JPH04320254A - High-contrast silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To provide a high-contrast silver halide reversal photosensitive material for a photomechanical process handleable in daylight and giving high-quality white-on-black characters by lap reversal. CONSTITUTION:A silver chloride emulsion or a silver chlorobromide emulsion having >=80mol% silver chloride content prepd. in the presence of a water-soluble rhodium salt added by 1X10<-7>-1X10<-4>mol per 1mol silver halide is used as a silver halide emulsion in a silver halide emulsion layer. A hydrazine deriv. is incorporated into the silver halide emulsion layer and a redox compd. having a hydrazine structure capable of releasing a development inhibitor when oxidized by the oxidized product of a developing agent as a redox group is incorporated into a hydrophilic colloidal layer other than the silver halide emulsion layer or a second silver halide emulsion layer to obtain a silver halide photosensitive material. At least a part of the released development inhibitor leaches out in a developing soln. and can be converted into a compd. having low inhibiting property by a reaction with a component of the developing soln.

Description

[Detailed description of the invention]

0001

[Field of Industrial Application] The present invention relates to a silver halide light-sensitive material for photolithography, and more specifically, to a silver halide light-sensitive material for photolithography, which can be handled in an environment that can be practically called a bright room, and which has high contrast image characteristics. This invention relates to a silver halide photosensitive material for return printing.

0002

2. Description of the Related Art In the field of printing reproduction, efforts are being made to improve the efficiency of the photolithography process and the working environment. Particularly in the collection and turning process, working in a brighter environment improves work efficiency and the working environment, and the work can be done in what can essentially be called a bright room. Development of silver halide photographic materials for plate making,
Development and improvements have been made to printer equipment. Here, the silver halide photosensitive material for bright rooms uses a fluorescent lamp with little ultraviolet light component or a fluorescent lamp equipped with a filter to cut the ultraviolet light component as a safe light.
It is a photosensitive material that can be handled in brightness of about 100 to 300 lux.

[0003] As a method of producing a photosensitive material that can be handled in a bright room by lowering its sensitivity to visible light, rhodium salts, bismuth salts, iridium salts, cupric chloride, etc. are added to silver halide emulsions mainly containing silver chloride. A well-known method is to use an emulsion containing an inorganic desensitizer or an organic desensitizer such as pinacryptol yellow or phenosafranin. In particular, rhodium salt and/or
Alternatively, a method using an organic desensitizer is preferably used (for example, JP-A-56-125,734, JP-A-56-1
No. 49,030, No. 59-157,633, etc.).

[0004] Silver halide photosensitive materials for bright room reversal use a developed film on which characters or halftone images are formed as an original, and these originals and the photosensitive material for reversal are exposed in close contact to form a negative image/positive image. Although it is used for conversion or positive image/positive image conversion, it is desirable that it have the ability to faithfully reproduce the original image. However, it is known that photosensitive materials that can be handled in a bright room have inferior performance when compared to photosensitive materials that can be handled in a dark room, and efforts have been made to improve this (for example, Japanese Patent Publication No. 2-28 , No. 856, JP-A-64-7
2,139 etc.). In particular, the character image performance (cutting character image quality) is poor when exposing a character image original and a halftone image original in a layered manner, and there are also problems with the marks left by the tape used when pasting a text or halftone image original onto a transparent base. It has been reported that adhesive marks (adhesive marks) appear in the returned image, impairing the quality of the finished product, and further improvements in this aspect have been desired.

[0005]

OBJECTS OF THE INVENTION The object of the present invention is to provide a method that can be handled in a bright room, and when used for turning in photolithography, has good cutout character image quality due to overlapping turning, and does not leave tape marks easily. An object of the present invention is to provide a high-contrast silver halide photosensitive material. A second object of the present invention is to provide a silver halide photographic material that can be stably obtained even during running processing without deteriorating its good return characteristics.

[0006]

[Means for Solving the Problems] An object of the present invention is to provide at least one silver halide emulsion layer on a support, and at least one hydrophilic colloid layer and/or a second silver halide emulsion layer different from this layer. 1) The silver halide emulsion in the silver halide emulsion layer contains a water-soluble rhodium salt in an amount of 1 x 10-7 to 1 x 10-4 mol per mol of silver halide. 2) a hydrazine derivative is contained in the silver halide emulsion layer; 3) a hydrophilic emulsion different from that of the emulsion layer; A redox compound having a hydrazine structure as a redox group that can be oxidized by an oxidation product of a developing agent to release a development inhibitor, which is contained in the sexual colloid layer or the second silver halide emulsion layer, the development inhibitor This was achieved by containing a redox compound, at least a part of which can be eluted into the developer and converted into a less inhibiting compound by reaction with the developer components.

Furthermore, by adding a dye compound represented by the following general formula (I) to the above structure, the handleability in a bright room can be further improved.

[0008]

[Case 2]

In the formula, R1 is an alkyl group, an alkoxy group,
Represents a hydroxy group, an amino group, a substituted amino group, an alkoxycarbonyl group, a carboxy group, a cyano group, a carbamoyl group, a sulfamoyl group, a ureido group, a thioureido group, an acylamido group, a sulfonamide group, or a phenyl group. Q represents a sulfoalkyl group, a sulfoalkoxyalkyl group, or an aryl group having at least one sulfo group. R2 represents a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, or a halogen atom. R3 and R4 may be the same or different and represent an alkyl group or a substituted alkyl group. Examples of the substituent include a halogen atom, an alkoxy group, a cyano group, a sulfo group, a carboxy group, an alkoxycarbonyl group, an acyloxy group, an acyl group, an acylamido group, a sulfonamide group, an alkylsulfonyl group, and a thioalkyl group. Further, R3 and R4 may form a 5- to 6-membered ring. However, R1, R3, and R4 do not have methyl groups at the same time. Here, dyes in which R1, R3, and R4 are all methyl groups are not preferred because they do not have an effect of improving safety against safelight light.

The dye added for the purpose of improving handling properties in a bright room environment lowers the sensitivity of the silver halide emulsion on the long wavelength side of its inherent sensitivity wavelength range, and is preferably used in the film. It has an absorption maximum in the film between 400 and 550 nm. Typical specific examples relating to the present invention are shown below.

[0011]

[Chemical formula 3]

0012

[C4]

[0013]

[C5]

[0014]

[C6]

[0015]

[C7]

[0016]

[Chemical formula 8]

[0017]

[Chemical formula 9]

[0018]

[Chemical formula 10]

[0019]

[Chemical formula 11]

[0020]

[Chemical formula 12]

[0021]

[Chemical formula 13]

[0022]

[Chemical formula 14]

[0023]

[Chemical formula 15]

[0024]

[Chemical formula 16]

The amount of the dye compound represented by formula (I) to be added is preferably 10 mg to 400 mg, more preferably 20 mg to 300 mg, per m 2 of the light-sensitive material.

In the present invention, the redox compound added to the hydrophilic colloid layer or the second silver halide emulsion layer different from the hydrazine-containing silver halide emulsion layer...is oxidized by the oxidation product of the developing agent. A redox compound having a hydrazine structure as a redox group capable of releasing a development inhibitor, in which at least a portion of the development inhibitor is eluted into a developer and converted into a compound with less inhibitory properties by reaction with developer components. I will explain in detail about redox compounds...

These redox compounds preferably have the following general formula (R-1), general formula (R-2), and general formula (R-2).
−3). Among these, the compound represented by the general formula (R-1) is particularly preferred.

[0028]

[Chemical formula 17]

In these formulas, R1 represents an aliphatic group or an aromatic group. G1 is -CO- group, -COCO- group,
-CS- group, -C(=NG2R2)- group, -SO-
group, -SO2 - group or -P(O)(G2 R2 )
- represents a group. G2 is a simple bond, -O- group, -S- group or -N
It represents a (R2)- group, R2 represents a group having the same definition as R1 or a hydrogen atom, and when a plurality of R2's exist in the molecule, they may be the same or different. A1
, A2 represents a hydrogen atom, an alkylsulfonyl group, an arylsulfonyl group or an acyl group, and may be substituted. In general formula (R-1), at least one of A1 and A2 is a hydrogen atom. A3 is synonymous with A1 or -CH2 CH(A4)-(Time)t -PUG
represents. A4 represents a nitro group, a cyano group, a carboxyl group, a sulfonyl group, or -G1-G2-R1 (in this case, two -G1-G2-R1's in the molecule may be the same or different). Time represents a divalent linking group, and t represents 0 or 1. P.U.
G represents a development inhibitor that can react with developer components and convert into a less inhibitory compound when flowing into the developer. Regarding these development inhibitors, for example, Japanese Patent Application No. 2-2589
No. 24, No. 2-254728, No. 2-258927, No. 3-15648, No. 2-258929, No. 2-
The descriptions in No. 258928 and the like can be referred to. PUG used in the present invention preferably has the following general formula (P
-1), (P-2), and (P-3).

[0030]

[Chemical formula 18]

In the formula, X1 represents a trivalent organic group,
2 represents a group that reacts with a developing treatment solution component and converts into an anionic group, and X3 represents a group that exhibits a nucleation and development inhibiting effect. Y1 represents a divalent organic group, Y2 represents a divalent group that can be cleaved by reacting with a developing treatment solution component,
Y3 represents a group that exhibits the effect of inhibiting nucleation development. Z1
~Z5 represents a hydrogen atom or a monovalent group, and further satisfies at least one of the following conditions (1), (2), and (3). Condition (1) At least one of Z2 and Z5 represents a nitro group. Condition (1) At least one of Z3 and Z4 is a nitro group, and at least two of Z1 to Z5 are electron-withdrawing groups. Condition (1) At least one of Z3 and Z4 is a nitro group, and Z1 is an aliphatic group or an aromatic group.

Further, general formulas (R-1), (R-2), (R
-3), R1 or Time is a ballast group commonly used in immobile photographic additives such as couplers or a general formula (R-1), (R-2), (R-3).
) may be incorporated with a group that promotes adsorption of the compound represented by () to silver halide. The ballast group is an organic compound that provides a sufficient molecular weight to substantially prevent the compounds represented by formulas (R-1), (R-2), and (R-3) from diffusing into other layers or processing liquids. It is a group consisting of a combination of one or more of an alkyl group, an aryl group, a heterocyclic group, an ether group, a thioether group, an amide group, a ureido group, a urethane group, a sulfonamide group, etc. The ballast group is preferably a ballast group having a substituted benzene ring, particularly a ballast group having a benzene ring substituted with a branched alkyl group.

Examples of the adsorption promoting group to silver halide include 4-thiazoline-2-thione, 4-imidazoline-2-thione, 2-thiohydantoin, rhodanine,
Thiobarbituric acid, tetrazoline-5-thione, 1,
2,4-triazoline-3-thione, 1,3,4-oxazoline-2-thione, benzimidazoline-2-thione, benzoxazoline-2-thione, benzothiazoline-2-thione, thiotriazine, 1,3- Cyclic thioamide group such as imidazoline-2-thione, chain thioamide group, aliphatic mercapto group, aromatic mercapto group, heterocyclic mercapto group (if the carbon atom to which the -SH group is bonded is a nitrogen atom, then 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,
5- to 6-membered nitrogen-containing heterocyclic groups consisting of a combination of nitrogen, oxygen, sulfur and carbon, such as benzothiazole, thiazole, thiazoline, benzoxazole, oxazole, oxazoline, thiadiazole, oxathiazole, triazine, azaindene, and benz Examples include heterocyclic quaternary salts such as imidazolinium. These may be further substituted with a suitable substituent. Examples of the substituent include those described as the substituent for R1. Specific examples of compounds used in the present invention are listed below, but the present invention is not limited thereto.

[0034]

[Chemical formula 19]

[0035]

[C20]

[0036]

[C21]

[0037]

[C22]

[0038]

[C23]

[0039]

[C24]

[0040]

[C25]

[0041]

[C26]

[0042]

[C27]

[0043]

[C28]

[0044]

[C29]

[0045]

[C30]

[0046]

[Chemical formula 31]

[0047] In addition to the above-mentioned redox compounds used in the present invention, for example, Japanese Patent Application No. 2-258928
No. 2-258929 and No. 3-15648 can be used. The method for synthesizing the redox compound used in the present invention is disclosed in, for example, JP-A No. 61-213
, No. 847, No. 62-260,153, U.S. Patent No. 4
, 684,604, Japanese Patent Application No. 63-98,803, U.S. Patent No. 3,379,529, U.S. Patent No. 3,620,746
No. 4,377,634, No. 4,332,878, JP-A-49-129,536, JP-A No. 56-153,3
No. 36, No. 56-153,342, Patent Application No. 1-290
, No. 563, No. 2-62, 337, No. 2-64, 71
The method described in No. 7 etc. will be helpful.

The redox compound of the present invention is used in an amount of 1 x 10-6 to 5 x 10-2 mol, more preferably 1 x 10-5 to 1 x 10-2 mol, per mol of silver halide. . The redox compounds of the present invention can be dissolved in suitable water-miscible organic solvents, such as alcohols (methanol, ethanol, propanol, fluorinated alcohols), ketones (acetone, methyl ethyl ketone), dimethyl formamide, dimethyl sulfoxide, methyl cellosolve, etc. It can be used after being dissolved. In addition, by the well-known emulsification and dispersion method, dibutyl phthalate, tricresyl phosphate, glyceryl triacetate, or diethyl phthalate can be dissolved using an auxiliary solvent such as ethyl acetate or cyclohexanone, and then mechanically emulsified and dispersed. You can also create and use things. Alternatively, a powder of a redox compound can be dispersed in water using a ball mill, a colloid mill, or an ultrasonic wave, using a method known as a solid dispersion method.

The silver halide emulsion used in the present invention is:
A silver chloride emulsion or a silver chlorobromide emulsion having a silver chloride content of 80 mol % or more, particularly preferably a silver chlorobromide emulsion or a silver chloride emulsion having a silver chloride content of 90 mol % or more. Emulsions with a high silver bromide content cannot ensure safety against safelight light when handled in a bright room.

The silver halide emulsion of the present invention is an emulsion in which grains are formed in the presence of 1.times.10@-7 to 1.times.10@-4 mol of a water-soluble rhodium salt per mol of silver. Rhodium salts include rhodium trichloride, rhodium hexachloride (I
II) Ammonium acid, sodium rhodium(III) hexachloride, potassium rhodium(III) hexachloride, etc. If the amount of rhodium salt added is less than 10-7 mol, safelight safety cannot be ensured, and if the amount exceeds 10-4 mol, the sensitivity becomes too low and it becomes difficult to achieve high contrast with hydrazine. I end up.

The silver halide emulsion of the present invention may contain a water-soluble iridium salt. Iridium salts include iridium trichloride, iridium tetrachloride, potassium iridium(III) hexachloride, potassium iridium(IV) hexachloride, ammonium iridium(III) hexachloride, and the like. The amount added is preferably in the range of 1 x 10-8 mol to 1 x 10-5 mol per mol of silver, and is preferably added by the same method as in the case of the rhodium salt.

The average grain size of the silver halide used in the present invention is preferably fine grains of 0.5 μm, more preferably 0.3 μm or less. The more monodisperse the particle size distribution is, the more preferable it is, and 90% or more of the total number of particles is within ±40% of the average particle diameter, more preferably ±20%.
It is preferable that it be within %. The silver halide grains preferably have regular crystal shapes such as cubic or octahedral shapes, but those having irregular crystal shapes such as spherical or plate shapes, or those having irregular crystal shapes such as spherical or plate shapes are preferable. It may be in a composite form of crystalline form.

[0053] The water-soluble silver salt (silver nitrate aqueous solution) and the water-soluble halogen salt may be reacted by one-sided mixing method, simultaneous mixing method, or a combination thereof. As one type of simultaneous mixing method, p in the liquid phase in which silver halide is produced is
A method of keeping Ag constant, ie, a controlled double jet method, can also be used. Grain formation can also be carried out using so-called silver halide solvents such as ammonia, thioethers, and tetrasubstituted thioureas. The controlled double jet method and the grain forming method using a silver halide solvent are effective means for producing a silver halide emulsion with a regular crystal shape and a narrow grain size distribution.

As the silver halide emulsion of the present invention, an emulsion which has not been chemically sensitized is preferably used.

A hydrazine derivative represented by the following general formula (II) is added to the silver halide emulsion layer of the present invention for the purpose of obtaining high contrast photographic properties. General formula (
II)

[0056]

[C32]

In the general formula (II), the aliphatic group represented by A preferably has 1 to 30 carbon atoms, particularly a straight chain, branched or cyclic alkyl group having 4 to 20 carbon atoms. Here, the branched alkyl group may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. Further, the alkyl group may have a substituent such as an aryl group, an alkoxy group, a sulfoxy group, or a sulfonamide group. For example, t-butyl group,
n-octyl group, t-octyl group, cyclohexyl group,
Examples include a pyrrolidyl group, an imidazolyl group, a tetrahydrofuryl group, and a morpholino group.

In the general formula (II), the aromatic group represented by A is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group is monocyclic or dicyclic.
It may be combined with the aryl group of the ring to form a heteroaryl group. Examples include a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, and a benzothiazole ring. Among these, those containing a benzene ring are preferred.

Particularly preferred as A is an aryl group. The aryl group or unsaturated heterocyclic group of A may have a substituent. Typical substituents include straight chain,
Branched or cyclic alkyl group (preferably 1 to 2 carbon atoms)
0), aralkyl groups (preferably monocyclic or bicyclic alkyl moieties having 1 to 3 carbon atoms), alkoxy groups (preferably 1 to 20 carbon atoms), substituted amino groups (preferably carbon amino group substituted with an alkyl group having 1 to 20 carbon atoms), acylamino group (preferably 2 to 3 carbon atoms)
0), a sulfonamide group (preferably having 1 to 30 carbon atoms), and a ureido group (preferably having 1 to 30 carbon atoms).

A may have a ballast group commonly used in immobile photographic additives such as couplers incorporated therein. The ballast group is a group having 8 or more carbon atoms and is relatively inert to photography, and is selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group, etc. Can be done. A may have a group incorporated therein to enhance adsorption to the silver halide grain surface. Such adsorption groups include thiourea groups, heterocyclic thioamide groups, mercapto heterocyclic groups, triazole groups, etc., such as U.S. Pat.
JP-A-59-195,233, JP-A-59-200,23
No. 1, No. 59-201,045, No. 59-201,0
No. 46, No. 59-201,047, No. 59-201,
Examples thereof include groups described in No. 048 and No. 59-201,049.

B specifically represents a formyl group, an acyl group (acetyl group, propionyl group, trifluoroacetyl group,
chloroacetyl group, benzoyl group, 4-chlorobenzoyl group, pyruvoyl group, methoxalyl group, methyloxamoyl group, etc.), alkylsulfonyl group (methanesulfonyl group, 2-chloroethanesulfonyl group, etc.), arylsulfonyl group (benzenesulfonyl group, etc.) ), alkylsulfinyl groups (methanesulfinyl groups, etc.), arylsulfinyl groups (benzenesulfinyl groups, etc.), carbamoyl groups (methylcarbamoyl groups, phenylcarbamoyl groups, etc.), sulfamoyl groups (dimethylsulfamoyl groups, etc.),
Alkoxycarbonyl groups (methoxycarbonyl group, methoxyethoxycarbonyl group, etc.), aryloxycarbonyl group (phenoxycarbonyl group, etc.), sulfinamoyl group (methylsulfinamoyl group, etc.), alkoxysulfonyl group (methoxysulfonyl group, ethoxysulfonyl group, etc.), Represents a thioacyl group (such as a methylthiocarbonyl group), a thiocarbamoyl group (such as a methylthiocarbamoyl group), or a heterocyclic group (such as a pyridine ring group). Particularly preferable B is a formyl group or an acyl group.

R0 and R1 are hydrogen atoms, alkylsulfonyl groups having 20 or less carbon atoms, and arylsulfonyl groups (preferably phenylsulfonyl groups or phenyl substituted so that the sum of Hammett's substituent constants is -0.5 or more) sulfonyl group), an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or a benzoyl group substituted such that the sum of Hammett's substituent constants is -0.5 or more, or a linear, branched, or cyclic Examples include unsubstituted and substituted aliphatic acyl groups (substituents include, for example, halogen atoms, ether groups, sulfonamide groups, carbonamide groups, hydroxyl groups, carboxy groups, and sulfonic acid groups). Hydrogen atoms are most preferred as R0 and R1.

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

[0064]

[Chemical formula 33]

[0065]

[C34]

[0066]

[C35]

[0067]

[C36]

[0068]

[C37]

[0069]

[C38]

[0070]

[C39]

[0071]

[C40]

[0072]

[C41]

[0073]

[C42]

[0074]

[C43]

[0075]

[C44]

[0076]

[C45]

[0077]

[C46]

The amount of the hydrazine derivative used in the present invention is preferably in the range of 5×10 −7 mol to 5×10 −2 mol per mol of silver halide, particularly 1×10 −2 mol.
A range of 6 mol to 1×10 −2 mol is preferred. When the hydrazine derivative used in the present invention is incorporated into a photographic light-sensitive material, if it is water-soluble, it may be contained in an aqueous solution, or if it is water-insoluble, it may be contained in alcohols (e.g. methanol, ethanol), esters (e.g. ethyl acetate), or ketones. It is added to the silver halide emulsion solution or hydrophilic colloid solution as a solution in a water-miscible organic solvent such as (eg acetone). When added to a silver halide emulsion solution, it can be added at any time from the start of chemical ripening of the emulsion until coating, but it is preferably added after chemical ripening, especially when prepared for coating. It is preferable to add it to the applied coating solution.

The photosensitive material of the present invention is disclosed in Japanese Patent Application Laid-Open No. 60-140.
, No. 340, No. 62-222, 241, No. 63-12
Various amine compounds described in No. 4,045 and the like can be added. By adding these compounds, the contrast enhancement effect of the hydrazine derivative can be promoted.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fogging during the manufacturing process, storage or photographic processing of the light-sensitive material, or for stabilizing photographic performance. That is, azoles (e.g. benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazole, aminotriazoles,
benzothiazoles, nitrobenzotriazoles, etc.)
, mercaptopyrimidines, mercaptotriazines (
thioketo compounds such as oxazolinthione),
Azaindenes (e.g. triazaindenes, tetrazaindenes... especially 4-hydroxy substituted-1,3,3a
, 7-tetrazaindenes, pentaazaindenes, etc.)
, benzenethiosulfonic acid, benzenesulfinic acid,
Many compounds known as antifoggants or stabilizers can be added, such as benzenesulfonic acid amides, hydroquinone derivatives, and the like. Among these things,
Preferred are benzotriazoles (e.g. 5-methylbenzotriazole) and nitroindazoles (e.g. 5-nitroindazole) and hydroquinone derivatives (e.g. hydroquinone, methylhydroquinone).
It is. Further, these compounds may be included in the treatment liquid.

The photographic material of the present invention contains an inorganic or organic hardening agent in the photographic emulsion layer and other hydrophilic colloid layers. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.) ), activated vinyl compound (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 (mucochromic acid, mucophenoxychromic acid, etc.), N-carbamoylpyridinium salts, haloamidinium salts (1-(1
-chloro-1-pyridinomethylenepyrrolidium-2-naphthalenesulfonate, etc.), etc. can be used alone or in combination. Among them, JP-A-53-41
, No. 221, No. 53-57257, No. 59-162,
546, etc., U.S. Pat.
, 325,287 are preferably used.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention contains coating aids for preventing static electricity, improving slipperiness, dispersing emulsions, preventing adhesion, and improving photographic properties (for example, accelerating development, increasing contrast, sensitizing ) Various surfactants can be added for purposes such as. For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkyl amines, silicone polyethylene nonionic surfactants such as glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars: alkyl carboxylates, alkyl sulfones acid salts, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkylpolyoxyethylene alkylphenyl ethers, Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups such as polyoxyethylene alkyl phosphates: amino acids, aminoalkyl sulfonic acids, amino Ampholytic surfactants such as alkyl sulfuric acid or phosphoric acid esters, alkyl betaines, and amine oxides; alkyl amine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium; and cationic surfactants such as phosphonium or sulfonium salts containing aliphatic or heterocycles can be used. When using a surfactant as an antistatic agent, a fluorine-containing surfactant (
For example, U.S. Patent No. 4,201,586, JP-A-60-8
No. 0,849) is preferably used.

The light-sensitive material of the present invention may contain a dispersion of a water-soluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. For example, alkyl (meth)acrylate, alkoxyalkyl (meth)acrylate,
(meth)acrylamide, vinyl ester, glycidyl (meth)acrylate, acrylonitrile, styrene, etc. alone or in combination, or in combination with acrylic acid, methacrylic acid α, β-unsaturated dicarboxylic acid, styrene sulfonic acid, etc. It can be used in combination with a polymer as a polymer component.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention may contain a compound having an acid group. Examples of compounds having acid groups include polymers or copolymers having organic acids such as salicylic acid, acetic acid, and ascorbic acid, and acid monomers such as acrylic acid, maleic acid, and phthalic acid as repeating units. Among these compounds, particularly preferred are ascorbic acid as a low molecular compound, and acid monomers such as acrylic acid and crosslinking monomers having two or more unsaturated groups such as divinylbenzene as high molecular compounds. It is a water-dispersible latex of copolymer.

As the binder or protective colloid for the emulsion layer and other hydrophilic colloid layers, it is advantageous to use gelatin such as lime-treated gelatin or acid-treated gelatin, but other hydrophilic colloids may also be used. can. 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 sulfate esters: Sugar derivatives such as starch derivatives: Polyvinyl alcohol,
Synthetic hydrophilic polymer compounds such as single or copolymers of polyacrylic acid, polyacrylamide, polymethacrylic acid, polyvinylimidazole, polyvinylpyrazole, etc. can be used.

In the present invention, other hydrophilic colloid layers other than the silver halide emulsion layer include a surface protective layer, an intermediate layer, a filter layer, an antihalation layer, an antistatic layer, and the like. A hydrophilic colloid layer such as a surface protective layer may contain a matting agent for the purpose of preventing adhesion. As a matting agent, U.S. Patent No. 2,701,24
No. 5, No. 2,992,101, No. 4,142,894
Homopolymers of polymethyl methacrylate, copolymers of methyl methacrylate and methacrylic acid, starch, silica, magnesium oxide, etc., as described in No. 4,396,706, can be used. In addition, the surface protective layer includes US Pat. No. 3,489,576 and US Pat.
, 958, Japanese Patent Publication No. 56-2
Colloidal silica described in No. 3,139, paraffin wax, higher fatty acid ester, etc. can be added.

Polyols such as trimethylolpropane, pentanediol, butanediol, ethoxy glycol, and glycerin can be used as plasticizers in the emulsion layer and other hydrophilic colloid layers. Furthermore, the emulsion layer and other hydrophilic colloid layers contain ultraviolet absorbers, brighteners, development accelerators, antioxidants, pH adjusters,
It may contain a thickener, an antistatic agent, etc.

In the silver halide photosensitive material of the present invention, it is also possible to provide a non-photosensitive layer in which a dye is dispersed in solid form on top of the silver halide emulsion layer. The dye used in a solid state dispersed in the non-photosensitive layer is called a solid disperse dye. Solid disperse dyes cannot exist in a molecular state in the non-photosensitive layer to which they are added due to the lack of solubility of the dye itself, and are microcrystals of a size that practically makes it impossible to diffuse in the layer. Exists in the layer as a solid state. The solid disperse dye preferably used in the present invention is 300 to 500n
It has an absorption peak at m.

[0089] Specific dye compounds include those shown below.

[0090]

[C47]

[0091]

[C48]

[0092]

[C49]

[0093]

[C50]

[0094]

[C51]

[0095]

[C52]

[0096]

[C53]

These dyes are covered by International Patent WO88/04
, 794, European Patent EP 0274,723A1
No. 276,566, No. 299,435, JP-A No. 52-92,716, No. 55-155,350, No. 55-155,351, No. 61-205,934,
No. 48-68,623, U.S. Patent No. 2,527,583
No. 3,486,897, No. 3,746,539, No. 3,933,798, No. 4,130,429,
No. 4,040,841, etc., and can be easily synthesized by a method similar to that method.

Regarding the preparation method, see International Patent WO88/0
No. 4,794, European Patent EP 0,276,566
A1, JP-A No. 63-197,945, etc., there is a method in which the dye is ground in a ball mill and stabilized with a surfactant and gelatin, and after dissolving the dye in an alkaline solution, p.
A method in which precipitation is performed by lowering H is preferably used. The solid disperse dye prepared by such a method can be added in a solid state to a coating solution for a non-photosensitive hydrophilic colloid layer.

As the support for the light-sensitive material of the present invention, cellulose triacetate, cellulose diacetate, nitrocellulose, polystyrene, polyethylene terephthalate, etc. can be used. Particularly preferably used is polyethylene terephthalate film. These supports may be corona-treated by a known method and, if necessary, may be subbed-treated by a known method. In addition, a waterproof layer containing a polyvinylidene chloride polymer may be provided in order to improve so-called dimensional stability, in which the dimensions change with changes in temperature and humidity.

The silver halide photosensitive material of the present invention uses dihydroxybenzenes as a developing agent and 1-phenyl-3-
Pyrazolidones or p-aminophenols are used as auxiliary developing agents, and a sufficient amount of sulfite is included as a preservative.
By processing with a developer of 10.5 to 12.3,
Images with ultra-high contrast photographic characteristics can be obtained.

Examples of dihydroxybenzenes as developing agents include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, , 5-dimethylhydroquinone, etc., and hydroquinone is particularly preferred. The 1-phenyl-3-pyrazolidones auxiliary developing agents used in the present invention include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4 -Hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-
3-pyrazolidone, 1-p-aminophenyl-4,4-
Dimethyl-3-pyrazolidone, 1-p-tolyl-4,4
-dimethyl-3-pyrazolidone, 1-p-tolyl-4-
Examples include methyl-4-hydroxymethyl-3-pyrazolidone. In addition, p-aminophenol-based auxiliary developing agents include N-methyl-p-aminophenol, p-
Aminophenol, N-(β-hydroxyethyl)-p
-aminophenol, 2-methyl-p-aminophenol, p-benzylaminophenol and the like. The dihydroxybenzene developing agent is usually preferably used in an amount of 0.2 to 0.8 mol/liter. Auxiliary developing agent is 0
．． It is used in an amount of 0.6 mole/liter or less.

Sulfites added as preservatives include compounds that provide free sulfite ions, such as sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite,
Examples include formaldehyde, sodium bisulfite, and the like. The amount of sulfite added is preferably in the range of 0.15 to 1.2 mol/liter, particularly preferably in the range of 0.3 to 0.8 mol/liter.

To set the pH value of the developer, use sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, tribasic sodium phosphate, tribasic potassium phosphate,
Alkaline agents such as sodium silicate and potassium silicate,
A pH adjuster and a buffer are used. In addition to the above components, additives used in the developer include compounds such as boric acid and borax; development inhibitors such as sodium bromide, potassium bromide, and potassium iodide; and mercapto compounds (for example, 1-
phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, etc.), indazole compounds (5-nitroindazole, etc.), benzimidazole compounds (e.g. 5-nitrobenzimidazole, etc.), triazole compounds (
Organic development inhibitors such as 5-methylbenzotriazole, etc.; Organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methylcellosolve, ethanol, methanol, etc.
Surfactants, chelating agents, color toning agents, water softeners, development accelerators, antifoaming agents, hardeners, silver stain preventive agents, and JP-A-56
The amino compounds described in No.-106,244 and the like can be used.

[0104] When the photosensitive material according to the present invention is developed with the above developer, the developing temperature is 18°C to 50°C, preferably 25°C.
The temperature range is from ℃ to 40℃, and the development time is from 10 seconds to 180 seconds.
Preferably, it is used within a range of 10 seconds to 60 seconds.

As the fixing agent, in addition to sodium thiosulfate, ammonium thiosulfate, sodium thiocyanate, and the like, organic sulfur compounds known to be effective as fixing agents can be used. Among them, sodium thiosulfate is preferred from the viewpoint of fixing speed. The amount of fixing agent used is 0.1-5
A range of moles/liter is preferably used. The fixing solution may contain water-soluble aluminum (eg, aluminum sulfate, aluminum chloride, potassium alum, etc.) as a hardening agent. The amount of aluminum salt is usually 0.2 to 2.
A range of 0 gA1/liter is preferably used. The pH of fixing is usually 3.8 or higher, preferably in the range of 4.0 to 5.5, and acetic acid or a dibasic acid (for example, tartaric acid, citric acid, sodium citrate, sodium tartrate, etc.) is used to adjust the pH. used. The fixing solution may further contain preservatives (e.g. sulfites, bisulfites), pH buffers (e.g. acetic acid, boric acid), pH adjusters (e.g. ammonia, sulfuric acid), image preservation enhancers (e.g. iodide), if desired. potassium)
It can contain a chelating agent and the like. The fixing temperature and time are the same as for development.

[0106] In addition, in the washing water, anti-mold agents (for example, "The Chemistry of Bacteria and Bacteria" by Horiguchi, Patent Application 1986-253, 80)
Compounds described in No. 7), water washing accelerators (sulfites, etc.),
It may also contain a chelating agent or the like. Washing with water is carried out to almost completely remove the silver salt dissolved by fixing, and approximately 2
A range of 10 seconds to 180 seconds at 5°C to 50°C is preferably used. Drying is preferably carried out at a temperature in the range of 30°C to 80°C, and the drying time can be changed as appropriate depending on the surrounding conditions.
Usually it is 5 seconds to 200 seconds.

[0107] It is convenient to use a roller conveyance type automatic developing machine which can carry out the processing steps of developing, fixing, washing with water and drying continuously, and is a method generally used in the art as an effective means. Automatic processors are described in US Pat. No. 3,025,779, US Pat. No. 3,545,971, etc.

[0108]

EXAMPLES The present invention will be explained in detail below based on examples. Example 1 [Preparation of emulsion A] Silver nitrate aqueous solution and sodium chloride aqueous solution (
5 x 10-6 moles of rhodium hexachloride (I) per mole of silver
II) (including ammonium acid) was added and mixed by a double jet method to prepare a silver chloride emulsion consisting of monodispersed cubes with an average grain size of 0.15 μm. After the particles were formed, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was added in an amount of 2.times.10@-3 mol per mol of silver, and soluble salts were removed by washing with water in a conventional manner. After washing with water, gelatin was added, and sodium chloride and sodium hydroxide were added to adjust the pH to 6.0 and pAg to 7.6, and 4-hydroxy-6-methyl-1,3,3a was used as a stabilizer.
, 7-tetrazaindene at 5 x 10-3 per mole of silver.
mol, 1-phenyl-5-mercaptotetrazole 4
x10-4 mol was added. 1 kg of emulsion contained 110 g of silver and 55 g of gelatin.

[Preparation of Emulsion B] In the same manner as Emulsion A,
Emulsion B was prepared containing 1.2.times.10@-5 moles of ammonium rhodium(III) hexachloride per mole of silver.

[Preparation of a coating solution for a silver halide emulsion layer containing a hydrazine derivative] Emulsion A was divided into equal amounts, and a dye of [I]-6 was used as a dye compound of general formula (I), and a dye of [I]-6 was used as a comparative compound. Compound (a) was added as shown in Table 1. The amount added was 120 mg per m2.

[0111]

[C54]

Further, as a hydrazine derivative compound of general formula (II), compound II-16 was added at 2×1 per mole of silver.
It was added in an amount of 0-3 to 4 x 10-3 mol. Furthermore, as a polymer latex, U.S. Patent No. 3,525,620
3 per m2 of the latex described in Manufacturing Recipe Example 3 of No.
00mg, 1,3-divinylsulfonyl- as hardener
A coating solution for a silver halide emulsion layer was prepared by adding 2-propanol in an amount of 100 mg per m2.

[0113]

[Table 1]

[Preparation of layer coating solution containing redox compound] Emulsion B was divided into equal amounts, and the redox compound of the present invention and comparative compound (b) were added in the amounts shown in Table 1. , and further ultraviolet absorbing dye compound (c) (
d) were added in an amount of 25 mg per m2.

[0115]

[C55]

[0116] Further, as a polymer latex, 200 mg/m2 of the latex described in Production Recipe Example 3 of US Pat. No. 3,525,620 was added, and as a hardening agent, 1,3-
Divinylsulfonyl-2-propanol was added in an amount of 50 mg per m 2 to prepare a coating solution for a redox-containing layer.

[Preparation of coating solution for protective layer] Add an amorphous silica matting agent with an average particle size of about 3.0 μm to a gelatin solution in an amount of 40 mg/m2, and 100 m of polyacrylamide.
g/m2, sodium p-dodecylbenzenesulfonate in an amount of 40 mg/m2, C8F17SO3N(C3H7)CH2COO as a fluorine-based surfactant.
A coating solution for a protective layer was prepared by adding K in an amount of 10 mg/m2.

[Coating for sample preparation] The coating solution for a silver halide emulsion layer containing a hydrazine derivative was coated on a 100 μm polyethylene terephthalate film support in an amount of 3 silver.
．． 0 g/m2, and on top of that, a layer of gelatin only coated at 0.5 g/m2,
Furthermore, a coating solution for a layer containing a redox compound is coated on the top layer so that the amount of coated silver is 0.3 g/m2, and the coating solution for a protective layer is applied as a protective layer on the top layer with an amount of gelatin of 0.
．． It was coated at a concentration of 5 g/m2.

[Evaluation of photographic properties using new solution] Each prepared sample was exposed through an optical wedge using a Meisho printer P-627FM manufactured by Dainippon Screen Co., Ltd., and a developer having the following composition was applied to an automatic processor FG-680A ( (manufactured by Fuji Photo Film Co., Ltd.) and processed for a developing time of 38° and 20 seconds. (Developer composition I) Hydroquinone

50.0g N-methyl-p-aminophenol 1/2 sulfate
0.3g sodium hydroxide

18.0g 5-sulfosalicylic acid
30.0g
Boric acid

25.0g potassium sulfite

110.0g Ethylenediaminetetraacetic acid disodium salt
1.0g potassium bromide

10.0g 5-methylbenzotriazole

0.4g 2-mercaptobenzimidazole-5-sulfonic acid
0.3g 3-(5-mercaptotetrazole)
Benzene sulfo 0.2g
sodium phosphate n-butyldiethanolamine
15
．． 0g Sodium toluenesulfonate

Add 10.0g water

1 liter

(Add potassium hydroxide to adjust pH to 11.6)

01
[20] Sensitivity is expressed as a relative value, which is the reciprocal of the exposure amount that gives a density of 3.0, with sample number (1) being 100. The γ value indicates the average gradation of the characteristic curve from density 0.3 to 3.0, and 2.7 is △ logE (logarithm of the exposure amount that gives a density of 3.0 and the exposure that gives a density of 0.3). The value obtained by dividing by the difference in the logarithms of the amounts. The larger the value, the higher the contrast image characteristics. Also, JP-A-2-29
Using an original having a structure as shown in Figure 1 of Publication No. 3736, appropriate exposure is carried out so that under the above processing conditions, a portion of the original having a halftone dot area of 50% forms a halftone dot area of 50% on the photosensitive material. We determined the conditions and formed a cutout character image. Observe the line width reproduction of the cut-out character image with a 100x magnifying glass, and select the one where the 30 μm line of the original is clearly cut out.
5", a document that is crushed even with a 100 μm line "
It was evaluated as ``1'' on a five-point scale.

[0121] Safety against safelight light is determined by Toshiba's anti-fading fluorescent lamp (FLR40SW-DL-X, NU/M
) and place each sample under a brightness of 200 lux from 0 to
After leaving it for 60 minutes, it was developed under the same conditions as above.
The fog density was measured. The irradiation time required for the fog density to increase by 0.02 was defined as the safelight irradiation limit time.

[Evaluation of photographic properties using running processing solution] Samples 1 to 18 prepared were evaluated in the total size (50.
A total of 80 sheets per day were continuously processed for 10 days while replenishing 75 cc of the developer composition I per sheet (8 x 61.0 cm), and 18 types of running solutions were prepared. Each sample was exposed to light and processed so that the blackening rate was 50% (50% of the total treated area was blackened by development). Using the 18 types of developer solutions obtained, sensitometry and evaluation of cutout character image quality were performed under the same exposure conditions as with the new solution. The results obtained are shown in Table 2.

[0123]

[Table 2]

First, hydrazine is not used (1)
(4) (7) (10) (16) Each sample is γ
The value is low, and the quality of the extracted characters is also at an extremely poor level. In contrast, samples (5) (6) (8) (9) (11
) (12) Both the new liquid and the running liquid have a high contrast with a γ value of 10 or more, and the change in sensitivity due to running is small and the quality of cut-out characters is good. Samples without redox compounds (2) (3)
In this case, the quality of the extracted characters is inferior. Also, the comparative compound (
In samples (14) and (15) using c), the cutout character image quality with the new solution is good, but the sensitivity change due to running is large and the cutout character image quality also deteriorates. This is because the released development inhibitor of Comparative Compound (c) accumulates in the developer for a long time without being decomposed, which inhibits nucleation development of hydrazine. Samples (16), (17), and (18) using the comparative dye compound (a) have poor safelight safety and do not have satisfactory handling properties as light-sensitive materials.

[0125]

According to the present invention, by the combination as shown in claim 1, the ease of handling in a bright room is improved, the suitability for cut-out characters is good,
We were able to provide a high-contrast photosensitive material that does not easily leave tape marks. Furthermore, the photosensitive material of the present invention has excellent suitability for running processing.

Claims (2)

[Claims] Claim 1: 1×10 − per mole of silver halide
Silver chloride emulsion prepared in the presence of 7 to 1 x 10-4 mol of water-soluble rhodium salt, or silver chloride content 80 mol%
It consists of the above silver chlorobromide emulsion, at least one photosensitive silver halide emulsion layer containing a hydrazine derivative, and a hydrazine structure that can be oxidized by an oxidation product of a developing agent and release a development inhibitor as a redox group. a hydrophilic colloid layer containing a redox compound in which at least a part of the development inhibitor can be eluted into a developer and converted into a compound with less inhibitory properties by reaction with developer components; A silver halide photosensitive material comprising a second silver halide emulsion layer as a layer separate from the layer containing the hydrazine derivative. 2. The silver halide photographic material according to claim 1, wherein the emulsion layer or other hydrophilic colloid layer contains a dye compound represented by the general formula (I). [Formula 1] In the formula, R1 is an alkyl group, an alkoxy group, a hydroxy group, an amino group, a substituted amino group, an alkoxycarbonyl group,
Represents a carboxyl group, a cyano group, a carbamoyl group, a sulfamoyl group, a ureido group, a thioureido group, an acylamido group, a sulfonamide group, or a phenyl group. Q represents a sulfoalkyl group, a sulfoalkoxyalkyl group, or an aryl group having at least one sulfo group. R2 is a hydrogen atom, an alkyl group, an alkoxy group,
Represents a hydroxy group or a halogen atom. R3, R
4 may be the same or different and represent an alkyl group or a substituted alkyl group. Further, R3 and R4 may form a 5- to 6-membered ring. However, R1, R3, and R4 do not have methyl groups at the same time.