-37732.
No. 54-40629, No. 54-74536, No. 54
-74729, 55-52055 and 55-90
940 and the like. In the above method for obtaining a direct positive image, a nucleating agent may be added to a developer, but a more general method is to add the nucleating agent to a photographic emulsion layer or another appropriate layer of a light-sensitive material.

As the nucleating agent added to the direct positive type silver halide light-sensitive material, a hydrazine compound is most known, and specifically, Research Disclosure No. 23510 (November 1953) and 15162. (1
151, November 976), and 17626.
(December 1978, Volume 176). Generally, the maximum concentration of hydrazine-based nucleating agent (Dma
x) and the minimum concentration (Dmin) are large, and are the best in terms of discrimination, but high pH (pH
(11 or more) is required and its improvement is required.

[0005]

SUMMARY OF THE INVENTION Therefore, the first object of the present invention is to provide a silver halide photographic light-sensitive material capable of obtaining extremely hard photographic properties with a gamma of more than 10 by using a stable developing solution. To do. A second object of the present invention is to provide a silver halide photographic light-sensitive material for plate making which has high processability and excellent storage stability. A third object of the present invention is to provide a direct positive light-sensitive material showing a sufficient reversal property even with a low pH processing liquid with a small addition amount.

[0006]

The object of the present invention has been achieved by the following (1) or (2). (1) A silver halide photographic light-sensitive material containing at least one compound represented by the following general formula (IA) or general formula (IB). General formula (IA)

[0007]

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General formula (IB)

[0009]

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In the formula, A represents an aryl group or an unsaturated heterocycle, and R ₁ , R ₂ , R ₃ and R ₄ are hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, aryl groups, alkoxy groups and aryl. Oxy group, acyl group, cyano group,
It represents a carbamoyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group. However, R ₄ may be a carboxy group. (2) In the general formulas (IA) and (IB), A is a compound represented by the general formula (II).
The silver halide photographic light-sensitive material as described in (1). General formula (II)

[0011]

[Chemical 6]

In the formula, B represents an aryl group, an alkyl group, a saturated or unsaturated heterocycle, L is a —SO ₂ NR 5 — group,
-NR5SO ₂ NR5 - based, -CONR5 - based, -NR5CONR5- group, -
NR5CO- group, and R5 represents a hydrogen atom, an alkyl group or an aryl group.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The compounds represented by formulas (IA) and (IB) will be described in more detail. R ₁ , R
₂ , R ₃ and R ₄ represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, a cyano group, a carbamoyl group, an alkoxycarbonyl group and an aryloxycarbonyl group. However, R ₄ may further be a carboxy group. The alkyl group of R ₁ , R ₂ and R ₃ has 1 carbon atom.
To 24, preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl,
Propyl, isopropyl, t-butyl, allyl, propargyl, 2-butenyl, 2-hydroxyethyl, benzyl, benzhydryl, trityl, 4-methylbenzyl,
2-methoxyethyl, cyclopentyl, 2-acetamidoethyl. The alkenyl group has 2 to 2 carbon atoms.
4, preferably those having 2 to 20 carbon atoms, such as vinyl and 2-styryl. Aryl group has 6 carbon atoms
To 24, preferably an aryl group having 6 to 20 carbon atoms, such as phenyl, naphthyl, p-alkoxyphenyl,
p-sulfonamidophenyl, p-ureidophenyl,
p-amidophenyl, m-sulfonamidophenyl, m
-Ureidophenyl, m-amidophenyl, o-sulfonamidophenyl, o-ureidophenyl, o-amidophenyl. The heterocyclic group has a carbon number of 1 to
5, a saturated or unsaturated 5- or 6-membered heterocyclic ring containing at least one oxygen atom, nitrogen atom, or sulfur atom, wherein the number of heteroatoms forming the ring and the kind of element are 1 Or more than one, for example, 2-furyl, 2-thienyl, 4-pyridyl. Examples of the alkoxy group, aryloxy group, carbamoyl group, alkoxycarbonyl group, and aryloxycarbonyl group include those alkyl groups and aryl moieties described in the alkyl and aryl groups. Further, the carbamoyl group may be unsubstituted.

R ₁ , R ₂ , R ₃ and R ₄ are preferably
A hydrogen atom, a halogen atom, (Cl, Br, F, I), an alkyl group, an alkenyl group, an aryl group, a cyano group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and more preferably a hydrogen atom or a halogen. Atom (Cl, Br, F, I), alkyl group, aryl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group.

R ₁ , R ₂ , R ₃ and R ₄ may be further substituted with a substituent, which may be an alkyl group,
An aralkyl group, an alkyl- or aryl-substituted amino group,
Ureido group, urethane group, alkoxy group, aryloxy group, sulfamoyl group, carbamoyl group, alkyl or arylthio group, alkyl or arylsulfonyl group, alkyl or arylsulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, alkoxycarbonyl Group, aryloxycarbonyl group, acyl group, amide group, sulfonamide group, carboxy group, phosphoric acid amide group and the like. These groups may be further substituted. Among these, a ureido group, a urethane group, an alkoxy group, an aryloxy group, an alkyl or arylthio group, a sulfonamide group, an amide group and a halogen atom are preferable, and a ureido group, an alkoxy group, an alkyl or arylthio group, a sulfonamide group, an amide group. A group and a halogen atom are more preferable. Most preferably, it is a halogen atom, especially a fluorine atom. R ₁ , R ₂ , R
When possible, ₃ may be linked to each other to form a ring.

A represents an aryl group or an unsaturated heterocyclic group. Examples of the aryl group and unsaturated heterocyclic group are:
Those mentioned for R ₁ , R ₂ , R ₃ and R ₄ can be mentioned.

The general formula (II) will be described in detail. B
Represents an aryl group, an alkyl group, or a saturated or unsaturated heterocycle, and examples of the aryl group, alkyl group, and saturated or unsaturated heterocycle include those described for R ₁ , R ₂ , R ₃ and R _4. To be B is preferably an aryl group or an aromatic heterocyclic group, and more preferably an aryl group. B may be further substituted with a substituent, and examples of the substituent include those described for R ₁ , R ₂ , R ₃ and R ₄ . L is, -SO ₂ NR5─ group, -NR5SO ₂ NR5 - based, -CO
NR5-group, -NR5CONR5-group, -NR5CO- group, R5
Represents a hydrogen atom, an alkyl group, or an aryl group. Examples of the alkyl group and aryl group of R5 include R ₁ , R ₂ , R ₃ and R ₄
The ones mentioned above are listed. R5 is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom. L is preferably -SO ₂ NR5-group, -NR5SO ₂ NR5-
Group, -CONR5 - group, a -NR5CONR5- group, more preferably -SO ₂ NR5- group, -NR5SO ₂ NR5 - group, a -CONR5- group.

A of the general formula (IA), (IB), or B of the general formula (II) is a non-diffusion group, an adsorption promoting group to silver halide, an alkylthio group or an arylthio group. , A heterocyclic thio group, a quaternary ammonio group, a nitrogen-containing heterocyclic group containing a quaternized nitrogen atom, an alkoxy group containing an ethyleneoxy or propyleneoxy unit, or a heterocyclic group containing a disulfide bond is incorporated. May be.

The diffusion resistant group means a diffusion resistant group in a photographic coupler or the like, a so-called ballast group, and when the compound of the present invention is added to a specific silver halide emulsion layer. A group that can prevent this substance from easily diffusing into other layers, or a group that can prevent it from being easily eluted in a developing solution during development. Specifically, it is a group having 8 or more total carbon atoms, preferably 8 to 16 total carbon atoms. As the ballast group, preferably, an alkyl group, an aryl group, an alkoxy group, an aryl group having 8 or more total carbon atoms is used. Examples include an oxy group, an oxycarbonyl group, a carbamoyl group, an acylamino group, a sulfonamide group, a carbonyloxy group, a ureido group, a sulfamoyl group, and a combination thereof.

The alkylthio group is a substituted or unsubstituted, branched, cyclic or linear alkylthio group having a total of 1 to 18 carbon atoms, and the substituent is preferably an aryl group or an alkoxy group (ethyleneoxy or propyleneoxy). (Including alkoxy groups containing repeating units), carboxy group, carbonyloxy group, oxycarbonyl group,
Examples thereof include an acylamino group, a quaternary ammonio group, a mercapto group, a heterocyclic group, a sulfonamide group and a ureido group. Specific examples of the alkylthio group include the following groups.

[0021]

[Chemical 7]

The arylthio group is a substituted or unsubstituted arylthio group having a total of 6 to 18 carbon atoms, and examples of the substituent are the same as those which Ar ₁ of the general formula (1) may have. To be The arylthio group is preferably a substituted or unsubstituted phenylthio group, and specific examples thereof include a phenylthio group, a 4-t-butylphenylthio group, a 4-dodecylphenylthio group and the like.

The heterocyclic thio group is a substituted or unsubstituted saturated or unsaturated heterocyclic thio group having 1 to 18 carbon atoms and is a 5-membered compound containing at least one oxygen atom, nitrogen atom or sulfur atom. It is a 6-membered monocyclic heterocycle or a condensed heterocycle. Specific examples thereof include a benzothiazolylthio group, a 1-phenyl-5-tetrazolylthio group, a 2-mercaptothiadiazolyl-4-thio group and a pyridyl-2-thio group.

The quaternary ammonio group represents a quaternary ammonium cation formed by a bond between a tertiary amino group and R ₂ and its counter anion. Here, the tertiary amino group is an aliphatic or aromatic tertiary amino group, and may be a cyclic tertiary amino group. The total number of carbon atoms in the tertiary amino group is 3
To 24 are preferable. Specific examples of the counter anion include a chloro anion, a bromo anion, an iodo anion, a sulfonate anion, and a carboxylate anion. The compound of the general formula (1) has a carboxy group or a sulfo group in the molecule. In some cases, an inner salt may be formed.

When X ₁ represents a nitrogen-containing heterocyclic group containing a quaternized nitrogen atom, the case where the nitrogen-containing heterocyclic group is quaternized by the bond between the nitrogen atom and R ₂ and originally 4 The graded nitrogen-containing heterocycle may be bonded to L ₂ at a carbon atom in the ring. In the former case, n ₁ is 1, and in the latter case, n ₁ is 0. Specific examples of the nitrogen-containing heterocyclic group containing a quaternized nitrogen atom include a pyridinium group, a quinolinium group, an isoquinolinium group, a triazolinium group, an imidazolinium group and a benzothiazolinium group. These groups may be substituted, and the substituent is preferably an alkyl group, an aryl group, an alkoxy group, a carbamoyl group, an amino group or the like.

Specific examples of the ethyleneoxy comb and the alkoxy group containing repeating propyleneoxy units include R4-O-
(C ₂ H ₄ ) _p- , R4-O- {CH ₂ CH (CH ₃ ) O} _p- , R4-O- {C
It is an alkoxy group represented by H ₂ CH (OH) CH ₂ O} _p − and the like. Here, p represents an integer of 1 or more, and R4 represents an aliphatic group or an aromatic group. R4 is preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. Specifically, CH ₃ (CH ₂ CH ₂ O) _3- , C ₆ H ₁₃ O (C ₂ H ₄ O)-, C ₄ H ₉ O (C ₃ H ₆ O)-
, C ₈ H ₁₇ OCH ₂ CH (OH) CH ₂ O-, C ₁₂ H ₂₅ O (C ₂ H ₄ O) _2- , C ₂ H ₅ O (C
_And groups such as ₂ H ₄ O) _6- .

Specific examples of the saturated heterocyclic group containing a sulfide bond or a disulfide bond include -S- and -SS-.
Represents a 5- or 6-membered saturated heterocycle containing a bond,
The groups shown below are preferable.

[0028]

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Adsorption-promoting groups for silver halide include alkylthio groups, arylthio groups, thiourea groups, thioamide groups, mercaptoheterocyclic groups, triazole groups and the like, US Pat. Nos. 4,385,108 and 4,459. , 347,
JP-A-59-195233 and JP-A-59-200231.
Nos. 59-201045 and 59-201046
Issue 59-201047 Issue 59-201048
No. 59-201049, JP-A-61-17073.
No. 3, No. 61-270744, No. 62-948, No. 63-234244, No. 63-234245, No. 6
The groups described in 3-234246 are mentioned. These adsorbing groups to silver halide may be precursors. Examples of such a precursor include groups described in JP-A-2-285344.

In the present invention, most preferred R ₁ , R ₂ ,
R ₃ and R ₄ are a hydrogen atom, a halogen atom (among others, a fluorine atom), an alkoxycarbonyl group, an alkyl group or an aryl group, wherein the alkyl group or the aryl group is an alkyl group substituted with at least one fluorine atom. In particular, an aryl group is particularly preferable. The compounds used in the present invention are listed below, but the present invention is not limited thereto.

[0031]

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[0032]

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[0033]

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[0034]

[Chemical 12]

[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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The compound of the present invention can be easily synthesized using a conventional synthetic method. Of the compounds of the present invention,
A specific example will be shown with the exemplified compound I-3 as an example, but other compounds can be similarly synthesized.

Exemplified compound I-3 was synthesized according to the following scheme.

[0045]

[Chemical 21]

Synthesis of B 60 g (0.39 mol) of A was suspended in 300 ml of acetonitrile, 45 g (0.78 mol) of 80% formic acid was added, and the mixture was heated under reflux for 3 hours. The crystals obtained after cooling were washed with a small amount of acetonitrile to obtain 63.8 g (0.35 mol) of compound B.

Synthesis of C and D 70.0 g of reduced iron was suspended in 700 ml of isopropyl alcohol, an aqueous solution prepared by dissolving 15 g of ammonium chloride in 70 ml of water was added, and the mixture was heated under reflux for 1 hour. B6 there
3.8 g was gradually added, and the mixture was heated under reflux for 2 hours. The reaction solution was filtered through Celite, the 3rd solution was cooled to 5 ° C. in an ice-water bath, 28 ml (0.35 mol) of pyridine was added, and m- was added under a nitrogen stream.
Nitrobenzenesulfonyl chloride 77.6 g (0.3
(5 mol) was gradually added, and the mixture was stirred at 5 ° C. for 2 hours and at room temperature for 3 hours. The reaction solution was poured into 10 liters of water, and the resulting solid was collected by filtration and dried to obtain 101 g (0.30 mol) of compound D.

Synthesis of E 30 g of reduced iron was suspended in 300 ml of isopropyl alcohol, an aqueous solution of 7 g of ammonium chloride in 30 ml of water was added, and the mixture was heated under reflux for 1 hour. D there 33.6g
(0.1 mol) was gradually added, and the mixture was heated under reflux for 1 hour. The reaction solution was filtered through Celite, the filtrate was poured into 3 liters of water, and the resulting solid was collected by filtration and dried to obtain 26.9 g of Compound E.
(0.089 mol) was obtained.

Synthesis of F Compound E (26.9 g, 0.089 mol) was dissolved in dimethylacetamide (250 ml) to give pyridine (7.1 ml, 0.08).
9 mol) was added and stirred. Cool to below 5 ° C in an ice water bath,
A solution of 17 g (0.089 mol) of n-decanoyl chloride in 30 ml of acetonitrile was gradually added. 5 ℃
The mixture was stirred for 1 hour below and at room temperature for 2 hours. The reaction solution was gradually added to a solution prepared by adding 10 ml of concentrated hydrochloric acid to 2 liters of water and 200 ml of isopropyl alcohol, and stirred for 1 hour. The resulting solid was collected by filtration and dried to give 37.3 g (0.0
81 mol) was obtained.

Synthesis of G 37.3 g (0.081 mol) of compound F was added to methanol 20
Dissolve in 0 ml, add 6.75 ml of concentrated hydrochloric acid (37%), and add 45
Stirred at C for 3 hours. After cooling to below 5 ° C, the resulting solid was collected by filtration and dried to obtain 31.9 g (0.068 mol) of compound G.
I got

Synthesis of Exemplified Compound I-3 9.4 g (0.02 mol) of Compound G was dissolved in 40 ml of dimethylacetamide, and triethylamine 2.
8 ml (0.02 mol) was added, and the mixture was stirred and cooled to 5 ° C or lower. 2.97 g (0.02 mol) of 2-methoxycarbonyl-2-propenoyl chloride was added to 10 ml of acetonitrile.
The solution dissolved in was gradually added, and the mixture was stirred at 5 ° C or lower for 1 hour and at room temperature for 3 hours. The reaction solution was gradually added to a solution prepared by adding 2 ml of concentrated hydrochloric acid to 500 ml of water, and the resulting solid was collected by filtration. The obtained crude crystal was recrystallized from acetonitrile to give I-3 of 8.1.
g was obtained. The structure was determined based on various spectral data.

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

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

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

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

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

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

The nucleation accelerator 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 nucleation accelerator of the present invention is 1 × 10 ⁻⁶ to 2 × 10 per mol of silver halide.
^-2 mol is preferable, 1 × 10 ⁻⁵ to 2 × 10 ⁻² mol is more preferable, and 2 × 10 ⁻⁵ to 1 × 10 ⁻² mol is most preferable.

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

In the present invention, a light-sensitive material suitable for high-illuminance exposure such as scanner exposure and a light-sensitive material for line drawing are
Rhodium compounds are included to achieve high contrast and low fog. As the rhodium compound used in the present invention, a water-soluble rhodium compound can be used. For example, a rhodium (III) halide compound, or a rhodium complex salt having a halogen, an amine, oxalate, etc. as a ligand, for example, hexachlororhodium (III) complex salt, hexabromorhodium (III) complex salt, hexaaminerhodium ( III) Complex salt, trisalathodium (II
I) Complex salts and the like can be mentioned. These rhodium compounds are
It is used by dissolving it in water or an appropriate solvent, but it is generally used to stabilize the solution of the rhodium compound, that is, an aqueous solution of hydrogen halide (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid, etc.), or halogenation. A method of adding an alkali (for example, KCl, NaCl, KBr, NaBr, etc.) can be used. Instead of using water-soluble rhodium, it is also possible to add and dissolve another silver halide grain which has been previously doped with rhodium when preparing the silver halide. The addition amount is 1 × 10 ^{−8 to} 5 × 10 ⁻⁶ mol, preferably 5 × 10 ⁻⁸ to 1 × 10 ⁻⁶ mol, per mol of silver in the silver halide emulsion. The addition of these compounds can be appropriately carried out at each stage before the production of the silver halide emulsion grains and before the coating of the emulsion, but it is particularly preferable to add them at the time of forming the emulsion and to incorporate them into the silver halide grains. . The photographic emulsion used in the present invention is Chimie et Physique Photograp by P. Glafkides.
hique (Paul Montel, 1967), by GFDufin
Photographic Emulsion Chemistry (The Focal Press
, 1966), by VL Zelikman et al Making and
Coating Photographic Emulsion (The Focal Press
Ed., 1964) and the like.

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

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

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

Known selenium compounds can be used as the selenium sensitizer used in the present invention. That is, it is usually carried out by adding an unstable and / or non-unstable selenium compound and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain time. Examples of unstable selenium compounds are JP-B-44-15748, JP-A-43-13489, JP-A-2-13097, JP-A-2-229300 and JP-A-3-22989.
The compounds described in No. 121798 and the like can be used. In particular, it is preferable to use the compounds represented by formulas (VIII) and (IX) in Japanese Patent Application No. 3-121798.

The tellurium sensitizer used in the present invention is a compound capable of producing silver telluride, which is presumed to be a sensitizing nucleus, on the surface or inside of silver halide grains. Regarding the formation rate of silver telluride in a silver halide emulsion, see Japanese Patent Application No.
It can be tested by the method described in No. 146739.
Specifically, U.S. Pat. Nos. 1,623,499, 3,320,069, 3,772,031, British Patent 235,211 and 1,121,496
No. 1,295,462, No. 1,396,69
6, Canadian Patent No. 800,958, Japanese Patent Application No. 2-33.
No. 3819, No. 3-53693, No. 3-131598
No. 4-129787, Journal of Chemical Society Chemical Communication (J.Chem.Soc.Chem.Commun.) 635 (1980), ibid
1102 (1979), ibid 645 (1979),
Journal of Chemical Society Perkin Transaction (J.Chem.Soc.Perkin.Trans.)
1, 2191 (1980), S.I. S. Patai
Hen, The Chemistry of Organic Selenium and Tellurium Companies (The Chemistr
y of Organic Serenium and Tellunium Compounds),
The compounds described in Vol 1 (1986) and Vol 2 (1987) can be used. In particular, Japanese Patent Application No. 4-14673
The compounds represented by the general formulas (II) (III) (IV) in No. 9 are preferable.

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

In the present invention, a silver halide emulsion particularly suitable as a reversing light-sensitive material is a silver halide comprising 90 mol% or more, more preferably 95 mol% or more, and silver bromide in an amount of 0 to 10%. It is silver chlorobromide or silver chloroiodobromide containing mol%. If the ratio of silver bromide or silver iodide increases, the safety of safelight in a bright room deteriorates, or γ
Is lowered, which is not preferable.

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

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

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

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

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

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

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

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

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

The sensitizing dye of the general formula (IV) described in Japanese Patent Application No. 5-201254 (page 14, line 14 to page 22, line 23) is preferably used for white light sources such as those photographed by a camera. . Specifically, the dyes S5-1 to S5-20 described in Japanese Patent Application No. 7-151194 are particularly preferably used.

The developer used in the development processing of the light-sensitive material according to the present invention may contain additives usually used (eg, developing agent, alkaline agent, pH buffering agent, preservative, chelating agent). . Any of known methods can be used for the developing treatment of the present invention, and known developing treatment solutions can be used. There is no particular limitation on the developing agent used in the developing solution used in the present invention, but it is preferable that the developing agent contains dihydroxybenzenes or an ascorbic acid derivative. Further, in view of developing ability, dihydroxybenzenes and 1-phenyl-3- Combination of pyrazolidones, combination of dihydroxybenzenes and p-aminophenols, combination of ascorbic acid derivative and 1-phenyl-3-pyrazolidones, or ascorbic acid derivative and p-
A combination of aminophenols is preferred.

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

Examples of the preservatives used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite.
The sulfite is used in an amount of 0.20 mol / liter or more, particularly 0.3 mol / liter or more, but if added in an excessively large amount, it causes silver stain in the developing solution, so the upper limit is 1.2 mol / liter. Is desirable. Particularly preferably, 0.
It is 35 to 0.7 mol / liter. As a preservative for a dihydroxybenzene-based developing agent, a small amount of an ascorbic acid derivative may be used in combination with sulfite. Examples of the ascorbic acid derivative include ascorbic acid, its stereoisomer, erythorbic acid, and alkali metal salts (sodium and potassium salts) thereof, and sodium erysorbate is preferably used from the viewpoint of material cost. The amount added is preferably in the range of 0.03 to 0.12, more preferably 0.05 to 0.10. In molar ratio to the dihydroxybenzene-based developing agent. When an ascorbic acid derivative is used as a preservative, it is preferable that the developer contains no boron compound.

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

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

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

Examples of aminopolycarboxylic acids include iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediaminemonohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, glycol ether tetraacetic acid, 1,2-diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid. Acetic acid,
Triethylenetetramine hexaacetic acid, 1,3-diamino-2
-Propanol tetraacetic acid, glycol ether diamine tetraacetic acid, and others, JP-A-52-25632, and JP-A-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. 4454 and 3794591, and West German Patent Publication 2
Hydroxyalkylidene-diphosphonic acid described in No. 227639 and the like, and Research Disclosure (Research Disclosure)
Disclosure) Volume 181, Item 18170 (197)
Compounds described in May 9). Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, and aminotrimethylenephosphonic acid. In addition, the above Research Disclosure 18170, JP-A-57-208554 and 54- 61125, 5
Examples thereof include compounds described in JP-A Nos. 5-29883 and 56-97347.

Organic phosphonocarboxylic acids include those disclosed in JP-A Nos. 52-102726, 53-42730, and 54.
No. 121127, No. 55-4024, No. 55-40
No. 25, No. 55-126241, No. 55-65955.
No. 55-69556, and the above-mentioned Research Disclosure 18170. These chelating agents may be used in the form of an alkali metal salt or an ammonium salt. The addition amount of these chelating agents is preferably 1 × 10 ^-4 to 1 × 10 ^-1 mol, more preferably 1 × 10 ^-1 mol per liter of developer.
It is 10 ^-3 to 1 × 10 ^-2 mol.

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

The developer used in the present invention contains a carbonate as a buffer, boric acid described in JP-A-62-186259, sugars (eg saccharose) described in JP-A-60-93433, and oximes. (Eg acetoxime),
Phenols (for example, 5-sulfosalicylic acid), tertiary phosphates (for example, sodium salt, potassium salt) and the like are used, and carbonate and boric acid are preferably used. The development temperature and time are interrelated and are determined in relation to the total processing time, but generally the development temperature is from about 20 ° C to about 5 ° C.
0 ° C., preferably 25 to 45 ° C., development time 5 seconds to 2
Minutes, preferably 7 seconds / 1 minute 30 seconds. When processing 1 square meter of a silver halide black and white photographic light-sensitive material, the replenisher amount of the developing solution is 500 ml or less, preferably 4
It is less than 00 ml. It is preferable to concentrate the treatment liquid and dilute it at the time of use for the purpose of transportation cost of the treatment liquid, packaging material cost, space saving and the like. In order to concentrate the developer, it is effective to potassium salt the salt component contained in the developer.

The fixing solution used in the fixing step of the present invention is sodium thiosulfate, ammonium thiosulfate, if necessary tartaric acid, citric acid, gluconic acid, boric acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanoic acid, tyron, ethylenediamine. Tetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid are aqueous solutions containing these salts.
From the viewpoint of recent environmental protection, it is preferable that boric acid is not contained. As the fixing agent of the fixing solution used in the present invention, sodium thiosulfate, ammonium thiosulfate and the like are used, and ammonium thiosulfate is preferable from the viewpoint of the fixing speed, but sodium thiosulfate may be used from the viewpoint of recent environmental protection. . The use amount of these known fixing agents can be appropriately changed and is generally about 0.1 to about 2 mol / liter. It is particularly preferably 0.2 to 1.5 mol / liter. The fixing solution may optionally contain a hardening agent (eg, a water-soluble aluminum compound), a preservative (eg, a sulfite,
Bisulfite), a pH buffer (eg, acetic acid), a pH adjuster (eg, ammonia, sulfuric acid), a chelating agent, a surfactant, a wetting agent, and a fixing accelerator. Examples of the surfactant include anionic surfactants such as sulfates and sulfonates, polyethylene surfactants, and amphoteric surfactants described in JP-A-57-6740. Further, a known antifoaming agent may be added. Examples of the wetting agent include alkanolamine and alkylene glycol. Examples of the fixing accelerator include, for example, JP-B Nos. 45-35754 and 58-122535.
No. 58-122536, alcohols having a triple bond in the molecule, U.S. Pat.
A thioether compound described in JP-A-126449;
And the like, and the compounds described in JP-A-2-44355 may be used. Examples of the pH buffer include organic acids such as acetic acid, malic acid, succinic acid, tartaric acid, citric acid, oxalic acid, maleic acid, glycolic acid, and adipic acid; and inorganic acids such as boric acid, phosphate, and sulfite. Buffers can be used. Acetic acid, tartaric acid, and sulfite are preferably used. Here, the pH buffering agent is used for the purpose of preventing the pH of the fixing agent from increasing due to carry-in of the developing solution, and 0.01 to
1.0 mol / liter, more preferably 0.02 to 0.1.
Use about 6 mol / l. Further, as the dye elution accelerator, the compounds described in JP-A No. 64-4739 can also be used.

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

The photosensitive material which has been developed and fixed is then washed with water or stabilized. In the washing or stabilizing treatment, the washing water amount is usually ² m ² per m ^{2 of the} silver halide photosensitive material.
It is performed at 0 liters or less, and a replenishment amount (0 liters or less
In other words, it can also be carried out by washing with water. That is, not only water saving processing can be performed, but also piping for installing the automatic processing machine can be eliminated. As a method for reducing the replenishing amount of washing water, a multi-stage countercurrent method (for example, 2
Stage, three stage, etc.) are known. If this multi-stage countercurrent method is applied to the present invention, the photosensitive material after fixing is gradually processed in the normal direction, that is, the processing solution which is not stained with the fixing solution is sequentially contacted, so that the efficiency is further improved. Washing is performed. When the washing with water is carried out with a small amount of water, JP-A-63-18
It is more preferable to provide a washing tank for a squeeze roller and a crossover roller described in JP-A Nos. 350 and 62-28725. Alternatively, various oxidizing agents may be added or a filter may be combined to reduce the pollution load which is a problem when washing with a small amount of water. Further, part or all of the overflow liquid from the washing or stabilizing bath produced by replenishing the water subjected to the antifungal means to the washing or stabilizing bath by the method of the present invention according to the treatment is disclosed in 235
As described in JP-A-133, it can also be used for a processing solution having a fixing ability, which is the preceding processing step. Further, a water-soluble surfactant or an antifoaming agent may be added in order to prevent 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 the dye eluted from the photosensitive material, JP-A-63-16345
The dye adsorbent described in No. 6 may be installed in a washing tank. In addition, a stabilization process may be performed following the water washing process,
Examples thereof include JP-A-2-201357 and JP-A-2-132.
No. 435, No. 1-102553, JP-A-46-444.
A bath containing the compound described in No. 46 may be used as a final bath of the light-sensitive material. If necessary, metal compounds such as ammonium compounds, Bi, and Al, fluorescent brighteners, various chelating agents, film pH regulators, hardeners, bactericides, fungicides, alkanolamines, and surfactants may be used in this stabilizing bath. Agents can also be added. The water used in the washing step or the stabilization step includes tap water, deionized water, halogen, ultraviolet sterilizing lamp, and water sterilized by various oxidizing agents (ozone, hydrogen peroxide, chlorate, etc.). It is preferable to use, and washing water containing the compounds described in JP-A-4-39652 and JP-A-5-241309 may be used. Washing or stabilizing bath temperature and time are 0-5
0 ° C. and 5 seconds to 2 minutes are preferred.

The treatment liquid used in the present invention is disclosed in JP-A-61-161.
It is preferable to store in a packaging material having low oxygen permeability described in No. 73147. The treatment liquid used in the present invention may be in the form of a powder and solidified. Known methods can be used, but it is preferable to use the methods described in JP-A-61-259921, JP-A-4-85533, and JP-A-4-16841. Particularly preferred is the method described in JP-A-61-259921. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. The roller transport type automatic developing machine is described in U.S. Pat. Nos. 3,025,779 and 3,545,971 and the like, and is simply referred to as a roller transport type processor in this specification. The roller conveyance type processor comprises four steps of developing, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, stopping step), but it is most preferable to follow these four steps. . Four steps of a stabilization step may be used instead of the washing step.

The hydrazine nucleating agent of the present invention is a method for directly obtaining a positive image by surface developing an internal latent image type silver halide photographic emulsion in the presence of a nucleating agent, and a photographic emulsion used in such a method. Alternatively, a light-sensitive material (for example, US Pat. Nos. 2,456,953, 2,497,875, 2,497,876, 2,588,982, 2,592,250, and 2,675). , 318, 3,227,552, 3,317,322, British Patents 1,011,062, 1,151,363,
No. 1,269,640, No. 2,011,391, Japanese Examined Patent Publication No. 43-29405, No. 49-38164, JP-A No. 53-16623, No. 53-137133, No. 5
4-37732, 54-40629, 54-7
No. 4536, No. 54-74729, No. 55-5205
No. 5, No. 55-90940, etc.)). In the above method for obtaining a direct positive image, a nucleating agent may be added to a developer, but a more general method is to add the nucleating agent to a photographic emulsion layer or another appropriate layer of a light-sensitive material.

There are no particular restrictions on the various additives used in the light-sensitive material of the present invention and the development processing method. For example, those described in the following sections can be preferably used. Item This section 1) Surfactant JP-A-2-12236, page 9, upper right column, line 7 to lower right column, line 7 and JP-A-2-18542, page 2, lower left column 13 From line 4 to page 4, lower right column, line 18. 2) Antifoggant JP-A-2-103536, page 17, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, lines 1 to 5, further JP-A 1-237538. Thiosulfinic acid compounds described in the public notice. 3) Polymer latex JP-A-2-103536, page 18, lower left column, lines 12 to 20. 4) Compounds having an acid group JP-A-2-103536, page 18, lower right column, line 6 to page 19, upper left column, line 1 5) Matting agent, slipping agent JP-A-2-103536, page 19, upper left column 15, plasticizer line to page 19, upper right column, line 15 6) Hardener JP-A-2-103536, page 18, upper right column, line 5 to line 17 thereof. 7) Dyes Dyes in the lower right column, lines 1 to 18 of JP-A-2-103536, solid dyes described in JP-A-2-294638 and Japanese Patent Application No. 3-187573. 8) Binder JP-A-2-18542, page 3, lower right column, lines 1 to 20. 9) Black spot inhibitor The compounds described in U.S. Pat. No. 4,956,257 and JP-A-1-118832. 10) Redox Compounds Compounds represented by the general formula (I) in JP-A No. 2-301743 (particularly compound examples 1 to 50), and general formulas (pages 3 to 20 in JP-A No. 3-174143). R-1), (R-2), (R-3), compound examples 1 to 75, and compounds described in Japanese Patent Application Nos. 3-69466 and 3-15648. 11) Monomethine compounds Compounds of general formula (II) described in JP-A-2-287532 (compound examples II-1 to II-26). 12) Dihydroxybenze Compounds described in JP-A-3-39948, page 11, upper left column to items, page 12, lower left column, and EP452772A.

[0095]

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

Example 1 The following developers were prepared.

<Developer A> Diethylenetriamine-5-acetic acid 2 g Potassium carbonate 33 g Sodium carbonate 28 g Sodium hydrogencarbonate 25 g Sodium erythorbate 45 g N-Methyl-p-aminophenol 7.5 g KBr 2 g 5-Methylbenzotriazole 0.004 g 1- Phenyl-5-mercaptotetrazole 0.02 g Sodium sulfite 2 g 2,4,6-Trimercapto-1,3,5-triazine 0.05 g Water was added to make 1 liter, and the pH was adjusted to 9.7.

<Developers B and C> Developer B having the same formulation as developer A was added to adjust pH to 10.2. Similarly, acetic acid was added to adjust the pH to 9.2.
Was adjusted to the developer C.

<Preparation of Emulsion A> 1-liquid water 1-liter gelatin 20 g sodium chloride 3.0 g 1,3-dimethylimidazolidine-2-thione 20 mg sodium benzenesulfonate 8 mg 2-liquid water 400 ml silver nitrate 100 g 3-liquid water 400 ml sodium chloride 27.1 g Potassium bromide 21.0 g Ammonium hexachloroiridium (III) (0.001% aqueous solution) 20 ml Potassium hexachloroiridium (III) (0.001% aqueous solution) 6 ml

To the 1st liquid kept at 42 ° C. and pH 4.5, the 2nd liquid and the 3rd liquid were added simultaneously for 15 minutes while stirring,
Core particles formed. Subsequently, the following liquids 4 and 5 were added over 15 minutes. Further, 0.15 g of potassium iodide was added to terminate the particle formation. 4-liquid water 400 ml Silver nitrate 100 g 5-liquid water 400 ml Sodium chloride 27.1 g Potassium bromide 21.0 g Potassium hexacyanoferrate (II) (0.1% aqueous solution) 10 ml

Thereafter, the product was washed with water by a flocculation method according to a conventional method, and 40 g of gelatin was added. pH
5.7, pAg was adjusted to 7.5, sodium thiosulfate 1.0 mg, chloroauric acid 4.0 mg, triphenylphosphine selenide 1.5 mg, sodium benzenethiosulfonate 8
mg and sodium benzenethiosulfinate 2 mg, and 55
Chemical sensitization was carried out at ℃ to obtain the optimum sensitivity. Further, 4-hydroxy-6-methyl-1,3,3a,
7 mg of 7-tetrazaindene, phenoxyethanol as a preservative, and finally 70 mol% of silver chloride, and a silver chloroiodobromide cubic emulsion A having an average particle size of 0.25 .mu.m.
I got

<Preparation of coating sample> Sensitizing dye was added to the emulsion.
(1) 3.8 × 10 ⁻⁴ mol / mol Ag was added to perform spectral sensitization. Further, KBr 3.4 × 10 ⁻⁴ mol / mol Ag,
Compound (1) 3.2 × 10 ⁻⁴ mol / mol Ag, compound (2)
8.0 × 10 ⁻⁴ mol / mol Ag, hydroquinone 1.2
× 10 ⁻² mol / mol Ag, citric acid 3.0 × 10 ⁻³ mol / mol Ag, 1.0 × 1 of the hydrazine derivative shown in Table 9.
0 ^-4 mol / mol Ag, compound (3) 6.0 × 10 ^-4 mol / mol Ag, 35 wt% polyethyl acrylate latex based on gelatin, 20 wt% based on gelatin
% Particle size 10μm of colloidal silica is added 4 wt% of the compound (4) with respect to gelatin, Ag2.5g / m ² on a polyester support was coated so as to gelatin 1.0 g / m ² . A protective layer upper layer and a protective layer lower layer having the following compositions were coated thereon, and a UL layer having the following composition was coated thereunder. The following compounds were used as comparative examples of the hydrazine derivative of the present invention.

[0103]

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[0104]

[Table 1]

(Upper Layer of Protective Layer) Gelatin 0.3 g / m ² Silica matting agent having an average of 3.5 μm 25 mg / m ² Compound (5) (Gelatin dispersion) 20 mg / m ² Colloidal silica having a particle size of 10 to 20 μm 30 mg / m ² compound (6) 5 mg / m ² sodium dodecylbenzenesulfonate 20 mg / m ² compound (7) 20 mg / m ² (protective layer lower layer) gelatin 0.5 g / m ² compound (8) 15 mg / m ² 1,5 -Dihydroxy-2-benzaldoxime 10 mg / m ² polyethyl acrylate latex 150 mg / m ² (UL layer) gelatin 0.5 g / m ² polyethyl acrylate latex 150 mg / m ² compound (4) 40 mg / m ² compound (9 ) 10 mg / m ²

The support of the sample used in the present invention has a back layer and a conductive layer having the following composition. (Back layer) Gelatin 3.3 g / m ² sodium dodecylbenzenesulfonate 80 mg / m ² compound (10) 40 mg / m ² compound (11) 20 mg / m ² compound (12) 90 mg / m ² 1,3-divinylsulfonyl 2-Propanol 60 mg / m ² Polymethylmethacrylate fine particles (average particle size 6.5 μm) 30 mg / m ² Compound (4) 120 mg / m ² (conductive layer) Gelatin 0.1 g / m ² Sodium dodecylbenzenesulfonate 20 mg / m ² SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25μ) 200 mg / m ²

[0107]

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[0108]

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<Evaluation> (1) Exposure and development treatment The above sample was exposed to xenon flash light having an emission time of 10 ⁻⁵ sec through a step wedge through an interference filter having a peak at 633 nm to obtain the above-mentioned developing solution A, B,
After developing with C using an AP-560 automatic developing machine manufactured by Fuji Photo Film Co., Ltd. at 32 ° C. for 15 seconds, fixing, washing with water and drying were performed. The replenisher amounts of the developing solution and the fixing solution at the time of processing were 100 ml per 1 m ² of the sample.

The fixer used was the fixer A having the following formulation. <Fixer A> Ammonium thiosulfate 120 g Ethylenediamine / tetraacetic acid / 2Na / 2-hydrate 0.03 g Sodium thiosulfate / 5-hydrate 11 g Sodium metasulfite 19 g Sodium hydroxide 12.4 g Acetic acid (100%) 30 g Tartaric acid 2.9 g Glucon Sodium acid salt 1.7 g Aluminum sulfate 8.4 g pH 4.8

(2) Photographic Sensitivity Sensitivity was expressed as a logarithmic value (S _1.5 ) of the exposure amount giving a density of 1.5. The smaller the value, the higher the sensitivity.

(3) Dependence of Photographic Sensitivity on Developer pH Using the sensitivity value S _1.5 at the time of development with developers B and C, the pH dependence of sensitivity on the developer was calculated by the following formula. pH dependence (ΔS _1.5 ) = S _1.5 (developer C) -S _1.5
(Developer B) The smaller the value, the smaller the dependence of photographic sensitivity on the developer pH,
That is, the processing stability is high. Practically, △
It is more preferable that S _1.5 is 0.1 or less and closer to 0.

(4) As an index showing the contrast of the gamma image, fog of the characteristic curve
A point at + concentration 0.1 and a point at fog + concentration 3.0 were connected by a straight line, and the slope of this straight line was expressed as a gamma value. That is, gamma = [(3.0-0.1) / (log (concentration 3.0
(Exposure amount that gives .gamma.)-Log (exposure amount that gives a density of 0.1)], indicating that the larger the gamma value, the harder the photographic characteristics. Even when the development processing is performed with the developing solution C having a lower pH than the developing solution A, the gamma value is preferably 15 or more.

The evaluation results are summarized in Table 2.

[0115]

[Table 2]

<Results> When the hydrazine derivative of the present invention was used, unexpectedly the treatment stability was remarkably improved.

Example 2 The same test as in Example 1 was conducted using the photosensitive materials shown below. Similar to Example 1, excellent processing stability was exhibited only when the compound of the present invention was used. However, this sensitive material is 780 nm
It was exposed through an interference filter having a peak at.

<Preparation of Emulsion B> 1-liquid water 1-liter gelatin 20 g sodium chloride 1.5 g 1,3-dimethylimidazolidine-2-thione 20 mg sodium benzenesulfonate 8 mg 2-liquid water 400 ml silver nitrate 100 g 3-liquid water 400 ml sodium chloride 27.1 g Potassium bromide 21.0 g Ammonium hexachloroiridium (III) (0.001% aqueous solution) 20 ml Potassium hexachlorodium (III) (0.001% aqueous solution) 10 ml

Solution 1 and Solution 3 were added simultaneously to Solution 1 maintained at 40 ° C. and pH 4.5 over 15 minutes while stirring.
Core particles formed. Subsequently, the following liquids 4 and 5 were added over 15 minutes. Further, 0.15 g of potassium iodide was added to terminate the particle formation. 4th liquid 400ml Silver nitrate 100g 5th liquid 400ml Sodium chloride 27.1g Potassium bromide 21.0g

Thereafter, the resultant was washed with water by a flocculation method according to a conventional method, and 40 g of gelatin was added. pH
5.7, pAg was adjusted to 7.5, sodium thiosulfate 1.0 mg, chloroauric acid 4.0 mg, triphenylphosphine selenide 1.5 mg, sodium benzenethiosulfonate 8
mg and sodium benzenethiosulfinate 2 mg, and 55
Chemical sensitization was carried out at ℃ to obtain the optimum sensitivity. Further, 4-hydroxy-6-methyl-1,3,3a,
100 mg of 7-tetrazaindene, phenoxyethanol as a preservative, and finally a silver chloroiodobromide cubic emulsion containing 70 mol% of silver chloride and having an average particle diameter of 0.22 μm B
I got

<Preparation of coating sample> Sensitizing dye (2) was added to Emulsion B.
8.0 × 10 ⁻⁵ mol / mol Ag was added for spectral sensitization. Further, KBr 3.4 × 10 ⁻⁴ mol / mol Ag, compound (13) 2.0 × 10 ⁻⁴ mol / mol Ag, compound (14) 1.
0 × 10 ⁻³ mol / mol Ag, hydroquinone 2.0 × 1
0 ^-2 mol / mol Ag, citric acid 2.0 × 10 ^-3 mol / mol Ag, 1.5 × hydrazine derivative (compound of Table 3)
10 ^-4 mol / mol Ag, compound (15) 9.0 × 10 ^-4 mol / mol Ag, compound (16) 2.3 × 10 ^-4 mol / mol Ag, compound (17) 1.4 × 10 ⁻⁴ mol / mol Ag, 35 wt% polyethyl acrylate latex based on gelatin, 20 wt% based on gelatin, particle size 10 m
4 wt% of compound (18) with respect to μ colloidal silica and gelatin was added, and Ag 3.2 was added on the polyester support.
It was coated at 5 g / m ² and gelatin at 1.4 g / m ² . An upper protective layer and a lower protective layer having the following composition were applied thereon.

[0122]

[Table 3]

(Upper layer of protective layer) Gelatin 0.3 g / m ² Silica matting agent having an average of 3.5 μm 25 mg / m ² Compound (19) (gelatin dispersion) 20 mg / m ² Colloidal silica having a particle size of 10 to 20 μm 30 mg / m ² compound (20) 5 mg / m ² sodium dodecylbenzenesulfonate 20 mg / m ² compound (21) 20 mg / m ² (protective layer lower layer) gelatin 0.8 g / m ² compound (22) 20 mg / m ² compound (23 ) 7 mg / m ² 1,5-dihydroxy-2-benzaldoxime 10 mg / m ² polyethyl acrylate latex 150 mg / m ²

The support of the sample used in the present invention has a back layer and a conductive layer having the following compositions. (Back layer) Gelatin 3.0 g / m ² Sodium dodecylbenzenesulfonate 40 mg / m ² Compound (23) 60 mg / m ² Compound (24) 30 mg / m ² 1,3-Divinylsulfonyl-2-propanol 60 mg / m ² Polymethylmethacrylate fine particles (average particle size 6.5 μm) 6 mg / m ² Polymethylmethacrylate fine particles (average particle size 3.5 μm) 25 mg / m ² Sodium sulfate 150 mg / m ² Compound (18) 110 mg / m ² (conductive layer) Gelatin 0.1 g / m ² Sodium dodecylbenzene sulfonate 20 mg / m ² SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25 μ) 200 mg / m ²

[0125]

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[0126]

[Chemical formula 26]

Example 3 The same test as in Example 1 was conducted using the following sensitive materials. Similar to Example 1, excellent processing stability was exhibited only when the compound of the present invention was used. However, this sensitive material is 488 nm
It was exposed through an interference filter having a peak at. <Preparation of emulsion C> 1 liquid water 1 liter gelatin 20 g sodium chloride 2.0 g 1,3-dimethylimidazolidine-2-thione 20 mg sodium benzenesulfonate 8 mg 2 liquid water 400 ml silver nitrate 100 g 3 liquid water 400 ml sodium chloride 27.1 g Potassium bromide 21.0 g Ammonium hexachloroiridium (III) (0.001% aqueous solution) 20 ml Potassium hexachloroiridium (III) (0.001% aqueous solution) 7 ml

To the 1st liquid kept at 40 ° C. and pH 4.5, the 2nd liquid and the 3rd liquid were added simultaneously with stirring for 15 minutes,
Core particles formed. Subsequently, the following liquids 4 and 5 were added over 15 minutes. Further, 0.15 g of potassium iodide was added to terminate the particle formation. 4th liquid 400ml Silver nitrate 100g 5th liquid 400ml Sodium chloride 27.1g Potassium bromide 21.0g

Thereafter, the resultant was washed with water by a flocculation method according to a conventional method, and 40 g of gelatin was added. pH
5.7, pAg was adjusted to 7.5, sodium thiosulfate 1.0 mg, chloroauric acid 4.0 mg, triphenylphosphine selenide 1.5 mg, sodium benzenethiosulfonate 8
mg and sodium benzenethiosulfinate 2 mg, and 55
Chemical sensitization was carried out at ℃ to obtain the optimum sensitivity. Further, 4-hydroxy-6-methyl-1,3,3a,
7-Tetrazaindene 100 mg, phenoxyethanol as a preservative, and finally contains 70 mol% of silver chloride, and a silver chloroiodobromide cubic emulsion C having an average particle diameter of 0.23 μm.
I got

<Preparation of coating sample> Sensitizing dye (3) was added to Emulsion C.
2.0 × 10 ⁻⁴ mol / mol Ag, sensitizing dye (4) 7.0 ×
Spectral sensitization was carried out by adding 10 ⁻⁴ mol / mol Ag. Further, KBr 3.4 × 10 ⁻⁴ mol / mol Ag, compound (25)
5.0 × 10 ⁻⁴ mol / mol Ag, compound (26) 8.0 × 1
0 ^-4 mol / mol Ag, hydroquinone 1.2 × 10 ^-2 mol / mol Ag, hydrazine derivative (compound of Table 4) 1.8 × 10 ^-4 mol / mol Ag, compound (27) 3.5. ×
10 ^-4 mol / mol Ag, 30 wt% with respect to gelatin
% Polyethyl acrylate latex, 4% by weight of compound (28) with respect to 15% by weight of gelatin and 15 μm of colloidal silica having a particle size of 10 mμ, Ag 3.4 g / m ² , gelatin 1. It was applied so as to be 5 g / m ² . A protective layer upper layer and a protective layer lower layer having the following compositions were coated thereon, and a UL layer having the following composition was coated thereunder.

[0131]

[Table 4]

(Upper layer of protective layer) Gelatin 0.3 g / m ² Silica matting agent having an average of 3.5 μm 25 mg / m ² Compound (29) (gelatin dispersion) 20 mg / m ² Colloidal silica having a particle diameter of 10 to 20 μm 30 mg / m ² compound (30) 5 mg / m ² sodium dodecylbenzenesulfonate 20 mg / m ² compound (31) 20 mg / m ² (protective layer lower layer) gelatin 0.5 g / m ² compound (32) 15 mg / m ² 1,5 -Dihydroxy-2-benzaldoxime 10 mg / m ² polyethyl acrylate latex 250 mg / m ² (UL layer) gelatin 0.5 g / m ² polyethyl acrylate latex 150 mg / m ² compound (28) 40 mg / m ²

The support of the sample used in the present invention has a back layer and a conductive layer having the following composition. Back layer Gelatin 3.3 g / m ² sodium dodecylbenzene sulfonate 80 mg / m ² compound (33) 90 mg / m ² compound (34) 20 mg / m ² compound (35) 40 mg / m ² 1,3-divinylsulfonyl-2 -Propanol 60 mg / m ² Polymethylmethacrylate fine particles (average particle size 3.5 μm) 20 mg / m ² Compound (28) 120 mg / m ² Conductive layer Gelatin 0.1 g / m ² Sodium dodecylbenzenesulfonate 20 mg / m ² SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25μ) 200 mg / m ²

[0134]

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[0135]

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Example 4 The same test as in Example 1 was conducted using the following photosensitive materials. Similar to Example 1, excellent processing stability was exhibited only when the compound of the present invention was used. However, exposure was performed with tungsten light of 3200 ° K through a step wedge.

<Preparation of Emulsion D> 1 liquid water 1 liter gelatin 20 g sodium chloride 2.0 g 1,3-dimethylimidazolidine-2-thione 20 mg sodium benzenesulfonate 8 mg 2 liquid water 400 ml silver nitrate 100 g 3 liquid water 400 ml sodium chloride 21.9 g Potassium bromide 31.5 g Ammonium hexachloroiridium (III) (0.001% aqueous solution) 10 ml Potassium hexachlorodium (III) (0.001% aqueous solution) 5 ml

To the 1st liquid kept at 42 ° C. and pH 4.5, the 2nd liquid and the 3rd liquid were added simultaneously for 15 minutes while stirring,
Core particles formed. Subsequently, the following liquids 4 and 5 were added over 15 minutes. Further, 0.15 g of potassium iodide was added to terminate the particle formation. Fourth liquid 400ml Silver nitrate 100g Five liquid 400ml Sodium chloride 25.4g Potassium bromide 24.5g

Thereafter, it was washed with water by the flocculation method according to a conventional method, and 62 g of gelatin was added. pH
5.9, pAg was adjusted to 7.5, sodium thiosulfate 2.0 mg, chloroauric acid 8.0 mg, triphenylphosphine selenide 2.0 mg, sodium benzenethiosulfonate 4
mg, 1 mg of sodium benzenethiosulfinate, and add
Chemical sensitization was carried out at ℃ to obtain the optimum sensitivity. Further, 4-hydroxy-6-methyl-1,3,3a,
150 mg of 7-tetrazaindene, phenoxyethanol as a preservative, and finally containing 60 mol% of silver chloride, and a silver chloroiodobromide cubic emulsion D having an average particle diameter of 0.24 μm.
I got

<Preparation of coating sample> Sensitizing dye (5) was added to Emulsion D.
Spectral sensitization was carried out by adding 7.0 × 10 ⁻⁴ mol / mol Ag. Further, KBr 4.0 × 10 ⁻³ mol / mol Ag, compound (36) 2.5 × 10 ⁻⁴ mol / mol Ag, compound (37) 8.
0 × 10 ^-4 mol / mol Ag, hydroquinone 1.5 × 1
0 ^-2 mol / mol Ag, hydrazine derivative (compound of Table 5) 2.0 x 10 ^-4 mol / mol Ag, compound (38) 5.0 x 10 ^-4 mol / mol Ag, and further to gelatin. 40 wt% of polyethyl acrylate latex, 25 wt% of gelatin to 25 μm of colloidal silica having a particle size of 10 μm, and 4 wt% of compound (39) to gelatin,
Ag3.2g / m ² on a polyester support was coated to a gelatin 1.8 g / m ^2. An upper protective layer and a lower protective layer having the following composition were applied thereon.

[0141]

[Table 5]

(Upper layer of protective layer) Gelatin 0.3 g / m ² Silica matting agent having an average of 3.5 μm 35 mg / m ² Compound (40) (gelatin dispersion) 20 mg / m ² Colloidal silica having a particle size of 10 to 20 μm 30 mg / m ² compound (41) 5 mg / m ² sodium dodecylbenzenesulfonate 20 mg / m ² compound (42) 20 mg / m ²

(Lower Layer of Protective Layer) Gelatin 0.5 g / m ² compound (43) 10 mg / m ² compound (44) 50 mg / m ² compound (45) 20 mg / m ² 1,5-dihydroxy-2-benzaldoxime 10 mg / m ² polyethyl acrylate latex 250 mg / m ²

The support of the sample used in the present invention has a back layer and a back protective layer having the following compositions. (Back layer) Gelatin 2.5 g / m ² Sodium dodecylbenzenesulfonate 30 mg / m ² compound (46) 50 mg / m ² compound (47) 30 mg / m ² compound (48) 30 mg / m ² compound (49) 90 mg / m ² compound (39) 140 mg / m ²

(Back protective layer) Gelatin 1.0 g / m ^2, 1,3-divinylsulfonyl-2-propanol 20 mg / m ² Polymethylmethacrylate fine particles (average particle size 3.5 μm) 10 mg / m ² Sodium dodecylbenzenesulfonate 20 mg / m ²

[0146]

[Chemical 29]

[0147]

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Example 5 A light-sensitive material was prepared in the same manner as in the light-sensitive material formulation of Example 4 except that the upper layer of the protective layer was changed to the following formulation, and was tested by the method described in Example 1. Similar to Example 1, excellent processing stability was exhibited only when the compound of the present invention was used. However,
The exposure was performed with 3200 ° K tungsten light through a step wedge.

(Upper layer of protective layer) Gelatin 0.4 g / m ² Silica matting agent having an average of 3.5 μm 160 mg / m ² Compound (40) (gelatin dispersion) 40 mg / m ² Colloidal silica having a particle size of 10 to ²⁰ μm 30 mg / m ² compound (41) 5 mg / m ² sodium dodecylbenzenesulfonate 20 mg / m ² compound (42) 20 mg / m ²

Example 6 <Preparation of Emulsion E> 3 × 10 ⁻⁵ mol of sodium benzenethiosulfonate per ⁵ mol of sodium chloride and silver kept at 38 ° C., 5 × 10 ⁻³ mol of 4-hydroxy-6- PH including methyl-1,3,3a, 7-tetrazaindene =
An aqueous solution of sodium chloride containing 5 × 10 ^-5 mol of K ₂ Ru (NO) Cl ₅ per mol of silver in a 2.0% 1.5% gelatin aqueous solution was applied by the double jet method at a potential of 95 mV for 3 minutes 30. Simultaneously add half of the silver amount of the final grain in a second,
0.12 μm of core particles were prepared. Thereafter, an aqueous solution of silver nitrate and an aqueous solution of sodium chloride containing 5 × 10 ⁻⁵ mol of K ₂ Ru (NO) Cl ₅ per mol of silver were added in the same manner as above for 7 minutes, and a silver chloride cube having an average grain size of 0.13 μm was added. Particles were prepared. (Coefficient of variation: 12%) Thereafter, the resultant was washed with water by a flocculation method well known in the art to remove soluble salts, and then gelatin was added.
Compound-F and phenoxyethanol as preservatives in silver 1
After adding 60 mg each per mole, pH 5.5, pAg = 7.
To 5 ×, and 4 × 10 ^-5 mol of chloroauric acid, 1 × 10 ^-5 mol of selenium compound SE and 1 × 10 ⁵ mol per mol of silver.
^-5 mol of sodium thiosulfate was added, and the mixture was heated at 60 ° C for 60 minutes for chemical sensitization, and then 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added as a stabilizer to silver. 1 × 10 ⁻³ mol was added per mol (as final particles, pH = 5.7, pAg = 7.5, Ru = 5 × 10 5).
^This resulted in silver chloride containing ^-5 mol / Ag mol. )

[0151]

[Chemical 31]

<Preparation of Coating Sample> (Silver Halide Emulsion Layer) The following compounds were added to Emulsion E to give a gelatin coating amount of 0.9 g on a support described below including an undercoat layer.
/ M ^2, the coating amount of silver coated with silver halide emulsion layer as a 2.75 g / m ^2. N-oleyl-N-methyltaurine sodium salt 19 mg / m ² Hydrazine derivative shown in Table 3 15 mg / m ² Nucleation accelerator Z 20 mg / m ² 3- (5-mercaptotetrazole) -benzenesulfonic acid sodium 11 mg / m ² Compound A 13 mg / m ² ascorbic acid 1 mg / m ² Compound B 15 mg / m ² Compound C 70 mg / m ² acetic acid Amount with which the film surface pH becomes 5.2 to 6.0 Compound D 950 mg / m ² Riborane-1400 (Lion Oil and fat) 47 mg / m ² Compound E (hardener) Amount that makes the swelling rate in water 80%

The following compounds were used as comparative examples of the hydrazine derivative of the present invention.

[0154]

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[0155]

[Table 6]

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

(Emulsion Protecting Lower Layer) The following compounds were added to a gelatin aqueous solution and coated so that the gelatin coating amount would be 0.8 g / m ² . Gelatin (Ca ⁺⁺ content 2700 ppm) 0.8 g / m ² compound F 1 mg / m ² 1,5-dihydroxy-2-benzaldoxime 14 mg / m ² C ₂ H ₅ SO ₂ SNa 3 mg / m ² compound C 3 mg / M ² p-dodecylbenzene sulfonate sodium 7 mg / m ²

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

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

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

(Back layer) The following compounds were added to a gelatin aqueous solution and coated so that the coating amount of gelatin would be 1.94 g / m ² . Gelatin (Ca ⁺⁺ content 30ppm) 1.94g / m ² of polymethyl methacrylate particles (average particle size 4.7μ) 7mg / m ² Compound H 233 mg / m ² Compound I 21 mg / m ² Compound G 146 mg / m ² Compound F 3mg / m ² p- sodium dodecylbenzenesulfonate 68 mg / m ² dihexyl -α- sulfosuccinates sodium _{^{21mg / m 2 C 8 F 17}} SO 3 Li 4mg / m 2 N- perfluorooctane sulfonyl -N- propyl glycine amount Potajiumu 6 mg / m ² sodium sulfate 177 mg / m ² compound -E (hardener) swelling rate in water is 90%

(Support, Undercoat Layer) Biaxially stretched polyethylene terephthalate support (thickness: 100 μm) was coated with the first and second undercoat layers having the following compositions on both sides. (Undercoat first layer) Core-shell type vinylidene chloride copolymer 15 g 2,4-dichloro-6-hydroxy-s-triazine 0.25 g Polystyrene fine particles (average particle size 3 μ) 0.05 g Colloidal silica (Snowtex) ZL; particle size 70 to 100 μm, manufactured by Nissan Kagaku Co., Ltd.) 0.12 g Water added 100 g Further, 10 wt% KOH was added, and the coating solution adjusted to pH = 6 was dried at a drying temperature of 180 ° C. for 2 minutes. Film thickness is 0.9
It was applied so that it became μ.

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

[0164]

[Chemical 33]

[0165]

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[0166]

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[0167]

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

<Drying conditions> After setting, the product was dried with a drying air of 30 ° C. until the weight ratio of water / gelatin reached 800%, and 8
Dry 200 to 200% with dry air at 35 ° C and 30%, apply air as it is, and after 30 seconds from when the surface temperature reaches 34 ° C (assuming the end of drying), dry for 1 minute at 48 ° C and 2% air. did. At this time, the drying time is 50 seconds from the start of drying to a water / gelatin ratio of 800% and 35 from 800 to 200%.
Seconds, 5% from 200% to the end of drying.

This photosensitive material was wound up at 40 ° C. at 23 ° C., then cut in the same environment and placed in a barrier bag conditioned for 6 hours to obtain 4 pieces.
After humidifying at 0 ° C. 10% for 8 hours, the sample was sealed with cardboard conditioned at 23 ° C. 40% for 2 hours to prepare a sample. When the humidity inside the barrier bag was measured, it was 40%.

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

The gamma and pH dependences were evaluated in the same manner as in Example 1. The evaluation results are summarized in Table 7.

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[Table 7]

<Results> When the hydrazine derivative of the present invention was used, a bright room reversal light-sensitive material having excellent processing stability was obtained.

Example 7 A developer D having the following composition whose storage form is solid (developing solution composition is the same as the developing solution A), a developing solution E and a fixing solution B (fixing solution composition is the same as the fixing solution A) are prepared. did.

<Developer D> The following storage form was used as a working solution (pH 9.7) by adding water to a solid developer to make it 1 liter. The composition of the solid developer is shown below. Sodium sulfite (bulk powder) 2 g Potassium carbonate (bulk powder) 33 g Sodium carbonate (bulk powder) 28 g Sodium hydrogencarbonate (bulk powder) 25 g The following are collectively briquetted. Diethylenetriamine-5-acetic acid 2 g Sodium erythorbate 45 g N-methyl-p-aminophenol 7.5 g KBr 2 g 5-methylbenzotriazole 0.004 g 1-phenyl-5-mercaptotetrazole 0.02 g

<Developer E> The composition of the solid developer is shown below. Sodium hydroxide (beads) 99.5% 11.5 g Potassium sulfite (bulk powder) 63 g Sodium sulfite (bulk powder) 46 g Potassium carbonate 62 g Hydroquinone (briquette) 40 g The following are collectively briquetted. Diethylenetriamine / 5-acetic acid 2 g 5-Methylbenzotriazole 0.35 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1.5 g 2-Mercaptobenzimidazole-5-sulfonic acid sodium salt 0.3 g 3- (5 -Mercaptotetrazol-1-yl) benzenesulfonic acid sodium 0.1 g sodium erythorbate 6 g potassium bromide 6.6 g This is dissolved in water to 1 liter. pH 10.65

Here, in the form of raw materials, the raw powder was used as a general industrial product, and the alkali metal salt beads used were commercially available products. If the raw material is briquette, it is pressed and compressed using a briquetting machine to give an irregular length of 4 to 6
A rugby ball shape having a size of about mm was prepared, crushed and used. For minor components, each component was blended before briquetting. 10 liters of the above treatment agent was filled in a foldable container made of high-density polyethylene,
The outlet was sealed with an aluminum seal. For dissolution and replenishment, Japanese Patent Application Nos. 7-235499 and 7-23549
The dissolution replenishing device with an automatic opening mechanism disclosed in No. 8 was used.

<Fixing Solution B> The composition of the solid fixing agent is shown below. Agent A (solid) Ammonium thiosulfate (compact) 125.0 g Anhydrous sodium thiosulfate (bulk powder) 19.0 g Sodium metabisulfite (bulk powder) 18.0 g Anhydrous sodium acetate (bulk powder) 42.0 g Agent B (liquid) Ethylenediamine ・ tetraacetic acid ・ 2Na ・ dihydrate 0.03 g Anhydrous citric acid 3.7 g Sodium gluconate 1.7 g Aluminum sulfate 8.4 g Sulfuric acid 2.1 g Dissolve in water to make 50 ml. Agent A and Agent B were dissolved in water to make 1 liter. pH 4.8

Ammonium thiosulfate (compact) was obtained by compressing flakes prepared by the spray-drying method with a roller compactor and crushing the chips into irregular shaped chips of about 4 to 6 mm, and blending them with anhydrous sodium thiosulfate. For other bulk powders, general industrial products were used. 10 liters of both Agent A and Agent B were filled in a foldable container made of high-density polyethylene, and the outlet of Agent A was sealed with an aluminum seal. The mouth of the agent B container was sealed with a screw cap. Patent application Hei 7 for dissolution and replenishment
A dissolution replenishing device having an automatic opening mechanism disclosed in Japanese Patent Application No. 235499 and Japanese Patent Application No. 7-235498 was used.

In Examples 1, 2, 3, 4, 5, and 6,
Similar results were obtained by using the developer D or the developer E instead of the developer A and the fixer B instead of the fixer A.

Claims (2)

[Claims] 1. A silver halide photographic light-sensitive material comprising at least one compound represented by the following general formula (IA) or general formula (IB). General formula (IA): General formula (IB): In the formula, A represents an aryl group or an unsaturated heterocycle,
R ₁ , R ₂ , R ₃ and R ₄ are hydrogen atom, halogen atom, alkyl group, alkenyl group, aryl group, alkoxy group,
It represents an aryloxy group, an acyl group, a cyano group, a carbamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. However, R ₄ may be a carboxy group. 2. The silver halide photographic light-sensitive material according to claim 1, wherein in the general formulas (IA) and (IB), A is a compound represented by the general formula (II). material. General formula (II): In the formula, B represents an aryl group, an alkyl group, a saturated or unsaturated heterocycle, and L represents a —SO ₂ NR5— group or —NR5SO ₂ NR5.
-Group, -CONR5-group, -NR5CONR5-group, -NR5CO- group,
And R5 represents a hydrogen atom, an alkyl group or an aryl group.