JP3108245B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material and, more particularly, to a super-high contrast silver halide photographic material used for photolithography.

[0002]

2. Description of the Related Art In a squirrel developing system, it is very difficult to keep the activity of a developing solution constant, and the instability of image formation due to this is a great disadvantage. Therefore, there is a demand for an image forming system which develops with a processing solution having good storage stability and obtains ultra-high contrast photographic characteristics. One of them is U.S. Pat. Nos. 4,166,742 and 4,168,977. ,
Specific acylhydrazine compounds as shown in JP-A-4,221,857, JP-A-4,224,401, JP-A-4,243,739, JP-A-4,272,606 and JP-A-4,311,781 Is added to a surface latent image type silver halide photographic light-sensitive material, which is treated with a developing solution having a pH of 11.0 to 12.3 and containing a sulfurous acid preservative of 0.15 mol / L or more and having good storage stability. , Γ of more than 10 have been proposed. However, changes in photographic performance such as sensitivity and Dmax due to fatigue of the developer cannot be ignored, and various attempts have been made to improve them. On the other hand, JP-A-62-247351 and 6
Nos. 2-270948, 63-249838, JP-A-3-102343, JP-A-3-152528, Japanese Patent Application No. 3
No. -128212, No. 3-246493, No. 4-26
Nos. 7332 and 4-267333 disclose the use of hydrazine compounds having different structures or properties in combination. However, none of these methods can sufficiently reduce the change in photographic performance due to fatigue of the developer.
Further improvements were needed.

[0003]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a photographic material for plate making which has a high contrast and a small change in photographic performance due to fatigue of a developer.

[0004]

An object of the present invention, in order to solve the problem] has at least one silver halide emulsion layer on a support, the general formula (1) or emulsion layers and other hydrophilic colloid layers Table In a silver halide photographic light-sensitive material containing at least one hydrazine derivative, the emulsion layer or another hydrophilic colloid layer contains at least one hydrazine derivative represented by the general formula (N). This has been attained by a silver halide photographic light-sensitive material. General formula (1)

[0005]

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Wherein X ¹ is an alkyl group, an alkoxy group,
Represents a substituted amino group or an alkylthio group. Y ¹ represents an alkoxy group, an aryloxy group , an alkylthio group or an arylthio group, and R ¹ represents an alkylene group.

[0007]

General formula (N)

[0009]

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[0010] formula, R ₁ represents an aliphatic group or an aromatic group, R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a hydrazino group, mosquitoes Rubamoiru group or an oxycarbonyl Represents a group,
G ₁ is a —CO— group, a —SO ₂ — group, a —SO— group, a —PO (R ₂ ) — group, a —CO-CO
-Represents a group, a thiocarbonyl group or an iminomethylene group, wherein A ₁ and A ₂ are both a hydrogen atom or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted arylsulfonyl group,
Or a substituted or unsubstituted acyl group.

The compound of the present invention will be described in detail.
Formula (1) in the alkoxy group represented by an alkyl group and X ¹ is represented by X ^1, the alkyl group contained in the alkylthio group is a linear, branched or cyclic alkyl group, representative examples Ethyl group, butyl group,
Examples thereof include an isopropyl group, an isobutyl group, a t-amyl group, a cyclohexyl group and the like. Examples of the substituent of the substituted amino group represented by X ¹ include an alkyl group and an aryl group,
Acyl group (R-CO- group, R is alkyl or aryl), alkoxy or aryloxycarbonyl group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted hydrazinocarbonyl group, alkyl or arylsulfonyl group, substituted or unsubstituted A substituted sulfamoyl group and the like are also included, and in the latter case, a carbonamido group, urethane group, ureido group, semicarbazide group, sulfonamido group and the like are formed. X ¹ may be substituted such as a 2-methoxyethoxy group and a 3,3-bis (2-hydroxyethyl) ureido group. In X ¹ , the total number of carbon atoms including the substituent is preferably 1 to 6, more preferably 2 to 6. 3 to 6 are particularly preferred. X ¹ is preferably a substituted amino group, and most preferably an amino group substituted to form a carboxamide group, a ureido group, or a sulfonamide group. The substitution position on the phenyl group of X ¹ may be any of the ortho, meta and para positions of the hydrazine moiety, but is preferably the meta or para position, and most preferably the para position. The phenylene group connecting X ¹ and the hydrazine moiety may be substituted, but these substituents and X
The total number of carbon atoms contained in ¹ is preferably 1 to 6.

The alkyl group contained in the alkoxy group or alkylthio group represented by Y ¹ in the general formula (1) is a linear, branched or cyclic alkyl group, and typical examples include a methyl group and a dodecyl group. , Isobutyl group, 2-
And an ethylhexyl group. The aryl group represented by the aryloxy group or the arylthio group represented by Y ¹ is preferably a monocyclic or bicyclic unsaturated carbocyclic group or unsaturated heterocyclic group. Representative examples include a benzene ring, a naphthalene ring, a pyridine ring, and a quinoline ring . As Y ¹ , an alkoxy group and an aryloxy group are preferable, and an aryloxy group is most preferable. The group represented by Y ¹ may be substituted, and typical substituents include, for example, an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group, a ureido group, a urethane group, Aryloxy, sulfamoyl, carbamoyl, alkyl or arylthio, alkyl or arylsulfonyl, alkyl or arylsulfinyl, hydroxy, halogen, cyano, sulfo, aryloxycarbonyl, acyl, alkoxycarbonyl , An acyloxy group, a carbonamide group, a sulfonamide group, a carboxyl group, a phosphoric acid amide group, a diacylamino group, an imide group, and the like. Preferred substituents are an alkyl group (preferably having 1 to 20 carbon atoms), an aralkyl group (preferably having 7 to 30 carbon atoms), an alkoxy group (preferably having 1 to 20 carbon atoms), and a substituted amino group (Preferably an amino group substituted with an alkyl group having 1 to 20 carbon atoms), an acylamino group (preferably having 2 to 3 carbon atoms)
0), a sulfonamide group (preferably having 1 to 30 carbon atoms), a ureido group (preferably having 1 to 30 carbon atoms), a phosphoric amide group (preferably having 1 to 30 carbon atoms) Things). These groups may be further substituted.

The alkylene group represented by R ¹ in the general formula (1) may be substituted, and typical substituents include those listed as examples of the substituent of Y ¹ . R ¹ is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 8 carbon atoms. Most preferably, R ¹ is a substituted or unsubstituted methylene group. The total number of carbon atoms contained in Y ¹ and R ¹ is preferably from 6 to 30, and particularly preferably from 8 to 20.

[0014]

[0015] Although listed compounds used in the present invention the following the present invention is not limited thereto.

[0016]

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[0017]

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[0018]

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[0019]

The hydrazine compounds of the present invention are described, for example, in JP-A-61-213,847 and JP-A-62-260,153.
No. 4,684,604, JP-A-1-26
9,936, U.S. Pat. Nos. 3,379,529, 3,620,746, 4,377,634, 4,332,878, and JP-A-49-129,536.
Nos. 56-153,336 and 56-153,34
No. 2, U.S. Pat. Nos. 4,988,604 and 4,99
No. 4,365, for example. A specific synthesis example is shown below.

Synthesis Example: Synthesis of Exemplified Compound 1-9 To a solution of imidazole (157 g) in tetrahydrofuran (1.5 L) was added, under a nitrogen atmosphere, a cooling raw material A (300 g) at 0 ° C. while stirring. After the reaction solution was returned to room temperature and stirred for 2 hours, a solution of p-nitrophenylhydrazine (153 g) dissolved in THF (200 ml) was added. The reaction solution was allowed to stand overnight, then poured into water (3 L), and the precipitated crystals were collected by filtration, washed with water and acetonitrile, and dried under reduced pressure to obtain Intermediate A (346 g).

Reduced iron (150 g) was gradually added to a mixture of intermediate A (150 g), ammonium chloride (15 g), isopropyl alcohol (1.5 liter) and water (150 ml) heated to reflux under a nitrogen atmosphere. did. 1
After heating under reflux for an hour, the mixture was filtered using celite to remove insolubles. The obtained filtrate was cooled and stirred, and the precipitated crystals were collected by filtration and dried under reduced pressure to obtain Intermediate B (98 g).

[0023]

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To a mixed solution of Intermediate B (18.0 g) and dimethylacetamide (100 ml), the mixture was cooled to 0 ° C. and stirred.
Triethylamine (8.0 ml) was added, followed by N,
N-Dimethylcarbamoyl chloride (5.9 g) was added dropwise. The reaction was returned to room temperature and left overnight. After completion of the reaction, the reaction solution was poured into a 0.5N hydrochloric acid aqueous solution, extracted with ethyl acetate, washed with saturated saline, dried over anhydrous magnesium sulfate, and the ethyl acetate was distilled off and isolated by silica gel chromatography. Purification gave the desired product (9.2 g).
The chemical structure was confirmed by the nmr spectrum and the ir spectrum. mp 138-139 ° C

[0025] with a hydrazine derivative represented by the general formula (1) in the present invention, represented by general formula (N), <br/> the general formula (1) is used in combination with hydrazine compounds that are not included.

In the general formula (N), the aliphatic group represented by R ₁ preferably has 1 to 30 carbon atoms, particularly a straight-chain, branched or cyclic alkyl group having 1 to 20 carbon atoms. is there. Here, the branched alkyl group may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. This alkyl group is
It may have a substituent such as an aryl group, an alkoxy group, a sulfoxy group, a sulfonamide group, and a carbonamide group.

The aromatic group represented by R ₁ in the general formula (N) is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a heteroaryl group. For example, benzene ring, naphthalene ring, pyridine ring,
There are a pyrimidine ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, a benzothiazole ring and the like, and among them, those containing a benzene ring are preferable.

Particularly preferred as R ₁ is an aryl group. The aryl group or unsaturated heterocyclic group represented by R ₁ may be substituted, and typical examples of the substituent include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group, and a ureido. Group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkyl or arylthio group,
Alkyl or aryl sulfonyl group, alkyl or aryl sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, carbonamide group, sulfonamide group, carboxyl group, Phosphoric acid amide group, diacylamino group, imide group,
R ₂ —NH—CO—NR ₂ —CO— groups and the like are mentioned, and preferred substituents are linear, branched or cyclic alkyl groups (preferably having 1 to 20 carbon atoms), aralkyl groups (preferably alkyl groups). A monocyclic or bicyclic C1-C3 moiety, an alkoxy group (preferably having 1-20 carbon atoms), or a substituted amino group (preferably an alkyl group having 1-20 carbon atoms) An amino group), an acylamino group (preferably having 2 to 30 carbon atoms), a sulfonamide group (preferably having 1 to 30 carbon atoms), a ureido group (preferably having 1 to 30 carbon atoms), And a phosphoric amide group (preferably having 1 to 30 carbon atoms).

The alkyl group represented by R ₂ in the general formula (N) is preferably an alkyl group having 1 to 4 carbon atoms, for example, a halogen atom, a hydroxyl group, a cyano group,
Carboxy group, sulfo group, alkoxy group, phenyl group,
A substituent such as an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkyl or arylsulfonyl group, a sulfamoyl group, a nitro group, a heteroaromatic ring group, an R ₁ -NA ₁ -NA ₂ -G ₁ -group; And these groups may be further substituted.

The aryl group is preferably a monocyclic or bicyclic aryl group, for example, one containing a benzene ring. The aryl group may be substituted, and examples of the substituent are the same as those in the case of the alkyl group. The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, and may be substituted with a halogen atom, an aryl group, or the like. The aryloxy group is preferably a monocyclic one, and the substituent includes a halogen atom. The amino group is preferably an unsubstituted amino group, an alkylamino group having 1 to 10 carbon atoms, or an arylamino group, and may be substituted with an alkyl group, a halogen atom, a cyano group, a nitro group, a carboxy group, or the like. The carbamoyl group is preferably an unsubstituted carbamoyl group, an alkylcarbamoyl group having 1 to 10 carbon atoms, or an arylcarbamoyl group, and may be substituted with an alkyl group, a halogen atom, a cyano group, a carboxy group, or the like. The oxycarbonyl group is preferably an alkoxycarbonyl group having 1 to 10 carbon atoms or an aryloxycarbonyl group, and may be substituted with an alkyl group, a halogen atom, a cyano group, a nitro group, or the like.

Among the groups represented by R ₂ , when G ₁ is a —CO— group, a hydrogen atom, an alkyl group (for example, methyl, trifluoromethyl, 3-hydroxypropyl, 3 A methanesulfonamidopropyl group, a phenylsulfonylmethyl group, an aralkyl group (eg, an o-hydroxybenzyl group), an aryl group (eg, a phenyl group, a 3,5-dichlorophenyl group, an o-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, 2-hydroxymethylphenyl group, etc.), and particularly preferably a hydrogen atom.

When G ₁ is a —SO ₂ — group, R ₂ is an alkyl group (eg, a methyl group), an aralkyl group (eg, an o-hydroxybenzyl group), an aryl group (eg, a phenyl group). Or a substituted amino group (eg, a dimethylamino group). G ₁ is -S
In the case of an O- group, preferred R ₂ include a cyanobenzyl group and a methylthiobenzyl group, and when G ₁ is a —PO (R ₂ )-group, R ₂ represents a methoxy group, an ethoxy group, a butoxy group, Phenoxy groups and phenyl groups are preferred, and phenoxy groups are particularly preferred. When G ₁ is an N-substituted or unsubstituted iminomethylene group, preferred R ₂ is a methyl group, an ethyl group, or a substituted or unsubstituted phenyl group. As the substituent for R _2, the substituents listed for R ₁ can also be applied. G in the general formula (N) is most preferably a -CO- group.

R ₂ is such that it causes a cyclization reaction that splits the G ₁ -R ₂ moiety from the remainder to form a cyclic structure containing atoms of the -GR ₂ moiety. More specifically, it can be represented by the general formula (a). In the general formula (a) -R ₃ -Z ₁ formula, Z ₁ is nucleophilically attacked to G _1, G ₁ -R ₃ -
A group capable of Z ₁ portion was split from the remaining molecule, R ₃ is one obtained by removing one hydrogen atom from R _2, Z ₁ is a nucleophilic attack to G _1, in G _1, R _3, Z ₁ A cyclic structure can be generated.

More specifically, Z ₁ easily undergoes a nucleophilic reaction with G ₁ when the hydrazine compound of the general formula (I) produces the next reaction intermediate by oxidation or the like, and R ₁ -N = N'- G ₁ -R ₃ -Z ₁ R ₁ -N = A group capable of splitting an N group from G ₁ , specifically, OH, SH or NHR ₄ (R ₄ is a hydrogen atom, an alkyl group, an aryl group,- COR ₅ , or —SO ₂ R ₅ ,
₅ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, etc., or a functional group which directly reacts with G ₁ such as COOH (here, OH, SH, NH
R ₄ and —COOH may be temporarily protected to generate these groups by hydrolysis of an alkali or the like), or —CO—R ₆ , —C (CNR ₇ ) —R ₆ (R ₆ , R ₇ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group) and reacts with G ₁ by reacting with a nucleophilic agent such as a hydroxyl ion or a sulfite ion. May be a functional group capable of G ₁ ,
The ring formed by R ₃ and Z ₁ is preferably a 5- or 6-membered ring.

Among the compounds represented by the general formula (a), preferred are the compounds represented by the general formulas (b) and (c). General formula (b)

[0036]

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[0037] In the formula, R _b ¹ ~R _b ⁴ is a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms), (ones preferably having 2 to 12 carbon atoms) alkenyl group, an aryl group (preferably And the like, and may be the same or different. B is an atom necessary to complete a 5- or 6-membered ring which may have a substituent, and m and n
Is 0 or 1, and (n + m) is 1 or 2.
The 5- or 6-membered ring formed by B includes, for example, a cyclohexene ring, a cyclopentene ring, a benzene ring, a naphthalene ring, a pyridine ring, a quinoline ring and the like. Z ₁ has the same meaning as in formula (a). General formula (c)

[0038]

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In the formula, R _c ¹ and R _c ² represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a halogen atom, and may be the same or different. R _c ³ represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group. p represents an integer value of 0 to 2, and q represents 1 to 4.
R _c ¹ , R _c ² and R _c ³ may combine with each other to form a ring as long as Z ₁ is capable of intramolecular nucleophilic attack on C ₁ . R _c ¹ and R _c ² are preferably a hydrogen atom, a halogen atom, or an alkyl group, and R _c ³ is preferably an alkyl group or an aryl group. q preferably represents 1-3, p is 1 or 2 when q is 1, p is 0 or 1 when q is 2, p is 0 or 1 when q is 3, and q is 2 Or when 3 is present (CR _c
¹ R _c ² ) may be the same or different. Z ₁ has the same meaning as in formula (a).

A ₁ and A ₂ are each a hydrogen atom or an alkylsulfur or arylsulfonyl group having 20 or less carbon atoms (preferably a phenylsulfonyl group or a substituent such that the sum of the substituent constants of Hammett is -0.5 or more. A phenylsulfonyl group), an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or a benzoyl group substituted so that the sum of Hammett's substituent constants is -0.5 or more; or a linear, branched, or cyclic group Unsubstituted and substituted aliphatic acyl groups (for example, examples of the substituent include a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxyl group, a carboxy group, and a sulfonic acid group). A ₁ , A
₂ is most preferably a hydrogen atom.

R ₁ or R _{2 in} the formula (N) may have a ballast group or a polymer commonly used in immobile photographic additives such as couplers incorporated therein. The ballast group is a group having a carbon number of 8 or more, which is relatively inert to photographic properties. For example, the ballast group is selected from an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group, and the like. Can be. As the polymer, for example, JP-A-1-100
No. 530.

R ₁ or R _{2 in} the general formula (N) may have a group in which a group that enhances adsorption to the surface of the silver halide grain is incorporated. Examples of such adsorbing groups include thiourea groups, heterocyclic thioamide groups, mercapto heterocyclic groups, and triazoles in U.S. Patent Nos. 4,385,108 and 4,459,347, and JP-A-59-195,233.
Nos. 59-200, 231 and 59-201, 04
No. 5, 59-201, 046, 59-201, 0
No. 47, 59-201, 048, 59-201,
No. 049, JP-A Nos. 61-170,733 and 61-2.
70,744, 62-948, 63-234,
No. 244, No. 63-234, No. 245, No. 63-23
4,246.

Specific examples of the compound represented by formula (N) are shown below. However, the present invention is not limited to the following compounds.

[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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As the hydrazine derivative used in the present invention, in addition to the above, RESEARCHDISCLOSURE Item 2
3516 (November 1983, p. 346) and references cited therein, as well as U.S. Pat. No. 4,080,207.
No. 4,269,929, 4,276,364
Nos. 4,278,748 and 4,385,108
Nos. 4,459,347 and 4,560,638
No. 4,478,928, British Patent 2,011,3
91B, JP-A-60-179834, JP-A-62-27
Nos. 0,948, 63-29,751, 61-17
Nos. 0,733, 61-270,744 and 62-9
No. 48, EP 217,310 or US 4,68
No. 6,167, JP-A-62-178,246, 63-63
-32,538, 63-104,047, 63
-121,838, 63-129,337, 6
3-223,744, 63-234,244, 63-234,245, 63-234,246,
Nos. 63-294,552 and 63-306,438
No., JP-A Nos. 1-100,530 and 1-105,94
No. 1, No. 1-105,943, JP-A-64-10,2
No. 33, JP-A-1-90,439, Japanese Patent Application No. 63-10 / 1988.
No. 5,682, No. 63-114, No. 118, No. 63-1
Nos. 10,051, 63-114,119, 63-
Nos. 116, 239, 63-147, 339, 63
-179,760, 63-229,163, Japanese Patent Application Nos. 1-18,377, 1-18,378, 1-
Nos. 18,379, 1-15,755, 1-16,
No. 814, No. 1-40,792, No. 1-42,615
No. 1-42,616, 1-123, 693,
Those described in JP-A-1-126,284 can be used.

In the present invention, the amount of the hydrazine derivative to be added is 1 × 10 5 per mole of silver halide, based on the total amount of the compound of the general formula (1) and the compound of the general formula (N).
^-6 mol to 5 × 10 ^-2 mol is preferable,
In particular, the range of 1 × 10 ⁻⁵ mol to 2 × 10 ⁻² mol is a preferable addition amount. The compound of the general formula (N) has the general formula
1: 100 to 100: molar ratio to the compound of (1)
1, preferably in a ratio of 1:20 to 20: 1.

The hydrazine derivative of the present invention can be prepared by using a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methylcell It can be used by dissolving it in Solve or the like.

Further, by a well-known emulsification and dispersion method, an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, or an auxiliary solvent such as ethyl acetate or cyclohexanone is used for dissolution and mechanical dissolution. An emulsified dispersion can be prepared and used. Alternatively, the powder of the hydrazine derivative can be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method and used.

There are no particular restrictions on the various additives used in the light-sensitive material of the present invention, the development processing method and the like, and for example, those described in the following places can be preferably used. Item The relevant place 1) Nucleation accelerator JP-A-2-103536, page 9, upper right column, line 13 to page 16, upper left column, line 10, general formulas (II-m) to (II-p) ) And compound examples II-1 to II-22 and compounds described in JP-A-1-179939. 2) Silver halide emulsion and JP-A-2-97937, page 20, lower right column, line 12 to production thereof, page 21 lower left column, line 14, JP-A-2-12236, page 7, right upper column, 19 The selenium sensitization method described from line 12 to line 12 in the lower left column of page 8, and Japanese Patent Application No. 3-189532. 3) Spectral sensitizing dyes JP-A-2-12236, page 8, lower left column, line 13 to right lower column, line 4, JP-A-2-103536, page 16, lower right column, line 3 to page 17, lower left Column 20, line 20. Further, spectral sensitizing dyes described in JP-A-1-112235, JP-A-2-124560, JP-A-3-7928, Japanese Patent Application Nos. 3-189532 and 3-4111064. 4) Surfactant JP-A-2-122363, page 9, upper right column, line 7 to right lower column, line 7, and JP-A-2-854424, page 2, lower left column, line 13 to page 4, right Line 18 in the bottom column. 5) Antifoggants JP-A-2-103536, page 17, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, lines 1 to 5, furthermore, JP-A 1-237538 Thiosulfinic acid compounds described in the gazette. 6) Polymer latex JP-A-2-103536, page 18, lower left column, lines 12 to 20. 7) Compound having an acid group JP-A-2-103536, page 18, lower left column, line 6 to page 19, upper left column, line 1. 8) Matting agent, slip agent, JP-A-2-103536, page 19, upper left column, line 15 to plasticizer, page 19, upper right column, line 15; 9) Hardener From page 5, right upper column, line 5 to page 17, JP-A-2-103536. 10) Dyes Dyes in lines 1 to 18 of the lower right column on page 17 of JP-A-2-103536, solid dyes described in JP-A-2-94638 and JP-A-3-185773. 11) Binder JP-A 2-18542, page 3, lower right column, lines 1 to 20. 12) Black potting inhibitor A compound described in US Pat. No. 4,956,257 and JP-A-1-18832. 13) Redox compounds The compounds represented by the general formula (I) (especially compounds 1 to 50) in JP-A-2-301743 and the compounds represented by the general formulas (3 to 20) described in JP-A-3-174143, pp. 3-20. R-1), (R-2), (R-3), compound examples 1 to 75, and compounds described in Japanese Patent Application Nos. 3-69466 and 3-15648.14) Monomethine compound Compounds of the general formula (II) of JP-A-287532 (especially compound examples II-1 to II-26). 15) Dihydroxybenze Compounds described in JP-A-3-39948, page 11, upper left column to page 12, lower left column, and EP452772A. 16) Developing solution and developing method JP-A-2-103536, page 19, upper right column, line 16 to page 21, upper left column, line 8

[0065]

Examples Example 1 (Developer solution formulation) Hydroquinone 25.0 g 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 0.5 g Sodium hydroxide 10.0 g Potassium sulfite 60.0 g Diethylenetriaminepentaacetic acid 2 0.0 g 2,3,5,6,7,8-hexahydro-2-thioxo-4- (1H) -quinazolinone 0.05 g potassium bromide 3.0 g 5-methylbenzotriazole 0.1 g 2-mercaptobenzimidazole- 0.15 g of 5-sulfonic acid Sodium 3- (5-mercaptotetrazole) benzenesulfonate 0.2 g 11.0 g of sodium carbonate Add water to adjust to 1 liter pH 10.4

(Preparation of emulsion) 0.13 M aqueous silver nitrate solution and (NH ₄ ) ₃ Rh equivalent to 1 × 10 ⁻⁷ mol per mol of silver
An aqueous solution of a halogen salt containing 0.06 M potassium bromide and 0.09 M sodium chloride containing Cl ₆ was added to a gelatin aqueous solution containing sodium chloride and 1,3-dimethyl-2-imidazolidinethione at 38 ° C. while stirring. At 12
The mixture was added by a double jet method for one minute to obtain silver chlorobromide particles having an average particle size of 0.15 μm and a silver chloride content of 70 mol%, thereby forming nuclei. Subsequently, 0.
A silver salt aqueous solution containing 87M silver nitrate aqueous solution, 0.26M potassium bromide and 0.65M sodium chloride was added over 20 minutes by a double jet method.

Thereafter, 1 × 10 ⁻³ mol of a KI solution was added to perform conversion, washed with water by a flocculation method according to a conventional method, and 40 g of gelatin was added.
5, adjusted to a pAg of 7.5, further added 5 mg of sodium thiosulfate and 8 mg of chloroauric acid per 1 mol of silver, heated at 60 ° C. for 60 minutes, subjected to a chemical sensitization treatment, and added 4 mg of a stabilizer.
150 mg of -hydroxy-6-methyl-1,3,3a, 7-tetrazaindene were added. The obtained grains were cubic silver chlorobromide grains having an average grain size of 0.27 μm and a silver chloride content of 70 mol%. (Coefficient of variation 10%).

(Preparation of Coated Sample) The hydrazine derivative of the present invention was added to the above emulsion as shown in Table 1. further,
The compound of the following structural formula (S) was converted to 3.4 × 1 per mole of silver.
^0-4 mol, 2 × 10 ^-4 mol of 1-phenol-5-mercaptotetrazole, 5 × 10 ^-4 mol of short-wave cyanine dye represented by the following structural formula (a), water-soluble latex represented by (b) (200 mg / m ² ), a dispersion of polyethyl acrylate (200 mg / m ² ), and 1 as a hardener
3-divinylsulfonyl-2-propanol (200 mg
/ M ² ).

[0069]

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An amine compound (20 mg / m ² ) represented by the following structural formula was added as a nucleation accelerator.

[0071]

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As a protective layer, gelatin 1.0 g / m ² , an irregular SiO ₂ matting agent 40 mg / m ² having a particle size of about 3.5 μm,
Methanol silica 0.1 g / m ² , polyacrylamide 1
00mg / m ^2, hydroquinone 200 mg / m ^2, a layer containing a fluorine surfactant and sodium dodecyl benzene sulfonate represented by the following structural formula as a silicone oil and a coating aid were conducted simultaneously coated with the emulsion layer.

[0073]

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The back layer and the back layer protective layer were applied according to the following formulation. [Back layer formulation] Gelatin 3 g / m ² latex Polyethyl acrylate 2 g / m ² Surfactant Sodium p-dodecylbenzenesulfonate 40 g / m ² SnO ₂ / Sb (weight ratio 90/10, average particle size 0.02 μm) 200 mg / M ² gelatin hardener

[0075]

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Dye Mixture of dyes [a], [b] and [c]

[0077]

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[Back protective layer] Gelatin 0.8 mg / m ² polymethyl methacrylate fine particles (average particle size 4.5 μ) 30 mg / m ² dihexyl-α-sulfosacnate sodium salt 15 mg / m ² sodium dodecylbenzenesulfonate Salt 15 mg / m ² Sodium acetate 40 mg / m ²

(Evaluation) Each of these samples was exposed to tungsten light at 3200 ° K through an optical wedge or an optical wedge and a contact screen (Fujifilm, 150L chain dot type), and then exposed to the developer 1 at 34 ° C. for 30 seconds. It was developed, fixed, washed with water and dried. As a fixing solution, GR-F1 manufactured by Fuji Photo Film Co., Ltd. was used. Regarding the photographic performance 1, the sensitivity was represented by a common logarithmic value of an exposure amount giving a density of fog +1.5. The value of sample A was set to 1, and the higher the value, the higher the sensitivity. γ is represented by the following equation. Dmax is represented by a density at an exposure amount of logE + 0.5 with respect to a sensitivity point having a density of 0.1 on the characteristic curve.

[0080]

(Equation 1)

The photographic performance 2 was used as a simulation of a developer that had been fatigued with time. The sensitivity, γ, and Dmax were taken as in Performance 1.

The results are shown in Table 1.

[0083]

[Table 1]

As in Samples A, B, C and D, pH 1
It is possible to obtain a gamma of 10 or more by processing with a developing solution of less than 1.0, but with a developing solution that has been fatigued over time, the softening is remarkably lowered, and Dmax becomes 4.0 or less, which is impractical. Even when a known hydrazine derivative such as Samples F, G, H, I, J, and K is used in combination, neither gamma nor Dmax has an improvement effect. The hydrazine derivative of the present invention is converted to a highly active hydrazine derivative (for example, N-37, N-67, N-6).
8, N-69), the variation in both gamma and Dmax is significantly reduced.

Example 2 (Formulation of developer) Hydroquinone 50.0 g N-methyl-p-aminophenol 0.3 g Sodium hydroxide 18.0 g 5-Sulfosalicylic acid 55.0 g Potassium sulfite 110.0 g Disodium ethylenediaminetetraacetate 1 0.0 g Potassium bromide 10.0 g 5-Methylbenzotriazole 0.4 g 2-Mercaptobenzimidazole-5-sulfonic acid 0.3 g Sodium 3- (5-mercaptotetrazole) benzenesulfonate 0.2 g Nn-butyldiethanolamine 15.0 g Nn-dimethyl-n-hexanolamine 1.0 g Sodium toluenesulfonate 8.0 g Add water to adjust to 1 liter pH = 11.8 (add potassium hydroxide) pH 11.8

(Preparation of Image Forming Layer Emulsion) Emulsion A was prepared by the following method. Emulsion A: containing 0.37 M silver nitrate aqueous solution, K ₂ Rh (H ₂ O) Cl ₅ corresponding to 1 × 10 ⁻⁷ mol and K ₃ IrCl ₆ corresponding to 2 × 10 ⁻⁷ mol per mol of silver 0.
An aqueous halide solution containing 16 M potassium bromide and 0.22 M sodium chloride was mixed with 0.08 M sodium chloride and 1,3-dimethyl-2-imidazolithione (0.00%).
3% with stirring in a 2% aqueous gelatin solution containing
Nucleation was performed by adding the mixture by a double jet method at 8 ° C. for 12 minutes to obtain silver chlorobromide grains having an average grain size of 0.20 μm and a silver chloride content of 55 mol%. Subsequently, a 0.63 M silver nitrate aqueous solution and a halogen salt aqueous solution containing 0.23 M potassium bromide and 0.43 M sodium chloride were similarly added by a double jet method over 20 minutes. Thereafter, a conversion was performed by adding a KI solution of 1 × 10 ⁻³ mol per mol of silver, followed by washing with water by a flocculation method according to a conventional method, and a gelatin solution per mol of silver.
The solution was adjusted to pH 6.0 and pAg 7.3, and sodium benzenethiosulfonate per mole of silver was added.
mg, 2 mg of benzenesulfinic acid, 10 mg of chloroauric acid and 5 mg of sodium thiosulfate, and heated at 60 ° C. for 100 minutes to perform chemical sensitization. Then, 4-hydroxy-6-methyl-1,3,3a was used as a stabilizer. , 7-Tetrazaindene 1
50 mg and proxel as preservative were added. The resulting grains had an average grain size of 0.27 μm and a silver chloride content of 6
It was 0 mol% silver chlorobromide cubic grains. (Coefficient of variation 1
0%)

The emulsion thus obtained was added to 7 × 10 ⁻⁴ mol of 5- [3- (4-sulfobutyl) -5-chloro-2-benzooxazolidylidene] ethylidene-1-hydroxy per 7 mol of silver. Ethoxyethyl-3- (2-
Pyridyl) -2-thiohydantoin potassium salt, 6 × 1
^0-4 mol of the short-wave cyanine dye represented by the following structural formula (A), 3 × 10 ^-4 mol of 1-phenyl-5-mercaptotetrazole, and 4 × 10 ^-4 mol of the following structural formula (B) 3 × 10 ⁻⁴ mol of a mercapto compound represented by the following structural formula (C), 4 × 10 ⁻⁴ mol of a triazine compound represented by the following structural formula (D), 9 × 1
^0-4 moles of 5-chloro-8-hydroxyquinoline was added. Further, the hydrazine derivative of the present invention and its comparative compound shown in Example 1 were added as shown in Table 2. Further N
-Oleyl-N-methyltaurine sodium salt 30 mg
/ M ² and a dispersion of polyethyl acrylate (5
200 mg / m ²⁾ as a hardening agent 1,2-bis (vinylsulfonyl acetamide) ethane 40 mg / m ² was added, pH 6.
It was adjusted to 0 to prepare a hydrazine-containing layer coating solution.

[0088]

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(Preparation of Redox Compound Content Emulsion)
1.0 M silver nitrate aqueous solution and 3 × 10 ⁻⁷ per mole of silver
An aqueous solution of a halogen salt containing 0.3 M potassium bromide and 0.74 M sodium chloride containing (NH ₄ ) ₃ RhCl ₆ in an amount of 0.08 M sodium chloride and 0.002%
Was added to a 2% aqueous gelatin solution containing 1,3-dimethyl-2-imidazolinethione at 45 ° C. for 30 minutes with stirring by a double jet method to give an average particle size of 0.1%.
Silver chlorobromide grains having a thickness of 30 μm and a silver chloride content of 70 mol% were obtained. Thereafter, a conversion was performed by adding a KI solution of 1 × 10 ⁻³ mol per mol of silver, followed by washing with water by a flocculation method according to a conventional method, and a gelatin solution per mol of silver.
0 g, adjusted to pH 6.0 and pAg 7.6, and further added 7 mg of sodium benzenethiosulfonate, 2 mg of benzenesulfinic acid, 8 mg of chloroauric acid and 5 mg of sodium thiosulfate per mole of silver, and heated at 60 ° C. for 60 minutes. After chemical sensitization, 4-hydroxy-
6-methyl-1,3,3a, 7-tetrazaindene 35
0 mg and proxel as preservative were added. The obtained grains had an average grain size of 0.30 μm and a silver chloride content of 70.
Mol% of silver chlorobromide cubic grains. (Coefficient of variation 9
%).

The emulsion thus obtained was added as a sensitizing dye to 5 × 10 ^-4 mol of 5- [3-
(4-sulfobutyl) -5-chloro-2-benzooxazolidylidene] ethylidene-1-hydroxyethoxyethyl-3- (2-pyridyl) -2-thiohydantoin potassium salt, and the following structural formula (J) 10 mg / m ^{2 of} a dye represented by
50 mg / m ² ) and the following redox compound (R-
1) was added as shown in Table 3.

[0091]

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(Preparation of Coating Solution for Intermediate Layer)
5 mg / m ^{2 of} sodium ethanethiosulfonate, 100 mg / m ^{2 of the} dye represented by (K) and 100 mg of hydroquinone
mg / m ² , the triol compound represented by (L)
350 mg / m ² of a dispersion of m ² and polyethyl acrylate was added to prepare an intermediate layer coating solution.

[0093]

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Then, an image forming layer (Ag 3.4 g / m ² ) containing a 0.3 g / m ² layer of gelatin containing 40 mg / m ² of bis (vinylsulfonyl) methane as the lowermost layer on a polyethylene terephthalate film undercoated with gelatin. ² , gelatin 1.6 g / m ² ) and a layer containing a redox compound (Ag 0.2 g / m ² ) via an intermediate layer (gelatin 1.0 g / m ² ).
m ² , gelatin 0.2 g / m ² ), further thereon gelatin 0.2 g / m ² as a protective layer, average particle size of about 3.5 μm
Amorphous SiO ₂ matting agent 60 mg / m ² , methanol silica 0.1 g / m ² , liquid paraffin 50 mg / m ² , 5 mg of a fluorine surfactant represented by the following structural formula (F) as a coating aid
/ M ² and sodium dodecylbenzenesulfonate 20 mg /
m ²

[0095]

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The back layer was applied according to the following formulation. (Back layer formulation) Gelatin 3.2 g / m ² Surfactant Sodium p-dodecylbenzenesulfonate 40 mg / m ² Dihexyl-α-sulfosuccinate sodium salt 40 mg / m ² Gelatin hardener 1,3-divinylsulfonyl-2 -Propanol 200 mg / m ² dye A mixture of the following dyes (M), (H), (I) and (J) Dye (M) 20 mg / m ² Dye (H) 50 mg / m ² Dye (I) 20 mg / m ² Dye (J) 30 mg / m ² Proxel 4 mg / m ²

[0097]

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(Back protective layer) Gelatin 1.3 g / m ² Polymethyl methacrylate fine particles (average particle size 2.5 μ) 20 mg / m ² Sodium p-dodecylbenzenesulfonate 15 mg / m ² Dihexyl-α-sulfosuccinate sodium Salt 15 mg / m ² Sodium acetate 60 mg / m ²

(Evaluation) These samples were exposed to tungsten light at 3200 ° K through an optical wedge and a contact screen (Fuji Film, 150 L chain dot type), and then the FG-710F automatic developing machine (Fuji 34 ° C3 using Photo Film Co., Ltd.
0 "processing was performed. As a fixing solution, GR-F1 (manufactured by Fuji Photo Film Co., Ltd.) was used.

The evaluation was performed by the following method. Photo Performance 1
Shows the results obtained by performing a treatment at 34 ° C. for 30 seconds using an FG-710F automatic developing machine (manufactured by Fuji Photo Film Co., Ltd.) with the developer having the above formulation. GR-F1 (manufactured by Fuji Photo Film Co., Ltd.) was used as the fixing solution. Example 1 for sensitivity and Dmax
It was digitized in the same way as. The halftone was represented by the following equation. * Halftone = 95% halftone dot area ratio gives the exposure (log E95
%) -5% Exposure to give halftone dot area ratio (log E5%) Photographic performance 2 is a simulation of a developer that has been fatigued over time. The sensitivity and Dmax were measured in the same manner as in photographic performance 1, using a developer having a formulation with a pH raised by 0.2.

The results are shown in Table 2.

[0102]

[Table 2]

As can be seen from Samples A, B and C, when a redox compound is introduced, the halftone gradation is remarkably widened, but Dmax is lowered by a fatigue liquid over time, which is not practically preferable. Dmax is not improved by using a known hydrazine derivative in combination, but by using the hydrazine derivative of the present invention in combination, Dmax becomes 4.0 or more even in a fatigue fluid. At that time, the halftone tone is also kept at 1.4 or more. According to the configuration of the present invention, it is possible to provide a photosensitive material having a wide halftone and a small dependence on the composition of the processing solution.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) G03C 1/06 501

Claims (1)

(57) [Claims] [Claim 1 further comprising at least one silver halide emulsion layer on a support, a halogen containing at least one hydrazine derivative represented by the general formula (1) or emulsion layers and other hydrophilic colloid layers A silver halide photographic light-sensitive material, characterized in that the emulsion layer or another hydrophilic colloid layer contains at least one hydrazine derivative represented by the formula (N). General formula (1) In the formula, X ¹ represents an alkyl group, an alkoxy group, a substituted amino group or an alkylthio group. Y ¹ is an alkoxy group,
Represents an aryloxy group , an alkylthio group or an arylthio group, and R ¹ represents an alkylene group. General formula (N) In the formula, R ₁ represents an aliphatic group or an aromatic group, R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a hydrazino group, mosquitoes Rubamoi <br/> group or Represents an oxycarbonyl group, G ₁ is a —CO— group,
A -SO ₂ -group, -SO- group, -PO (R ₂ )-group, -CO-CO- group, thiocarbonyl group or iminomethylene group, wherein A ₁ and A ₂ are both hydrogen atoms or one of them is hydrogen. The other atom is a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.