JPH0619031A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a photosensitive material having excellent in rapid treatment and treatment stability and to enable development at a low pH by incorporating a specified compd. CONSTITUTION:The photosensitive material contains a compd. expressed by formula. In formula, L<1> denotes-O-,-S-,-SO-,-SO2,-N(R<4>)-, CONR<4>,-NR<4>CO-,- OCONR<4>-, etc., L<2>-L<4> are bivalent aliphatic groups or aromatic groups, G denotes-CO-,-SO2,-SO-,-COCO-, thiocarbonyl group, iminomethylene group, etc., R<1> is an aliphatic group or aromatic group, R<2> is a univalent substituent, (n) is an integer between 0 and 4, R<3> is a hydrogen atom, aliphatic group, aromatic group, alkoxy group, aryloxy group, or amino group, R<4> is a hydrogen atom, aliphatic group, or aromatic group, and X<-> denotes a paired aninon when the compd. forms a paired anion or inner salt.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material and a superhigh contrast negative image forming method using the same, and more particularly to a silver halide photographic light-sensitive material used in a photomechanical process.

[0002]

2. Description of the Related Art In the field of graphic arts, ultra-high contrast (especially when gamma is 1
An image forming system showing a photographic characteristic of 0 or more) is required. As a method of obtaining a photographic characteristic of high contrast using a stable developing solution, US Pat. Nos. 4,224,401, 4,168,977, and 4,166,742 are disclosed.
No. 4,311,781, No. 4,272,606
No. 4,211,857 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 not improved in the lith developer. Greatly improved compared to. However, hitherto, it has been found that the known hydrazine compounds have some drawbacks. That is, it has been attempted to make the structure of the hydrazine compound a diffusion-resistant structure with a conventionally known hydrazine compound for the purpose of reducing the adverse effect on other photographic light-sensitive materials caused by flowing out into the developing solution. These diffusion-resistant hydrazine compounds are required in a large amount for sensitizing and hardening, which causes problems that the physical strength of the obtained photosensitive layer is deteriorated and that 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. Also,
Conventionally, a super-high contrast system using a hydrazine compound requires a relatively high pH, for example, a developing solution having a pH of 11.5 or 11.8, resulting in a high handling risk.
There are problems such as high BOD and COD when treating the waste liquid. Also, since it is necessary to use a large amount of pH buffering agent to keep the pH of the developer constant, the solid concentration of the developer becomes high, the solution becomes sticky, and the scattered solution is difficult to wipe off. was there. Therefore, lower p
It has been desired to develop a hydrazine compound capable of increasing the contrast with an H developer. Further, the reversing sensitized material generally handled in a bright room has a large field as one of the sensitizing materials for plate making, and in this field, high quality of blank characters for reproducing thin Mincho characters is required. . Therefore, the development of a more active nucleating agent has been desired. In particular, in a low-sensitivity bright room light-sensitive material that can be handled even in a bright room, it is difficult for the nucleating agent to produce a high contrast, and there is a demand for the development of a highly active nucleating agent.

[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.
A second object of the present invention is to provide a silver halide photographic light-sensitive material for plate making which can be developed at a lower pH.

[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). General formula (1)

[0005]

[Chemical 2]

Where L¹Is -O- group, -S- group, -SO
-Group, -SO₂-Group, -N (R^Four) -Group, -CONR^Four
-Group, -NR^FourCO- group, -OCONR^Four-Group, -NR
^FourCONR^Four-Group, -SO₂NR^Four-Group, -NR^FourSO
₂-Group, -NR^FourSO₂NR ^Four-Group (but these 2
It is assumed that it is attached to the pyridine ring on the right side of the valent group. )
Represents L², L³, L^FourIs a divalent aliphatic group or
Represents an aromatic group, G represents a -CO- group, -SO₂-Group, -S
O- group, -COCO- group, thiocarbonyl group, iminome
Tylene group or -P (O) (G¹R^Four) -Represents a group,
G¹Is a single bond, -O- group, -NR^FourRepresents a group. R¹
Represents an aliphatic group or an aromatic group, and R²Is a monovalent replacement
Represents a group, and n represents an integer of 0 to 4. R³Is hydrogen
Child, aliphatic group, aromatic group, alkoxy group, aryloxy
Represents a group or an amino group, R^FourIs a hydrogen atom, an aliphatic group
Or, it represents an aromatic group, and a plurality of R¹And R^FourBut
When present, they may be the same or different
Yes. X^-Is a counter anion or an inner salt
Represents the counter anion part.

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 as typical substituents, those enumerated below as examples of R ² are applicable. R ² is a monovalent substituent, and preferred examples thereof 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,
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, Examples thereof include 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 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), Examples thereof include an ureido group (preferably having 1 to 30 carbon atoms) and a phosphoric acid amide group (preferably having 1 to 30 carbon atoms). These groups may be further substituted.

The aliphatic group represented by R ³ in the general formula (1) is preferably an alkyl group having 1 to 4 carbon atoms, and the aromatic group is preferably a monocyclic or bicyclic aryl group (for example, Including benzene ring). G is -C
In the case of an O-group, preferred among the groups represented by R ³ are a hydrogen atom, an alkyl group (eg, methyl group, trifluoromethyl group, 3-hydroxypropyl group, 3-methanesulfonamidopropyl group, phenylsulfonyl group). Methyl group, etc.), aralkyl group (eg, o-hydroxybenzyl group, etc.), aryl group (eg, phenyl group,
3,5-dichlorophenyl group, o-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, 2-
(Eg, a hydroxymethylphenyl group), and a hydrogen atom is particularly preferable. R ³ may be substituted, and as the substituent, the substituents listed as examples of R ² can be applied. Most preferably, G in the general formula (1) is a -CO- group. R ³ may also be one which splits the portion of GR ³ from the rest of the molecule to give rise to a cyclization reaction which produces a cyclic structure containing atoms of the portion -GR ^3. Examples include those described in JP-A-63-29751. R ⁴ is a hydrogen atom or a carbon number of 1 to
An alkyl group of 6 is preferable, and a hydrogen atom is particularly preferable.
Further, the compound represented by the general formula (1) has two or more R ^{4 s.}
When G and G ¹ are contained, they may be the same or different.

In the general formula (1), L¹2 represented by
Valuable linking groups include -O-, -S-, -N (R^Four) −
Group, -CONR^Four-Group, -OCONR^Four-Group, -SO₂
NR_Four-Groups are preferred. In the general formula (1), L²,
L³, L^FourThe divalent aliphatic group represented by is preferably charcoal.
Prime number 1-30, especially carbon number 1-20
It is a chain, branched or cyclic alkylene group. General formula
L in (1)², L³, L^FourDivalent valency represented by
The aromatic group is a monocyclic or bicyclic arylene group or an unsaturated heterocyclic group.
It is a terror group. Here, the unsaturated heterocyclic group is an aryl group
And may be condensed. L², L³, L^FourThe aliphatic radical
Or an aromatic group may be substituted, and a typical substituent
As R²The ones listed as examples of are applicable. L
²Is preferably an alkylene group, particularly preferably
Or-(CH₂) _m-(Where m is an integer from 1 to 4)
Of the groups represented, the methylene group is most preferred.
L³, L^FourPreferred as is an arylene group,
Particularly preferred is one containing a benzene ring. L³age
Most preferably a substituted or unsubstituted phenylene group,
L^FourIs most preferably a p-phenylene group.

[0010] X ^- anion represented by is a counter anion of the pyridinium moiety, a halide ion Examples include sulfonate, sulfate, phosphonate ion, phosphate _{^{ion, BF 4 -, ClO 4 -}} , PF
₆ ^- and the like, particularly preferably Cl ^-, B
F ₄ ⁻ , PF ₆ ⁻ and sulfonate ions. X
^{- R 1, R 2, R} 3 of the general formula ^{(1), L 1, L} 2, L
^It may combine with the moiety represented by ³ or L ⁴ to form an inner salt.

R ¹ , R ² , R ³ , L ^{2 of} the general formula (1),
L ³ or L ⁴ may have a ballast group or a polymer, which is 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 , L ^{2 of} the general formula (1),
L ³ or L ⁴ may be one in which a group that enhances adsorption to the surface of the silver halide grain is incorporated. Examples of the adsorptive group include thiourea groups, heterocyclic thioamide groups, mercaptoheterocyclic groups, triazole groups, and the like, U.S. Pat. Nos. 4,385,108 and 4,459,347,
JP-A-59-195,233 and 59-200,23.
No. 1, No. 59-201, 045, No. 59-201, 0
No. 46, No. 59-201, No. 047, No. 59-201,
048, 59-201, 049, 61-17
0,733, 61-270,744, 62-9
48, 63-234, 244, 63-234,
The groups described in No. 245 and No. 63-234,246 are mentioned. The compounds used in the present invention are listed below, but the present invention is not limited thereto.

[0013]

[Chemical 3]

[0014]

[Chemical 4]

[0015]

[Chemical 5]

[0016]

[Chemical 6]

The hydrazine compound of the present invention is disclosed in, for example, JP-A-61-213,847 and JP-A-62-260,153.
No. 4,684,604, JP-A 1-26.
9,936, U.S. Pat. Nos. 3,379,529, 3,620,746, 4,377,634, 4,332,878, and JP-A-49-129,536.
No. 56-153,336, No. 56-153,34
2, U.S. Pat. Nos. 4,988,604 and 4,994.
It was synthesized by utilizing the method described in No. 365 or the like.

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 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 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. In particular, it is 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. ,
A silver halide having 75 mol% or more of silver chloride is particularly preferable. 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%, 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. The monodispersion as used herein 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 regular crystal bodies such as cubes and octahedra, or may have irregular crystal grains such as spherical and plate-like grains. 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.

The silver halide emulsion used in the present invention contains 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. in the process of forming silver halide grains or physically ripening them. 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, 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. Good. Among the noble metal sensitizing methods, the gold sensitizing method is a typical one, which uses a gold compound, mainly a gold complex salt. Noble metals other than gold, for example, complex salts of platinum, palladium, iridium, etc. may be contained. Specific examples are 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, rhodanins and the like 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 Vol. 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, 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 production process of the light-sensitive material, storage during storage or 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 .; hydroquinone and its derivatives; disulfides such as thioctic acid; antifoggants such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. 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 preferable 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. Suitable development accelerators or nucleation infectious development accelerators for use in the present invention are those disclosed in JP-A-53-7761.
6, compounds 54-37732, compounds 53-137, 133, compounds 60-140, 340, compounds 60-14959, etc., as well as various compounds containing an N or S atom are effective. Specific examples are listed in.

[0027]

[Chemical 7]

[0028]

[Chemical 8]

[0029]

[Chemical 9]

[0030]

[Chemical 10]

These accelerators depend on the type 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,
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, ie,
Insensitivity farther than the silver halide emulsion layer with respect to the support
For fixing by adding together 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
Soluble, 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
Body examples are described in JP-A-63-64039.
Others, U.S. Pat. Nos. 3,533,794 and 3,31
4,794, 3,352,681, JP-A-46-
2784, U.S. Pat. Nos. 3,705,805 and 3,7.
07,375, 4,045,229, 3,70
0,455, 3,499,762, West German patent application
Ultraviolet rays described in Announcement 1,547,863
Absorption dyes are also used. Others, US Pat. No. 2,27
Pyrazolone oxonol dyes 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. 3,
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 and other hydrophilic colloid layers. For example, chromium salts (chromium vanadium, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, 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.

For a photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material produced by using the present invention, a coating aid, an antistatic agent, an improvement in slipperiness, an emulsion dispersion, an adhesion prevention and an improvement in photographic characteristics (for example, development acceleration). , Contrast enhancement, sensitization), and various other 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 alkyl amines or amides, silicone polyethylene oxide adducts), 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 alkylphenyl 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, alkyl betaines, 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. Particularly, 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 a polyalkyl acrylate may be incorporated for dimensional stability.

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. It is not necessary to use a stable developing solution. 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 treated with a developing solution having a pH of 10.5 to 12.3, and 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. For example, dihydroxybenzenes (for example, hydroquinone), 3-pyrazolidones (for example, 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. Preferably, in this developer, dihydroxybenzenes are 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 speed 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. Further, if necessary, a water softener, a dissolution aid, a color tone agent, a development accelerator, a surfactant (particularly preferably the above-mentioned polyalkylene oxides), a defoaming 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 be effective 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 process of the present invention is usually from 18 ° C to
Selected during 0 ° C. Although it is preferable to use an automatic processor for photographic processing, even if the total processing time from putting the light-sensitive material into the automatic developing machine until it comes out is set to 90 seconds to 120 seconds by the method of the present invention. , Photographic characteristics of negative gradation of ultra-high contrast can be obtained. The compounds described in JP-A-56-24,347 can be used as a silver stain inhibitor in the developer of the present invention. The compounds described in JP-A-61-267,759 can be used as a dissolution aid added to the developing solution. Further, the compounds described in JP-A-60-93,433 or the compounds described in JP-A-62-186,259 can be used as the pH buffer used in the developing solution.

[0037]

【Example】

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 ^-4 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 0.0
It was a monodisperse emulsion having a cubic crystal shape of 8 μm. To this emulsion was added a hydrazine compound selected from the general formula (1) shown in Table-1 or the following comparative compound,

[0038]

[Chemical 11]

Further, polyethyl acrylate latex was added in an amount of 30 wt% based on the solid content of gelatin, 1,3-di-vinylsulfonyl-2-propanol was added as a hardening agent, and 3.8 g / m 2 was added on the polyester support. ^It was applied so that the Ag amount was ² . The gelatin was 1.8 g / m ² . On this, 8 mg / m ² of the following nucleation accelerator as a gelatin intermediate layer, 30 mg / m ² of solid fine particle dispersion of Dye A,
Gelatin 0.8 g / m ² ,

[0040]

[Chemical 12]

As a hardener, 1,3-divinylsulfonyl-2-propanol was added and applied. On top of this, as a protective layer, the following solid fine particle dispersion of Dye B was added at 60 mg /
m ^2, as a matting agent, polymethyl methacrylate (particle size 2.5 [mu]) of 0.3 g / m ^2, gelatin 0.7 g / m ^2, as a coating aid, were coated added the following compounds. The total amount of the hardener added was 2.0 wt% of the total gelatin amount.

[0042]

[Chemical 13]

[0043]

[Chemical 14]

2) Evaluation of photographic property The coating sample thus obtained was applied to a bright room printer P-627FM manufactured by Dainippon Screen Co., Ltd., and was disclosed in JP-A-2-29373.
Image exposure through the document shown in FIG.
It was developed at 38 ° C. for 20 seconds with the 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. 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 Nn-butyldiethanolamine 15. 0 Sodium toluene sulfonate 8.0 Add water to 1 liter Adjust to pH = 11.6 (add potassium hydroxide) pH11.6 Table 1 shows the results of evaluation of the blank character image quality and Dmax of each sample. Indicated. The blank character image quality 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 a character 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 at the time of exposure 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.

[0045]

[Table 1]

Example 2 (Emulsion preparation) Emulsion A: 0.04 M potassium bromide containing 0.13 M silver nitrate aqueous solution and (NH ₄ ) ₃ RhCl ₆ corresponding to 1 × 10 ⁻⁷ mol per mol of silver. And an aqueous solution of halogen salt containing 0.09M sodium chloride, sodium chloride,
An average particle size of 0.15 was added to a gelatin aqueous solution containing 1,3-dimethyl-2-imidazolidinethione by a double jet method at 38 ° C. for 12 minutes while stirring.
Nucleation was performed by obtaining silver chlorobromide grains having a particle size of 70 μm and a silver chloride content of 70 mol%. Then, similarly, 0.87 M silver nitrate aqueous solution, 0.26 M potassium bromide, and 0.6
A halogen salt aqueous solution containing 5 M sodium chloride was added by the double jet method over 20 minutes. Then 1
A KI solution of × 10 ^-3 mol was added for conversion, followed by washing with water by a flocculation method according to a conventional method, 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. Then, 8 mg of chloroauric acid was added, and the mixture was heated at 60 ° C. for 60 minutes for chemical sensitization, and 150 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added as a stabilizer. The obtained grains were cubic silver chlorobromide grains having an average grain size of 0.27 μm and a silver chloride content of 70 mol%.
(Coefficient of variation 10%).

(Preparation of Coating Sample) The hydrazine derivative of the present invention and the comparative compound were added to this emulsion as shown in Table 2.

[0048]

[Table 2]

Further, the compound of the following structural formula (S) is represented by the following structural formula (a): 3.4 × 10 ^-4 mol, and 1-phenyl-5-mercaptotetrazole is 2 × 10 ^-4 mol per mol of silver. 5 × 10 ⁻⁴ mol of a short-wave cyanine dye, and a water-soluble latex represented by (b) (200 mg /
m ² ), polyethyl acrylate dispersion (200 mg /
m ² ), and 1,3-divinylsulfonyl-2-propanol (200 mg / m ² ) as a hardener.

[0050]

[Chemical 15]

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

[0052]

[Chemical 16]

Gelatin as protective layer 1.0 g / m²,particle
Amorphous SiO about size 3.5μ ₂Matting agent 40mg /
m², Methanol silica 0.1g / m², Polyacrylic
100 mg / m², Hydroquinone 200mg / m², Silico
As the coating oil and coating aid, the flux represented by the following structural formula
Fluorine surfactant and sodium dodecylbenzene sulfonate
The layer containing the coating was coated simultaneously with the emulsion layer. Back again
The layer and the back layer protective layer were applied by the following formulation.

[0054]

[Chemical 17]

[Back layer formulation] Gelatin 3 g / m ² latex Polyethyl acrylate 2 g / m ² Surfactant Sodium p-dodecylbenzenesulfonate 40 mg / m ² Gelatin hardening agent

[0056]

[Chemical 18]

Dye A mixture of dyes [a], [b] and [c]

[0058]

[Chemical 19]

[Back protective layer] Gelatin 0.8 mg / 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

(Evaluation of Photographic Properties) These samples were tested for 32
After exposing with optical wedge or optical wedge and contact screen (Fujifilm, 150L chain dot type) with tungsten light of 00 ° K, 38 with the next developing solution B.
It was developed at 30 ° C. for 30 seconds, fixed, washed with water and dried. As the fixing solution, GR-F1 manufactured by Fuji Photo Film Co., Ltd. was used.

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-Methylbenzo Triazole 0.4 2-Mercaptobenzimidazole-5-sulphonic acid 0.3 3- (5-Mercaptotetrazole) benzenesulphonic acid sodium 0.2 Sodium toluene sulphonate 8.0 Water is added to adjust to pH 10.6. The photographic characteristics obtained are shown in Table 2. Halftone quality is visual
It was evaluated in 5 stages. "5" is the best for the five-level evaluation,
"1" indicates the worst quality. As halftone dot original plate for plate making
"5" and "4" are practical, and "3" is practical
It is the limit level, and "2" and "1" are unusable quality
Is. Dmax is also exposed through an optical wedge,
Amount of exposure that gives an optical density of 1.5 of the processed sample
(Log E₃), 0.5 more exposure (0.5 + log E
₃), The optical density (Dmax). pH 10.
Even with the developer of No. 6, when the compound of the present invention is used, a high Dmax is obtained.
It can be seen that a high halftone dot quality is maintained by maintaining It
On the other hand, with the hydrazine compound of Comparative Example, the pH was 10.
With the developer of No. 6, sufficient halftone dot quality cannot be obtained.

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[Procedure amendment]

[Submission date] July 27, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0007

[Correction method] Change

[Correction content]

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 as typical substituents, those enumerated below as examples of R ² are applicable. R ² is a monovalent substituent, and preferred examples thereof 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,
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, Examples thereof include 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 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), Examples thereof include an ureido group (preferably having 1 to 30 carbon atoms) and a phosphoric acid amide group (preferably having 1 to 30 carbon atoms). These groups may be further substituted. Further, n is preferably 0.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0043

[Correction method] Change

[Correction content]

[0043]

[Chemical 14]

Claims (1)

[Claims] 1. A compound represented by the following general formula (1):
A silver halide photographic light-sensitive material characterized by containing.
General formula (1)Where L¹Is -O- group, -S- group, -SO- group, -SO
₂-Group, -N (R^Four) -Group, -CONR^Four-Group, -NR
^FourCO- group, -OCONR^Four-Group, -NR^FourCONR^Four
-Group, -SO₂NR^Four-Group, -NR^FourSO₂-Group, -N
R^FourSO₂NR ^Four-Group (but to the right of these divalent groups
Assume that it is bonded to the pyridine ring. ) Is represented. L
², L³, L^FourRepresents a divalent aliphatic group or aromatic group
, G is a -CO- group, -SO₂-Group, -SO- group, -C
OCO- group, thiocarbonyl group, iminomethylene group or
Is -P (O) (G¹R^Four) -Represents a group, G¹Is single
, -O- group, -NR^FourRepresents a group. R¹Is an aliphatic group
Or represents an aromatic group, R²Represents a monovalent substituent
However, n represents the integer of 0-4. R³Is hydrogen atom, fat
Group, aromatic group, alkoxy group, aryloxy group or
Represents an amino group, R^FourIs a hydrogen atom, an aliphatic group or
Represents an aromatic group and contains multiple R groups in the molecule.¹And R^FourExists
Sometimes, they may be the same or different. X^-
Is a counter anion or an anion if it forms an inner salt.
It represents a part.