GB2198252A - Method for development processing of silver halide photographic material - Google Patents

Description

- 1 METHOD FOR DEVELOPMENT PROCESSING OF SILVER HALIDE PHOTOGRAPHIC

MATERIAL 219 8 2 c' 2 This invention relates to a method for developing a silver halide photographic material, and more particularly to a method for development processing of a photographic material containing a surface lateiit image - type of --: silver halide emulsion, by which developer fog can be inhibited.

A density increase in unexposed areas of a silver halide photographic material (hereinafter referred to as a "light-sensitive material") due to development processing is called "developer fog". This phenomenon is more likely to occur when the light-sensitive material has higher sensitivity, is preserved for a longer period of time, or under severer conditions, i.e., 'higher temperature and higher humidity.

Further, fog is extremely apt to occur in high15 temperature rapid processing or high-activity rapid process- ing which is often adopted for reduction of processing time. Generation of developer fog should be minimized as it brings about deterioration of photographic properties, such as reduction in image contrast.

Conventional techniques for the inhibition of devel oper fog include addition of antifoggants to light-sensitive 2 1 C_ materials or a developer. A number of compounds have been proposed as antifoggants as disclosed, e.g., in Birr, Stabilization of Photographic Silver Halide Emulsions (Focal Press, 1974). However, these conventional antifoggants are disadvantageous in that they decrease sensitivity or gradation of the light-sensitive materials, or tend to interfere with the adsorption of a sensitizing dye onto silver halide grains, thus hindering color sensitization. Also, these disadvantages become more conspicuous as the activity of the antifoggants becomes higher. A compound is eagerly sought which can inhibit fog generation without impairing sensitivity and gradation or adversely affecting color sensitization.

one object of this invention is to provide a method for development processing by which developer fog can be inhibited effectively without reduction of sensitivity.

Another object of the invention is to provide a method for development processing by which developer fog can be inhibited without decreasing gradation of the lightsensitive material.

Yet another object of the invention is to provide a method for development processing by which developer fog can be inhibited without adversely affecting color sensitization.

3 71 0 It has now been found that - these - ---objects of the invention can be accomplished by developing a light- sensitive silver halide photographic material including a support having thereon at least one surface latent image type silver halide emulsion layer in the presence of a compound represented by formula (I):

1 E (X.---A-BI n -m wherein Q represents an atomic -group necessary for completing a 1 5- or 6-membered heterocyclic ring which may be fused with '-an aromatic carbocyclic ring or an aromatic heterocyclic ring; X represents a divalent linking group containing at least one atom selected from a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom; A represents a linking group containing at least one group selected from a straight or branched chain alkylene group, a straight or branched chain alkenylene group, a straight or branched chain aralkylene group and an arylene group; B represents a substituted or unsubstituted amino group or a nitrogencontaining heterocyclic ring; M represents a hydrogen atom, an alkali metal atom or an ammonium group; m is 1 or 2; and n is 0 or 1.

4 c In formula (I), Q preferably represents an atomic group necessary for forming a 5- or 6-membered heterocyclic ring composed of at least one of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom. The heterocyclic ring may be fused to an aromatic carbocylic ring or an aromatic heterocyclic ring. Examples of the heterocyclic ring formed by Q include an indazole ring, a benzimidazole ring, a benzotriazole ring, an imidazole ring, a triazole ring, a tetrazole ring, a tetraazaindene ring, a triazain- dene ring, a pentaazaindene ring, a diazaindene ring, a pyrazole ring and an indole ring.

These heterocyclic rings- mLy be nitro group, a halogen atom (e.g., bromine atom), substituted or substituted with a a chlorine atom, a a mercapto group, a cyano group. a unsubstituted alkyl group (e.g., a methyl group, an ethyl group, a propyl group, a t-butyl group, a methoxyethyl group, a methylthioethyl group, a methylthio methyl group, a methoxyethoxyethoxyethyl group, a trimethyl ammonioethyl group, a cyanoethyl group, etc.), a substituted or unsubstituted aryl group (e.g., a phenyl group, a 4 methanesulfonamidophenyl group, a 4-methylphenyl group, a 3 methoxyphenyl group, a 3,4-dichlorophenyl group, a naphthyl group), a substituted or unsubstituted alkenyl group (e.g., an allyl group), a substituted or unsubstituted %,ell aralkyl group (e.g., a benzyl group, a 4-methylbenzyl group, a phenethyl group, a 4-methoxybenzyl group), a-substi tuted or unsubstituted alkoxy group (e.g., a methoxy group, an ethoxy group, a methoxyethoxy group, a methylthioethoxy group), '-. a substituted or unsubstituted aryloxy group (e.g., a phenoxy group, a 4-methoxyphenoxy group), a substituted or unsubstituted alkylthio group (e.g., a methylthio group, an ethylthio group, a propylthio group, a methylthioethyl group, a methoxyethylthio group), a substi-tuted or unsubstituted arylthio group (e.g., a phenyl thic group), a substituted or unsubstituted sulfonyl group (e.g., a methanesulfonyl group, an ethanesulfonyl group. a p-toluenesulfonyl group, a methoxye,ihylsulfonyl group), a substituted or unsubstituted carbamoyl group (e.g., a carbamayl group, a methylcarbamoyl group, a meth oxyethylcarbamoyl group, a methylthioethylcarbamoyl group, a phenylcarbamoyl group), - a substituted or unsubstituted sulfamoyl group (e.g., a sulfamoyl group, a methylsulfamoyl group, a phenylsulfamoyl group), a substituted or unsubstituted carbonamido group (e.g., an acetamido group, a benzamido group, a methoxypropionamido group), a substituted or unsubstituted sulfonaTido group (e.g., a methanesulfonamido group, a benzenesulfonamido group, a p toluenesulfonamido group), a substituted or unsubsti tuted acyloxy group (e.g., an acetyloxy group, a benzoyloxy 0 25 - 6 I\,group), a substituted or unsubstituted sulfonyloxy group (e.g., a methanesulfonyloxy group), a substi tuted or unsubstituted ureido group (e.g., a ureido group, a methylureido group, an ethylureido group, a methoxyethyl ureido group, a methylthioethylureido group, a phenylureido group), a substituted or unsubstituted thioureido group (e.g., a thioureido group, a methylthioureido group, a methoxyethylthioureido groupl), a substituted or unsub stituted acyl group (e.g., an acetyl group, a benzoyl group, a 4-methoxybenzoyl group), a substituted or unsubsti tuted heterocyclic group (e.g., a 1-morpholino group, a I piperidino group, a 2-pyridyl group, a 4-pyridyl group, a 2 thienyl group, a 1-pyrazolyl group, a 1-imidazolyl group, a 2-tetrahydrofuryl-'group, a tetrahydrothienyl group), substituted or unsubstituted hydroxycarbonyl group a (e.g., a methoxycarbonyl group, a phenoxycarbonyl group, a methoxy ethoxycarbonyl group, a methylthioethoxycarbonyl group, a methoxyethoxyethoxyethoxycarbonyl group), a substi tuted or unsubstituted hydroxycarbonylamino group (e.g., a methoxycarbonylamino group, a phenoxycarbonylamino group, a 2-ethylhexyloxycarbonylamino group), a substituted or unsubstituted amino group (e.g., an amino group, a dimethyl amino group, a methoxyethyl amino group, an anilino group), a carboxyl group or a salt thereof, a sulfo group or a salt thereof or a hydroxy group, pre.' c - 7 0 each having up to 12 carbon atoms.

Preferred examples of substituents on the'heterocyclic group include a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, a sulfonyl group, a carbamoyl group, a sulfamoyl group, a sulfonamido group, and a ureido group, and the most preferred groups include a halogen atom, an alkyl group, and an alkoxy group.

The divalent linking group represented by X includes 0 0 0 0 1 1 11 11 -S-, -0-, -N-, -Cu-, -OC-, -C-N-, -N-C-, -SO N-, -N-SO - 1 2 1 1 2 R 3 R 4 R5 0 0 0 11, 11 11 -C-, -bu-i -Ub-, e-cc., 11 11 U U wherein R,, R 2' R 3' R4, R5, R 6, R 7, R8, R9, and R10, which may be the same or different, each represents a hydrogen atom, a substituted or unsubstituted alkyl group (e.g., a methyl group, an ethyl group, a propyl group, an n-butyl group a substituted or unsubstituted aryl group (e.g., a phenyl group, a 2-methylphenyl group), a substituted or unsubstituted alkenyl group (e.g., a propenyl group, a 1-methylvinyl group) or a substituted or un substituted aralkyl group (e.g., a benzyl group, a phenethyl group). The alkyl, aryl, alkenyl and aralkyl groups represented by R 1 to R,, preferably have up to 12 carbon 0 R 1 S 0 11 - 11 11 -N-C-N-, -N-C-N-, -N-CO-, -SO 2-' 1 1 1 1 1 R 6 R 7 X 8 R 9 R 10 - 8 atoms and more preferably up to 7 carbon atoms. The most preferred carbon atom range for the alkyl and alkenyl group is from 1 to 3.

Particularly preferred examples of R 1 to '10 include an alkyl group such as methyl and ethyl, an aryl group such as phenyl, an alkenyl group such as propenyl, and an aralkyl group such as benzyl.

These linking groups may be linked to Q either directly or via a straight or branched chain alkylene group, e.g., a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, a 1methylethylene group.

Group A specifically includes a straight or bran ched chain'alky!'ene group, e.g., a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene, etc.; a straight or branche.g., a vinylene group, a 1 a straight or branched chain group, a 1-methylethylene group ed chain alkenylene group.

methylvinylene group; aralkylene group, e.g., a benzylidene group, etc.; or an arylene group, e.g., a phenylene group, a naphthylene group, etc.; and a linking group formed by any combination of these groups and the above-described X group. The group A prefer ably contains up to 12 carbon atoms, and more preferably up to 7 carbon atoms, and most preferably up to 3 carbon atoms.

Specific examples of the substituted or unsubsti- 1 (D tuted amino group (inclusive of its salt) represented by B include an amino group or a hydrochloride thereof, a-methylamino group, a dimethylamino group or a hydrochloride thereof, a diethylamino group, a dibutylamino group, a dipropyla.nino group and an N-dimethylaminocthyl-N- methylamino group. The nitrogen-containing heterocyclic ring as repye-sented by B is a 5- or 6-membered heterocyclic ring containing at least one nitrogen atom and optionally a sulfur and/or oxygen atom and may be an aromatic.' saturated or unsaturated heterocyclic group. The heterocyclic group may be substituted with an alkyl group or a halogen atom.

Specific examples of the nitrogen-coptaining heterocyclic ring as represented by B include a-l-morpholino group, a 1 piperidino group,'a 2-pyridyl group, a 4-pyridyl-group, a 1 imidazolyl group, a 2-imidazol-%,rl group and a 1-pyrazolyl group.

M specifically represents a hydrogen atom, an alkali metal atom, e.g., a sodium atom, a potassium atom, etc.; or an ammonium group, e.g., a trimethyl ammonium group, or dimethylbenzylammonium, group.

Of the compounds represented by formula (I), preferred are those represented by formula (II) C N /, (X A-Bn N m and those represented by formula (III) m 1 N N X- n A-B] m 0 (ii) (III) wherein X, A, B, M, m and n are as defined in formula (I).

In formulae (II) and (III), the heterocyclic rings may be substituted with the substituent groups for the heterocyclic group formed by Q in formula (I).

Specific but non-limiting examples of the compounds represented by formula (I), (II) or (III) are shown below.

1 0 2.

1 P cj' H 01 NL\,,:cr H ,,C H 3 C 0 N H -- C H 2 J-7-N 11 C H 3 2 H 5 COL' C H 2 --2Ni 1m 11 3.

4.

6.

P Nl C ON H--C H 2 --3N C 2115 N,,' N C 2 H 5 H N-, 'C 0 N M-CC 112 7 N // 2 n C 4 H 9 \N'- H ,NI N\ N)G1 H CONH-CCH2 N N 'H C 0 -- C H 2 --2-N,,-C 2 115 N // ""C 2 H 5 \N)0 H 12 - k 1 ' - j ,-C 2 H 5 N) NHS02--CH2)2 N N // "C 2 H 5 \N H 8 9.

10.

CH3 /k N CONH-eC-H2)3 N l,", N\ J) H 0 ,C H 3 N 'll 2)-2-N C H.3 H 0 11 N NW- NhV- H 2 t-2N \ N H l-l ,C 2 H 5 C 2 H 5 G.

N NHC 0--CH 2)3 N // ' J3 N \ N CH3 H 12.

N INHS02(-CH2)2 NJ 1., N\ N:c OCH3 H 13.

C 2 5 //N C OO-C H 2--3 N "C N,\ N 1-1 14. C 2H5 1,ú 2 H 5 N // N-, CONG(-CH2)-T- N-CH 2 Y-2 N,,C 2 H 5 \N H cl m 15.

16.

N N "::c N H /C 2145 CON1ItCH 2)-2_ S-r-H 2 - -2 N C 0 Ii <) NH-L-O-eCE2 H S --,C 3 1-17 17. 11 -,C H 2 C 1-12 01-1 N NI-I-C-NH--CII2 -3N "'CII 2 CH 2 01-1 N h]) \N H 18.,C 2H 5 // N C H 2 C 0 N H -- C H 2 -2 IN\ ""C 2 H 5 N \N J17 K - 15 G.

19.

20.

21.

22.

0 N 5,51 l \ N)0 H H 11 ri ti C N H -- CH -,C 2 H 5 2 --3N '-,C 2H5- -"C 2 115 Nz:-C N (_11 2 C ONB-CC H 2--3N -, C 2H5 \ N N 0 /C? CH2 COI13^-CH2---2N N 2 H,5 N,-N 0 .,-C H 3 H CH2CONLH--CH2)3 N' N N ""C H 3 N \N N 0 16 G 23.

24.

25.

26.

2 -2 -,N \N - 1 N' N CH2CONH 0 N-11"-'-N / N L j) H -'C 2 l 5 N H -- C H 2 -,3- N,,' C 1 21-15 0 1-1 C H 3 N H -- C H 2 , IN 0 N H H ,,C 2 H s N ii, C 0 -- C H 2 - -2 N-N 0 ,/C H 3 113 0 27.

28.

29.

30.

1-1,,C H 3 N N CH2SCI-12CH2N '-,c 0 0 11,C 2 H 5 NHLNH--CH2-3N,_C 21d 5 F.

C 0 N H--C H 2 /C2H5 1 -N 2 ""C 2 H 5 - HC2 N H C 0 -- C H 2 -)2--NI N S 1 -ce N a ,'C 113 "'C H 3 c 31.

32.

33.

34.

a 18 0 CH3 N N H - C 2 1-15 N:,:::yNi H SO 2--(- H 2-Y-3N "C 2 H,5 N H C2H5- N-CH2 / 11.1 -(/":o C 2 H 5 N H .'C H 3 C 0 N H--C H 2 C H 3 -/ ', Y:

N Br H 4 0 19 - 35.

36.

37.

38.

0 N N H GIMR - 1-H 2 -2-N 0 NjO 'H --'C 14 3 N-P CH 2 -2N r 11 -, c N- 1-1 0 H 3 N-N 11 /C 2H i N "T 2 115 N-N H 0 ,'C 2 H 5 11 N HL N H-CL bl 2 -2N C N.' H 0 The compounds according to the present invention can be synthesized by the processes described, e.g., in Japanese Patent Publication Nos. 29390/85 and 29391/85, Japanese Patent Application (OPI) Nos. 159162/84, 217358/85, 162235/83, and 83420/79 (the term "OPI't as used herein refers to a "published unexamined Japanese patent application"), and U.S. Patents 3,082,088 and 4,311,781. Typical examples of syntheses of the compounds are given below.

SYNTHESIS EXAMPLE 1 Synthesis of Compound (1) To a mixture of 11.2 g of 5-phenoxycarbonylbenzotriazole and 4.4 g of N,N- dimethylethylqnediamine was added 150 ml of benzene, followed by heat- refluxing for 4 hours. After cooling to room temperature, the precipitated crystals were collected by filtration and recrystallized from methanol to obtain 7. 9 g of Compound (1) having a melting point of 182 to 184'C.

SYNTHESIS EXAMPLE 2 Synthesis of Compound (2) To 60.0 g of 5-phenoxycarbonylbenzotriazole were added 500 ml of acetonitrile and 32.0 g of N,N-diethylethylenediamine, and the mixture was heat-refluxed for 4 hours. After the reaction, the reaction mixture was stirred in an ice bath. The precipitated crystals were collected by filtration and recrystallized from 400 ml of methanol to 21 0 obtain 56.1 g of Compound (2) having a melting point of 164 to 165"C. - SYNTHESIS EXAMPLE 3 Synthesis of Compound (3) To 23.9 9 of 5-phenoxycarbonylbenzotriazole were added 200 ml of acetonitrile and 14.3 g of N,N-diethyltrimethylenediamine, and the mixture was heated at reflux for 4 hours. After the reaction, the reaction mixture was stirred in an ice bath. The precipitated crystals were,collected by filtration and recrystallized from 200 ml of a mixed solvent of acetonitrile and ethanol (1:1 by volume) to obtain 23.0 g of Compound (3) having a melting point of 104 to 1080C.

SYNTHESIS EXAMPLE 4 Synthesis of Compound (5) To 23.9 g of 5-phenoxycarbonylbenzotriazole were added 200 ml of acetonitrile and 15.8 g of 3-aminopropylmorpholine, and the mixture was heated at reflux for 4 hours. After the reaction, the reaction mixture was concentrated to dryness under reduced pressure, and the resulting oily substance was recrystallized from 250 ml of a mixed solvent of ethanol, ethyl acetate, and n-hexane (4:3:3 by volume) to obtain 23.4 g of Compound (5) having a melting point of 136 to 138C.

- 22 C SYNTHESIS EXAMPLE 5 Synthesis of Compound (8) To 23.9 g of 5-phenoxycarbonylbenzotriazole were added 200 ml of acetonitrile and 15.3 g of 1-(3-aminopropyl)-2-methylimidazole, and the mixture was heat-refluxed for 4 hours. After the reaction, the reaction mixture was stirred in an ice bath, and the precipitated crystals were recrystallized from 200 ml of methanol to obtain 15.9 g of Compound (8) having a melting point of 231 to 2330C.

SYNTHESIS EXAMPLE 6 Synthesis of Compound (10) To 62.1 g of 5-aminobenzotria.zole dihydrochloride was added 500 ml of dimethylacetamide, and 83,7 ml of triethylamine was added dropwise thereto while being cooled in an ice bath. To the mixture was further added dropwise 21.0 ml of pyridine, and 42.3 g oil phenyl chlorocarbonate was then added dropwise thereto while maintaining the system at 5'C or lower, followed by stirring at room temperature for 2 hours. After the reaction, the reaction mixture was poured into 2 k of ice-water for crystallization, followed by filtration to obtain 60.8 g of 5phenoxycarbonylaminobenzotriazole.

To the resulting compound (5.1 g) was added 40 ml of acetonitrile, followed by stirring for 5 minutes at 450C. To the mixture was added dropwise 2.6 g of N,N-diethylethyl- - 23 0 enediamine while stirring, and the stirring was continued for an additional 2 hours. The reaction mixture was cooled in an ice bath, and the precipitated crystals were collected by filtration and recrystallized from 60 ml of a mixed sol- vent of inethanol and acetonitrile (1:5 by volume) to obtain 3.8 g of Compound (10) having a melting point of 149 to 150"C.

is SYNTHESIS EXAMPLE 7 Synthesis of Compound (19) To 7.6 g of 5-phenoxycarbonylaminobenzotriazole as prepared in Synthesis Example 6 was added 40 ml of aceto nitrile, followed by stirring at 450C. To the mixture was added dropwise 4.8 g of N,N-diethyltrimethylenediamine while stirring at 45C, and the stirring was continued for an additional 3 hours at 45'C. After the reaction, the reac tion mixture was cooled in an ice bath, and the precipitated crystals were filtered and recrystallized from 55 ml of a mixed solvent of methanol and acetonitrile (3:8 by volume) to obtain 5.4 g of Compound (19) having a melting point of 151 to 1520C.

SYNTHESIS EXAMPLE 8 Synthesis of Compound (9) To 7.6 g of 5-phenoxycarbonylaminobenzotriazole as prepared in Synthesis Example 6 was added 40 ml of aceto nitrile, followed by stirring at 40C. To the mixture was - 24 is added dropwise 3.2 g of N,N-dimethylethylenediamine while stirring at 400C, and the stirring was continued for an additional one hour at 40C. The reaction mixture was cooled in an ice bath, and the precipitated crystals were collected by filtration and recrystallized from 130 ml of a mixed solvent of methanol and dimetliylformamide (10:3 by volume) to obtain 4.1 g of Compound (9) having a melting point of 207 to 210C.

SYNTHESIS EXAMPLE 9 Synthesis of Compound (27) To 28.3 g of 2-dimethylaminoethanethiol hydrochlo ride was added 200 ml of acetonitrile, and 80 ml of a 28 wt% solution o- sodium methoxide in methanol was added thereto in a water bath at 20'C. Further, 32.9 g of ethyl 4-chloro acetacetate was added dropwise thereto while cooling in an ice bath. After the addition was comDleted, the mixture was stirred at 400C for 2 hours, followed by filtration to remove the inorganic salts. The filtrate was concentrated to dryness under reduced pressure, and the resulting oily substance was purified by silica gel column chromatography using a chloroform/methanol mixture (10:1 by volume) as a developing solvent to obtain 41.8 g of ethyl 4-(2-dimethyl aminoethylthio)acetacetate.

To the resulting product (23.3 g) were added 8.4 g of3-amino-1,2,4-tr-Lazole and 4.0 ml of acetic acid, and the C) mixture was heat-refluxed for 4 hours. After the reaction, 100 ml of methanol was added to the reaction mixture, followed by stirring for 1 hour in an ice bath. The precipitated crystals were collected by filtration and recrystal- lized from 300 ml of methanol to obtain 10.2 g of Compound (27) having a melting point of 109 to 1100C.

SYNTHESIS EXAMPLE 10 Synthesis of Compound (20) To a mixture of 19.4 g of 6-carboxymethyl-4-hydroxy1,3,3a,7- tetraazaindene and 14.3 g of N,N-diethyltrimethylenediamine was added 250 ml of dimethylformamide, and 22.6 g of dicyclohexylcarbodiimide was added dropwise to -the mixture at room temperature. The stirring was continued for 5 hours, and the precipitated crystals were removed by filtration. The f iltrate - was concentrated to dryness under reduced pressure, and the resulting solid was recrystallized from 400 ml of a 1:1 (by volume) mixture of methanol and acetone to obtain 18.0 g of Compound (20) having point of 214 to 215"C.

a melting According to the development processing of the present invention, an exposed silver halide photographic material is processed with a known developing solution in the presence of the compound represented by formula (I). It is preferred that the compound be incorporated into lightsensitive materials, and particularly emulsion layers or 26 C) other hydrophilic colloidal layers, in the course of their preparation, or that the compound be incorporated into a developer or a prebath thereof. It is more preferred for the compound to be originally incorporated into the.lightsensitive materials. Examples of lightsensitive material include black-and-white negative film, color negative films, X-ray films, graphic arts films and the like.

Incorporation of the compound of the present inven tion can be carried out by dissolving it in water or an appropriate water-miscible organic solvent, such as an zlcohol, ether, -glycol, ketone, ester or amide.

"'he compound should be added in an amount at least sufficient to produce significant inhibition of fog. Such an amoun t usually ranges from about 10- 7 to 10- 2 mol, and preferably from about 10- 6 to 10- 2 mol, per mol of silver in the case of addition of a light-sensitive material, and from about 10- 6 to 10- 1 mol, and preferably from about 10 5 to x 10-2 mol, ter of a processing solution in the case 3 per lit of addition to a developer or a prebath thereof.

Surface latent image type silver halide emulsions which can be used in the present invention are generally prepared by mixing a water-soluble silver salt, e.g., silver nitrate, and a watersoluble halogen salt, e.g., potassium bromide, in the presence of a solution of a water-soluble high polymer, e.g., gelatin. The silver halide used is not - 27 n limited, and includes silver chloride, silver bromide and, in addition, mixed silver halides, e.g., 'silver chlorobromide, silver iodobromide, silver chloroiodobromide.

The silver halide grains of th e emulsion preferably have a mean grain size of about 2 11m or smaller, and more preferably about 0.4 pm or smaller, in terms of diameter for spherical or nearly spherical grains or edge length for cubic grains, being averaged based on a projected area. The grain size distribution may be either narrow or- broad.

The silver halide grains may have any crystal form, such as a cubic form, an octahedral form, a composite form thereof, and tabular form as described in Japanese Patent Application (OPI) Nos. 127921/83 and 113926/83. FurtIier, they may have a homogeneous structure throughout the individual grains or a heterogeneous layered structure. Conversion type grains as described in British Patent 635,841 and U.S. Patent 3,622,318 may also be used.

Two or more different silver halide emulsions separately prepared may be used as a mixture thereof.

During the formation of silver halide grains or their physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an i3:idium salt or a complex salt thereof, a rhodium salt or 'a complex salt thereof, an iron salt or a complex salt thereof, etc. may be present in the system.

- 28 I The silver halide emulsion may be used in its primi tive form, but is usually subjected to chemical sensitiza tion. Chemical sensitization can be carried out by sulfur sensitization using active gelatin or a compound containing sulfur capable of reacting with silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines, etc.), reduction sensitization using a reducing substance (e.g., stannous salts, amines, hydrazine derivatives, formamidinesulfinic acid, silane compounds), noble metal sensitization using a noble metal compound (e.g., gold compounds, complex salts of the group VIII elements, e.g., platinum, iridium, palladium or a combination thereof.

Binders or protective colloids which can be used in the emulsion lavers or intermediate layers of the lightsensitive materials typically include gelatin, although hydrophilic colloids may also be employed. Examples of useful hydrophilic colloids other than gelatin include gelatin derivatives, graft polymers of other high polymers, albumin, casein, etc.; cellulose derivatives, such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfate, etc.; sugar derivatives, e.g., sodium alginate, dextran, starch derivatives, etc.; and a wide variety of synthetic hydrophilic high polymers, such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, proteins, such as gelatin and 29 - 0 is polymethacrylic acid, polyacrylamide, p9lyvinylimidazole, polyvinylpyrazole, etc., and copolymers of monomers-c onstituting these homopolymers.

The gelatin used includes not only lime-processed gelatin but acidprocessed gelatin and enzyme-processed gelatin. Hydrolysis products or enzymatic decomposition products of gelatin may also be used.

The emulsion layers or other hydrophilic colloidal layers of the photographic materials processed according to the present invention can contain organic or inorganic hardening agents, such as chromium salts (e.g., chromium alum, chromium acetate, etc.), aldehydes (e.g., formaldehyde, glyoxal, gliataraldehyde, etc.), N- methylol compounds (e.g., dimethylolurea, methyloldimethylhydantoin, etc. ), dioxane derivatives (e.g., 2,3-dihydroxydioxane, etc.), active vinyl compounds (e.g., 1,3,5-triacryloyl-hyxahydro-striazine, 1,3-vinylsulfonyl2-propanol, etc.), active halogen compounds (e.g., 2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogenic acids (e.g., mucochloric acid, muco- phenoxychloric acid, etc.), N-carbamoylpyridinium salts (e.g., (1- morpholinocarbonyl-3-pyridinio)methanesulfonate, etc.), and the like, either individually or in a combination thereof. Preferred hardening agents are active vinyl compounds and active halogen compounds.

The photographic emulsion layers and other hydro- - 30 C) philic colloidal layers can further contain various surface active agents for various purposes, such as coating aids, for static charge prevention, improvement of slipperiness, emulsification and dispersion aids, prevention of adhesion, improvement of photographic characteristics (e.g., development acceleration, increase in contrast, and increase in sensitivity), and the like. Examples of useful surface active agents include nonionic surface active agents, such as saponin (steroid type), alkylene oxide derivatives (e.g., polyethylene glycol, polyethylene glycol/polypropylerie glycol condensates, polyethylene glycol alkyl ethers or aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines -or amides, of silicone, etc.), glycidol polyglycerides, alkyl- polyethylene oxide adducts derivatives (e.g., alkenylsuccinic phenyl polyglycerides, etc.), fatty acid esters of polyhy dric alcohols, alkyl esters of sugars, and the like; anionic surface active agents containing an acid radical, such as carboxyl, sulfo, phospho, sulfate, phosphate and like groups, e.g., alkylcarboxylates, alkylsulfonates, alkylben zenesulfonates, alky1naphthalenesulfonates, alkylsulfates, alkylphosphates, N-acyl-N-alkyltaurines, sulfosuccinates,sulfoalkylpolyoxyethylene alkyl phenyl ethers, polyoxyethyl ene alkylphosphates, and the like; amphoteric surface active agents, such as amino acids, amincalkylsulfonic acids, 31 0 1 aminoalkyl sulfates or phosphates, alkylbetaines, amine oxides, and the like; and cationic surface active-agents, such as alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium -salts, e.g., pyridinium, imidazolium, etc., aliphatic or heterocyclic phosphonium or sulfonium salts, and the like. As antistatic agents, fluorine-containing compounds are particularly preferred.

The photographic emulsions to be used in the present invention may be spectrally sensitized with methine dyes or other dyes, such as cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyqs, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful. dyes are cyanine dyes, merocyanine dyes, 15. and complex merocyanine dyes. Any of nuclei commonly utilized for cyanine dy es can be employed as a basic heterocyclic nucleus in these dyes. Such nuclei include a pyrroline nucleus, an oxazoline nucleus, a thiszoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, etc.; any of these nuclei to which an alicyclic hydrocarbon ring is fused; and any of these nuclei to which an aromatic hydrocarbon ring is fused, e.g., an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxazole nucleus, a naphthoxazole 32 - nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, etc. These nuclei may have a substituent at the carbon atom thereof.

Merocyanine dyes or complex merocyanine dyes can contain a 5- to 6membered heterocyclic nucleus having a ketomethylene structure, e.g., a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, a thiobarbituric acid nucleus, etc. These sensitizing dyes may be used either individually or in combinations thereof. In particular, combinations of sensitizing dyes are often used for the purpose of supersensitization.

is trast For the purpose of increasing sensitivity or conor accelerating development, the photographic emulsions may contain, for example, polyalkylene oxides or derivatives thereof, such as ethers, esters, amines, etc,, thioether compounds, thiomcrpholines, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives and 3-pyrazolidones.

For the purpose of improving dimensional stability and the like, the photographic emulsion layers or other hydrophilic colloidal layers may further contain a dispersion of a water-soluble or sparingly watersoluble synthetic polymer. Such a polymer includes homo- or copolymers of - 33 0 alkyl (meth)acrylates, etc., and copolymers methacrylic acid, etc.

The hydrophilic colloidal layers of the light-sensi- tive materials used may contain a water-soluble dye as a filter dye or for other purposes! for example, prevention of irradiation. Such water- soluble dyes include oxonol dyes, glycidyl (Meth)acrylates, styrene, of these mono mers and acrylic acid, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, and azo dyes, with oxonol dyes, hemioxonol dyes, and merocyanine dyes being particularly useful.

For the purpose of preventing fog during preparation, preservation or photographic processing of the lightsensitive material or for stabilizing photographic performance, the photographic emulsions can contain a variety of compounds known'as antifoggants or stabilizers in addition to the compounds of formula (I) according to the present invention. Examples of these compounds are azoles, e.g., benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidaz oles, nitroindazoles, benzotriazoles, aminotriazoles, etc.; mercapto compounds, e.g., mercaptothiazoles, mercaptobenzo thiazoles, mercaptobenzimidazoles, mercaptotbiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetraz ole), mercaptopyrimidines, mercaptotriazines, etc.; thioketo compounds, e.g., oxazolinethione, etc.; azaindenes, e.g., 34 7) triazaindenes, tetraazaindenes (especially, 4-hydroxy-substituted(1,3,3a,7)tetraazaindenes), pentaazaindenes, etc.; benzenethiosulfonic acid, benzenesulfinic acid, benzenesul- fonic acid amide; and so on.

the stabilizer can be used Each of the antifoggant and in an amount approximately equivalent to the amount of the compound of formula (I).

The light-sensitive materials may contain dye image forming couplers, i.e. , compounds capable of developing a color upon oxidative coupling with an aromatic primary amine developing agent (e.g., phenylenediam'ne derivatives and aminophenol derivatives) when subjected to color development processing. The couplers to be used preferably have a hydrophobic group called a. "ballast group" by which the molecule-is rendered non-diffusib le, or they preferably have a polymerized form. The couplers may be either 4-equivalent or 2- equivalent with reference to silver ions. The lightsensitive materials may further contain colored couplers having color correction effects, so- called DIR couplers that are capable of releasing a development inhibitor upon development processing, or colorless DIR coupling compounds which produce a colorless product by a coupling reaction to release a developing inhibitor.

Magenta forming couplers to be used include 5pyrazolone couplers, pyrazolotriazole couplers, pyrazolobenzimidazole couplers, cyanoacetylcumarone couplers, open- 0 is chain acylacetonitrile couplers, etc. Yellow forming couplers to be used include acrylacetamide couplers (e.g., benzoylacetanil ides and pivaloylacetanil ides). Cyan forming couplers to be used include naphthol couplers and-phenol couplers.

In order to satisfy particular requirements, two or more of these couplers may be incorporated into the same layer, or two or more layers may contain the same coupler.

The introduction of couplers into silver halide emulsion layers can be carried out by known methods, such as the method described in U.S. Patent 2,322,027. For example, the coupler can be dissolved in a-high-boiling organic -solvent, such as alkyl phthalates (e.g., dibutyl phthalate, dioctyl phthalate, etc.), phosphoric esters (e.g., diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctylbutyl phosphate, etc.), citric esters (e.g., acetyl tributyl citrate), benzoic esters (e.g., octyl benzoate), alkylamides (e.g., diethyl laurylamide), fatty acid esters (e.g., dibutoxyethyl succinate, diethyl azelate, etc.), and trimesic esters (e.g., tributyl trimesate); or a low-boiling organic solvent having a boiling point of from about 300C to 1500C, such as lower alkyl acetates (e.g., ethyl acetate, butyl acetate, etc.), ethyl propionate, sec-butyl alcohol, methyl isobutyl ketone, -ethoxyethyl acetate, and methyl cellosolve acetate7 or a mixture thereof, and the solution - 36 cl is dispersed in a hydrophilic colloid.

Introduction of couplers can also be effected in accordance with the dispersion method using polymers de scribed in Japanese Patent Publication No. 39853/76 and Japanese Patent Application (OPI) No. 59943/76.

When the coupler has an acid radical, e.g., a car- boxyl group or a sulfo group, it is introduced into a hydro- philic colloid in the form of an alkaline aqueous solution.

The light-sensitive materials can contain known discoloration inhibitors, such as callic acid derivatives hydroquinone derivatives, p-alkoxyphenols, p-oxyphenol derivatives, and bisphenols.

In addition to the aforesaid additives, the lightsensitive materials can contain various other additives as desired. Specific examples of the addi tives which can be used in the present invention are de- scribed in Research Disclosure, No. 17643 (December, 19'/8) and ibid, No. 18716 (November, 1979) as tabulated below:

37 U, Photographic Additives Kind RD 17643 Chemical sensitizer RD 18716 p - 648 right column (RC) Sensitivity increasing agent it Spectral sensitizer.and pp. 23-24 p. 648 RC-p. 649 RC supersensitizer Brightening agent p. 24 Antifoggant and pp. 24-25 p. 649-RC stabilizer Light absorbent, filter pp. 25-26 p. 649 RC-p. 650 dye., and ultraviolet left column (LC) absorbent Stain inhibitor p. 25 RC -P. 650 LC-RC Dye image stabilizer P. 25 Hardening agent P. 16 p. 651 RC Binder P. 26 Plasticizer and P. 27 p. 650 RC lubricant Coating aid and surface pp. 26-27 active agent Antistatic agent p. 27 at Photographic processing of the silver halide photo- graphic material, whether for black-and-white image formation or for color image formation, can be carried out in a known manner with known processing solutions, provided that development is effected in the presence of the compound 38 C) (I) used in the present invention. The processing temperature is usually between about 180C and 50C, but temperatures lower than 180C or higher than 50'C may also be employed.

A black-and-white developer contains one or more known developing agents, such as dihydroxybenzenes (e.g., hydroquinone), 3-pyrazolidones (e.g., 1phenyl-3-pyrazolidone), and aminophenols (e.g., N-methyl-p-aminophenol).

A color developer generally is an alkaline aqueous solution containing, as a main component, a known aromatic primary amine developing agents include, agent. Useful color developing for example, phenylqnediamine compounds, e.g., 4-amino-N,N-diethylaniline, 3-methyl-4-amino-N,N diethylaniline, 4-amino-N-ethyl-N--hydroxyethylaniline, 3 methyl-4-amino-N-ethyl-N--hydroxyethylaniline, 3-methyl-4 a.mino-N-ethyl-N--methanesulfonamidoethylaniline, 4-amino-3 methyl-N-ethyl-N--methoxyethylaniline, etc. Other devel oping agents, such as those described in L.F.A. Mason, Photographic Processing Chemistry, 226-229 (Focal Press, 1966), U.S. Patents 2,193,015 and 2,592,364, and Japanese Patent Application (OPI) No. 64933/73, may also be emploved.

The developers generally contain pH buffers, such as sulfites, carbonates, borates or phosphates of alkali metals, and developing inhibitors or antifoggants, such as bromides, iodides, and organic antifoggants other than the 39 0 compounds of the present invention. If de.sired, the devel opers may further contain water softeners; preservatives, e.g., hydroxylamines, etc.; organic solvents, e.g., benzyl alcohol, diethylene glycol, etc.; development accelerators, e.g., polyethylene glycol, quaternary ammonium salts, amines, etc.; color forming couplers; comptting couplers; nucleating agents, e.g., sodium boron hydride, etc.; auxil iary developing agents, e.g., 1-phenyl-3-pyrazolidone, etc.; tackifiers; polycarboxylic acid type chelating agents dis- closed in U.S. Patent 4,083,723; and antioxidants, e.g., those described in West German Patent Publication No. 2,622,950.

in color photographic processing, the photographic emulsion layers after color development are usually subject- ed to bleaching. Bleaching may be effected simultaneously with fixation, or these two steps may be carried out separately. Useful bleaching agents include compounds of polyvalent metals, e.g., iron (III), cobalt (III), chromium (VI), copper (II), etc., peracids, quinones, nitroso com- pounds, and the like. Examples of these bleaching agents are ferricyanides; bichromates; organic complex salts of iron (III) or cobalt (III), such as complex salts with aminopolycarboxylic acids, e.g., ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2- propanoltetraacetic acid, etc., or organic acids, e.g., citric acid, 3 is tartaric acid, malic acid, etc.; persulfates; manganates; nitrosophenol; and so on. Of these, sodium (ethylenediaminetetraacetato)iron (III), and ammonium (ethylenediaminetetraacetato)iron (III) are particularly useful. In particular, (ethylenediaininetetraacetato)iron (III) salts are useful in both a separate bleaching bath and a bleach-fix monobath.

The bleaching or bleach-fix bath can contain a bleaching accelerator as described in U.S. Patents 3,042,520 and 3,241,966 and Japanese Patent Publication Nos. 8506/70 and 8836/70, a thiol compound as described in Japanese Patent Application (OPI) No. 65732/78, and various other additives.

The present invention will now be illustrated in greater detail by way of the following examples, but the present invention is not to be construed as being limited thereto. Unless otherwise indicated, all parts, percents and ratios are by weight.

EXAMPLE 1

A silver iodobromide-gelatin emulsion containing 1.5 mol% of silver iodide (mean grain size: 0.9 im) was chemically sensitized by adding sodium thiosulfate and potassium chloroaurate. To the resulting emulsion was added 3,3'-disulfopropyl-5,5'-dichloro-9-ethyl-oxacarbocyanine sodium salt, and then a compound usecf in the pceantinvention or 41 - 0 a comparative compound was added thereto as shown in Table A coating aid (sodium dodecylbenzenesulfonate) and a (2,4-dichloro-6-hydroxy-s-triazine) The resulting coating cellulose triacetate 1 hardening agent were further added to the emulsion. com position was coated on a _support and dried to obtain Samples 1 to 12.

Each of Samples 1 to 12 was exposed to light through an optical wedge having a yellow filter for 1/20 second by means of a sensitometer. The exposed sample was developed with a PQ developer having the formulation shown below at 350C for 35 seconds, followed by fixation, washing, and drying in a usual manner. The potographic properties were evaluated by determining sensitivity and fog, and the results obtained are shown in Table 1. In the Table, photographic sensitivity is the reciprocal of a logarithm _of the exposure.required for obtaining an optical density of fog + 0.2, and the results are relatively expressed taking the sensitivity of Sample 1 as 100 (standard). Formulation of Developer:

Sodium sulfite 40 g Hydroquinone 25 g Boric acid 10 g 1-Phenyl-3-pyrazolidone 1.5 g Potassium hydroxide 30 g 5-Methylbenzotriazole 0.15 g 42 I'') Glutaraldehyde bisulfite Acetic acid Potassium bromide Water to make g 12 g g 1 9, - 43 1 -10 TABLE 1

Photographic Properties Sample Compound Amount Relative No. Added added _Fog Sensitivity (mol/mol-AgX) 1 - 0.25 100 2 Compound 1 4.5 x lo- 4 0.1896 3 18.0 x 10- 4 0.10 92 4 54.0 X 10-4 0.06 86 Compound 10 18.0 X 10- 4 0.11 91 6 19 54.0 X 10- 4 0.06 84 7 Compound 5 54.0 X 10-4 0.06 89 8 Compound 20 54.0 X 10-4 0.14 88 9 Compoun4 27 54.0 X 10-4 0.10 87 Compound 36 54.0 X 10- 4 0.10 87 11 Comparative 18.0 X 10-4 0.06 72 Compound (a) ive 54.0 X 10- 4 0.20 88 12 Comparat Compound (b) Note:

Comparative Compound (a) Comparative Compound (b) CH3 N N C H.3 N /J 1 N NN H 44 - As is apparent from Table 1, Samples 4, 6, and 7 according to the present invention show a fog preventing effect equal to that of Sample 11 using Comparative Compound (a) but undergo reduction in sensitivity to lesser degrees as compared with Sample 11. Further, Samples 7, 8, 9, 10, and 11 according to the present invention undergo reduction in sensitivity to the same degree as observed in Sample 12 using Comparative Compound (b) but inhibit fog more significantly than Sample 12.

It can be seen from these observations that the compounds of the present invention causative of sensitivity reduction than Compounds (a) and (b) which are broadly employed 15 antifoggants, while exhibiting fog inhibitory effects to the same degree as produced by these known antifoggants.

Further, the reflection spectra of the unexposed samples revealed that Samples 11 and 12 show greater reduction of absorption of the sensitizing dye as compared with Sample 1, while Samples 2 to 10 show lesser reduction of absorption, indicating that the compounds of the present invention are less causative of hindrance to adsorption of a sensitizing dye.

are less Comnarative - 1,3 1 EXAMPLE 2

To a silver iodobromide-gelatin emulsion containing 7.5 mol% of silver iodide (mean grain size: 0.6 4m) were added potassium chloroaurate, ammonium thiocyanate, and sodium thiosulfate, and the emulsion was heated at 60'C for 60 minutes to effect chemical sensitization.

A compound of the present invention or a comparative compound was added to the resulting emulsion as shown in Table 2, and the following additives were further added thereto.

Additives: Coupler::l-(2,4,6-Trichlorophenyl)-3-[3-(2,4-di-t-amylphenoxy)-acetamido]benzamido-5-pyrazolone Spectral Sensitizer:

Bis-[2-[l-ethyl-3-(3-sulfopropyl)-5,6-dichlorobenzimidazolej]trimethinecyanine sodium salt Hardening Agent:

2,4-Dichloro-6-hydroxy-1,3,5-triazine sodium salt Coating Aid:

Sodium p-dodecylbenzenesulfonate and sodium p-nonylphenoxypoly(ethyleneoxy)propanesulfonate The resulting coating composition was coated on a support and dried to obtain Samples 13 to 16.

46 I'- Each of the samples was exposed to light for 1/20 second through a yellow filter and then subjected to color development processing according to the following procedures. The photographic properties of the processed samples were determined as in Example 1, and the results in Table 2.

Processing Procedure:

in the same manner obtained are shown Processing Step Time Temoerature Color Development 2145" 38'C Bleaching 6130" Washing 3115" Fixation 6130" Washing 3115" Stabilization 3'15" The processing solution used in each step had the following formulation.

Color Develooer Formulation:

Sodium nitrilotriacetate 1.0 g Sodium sulfite 4.0 g Sodium carbonate 30.0 g Potassium bromide 1.4 g Hydroxylamine sulfate 2.4 g 4-(N-Ethyl-N--hydroxyethylamino)- 4.5 g 2-methyl-aniline sulfate Water to make 1 113 Bleaching Bath Formulation:

Ammonium bromide Aqueous ammonia (28 wt%) Sodium (ethylenediaminetetraacetato)iron Glacial acetic acid Water to make Fixing Bath Formulation:

160.0 g 25.0 ml 130.0 g 14.0 mI 1 1 Sodium tetrapolyphosphate 2.0 g Sodium sulfite 4.0 g Ammonium thiosulfate (70 wt%) 175.0 ml Sodium bisulfite 4.6 9 Water to make. 1 Stabilizing 8ath Formulation:

Formalin 8.0 M1 Water to make 1 A TABLE 2

Photographic Properties Sample Compound Amount Relative No. Added added Fog Sensitivity (mol/mol-AgX) 13 - - 0.21 100 14 Compound 1 1.8 X 10- 3 0.06 85 15 Compound 20 1.8 x 10- 3 0.06 81 16 Comparative 1.8 x 10- 3 0.05 76 Compound (a) It can be seen from Table 2 that the compounds used in the present invention are advantageous 48 1 U also when applied to color development in that reduction in sensitivity can be suppressed while producing a fog preventing effect equal to that of Comparative Compound (a).

EXAMPLE 3

In order to demonstrate -the effectiveness of the compounds according to the present invention when added to a developer, Sample 1 as prepared in Example 1 was exposed to light in the same manner as in Example 1 and subjected to development processing in the same manner as in Example 1, except that the developer farther contained a compound shown in Table j. The photographic properties of the processed samples are also shown in Table 3.

1 TABLE

Run Compound No. Added 1 2 Compound 1 3 Comoarative Compound (a) As can of the present reduction in sensitivity i with Comparative Compound (a) effect being equal to that (a).

Amount added (mol/mol-AgX) 8 x 10- 4 1.5 x 10- 3 3 Photographic Properties Relative _Fog Sensitivity 0.26 0.08 0.08 92 83 be seen from Table 3, the compound invention is advantageous in that s suppressed as compared with its fog preventing of Comparative Compound 0

Claims (16)

CLAIMS:

1. A method for development processing of a silver halide photographic material, comprising the step of developing a light-sensitive silver halide photographic material comprising a support having thereon at least one surface latent image type silver halide emulsion layer in the presence of a compound represented by formula (I):

Q N-M E (X--A-BI n m (I) wherein Q represents an atomic group necessary for completing a 5- or 6- membered heterocyclic ring which may be fused with an aromatic carbocyclic ring, or an aromatic heterocyclic ring; X represents a divalent linking group containing at least one atom selected from a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom; A represents a linking group containing at least one group selected from a straight or branched chain alkylene group, a straight or branched chain alkenylene group, a straight or branched chain aralkylene group and an arylene group; B represents a substituted or unsubstituted amino group or a nitrogencontaining heterocyclic ring; M represents a hydrogen atom, an alkali metal atom or an ammonium group; m is 1 - so - 0 is or 2; and n is 0 or 1.

2. - A method as claimed in Claim 1, wherein said heterocyclic ri-ng formed by Q--'is -selected from an indazole ring, a benzimidazole ring, a benzotriazole ring, an imidazole ring, a triazole ring, a tetrazole ring, a tetraazaindene ring, a triazaindene ring, a pentaazaindene ring, a diazaindene ring, a pyrazole ringand an indole ring.

3. A method as - claimed in Claim I or 2, wharein in said formula (I) Q is selecte,L so that the compounc! is represented by formula (II):

IN N / (X-- A- B 1 ""N n m 1 m (II) wherein X, A, M, m and n are as defined for formula (1).

4. A method as claimed in Claim 1 or 2, wherein ii-n said formula (I) Q is selected so that the co...ii-oounc, 1 represented by formula (III):

m (X n A-B] m N N ? 0 wherein X, A, B, M, m and n are as defined for formula (1) (III) 1 0

5. A method as claimed in any of Claims 1 to 4, wherein sai(-I heterocyclic ring formed by 0 is substituted with. at least one substituent selected from a nitro group, a halogen atom, a mercapto group, a cyano group, a substituted or unsubstituted alkyl:'grouP, a substituted or unsubstituted aryl group, a 'substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted. arylthio group, a substituted or unsubstituted sulfonyl. group, a substituted or unsubstituted carbamoyl group, a substituted or 'unsubstituted sulfamoyl group, a substituted or unsubstituted carbonamido-group, a substi- tuted or unsubstituted sulfonamido group, a substituted or unsubstituted acyloxy group, a substituted or unsubstituted sulfonyloxy group, a substituted or unsubstituted ureido group, a substituted or unsubstituted thioureido groupip a substituted or unsubstituted acyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted hydroxycarbonyl group, a substituted or unsubstituted hydroxycarbonyl. amino group, a substituted or unsubstituted amino group, a carboxyl group, a carboxyl salt, a sulfo group, a sulfo salt, and hydroxyl group.

6. A mathod as claimed in any preceding claim, wherein said divalent linking group represent-ed 'by X is selected from - 52 0 0 0 0 the groups -S-, -0-, -N-, -CO-, -OC, 1 1 1 R 1 R 2 M 3 0 S 0 0 0 11 ' 1 11 -SO N-, -N-SO - -N-C-N-, -N-C-N-, -NJ0-, -SO ki-, -.,)U-# 2 1.1 2 ' 1 ' 1 1 1 1. 2-' 11 R 4 R 5. m 6 R 7 R a R 9 m 10 U 0 0 1 1 and -OS-, wherein R,. R 2' R 3' R 4' R 5, R 6' R 7' R8# R 9 and 11 U R 101 which may be the saw or different, each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group or a substituted or unsubstituted aralkyl group.

7. k method as claimed in Claim 6, wherein said divalent linking group represented by X is linked to Q via a straight or branched chain alkyl,ene group.

8. A method as claimed in any preceding claim, wherein the group A also includes a linking group as defined for X in Claim 6.

9. A method as claimed in any preceding claim, wherein the group A contains up to 12 carbon atoms.

10. A method as claimed in any preceding claim, wherein said compound (I) is any of the compounds 1 to 38 shown hereinbefore.

1 1. A method as claimed iii any off- Claims 1 to 10, vierein sai,,7. com pound is present in at least one layer of said silver halide photographic material.

1 2. k - method as cla imed in Cla in,. 11, wherein said. com- 1 1 ki pound is present in an amount of from -10 to 10- mol per mol of silver.

13. - A method as claimed in Claim 12, wherein said compound is present in an amount of from 10-6 to -10- 2 mol per raol of silver in said silver halide.

14. A riye-thod as claimed in any of Claims 1 to 10, wherein said co-M. pound is present in a processing solution which is a developer solution or a predevelopment bath solution.

15. A method as claimed in Claim -14, wherein said com- pound is present in an c-unount of from.10- 6 to 10- 1 mol per liter of said processing solution.

16. A method as claimed in Claim 15, wherein said compound is present in an amount of from 10- 6 to 3 x 10- 2 mol per liter of said processing solution.

17- A method of development processing of silver halide photographic material, substantially as hereinbefore described with reference to any of Samples 2 to 10, 14 or 15 of the Examples.

18 - A photograph developed by a method as claimed in any preceding claim.

Published 1988 at The Patent Office, State House, 66.71 High Holborn, London WC1R 4TP. Further copies may be obtained from The Fatent Office,