JPH0545762A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide photographic sensitive material for forming a printing plate and superior in rapid processability and high in processing stability. CONSTITUTION:The silver halide photographic sensitive material contains a nucleating agent represented by formula (R<1>-L<1>-R<2>-L<2>-R<3>-NHNH-G<1>-R<4>) in which L<1> is -SO2NR<5>-, or G<2>P(O)(G<2>R<5>)-NR<5>)-; L<2> is -NR<5>- SO2NR<5> or -G<2>P(O)(G<2>R<5>)- NR<5>-, or the like; G<1> is -CO- or -P(O)(G<2>R<5>)- or the like; G<2> is a simple bond, -O-, or -NR<5>-; R<1> is an aliphatic or aromatic group having >=4 repeating units of ethylene oxide or having a quaternary ammonium cation; each of R<2> and R<3> is a divalent divalent aliphatic or aromatic group; R<4> is H, an divalent aliphatic or aromatic group; R<4> is H, an aliphatic or aromatic group or the like; and R<4> is H, an aliphatic or aromatic group.

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

[0002]

2. Description of the Related Art In the field of graphic arts, ultra-high contrast (especially gamma is 1
An image forming system showing a photographic characteristic of 0 or more) is required. As a method for obtaining a photographic characteristic of high contrast using a stable developing solution, U.S. Pat. Nos. 4,224,401, 4,168,977 and 4,166,742,
No. 4,311,781, No. 4,272,606
No. 4,211,857 and the like, a method using a hydrazine derivative is known. According to this method, photographic characteristics with high contrast and high sensitivity can be obtained, and since it is permissible to add a high concentration of sulfite to the developing solution, the stability of the developing solution against air oxidation is Greatly improved compared to. However, conventionally, it has been found that the known hydrazine compounds have some drawbacks. That is, it has been attempted to make the structure of the hydrazine compound a diffusion-resistant structure with a conventionally known hydrazine compound for the purpose of reducing the adverse effect on other photographic light-sensitive materials caused by flowing out to the developing solution. These diffusion-resistant hydrazine compounds are required in a large amount for sensitizing and hardening, which causes problems that the physical strength of the obtained photosensitive layer is deteriorated and the hydrazine compound is precipitated in the coating solution. Further, it was also found that a sufficient hardness could not be obtained when a large amount of a light-sensitive material was treated with a fatigue developing solution.

[0003]

SUMMARY OF THE INVENTION A first object of the present invention is to provide a silver halide photographic light-sensitive material for plate making which is excellent in rapid processability and has high process stability.
The second object of the present invention is to obtain D even when processed with a fatigued developer.
An object of the present invention is to provide a silver halide photographic light-sensitive material for plate-making which has a small fluctuation in max.

[0004]

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). Formula ^{(1) R 1 -L 1 -R} 2 -L 2 -R 3 in -NHNH-G ¹ -R ⁴ Formula, L ¹ is -SO ₂ NR ⁵ - group, -NR ⁵ SO ₂ NR
⁵ - group, -CONR ⁵ - group, -NR ⁵ CONR ⁵ - group or ^{-G 2 P (O) (G} 2 R 5) -NR 5 - represents a group, L
² is -NR ⁵ SO ₂ NR ⁵ -group, -CONR ⁵ -group,-
NR ⁵ CONR ⁵ — group, or —G ² P (O) (G ² R ⁵ ).
It represents a —NR ⁵ — group. G ¹ is a —CO— group, —SO ₂ —
Group, -SO- group, -COCO- group, thiocarbonyl group,
Iminomethylene group or ^{-P (O) (G 2 R} 5) - represents a group - group, G ² represents a single bond, -O- group, -NR ^5.
R ¹ represents an aliphatic group or aromatic group containing four or more ethylene oxide repeating units, or an aliphatic group or aromatic group containing a quaternary ammonium cation. R ² ,
R ³ represents a divalent aliphatic group or aromatic group, R ⁴ represents a hydrogen atom, an aliphatic group, an aromatic group, an alkoxy group, an aryloxy group or an amino group, and R ⁵ represents a hydrogen atom or an aliphatic group. Alternatively, it represents an aromatic group.

The compound represented by 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. The aromatic group represented by R ¹ in the general formula (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. The aliphatic group or aromatic group of R ¹ may be substituted, and typical examples of the substituent include, for example, an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group and a ureido group. , 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 , An alkoxycarbonyl group, an acyloxy group, a carbonamide group, a sulfonamide group, a carboxyl group, a phosphoric acid amide group, a diacylamino group, and an imide group. Preferred substituents are an alkyl group (preferably having 1 to 20 carbon atoms), an aralkyl group (preferably having 7 to 30 carbon atoms), an alkoxy group (preferably having 1 to 20 carbon atoms), a substituted amino group. (Preferably an amino group substituted by an alkyl group having 1 to 20 carbon atoms), an acylamino group (preferably 2 to 3 carbon atoms)
0), sulfonamide group (preferably having 1 to 30 carbon atoms), ureido group (preferably having 1 to 30 carbon atoms), phosphoric acid amide group (preferably having 1 to 30 carbon atoms) Things). These groups may be further substituted. The ethylene oxide group and the quaternary ammonium cation group contained in R ¹ may be contained in these substituents. The group represented by R ¹ is preferably represented by the following general formula (2), general formula (3), general formula (4) or general formula (5).

[0006]

[Chemical 1]

In these formulas, R ¹¹ represents an aliphatic group or an aromatic group. The aliphatic group represented by R ¹¹ 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. 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 an aryl group. In addition, 3 in the general formula (5)
The R ^11's may be the same or different, and may be bonded to each other to form a ring. Z ¹ represents an atomic group necessary for forming a nitrogen-containing heteroaromatic ring. Z
Examples of the nitrogen-containing heteroaromatic ring formed by ¹ and a nitrogen atom include a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, an imidazole ring, an oxazole ring, a thiazole ring, a benzofused ring thereof, a pteridine ring, and a naphthyridine ring. Can be mentioned. p and r represent an integer of 1 to 20, preferably an integer of 2 to 10. General formula (4)
In, p may be 0. q is 0 or 1, and m represents an integer of 4 to 20. X ⁻ represents a counter anion or a counter anion portion when forming an inner salt. R ¹¹ and Z ¹ may be substituted, and examples of the substituent include those enumerated as the substituents of R ¹ in the general formula (1). Furthermore - (CH _{2) p} - or -
In the group represented by (CH ₂ ) _q- , one or more hydrogen atoms may be replaced by a substituent,
For that example, those enumerated as the substituents of R ¹ also apply.

In the general formula (1), the aliphatic groups represented by R ² and R ³ are preferably those having 1 to 30 carbon atoms, and particularly straight-chain, branched or cyclic ones having 1 to 20 carbon atoms. It is an alkyl group. The aromatic group represented by R ² and R ³ in the general formula (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. An aryl group is preferred as R ² and R ³ , and a benzene ring is particularly preferred. The aliphatic group or aromatic group of R ² and R ³ may be substituted, and a typical substituent is R ¹
Those enumerated as the substituents of are applicable.

The alkyl group represented by R ⁴ in the general formula (1) 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, a benzene ring). Including). G ¹
Is a —CO— group, preferred among the groups represented by R ⁴ are a hydrogen atom, an alkyl group (for example, a methyl group,
Trifluoromethyl group, 3-hydroxypropyl group, 3
-Methanesulfonamidopropyl group, phenylsulfonylmethyl group and the like), aralkyl group (for example, o-hydroxybenzyl group and the like), aryl group (for example, phenyl group, 3,5-dichlorophenyl group, o-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group,
2-hydroxymethylphenyl group) and the like, and a hydrogen atom is particularly preferable. R ⁴ may be substituted,
As the substituent, the substituents listed for R ¹ can be applied. Most preferably, G ^{1 in the} general formula (1) is a —CO— group. Further, R ⁴ disrupts the portion of the G ¹ -R ⁴ from the remainder molecule may be such as to rise to cyclization reaction to form a cyclic structure containing a -G ¹ -R ⁴ moiety of atoms ,
Examples thereof include those described in JP-A-63-29751. R ⁵ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and particularly preferably a hydrogen atom. When the compound represented by the general formula (1) contains two or more R ⁵ and G ² , they may be the same or different.

R ¹ , R ² , R ³ or R of the general formula (1)
⁴ may have a ballast group or polymer commonly used in a non-moving photographic additive such as a coupler incorporated therein. 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, examples of the polymer include those described in JP-A-1-100530.

R ¹ , R ² , R ³ or R in the general formula (1)
⁴ may have a group incorporated therein to enhance adsorption to the surface of the silver halide grain. Examples of the adsorptive group include thiourea group, heterocyclic thioamide group, mercaptoheterocyclic group, and triazole group.
5,108, 4,459,347, JP-A-59-
195, 233, 59-200, 231 and 59.
-201, 045, 59-201, 046, 5
9-201, 047, 59-201, 048, 59-201, 049, 61-170, 733,
61-270,744, 62-948, 63.
-234, 244, 63-234, 245, 6
The groups described in 3-234,246 are mentioned. The compounds used in the present invention are listed below, but the present invention is not limited thereto.

[0012]

[Chemical 2]

[0013]

[Chemical 3]

[0014]

[Chemical 4]

[0015]

[Chemical 5]

[0016]

[Chemical 6]

The hydrazine compound of the present invention is disclosed, for example, in JP-A-61-213,847, JP-A-62-260,153,
U.S. Pat. No. 4,684,604, Japanese Patent Application No. 63-98,
803, U.S. Pat. Nos. 3,379,529 and 3,6.
20,746, 4,377,634, 4,33
2,878, JP-A-49-129,536, 56
No. 153,336, No. 56-153,342, U.S. Pat. Nos. 4,988,604, and 4,994,365. A specific example is shown below.

Synthetic Example: Synthesis of Exemplified Compound 9 A mixed solution (70 ml) of ethyltetraethyleneoxythiol (11.0 g) and dimethylformamide was cooled to 10 ° C., 50% NaH (2.24 g) was added, and the mixture was cooled to room temperature. A mixed solution of the following raw material compound A (16.4 g) and dimethylformamide (50 ml) was added dropwise to the reconstituted product, and the mixture was stirred at room temperature overnight. The reaction solution was poured into a 1N HCl aqueous solution containing ice, extracted with ethyl acetate, washed with saturated saline, dried over anhydrous magnesium sulfate, and then ethyl acetate was distilled off, followed by isolation and purification by silica gel chromatography to obtain the desired product. (10.2
g) was obtained. The structure of the compound was confirmed by nmr spectrum and ir spectrum.

[0019]

[Chemical 7]

The hydrazine derivative of the present invention is a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methylcell. It can be used by dissolving it in sorb or the like. 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, the redox compound powder may be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves according to a method known as a solid dispersion method. The addition amount of the hydrazine derivative in the present invention is 1 × 10 ⁻⁶ mol to 5 × 1 mol per mol of silver halide.
It is preferably contained in an amount of 0 ^-2 mol, and particularly preferably in the range of 1 x 10 ^-5 mol to 2 x 10 ^-2 mol.

In the present invention, when the compound represented by the general formula (1) is contained in the photographic light-sensitive material, it is preferably contained in the silver halide emulsion layer, but other non-photosensitive hydrophilic colloid layers are contained. (For example, a protective layer, an intermediate layer, a filter layer, an antihalation layer, etc.) may be contained. When it is added to the silver halide emulsion layer, it may be added at any time from the start of chemical ripening to before coating, but it is preferably added after the completion of chemical ripening and before coating. It is particularly preferable to add it to the coating solution prepared for coating.

The silver halide emulsion used in the present invention may have any composition such as silver chloride, silver chlorobromide, silver iodobromide and silver iodochlorobromide, but in the case of a light-sensitive material for a reversing process, it is 60 mol% or more. ,
Particularly preferred is a silver halide containing 75 mol% or more of silver chloride. Silver chlorobromide or silver chloroiodobromide containing 0 to 5 mol% of silver bromide is preferred. 70 in case of sensitive material for screen shot process
A silver halide having a silver bromide content of at least 90 mol% and particularly at least 90 mol% is preferred. The content of silver iodide is 10 mol% or less,
It is particularly preferably 0.1 to 5 mol%. 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 monodisperse 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 average particle size. The silver halide grains in the photographic emulsion may have a regular crystal such as a cube or octahedron, or may have a regular irregular crystal such as a sphere or a plate. Alternatively, it may have a composite form of these crystal forms. A cube is particularly preferable. 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, a cadmium salt, a sulfite salt, a lead salt, a thallium salt, a rhodium salt or a complex salt thereof, an iridium salt or a complex salt thereof, etc. are formed in the process of formation of silver halide grains or physical ripening. May coexist. Examples of the rhodium salt include rhodium monochloride, rhodium dichloride, rhodium trichloride, ammonium hexachlororhodate, and the like, preferably a water-soluble trivalent rhodium halogeno complex compound such as hexachlororhodium (III) acid or a salt thereof. (Ammonium salt, sodium salt, potassium salt, etc.). The amount of these water-soluble rhodium salts added is in the range of 1.0 × 10 ⁻⁸ mol to 1.0 × 10 ⁻³ mol per mol of silver halide. Preferably, it is 1.0 × 10 ⁻⁷ mol to 5.0 × 10.
^-4 mol.

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, platinum, palladium, iridium and other complex salts may be contained. A specific example is US Patent 2,
No. 448,060, British Patent No. 618,061 and the like. 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 spectral sensitizing dye may be added to the silver halide emulsion layer used in the present invention. Spectral sensitizing dyes are useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are Research Disclosure 176: 1764.
3 (issued in December 1978), page 23, IV, section J.

Gelatin is advantageously used as the binder or protective colloid of the photographic emulsion, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as 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 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 and the like; hydroquinone and its derivatives; disulfides such as thioctic acid; antifoggants such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide or the like. Many compounds known as stabilizers can be added. Among these, preferred are benzotriazoles (eg, 5
-Methyl-benzotriazole) and nitroindazoles (eg 5-nitroindazole). Also,
These compounds may be contained in the treatment liquid.

The light-sensitive material of the present invention may contain an organic desensitizer. Preferred organic desensitizers have at least one water-soluble group or alkali-labile group. These preferred organic desensitizers are exemplified in Japanese Patent Application No. 61-209169. When an organic desensitizer is used, 1.0 × 10 ^{−8 to} 1.0 × 10 ⁻⁴ mol / m ² , preferably 1.0 × 10 ^{−7 to} 1.0 × 10 ^{− in the} silver halide emulsion layer. ^It is suitable that ⁵ mol / m ^{2 is} present.

The light-sensitive material of the present invention may contain a development accelerator. Development accelerators or nucleation-infectious development accelerators suitable for use in the present invention are disclosed in JP-A-53-7761.
6, compounds 54-377732, compounds 53-137, 133, compounds 60-140, 340, compounds 60-14959, etc., as well as various compounds containing N or S atoms are effective. Specific examples are listed in.

[0029]

[Chemical 8]

[0030]

[Chemical 9]

[0031]

[Chemical 10]

[0032]

[Chemical 11]

These accelerators depend on the kind of compound.
Optimal addition amount is different, but 1.0 × 10 ^-3~ 0.5 g / m²,
Preferably 5.0 × 10^-3~ 0.1 g / m²Used in the range of
Is desirable. These promoters are suitable solvents (H
₂O) alcohols such as methanol and ethanol,
Cetone, dimethylformamide, methyl cellosolve
Etc.) and added to the coating solution. These additives
You may use together several types. The emulsion layer of the present invention or
On the other hydrophilic colloid layer of
Rui is water for various purposes such as prevention of irradiation.
It may contain a soluble dye. As a filter dye,
Dyes to further reduce photographic sensitivity, preferably halo
Ultraviolet absorption having a spectral absorption maximum in the intrinsic sensitivity region of silver genide
A safer when used as a collecting agent or as a light-sensitive room light-sensitive material.
Primarily 310 to enhance safety against light
Dyes that have substantial light absorption in the range of nm to 600 nm
Used. These dyes may be added to the emulsion layer according to the purpose.
Or on top of the silver halide emulsion layer, i.e.
Insensitivity farther than the silver halide emulsion layer with respect to the support
For fixing by adding it with a mordant to the hydrophilic colloid layer
Is preferred. Depends on the molar absorption coefficient of the dye
But usually 10^-3g / m²~ 1g / m²It is added in the range of.
Preferably 10 mg to 500 mg / m²Is. The above dyes are suitable
Such solvents [eg water, alcohols (eg methanol,
Ethanol, propanol, etc.), acetone, methyl
Rosolve, etc., or a mixed solvent thereof]
Can be added to the coating solution. These dyes are 2
It is also possible to use a combination of two or more species. These dye ingredients
A body example is described in Japanese Patent Application No. 61-209169.
It In addition, U.S. Patents 3,533,794 and 3,3
14,794, 3,352,681, JP-A-46
-2784, U.S. Pat. Nos. 3,705,805, and 3,
707,375, 4,045,229, and 3,7
00,455, 3,499,762, West German patent issued
Ultraviolet light described in application publication No. 1,547,863
Line absorbing dyes are also used. Others, US Pat. No. 2,27
Pyrazolone oxonol dye described in 4,782, rice
Diarylazo described in Japanese Patent No. 2,956,879
Dyes, US Pat. Nos. 3,423,207 and 3,38
Styryl dyes and butadienyl dyes described in 4,487
Materials, merosa described in US Pat. No. 2,527,583
Nin dye, U.S. Pat. Nos. 3,486,897, and 3,
652,284 and 3,718,472
Merocyanine dyes and oxonol dyes, US Pat.
No. 976,661, enaminohemioxonol dyeing
And British Patent Nos. 584,609 and 1,177,
429, JP-A-48-85130, and JP-A-49-996.
20, No. 49-114420, and U.S. Pat. No. 2,53.
No. 3,472, No. 3,148,187, No. 3,1
77,078, 3,247,127, 3,
No. 540, 887, No. 3,575, 704, No.
The dyes described in No. 3,653,905 can also be used.
Wear.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer. For example, chromium salts (chromium deuterium, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane). Etc.), active vinyl compounds (1,
3,5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids ( Mucochloric acid, mucophenoxycyclo acid, etc.), an epoxy compound (tetramethylene glycol diglycidyl ether, etc.), an isocyanate compound (hexamethylene diisocyanate, etc.), etc. can be used alone or in combination. In addition, JP-A-56-66841, British Patent 1,322,971 and US Patent 3,671,25.
The polymer hardener described in 6 can also be used.

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 aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines 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-alk Such as taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphates, etc., such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc. Anionic surfactants containing acidic groups; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric acid esters, alkylbetaines, amine oxides; alkylamine salts, aliphatic or aromatic primary surfactants. Quaternary ammonium salts, pyridinium,
Heterocyclic quaternary ammonium salts such as imidazolium,
And cationic surfactants such as phosphonium or sulfonium salts containing aliphatic or heterocyclic rings 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.

In order 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 close to pH 13 described in US Pat. No. 2,419,975 is used. There is no need to use a stable developer. That is, the silver halide light-sensitive material of the present invention contains 0.15 mol / liter or more of sulfite ion as a preservative, and is sufficiently prepared by a developing solution having a pH of 10.5 to 12.3, particularly a pH of 11.0 to 12.0. It is possible to obtain a super-high contrast negative image. There is no particular limitation on the developing agent that can be used in the method of the present invention, and examples thereof include dihydroxybenzenes (eg hydroquinone), 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone,
4,4-Dimethyl-1-phenyl-3-pyrazolidone), aminophenols (for example, N-methyl-p-aminophenol) 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 US Pat. No. 4,269,929, by adding amines to a developing solution, the developing rate can be increased and the developing time can be shortened. Other developers include pH buffers such as alkali metal sulfites, carbonates, borates, and phosphates, bromides, iodides, and organic antifoggants (particularly preferably nitroindazoles or benzotriazoles). Development inhibitor or 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 agent 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 from 18 ° C to 5 ° C.
Selected during 0 ° 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 Japanese Patent Application No. 60-109,743 can be used as a dissolution aid added to the developing solution. Further, as the pH buffer used in the developing solution, the compounds described in JP-A-60-93,433 or the compounds described in Japanese Patent Application No. 61-28,708 can be used.

[0039]

【Example】

[Example 1] 1) Preparation of coating sample 5.0 x per mol of silver in a gelatin aqueous solution kept at 40 ° C.
An aqueous solution of silver nitrate and an aqueous solution of sodium chloride were simultaneously mixed in the presence of 10 ^-6 mol of NH ₄ RhCl ₆ , and then soluble salts were removed by a method well known in the art, and then gelatin was added for chemical ripening. Instead, 2-methyl-4-hydroxy-1,3,3a, 7-tetraazaindene was added as a stabilizer. This emulsion has an average grain size of 0.2
It was a monodisperse emulsion having a cubic crystal form. Table 1 shows hydrazine compounds selected from the general formula (1) shown in Table 1 and comparative compounds in this emulsion.

[0040]

[Chemical formula 12]

After adding the nucleation accelerator in an amount of 15
mg / m ² addition,

[0042]

[Chemical 13]

Furthermore, polyethyl acrylate latex was added to the solid content of 30 wt% to gelatin, 1,3-di-vinylsulfonyl-2-propanol was added as a hardener, and 3.8 g / m 2 was added on the polyester support. ^It was applied so that the Ag amount was ² . Gelatin was 1.8 g / m ² . Gelatin 1.5 g / m ² as a protective layer thereon, and applying a layer of polymethyl methacrylate 0.3 g / m ² of particle size 2.5 [mu]. Developer A Hydroquinone 50.0 g N-methyl-p-aminophenol 0.3 Sodium hydroxide 18.0 Potassium hydroxide 55.0 5-Sulfosalicylic acid 45.0 Potassium sulfite 110.0 Disodium ethylenediaminetetraacetate 1.0 Potassium bromide 10.0 5-Methylbenzotriazole 0.4 2-Mercaptobenzimidazole-5-sulfonic acid 0.3 3- (5-Mercaptotetrazole) benzenesulfonic acid 0.2 Sodium Nn-butyldiethanolamine 15. 0 Sodium toluene sulfonate 8.0 Water is added to adjust to pH = 11.6 (add potassium hydroxide) pH 11.62) Photographic evaluation The coating sample obtained was applied to Dainippon Screen ) Bright room printer P-627FM manufactured by -2,937
Image exposure through the document shown in FIG.
It was developed at 38 ° C. for 20 seconds with Developer A using an automatic processor FG710NH of Fuji Film Co., Ltd., fixed with a fixing solution GR-F1 of Fuji Photo Film Co., Ltd., washed with water and dried.
Table 1 shows the results of evaluation of the extracted character image quality and Dmax of each sample. The character quality of the blank character 5 means that a halftone dot area of 50% is 5 on the return photosensitive material using the original document as shown in FIG.
This is an image quality in which a character with a width of 30 μm is reproduced when properly exposed so that a halftone dot area is 0%, which is a very good extracted 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 appropriate exposure is given, and is between 4 and 2 in the sensory evaluation between 5 and 1. Rank is set. A level of 3 or more is a practical level. Similarly, Dmax is Dmax when exposure is performed so that the halftone dot area of 50% of the original becomes the halftone dot area of 50%. The sample of the present invention has a high Dmax and is excellent in character image quality.

[0044]

[Table 1]

3) Photographic properties when processed with air-developed developer The developer A is used as an automatic processor FG710 of FUJIFILM Corporation.
Table 2 shows the performance when the film was exposed to NH, operated at 38 ° C. for 8 hours a day without passing through the film, and after 5 days, development processing was performed. ΔD is the value of Dmax in Table 1 and Dmax in Table 2
It is the difference from the value of. The sample of the present invention has a small variation in Dmax.

[0046]

[Table 2]

Example 2 (Preparation of Photosensitive Emulsion) 4 × 10 ⁻⁷ mol of iridium (III) chloride per mol of silver was added to a gelatin aqueous solution kept at 50 ° C.
In the presence of potassium and ammonia, an aqueous solution of silver nitrate and an aqueous solution of potassium iodide and potassium bromide were added simultaneously for 60 minutes, and the pAg was maintained at 7.8 during that period to obtain an average grain size of 0.28μ and an average silver iodide content of A cubic monodisperse emulsion having an amount of 0.3 mol% was prepared. This emulsion was desalted by the flocculation method and then 4 mol per mol of silver.
After adding 0 g of inactive gelatin, the temperature was kept at 50 ° C., and 5,5′-dichloro-9-ethyl-3,3′-bis (3-sulfopropyl) oxacarbocyanine was used as a sensitizing dye.
It was added to a KI solution of 10 ⁻³ mol per mol of silver, and the temperature was lowered for 15 minutes. (Coating of Photosensitive Emulsion Layer) This emulsion was redissolved, the compounds of the present invention shown in Table 3 and the compounds of Comparative Examples were added at 40 ° C., and 5-methylbenztriazole and 4-hydroxy-1 were further added. , 3,3a, 7-tetrazaindene, 30 wt% with respect to the following compounds (a), (b) and gelatin
The following compound (c) was added as a polyethyl acrylate and gelatin hardening agent, and the amount of silver was 3.8 g / m on a polyethylene terephthalate film (150 μ) having an undercoat layer (0.5 μ) made of a vinylidene chloride copolymer. ^It was applied so as to be ² .

[0048]

[Chemical 14]

(Coating of protective layer) On this, as a protective layer,
Gelatin 1.5 g / m ² , polymethylmethacrylate particles (average particle size 2.5 μ) 0.3 g / m ² , AgCl fine particles (0.08 μ) prepared by the following method in an amount of 0.3 g
/ M ² was applied using the following surfactants.

[0050]

[Chemical 15]

(Evaluation of Performance) These samples were tested for 3200
Optical wedge and contact screen with tungsten light of ° K (Fujifilm, 150L chain dot type)
After exposure through the through-hole, it was developed with the developer A at 34 ° C. for 30 seconds, fixed, washed with water and dried. Table 3 shows the results of measuring the dot quality and Dmax of the obtained sample.

[0052]

[Table 3]

The halftone dot quality was visually evaluated on a 5-point scale. 5
In the graded evaluation, "5" is the best and "1" is the worst quality. As the halftone dot original plate for plate making, "5" and "4" are practical, and "3" is the practical limit level,
"2" and "1" are unusable qualities. Dmax is
The amount of exposure (log E ₃ ) that gives an optical density of 1.5 of a sample that was similarly exposed through an optical wedge and developed,
The optical density (Dmax) of a point that was exposed 0.5 times more (0.5 + log E ₃ ) was shown. It can be seen that the compound of the present invention maintains a high Dmax and gives a high halftone dot quality as compared with the comparative compound. Next, in the same manner as in Example 1, the developing treatment was performed with the developer A that was air-fatigue. The results are shown in Table 4. The sample of the present invention has a small variation in Dmax.

[0054]

[Table 4]

[Procedure amendment]

[Submission date] September 29, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0039

[Correction method] Change

[Correction content]

[0039]

EXAMPLES [Example 1] 1) Preparation of coating sample 5.0 × per mol of silver in gelatin aqueous solution kept at 40 ° C.
An aqueous solution of silver nitrate and an aqueous solution of sodium chloride were simultaneously mixed in the presence of 10 ⁻⁶ mol of (NH ₄ ) ₃ RhCl ₆ , and then soluble salts were removed by a method well known in the art, followed by addition of gelatin, 2-Methyl-4-hydroxy-1,3,3a, 7-tetraazaindene was added as a stabilizer without chemical aging. This emulsion was a cubic monodisperse emulsion having an average grain size of 0.2μ. Table 1 shows hydrazine compounds selected from the general formula (1) shown in Table 1 and comparative compounds in this emulsion.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0043

[Correction method] Change

[Correction content]

Further, polyethyl acrylate latex was added in an amount of 30 wt% with respect to gelatin in terms of solid content, 1,3-divinylsulfonyl-2-propanol was added as a hardening agent, and 3.8 g / m ² of polyester support was added. The amount of Ag was applied. The gelatin was 1.8 g / m ² . On top of this, as a protective layer, 1.5 g / m ² of gelatin and 0.3 g / m ^{2 of} polymethylmethacrylate having a particle diameter of 2.5 μm.
Layers were applied. Developer A Hydroquinone 50.0 g N-methyl-p-aminophenol 0.3 Sodium hydroxide 18.0 Potassium hydroxide 55.0 5-Sulfosalicylic acid 45.0 Potassium sulfite 110.0 Ethylenediaminetetraacetic acid disodium 1.0 Potassium bromide 10.0 5-Methylbenzotriazole 0.4 2-Mercaptobenzimidazole-5-sulfonic acid 0.3 3- (5-Mercaptotetrazole) benzenesulfonic acid 0.2 Sodium N-n-butyldiethanolamine 15. 0 Sodium toluene sulfonate 8.0 Water is added to adjust to pH = 11.6 (potassium hydroxide is added) pH 11.62) Evaluation of photographic property ) Bright room printer P-627FM manufactured by -2,937
Image exposure through the document shown in FIG.
It was developed at 38 ° C. for 20 seconds with the developer A using an automatic developing machine FG710NH of Fuji Film Co., Ltd., fixed with a fixing solution GR-Fl of Fuji Photo Film Co., Ltd., washed with water and dried.
Table 1 shows the results of evaluation of the extracted character image quality and Dmax of each sample. The extracted character image quality 5 is a character having a width of 30 μm reproduced when properly exposed such that a halftone dot area of 50% is 50% halftone dot area on the return light-sensitive material by using the original as shown in FIG. The image quality is very good and the character quality is very good. 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 appropriate exposure is given, and is between 4 and 2 in the sensory evaluation between 5 and 1. Rank is set. A level of 3 or more is a practical level. Similarly, Dmax is Dm when exposed so that the halftone dot area of 50% of the original becomes the halftone dot area of 50%.
It is ax. The sample of the present invention has a high Dmax and is excellent in character image quality.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0047

[Correction method] Change

[Correction content]

Example 2 (Preparation of Photosensitive Emulsion) In a gelatin aqueous solution kept at 50 ° C., 4 × 10 ⁻⁷ mol of iridium hexachloride (I) was added per mol of silver.
II) In the presence of potassium and ammonia, an aqueous solution of silver nitrate and an aqueous solution of potassium iodopotassium bromide are added simultaneously for 60 minutes and the pAg between them is kept at 7.8 to obtain an average grain size of 0.28μ and an average iodination. A cubic monodisperse emulsion having a silver content of 0.3 mol% was prepared. This emulsion was desalted by the flocculation method, and then 40 g of inactive gelatin was added per mol of silver, and the mixture was kept at 50 ° C. to give 5,5′-dichloro-9-ethyl-3, as a sensitizing dye.
3'-bis (3-sulfopropyl) oxacarbocyanine and ^10-3 mol of KI solution per mol of silver were added,
The temperature was lowered after 15 minutes. (Coating of Photosensitive Emulsion Layer) This emulsion was redissolved, the compounds of the present invention shown in Table 3 and the compounds of Comparative Examples were added at 40 ° C., and 5-methylbenztriazole and 2-methyl-4 were further added. -Hydroxy-1,3,3a, 7-tetrazaindene, the following compounds (a), (b) and 30 wt% of polyethyl acrylate with respect to gelatin, and the following compound (c) as a gelatin hardening agent were added and chlorinated. 2. Amount of silver on a polyethylene terephthalate film (150μ) having an undercoat layer (0.5μ) made of vinylidene copolymer.
It was applied at 8 g / m ² .

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0048

[Correction method] Change

[Correction content]

[0048]

[Chemical 14]

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material containing a compound represented by the following general formula (1). Formula ^{(1) R 1 -L 1 -R} 2 -L 2 -R 3 in -NHNH-G ¹ -R ⁴ Formula, L ¹ is -SO ₂ NR ⁵ - group, -NR ⁵ SO ₂ NR
⁵ - group, -CONR ⁵ - group, -NR ⁵ CONR ⁵ - group or ^{-G 2 P (O) (G} 2 R 5) -NR 5 - represents a group, L
² is -NR ⁵ SO ₂ NR ⁵ -group, -CONR ⁵ -group,-
NR ⁵ CONR ⁵ — group or —G ² P (O) (G ² R ⁵ ) —
Represents a NR ⁵ — group. G ¹ is a —CO— group, —SO ₂ —
Group, -SO- group, -COCO- group, thiocarbonyl group,
Iminomethylene group or ^{-P (O) (G 2 R} 5) - represents a group - group, G ² represents a single bond, -O- group, -NR ^5.
R ¹ represents an aliphatic group or aromatic group containing four or more ethylene oxide repeating units, or an aliphatic group or aromatic group containing a quaternary ammonium cation. R ² ,
R ³ represents a divalent aliphatic group or aromatic group, R ⁴ represents a hydrogen atom, an aliphatic group, an aromatic group, an alkoxy group, an aryloxy group or an amino group, and R ⁵ represents a hydrogen atom or an aliphatic group. Alternatively, it represents an aromatic group.