JPH02293736A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance retouch work, such as traces of applied tapes, by incorporating a hydrazine derivative, and a redox compound to be allowed to release a development inhibitor by being oxidized in a specified emulsion layer or another hydrophilic colloidal layer. CONSTITUTION:The silver halide photographic sensitive material is provided on a substrate with at least one of photosensitive silver halide emulsion layer containing 1X10<-6>mol of a rhodium salt per mol of silver and silver chloride in an amount of >=90mol% of the total silver halide and in a grain size of <=0.12mum, and this emulsion layer or another hydrophilic colloidal layer contains the hydrazine derivative and the redox compound to be allowed to release the development inhibitor by being oxidized, thus permitting the obtained photosensitive material to be handled in an environment substantially comparable with the lightroom and enhanced in retouch work, such as traces of erased letters and applied tapes.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention is a photosensitive material, which can be produced in an environment that can be practically called a bright room in the process of photolithography, and which can be used for cutting out characters and pasting. This invention relates to a silver halide photographic light-sensitive material with improved return characteristics such as embossed marks.

(Prior Art) In the field of printing reproduction, there is a need to improve the efficiency of the photolithography process in order to cope with the diversity and complexity of printed matter.

Particularly in the collection and reversing processes, efforts have been made to improve work efficiency by performing the work in a brighter environment, and for this reason it is necessary to work in an environment that can essentially be called a bright room. Progress has been made in the development of photosensitive materials for plate making and exposure printers that can be used for printing.

The photosensitive material for bright room use described in this patent refers to a photosensitive material that can safely use light with a wavelength of 400 nm or more as safelight light, which does not contain any ultraviolet light components, for a long period of time. .

The photosensitive material for bright room use used in the collection and reversing processes uses a developed film on which characters or halftone images have been formed as a document, and the document and the photosensitive material for reversing are exposed in close contact to form a negative image/image. It is a photosensitive material used for positive image conversion or positive image/positive image conversion. ■ Halftone dot images, line drawings, and character images are converted into negative/negative images according to their respective halftone dot areas, line widths, and character image widths. It is desired to have the ability to perform positive image conversion ■ It is desired to have the ability to adjust the tone of halftone images and the in-line adjustment of character line images, and light-sensitive materials for bright room reversal have been provided to meet this demand. Ta.

However, in the advanced image conversion work of forming cut-out character images by overlapping and repeating, the conventional method using a bright room reversing process using a light-sensitive material for use in a bright room is not suitable for the conventional method using a darkroom reversing process using a conventional reversing photosensitive material for darkrooms. Compared to other methods, this method has the disadvantage that the quality of the extracted character image deteriorates.

To explain in more detail the method of forming cut-out character images by overlapping, as shown in Fig. 1, transparent or translucent pasting bases (A) and (C) (polyethylene terephthalate usually having a thickness of about 100 μm) are used. (2) A film on which characters or line images are formed (line drawing original) (opening) and a film on which a halftone dot image is formed (halftone original) (2).
The halftone dot original (2) is overlapped with the pasted one to form an original, and the emulsion side of the return photosensitive abrasive (BO) is brought into close contact with the dot original (2) and exposed.

After exposure, a development process is performed to form blank white portions of line drawings in the halftone image.

The important points in this method of forming a character image are:
Ideally, negative image/positive image conversion is performed according to the halftone dot area and image line of each halftone dot original and line drawing original. However, as is clear from Figure 1, halftone originals are exposed by being brought into direct contact with the emulsion surface of the photosensitive material for return, whereas line drawing originals are exposed using a pasting base (C) and a halftone original. (2) The photosensitive material for return is exposed to light through the intermediate layer.

For this reason, if you apply an exposure amount that faithfully converts a halftone original from a negative image to a positive image, the line drawing original will be exposed out of focus through the pasting base (c) and the halftone original (second), which will cause the line drawing to be exposed out of focus. The width of the drawing line in the white part becomes narrower. This is the cause of deterioration in the quality of the extracted character image.

In order to solve the above problems, a system using hydrazine is disclosed in Japanese Patent Application Laid-open Nos. 62-80640 and 62-23593.
No. 8, No. 62-235939, No. 63-104046
No. 63-103235, No. 63-296031, No. 63-314541, and No. 64-13545. When it is fixed with transparent plate-making tape, traces of this tape remain, and improvements are desired in this respect as well.

An example of a silver halide photographic light-sensitive material for bright room reversal using hydrazine containing a hydrazide compound that releases a development inhibitor after being oxidized is disclosed in JP-A-64-72139; Although it gets better, Dm
The ax is low, which poses a practical problem. Regarding high silver chloride ultrafine grain emulsion using hydrazine, JP-A-63-296
No. 031 and No. 63-296034.

(Problems to be Solved by the Present Invention) The first object of the present invention is to improve the quality of cut-out characters by overlapping and to improve the image quality of pasting marks etc. in a light-sensitive material that can be handled under a safe light in a bright room. An object of the present invention is to provide a photographic material with excellent return characteristics.

A second object of the present invention is to provide a silver halide photographic material for bright room use that has a high maximum density.

(Means for Solving the Problems) The above object of the present invention is to provide a silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support, in which the emulsion layer has at least I
X 1 0-6 mol of rhodium salt with a silver chloride content of at least 90 mol % and a grain size of 0.12
A silver halide comprising silver halide grains of μ or less in size, and containing a hydrazine derivative and a redox compound that releases a development inhibitor when oxidized in the emulsion layer or other hydrophilic colloid layer. This was achieved using photographic materials.

Examples of the redox group of the redox compound used in the present invention that can release a development inhibitor when oxidized include hydroquinones, catechols, naphthohydroquinones, aminophenols, pyrazolidones, hydrazines, hydroxylamines, Examples include reductones. The redox group is preferably a hydrazine neck, and the redox group is particularly preferably a compound represented by the following general formula (II).

General formula (II) R-N-N-V+Time→τ-PUGA,A. (In the formula, A, , A. are both hydrogen atoms, or one is a hydrogen atom and the other is a sulfinic acid residue or { C + r
Ro (wherein R. represents an alkyl group, alkenyl group, aryl group, alkoxy group or aryloxy group, and l represents 1 or 2). Time represents a divalent linking group, and t represents O or 1. PUG
represents a development inhibitor.

(2) represents a carbonyl group, -C-C-, a sulfonyl group, a sulfoxy group, 1p (R+ represents an alkoxy group or an aryloxy group), an iminomethylene group, or a thiocarbonyl group. R represents an aliphatic group, an aromatic group or a heterocyclic group. ) General formula (II) will be explained below.

l In the general formula (II), A1 and A2 are a hydrogen atom, an alkylsulfonyl group having 20 or less carbon atoms, and an arylsulfonyl group (preferably a phenylsulfonyl group or a sum of Hammett's substituent constants of -0.5 or more). phenylsulfonyl group substituted so that 60+TRo (R0
is preferably a straight-chain, branched or cyclic alkyl group, alkenyl group, or aryl group having 30 or less carbon atoms (preferably a phenyl group, or a group whose sum of Hammett's substituent constants is −0
．． 5 or more phenyl groups), alkoxy groups (e.g. ethoxy groups, etc.), aryloxy groups (
These groups may have a substituent, and examples of the substituent include the following. These groups may be further substituted.

For example, alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, aryl groups, substituted amino groups,
Acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group and carboxyl group, Aryloxycarbonyl group, acyl group, alkoxycarbonyl group,
Examples include acyloxy group, carbonamide group, sulfonamide group, nitro group, alkylthio group, and arylthio group. ), and the sulfinic acid residues represented by A, , At specifically represent those described in US Pat. No. 4,478,928.

In addition, A, & may be connected to +Time h-, which will be described later, to form a ring.

A hydrogen atom is most preferable as A+ and Am.

Time represents a divalent linking group and may have a timing adjustment function. t represents O or 1, L=O
In the case of , it means that PUG is directly connected to .

The divalent linking group represented by Time represents a group that releases PUG from Time-PUG released from the oxidized product of the redox mother nucleus through one or more reaction steps.

As the divalent linking group represented by Time, for example, U.S. Pat.
No. 135), etc., which releases a photographically useful group (PUG) through an intramolecular ring-closing reaction of a P-toro phenoxy derivative; US Pat.
U.S. Pat. No. 4,330,617, U.S. Pat.
No. 46,216, No. 4,483.919, Japanese Unexamined Patent Publication No. 1973
-121.328 etc., which releases PUG with the production of acid anhydride through intramolecular ring-closing reaction of the carboxyl group of succinic acid monoester or its analog; US Pat. No. 4,409,323 , 4,421,845
issue, Research Disclosure Magazine No. 21, 22
8 (December 1981), U.S. Patent No. 4,416,9
No. 77 (Japanese Unexamined Patent Publication No. 135,944, 1983), Unexamined Japanese Patent Application No. 58
209,736, No. 58-209,738, etc., by electron transfer via a double bond conjugated with an aryloxy group or a heterocyclic oxy group to generate quinomonomethane or an analog thereof and release PUG. U.S. Patent No. 4,420,554
0), JP-A-57-135,945, JP-A No. 57-18
No. 8,035, No. 5B-98,728 and No. 582
P from the γ-position of the enamine by electron transfer of the part having the enamine structure of the nitrogen-containing heterocycle described in No. 09.131 etc.
Those that release UG; PUG is released through an intramolecular ring-closing reaction of an oxy group generated by electron transfer to a carbonyl group conjugated with the nitrogen atom of a nitrogen-containing heterocycle described in JP-A No. 57-56,837. U.S. Patent No. 4,146;
No. 396 (JP-A-52-90932), JP-A-599
3.442, those which release PUG with the formation of aldehydes as described in JP-A-59-75-47-5, etc.; JP-A-51-146,828, JP-A-57-179
, No. 842 and No. 59-104.641 which releases PUG with decarbonization of the carboxyl group; -(
One that has the structure 1-COOCR2Rb-PUG and releases PUG with decarboxylation and subsequent production of aldehydes; releases PUG with production of isocyanate as described in JP-A No. 607,429. Examples include those that release PUG through a coupling reaction with an oxidized product of a color developer described in US Pat. No. 4,438,193 and the like.

For specific examples of these divalent linking groups represented by Time, see JP-A No. 61-236,549 and Japanese Patent Application No. 63-Sho.
Although it is described in detail in No. 98,803, etc., preferred specific examples are shown below.

Here, (*) represents the site where {-Time-h-PUG binds to V in the general formula (1), and (*) represents the site where PUG binds to (*).

1 5-T - (5) (ne) CH3 C2HS 1 ma C2H5 COUCth /1) CI. 0 T (*) C1)3 T (*)? ll■ C1)3 C C1)3 2l C2H, T C■2 (*ノ (*ノT T T C1)3 T 1l (*)-0-C CI+3 0 C-(*) (*) 0-{ -CH2Na rN T (*) C■2 (*) (*) T (*) CB (*) (*) COOC2HS T 0 CH3 (*) -0 -C-N + CH2÷rN-C- (* )
(*)CH3 TSOReTC21)5 PUG is (Time}-r PUG or
G represents a group having a development inhibiting effect.

The development inhibitor represented by PUG or (Time}yPUG is a known development inhibitor that has a heteroatom and is bonded via the heteroatom, and these are known as, for example, C.E.K. Mees (C.E.K.Mees)
) and T.t{.James
"The Theory of the Photographic Process" by S)
graphicProcesses) J 3rd edition, 19
66 Macmillan Publishing, 344
It is described on pages 346 to 346. Specifically, mercaptotetrazoles, mercaptotriazoles, mercaptoimidazoles, mercaptopyrimidines, mercaptohenzimidazoles, mercaptobenzthiazoles, mercaptohenzuoxazoles, mercaptothiadiazoles, penztriazoles, penzimidazoles, Examples include indazoles, adenines, guanines, tetrazoles, tetraazaindenes, triazaindenes, and mercaptoaryls.

The development inhibitor represented by PUG may be substituted. Examples of substituents include the following,
These groups may be further substituted.

For example, alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, aryl groups, substituted amino groups,
Acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, alkyloxy group rubanyl group,
These include an aryloxycarbonyl group, an acyl group, an alkoxycarbonyl group, an acyloxy group, a carbocyamide group, a sulfonamide group, a carboxyl group, a sulfoxy group, a phosphono group, a bosfinico group, a phosphoric acid amide group, and the like.

Preferred substituents include a nitro group, a sulfo group, a carboxyl group, a sulfamoyl group, a phosphono group, a phosphinico group, and a sulfonamide group.

The main development inhibitors are shown below.

Nole (2) 1-(4-hydroxyphenyl)-5-mercapto (3) 1-(4-aminophenyl)-5-mercaptotetrazole (4) 1-(4-carpoxyphenyl)-5-mercaptotetrazole (5) 1-(4-chlorophenyl)-5-mercaptotetrazole (6) 1-(4-methylphenyl)-5-mercaptotetrazole (7) 1-(2.4-dihydroxyphenyl) 5-mercaptotetrazole (8 ) 1-(4-sulfamoylphenyl)-5-mercaptotetrazole (9) 1-(3-carboxyphenyl)-5-mercaptotetrazole (to) 1-(3.5-dicarboxyphenyl)
5-mercaptotetrazole (II1)-(4-methoxyphenyl)-5-mercaptotetrazole 02) 1-(2-methoxyphenyl)-5-mercaptotetrazole 03) 1-(4-(2-hydroxyethoxy) ) phenyl]-5-mercaptotetrazole 1-(2.4
-dichlorophenyl)-5-mercaptotetrazole 05) 1-(4-dimethylaminophenyl)-5-mercaptotetrazole 0ω 1-(4-nitrophenyl)-5-mercaptotetrazole 07) 1,4-bis(5-mercapto- 1-Tetrazolyl)benzene 08) 1-(α-naphthyl)-5-mercaptotetrazole Q9) 1-(4-sulfophenyl)-5-mercaptotetrazole QΦ 1-(3-sulfophenyl)-5-mercaptotetrazole (21) 1 -(β-naphthyl)-5-mercaptotesol (22) 1-Methyl-5-mercaptotetrazole (23) 1-ethyl-5-mercaptotetrazole (24) 1-propyl-5-mercaptotetrazole (25) 1-octyl-5-mercaptotetrazone (26) 1-dodecyl-5-mercaptotetrazone (27) 1-cyclohexyl-5-mercaptotetrazole (28) 1-valmityl-5-mercaptotetrazone ( 29) 1-Carboxyethyl-5-mercaptotetrazole (30) 1-(2,2-diethoxyethyl)-5-mercaptotetrazole (31) 1-(2-aminoethyl)-5-mercaptotetrazole hydrochloride (32) 1-(2-diethylaminoethyl)-5-mercaptotetrazole (33) 2-(5-mercapt-1-te1-razole)
Ethyltrimethylammonium chloride (34) 1-(
3-phenoxylphenyl)-5-mercaptotetrazole (35) 1-(3-maleinimidophenyl)-6-mercaptotetrazole (2) 4-phenyl-5-methyl-3-mercaptotriazole (3) 4. 5-Diphenyl-3-mercaptotriazole (4) 4-(4-carpoxyphenyl)-3-mercaptotriazole 33-(5) 4-Methyl-3-mercaptotriazole (6)
4-(2-dimethylaminoethyl)-3-mercaptotriazole (7) 4-(α-naphthyl)-3-mercaptotriazole (8) 4-(4-sulfophenyl)-3-mercaptotriazole (9) 4-(3 -nitrophenyl)-3-mercaptotriazole (2) 1,5-diphenyl-2-carcabutoimidazole (3) 1-(4-carboxyphenyl)-2-mercaptoimidazole (4) to 1-(4- xylcarbamoyl)-2-mercaptoimidazole (5) 1-(3-nitrophenyl)-2-mercaptoimidazole (61l-(4-sulfophenyl)-2-mercaptoimidazole 4 Mercaptopymidineio(1) Thiouracil (2) Methylthiouracil ( 3) Ethylthiouracil (4) Probylthiouracil (5) Nonylthiouracil (6) Aminothiouracil (7) Hydroxythiouracil 5 Mercaptobenzimidazole (1) 2-Mercaptobenzimidazole (2) 5-Carboxy-2 -Mercaptobenzimidazole (3) 5-amino-2-mercaptohenzimidazole (4) 5-nitro-2-mercaptohenzimidazole (5) 5-chloro-2-mercaptobenzimidazole (6) 5-methoxy-2-mercapto Benzimidazole (7) 2-mercapto-naphthoimidazole (8) 2-mercapto-5-sulfobenzimidazole (9) l(2-hydroxydiethyl)-2-mercaptobenzimidazole 00) 5-cabroamido-2-mercaptopenzimidazole ( II) 5-(2-ethylhexanoylamino)2-mercaptobenzimidazole 6 mercap thiadiazole (1) 5-methylthio-2-mercapto-1.3.4-
Thiadiazole (2) 5--ethylthio-2-mercapto-1,34-
Thiadiazole (3) 5-(2-dimethylaminoethylthio)2-mercapto-1.3.4-thiadiazole(2-carboxypropylthio)-2 Mercabuto-1.3.4-thiadiazole (5) 2-phenoxy Luponylmethylthio-5mercapto-1.3
．． 4-thiadiazole 7 Mercap benzthiazole (1) 2-mercap 1-benzthiazole (2) 5-nitro-2-mercap 1-benzthiazole (3) 5-carboxy-2-mercaptohenzthiazole (4) 5 -Sulfo 2-mercap 1/penzthiazole 8 Mercap Benzoxazole (1) 2-mercaptobenzoxazole (2) 5-nitro-2-mercap 1/penzoxazole (3) 5-carboxy-2-mercaptobenzoxazole (4) 5-Sulfo-2-mercaptopenezthiazonore9 Hens 1A-Rio(1)5, (6)5, (7)4, Nore00)4, Nore6-dimethylbenzotriazolebutylbenzo Triazole methylbenzotriazole chlorohenzotriazole promobenzotriazole 6-dichlorobenzotriazole 6-dichloropenzotriazole nitrobenzotriazole nitro 6-chloropensotriazole 5.6-triclopenzotriazole (II) 5 carboxybenzotriazole 02) 5-Sulfobenzotriazole Na salt 03)5
-Methoxyluponylbenzotriazole 5-Aminohenzotriazole 5-Butoxybenzotriazole 5-ureidobenzotriazole Henzotriazole 08) 5-Phenoxyluponylbenzotriazole 09) 5- (2.3-Dichloropropyl Benzo 1 to Riazole 10 Henzimizole (1) Henzimidazole (2) 5-chlorohenzimidazole (3) 5
-Nitropenzimidazole (4) 5-n-butylhenzimidazole (5) 5-methylhenzimidazole (6) 4-chlorohenzimidazole (7) 5.6
-dimethylhenzimidazole (8) 5-nitro-2-
(Trifluoromethyl)henzimidazole l1 Indazole - (1) 5-Nitroindazole (2) 6-Nitroindazole (3) 5-Aminoindazole (4) 6-Aminoindazole (5) Indazole (6) 3 -Nitroindazole (7) 5-Nitro-31-Nitrointasol (8)
3-chloro-5-nitroindazole (9) 3-
Carboxy 5-nitroindazole 12- -zole (1) 5-(4-nitrophenyl)tetrazole (2)
5-phenyltetrazole (3) 5-(3-carpoxyphenyl)-tetrazole 13-tozaine-ene (1) 4-hydroxy-6-methyl-5-1,3
．． 3a,7-tetraazaindene (2) 4-mercapto-6-methyl-5-1,3.3a,7-tetraazaindene 14 Merkab Air (1) 4-nitrothiophenol (2 ) Thiophenol (3) 2-Carpoxythiophenol ■ is a carbonyl group, -c-c-, sulfonyl group {1) 1 Sulfoxy group, -p-CRrl, alkoxy group or R
I4 represents an aryloxy group. ), iminomethylene group, or thiocarbonyl group, and (2) is preferably a carbonyl group.

The aliphatic group represented by R is a straight chain, branched or cyclic noalkyl group, alganyl group, or haalkynyl group, and preferably has 1 to 3 carbon atoms, particularly 1 to 3 carbon atoms.
~2o. The branched alkyl group herein may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein.

For example, methyl group, t-butyl group, n-octyl group, t-
Examples include octyl group, cyclohexyl group, hexenyl group, pyrrolidyl group, tetrahydrofuryl group, and n-dodecyl group.

The aromatic group is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group and a naphthyl group.

The heterocyclic group is a 3- to 10-membered saturated or unsaturated heterocycle containing at least one of N, O, or S atoms, and may be a single ring or may be combined with another aromatic ring or a petro ring. A condensed metal ring may be formed. Preferred heterocycles are 5- to 6-membered aromatic heterocycles, such as pyridine rings, imidazolyl groups, quinolinyl groups, penzimidazolyl groups, pyrimidinyl groups, pyrazolyl groups, isoquinolinyl groups, penzthiazolyl groups, and thiazolyl groups. Examples include.

R may be substituted with a substituent. Examples of substituents include, for example, the following. These groups may be further substituted.

For example, alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, aryl groups, substituted amino groups,
Acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfotyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, alkyloxy group rubonyl group,
Examples include aryloxy carbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, carbonamide group, sulfonamide group, carboxy group, and phosphoric acid amide group.

Further, in general formula (1), R or +T imeh
- PU G contains a ballast group commonly used in immobile photographic additives such as couplers and the general formula (1
) may be incorporated with a group that promotes adsorption of the compound represented by () to silver halide.

The ballast group is an organic group that provides a sufficient molecular weight to substantially prevent the compound represented by the general formula (1) from diffusing into other layers or the processing solution, and includes an alkyl group, an aryl group, a heterocyclic group, It consists of a combination of one or more of ether groups, thioether groups, amide groups, ureido groups, urethane groups, sulfonamide groups, etc. The ballast group is preferably a hallast group having a substituted benzene ring, particularly a ballast group having a benzene ring substituted with a branched alkyl group.

Specifically, the adsorption promoting group to silver halide is 4-
Thiazoline-2-thione, 4-imidazolJ:/-2-
Thione, 2-thiohydantoin, rhodanine, thioparbylic acid, tetrazoline-5thione, 1,2.4-}
Riazoline-3-thione, 1,3.4-oxazoline-
Cyclic thioamide groups, chain thioamide groups, aliphatic groups such as 2-thione, henzimidazoline-2-thione, penzoxazoline-2-thione, penzothiazoline-2-thione, thiotriazine, 1,3-imidazoline-2-thione Mercapto group, aromatic mercapto group, heterocyclic mercapto group (if the carbon atom to which the -SH group is bonded is a nitrogen atom, it has the same meaning as a cyclic thioamide group, which has a tautomeric relationship with this group, and Specific examples are the same as those listed above.) Groups having a disulfide bond, penzotriazole, triazole, tetrazole, indazole, penzimidazole, imidazole, benzothiazole, thiazole, thiazoline, penzoxazole, oxazole, oxazoline, Nitrogen such as thiadiazole, oxathiazole, 1-riazine, azaindene,
Examples include a 5- to 6-membered nitrogen-containing heterocyclic group consisting of a combination of oxygen, sulfur, and carbon, and a quaternary heterocyclic salt such as penzimidazolinium.

These may be further substituted with a suitable substituent.

Examples of the substituent include those described as the substituent for R.

Specific examples of compounds used in the present invention are listed below, but the present invention is not limited thereto.

ε 49. 50. The method for synthesizing the redox compound used in the present invention is, for example, JP-A Nos. 61-213,847 and 62-260,1.
No. 53, U.S. Patent No. 4,684,604, Patent Application No. 6
3-98803, U.S. Patent No. 3,379,5
No. 29, No. 3,620.746, No. 4,377,63
No. 4, 4, 332. No. 878, Japanese Unexamined Patent Publication No. 1983-
No. 129,536, No. 56153.336, No. 56-
No. 153,342, etc.

The redox compound of the present invention is 1.0% per mole of silver. OX
1 0-'moj! ~5. OX 1 0-2m
oA, preferably 1. OXIO-”1.OXIO-2m
Used within the range of oA'.

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 also be used by dissolving dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate in an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate using a co-solvent such as ethyl acetate or cyclohexanone using the well-known emulsification dispersion method. It can also be used by mechanically preparing an emulsified dispersion. 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 i%2N=hydrazine used in the present invention is preferably a compound represented by the following general formula (1).

General formula (I) R+ N N GI R2B. B
2 In the formula, R represents an aliphatic group or an aromatic group, R2 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a carbamoyl group, or an oxycarbonyl group, and G1 represents a carbonyl group. group, a sulfonyl group, a sulfoxy group, a P group, or an iminomethylene group, and R2 B1 and B2 are both hydrogen atoms, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted alkylsulfonyl group. Represents an arylsulfonyl group or a substituted or unsubstituted acyl group.

In general formula (1), the aliphatic group represented by R1 preferably has 1 to 30 carbon atoms, particularly 1 to 30 carbon atoms.
20 straight chain, branched or cyclic alkyl groups. The branched alkyl group herein may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. In addition, this alkyl group is an aryl group,
It may have a substituent such as an alkoxy group, a sulfoxy group, a sulfonamide group, or a carbonamide group.

The aromatic group represented by R1 in general formula (1) is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group.

Here, the unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a heteroaryl group.

For example, benzene ring, naphthalene ring, pyridine ring, pyrimidine ring, imidazole ring, pyrazole ring, quinoline ring,
Examples include an isoquinoline ring, a henzimidazole ring, a thiazole ring, and a penzothiazole ring, among which those containing a benzene ring are preferred.

Particularly preferred as R1 is a 7-aryl group.

R. The aryl group or unsaturated heterocyclic group may be substituted, and typical substituents include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a Km amino group, and an acylamino group. ,
Sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, alkyloxycarbonyl group, Preferred substituents include an aryloxycarbonyl group, an acyl group, an alkoxycarbonyl group, an acyloxy group, a carponamide group, a sulfonamide group, a carboxyl group, a phosphoamide group, a diacylamino group, and an imide group. Chain, branched or cyclic alkyl group (preferably one or more carbon atoms)
20 carbon atoms), aralkyl groups (preferably monocyclic or bicyclic alkyl groups having 1 to 3 carbon atoms), alkoxy groups (preferably carbon atoms 1 to 20 carbon atoms), substituted amino groups (preferably carbon atoms (amino group substituted with an alkyl group having 1 to 20 carbon atoms), acylamino group (preferably 2 to 20 carbon atoms)
30), sulfonamide F' group (preferably has 1 to 30 carbon atoms), ureido group (preferably has 1 to 30 carbon atoms), phosphoamide group (preferably has 1 to 30 carbon atoms) ) etc.

The alkyl group represented by R2 in general formula (1) is preferably an alkyl group having 1 to 4 carbon atoms,
It may have a substituent such as a halogen atom, cyano group, carboxy group, sulfo group, alkoxy group, phenyl group, or sulfonyl group.

The aryl group is preferably a monocyclic or bicyclic aryl group, such as one containing a benzene ring. This aryl group is, for example, a halogen atom, an alkyl group, a cyano group,
It may be substituted with a carpoxyl group, a sulfo group, a sulfonyl group, etc.

The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, and may be substituted with a halogen atom, an aryl group, or the like.

The aryloxy group is preferably monocyclic, and the substituent includes a halogen atom.

Amino groups include unsubstituted amino groups and 1 to 1 carbon atoms.
0 alkylamino group and arylamino group are preferable,
It may be substituted with an alkyl group, a halogen atom, a cyano group, a ditro group, a carboxy group, etc.

The carbamoyl group is preferably an unsubstituted carbamoyl group, an alkylcarbamoyl group having 1 to 10 carbon atoms, or an arylcarbamoyl group, and may be substituted with an alkyl group, a halogen atom, a cyano group, a carboxy group, or the like.

The oxycarbonyl group is preferably an alkoxycarbonyl group having 1 to 1 carbon atoms or a ryoloxycarbonyl group, which may be substituted with an alkyl group, a halogen atom, a cyano group, a nitro group, or the like.

Among the groups represented by R2, when G is a carbonyl group, preferred are a hydrogen atom, an alkyl group (e.g.
Methyl group, trifluoromethyl group, 3-hydroxypropyl group, 3-methanesulfonamidoprobyl group, phenylsulfonylmethyl group, etc.), aralkyl group (e.g.
0-hydroxybenzyl group, etc.), aryl groups (e.g., phenyl group, 3.5-dichlorophenyl group, 0-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, etc.), and hydrogen atoms are particularly preferred. .

Furthermore, when G is a sulfonyl group, R2 is an alkyl group (e.g., methyl group, etc.), an aralkyl group (e.g., 0
-hydroxyphenylmethyl group), aryl group (e.g. phenyl group etc.) or substituted amino group (e.g.
dimethylamino group, etc.) are preferred.

When G1 is a sulfoxy group, R2 is preferably a cyanobenzyl group, a methylthiobenzyl group, a methoxy group,
An ethoxy group, a butoxy group, a phenoxy group, and a phenyl group are preferred, and a phenoxy group is particularly preferred.

When G1 is an N-substituted or unsubstituted iminomethylene group,
Preferred R2 is a methyl group, an ethyl group, or a substituted or unsubstituted phenyl group.

As the substituent for R2, the substituents listed for R1 can be applied.

G in general formula (1) is most preferably a carbonyl group.

Also, R2 splits the G, -R* part from the remaining molecule, -
It may be one that causes a cyclization reaction to produce a cyclic structure containing atoms of G, -R, moieties, and specifically, one that can be represented by general formula (a). .

General formula <a> R3 Zl In the formula, C attacks G1 nucleophilically, and G + R
: + Z is a group that can split the + moiety from the remaining molecule, and R3 is the one hydrogen atom removed from R2, and it makes a nucleophilic attack on the bond, and a cyclic structure can be generated with G + , R3, and ZI. It is something.

More specifically, Z easily undergoes a nucleophilic reaction with G when the hydrazine compound of general formula (1) generates the following reaction intermediate by oxidation etc., resulting in Rl'-N=N-G. -R3 -Z. R, -N=A group that can split N from 01, specifically OH, SH or N H R 4 (R 4
is a hydrogen atom, an alkyl group, an aryl group, C O R
s, or -So2R5, where R represents a hydrogen atom, a 7-alkyl group, an aryl group, a heterocyclic group, etc.), CO
It may be a functional group that directly reacts with G1, such as OH, (here, OH, SH.NHRa, - CO
OH may be temporarily protected so as to generate these groups by hydrolysis with an alkali, etc.) N-R, 0 C-R6 or -C Rb (R6 and R7 are hydrogen atoms, alkyl groups, Even if it is a functional group that can react with G by reacting with a nucleophile such as a hydroxyl ion or a sulfite ion, such as an alkenyl group, an aryl group, or a heterocyclic group), good.

Furthermore, the ring formed by GI1R3 and zI is preferably a 5- or 6-membered ring.

Among those represented by general formula (a), preferred are those represented by general formulas (b) and (C).

General formula (b) z. -tcR. 3Rb 4<° where R. ．． 1 ~R. ．． 4 is a hydrogen atom, an alkyl group,
(preferably those with 1 to 12 carbon atoms), alkenyl groups (
(preferably one having 2 to 12 carbon atoms), a ryol group (preferably one having 6 to 12 carbon atoms), etc., and may be the same or different. B is an atom necessary to complete a 5- or 6-membered ring which may have a substituent, m and n are O or 1, and (n+m) is 1 or 2.

Examples of the 5- or 6-membered ring formed by B include a cyclohexene ring, a cycloheptene ring, a benzene ring, a naphthalene ring, a pyridine ring, and a quinoline ring.

Z1 has the same meaning as the general formula <a>.

General formula (C) Rc −{-N+T-+C Rc ' Rc ”}r Z,
In the formula, Rc' % Rc'' represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a halogen atom, etc., and may be the same or different.

Rc3 represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group.

p does not represent O or 1. q represents 1-4.

Rcl, Ret and Rc'' may be bonded to each other to form a ring as long as Z1 can make an intramolecular nucleophilic attack on G.

Rc'-. Re2 is preferably a hydrogen atom, a halogen atom, or an alkyl group, and Rc'' is preferably an alkyl group or an aryl group.

q preferably represents 1 to 3; when q is 1, p represents 1 or 2; when q is 2, p represents 0 or 1; when q is 3, p represents 0 or l; When lj)<2 or 3, CRc'Rc'' may be the same or different.

Z1 has the same meaning as in general formula (a).

A+ and Ax are hydrogen atoms, alkylsulfonyl groups and arylsulfonyl groups having 20 or less carbon atoms (preferably phenylsulfonyl groups or Hammett's sum of substituent constants is -0
．． 5 or more), an acyl group having 20 or less carbon atoms (preferably a penzoyl group, or a benzoyl substituted so that the sum of Hammett's substituent constants is -0.5 or more) group, or a linear, branched or cyclic unsubstituted and substituted aliphatic acyl group (substituents include, for example, a halogen atom, an ether group, a sulfonamide F group, a carbonamide group, a hydroxyl group, a carboxy group, a sulfonic acid group) )) Hydrogen atoms are most preferred as Bl and B2.

R1 or R2 in formula (n) is a ballast commonly used in immobile photographic additives such as couplers.
It may be one in which l is incorporated.

A ballast group is a group having 8 or more carbon atoms and is relatively inert with respect to photography, such as an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group, etc. You can choose from.

R or R2 in the general formula (It) 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., as described in U.S. Pat. Nos. 4,385,108 and 4,45.
No. 9,347, JP-A No. 51-195.233, No. 59
-200,231, 59-201,045, 5
No. 9201.046, No. 59-201.047, No. 5
9-201.048, 59-201,049, JP 61-170,733, JP 61-270.744, JP 62-948, JP 62-67,508, l
/62-67,501 and 62-67,510.

Specific examples of the compound represented by the general formula (+) are shown below.

However, the invention is not limited to the following compounds.

I-2》 I-3) ■-4) CtHs! -6) H ■ S ■ H ■ ■ ■ ■ I-14) SH ■ I ■ CzHs ■ CN ■ ■ 30》 ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ As the hydrazine derivative used in the present invention, , in addition to the above, RESEARCH DISCLOSUR
E I tem23516 (January 1983) Monthly issue, P
．． 346) and the documents cited therein, as well as U.S. Pat.
, No. 276,364, No. 4,278,748, No. 4,
No. 385,108, No. 4,459,347, No. 4,5
No. 60.638, 4, 478. No. 928, British Patent No. 2,01), 391B, 7 JP-A-60-179734
No. 62-270,948, No. 63-29,751
No., JP-A-61-170,733, JP-A No. 61-270,
No. 744, No. 62-948, EP No. 217,310,
Patent Application No. 61-175,234, 61-251,48
No. 2, ll61-26L No. 249, //61-276
, No. 283, No. 62-67528, No. 62-67, 5
No. 09, No. 62-67, 510, No. 62-58, 51
No. 3, No. 62-130.819, No. 62-143.4
No. 67, No. 62-166, 1) No. 7, or US 4,6
No. 86,167, JP-A-62-178,246, No. 6
No. 3-234.244, No. 63-234,245, No. 63-234,246, No. 63-294,552,
No. 63306.438, Japanese Patent Application No. 1983-166, 1) 7
No. 62-247,478, 63-105,68
No. 2, 63-1) 4, 1) No. 8, 631) 0,05
No. 1, 63-1) 4.1) No. 9, 63-1) 6.2
No. 39, No. 63-14.7, No. 339, No. 63-179
, No. 760, No. 63-229, 163, Patent Application No. 1-1
No. 8,377, No. 1-18,378, No. 1-18.37
No. 9, No. 1-15, 755, No. 1-16, 814
No., 1-40.792, 1-42.615, 1
-42,616 can be used.

In the present invention, when the hydrazine derivative represented by the general formula (1) is contained in a photographic light-sensitive material, it is preferably contained in a silver halide emulsion layer, but it is preferably contained in a non-photosensitive hydrophilic colloid layer (for example, a protective layer). , intermediate layer, filter layer, antihalation layer, etc.). Specifically, when the compound used is water-soluble, it is prepared as an aqueous solution, and when it is poorly water-soluble, it is prepared as a solution of water-miscible organic solvents such as alcohols, esters, and ketones, and as a hydrophilic colloid solution. It can be added to. When 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 between after the end of chemical ripening and before coating. In particular, it is preferable to apply it in a coating solution prepared for coating.

In the present invention, the hydrazine derivative represented by the general formula (1) is preferably contained in an amount of 1 x 10-6 mol to 1 x 10-' mol per 1 mol of silver halide.
Preferably, it is contained in an amount of 10@-5 to 4.times.10@-3 moles.

The silver halide emulsion of the silver halide photographic light-sensitive material used in the present invention is 90 mol% or more, preferably 95 mol%
The above is silver halide consisting of silver chloride, and silver bromide is O
It is silver chlorobromide or silver chloroiodobromide containing ~10 mol%.

An increase in the proportion of silver bromide or silver iodide is undesirable because it deteriorates safelight safety in a bright room or lowers γ.

In order to contain rhodium atoms, any metal salt such as a single salt or a complex salt can be added at the time of particle preparation.

Examples of rhodium salts include rhodium monochloride, rhodium dichloride, rhodium trichloride, ammonium hexachlororhodate, etc., but preferably water-soluble trivalent rhodium halogen complex compounds such as hexachlororhodium (I
[[) An acid or its salt (ammonium salt, sodium salt, potassium salt, etc.).

The amount of these water-soluble rhodium salts to be added is 1.0% per mole of silver halide. OX10-'mol~1. OX is used in a range of 10-3 moles. Preferably 1.0X10-5 mol~
1.0X10-3 mol, particularly preferably 5,OX10-
'Mole~5. OX10-' mole.

If the amount of rhodium salt is 10@-3 mol or more, it will be impossible to achieve sufficient contrast. On the other hand, if the amount is less than 10@-6 mol, it will not be possible to achieve a low sensitivity suitable for light-sensitive materials.

The silver halide used in the present invention is preferably a so-called core/shell type silver halide, particularly a core/shell type silver halide in which the rhodium content of the shell is higher than that of the core.

In order to make the above-mentioned water-soluble rhodium salt exist in silver halide grains, it is preferable to add it to the water-soluble silver salt or to the halide solution when simultaneously mixing the water-soluble root salt and the water-soluble halide solution. .

Alternatively, when silver salt and halide solutions are mixed simultaneously, silver halide grains may be prepared by a method of simultaneous mixing of three solutions as a third solution.

The grain size of the silver halide emulsion of the present invention is preferably 0.15 μm or less, and more preferably 0.12 μm or less.

In order to prepare silver halide fine grains in the present invention, the mixing conditions are such that the reaction temperature is 50°C or lower, preferably 40°C or lower, more preferably 30°C or lower, and the stirring rate is sufficiently high to uniformly mix the silver. The potential is 100 mV or more, preferably 150 mV to 400 mV. Good results can be obtained when p}{ is 3 to 8, preferably 5 to 7. In the case of silver chloride fine particles, due to their high solubility, particle growth may occur during the water washing and dispersion processes, so the temperature must be 35°C or lower, or the coexistence of nucleic acids, mercapto compounds, tetrazaindene compounds, etc. that suppress particle growth. can be done.

The particle size distribution is basically not limited, but it is preferable that it be monodisperse. Monodisperse herein means that at least 95% of the particles by weight or number of particles are comprised of particles having a size within ±40% of the average particle size, and more preferably within ±20%.

The silver halide grains of the present invention preferably have regular crystal bodies such as cubes and octahedrons, and cubic shapes are particularly preferred.

In addition to rhodium salts, cadmium salts, lead salts, thallium salts, and iridium salts can also be coexisting.

The silver halide emulsion used in the method of the present invention does not need to be chemically sensitized, but may be chemically sensitized. Sulfur sensitization, reduction sensitization, and noble metal sensitization methods are known as methods for chemical sensitization of silver halide emulsions, and any of these methods can be used alone or in combination for chemical sensitization. Good too.

Among the noble metal sensitization methods, the gold sensitization method is a typical method and uses a gold compound, mainly a gold complex salt. There is no problem in containing complex salts of noble metals other than gold, such as platinum, palladium, and iridium. Specific examples are described in US Patent No. 2,448,060, British Patent No. 618,061, and the like.

As the sulfur sensitizer, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines, etc. can be used.

As the reduction sensitizer, stannous salts, amines, formamidine sulfinic acid, silane compounds, etc. can be used.

The silver halide photographic material of the present invention may contain an organic desensitizer. The Ia desensitizer preferably has at least one water-soluble group or alkali-dissociable group.

The organic desensitizer used in the present invention is defined by its boularographic half-wave potential, that is, the redox potential determined by boularography, and the sum of the polar anodic potential and the cathodic potential is positive.

A method for measuring redox potential using a boularogram is described, for example, in US Pat. No. 3,501,307. At least one water-soluble group preserved in the organic desensitizer includes, for example, a sulfonic acid group, a carboxylic acid group, and a phosphonic acid group. piberidine, morpholine, etc.) or alkali metals (e.g. sodium,
It may form a salt with potassium, etc.).

The alkali-dissociable group refers to the pH of the developing solution (usually pH 9 to
Although the pH is in the range of 13, there may be treatment liquids with pH values other than this. ) or below, a substituent that undergoes a deprotonation reaction and becomes anionic. Specifically, a hydrogen atom bonded to a nitrogen atom with a substituent such as a substituted or unsubstituted sulfamoyl group, a substituted or unsubstituted carhamoyl group, a sulfonamido group, an acylamino group, a substituted or unsubstituted octa-substituted ureido group, etc. Refers to one substituent and hydroxy group.

Further, a heterocyclic group having a hydrogen atom on the nitrogen atom constituting the nitrogen-containing heterocycle is also included in the alkali dissociable group.

These water-soluble groups and alkali-dissociable groups may be connected to any part of the organic desensitizer, and two or more types may be present at the same time.

- Preferred specific examples of mH sensitizers used in the present invention are described in Japanese Patent Application No. 61-209169, and some examples are listed below.

H The organic desensitizer is 1.0 x 10-8 in the silver halide emulsion layer.
~1. OX10-' mol/rtr, especially 1,0×10~
7-1. Preferably, OX10-'mol/d is present.

In the emulsion layer of the present invention or other hydrophilic colloid 1° layer,
A water-soluble dye may be contained as a filter dye or for various purposes such as preventing irradiation. Filter dyes include dyes for further lowering photographic sensitivity, preferably ultraviolet absorbers having a spectral absorption maximum in the intrinsic sensitivity range of silver halide, and Safely 1, which is safe against light when handled as a light-sensitive material. A dye having substantial light absorption mainly in the region of 350 nm to 600 nm is used to enhance the properties.

Although it varies depending on the molar absorption coefficient of the dye, it is usually 10-2 g/
It is added in the range of rd to 1 g/m. Preferably it is 10 to 100 μ/M.

Specific examples of dyes are described in detail in Japanese Patent Application No. 61-209169, and some are listed below.

The above-mentioned dye is dissolved in a suitable solvent [e.g., water, alcohol (e.g., methanol, ethanol, propanol, etc.), acetone, methyl cellosolve, etc., or a mixed solvent thereof] for use in the non-photosensitive hydrophilic colloid layer of the present invention. Added to coating solution.

Gelatin is advantageously used as a binder or protective colloid in photographic emulsions, 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: hydroxyethyl cellulose,
Cellulose derivatives such as carboxymethyl cellulose and cellulose sulfate esters, ￥fM derivatives such as sozo alginate and starch derivatives, polyvinyl alcohol, polyvinyl alcohol partial acetal, polyN vinyl pyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers such as polyvinylpyrazole.

As the gelatin, in addition to lime-treated gelatin, acid-treated gelatin may be used, and gelatin hydrolyzate and gelatin oxygen decomposition product may also be used.

Supports for the photosensitive material of the present invention include cellulose triacetate, cellulose diacetate, nitrocellulose,
Boristyrene, polyethylene terephthalate paper, baryta coated paper, polyolefin coated paper, etc. can be used.

Examples of development accelerators or nucleating and infectious development accelerators suitable for use in the present invention include JP-A-53-77616, JP-A-54-37732, JP-A-53-137133, and JP-A-60.
In addition to the compounds disclosed in No. 140340 and No. 6014959, various compounds containing N or S atoms are effective.

Next, specific examples are listed.

C2HS 2C7! e? C21{S)2 NC82CH-CI{■OHOH The optimum amount of these accelerators to be added varies depending on the type of compound, but 1. It is desirable to use the accelerator in the range of OX10-3 to 0.5 g/nr, preferably 5.OX10-3 to 0.1 g/nr.
It is dissolved in alcohols such as methanol and ethanol, acetone, dimethylformamide, methylcellosolve, etc.) and added to the coating solution.

Multiple types of these additives may be used in combination.

The light-sensitive materials used in the present invention include sensitizing dyes (e.g., cyanine dyes, merocyanine dyes, ) can also be added, but it is preferable not to.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Along with the seductive dye, it is a dye that itself does not have a spectral seductive effect or a substance that does not substantially absorb visible light,
Substances exhibiting superchromic enhancement may also be included in the emulsion.

Useful sensitizing dyes, dye combinations exhibiting supersensitization, and substances exhibiting supersensitization are listed in Research Disclosure (Re
Search Disclosure) 176, Vol. 17643 (published December 1978), page 23, Section J.

The light-sensitive material of the present invention may contain various compounds in addition to the thiosulfinic acid compound of the present invention for the purpose of preventing fogging or stabilizing photographic performance during the manufacturing process, storage, or photographic processing of the light-sensitive material. be able to. That is, azoles such as penzothiazolium salts, nitroindazoles, chlorohenzimidazoles, promohenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, penzothiazoles, nitrohenzotriazoles, etc.; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinthione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-
hydroxy-substituted (1,3.3a,7)tetraazaindenes), pentaazaindenes, etc.; as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfonic acid, benzenesulfonic acid amide, etc. Many known compounds can be added.

The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer.

For example, chromium salts (chromium 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 compounds (1,3.5 -}lyacryloyl-hexahydro-s-}lyazine, 1,3-
vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-S-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), etc. alone or in combination. It can be used as

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (e.g.
Various surfactants may be included for various purposes such as development accelerator, contrast enhancement, and sensitization.

For example, sabonin (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polybropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbicne esters) , polyalkylene glycol alkylamines or amides, silicone polyethylene oxide adducts), glycitol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Ionic surfactants; alkyl carboxylates, alkyl sulfonates, alkyl hanzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurine carboxy groups, such as sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphates, etc.
Anionic surfactants containing acidic groups such as sulfo groups, phospho groups, sulfate esters, phosphate ester groups; amino acids,
Amphoteric surfactants such as aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, and amine oxides; complexes such as alkyl amine salts, aliphatic or aromatic quaternary ammonium salts, pyridinium, and imidazolium. Cationic surfactants such as ring quaternary ammonium salts and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used.

In particular, surfactants preferably used in the present invention are polyalkylene oxides having a molecular weight of 600 or more and described in Japanese Patent Publication No. 58-9412.

Further, in order to prevent static electricity, it is preferable to use a fluorine-containing surfactant described in JP-A-60-80949.

Specific examples thereof include U.S. Pat. No. 3,379.529, U.S. Pat. No. 3,620,746, and U.S. Pat.
No. 4, U.S. Patent No. 4,332,878, Japanese Unexamined Patent Publication No. 49-1
No. 29,536, JP-A No. 5467.419, JP-A-5
6-153.336, JP 56-153,342, JP 59278.853, JP 59-90435, JP 59-90436, JP 59-138808, etc. I can do it.

The photographic light-sensitive material of the present invention may contain a matting agent such as silica, magnesium oxide, polymethyl methacrylate, etc. in the photographic emulsion layer and other hydrophilic colloid layers for the purpose of preventing adhesion.

The light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of dimensional stability. For example, a polymer containing as a monomer component alkyl (meth)acrylate, alkoxy acrylic (meth)acrylate, glycidyl (meth)acrylate, etc. alone or in combination, or a combination of these with acrylic acid, methacrylic acid, etc. is used. be able to.

It is preferable that the silver halide emulsion layer and other layers of the photographic light-sensitive material of the present invention contain a compound having an acid group. Examples of the compound having an acid group include polymers or copolymer having repeating units of organic acids such as salicylic acid, acetic acid, and ascorbic acid, and acid monomers such as acrylic acid, maleic acid, and phthalic acid. Regarding these compounds, Japanese Patent Application No. 1-66179, No. 60
-68873, 60-163856, and 60
-195655 specification can be referred to. Among these compounds, particularly preferred is ascorbic acid as a low-molecular compound, and as a high-molecular compound, an acid monomer such as acrylic acid and a crosslinking monomer having two or more unsaturated groups such as divinylbenzene are particularly preferred. It is a copolymer water-dispersible latex.

In order to obtain ultra-high contrast and high sensitivity photographic properties using the silver halide photosensitive material of the present invention, it is necessary to use a conventional infectious developer or a highly alkaline developer with a pH close to 13 described in U.S. Pat. No. 2,419,975. It is not necessary to use a liquid, and a stable developer can be used.

That is, the silver halide photosensitive material of the present invention contains sulfite ions as a preservative at 0.15 mol/7! Including the above, p
H10.5-12.3, especially pH 1). 0-12.
A sufficiently ultra-high contrast negative image can be obtained using a developer of 0.

There is no particular restriction on the developing agent used in the developer used in the present invention, but it preferably contains dihydroxybenzenes, and dihydroxybenzenes and 1-phenyl-3-pyrazolidone are preferred since it is easy to obtain good halftone quality. or a combination of dihydroxybenzenes and p-aminophenols may be used.

The dihydroxybenzene developing agent used in the present invention includes hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-
Examples include dichlorohydroquinone, 2,3-dibromohydroquinone, dimethylhydroquinone, and dimethylhydroquinone, with hydroquinone being particularly preferred.

As the developing agent for 1-phenyl-3-pyrazolidone or its derivative used in the present invention, 1-phenyl-3-pyrazolidone, 1-phenyl-4.4dimethyl-3-pyrazolidone, 1-phenyl-4methyl-4-hydroxymethyl -3-pyrazolidone, 1-phenyl-4,-4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-
Methyl-3-pyrazolidone, 1-p-aminophenyl 4
, 4-dimethyl-3-pyrazolidone, t-tolyl-4
．． Examples include 4-dimethyl-3-pyrazolidone.

Examples of the p-aminophenol developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N-(β-hydroxyethyl>-p-aminophenol, N-(4-hydroxyphenyl) glycine,
There are 2-methyl-p-aminophenol, p-pendylaminophenol, etc., and among them, N-methyl to p-aminophenol are preferred.

The developing agent is usually 0.05 mole #-0.8 mole/7! Preferably, it is used in an amount of . Also, dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p. When using a combination with amino/phenols, the former should be 0.
05 mol/2-0.5 mol/l the latter 0.06 mol/l
It is preferable to use the following amounts.

Preservatives for sulfite used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite,
Examples include formaldehyde and sodium bisulfite. Sulfites are o゛. 4 moles/7! Above, 0.5 mol/l or more is particularly preferable. Further, the upper limit is preferably 2.5 mol/l.

Alkaline agents used to set pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, trisodium phosphate, and potassium triphosphate.
Contains H regulators and buffers. The pH of the developer is 10.5-1
It is set between 2.3.

Additives used in addition to the above components include compounds such as boric acid and borax, development inhibitors such as sodium bromide, potassium bromide, and potassium iodide; ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, and methyl cellosolve. , hexylene glycol, ethanol, methanol, and other organic solvents; antifoggants such as indazole compounds such as 1-phenyl-5-mercaptotetrazole and 5-nitroindazole, and penttriazole compounds such as 5-methylbenttriazole; It may also contain a black pepper preventive agent, and if necessary, a color toning agent, a surfactant, an antifoaming agent, a water softener, a hardening agent, and JP-A-56-106.
The amino compounds described in No. 244 may also be included.

In the developing solution of the present invention, JP-A-56-2 is used as a silver stain preventive agent.
Compounds described in No. 4,347 can be used. As a solubilizing agent added to the developing solution, patent application No. 109/1986.
, 743 can be used. In addition, as a pH buffering agent for developing solutions,
Compounds described in No. 433 or Japanese Patent Application No. 1987-2870
Compounds described in No. 8 can be used.

As the fixing agent, those having commonly used compositions can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used.

The fixing solution may contain water-soluble aluminum (eg, aluminum sulfate, alum, etc.) as a hardening agent. Here, the amount of water-soluble aluminum salt is usually 0.4 to 2.0
g-Ajl! /fi. Furthermore, a trivalent iron compound can also be used as an oxidizing agent in the form of a complex with ethylenediaminetetraacetic acid.

The development temperature is usually selected between 18°C and 50°C, more preferably between 25°C and 43°C.

The present invention will be explained in detail below with reference to Examples.

In the Examples, a developer having the following formulation was used.

Developer Hydroquinone 50.0g N-methyl-p-aminophenol l/2 sulfate 0.3g Sodium hydroxide 18.0g 5-sulfosalicylic acid 55.0g Potassium sulfite
1) 0.0g ethylenediaminetetraacetic acid disodium salt 1.0g 2-mercaptobenzimidazole-5-sulfonic acid 0.3g potassium bromide 10.0g 5-methylbenzotriazole 0.68n-butyldiethanolamine 15.0g 1.luenesulfonic acid sodium
Add 8.0g water
1 l (add potassium hydroxide p}I=1). Set to 6. ) (Example 1) Emulsions A to C were prepared by the following method.

(Emulsion A: Invention) Silver nitrate aqueous solution and 1×1 gelatin aqueous solution kept at 35°C
0-' moles of (NH4)3RhCj! Add a sodium chloride aqueous solution containing b at the same time for 10 minutes,
By controlling the potential between them to 200 mV, monodisperse cubic silver chloride particles with an average particle size of 0.10 μm were prepared. After removing soluble salts by a conventional method, 6-methyl-4hydroxy-1.3.
3a,7-tetraazaindene and gelatin were added. (Unripened emulsion) (Emulsion B: the present invention) Silver nitrate aqueous solution and 1×1 gelatin aqueous solution kept at 35°C
0-' moles of (NH a) a R h C 1
A sodium chloride aqueous solution containing a was added at the same time for 10 minutes, and the potential during that time was controlled at 400 mV to prepare monodisperse silver chloride cubic particles with an average particle size of 0.08 μm. After removing soluble salts by a conventional method, 6-methyl-4hydroxy-1.
3. Added 3a,7-tetraazaindene and gelatin. (Unripened emulsion) (Emulsion C: comparison) Silver nitrate aqueous solution was added to gelatin aqueous solution kept at 40°C.
0-' moles of (NH4)3 R h C 7! A sodium chloride aqueous solution containing b was added at the same time for 20 minutes, and the potential during this time was controlled at 200 mV to prepare monodisperse silver chloride cubic particles with an average particle size of 0.15 μm. After removing soluble salts by a conventional method, 6-methyl-4hydroxy-1.3.3a,
7-Tetraazaindene and gelatin were added. (Unripened emulsion) After adding the compound of general formula (II) of the present invention and the hydrazine compound of general formula (I) to these emulsions as shown in Table 1, 5 Orrg of the following nucleation accelerator (2) was added.
/rd, hydrazine compound (I-5) at 1 x 10-3 mol/mol Ag, dye 30+ng/rrr, solid content of polyethyl acrylate latex 3Qwt% based on gelatin, and l,3- as a hardening agent. Divinylsulfonyl-2-propanol was added and coated onto a polyester support at a silver level of 3.8 g/rd.

Gelatin was 1.8 g/bo.

On top of this, as a protective layer, gelatin 1.5g/n? , polymethyl methacrylate with a particle size of 3.0μ 150 / m',
Hydroquinone 50■/I'rr, thioctic acid 6■/M
, sodium dodecylbenzenesulfonate as a coating agent, a surfactant represented by the following structure 2〇, and a dye that absorbs UV light represented by the structural formula ■ at 75■/n
1 was added.

The sample thus obtained was exposed to light through a light wedge using a bright room printer P-607 manufactured by Dainippon Screen Co., Ltd.
The film was developed at 8° C. for 20 seconds, fixed, washed with water, and dried. (
Automatic processor FG-660F)'j ■ co FI? SO2 NCHz COOK
C. H. As is clear from Table 1, samples 2-4, 6-1 of the present invention
0, 12 to 13 have high Dmax and good return characteristics.

C H 3 (Example 2) Emulsions D and E were prepared in the following manner.

(Emulsion D; present invention) Silver nitrate aqueous solution and 1×1 gelatin aqueous solution kept at 35°C
By simultaneously adding a sodium chloride aqueous solution containing 0-5 mol of (NH4)3R h C 7!6 over a period of 10 minutes and controlling the potential at 200 mV during that time, silver chloride cubes with an average particle size of 0.10 μ were produced in a monodisperse manner. Particles were prepared. After removing soluble salts by a conventional method, 6-methyl-4hydroxy-1.3.3a. 7-
Tetraazaindene and gelatin were added. (Unripened emulsion) (Emulsion E; comparison) Silver nitrate aqueous solution was added to gelatin aqueous solution kept at 40°C.
0-5 mol of (NH*) 3R h C j! b
A sodium chloride aqueous solution containing . After removing soluble salts by a conventional method, 6-methyl-4hydroxy-1.3 was added as a stabilizer.
．． 3a. 7-Tetraazaindene and gelatin were added. (Unripened emulsion) After adding the compound of the general formula (n) of the present invention and the hydrazine compound of the general formula (1) to this emulsion as shown in Table 2, the following nucleation accelerator (2) was added at a rate of 50 /
2. hydrazine compound I-5). X10-'mol/
Mol Ag, I-30) 5xlO-'mol/molAg, dye■50■/I■ Polyethyl acrylate latex was added in a solid content of 3 Qwt% based on gelatin, and 1.3-divinylsulfonyl- was added as a hardening agent. 2-Probanol was added and coated onto a polyester support to give a silver content of 3.8 g/rd. Gelatin was 1.8 g/d.

On top of this, as a protective layer, gelatin 1.5g/%, particle size 3
．． 0μ polymethyl methacrylate 50■/d, hydroquinone 50■/n? , thioctic acid 6■/n{ ,
WJ As a fabric agent, sodium dodecylbenzenesulfonate, a surfactant represented by the following structural formula (2), and a UV light absorbing dye represented by the structural formula (2) were added at 50 cm/pot.

The sample thus obtained was exposed to light through a light wedge using a light room printer P-607 manufactured by Dainippon Screen Co., Ltd. at 38°C.
The film was developed for 20 seconds, fixed, washed with water, and dried. (Automatic developing machine FC-660F) ■ Cll F
+tS Ox N C H2 C O O KC3
H? ■ As is clear from Table 2, samples 2 to 13 of the present invention are D
max is high and return characteristics are also good.

(Photographic performance evaluation method) +1) γ is defined as follows.

(2) Cut-out character image quality Cut-out character image quality 5 is 30 μm wide when properly exposed so that 50% of the halftone dot area becomes 50% of the halftone dot area on the photosensitive material for return using an original as shown in Figure 1. This refers to the image quality in which characters are reproduced, and the image quality is very good. On the other hand, character image quality 1
is an image quality that can only reproduce characters with a diameter of 150 μm or larger when given the same appropriate exposure, and is considered poor character extraction quality, and is ranked between 5 and 1 in terms of sensory evaluation of 4 to 2. A value of 3 or higher is a practical level.

(3) Pasting marks In Figure 1, the mesh film (2) was placed on the pasting base (c), the periphery of the mesh film was further fixed with transparent scotch tape for plate making, and exposed and developed. Evaluation was made on a five-point scale, with 15 indicating that there was no tape mark (pasting mark) and 1 being the worst level where the mark was noticeable.

[Brief explanation of drawings]

FIG. 1 schematically shows the evaluation method used in the examples, and (a) to (e) represent the following. (B) Transparent or semi-transparent pasting base (opening) Line drawing original (black areas indicate line drawings) (C) Transparent or semi-transparent pasting base (2) Halftone dot original (black areas indicate halftone dots) (shown) (e) Photosensitive material for return (the shaded area indicates the photosensitive layer) Patent applicant: Fuji Photo Film Co., Ltd. Procedural amendment 4. Subject of amendment: Description column “Detailed description of the invention” 1. 2.

Claims (4)

[Claims] (1) In a silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support, the emulsion layer has a density of at least 1×10^-^6 per mole of silver.
mol of rhodium salt and a silver chloride content of at least 9
The emulsion layer or other hydrophilic colloid layer contains a hydrazine derivative and a redox compound that releases a development inhibitor when oxidized. A silver halide photographic material characterized by: (2) The redox compound has a redox group such as hydroquinones, catechols, naphthohydroquinones,
Aminophenols, pyrazolidones, hydrazines,
The silver halide photographic material according to claim (1), which contains hydroxylamines and reductones. (3) Claim (1) characterized in that the redox compound has a hydrazine as a redox group.
The silver halide photographic material described in Section 1. (4) The silver halide photographic material according to claim (1), wherein the redox compound is represented by the following general formula (I). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, A_1 and A_2 are both hydrogen atoms, or one is a hydrogen atom and the other is a sulfinic acid residue, or ▲There are mathematical formulas, chemical formulas, tables, etc.) In the formula, R_0 represents an alkyl group, an alkenyl group, an aryl group, an alkoxy group, or an aryloxy group, and l represents 1 or 2. Time represents a divalent linking group, and t represents 0 or 1. PUG represents a development inhibitor. V is a carbonyl group, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼, sulfonyl group, sulfoxy group, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼ (R_1 is an alkoxy group or an aryl group) ), iminomethylene group, or thiocarbonyl group.R
represents an aliphatic group, an aromatic group or a heterocyclic group. )