JP2709760B2 - 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 light-sensitive material and a method for forming an ultra-high contrast negative image using the same. It relates to a negative photosensitive material.

[0002]

2. Description of the Related Art In the field of photoengraving, there is a demand for a photographic light-sensitive material having good original reproducibility, a stable processing solution, or a simple replenishment in order to cope with the variety and complexity of printed matter. . Particularly in the line drawing photographing process, the manuscript is made by pasting typesetting characters, handwritten characters, illustrations, halftone pictures, and the like. Therefore, the manuscript contains
Images having different densities and line widths are mixed, and a plate-making camera, a photographic material, or an image forming method for finishing these originals with good reproducibility is strongly desired. On the other hand, in plate making of catalogs and large posters, enlargement (enlargement) or reduction (shrinkage) of a halftone picture is widely performed, and in plate making using enlarged halftone dots, the number of lines becomes coarse and blurred. Shooting. In the reduction, the number of lines / inch is larger than that of the original, and a thin point is photographed. Therefore, there is a demand for an image forming method having a wider latitude in order to maintain the reproducibility of halftone. A halogen lamp or a xenon lamp is used as a light source of a plate making camera. In order to obtain a photographic sensitivity with respect to these light sources, a photographic light-sensitive material is usually subjected to orthosensitization. However, it has been found that the ortho-sensitized photographic material is more strongly affected by the chromatic aberration of the lens, so that the image quality is liable to deteriorate. This deterioration is more remarkable for a xenon lamp light source.

As a system that meets the demands of a wide latitude, a lithographic silver halide light-sensitive material composed of silver chlorobromide (at least a silver chloride content of 50% or more) has an extremely low effective concentration of sulfite ions (usually 0.1%). 1 mol /
There is known a method of obtaining a line image or a halftone dot image having a high contrast and a high blackening density in which an image area and a non-image area are clearly distinguished by processing with a hydroquinone developer. However, in this method, since the concentration of sulfurous acid in the developer is low, development is extremely unstable against air oxidation, and various efforts and efforts have been made to keep the solution activity stable. Was extremely slow, and the work efficiency was reduced. For this reason, an image forming system that eliminates instability of image formation by the above-described developing method (lith developing system), develops with a processing solution having good storage stability, and obtains ultra-high contrast photographic characteristics is provided. There has been a request, one of which is disclosed in U.S. Patent Nos. 4,166,742 and 4,168,977.
Nos. 4,221,857 and 4,224,401
Nos. 4,243,739 and 4,272,606
No. 4,311,781, a surface latent image type silver halide photographic material to which a specific acylhydrazine compound is added, and a sulfite preservative at pH 11.0 to 12.3. There has been proposed a system for forming a super-high contrast negative image having a γ of more than 10 by processing with a developer containing 15 mol / l or more and having good storage stability. This new image forming system can use only silver chlorobromide having a high silver chloride content in conventional ultra-high contrast image formation, but can also use silver iodobromide and silver chloroiodobromide. There is. Although the above-described image system shows excellent performance in terms of sharp halftone dot quality, processing stability, speed and original reproducibility, the original reproducibility has been further improved to cope with the variety of printed materials in recent years. A system is desired. JP-A-61-213847 and JP-A-62-18474
2-260,153, JP-A-64-88451, JP-A-64-72140, and U.S. Pat.
No. 4 discloses a photosensitive material containing a redox compound which releases a development inhibitor by oxidation, and discloses an attempt to expand the gradation reproduction range. However, in a super-high contrast treatment system using a hydrazine derivative, these redox compounds are:
When an amount sufficient to improve line image reproducibility and halftone dot image reproducibility is added to the light-sensitive material, a part of the inhibitor released during the development processing flows out. When a large amount of the light-sensitive material containing these redox compounds is continuously processed, the inhibitor gradually accumulates in the developer. Therefore, when the development processing is performed using the thus-processed fatigue developer, inhibition of high contrast and a decrease in sensitivity are caused. In particular, when one automatic developing machine is used for developing other photosensitive materials including these redox compounds, other various photographing materials, contact materials, scanner materials, or photographic materials, The photographic adverse effect on other materials is problematic. Therefore, since the amount of such a redox compound used is limited, a sufficiently satisfactory effect cannot be exhibited, or only a closed system in which the photosensitive material and the developing solution are limited in a narrow range is required. No improvement was desired.

[0004]

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a novel compound which is excellent in storage stability and rapidly releases a development inhibitor. The second object is to provide a compound which does not cause fatigue in the developer even when used in an amount sufficient to improve the image reproducibility in a high contrast material system. A third object of the present invention is to provide a plate-making photosensitive material capable of obtaining a high-contrast image using a highly stable developer. Fourth, it is an object of the present invention to provide a plate-making photosensitive material having a wide halftone gradation with a high contrast material using a hydrazine nucleating agent. Fifth, it is an object of the present invention to provide a photosensitive material for plate making having good development processing running stability.

[0005]

These objects of the present invention have been attained by a silver halide photographic light-sensitive material containing a compound represented by the following general formula (1). General formula (1)

[0006]

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In the formula, R ₁ represents an aliphatic group or an aromatic group, and further has --O-(CH ₂ CH ₂ O)
_{n -, - O - (CH} 2 CH (CH 3) O) n - or -O - (CH ₂ CH
It is a group containing a partial structure of (OH) CH ₂ O) _n- (where n is an integer of 3 or more). G ₁ represents a —CO— group, a —COCO— group,
CS- _{group, -C (= NG 2 R 2} ) - represents the group - group, -SO- group, -SO ₂ - group or _{-P (O) (G 2 R} 2). G ₂ is a mere bond, -O
—, —S— or —N (R ₂ ) —, wherein R ₂ represents an aliphatic group, an aromatic group or a hydrogen atom, and when _two or more R ₂ are present in the molecule, they are the same. It may be different. One of A ₁ and A ₂ is a hydrogen atom, and the other is a hydrogen atom or an acyl group, an alkyl or an arylsulfonyl group. Time represents a divalent linking group,
t represents 0 or 1. PUG represents a development inhibitor.

The general formula (1) will be described in more detail. In the general formula (1), the aliphatic group represented by R ₁ preferably has 1 to 30 carbon atoms, and particularly is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms.
This alkyl group has a substituent. In the general formula (1), the aromatic group represented by R ₁ is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with an aryl group to form a heteroaryl group. For example, there are a benzene ring, a naphthalene ring, a pyridine ring, a quinoline ring and an isoquinoline ring. Among them, those containing a benzene ring are preferred. Particularly preferred as R ₁ is an aryl group. The aryl group or unsaturated heterocyclic group of R ₁ is substituted.

The aliphatic or aromatic group of R ₁ is substituted, and typical substituents include, for example, an alkyl group,
Aralkyl, alkenyl, alkynyl, alkoxy, aryl, substituted amino, ureido, urethane, aryloxy, sulfamoyl, carbamoyl, alkylthio, arylthio, sulfonyl, sulfinyl, hydroxy, A halogen atom, a cyano group, a sulfo group, an aryloxycarbonyl group, an acyl group, an alkoxycarbonyl group, an acyloxy group, a carbonamide group, a sulfonamide group, a carboxyl group, a phosphoric acid amide group, and the like. A branched or cyclic alkyl group (preferably having 1 carbon atom)
To 20), an aralkyl group (preferably having 7 to 7 carbon atoms)
30), an alkoxy group (preferably having 1 to 3 carbon atoms)
0), a substituted amino group (preferably having 1 to 30 carbon atoms)
An amino group substituted with an alkyl group), an acylamino group (preferably having 2 to 40 carbon atoms), a sulfonamide group (preferably having 1 to 40 carbon atoms), a ureido group (preferably having 1 carbon atom) And a phosphoric acid amide group (preferably having 1 to 40 carbon atoms).

The aliphatic group or aromatic group of R ₁ or a substituent thereof is —O— (CH ₂ CH ₂ O) _n —, —O— (CH ₂ CH (CH ₃ ) O)
_n - or _{-O - (CH 2 CH (OH} ) CH 2 O) n - it contains a. n is an integer of 3 or more, preferably an integer of 3 or more and 15 or less. R ₁ is preferably represented by the following general formula (2). General formula (2)

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In the formula, L ₁ represents a —CH ₂ CH ₂ O— group, —C
H ₂ CH (CH ₃ ) O— group, or —CH ₂ CH (O
It represents H) _CH 2 O-group, n represents in the general formula (1) synonymous. L ₂ and L ₃ represent a —CONR ₇ — group, and —NR ₇ CON
R ₈ — group, —SO ₂ NR ₇ — group, or NR ₇ SO ₂ N
R ₈ represents the same or different groups. R ₇ and R ₈ are a hydrogen atom or a carbon number of 1 to 6;
Represents an alkyl group, an aryl group having 6 to 10 carbon atoms,
Hydrogen atoms are preferred. m is 0 or 1. R ₃ represents an aliphatic group or an aromatic group, and may be substituted. Specific embodiments are described for R ₁ apply it, not necessarily have to be substituted. R
₄ , R ₅ and R ₆ are a divalent aliphatic group or an aromatic group, preferably an alkylene group, an arylene group or a combination thereof with an —O— group, a —CO— group, a —S— group, and a —SO— group. , −
SO ₂ — group, —NR ₉ — group (R ₉ is R _{7 of the} general formula (2)
Synonymous with). More preferably, R ₄ is an alkylene group having 1 to 10 carbon atoms or a combination thereof with a —S— group, a —SO— group, a —S
A divalent group formed by combining an O ₂ — group,
₅ , R ₆ is an arylene group having 6 to 20 carbon atoms. Particularly, R ₆ is preferably a phenylene group. R ₄ , R ₅ and R ₆
May be substituted, and a preferred substituent is R ₁
The substituents listed above apply.

In the general formula (1), G ₁ is -CO-
Group, -SO ₂ - groups are preferred, -CO- group is most preferred.
A ₁ and A ₂ are preferably hydrogen atoms.

In the general formula (1), Time represents a divalent linking group, and may have a timing adjusting function. The divalent linking group represented by Time represents a group that releases PUG from Time-PUG released from the oxidized form of the redox nucleus through one or more steps of reaction. As the divalent linking group represented by Time, for example, PUG is obtained by an intramolecular ring closure reaction of a p-nitrophenoxy derivative described in U.S. Pat. No. 4,248,962 (Japanese Patent Application Laid-Open No. 54-145,135). What emits: U.S. Pat. No. 4,310,612
Which release PUG by an intramolecular ring closure reaction after ring opening described in US Pat. Nos. 4,330,617 and 4,4,459.
46,216 and 4,483,919;
U.S. Pat. No. 4,409,323, which releases PUG with the formation of an acid anhydride by an intramolecular ring-closure reaction of a carboxyl group of a succinic acid monoester or an analog thereof described in U.S. Pat. No. 121,328; 4,421,845
No., Research Disclosure Magazine No. 21, 228
(December 1981), US Patent No. 4,416,977.
(JP-A-57-135,944), JP-A-58-2
No. 09,736, No. 58-209,738, etc., to produce quinomonomethane or an analog thereof by electron transfer via a double bond in which an aryloxy group or a heterocyclic oxy group is conjugated, thereby releasing PUG. U.S. Pat. No. 4,420,554 (JP-A-57-136,640).
No.), JP-A-57-135,945 and JP-A-57-18.
Nos. 8,035, 58-98,728 and 58-
No. 209,737, etc., which release PUG from the γ-position of an enamine by electron transfer of a portion having an enamine structure of a nitrogen-containing heterocyclic ring described in JP-A-57-56,837. US Patent No. 4,14, which releases PUG by an intramolecular ring closure reaction of an oxy group generated by electron transfer to a carbonyl group conjugated to a nitrogen atom;
No. 6,396 (JP-A-52-90932) and JP-A-5-90932.
No. 9-93,442, JP-A-59-75475, JP-A-60-249148, JP-A-60-249149, etc., which release PUG with generation of aldehydes; 51-146,828, 57-17
No. 9,842 and No. 59-104,641, which release PUG with decarboxylation of a carboxyl group;
O-COOCR _a R _b -PUG (where R _a and R _b represent a monovalent group), which releases PUG with decarboxylation and subsequent formation of aldehydes;
U.S. Pat. No. 4,438,193 which releases PUGs with the formation of isocyanates as described in US Pat.
And the like, which release PUG by a coupling reaction with an oxidized color developing agent described in JP-A No. 5-211. Specific examples of the divalent linking group represented by Time are described in JP-A-61-236549, and Japanese Patent Application No. 6-86.
Nos. 3-98,803 and Japanese Patent Application No. 2-93487 are also described in detail.

In the general formula (1), PUG is a development inhibitor. PUG has a hetero atom and is bonded to another portion of the compound represented by the general formula (1) via the hetero atom. Examples of generally known development inhibitors include, for example, "The Theory," by TH James.
The Theory of the Photographic Process
of the Photographic Process), 4th edition, 1977,
It is described in Macmillan, pp. 396-399, and Japanese Patent Application No. 2-93,487, pages 56-69. These development inhibitors may have a substituent. Useful substituents include, for example, mercapto, nitro, carboxyl, sulfo, phosphono, hydroxy, alkyl, aralkyl, alkenyl,
Alkynyl group, aryl group, alkoxy group, aryloxy group, amino group, acylamino group, sulfonylamino group, ureido group, urethane group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, halogen atom, Examples include a cyano group, an aryloxycarbonyl group, an acyl group, an alkoxycarbonyl group, an acyloxy group, a carbonamido group, a sulfonamido group and a phosphonamido group, and these groups may be further substituted.

The development inhibitor represented by PUG used in the present invention is preferably a compound which inhibits nucleation and development. The nucleation and infectious development is carried out by Fujifilm GRANdex System (Fuji Photo Film Co., Ltd. and Kodak Ult)
ratec system (Eastman Kodak C
o., Ltd. This is a new development chemistry used in the image forming method of (1). This development chemistry is described in “The Journal of the Photographic Society of Japan, Vol. 52, No. 5, pp. 390-394 (1989).
And the Journal of Photographic Science, Vol. 35, p. 162 (1987), describes the process of developing exposed silver halide grains with a normal developing agent and the resulting oxidation products of the developing agent. A nucleating active species is generated based on the cross-oxidation between the nucleating agent and the nucleating agent. . Therefore, since the entire development process consists of the sum of the normal development process and the nucleation development process, in addition to the conventional development inhibitor conventionally known as a development inhibitor, a new nucleation transmission development process is newly suppressed. Compounds can exert an inhibitory action. The latter is referred to herein as a nucleation development inhibitor. The development inhibitor represented by PUG used in the present invention is preferably a nucleation development inhibitor. As the compound acting as a nucleation development inhibitor, a conventionally known development inhibitor is also effective. Particularly effective compounds are compounds having at least one or more nitro group or nitroso group, pyridine, pyrazine, A compound having a nitrogen-containing heterocyclic skeleton such as quinoline, quinoxaline, or phenazine, particularly a compound having a 6-membered nitrogen-containing heteroaromatic ring skeleton, a compound having an N-halogen bond,
Examples include quinones, tetrazoliums, amine oxides, azoxy compounds, coordination compounds having oxidizing ability, and the like. Among them, compounds having a nitro group and compounds having a pyridine skeleton are particularly effective.

These nucleating development inhibitors may have substituents, and the properties of the substituents, for example, electron-withdrawing, electron-donating, hydrophobic, hydrophilic, electric charges, and adsorptivity to silver halide Various properties such as the strength of development suppression and the ease of diffusion can be controlled by such properties. Examples of useful substituents include those listed above as examples of substituents of general development inhibitors. Specific examples of these nucleating development inhibitors useful in the present invention are described in detail in Japanese Patent Application Nos. 2-258927 and 2-258929, and in Japanese Patent Application Nos. 2-258929 and 3-25829. No. 15648, No. 3-70388, No. 3-704
No. 11 also describes it as Ind. Further, as another series of nucleation development inhibitors, an adsorptive compound to silver halide grains having an anionic charged group or a dissociable group capable of dissociating in a developer to generate anionic charge is also effective. .

In the general formula (1), R ₁ or T
The im may have a ballast group commonly used in immobile photographic additives such as couplers or a group for promoting the adsorption of the compound represented by the general formula (1) to silver halide. Good. The ballast group is an organic group giving a molecular weight sufficient to prevent the compound represented by the general formula (1) from substantially diffusing into another layer or the processing solution, and includes an alkyl group, an aryl group, a heterocyclic group,
Ether group, thioether group, amide group, ureido group,
It comprises one or more combinations of a urethane group, a sulfonamide group and the like. The ballast group is preferably a ballast group having a substituted benzene ring, and particularly preferably a ballast group having a benzene ring substituted with a branched alkyl group.

Specific examples of the group for promoting adsorption to silver halide include 4-thiazoline-2-thione, 4-imidazoline-2-thione, 2-thiohydantoin, rhodanine,
Thiobarbituric acid, tetrazoline-5-thione, 1,
2,4-triazoline-3-thione, 1,3,4-oxazoline-2-thione, benzimidazoline-2-thione, benzoxazoline-2-thione, benzothiazoline-2-thione, thiotriazine, 1,3- A cyclic thioamide group such as imidazoline-2-thione, a chain thioamide group, an aliphatic mercapto group, an aromatic mercapto group, a heterocyclic mercapto group (when a nitrogen atom is next to a carbon atom to which a -SH group is bonded, This is synonymous with the cyclic thioamide group in a tautomeric relationship, and specific examples of this group are the same as those listed above.), A group having a disulfide bond, benzotriazole, triazole, tetrazole, indazole, benz Imidazole, imidazole, benzothiazole, thiazole, thiazoline, benzoxazole, ox 5- or 6-membered nitrogen-containing heterocyclic group consisting of a combination of nitrogen, oxygen, sulfur and carbon such as sol, oxazoline, thiadiazole, oxathiazole, triazine and azaindene; and heterocyclic quaternary such as benzimidazolinium And the like. These may be further substituted with a suitable substituent. Examples of the substituent include those described as the substituent of R ₁ . Hereinafter, specific examples of the compound used in the present invention are listed, but the present invention is not limited thereto.

[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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As the redox compound used in the present invention, in addition to those described above, for example, JP-A-61-213,8
No. 47, 62-260, 153, Japanese Patent Application No. 1-10
No. 2,393, No. 1-102,394, No. 1-10
No. 2,395, No. 1-114,455, No. 1-290
No. 563, No. 2-62337, No. 2-64717,
2-258927, 2-258929, 2-
No. 258929, No. 3-15648, No. 3-7038
Nos. 8 and 3-70411 can be used. The method of synthesizing the redox compound used in the present invention is described in the above-mentioned materials, and for example, in U.S. Pat. No. 4,684,604, Japanese Patent Application No. 63-98,803.
Nos. 3,379,529 and 3,620,
746, 4,377,634, 4,332,8
No. 78, JP-A-49-129,536 and JP-A-56-15
3,336, 56-153,342 and the like.

The redox compound of the present invention is used in the range of 1 × 10 ^{-6 to} 5 × 10 ^-2 mol, more preferably 1 × 10 ^-5 to 1 × 10 ^-2 mol, per mol of silver halide. . The redox compound of the present invention may be any suitable water-miscible, organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methylethylketone), dimethylformamide, dimethylsulfoxide, methylcellosolve, etc. Can be dissolved and used. Also, by an already well-known emulsification dispersion method, an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified and dispersed. Objects can also be created and used. Alternatively, by a method known as a solid dispersion method, a powder of a redox compound is put into water using a ball mill, a colloid mill,
Alternatively, they can be used by being dispersed by ultrasonic waves.

The redox compound of the present invention is added to a silver halide emulsion layer or another hydrophilic colloid layer. Further, it may be added to at least one of a plurality of silver halide emulsion layers. Although some configuration examples are given, the present invention is not limited to these. Structural Example 1) A silver halide emulsion layer containing the redox compound of the present invention and a protective layer are provided on a support. These emulsion layers or protective layers may contain a second hydrazine compound as a nucleating agent. Structural Example 2) A first silver halide emulsion layer and a second silver halide emulsion layer are sequentially provided on a support, and the first silver halide emulsion layer and the adjacent hydrophilic colloid layer And the second hydrazine compound, and the second silver halide emulsion layer or the adjacent hydrophilic colloid layer contains the redox compound. Configuration Example 3) In the configuration example 2), the order of the two emulsion layers is reversed. In Structural Examples 2) and 3), an intermediate layer containing gelatin or a synthetic polymer (such as polyvinyl acetate or polyvinyl alcohol) may be provided between the two photosensitive emulsion layers. Structural Example 4) A silver halide emulsion layer containing a second hydrazine compound is provided on a support, and on the emulsion layer, or
A hydrophilic colloid layer containing the redox compound is provided between the support and the silver halide emulsion layer. A particularly preferred configuration is Configuration Example 2) or 3).

The compound used in the present invention as a nucleating agent is preferably a compound represented by the following general formula (3). General formula (3)

[0029]

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In the formula, R ₁₁ represents an aliphatic group or an aromatic group, R ₁₂ represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group or a hydrazine group, and G ₁₁ represents- CO- group, -SO ₂ - group, -SO-
Group, -P (O) R ₁₃ - group, -COCO- group, a thiocarbonyl group or an iminomethylene group, A _11, A ₁₂ are both hydrogen atoms or alkyl of one and the other is substituted or unsubstituted with a hydrogen atom Represents a sulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. Selected from the same range as radical as defined R _13, R _12, may be different from R _12.

In the general formula (3), the aliphatic group represented by R ₁₁ preferably has 1 to 30 carbon atoms,
Particularly, it is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. This alkyl group may have a substituent. In formula (3), the aromatic group represented by R ₁₁ is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with the aryl group. Preferred as R ₁₁ is an aryl group, particularly preferably a group containing a benzene ring. R ₁₁
The aliphatic group or the aromatic group may be substituted.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, a ureido group, and a urethane. 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, aryloxycarbonyl group, acyl group, alkoxy Carbonyl group, acyloxy group, carbonamido group,
Sulfonamide group, carboxyl group, phosphoric acid amide group,
Diacylamino group, imide group, R ₁₄ -NHCO-N (R ₁₅ ) -CO- group (R ₁₄ and R ₁₅ are selected from the same groups as defined for R ₂ and may be different from each other) and the like. Preferred examples of the substituent include 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), Amino group (preferably an amino group substituted with an alkyl group having 1 to 20 carbon atoms), acylamino group (preferably having 2 to 30 carbon atoms), sulfonamide group (preferably having 1 to 30 carbon atoms) ), Ureido groups (preferably having 1 to 30 carbon atoms), and phosphoric amide groups (preferably having 1 to 30 carbon atoms).
These groups may be further substituted. As the alkyl group represented by R ₁₂ in the general formula (3),
It is preferably an alkyl group having 1 to 4 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group (for example, one containing a benzene ring).

When G ₁₁ is a —CO— group, preferred of the groups represented by R ₁₂ are a hydrogen atom, an alkyl group (for example, a methyl group, a trifluoromethyl group, a 3-hydroxypropyl group, a 3-methane group). Sulfonamidopropyl group, phenylsulfonylmethyl group, etc., aralkyl group (eg, o-hydroxybenzyl group, etc.), aryl group (eg, phenyl group, 3,5-dichlorophenyl group, o-
Methanesulfonamidophenyl, 4-methanesulfonylphenyl, 2-hydroxymethylphenyl, etc.)
And a hydrogen atom is particularly preferable. R ₁₂ may be substituted, and as the substituent, the substituents listed for R ₁₁ can be applied. G _{11 in the} general formula (3) is -CO
-Groups are most preferred. R ₁₂ may also be such as to cause a cyclization reaction that cleaves the G ₁₁ -R ₁₂ moiety from the residual molecule to form a cyclic structure containing the atoms of the -G ₁₁ -R ₁₂ moiety. Examples thereof include, for example, JP-A-63-297.
No. 51 and the like. A ₁₁ and A ₁₂ are most preferably hydrogen atoms.

R ₁₁ or R _{12 in} the general formula (3) may have a ballast group or 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 and an alkylphenoxy group. Can be. Further, as a polymer, for example, JP-A-1-1005
No. 30.

R ₁₁ or R _{12 in} the general formula (3) may have incorporated therein a group which enhances the adsorption to the silver halide grain surface. Examples of such an adsorptive group include thiourea group, heterocyclic thioamide group, mercapto heterocyclic group, and triazole group in US Pat. No. 4,285,108;
No. 4,459,347, 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,
Nos. 049, 61-170, 733, 61-27
Nos. 0,744, 62-948, 63-234,2
No. 44, No. 63-234, No. 245, No. 63-234,
No. 246. Specific examples of the compound represented by the general formula (3) are shown below. However, the present invention is not limited to the following compounds.

[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 hydrazine compound as a nucleating agent used in the present invention includes, in addition to those described above, RESEARCH DIS
CLOSURE Item 23516 (November 1983, p.3
46) and references cited therein, as well as U.S. Pat.
080,207, 4,269,929, 4,2
No. 76,364, No. 4,278,748, No. 4,38
5, 108, 4,459,347, 4,56
0,638, 4,478,928, British Patent 2,
011,391B, JP-A-60-179,734,
Nos. 62-270,948, 63-29,751,
Nos. 61-170,733 and 61-270,744
No. 62-270,948, EP 217,310
No., EP356,898, US4,686,167
And JP-A-62-178,246 and JP-A-61-32,5.
No. 38, No. 63-104, 047, No. 63-121,
No. 838, No. 63-129, 337, No. 63-22
3,744, 63-234,244, 63-2
Nos. 34, 245, 63-234, 246, 63-
294,552, 63-306,438, JP-A-1-100,530, 1-105,941, 1
-105,943, JP-A-64-10,233, JP-A-1-90,439, JP-A-1-276,128
No. 1-280,747, No. 1-283,548
Nos. 1-283,549 and 1-285,940
Nos. 2-2541, 2-139,538, 2
-77057, Japanese Patent Application No. 1-18,377, 1-1
No. 8,378, No. 1-18, 379, No. 1-15, 7
No. 55, No. 1-16,814, No. 1-40,792
Nos. 1, 42, 615, 1-42, 616, 1-123, 693 and 1-126, 284 can be used. The additive of the hydrazine compound as a nucleating agent in the present invention is preferably contained in an amount of 1 × 10 ⁻⁶ mol to 5 × 10 ⁻² mol per mol of silver halide, more preferably 1 × 10 ⁻⁵ mol to 2 × 10 ⁻² mol.
A range of × 10 ^-2 mol is a preferable addition amount. The method of dissolving and dispersing these hydrazine nucleating agents is represented by the general formula (1)
The same method as that for the compound of can be used.

The silver halide used in the present invention may have any composition such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver iodochlorobromide and the like. The average grain size of the silver halide used in the present invention is preferably fine grains (for example, 0.7 μm or less), particularly preferably 0.5 μm or less. The particle size distribution is basically not limited, but is preferably monodispersed. The term “monodisperse” as used herein means that at least 95% by weight or the number of particles is composed of a group of particles having a size within ± 40% of the particle size. The silver halide grains in the photographic emulsion may have regular crystals such as cubic and octahedral, and may be spherical,
It may be one having irregular crystals such as a plate-like or the like, or one having a complex form of these crystal forms. In the silver halide grains, the inside and the surface layer may be composed of a uniform phase or may be composed of different phases. Two or more kinds of silver halide emulsions formed separately may be used as a mixture. In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite, a lead salt, a thallium salt, a rhodium salt or a complex salt thereof, an iridium salt or a complex salt thereof and the like are co-present in the course of forming silver halide grains or physical ripening. Is also good.

The emulsion layer or other hydrophilic colloid layer of the present invention may contain a water-soluble dye as a filter dye or for various purposes such as prevention of irradiation. As the filter dye, a dye for further lowering the photographic sensitivity, preferably an ultraviolet absorber having a spectral absorption maximum in the intrinsic sensitivity range of silver halide, or safety against safelight light when handled as a light room photosensitive material 350 nm to 600 nm for increasing
A dye having substantial light absorption in the region is used. These dyes may be added to the emulsion layer depending on the purpose, or may be added together with the mordant to the non-light-sensitive hydrophilic colloid layer above the silver halide emulsion layer, that is, a layer farther from the silver halide emulsion layer with respect to the support. It is preferable to use it fixed. Alternatively, International Application Publication (WO) 88/04794,
European Patent (EP) 0276566A1, JP-A-6
As described in 3-197943 and the like, a gelatin dispersion in which a water-insoluble dye is dispersed in a microcrystalline state can be used. Depending on the molar extinction coefficient of the dye,
It is added in an amount of usually ^{10 -2 g / m 2 ~1g /} m 2. Preferably it is 50 mg to 500 mg / m ² . Specific examples of the dye are described in detail in JP-A-63-64039. These dyes are dissolved in a suitable solvent (eg, water, alcohol (eg, methanol, ethanol, propanol, etc.), acetone, methyl cellosolve, etc., or a mixed solvent thereof) to form the non-photosensitive hydrophilic colloid layer of the present invention. It is added to the coating liquid for use. These dyes can be used in combination of two or more kinds. The dye of the present invention is used in an amount necessary to enable bright room handling. The specific amount of the dye to be used is generally 10 ⁻³ g / m ^{2 to} 1 g / m ² , particularly 10 ⁻³ g / m ^2.
Preferred amounts can be found in the range of ０．５0.5 g / m ² .

As the binder or protective colloid of the photographic emulsion, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol , Polyvinyl alcohol partial acetal, poly-
N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole,
Various kinds of synthetic hydrophilic polymer substances such as a single or copolymer such as polyvinylpyrazole can be used. As gelatin, in addition to lime-processed gelatin, acid-processed gelatin may be used, and gelatin hydrolyzate and gelatin enzyme hydrolyzate can also be used.

The silver halide emulsion used in the method of the present invention may not be chemically sensitized, but may be. As methods of chemical sensitization of silver halide emulsions, sulfur sensitization, reduction sensitization and noble metal sensitization are known, and any of these can be used alone or in combination with chemical sensitization. Is also good. Among the noble metal sensitization methods, the gold sensitization method is a typical one and uses a gold compound, mainly a gold complex salt. Noble metals other than gold, for example, complex salts such as platinum, palladium, and iridium may be contained. Specific examples thereof are described in U.S. Pat. No. 2,448,060 and British Patent 618,061. As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines and the like can be used in addition to the sulfur compounds contained in gelatin. Stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used as the reduction sensitizer. A known spectral sensitizing dye may be added to the silver halide emulsion layer used in the present invention.

The light-sensitive material of the present invention can contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the light-sensitive material or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles,
Mercaptothiadiazoles, aminotriazoles,
Benzothiazoles, nitrobenzotriazoles, etc .; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,
3,3a, 7) tetrazaindenes), pentaazaindenes and the like; many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonamide and the like are added. be able to. Among these, preferred are benzotriazoles (eg, 5-methyl-benzotriazole) and nitroindazoles (eg, 5-nitroindazole). Further, these compounds may be contained in the treatment liquid.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers. For example, chromium salt (chrom alum, etc.), aldehydes (glutal aldehyde, etc.), N
-Methylol compounds (dimethylol urea, etc.), dioxane derivatives, active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, 1,3-
Di-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-
s-triazine, etc.), mucohalogenic acids, and the like can be used alone or in combination.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared by using the present invention may have coating aids, antistatic properties, improved slipperiness, emulsified dispersion, improved adhesion and improved photographic properties (for example, development acceleration For various purposes such as contrast enhancement, sensitization, and the like, various surfactants may be contained. For example, saponins (steroids), alkylene oxide derivatives (eg, polyethylene glycol, polyethylene glycol /
Polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl alcohol ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives ( For example, nonionic surfactants such as alkenyl succinic acid polyglyceride and alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols and alkyl esters of sugars; alkyl carboxylate, alkyl sulfonate, alkyl benzene sulfonate, alkyl Naphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-al Acidity such as carboxy group, sulfo group, phospho group, sulfate group, phosphate group such as rutaurine, sulfosuccinate, sulfoalkyl polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl phosphate, etc. Anionic surfactants containing a group; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, amine oxides; alkylamine salts, aliphatic or aromatic quaternary surfactants Cationic surfactants such as quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocyclic rings can be used. Particularly preferred surfactants used in the present invention are those having a molecular weight of 60 described in JP-B-58-9412.
Zero or more polyalkylene oxides. Further, a polymer latex such as polyalkyl acrylate can be contained for dimensional stability.

There are development accelerators suitable for use in the present invention.
Or as an accelerator for nucleation and development.
No. 7,616, No. 54-37,732, No. 53-13
7,133, 60-140,340, 60-1
4,959, etc., and N or
Various compounds containing an S atom are effective. Promote these
The optimum amount of the agent varies depending on the type of the compound.
0x10 ^-3~ 0.5g / m^Two, Preferably 5.0 × 10^-3
~ 0.1g / m^TwoIt is desirable to use within the range. these
The promoter is a suitable solvent (H_TwoO, methanol and ethanol
Alcohols such as acetone, dimethylformami
, Methylcellosolve, etc.)
It is. A plurality of these additives may be used in combination.

In order to obtain ultra-high contrast photographic characteristics using the silver halide light-sensitive material of the present invention, a conventional infectious developer or a highly alkaline developer close to pH 13 described in US Pat. No. 2,419,975 and having a pH of about 13 can be used. It is not necessary to use a stable developer. That is, the silver halide light-sensitive material of the present invention contains 0.10 mol / L or more of sulfite ions as a preservative and has a pH of 9.0 to 12.3, particularly
With a developer of 10.0 to 12.0, a negative image having a sufficiently high contrast can be obtained. There is no particular limitation on the developing agent that can be used in the method of the present invention.
he Theory of the PhotographicProcess ”, 4th edition, Ma
Various compounds described on pages 298 to 327 of cmillan can be used. For example, dihydroxybenzenes (eg, hydroquinone), 3-pyrazolidones (eg, 1-phenyl-3-pyrazolidone, 4,4-
Dimethyl-1-phenyl-3-pyrazolidone), aminophenols (eg, N-methyl-p-aminophenol), ascorbic acid, hydroxyamines and the like can be used alone or in combination. The silver halide light-sensitive material of the present invention is particularly suitable to be processed with a developer containing dihydroxybenzenes as a main developing agent and 3-pyrazolidones or aminophenols as an auxiliary developing agent. Preferably, in this developer, dihydroxybenzenes are used in an amount of 0.05 to 0.5 mol / l, and 3-pyrazolidones or aminophenols are used in an amount of 0.06 mol / l or less. Further, as described in U.S. Pat. No. 4,269,929, the addition of amines to a developer can increase the development speed and reduce the development time. Other developers include pH buffers such as alkali metal sulfites, carbonates, borates, and phosphates, bromides, iodides,
And a development inhibitor such as an organic antifoggant (particularly preferably nitroindazoles or benzotriazoles) or an antifoggant. If necessary, a water softener, a dissolution aid, a color tone agent, a development accelerator, a surfactant (particularly preferably the above-mentioned polyalkylene oxides), an antifoaming agent, a hardening agent, a silver stain preventing agent for a film. (For example, 2-mercaptobenzimidazolesulfonic acids).

As the fixing solution, those having a commonly used composition can be used. Thiosulfate as fixing agent,
In addition to the thiocyanate, an organic sulfur compound known to have an effect as a fixing agent can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

The processing temperature in the process of the present invention is usually 18
Between 50 ° C and 50 ° C. Although it is preferable to use an automatic developing machine for photographic processing, according to the method of the present invention, even if the total processing time from when the photosensitive material is put into the automatic developing machine to when it comes out is set to 90 seconds to 120 seconds. Thus, a photographic characteristic of a negative tone with a sufficiently high contrast can be obtained. In the developer of the present invention, compounds described in JP-A-56-24347 can be used as silver stain inhibitors. Compounds described in JP-A-61-267759 can be used as a dissolution aid to be added to the developer. Further pH used for developer
Compounds described in JP-A-60-93,433 can be used as buffering agents.

The compound of the present invention can be used in a color photographic light-sensitive material. For other techniques and inorganic / organic materials in that case, refer to the following description in Japanese Patent Application No. 3-161745. it can.

1. Layer structure: page 28, lower left column, first line to second
Page 9, upper right column, 7th line Silver halide emulsion: page 29, upper right column, line 8 to 30
12th line in the upper right column of the page 3. Yellow coupler: page 30, lower right column, lines 5 to 11 Magenta coupler: page 30, lower right column, line 12 to third
4th line on page 1 5. Cyan coupler: page 31, upper left column, lines 4 to 16 6. Polymer coupler: page 31, upper left column, line 17 to upper right column, first line Functional coupler: page 31, upper right column, second line to lower right column, 5
Line 8 8. Antiseptic / antifungal agent: page 32, top right column, lines 10-17. Formalin scavenger: page 30, lower left column, lines 16 to 20 10. Other additives: page 35, lower right column, lines 19 to 36
Page 14 upper left column, line 14 and page 30 upper right column, line 13 to lower left column, line 15 11. Dispersion method: page 31, lower right column, line 8 to page 32, upper right column, line 9 12. Support: Page 32, lower left column, lines 4 to 6 13. Film thickness / film properties: page 32, lower left column, line 7 to lower right column 10
Line 14. Color development step: page 32, lower right column, line 15 to page 33, lower right column, line 16 15. Desilvering step: page 32, lower right column, line 17 to page 35, upper left column, line 16 16. Automatic processor: page 35, lower left column, line 17 to upper right column, line 5 17. Rinse / stabilization process: page 35, upper right column, line 6 to lower right column 1,
5th line

[0057]

The present invention will be described below in detail with reference to specific examples of the present invention. However, the present invention is not limited to these examples. Example 1 (First Photosensitive Emulsion Layer) Preparation of Photosensitive Emulsion A 0.37 M aqueous silver nitrate solution and 1 × 10 5 per mol of silver
(NH ₄ ) ₃ RhCl ₆ corresponding to ⁻⁷ mol and 5 × 10
^An aqueous solution of a halogen salt containing ⁻⁷ mol of K ₃ IrCl ₆ 0.11 M potassium bromide and 0.27 M sodium chloride is stirred into an aqueous gelatin solution containing sodium chloride and 1,3-dimethyl-2-imidazolidinthione. While adding by a double jet method at 45 ° C. for 12 minutes,
Average grain size 0.20 µm, silver chloride content 70 mol%
Nucleation was carried out by obtaining silver chlorobromide grains of Subsequently, a silver salt aqueous solution containing 0.63 M silver nitrate aqueous solution, 0.19 M potassium bromide, and 0.47 M sodium chloride was similarly added by a double jet method over 20 minutes. Thereafter, a KI solution of 1 × 10 ⁻³ mol was added to perform conversion, washed with water by a flocculation method according to a conventional method, and 40 g of gelatin was added.
6.5 and pAg 7.5, and 5 mol of sodium thiosulfate, 8 mg of chloroauric acid and 7 mg of sodium benzenethiosulfonate per 1 mol of silver were added.
And a chemical sensitization treatment, and 150 mg of 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene as a stabilizer and proxel (trade name: I
CI Co. Ltd. And phenoxyethanol. The resulting grains were silver chlorobromide cubic grains having an average grain size of 0.28 μm and a silver chloride content of 70 mol%.
(Coefficient of variation: 9%) Coating of first photosensitive emulsion layer These emulsions were divided and used as a sensitizing dye at 1 × 10 ^-3 mol of 5-｛[3- (4-sulfobutyl) per mol of silver.
-5-chloro-2-benzoxazolidylidene] ethylidene {-1-hydroxyethoxyethyl-3- (2-pyridyl) -2-thiohydantoin potassium salt, and 2 × 10 ^-4 mol of 1-phenyl -5-mercaptotetrazole, 5 × 10 ⁻⁴ mol of a short-wave cyanine dye of the compound (a) represented by the following structural formula, a polymer of the compound (b) (200 mg / m ² ), hydroquinone (50
mg / m ² ) and a dispersion of polyethyl acrylate (200 mg / m ² ), 1,3-bisvinyl-sulfonyl-2-propanol (200 mg / m ²
m ² ), the following hydrazine compound (c) was added as a nucleating agent, and the coated silver amount was 3.6 g / m ² , and the gelatin was 2.0 g / m ² .
² was applied.

[0058]

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(Coating of Intermediate Layer) Gelatin 1.0 g / m ² 1,3-bisvinylsulfonyl-2-propanol 4.0 wt% to gelatin (second photosensitive emulsion layer) Preparation of photosensitive emulsion B 0M silver nitrate aqueous solution and 3 × 10 ^-7 per mole of silver
An aqueous halide solution containing molar (NH ₄ ) ₃ RhCl ₆ , containing 0.3 M potassium bromide and 0.74 M sodium chloride, containing sodium chloride and 1,3-dimethyl-2-imidazolidinthione Added to the aqueous gelatin solution by double jet method at 45 ° C. for 30 minutes while stirring,
Average grain size 0.28 µm, silver chloride content 70 mol%
Of silver chlorobromide particles were obtained. Thereafter, it was washed with flocculation according to a conventional method, and 40 g of gelatin was added.
6.5 and pAg 7.5, and 5 mg of sodium thiosulfate and 8 mg of chloroauric acid per 1 mol of silver were added.
The mixture was heated at 60 ° C. for 60 minutes, subjected to a chemical sensitization treatment, and 150 mg of 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene was added as a stabilizer. The resulting grains were silver chlorobromide cubic grains with an average grain size of 0.28 μm and a silver chloride content of 70 mol%. (Coefficient of variation 10%)

Coating of Second Photosensitive Emulsion Layer Photosensitive Emulsion B was re-dissolved and, at 40 ° C., 1.0 × 10 ⁻³ mol of 5-（[3- (4
-Sulfobutyl) -5-chloro-2-benzooxazolidylidene] ethylidene {-1-hydroxyethoxyethyl-3- (2-pyridyl) -2-thiohydantoin potassium salt and 1.0 × 10 ^-3 mol of KI The solution was added, and a dispersion of 2 × 10 ⁻⁴ mol of 1-phenyl-5-mercaptotetrazole and polyethylene acrylate was further added to 50 mol.
mg / m ² , 1,3-bisvinylsulfonyl-2-propanol as a hardening agent was 4.0 wt% based on gelatin,
Redox compound of the present invention or comparative example 5.8 × 10 ⁻⁵
mol / m ² as shown in Table 1, and the coated silver amount was 0.3 g / m ^2.
m ² and gelatin 0.4 g / m ² .

(Coating of protective layer)
Gelatin 0.5 g / m ^2, polymethyl methacrylate particles (average particle size 2.5μ) 0.3g / m ² was coated with the following surface active agents.

[0062]

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The back layer and the back 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 mg / m ²

[0064]

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Dye Mixture of dyes [a], [b] and [c] Dye [a] 50 mg / m ² Dye [b] 100 mg / m ² Dye [c] 50 mg / m ²

[0066]

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[Back protective layer] Gelatin 0.8 g / m ² polymethyl methacrylate fine particles (average particle size 4.5 μ) 30 mg / m ² dihexyl-α-sulfosuccinate sodium salt 15 mg / m ² dodecylbenzenesulfonic acid sodium salt 15 mg / m ² sodium acetate 40 mg / m ²

[0068]

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On a polyester film (100μ) support, a first photosensitive emulsion layer was formed as a lowermost layer, a second photosensitive emulsion layer containing a redox compound was further provided via an intermediate layer, and a protective layer was further coated thereon. Then, the samples shown in Table 1 were prepared.

The samples shown in Table 1 were exposed to tungsten light at 3200 ° K through an optical wedge and a contact screen (Fujifilm, 150L chain dot type), developed with the following developer A at 34 ° C for 30 seconds, fixed, and washed with water. And dried. Developer A Hydroquinone 50.0 g N-methyl-p-aminophenol 0.3 Sodium hydroxide 18.0 5-Sulfosalicylic acid 55.0 Potassium sulfite 24.0 Disodium ethylenediaminetetraacetate 1.0 Potassium bromide 10.0 5-methylbenzotriazole 0.4 2-mercaptobenzimidazole-5-sulfonic acid 0.3 sodium 3- (5-mercaptotetrazole) benzenesulfonate 0.2 N-n-butyldiethanolamine 15.0 sodium toluenesulfonate 8 PH was adjusted to 11.6 by adding 1.0 water (adding potassium hydroxide). PH 11.6 Halftone was expressed by the following formula. * Exposure amount (log E giving halftone area ratio of 95%)
95%) — Exposure dose (log E giving 5% halftone dot area ratio)
5%) The dot quality was visually evaluated on a 5-point scale. The five-point rating is
"5" indicates the best quality and "1" indicates the worst quality. "5" and "4" can be used as halftone dot masters for plate making.
"3" is a practical limit level, "2", "1"
Is of impractical quality. Table 1 shows the results.

[0071]

[Table 1]

The structural formula of the comparative compound is shown below.

[0073]

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[0074]

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As can be seen from the results in Table 1, Comparative Sample 1-f and all the samples of the present invention show high halftone and high halftone quality.

Example 2 A photosensitive material was prepared in which the following changes were made to Example 1. First photosensitive emulsion layer: As a nucleating agent, hydrazine compound 2-21 was added in an amount of 1.0 × 10 ⁻⁵ mol / m ² . Intermediate layer: gelatin (1.0 g / m ² ), the following compound (15
mg / m ² ), and 1,3-bisvinylsulfonyl-2-
Contains 2.0 wt% propanol to gelatin.

[0077]

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Second photosensitive emulsion layer: Redox compound of the present invention and Comparative Example 9.5 × 10
^-5 mol / m ² was added as shown in Table 2, and the coated silver amount was 0.4 g.
/ M ² and gelatin at 0.5 g / m ² . The performance was evaluated in the same manner as in Example 1 using the following developer B. Developer B Hydroquinone 30.0 g N-methyl-p-aminophenol 0.3 Sodium hydroxide 10.0 Potassium sulfite 60.0 Diethylenetriaminepentaacetic acid 1.5 Potassium bromide 10.0 5-Methylbenzotriazole 0.42 -Mercaptobenzimidazole-5-sulfonic acid 0.3 Sodium 3- (5-mercaptotetrazole) benzenesulfonate 0.2 Sodium toluenesulfonate 8.0 Add water and adjust to 1 liter pH = 10.5 (hydroxylation PH was added (with addition of potassium). The results are shown in Table 2. The samples of the present invention exhibited a wide halftone and high halftone quality.

[0079]

[Table 2]

Example 3 (Preparation of Photosensitive Emulsion C) A silver nitrate aqueous solution and sodium chloride were added to a gelatin aqueous solution kept at 50 ° C. in the presence of 5.0 × 10 ⁻⁶ mol of (NH ₄ ) ₃ RhCl ₆ per mol of silver. After the aqueous solutions are mixed simultaneously, the soluble salts are removed and removed by a method well known in the art, and gelatin is added thereto. As a stabilizer without chemical ripening, 6-methyl-4-hydroxy-1, 3,3
a, 7-Tetrazaindene was added. This emulsion was a cubic monodispersed emulsion having an average size of 0.15 μm.

(Coating of Photosensitive Emulsion Layer) The hydrazine compound 2-8 (75 mg /
m ² ), 5-methylbenzotriazole (5 × 10 ⁻³ mol /
Ag mol), polyethyl acrylate latex (30wt
% Of gelatin), and 1,3-bisvinylsulfonyl-2-propanol (2.0 wt% of gelatin). The amount of silver applied was 3.5 g / m ² and gelatin was 2 g / m ² . Second layer Gelatin (1.0 g / m ² ) Third layer Photosensitive emulsion C was mixed with 5-methylbenzotriazole (5 × 1
0 ^-3 mol / Ag mol), polyethyl acrylate latex (30 wt% vs. gelatin), 1,3-divinylsulfonyl-2-propanol (2 wt% vs. gelatin), and
The redox compound of the present invention shown in No. 3 was added, and coating was performed so that the coated silver amount was 0.4 g / m ² and the gelatin was 0.5 g / m ² . Fourth layer (protective layer) Gelatin 1.5 g / m ² and polymethyl methacrylate particles (average particle size 2.5 μ) 0.3 g /
m ² , and a protective layer containing the following surfactant, stabilizer, and ultraviolet absorbing dye as a coating aid were applied and dried.

[0082]

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Stabilizer Thioctic acid 2.1 mg / m ²

[0084]

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The sample was applied to a light room printer p-607 manufactured by Dainippon Screen Co., Ltd.
The image was exposed through a document as shown in FIG. 1 and developed with a developing solution A at 38.degree. C. for 20 seconds. After fixing, washing and drying, the quality of the blank characters was evaluated. The extracted character image quality 5 is defined by using an original as shown in FIG. 1 of JP-A-1-240966.
This is an image quality in which a character having a width of 30 μm is reproduced when properly exposed so that a dot area of 0% becomes a dot area of 50% on a return photosensitive material. On the other hand, the character extraction quality 1 is an image quality that can only reproduce characters having a width of 150 μm or more when the same appropriate exposure is given. Rank was set. Three or more is a practical level. The results are shown in Table 3.

[0086]

[Table 3]

As can be seen from the results shown in Table 3, the samples of the present invention have excellent image quality of cut characters.

[0088]

According to the present invention, the use of the compound represented by the general formula (1) has provided a silver halide photographic light-sensitive material capable of obtaining good halftone, halftone dot quality and character-free image quality. .

Claims (2)

(57) [Claims] 1. A silver halide photographic light-sensitive material comprising a redox compound represented by the following general formula (1). General formula (1) In the formula, R ₁ represents an aliphatic group or an aromatic group, -O as further part of the substituent _{- (CH 2 CH 2 O)} n -, - O -
(CH ₂ CH (CH ₃ ) O) _n -or -O-(CH ₂ CH (OH) CH ₂ O) _n
-(Where n is an integer of 3 or more). G ₁ represents a —CO— group, a —COCO— group, a —CS— group, a —C
(= NG ₂ R ₂ )-, -SO-, -SO _2- or -P (O) (G
₂ R ₂ )-represents a group. G ₂ is a mere bond, -O-group,-
S - group, or -N (R ₂₎ - represents a group, R ₂ represents an aliphatic group,
Represents an aromatic group or a hydrogen atom, and a plurality of R ₂
May be the same or different when are present. One of A ₁ and A ₂ is a hydrogen atom, and the other is a hydrogen atom or an acyl group, an alkyl or an arylsulfonyl group. Time represents a divalent linking group, and t represents 0
Or represents 1. PUG represents a development inhibitor. 2. The image forming layer containing a silver halide emulsion or another hydrophilic colloid layer contains a hydrazine compound different from the compound represented by the general formula (1). 2. The silver halide photographic light-sensitive material according to item 1.