JPH0545767A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To stabilize a developing solution, to enhance contrast and image quality, and to widen dot gradation of an image by incorporating a specified redox compound. CONSTITUTION:The silver halide photographic sensitive material contains the redox compound represented by formula I in which R1 is an aliphatic or aromatic group optionally substituted by =0-(CH2CH2O)n- or -O-@{9146/28H2CH (CH3)O]n- or the like; n is an integer of >=3; G<1> is -CO2--SOt2--SOt, -COCO-, -CS-, or the like; R2 is an aliphatic or aromatic group or H; one of A1 and A2 is H and the other is acyl or alkyl or the like; Time is a divalent bonding group: t is 0 or 1; and PUG is a development inhibitor.

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 super-hard tone negative image forming method using the same. The present invention relates to a negative photographic light-sensitive 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 easy replenishment in order to cope with the variety and complexity of printed matter. .. Especially in the line drawing process, the manuscript is made by pasting typesetting characters, handwritten characters, illustrations, and half-tone dots. Therefore, in the manuscript,
There is a strong demand for a plate-making camera, a photographic light-sensitive material, or an image forming method that mixes images having different densities and line widths and finishes these originals with good reproduction. On the other hand, halftone pictures are enlarged (expanded) or reduced (closed) widely in the production of catalogs and large posters, and in the production of enlarging halftone dots, the number of lines becomes rough and blurred. Will be taken. In reduction, the number of lines / inch is larger than that of the original, and a thin dot is captured. Therefore, an image forming method having a wider latitude is required 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 photographing sensitivity with respect to these light sources, the photographic light-sensitive material is usually ortho-sensitized. However, it has been found that the ortho-sensitized photographic light-sensitive material is more strongly affected by the chromatic aberration of the lens, so that the image quality is likely to deteriorate. Further, this deterioration becomes more remarkable for the xenon lamp light source.

As a system which meets the demand for a wide latitude, a lith-type silver halide light-sensitive material made of silver chlorobromide (at least a silver chloride content of 50% or more) has an extremely low effective concentration of sulfite ion (usually 0. 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 portion and a non-image portion are clearly distinguished by processing with a hydroquinone developer. However, with this method, the concentration of sulfurous acid in the developer is low, so development is extremely unstable against air oxidation, and various efforts and efforts have been made to maintain stable solution activity. The current situation is that it is extremely slow and reduces work efficiency. Therefore, an image forming system that eliminates the instability of image formation due to the above-described developing method (lith development system) and develops with a processing solution having good storage stability to obtain super-high contrast photographic characteristics is provided. There is a demand, and one of them is U.S. Pat. Nos. 4,166,742 and 4,168,977.
No. 4,221,857, 4,224,401
No. 4,243,739, 4,272,606
No. 4,311,781, a surface latent image type silver halide photographic light-sensitive material containing a specific acylhydrazine compound is added at a pH of 11.0 to 12.3 with a sulfite preservative. A system has been proposed in which a super-high contrast negative image having a γ of more than 10 is formed by processing with a developer containing 15 mol / liter or more and having good storage stability. This new image forming system can only use silver chlorobromide, which has a high silver chloride content in conventional super-high contrast image formation, whereas silver iodobromide and silver chloroiodobromide can also be used. There is. Although the above image system exhibits excellent performance in terms of sharp halftone dot quality, processing stability, speediness and original reproducibility, the original reproducibility was further improved to cope with the recent variety of printed matter. A system is desired. JP-A-61-213847 and JP-A-6-6138
2-260,153, JP-A-64-88451, JP-A-64-72140, and US Pat. No. 4,684,60.
No. 4 shows a light-sensitive material containing a redox compound that releases a development inhibitor upon oxidation, and an attempt to widen the gradation reproduction range is shown. However, in the ultrahigh contrast processing system using a hydrazine derivative, these redox compounds are
When a sufficient amount is added to the light-sensitive material to make the line image reproducibility and the halftone dot image reproducibility good, a part of the inhibitor released during the development processing flows out. When a large amount of a light-sensitive material containing these redox compounds is continuously processed, the inhibitor gradually accumulates in the developing solution. Therefore, when development processing is performed using the fatigue developing solution which has been processed in this way, inhibition of contrast enhancement and reduction in sensitivity occur. In particular, when one automatic developing machine is used for developing various other photographic light-sensitive materials, contact light-sensitive materials, scanner light-sensitive materials, or photographic light-sensitive materials in addition to light-sensitive materials containing these redox compounds, Photographic adverse effects on other sensitive materials pose a problem. Therefore, since the amount of such a redox compound used is limited, it is not possible to exert a sufficiently satisfactory effect, and it is required only for a closed system in which the photosensitive material and the developing solution are limited to a narrow range. No, improvement was desired.

[0004]

SUMMARY OF THE INVENTION It is, therefore, an object of the present invention, firstly, to provide a novel compound which is excellent in storage stability and rapidly releases a development inhibitor. Secondly, it is to provide a compound that causes less fatigue of the developing solution even when used in an amount sufficient to provide good image reproducibility in the contrast sensitive material system. Thirdly, it is to provide a photographic material for plate making which can obtain a high contrast image by using a highly stable developing solution. Fourthly, it is to provide a light-sensitive material for plate-making, which is a hard-sensing material using a hydrazine nucleating agent and has a wide halftone gradation. Fifth, it is to provide a photosensitive material for plate making which has good running stability during development processing.

[0005]

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

[0006]

[Chemical 2]

In the formula, R ₁ represents an aliphatic group or an aromatic group, and as a part of the substituent, —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} - ( where n is a group containing a partial structure of an integer of 3 or more). G ₁ is 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
Represents a group, a —S— group or a —N (R ₂ ) — group, R ₂ represents an aliphatic group, an aromatic group or a hydrogen atom, and when a plurality of R _2's are present in the molecule, they are the same. It may or may not be. 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 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 is preferably an aliphatic group having 1 to 30 carbon atoms, and particularly 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. Examples thereof include a benzene ring, a naphthalene ring, a pyridine ring, a quinoline ring and an isoquinoline ring. Of these, those containing a benzene ring are preferable. Particularly preferred as R ₁ is an aryl group. The aryl group or unsaturated heterocyclic group of R ₁ is substituted.

The aliphatic group or aromatic group of R ₁ is substituted, and a typical substituent is, for example, an alkyl group,
Aralkyl group, alkenyl group, alkynyl group, alkoxy group, aryl group, substituted amino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, Examples thereof include a halogen atom, a cyano group, a sulfo group, an aryloxycarbonyl group, an acyl group, an alkoxycarbonyl group, an acyloxy group, a carbonamido group, a sulfonamide group, a carboxyl group, and a phosphoric acid amide group. A branched or cyclic alkyl group (preferably having 1 carbon atom)
To 20) and aralkyl groups (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 a carbon number of 1 to 30)
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), an ureido group (preferably having 1 carbon atom). And a phosphoric acid amide group (preferably having 1 to 40 carbon atoms).

The aliphatic group, aromatic group or their substituents for R ₁ 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)

[0011]

[Chemical 3]

In the formula, L ₁ is a --CH ₂ CH ₂ O-- group, --CH ₂ CH (CH
₃₎ O - group, or represents _{-CH 2 CH (OH) CH 2} O- radical, n is as in formula (1) synonymous. L _2, L ₃ is -CONR ₇ -
Group, --NR ₇ CONR ₈ --group, --SO ₂ NR ₇ --group, or --NR ₇ SO ₂ NR
_It represents ₈ groups and may be the same or different. R ₇ and R ₈ represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, and a hydrogen atom is preferable. n is 0 or 1. R ₃ represents an aliphatic group or an aromatic group and may be substituted.
The description of R ₁ is applicable to the specific embodiment as it is, but it is not always necessary to be substituted. R ₄ ,
R ₅ and R ₆ are divalent aliphatic groups or aromatic groups, preferably an alkylene group, an arylene group, or
O- group, -CO- group, -S- group, -SO- group, -SO ₂ - group,
-NR ₉ - group (R ₉ of the general formula (R ₇ as defined in 2)) is a divalent group produced by combining a. More preferably, R ₄ is an alkylene group having 1 to 10 carbon atoms or a divalent group formed by combining them with an —S— group, —SO— group, or —SO ₂ — group, and R ₅ , R ₆ Has 6 carbon atoms
To 20 arylene groups. Particularly, R ₆ is preferably a phenylene group. R ₄ , R ₅ and R ₆ may be substituted, and preferable substituents include those enumerated as the substituents for R ₁ .

As G ₁ in the general formula (1), --CO--
Group, -SO ₂ - groups are preferred, -CO- group is most preferred.
A hydrogen atom is preferable as A ₁ and A ₂ .

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 capable of releasing PUG from Time-PUG released from the oxidized product of the redox mother nucleus through one or more steps of reaction. Examples of the divalent linking group represented by Time include PUG by an intramolecular ring-closing reaction of a p-nitrophenoxy derivative described in, for example, US Pat. No. 4,248,962 (Japanese Patent Laid-Open No. 54-145,135). Emitting substance; U.S. Pat. No. 4,310,612 (JP-A-55)
-53,330) and 4,358,525 and the like to release PUG by an intramolecular ring closure reaction after ring opening; US Pat. Nos. 4,330,617 and 4,4.
46,216, 4,483,919, JP-A-59.
-121,328 and the like, which release PUG with the formation of an acid anhydride by the intramolecular ring closure reaction of the carboxyl group of the succinic acid monoester or its analogs; US Pat. No. 4,409,323 , Ibid. 4,421,845
Issue, Research Disclosure No. 21,228
(December 1981), U.S. Pat. No. 4,416,977.
(Japanese Patent Laid-Open No. 57-135,944), Japanese Patent Laid-Open No. 58-2
09,736, 58-209,738, etc. to generate quinomonomethane or an analog thereof by electron transfer through a double bond conjugated with an aryloxy group or a heterocyclic oxy group to release PUG. U.S. Pat. No. 4,420,554 (JP-A-57-136,640)
No. 57 / 135,945, 57-18.
8,035, 58-98,728 and 58-
Nos. 209,737 and the like, which release PUG from the γ-position of enamine by electron transfer of the portion having the enamine structure of the nitrogen-containing heterocycle; the nitrogen-containing heterocycle described in JP-A-57-56,837. Release of PUG by intramolecular ring closure reaction of oxy group formed by electron transfer to carbonyl group conjugated with nitrogen atom; US Pat. No. 4,14
6,396 (JP-A-52-90932), JP-A-5
No. 9-93,442, JP-A-59-75475, JP-A-60-249148, JP-A-60-249149, etc., which release PUG with the formation of aldehydes; 51-146,828, ibid. 57-17
Those releasing PUG with decarboxylation of the carboxyl group described in Nos. 9,842 and 59-104,641;
O-COOCR _a R _b -PUG (R _a and R _b represent a monovalent group) and releases PUG with decarboxylation and subsequent formation of aldehydes;
Release of PUG with formation of isocyanate as described in US Pat. No. 4,438,193;
And the like, which release PUG by a coupling reaction with an oxidant of a color developing agent described in JP-A No. 1994-242242 and the like. Specific examples of these divalent linking groups represented by Time are described in JP-A No. 61-236,549 and Japanese Patent Application No.
3-98,803, Japanese Patent Application No. 2-93487, and the like.

In the general formula (1), PUG is a development inhibitor. PUG has a hetero atom and is bonded to the other part of the compound represented by the general formula (1) through the hetero atom. Examples of commonly known development inhibitors are, for example, "The Theory," by TH James.
The Theory Process
of the Photographic Process) "4th edition, 1977,
It is described in pp. 396 to 399 and pp. 56 to 69 of Japanese Patent Application No. 2-93,487, published by Macmillan. These development inhibitors may have a substituent. Examples of useful substituents include mercapto group, nitro group, carboxyl group, sulfo group, phosphono group, hydroxy group, alkyl group, aralkyl group, alkenyl group,
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 thereof include a cyano group, an aryloxycarbonyl group, an acyl group, an alkoxycarbonyl group, an acyloxy group, a carbonamido group, a sulfonamide 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 that inhibits nucleation infectious development. Nucleating and infectious development is based on the Fujifilm GRANDEX system (Fuji Photo Film Co., Ltd. and Kodak Ult.
ratec system (Eastman KodakC
o., Ltd. ) Is a new development chemistry used in the image forming method of 1). This development chemistry is described in "Journal of the Photographic Society of Japan, Vol. 52, No. 5, pp. 390-394 (1989).
And "Journal of Photographic Science", Vol. 35, p. 162 (1987), the development process of exposed silver halide grains with a normal developing agent and the oxidation product of the developing agent thus produced. Nucleating active species are generated on the basis of cross-oxidation between the nucleating agent and the nucleating agent, and are composed of two processes, i.e., the unexposed surroundings to the nucleating and developing process of weakly exposed silver halide grains by the active species. .. Therefore, the entire development process consists of the sum of the normal development process and the nucleation development process. Therefore, in addition to the normal development inhibitor conventionally known as a development inhibitor, the nucleation-infectious development process is newly suppressed. Compounds that exert the inhibitory effect. 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, conventionally known development inhibitors are also effective, but particularly effective compounds include 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 thereof include quinones, tetrazoliums, amine oxides, azoxy compounds, and coordination compounds having oxidizing ability. Among them, a compound having a nitro group and a compound having a pyridine skeleton are particularly effective.

These nucleation development inhibitors may have a substituent, and the properties of the substituent, such as electron-withdrawing property, electron-donating property, hydrophobicity, hydrophilicity, charge and adsorptivity to silver halide. It is possible to control various characteristics such as the strength of development inhibition and easiness of diffusion depending on such properties. Examples of useful substituents include those listed above as examples of common development inhibitor substituents. Specific examples of these nucleation development inhibitors useful in the present invention are described in detail in Japanese Patent Application Nos. 2-258927 and 2-258928, and also in Japanese Patent Application Nos. 2-258929 and 3-258929. 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 a silver halide grain having an anionic charged group or a dissociative group capable of dissociating in a developing solution to generate anionic charge is also effective. ..

In the general formula (1), R ₁ or T
ime may include a ballast group that is commonly used in a non-moving photographic additive such as a coupler or a group that promotes adsorption of a compound represented by the general formula (1) to silver halide. Good. The ballast group is an organic group that gives a molecular weight sufficient to prevent the compound represented by the general formula (1) from substantially diffusing into another layer or the treatment liquid, and an alkyl group, an aryl group, a heterocyclic group,
Ether group, thioether group, amide group, ureido group,
It is composed of a combination of one or more urethane groups, sulfonamide groups 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 adsorption promoting group for 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- Cyclic thioamide group such as imidazoline-2-thione, chain thioamide group, aliphatic mercapto group, aromatic mercapto group, heterocyclic mercapto group (If the carbon atom next to the -SH group is a nitrogen atom, It has the same meaning as a 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, oki 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 compounds such as benzimidazolinium Examples include salt. These may be further substituted with appropriate substituents. Examples of the substituent include those mentioned as the substituent of R ₁ . Specific examples of the compound used in the present invention are listed below, but the present invention is not limited thereto.

[0020]

[Chemical 4]

[0021]

[Chemical 5]

[0022]

[Chemical 6]

[0023]

[Chemical 7]

[0024]

[Chemical 8]

As the redox compound used in the present invention, in addition to the above-mentioned compounds, for example, JP-A-61-213,8 can be used.
No. 47, No. 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,
No. 2-258927, No. 2-258928, No. 2-
258929, 3-15648, 3-7038.
No. 8 and No. 3-70411 can be used. The method for synthesizing the redox compound used in the present invention is described in the above-mentioned materials, and for example, US Pat. No. 4,684,604 and Japanese Patent Application No. 63-98,803.
U.S. Pat. Nos. 3,379,529 and 3,620,
No. 746, No. 4,377, 634, No. 4,332, 8
78, JP-A-49-129,536 and JP-A-56-15.
No. 3,336,56-153,342.

The redox compound of the present invention is used in the range of 1 × 10 ^{-6 to} 5 × 10 ^-2 mol, and more preferably 1 × 10 ^-5 to 1 × 10 ^-2 mol, per mol of silver halide. .. The redox compound of the present invention is a suitable water-miscible organic solvent, for example, alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl cellosolve, etc. It can be dissolved in and used. Further, by a well-known emulsification and dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified and dispersed. It is also possible to create and use things. Alternatively, by a method known as a solid dispersion method, the powder of the redox compound is ball milled in water, a colloid mill,
Alternatively, they can be dispersed by ultrasonic waves and used.

The redox compound of the present invention is added to a silver halide emulsion layer or other hydrophilic colloid layer. Further, it may be added to at least one of a plurality of silver halide emulsion layers. Although some constitutional examples are given, the present invention is not limited to these. Structural Example 1) A support has a silver halide emulsion layer containing the redox compound of the present invention and a protective layer. The emulsion layer or the protective layer 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 or the adjacent hydrophilic colloid layer is provided. , The second hydrazine compound, and the second silver halide emulsion layer or the adjacent hydrophilic colloid layer contains the redox compound. Structure Example 3) In Structure Example 2), the order of the two emulsion layers is reversed. In the constitution examples 2) and 3), an intermediate layer containing gelatin or a synthetic polymer (polyvinyl acetate, polyvinyl alcohol, etc.) may be provided between the two photosensitive emulsion layers. Structural Example 4) Having a silver halide emulsion layer containing a second hydrazine compound 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. Particularly preferable configuration is the 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]

[Chemical 9]

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 It represents a sulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. It may be selected from the same range as the groups defined for R ₁₃ and R ₁₂ and 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. The aromatic group represented by R ₁₁ in the general formula (3) is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with an aryl group. Preferred as R ₁₁ is an aryl group, and particularly preferred is one containing a benzene ring. R ₁₁
The aliphatic group or aromatic group 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, a ureido group, and 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 may be selected from the same groups as defined for R ₂ and may be different from each other) As preferred substituents, 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), a substituent Amino group (preferably an amino group substituted with an alkyl group having 1 to 20 carbon atoms), an acylamino group (preferably having 2 to 30 carbon atoms), a sulfonamide group (preferably having 1 to 30 carbon atoms) ), An ureido group (preferably having 1 to 30 carbon atoms), a phosphoric acid amide group (preferably having 1 to 30 carbon atoms), and the like.
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 groups among R ₁₂ are a hydrogen atom, an alkyl group (eg, methyl group, trifluoromethyl group, 3-hydroxypropyl group, 3-methane). Sulfonamidopropyl group, phenylsulfonylmethyl group, etc.), aralkyl group (eg, o-hydroxybenzyl group, etc.), aryl group (eg, phenyl group, 3,5-dichlorophenyl group, o-
(Methanesulfonamidephenyl group, 4-methanesulfonylphenyl group, 2-hydroxymethylphenyl group, 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. As G _{11 in the} general formula (3), -CO
-Groups are most preferred. Further, R ₁₂ may be such as to rise to cyclization reaction to form a cyclic structure containing disrupts portion G ₁₁ -R ₁₂ from the remainder molecule, -G ₁₁ -R ₁₂ parts of atoms For example, Japanese Patent Laid-Open No. 63-297
51, etc. are mentioned. A hydrogen atom is most preferable as A ₁₁ and A ₁₂ .

R ₁₁ or R _{12 in} the general formula (3) may have a ballast group or a polymer incorporated therein which is commonly used in a non-moving photographic additive such as a coupler. The ballast group is a group having a carbon number of 8 or more and relatively inert to photographic properties, and is selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group and an alkylphenoxy group. You can Further, as a polymer, for example, JP-A-1-1005
Those described in No. 30 are mentioned.

R ₁₁ or R _{12 in} the general formula (3) may be one in which a group for enhancing adsorption to the surface of the silver halide grain is incorporated. Examples of the adsorptive group include US Pat. No. 4,285,108 such as thiourea group, heterocyclic thioamide group, mercaptoheterocyclic group and triazole group,
U.S. Pat. No. 4,459,347, JP-A-59-195,233.
No. 59-200, 231, 59-201, 04
No. 5, No. 59-201, 046, No. 59-201, 0
47, 59-201, 048, 59-201,
049, 61-170, 733, 61-27.
0,744, 62-948, 63-234,2.
44, 63-234, 245, 63-234,
The groups described in No. 246 are mentioned. 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]

[Chemical 10]

[0036]

[Chemical 11]

[0037]

[Chemical formula 12]

[0038]

[Chemical 13]

[0039]

[Chemical 14]

[0040]

[Chemical 15]

[0041]

[Chemical 16]

[0042]

[Chemical 17]

As the hydrazine compound used as the nucleating agent in the present invention, in addition to the above-mentioned ones, RESEARCH DIS
CLOSURE Item 23516 (November 1983, p.3)
46) and the references cited therein, as well as US Pat.
080,207, 4,269,929, 4,2
76,364, 4,278,748, 4,38
5, 108, 4,459,347, 4,56
0,638, 4,478,928, British Patent 2,
011,391B, JP-A-60-179,734,
62-270,948, 63-29,751,
61-170,733, 61-270,744
No. 62-270,948, EP217,310.
No., EP356,898, US4,686,167
No. 62-178,246, 61-32,5.
No. 38, No. 63-104, 047, No. 63-121,
838, 63-129, 337, 63-22
3,744, 63-234,244, 63-2
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. 1-228, 747, 1-283, 548
No. 1-253, 549, 1-285, 940
No. 2-2541, No. 2-139, 538, No. 2
-77057, Japanese Patent Application Nos. 1-18,377 and 1-1.
8,378, 1-18,379, 1-15,7
55, 1-16,814, 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 the nucleating agent in the present invention is preferably contained in an amount of 1 × 10 ^-6 mol to 5 × 10 ^-2 mol, and particularly 1 × 10 ^-5 mol to 2 mol, per mol of silver halide.
The preferable addition amount is in the range of ^{x10 -2} mol. The method for dissolving and dispersing these hydrazine nucleating agents is described in the general formula (1) above.
The same method can be used as that of the compound of.

The silver halide used in the present invention may have any composition such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide and silver iodochlorobromide. The average grain size of silver halide used in the present invention is preferably fine grains (for example, 0.7 μ or less), and particularly preferably 0.5 μ or less. The particle size distribution is basically not limited, but it is preferably monodisperse. Here, the monodispersion means that at least 95% by weight or the number of particles is composed of a particle group having a size within ± 40% of the particle size. The silver halide grains in the photographic emulsion may have a regular crystal such as a cube and an octahedron, and may have a spherical shape.
It may have an irregular crystal such as a plate, or may have a composite form of these crystal forms. The silver halide grains may have a uniform phase in the inside and the surface layer, or may have different phases. Two or more kinds of silver halide emulsions formed separately may be mixed and used. In the silver halide emulsion used in the present invention, cadmium salt, sulfite salt, lead salt, thallium salt, rhodium salt or its complex salt, iridium salt or its complex salt and the like are allowed to coexist in the process of formation or physical ripening of silver halide grains. Good.

The emulsion layer of the present invention or the other hydrophilic colloid layer may contain a water-soluble dye as a filter dye or for various purposes such as prevention of irradiation. As a filter dye, a dye for further reducing photographic sensitivity, preferably an ultraviolet absorber having a spectral absorption maximum in the intrinsic sensitivity region of silver halide, and safety against safelight light when handled as a light-sensitive material in a bright room 350 nm to 600 nm for increasing the
A dye having a substantial light absorption in the region is used. These dyes are added to the emulsion layer depending on the purpose, or added together with a mordant to the upper portion of the silver halide emulsion layer, that is, to the non-photosensitive hydrophilic colloid layer farther from the silver halide emulsion layer with respect to the support. It is preferable to fix it before use. Or International Application Publication (WO) 88/04794,
European Patent (EP) 0276566 A1, JP-A-6
As described in 3-197943 and the like, a water-insoluble dye can also be used in a gelatin dispersion liquid in which it is dispersed in a microcrystalline state. 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. It is preferably 50 mg to 500 mg / m ² . Specific examples of dyes 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. These dyes can be used in combination of two or more. The dye of the present invention is used in an amount necessary to enable light room handling. The specific amount of the dye used is generally 10 ⁻³ g / m ^{2 to} 1 g / m ² , especially 10 ⁻³ g / m ^2.
A preferred amount can be found in the range of ~ 0.5 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 hydroxyethyl cellulose, carboxymethyl cellulose 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,
A wide variety of synthetic hydrophilic polymeric substances such as polyvinylpyrazole and other single or copolymers can be used. As the gelatin, acid-treated gelatin may be used in addition to lime-treated gelatin, and gelatin hydrolyzate and gelatin enzyme-decomposed product may also be used.

The silver halide emulsion used in the method of the present invention may not be chemically sensitized, but may be chemically sensitized. As a method of chemically sensitizing a silver halide emulsion, sulfur sensitization, reduction sensitization and noble metal sensitization are known, and any of these may be used alone or in combination for chemical sensitization. Good. The gold sensitization method is a typical one of the noble metal sensitization methods, and a gold compound, mainly a gold complex salt is used. Noble metals other than gold, for example, complex salts of platinum, palladium, iridium, etc. may be contained. Specific examples thereof are described in US Pat. No. 2,448,060 and British Patent 618,061. As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, thiazoles, and rhodanines can be used in addition to the sulfur compounds contained in gelatin. As the reduction sensitizer, a primary tin salt, an amine, formamidinesulfinic acid, a silane compound or the like can be used. 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 may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing 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, etc .; Add many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. 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 salts (chromium vanilla, etc.), aldehydes (glutaraldehyde, 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.), mucohalogen acids, etc. can be used alone or in combination.

In the photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material produced by using the present invention, coating aids, antistatic agents, slipperiness improvement, emulsion dispersion, adhesion prevention and photographic property improvement (for example, development acceleration) , Hardening, and sensitization), various surfactants may be included. For example, saponin (steroidal), alkylene oxide derivative (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 alkyl amines or amides, polyethylene oxide adducts of silicones), glycidol derivatives ( Nonionic surfactants such as alkenyl succinic acid polyglyceride, alkylphenol polyglyceride, fatty acid esters of polyhydric alcohols, alkyl esters of sugars; alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkyls Naphthalene sulfonate, alkyl sulfates, alkyl phosphates, N-acyl-N-al Acidity of carboxy group, sulfo group, phospho group, sulfuric acid ester group, phosphoric acid ester group, etc., such as lutarine, sulfosuccinic acid ester, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphoric acid ester, etc. Anionic surfactants containing groups; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric acid esters, alkylbetaines, amine oxides; alkylamine salts, aliphatic or aromatic fourth groups Cationic surfactants such as quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts containing an aliphatic or heterocyclic ring can be used. In particular, the surfactant preferably used in the present invention has a molecular weight of 60 described in JP-B-58-9412.
It is 0 or more polyalkylene oxides. Also, a polymer latex such as polyalkyl acrylate may be incorporated for dimensional stability.

Development accelerators suitable for use in the present invention
As an accelerator for developing nucleating and infectious development, JP-A-53-7 is used.
7,616, 54-37,732, 53-13
No. 7,133, No. 60-140, No. 340, No. 60-1
In addition to the compounds disclosed in US Pat. No. 4,959, N or
Various compounds containing S atom are effective. These promotion
Although the optimum addition amount of the agent varies depending on the type of compound,
0x10 ^-3~ 0.5 g / m², Preferably 5.0 × 10^-3
~ 0.1 g / m²It is desirable to use in the range of. these
The accelerator is a suitable solvent (H₂O, methanol and ethanol
Alcohols such as acetone, dimethylformami
Solution, etc.) and added to the coating solution.
Be done. Plural kinds of these additives may be used in combination.

To obtain ultrahigh contrast photographic characteristics using the silver halide light-sensitive material of the present invention, a conventional infectious developer or a highly alkaline developer described in US Pat. No. 2,419,975 and having a pH value close to 13 is used. It is not necessary to use, and a stable developing solution can be used. That is, the silver halide light-sensitive material of the present invention contains 0.10 mol / liter or more of sulfite ion as a preservative and has a pH of 9.0 to 12.3, particularly a pH of
With a developer of 10.0 to 12.0, a sufficiently high-contrast negative image can be obtained. There are no particular restrictions on the developing agents that can be used in the method of the present invention, see TH James, “T
he Theory of the Photographic Process ", 4th Edition, Ma
Various compounds described in cmillan, pp. 298-327 can be used. For example, dihydroxybenzenes (eg hydroquinone), 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone, 4,4-
Dimethyl-1-phenyl-3-pyrazolidone), aminophenols (for example, 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 for being processed with a developing solution containing dihydroxybenzenes as a main developing agent and 3-pyrazolidones or aminophenols as an auxiliary developing agent. In this developer, dihydroxybenzenes are preferably used in an amount of 0.05 to 0.5 mol / liter, and 3-pyrazolidones or aminophenols are used in an amount of 0.06 mol / liter or less. Further, as described in U.S. Pat. No. 4,269,929, by adding amines to a developing solution, the developing rate can be increased to shorten the developing time. The developer may also include a pH buffer such as alkali metal sulfite, carbonate, borate, and phosphate, bromide, iodide,
And a development inhibitor such as an organic antifoggant (particularly preferably nitroindazoles or benzotriazoles) or an antifoggant. Also, 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 hardener, and a silver stain preventing agent for the film. (For example, 2-mercaptobenzimidazole sulfonic acids, etc.) may be included.

As the fixing liquid, those having a generally used composition can be used. Thiosulfate as a fixing agent,
In addition to 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 or the like as a hardening agent.

The processing temperature in the method of the present invention is usually 18
It is selected between 0 ° C and 50 ° C. Although it is preferable to use an automatic developing machine for photographic processing, even if the total processing time from putting the light-sensitive material in the automatic developing machine until it comes out is set to 90 seconds to 120 seconds by the method of the present invention. The photographic characteristics of a super gradation of negative gradation can be obtained. The compounds described in JP-A-56-24,347 can be used in the developer of the present invention as a silver stain preventing agent. The compounds described in JP-A-61-267759 can be used as dissolution aids added to the developing solution. Furthermore, the pH used for the developer
As the buffer, the compounds described in JP-A-60-93,433 can be used.

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

1. Layer structure: Page 28, lower left column, 1st line to 2nd
Page 9, upper right column, line 7 2. Silver halide emulsion: page 29, upper right column, line 8 to 30
Top right column, line 12 3. Yellow coupler: page 30, lower right column, lines 5 to 11 4. Magenta coupler: page 30, lower right column, line 12 to 3
Page 1, line 3 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, line 1 7. Functional coupler: Page 31, upper right column, second line to lower right column 5,
Line 8. Antiseptic / antifungal agent: Page 32, upper right column, lines 10 to 17 9. Formalin scavenger: Page 30, lower left column, lines 16 to 20 10. Other additives: Page 35, lower right column, lines 19 to 36
Page top left column, line 14 and page 30 top right column, line 13 to bottom left column, line 15 11. Dispersion method: Page 31, bottom right column, line 8 to page 32 top right column, line 9 12. Support: No. Page 32, lower left column, lines 4 to 6 13. Film thickness and film properties: Page 32, lower left column, line 7 to lower right column 10
Line 14. Color development process: page 32, lower right column, line 15 to page 33, lower right column, line 16 15. desilvering process: page 32, lower right column, line 17 to page 35, upper left column, line 16 Item 16. Automatic processor: Page 35, lower left column, line 17 to upper right column, line 5 17. Water washing / stabilization process: Page 35, upper right column, line 6 to lower right column 1
5th line

[0057]

EXAMPLES The effects of the present invention will be described in detail below by showing specific examples of the present invention, but the present invention is not limited thereto. Example 1 (First Photosensitive Emulsion Layer) Preparation of Photosensitive Emulsion A A 0.37 M silver nitrate aqueous solution and 1 × 10 1 mol of silver
^-7 moles of (NH ₄ ) ₃ RhCl ₆ and 5 × 10 ^-7 moles of K ₃ Ir
Cl ₆ 0.11M potassium bromide and 0.27M sodium chloride containing an aqueous solution of halogen salt, sodium chloride,
An average particle size of 0.20 was added to a gelatin aqueous solution containing 1,3-dimethyl-2-imidazolidinethione by a double jet method at 45 ° C. for 12 minutes while stirring.
Nucleation was performed by obtaining silver chlorobromide grains having a particle size of μm and a silver chloride content of 70 mol%. Then, similarly, a 0.63 M silver nitrate aqueous solution, 0.19 M potassium bromide, and 0.4
An aqueous solution of halogen salt containing 7M sodium chloride was added by the double jet method over 20 minutes. Then 1
A KI solution (× 10 ^-3 mol) was added for conversion, followed by washing with water according to a conventional method by flocculation, 40 g of gelatin was added to adjust pH to 6.5 and pAg to 7.5, and further 5 mg of sodium thiosulfate per mol of silver. , 8 mg of chloroauric acid and 7 mg of sodium benzenethiosulfonate were added, and the mixture was heated at 60 ° C. for 45 minutes for chemical sensitization treatment, and 6-methyl-4-hydroxy-1, as a stabilizer.
150 mg of 3,3a, 7-tetrazaindene, proxel (trade name: manufactured by ICI Co. Ltd.) and phenoxyethanol were added. The obtained grains were cubic silver chlorobromide 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 into 1 × 10 ⁻³ mol of 5- [3- (4-sulfobutyl) -5 as a sensitizing dye per mol of silver.
-Chloro-2-oxazolidylidene] -1-hydroxyethyl-3- (2-pyridyl) -2-thiohydantoin was added, and further 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 (200 mg / m ² ) of the compound (b), hydroquinone (50 mg / m ² ) and a dispersion of polyethyl acrylate (200 mg / m ² ). m ² ), 1,3-bisvinyl-as a hardening agent
Sulfonyl-2-propanol (200 mg / m ² ) and the following hydrazine compound (c) as a nucleating agent were added, and coating was performed so that the coating silver amount was 3.6 g / m ² and gelatin was 2.0 g / m ² .

[0058]

[Chemical 18]

(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 1. 0M silver nitrate aqueous solution and 3 × 10 ⁻⁷ per mol of silver
Aqueous halogen salt solution containing 0.3M potassium bromide and 0.74M sodium chloride, containing ₃ moles of (NH ₄ ) ₃ RhCl ₆ , sodium chloride and 1,3-dimethyl-2-imidazolidinethione. Add to the aqueous gelatin solution with stirring by the double jet method at 45 ° C for 30 minutes,
Average grain size 0.28 μm, silver chloride content 70 mol%
To obtain silver chlorobromide grains. After that, it was washed with water according to the usual method by flocculation, 40 g of gelatin was added,
Adjusted to 6.5 and pAg of 7.5, and further added 5 mg of sodium thiosulfate and 8 mg of chloroauric acid per 1 mol of silver.
The mixture was heated at 60 ° C. for 60 minutes for chemical sensitization, and 150 mg of 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene was added as a stabilizer. The resulting grains were cubic grains of silver chlorobromide having an average grain size of 0.28 μm and a silver chloride content of 70 mol%. (Variation coefficient 10%)

Coating of the Second Photosensitive Emulsion Layer The photosensitive emulsion B was redissolved at 40 ° C. and 1.0 × 10 ⁻³ mol of 5- [3- (4- Sulfobutyl) -5-chloro-2-oxazolidylidene]
-1-Hydroxyethyl-3- (2-pyridyl) -2-
Thiohydantoin and 1.0 × 10 ⁻³ mol of a KI solution were added, and 2 × 10 ⁻⁴ mol of 1-phenyl-5-mercaptotetrazole and a dispersion of polyethylene acrylate were added at 50 mg / m ^{2 as} a hardening agent. , 3-bisvinylsulfonyl-2-propanol was added to gelatin in an amount of 4.0% by weight,
The redox compound of the present invention or the comparative example 5.8 × 10 ⁻⁵ mo
l / m ² was added as shown in Table 1 and coated so that the amount of coated silver was 0.3 g / m ² and gelatin was 0.4 g / m ² .

(Coating of protective layer) On this, as a protective layer,
Gelatin 0.5 g / m ² and polymethylmethacrylate particles (average particle size 2.5 μm) 0.3 g / m ² were coated using the following surfactants.

[0062]

[Chemical 19]

The back layer and the back protective layer were coated by 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]

[Chemical 20]

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]

[Chemical 21]

[Back protective layer] Gelatin 0.8 g / m ² Polymethylmethacrylate 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]

[Chemical formula 22]

Simultaneous coating of the first photosensitive emulsion layer as the lowermost layer on a polyester film (100 μ) support, a second photosensitive emulsion layer containing a redox compound through an intermediate layer, and a protective layer thereon. Then, the samples shown in Table 1 were prepared.

The samples shown in Table 1 were exposed with a tungsten light of 3200 ° K through an optical wedge and a contact screen (Fujifilm, 150 L chain dot type), and then developed with the following developer A at 34 ° C for 30 seconds, fixed and washed with water. 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 Ethylenediaminetetraacetic acid disodium 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 0.0 liter of water was added to adjust to pH = 11.6 (with potassium hydroxide added) pH11.6 The halftone gradation was represented by the following formula. * Amount of exposure that gives a dot area ratio of halftone = 95% (log E
95%)-exposure amount giving a dot area ratio of -5% (log E
5%) The halftone dot quality was visually evaluated in 5 levels. Five-level evaluation is
“5” indicates the best quality, and “1” indicates the worst quality. As a halftone original plate for plate making, "5" and "4" are practical,
“3” is the practical limit level, and “2” and “1”
Is an impractical quality. The results are shown in Table 1.

[0071]

[Table 1]

The structural formulas of comparative compounds are shown below.

[0073]

[Chemical formula 23]

[0074]

[Chemical formula 24]

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

Example 2 A light-sensitive material was prepared by making the following changes from Example 1. First photosensitive emulsion layer: 1.0 × 10 ⁻⁵ mol / m ^{2 of} hydrazine compound 2-21 was added as a nucleating agent. 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]

[Chemical 25]

Second photosensitive emulsion layer: The redox compound of the present invention and the comparative example 9.5 × 10 ^-5 mol / m ² was added as shown in Table 2, and the coating silver amount was 0.4 g / m ² and gelatin was used. 0.5 g /
It was applied so as to be m ² . Using Developer B below, the performance was evaluated in the same manner as in Example 1. Developer B Hydroquinone 30.0 g N-methyl-p-aminophenol 0.3 Sodium hydroxide 10.0 Potassium sulfite 60.0 Ethylenediaminetetraacetic acid disodium 1.0 Potassium bromide 10.0 5-Methylbenzotriazole 0. 4 2-Mercaptobenzimidazole-5-sulfonic acid 0.3 Sodium 3- (5-mercaptotetrazole) benzene sulfonate 0.2 Sodium toluene sulfonate 8.0 Water is added to adjust to 1 liter pH = 10.5 ( PH 10.5 (with addition of potassium hydroxide) The results are shown in Table 2. The samples of the present invention showed 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 1 mol of silver. After the aqueous solution was mixed at the same time, the soluble salt was removed by a method well known in the art, and then gelatin was added to the mixture to prepare 6-methyl-4-hydroxy-1, as a stabilizer without chemical ripening. 3,3
a, 7-Tetrazaindene was added. This emulsion was a cubic-shaped monodisperse emulsion having an average size of 0.15μ.

(Coating of Photosensitive Emulsion Layer) The first layer of Photosensitive Emulsion C was mixed with hydrazine compound 2-8 (75 mg /
m ² ), 5-methylbenzotriazole (5 × 10 ⁻³ mol /
Ag mol), polyethyl acrylate latex (30wt
% To gelatin), and 1,3-bisvinylsulfonyl-2-propanol (2.0 wt% to gelatin). The coated silver amount 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 contains 5-methylbenzotriazole (5 × 1)
0 ^-3 mol / Ag mol), polyethyl acrylate latex (30 wt% to gelatin), 1,3-vinylsulfonyl-2-propanol (2 wt% to gelatin), and Table -
The redox compound of the present invention shown in No. 3 was added and coated so that the coated silver amount was 0.4 g / m ² and gelatin was 0.5 g / m ² . Fourth layer (protective layer) 1.5 g / m ^{2 of} gelatin and 0.3 g of polymethylmethacrylate particles (average particle size 2.5 μ) as matting agent
A protective layer containing m ² and the following surfactant, stabilizer and UV absorbing dye as a coating aid was coated and dried.

[0082]

[Chemical formula 26]

Stabilizer thioctic acid 2.1 mg / m ²

[0084]

[Chemical 27]

This sample was measured with a bright room printer p-607 manufactured by Dainippon Screen Co., Ltd. using JP-A-1-240966.
Image exposure through a document as shown in FIG. 1 of the publication, development processing with developer A at 38 ° C. for 20 seconds, fixing, washing with water, and drying were performed, and then the image quality of extracted characters was evaluated. The extracted character image quality 5 is 5 using an original document as shown in FIG. 1 of Japanese Patent Laid-Open No. 1-240966.
This is an image quality in which a character having a width of 30 μm is reproduced when subjected to appropriate exposure such that a halftone dot area of 0% results in a halftone dot area of 50% on a reversal light-sensitive material, which is a very good blank character image quality. On the other hand, the extracted character image quality 1 is an unexplained extracted character quality, which is an image quality that can reproduce only characters having a width of 150 μm or more when the same suitable exposure is given. Rank is set. A level of 3 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 sample of the present invention is excellent in the image quality of extracted characters.

[0088]

INDUSTRIAL APPLICABILITY By using the compound represented by the general formula (1), the present invention can provide a silver halide photographic light-sensitive material which can obtain good halftone gradation, halftone dot quality and image quality of blank characters. ..

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] January 10, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0012

[Correction method] Change

[Correction content]

In the formula, L ₁ is 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, L 3} is -CONR ₇ - _group, -NR 7 CON
R ₈ — group, —SO ₂ NR ₇ — group, or NR ₇ SO ₂ N
Represents R ₈ groups, which may be the same or different. R ₇ and R ₈ are hydrogen atoms or have 1 to 6 carbon atoms.
Represents an alkyl group having 6 to 10 carbon atoms,
A hydrogen atom is preferred. m is 0 or 1. R ₃ represents an aliphatic group or an aromatic group and may be substituted. The description of R ₁ is applicable to the specific embodiment as it is, but it is not always necessary to be substituted. R
₄ , R ₅ and R ₆ are each 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, a —SO— group. ,-
SO ₂ - group, -NR ₉ - _{R 7} group _{(R 9} of the general formula (2)
Synonymous with) and is a divalent group created by combining them. More preferably, R ₄ is an alkylene group having 1 to 10 carbon atoms or a combination thereof with an —S— group, a —SO— group, a —S.
R 2 is a divalent group formed by combining O ₂ − groups.
₅ and R ₆ are arylene groups 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 preferable substituent is R ₁
Those enumerated as the substituents of are applicable.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0057

[Correction method] Change

[Correction content]

[0057]

EXAMPLES The effects of the present invention will be described in detail below by showing specific examples of the present invention, but the present invention is not limited thereto. Example 1 (First Photosensitive Emulsion Layer) Preparation of Photosensitive Emulsion A A 0.37 M silver nitrate aqueous solution and 1 × 10 1 mol of silver
Corresponding to ^-7 mol _{(NH 4)} 3 RhCl ₆ to 5 × 10
The halogen salt aqueous solution containing sodium chloride potassium bromide and 0.27M ^-7 mol of _K 3 IrCl ₆ 0.11 M, sodium chloride, an aqueous gelatin solution containing 1,3-dimethyl-2-imidazolidinethione, stirring While adding by the 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. Then, similarly, a 0.63 M silver nitrate aqueous solution, a 0.19 M potassium bromide, and a 0.47 M sodium chloride-containing halogen salt aqueous solution were added over 20 minutes by the double jet method. Thereafter, 1 × 10 ⁻³ mol of KI solution was added for conversion, followed by washing with water by the flocculation method according to a conventional method, and 40 g of gelatin was added to adjust pH.
Adjusted to 6.5 and pAg 7.5, and further added 5 mg of sodium thiosulfate, 8 mg of chloroauric acid and 7 mg of sodium benzenethiosulfonate per mol of silver, and added at 60 ° C.
The mixture is heated at 45 ° C. for 45 minutes for chemical sensitization, and 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene 150 mg as a stabilizer and proxel (trade name: I
CI Co. Ltd. Manufactured) and phenoxyethanol were added. The obtained grains were cubic silver chlorobromide 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 into 1 × 10 ⁻³ mol of 5-{[3- (4-sulfobutyl) mol as a sensitizing dye per mol of silver.
-5-chloro-2-benzoxazolidylidene] ethylidene} -1-hydroxyethoxyethyl-3- (2-pyridyl) -2-thiohydantoin potassium salt was added, and 2 × 10 ⁻⁴ mol of 1-phenyl was added. -5-mercaptotetrazole, 5 × 10 ⁻⁴ mol of the short-wave cyanine dye of the compound (a) represented by the following structural formula, the polymer (200 mg / m ² ) of the compound (b), and hydroquinone (50
mg / m ² ) and a dispersion of polyethyl acrylate (200 mg / m ² ), 1,3-bisvinyl-sulfonyl-2-propanol as a hardener (200 mg / m ² ).
m ² ), the following hydrazine compound (c) was added as a nucleating agent, and the amount of coated silver was 3.6 g / m ² and gelatin was 2.0 g / m.
^It was applied so as to be ² .

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0060

[Correction method] Change

[Correction content]

Coating of the Second Photosensitive Emulsion Layer The photosensitive emulsion B was redissolved, and 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 KI The solution was added, and a dispersion of 2 × 10 ⁻⁴ mol of 1-phenyl-5-mercaptotetrazole and polyethylene acrylate was further added.
mg / m ² , 1,3-bisvinylsulfonyl-2-propanol as a hardener, 4.0 wt% with respect to gelatin,
The redox compound of the present invention or the comparative example 5.8 × 10 ⁻⁵
mol / m ² was added as shown in Table 1, and the coated silver amount was 0.3 g /
m ² and gelatin were applied at 0.4 g / m ² .

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0078

[Correction method] Change

[Correction content]

[0078] The second light-sensitive emulsion layer: the redox compound 9.5 × ^{10 -5} mol / ^{m 2} of the present invention and comparative examples Table 2
The amount of coated silver is 0.4 g / m ² , gelatin is 0.
It was applied so as to be 5 g / m ² . Using Developer B below, the performance was evaluated in the same manner as in Example 1. 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 to 1 liter Adjust to pH = 10.5 PH 10.5 (with addition of potassium) The results are shown in Table 2. The samples of the present invention showed wide halftone and high halftone quality.

Claims (2)

[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, and as a part of the substituent, —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 is a group containing a partial structure of- (where n is an integer of 3 or more). G ₁ is -CO- group, -COCO- group, -CS- group, -C
(= NG ₂ R ₂₎ - group, -SO- group, -SO ₂ - group or -P (O) (G
₂ R ₂ )-group. G ₂ is a mere bond, -O-group,-
Represents an S-group or a -N (R ₂ ) -group, R ₂ is an aliphatic group,
Represents an aromatic group or a hydrogen atom, and has a plurality of R _{2 s} in the molecule.
, They may be the same or 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 arylsulfonyl group. Time represents a divalent linking group, and t is 0.
Or represents 1. PUG represents a development inhibitor. 2. A hydrazine compound other than the compound represented by the general formula (1) is contained in the image forming layer containing the silver halide emulsion or the hydrophilic colloid layer. 1. A silver halide photographic light-sensitive material as described in 1.