METHOD OF TREATING SILVER HALIDE PHOTOGRAPHIC MATERIAL

Description

TECHNICAL FIELD

[0001] This invention relates to a method for forming ultra-high-contrast negative image using a silver halide photographic material. More particularly, it relates to a processing method of an ultra-high-contrast negative type photographic material for use in a silver halide photographic material used for photomechanical process.

TECHNICAL BACKGROUND

[0002] It is demanded to provide photographic materials having good original reproducibility and stable processing solutions or to simplify replenishment to comply with the diversity and complexity of prints in the field of photomechanical process.

[0003] The originals in line camera work in particular are formed by sticking e.g. phototypeset letters, handwritten letters, illustrations or dotted photographs. Accordingly, images having e.g. different densities and line widths coexist in the originals, and it is highly demanded to provide process cameras, photographic materials or image forming methods for finishing the originals with good reproducibility. On the other hand, the enlargement (spread) or reduction (choke) of halftone photographs is widely carried out to make plates for catalogs or large-sized posters. In making plates having enlarged halftone dots, screen ruling becomes loose and the photographing of out-of-focus dots is made, while in reduction, screen ruling/inch is larger than that of the original and the photographing of finer dots is made. Accordingly, it is demanded to provide an image forming method which has a still wider latitude for halftone photographing to keep the reproducibility of halftone gradation and which can form high-contrast image.

[0004] Halogen lamp or xenon lamp is used as a light source for process cameras. Generally, photographic materials are subjected to ortho-sensitization to obtain photographing sensitivity for these light sources. However, it has been found that ortho-sensitized photographic materials are more intensively affected by chromatic aberration of a lens and image quality is liable to be deteriorated. The deterioration is particularly remarkable with xenon lamp light source.

[0005] It is known a method for obtaining line works or halftone images having a high contrast and a high blackening density wherein image area and non-image area are clearly distinguished from each other by processing lith type silver halide photographic materials comprising silver chlorobromide (having a silver chloride content of at least 50%) with hydroquinone developing solutions containing sulfite ion at a very low effective concentration (generally not higher than 0.1 mol/ℓ) as a system which complies with a demand of wide latitude. In this method, however, the concentration of sulfite ion in the developing solutions is low so that the developing solutions are very unstable against oxidation by air and must be used with a great effort and device to keep stable solution activity. Further, processing speed is remarkably slow and working efficiency is low.

[0006] It has been demanded to provide image forming systems which solve a problem with regard to the unstable image formation of the aforesaid developing methods (lith type development systems), allows photographic materials to be processed with processing solutions having good shelf stability and give ultra-high-contrast photographic characteristics. There have been suggested systems, as one type of such image forming systems, in which surface latent image type silver halide photographic materials containing specific acylhydrazine compounds are processed with developing solutions having a pH of 11.0 to 12.3, containing sulfite preservative in an amount of at least 0.15 mol/ℓ and having good shelf stability to thereby form ultra-high-contrast negative images having γ of exceeding 10 as described in U.S. Patents 4,166,742, 4,168,977, 4,221,857, 4,224,401, 4,243,739, 4,272,606 and 4,311,781. These new image forming systems are characterized by that silver iodobromide and silver chloroiodobromide can also be used, while only silver chlorobromide having a high silver chloride content can be used in conventional ultra-high-contrast image formation.

[0007] Though the aforesaid image forming systems have excellent performances with regard to sharp halftone dot quality, processing stability, rapidity and original reproducibility, it is demanded to provide systems which are stable and have improved original reproducibility to comply with the diversity of prints in recent years.

[0008] An improvement in working efficiency is intended by carrying out working under much lighter environmental conditions in page make-up stage and dot to dot work stage. Hence, light-sensitive materials for making plates and exposure printers are being developed which are capable of being handled under environmental conditions which are allowed to be substantially called daylight.

[0009] The term "light-sensitive material for daylight" as used herein refers to light-sensitive materials which allow light containing no ultraviolet light component and having a wavelength of substantially at least 400 nm as safelight to be used stably over a long period of time.

[0010] Light-sensitive materials for daylight used in page make-up stage and dot to dot work stage are light-sensitive materials which are utilized for carrying out negative image/positive image conversion or positive image/positive image conversion by using processed films having letters or halftone images formed thereon as the originals, bringing these originals into closely contact with light-sensitive materials for dot to dot work and exposing them. The light-sensitive materials are demanded to have such performances that (1) negative image/positive image conversion of halftone images, line works and letter images can be made according to dot area, line width and letter image width; and (2) the tone control of halftone images and the line width control of letter line images can be made.

[0011] Light-sensitive materials for daylight dot to dot work which comply with the requirements have been provided.

[0012] However, there is a disadvantage that in the formation of superimposed letter image by overlay contact work which requires an image conversion operation of a high order, the quality of superimposed letter image is deteriorated in conventional methods which utilize daylight dot to dot work using light-sensitive materials for daylight in comparison with methods which utilize darkroom dot to dot work using light-sensitive material for conventional darkroom dot to dot work.

[0013] A method for forming superimposed letter image by overlay contact work are illustrated below in a little more detail.

[0014] Referring to Fig. 1, a film (b) having letters or line works formed thereon (the line original) and a film (d) having halftone image formed thereon (the halftone original) are laminated onto transparent or semitransparent laminating bases (a) and (c) (generally a polyethylene terephthalate film of about 100 µm being used), respectively. The resulting laminates are superposed with each other to obtain the original. The emulsion surface of a light-sensitive material (e) for dot to dot work is brought into closely contact with the halftone original (d), and exposure is then carried out.

[0015] After exposure, development is carried out to form transparent line work portions in halftone images.

[0016] An important matter in the method of forming such superimposed letter image is that negative image/ positive image conversion is ideally made according to the dot area and printing image width of each of the halftone original and the line original. However, the halftone original in directly close contact with the emulsion surface of the light-sensitive material for dot to dot work is exposed, while the line original is exposed through the laminating base (c) and the halftone original (d) interposed between the line original and the light-sensitive material for dot to dot work as shown in Fig. 1.

[0017] Hence, when there is applied sufficient exposure amount to faithfully make negative image/positive image conversion of the halftone original, the line original is to be subjected out-of-focus exposure through the spacers of the laminating base (c) and the halftone original (d) and the printing image width of the transparent line work portions becomes narrow. The deterioration of the quality of the superimposed letter image is caused thereby.

[0018] Method for solving the above-described problem in the ultra-high-contrast image forming systems are disclosed in JP-A-62-80640 (the term "JP-A" as used herein means an "unexamined published Japanese patent application"), JP-A-62-235938, JP-A-62-235939, JP-A-63-104046, JP-A-63-103235, JP-A-63-296031, JP-A-63-314541 and JP-A-64-13545. However, these methods are still insufficient to solve the problem, and it is demanded to develop improved methods.

[0019] JP-A-61-213847, U.S. Patent 4,684,604, JP-A-64-72140 and JP-A-64-72139 disclose the use of redox compounds which release a development restrainer when oxidized in silver halide photographic materials.

[0020] However, when the redox compounds are used in negative type ultra-high-contrast photographic materials containing hydrazine derivatives, various troubles are caused and hence the characteristics of the redox compounds cannot be fully utilized.

[0021] One of the trouble is that high contrast is deteriorated, and the other is that an effect of improving original reproducibility cannot be sufficiently obtained.

[0022] U.S. Patent 4,569,904 discloses a method for developing an exposed negative silver halide photographic light-sensitive material in the presence of a hydrazine derivative, comprising treating the material with a developer containing at least a developing agent, not less than 0.25 mol/l of a sulfite preservative and not less than 0.1 mol/l of a compound having an acid dissociation constant of from 1x10^-11 to 3x10^-13, and having a pH of from 10.5 to 12.3.

[0023] European Patent 21,005 (corresponding to JP-A-55-153939) discloses an aqueous hardening-fixing bath containing 0.015 to 0.1 mol/l of a water-soluble aluminum salt and a formiate for processing an exposed and developed photographic material.

[0024] JP-A-60-136741 discloses a method for processing a photosensitive material wherein an exposed photosensitive silver halide material is developed with a developing solution having a pH of from 10.7 to 12.5 and containing dihydroxybenzenes and optionally 3-pyrazolidones, and fixed with a fixing solution containing an aluminum salt.

[0025] JP-A-48-5502 discloses the use of phenol compounds in a photographic material.

[0026] An object of the present invention is to provide a stable rapid processing method of a silver halide photographic material used in the field of photomechanical process, particularly a photographic material having excellent original reproducibility in the photographing of the letter original and the halftone original.

[0027] Another object of the present invention is to provide a stable rapid processing method of a photographic material which gives superimposed letter image of excellent quality and is a light-sensitive material for contact dot to dot work, which is capable of being handled under environmental conditions which are allowed to be called daylight used in the field of photomechanical process.

DISCLOSURE OF THE INVENTION

[0028] The objects of the present invention have been achieved by providing a processing method of a silver halide photographic material characterized by processing a light-sensitive silver halide photographic material containing a hydrazine nucleating agent and a redox compound capable of releasing a development restrainer when oxidized, with a developing solution containing a phenol having an acid dissociation constant of 1x10^-11 to 3x10^-13 in an amount of at least 0.05 mol/l and then processing it with an acid hardening fixer containing a water-soluble aluminum compound.

[0029] Preferred examples of said redox compound include compounds having hydroquinones, catechols, naphthohydroquinones, aminophenols, pyrazolidones, hydrazines, hydroxylamines and reductones as redox groups. More preferred redox compounds are compounds having hydrazines as redox groups. Particularly preferred examples of the redox compounds are compounds represented by the following general formula (I). The compounds are compounds which are oxidized by the oxidation products of developing agents and then release a development restrainer by a nucleophilic reaction, a hydrolysis reaction or an elimination reaction.

wherein both A₁ and A₂ represent hydrogen atom, or one of A₁ and A₂ represents hydrogen atom and the other represents a residue of a sulfinic acid or

wherein R₀ represents an alkyl group, an alkenyl group, an aryl group, an alkoxy group or an aryloxy group and ℓ represents 1 or 2; A₁ may be combined together with (̵Time)̵_t to form a ring; Time represents a divalent linking group; t represents 0 or 1; PUG represents a development restrainer; V represents carbonyl group,

a sulfonyl group, a sulfoxy group,

(wherein R₁ represents an alkoxy group or an aryloxy group), an iminomethylene group or a thiocarbonyl group; and R represents an aliphatic group, an aromatic group or a heterocyclic group.

[0030] The compounds of general formula (I) are illustrated in more detail below.

[0031] In general formula (I), A₁ and A₂ preferably are each hydrogen atom, an alkylsulfonyl group having not more than 20 carbon atoms, an arylsulfonyl group having not more than 20 carbon atoms (preferably phenylsulfonyl group or a substituted phenylsulfonyl group wherein the sum of Hammett's substituent constant is at least -0.5) or

[R₀ is preferably a straight-chain, branched or cyclic alkyl group having not more than 30 carbon atoms, an alkenyl group, an aryl group (preferably phenyl group or a substituted phenyl group wherein the sum of Hammett's substituent constant is at least -0.5), an alkoxy group (e.g., ethoxy group) or an aryloxy group (preferably a monocyclic aryloxy group). These groups may have one or more substituent groups which may be further substituted, and examples of said substituent groups include an alkyl group, an aralkyl group, an alkenyl group, an alkinyl group, an alkoxy group, an aryl group, a substituted amino group, an acylamino group, a sulfonylamino group, a ureido group, a urethane group, an aryloxy group, a sulfamoyl group, a carbamoyl group, an alkylthio group, an arylthio group, a sulfonyl group, a sulfinyl group, hydroxyl group, a halogen atom, cyano group, sulfo group, carboxyl group, an aryloxycarbonyl group, an acyl group, an alkoxycarbonyl group, an acyloxy group, a carbonamido group, a sulfonamido group, nitro group, an alkylthio group and an arylthio group.

[0032] Examples of the residue of a sulfinic acid represented by A₁ and A₂ include concretely those described in U.S. Patent 4,478,928.

[0033] Most preferably, A₁ and A₂ are each hydrogen atom.

[0034] Time is a divalent linking group and may have a timing controlling function, and t is 0 or 1. When t=0, PUG is bonded directly to V.

[0035] The divalent linking group represented by Time is a group which releases PUG from Time-PUG through one-stage reaction or multi-stage reaction, said Time-PUG being released from the oxidant of the parent redox nucleus.

[0036] Examples of the divalent linking group represented by Time include those which release a photographically useful group (PUG) by the intramolecular ring closure reaction of p-nitrophenoxy derivatives as described in U.S. Patent 4,248,962 (JP-A-54-145135); those which release PUG by intramolecular ring closure reaction after ring cleavage as described in U.S. Patents 4,310,612 (JP-A-55-53330) and 4,358,252; those which release PUG with the formation of acid anhydrides by the intramolecular ring closure reaction of carboxyl group of monoesters of succinic acid or analogs thereof as described in U.S. Patents 4,330,617, 4,446,216 and 4,483,919, and JP-A-59-121328; those which release PUG with the formation of quinomonomethane or analogs thereof by the electron transfer of an aryloxy group or a heterocyclic oxy group through conjugated double bond as described in U.S. Patents 4,409,323 and 4,421,845, Research Disclosure No. 21,228 (December 1981), U.S. Patent 4,416,977 (JP-A-57-135944), JP-A-58-209736 and JP-A-58-209738; those which release PUG from the γ-position of enamine by the electron transfer of the moiety having an enamine structure of nitrogen-containing heterocyclic rings as described in U.S. Patent 4,420,554 (JP-A-57-136640), JP-A-57-135945, JP-A-57-188035, JP-A-58-98728 and JP-A-58-209737; those which release PUG by the intramolecular ring closure reaction of oxy group formed by electron transfer to carbonyl group conjugated with nitrogen atom of a nitrogen-containing heterocyclic ring as described in JP-A-57-56837; those which release PUG with the formation of aldehydes as described in U.S. Patent 4,146,396 (JP-A-52-90932), JP-A-59-93442 and JP-A-59-75475; those which release PUG with the decarboxylation of carboxyl group as described in JP-A-51-146828, JP-A-57-179842 and JP-A-59-104641; those which has a structure of

(wherein R_a and R_b are each a substituent group) and release PUG with the formation of aldehydes subsequent to decarboxylation; those which release PUG with the formation of an isocyanate as described in JP-A-60-7429; and those which release PUG by coupling reaction with the oxidants of color developing agents as described in U.S. Patent 4,438,193.

[0037] Concrete examples of the divalent linking group represented by Time are described in JP-A-61-236549 and JP-A-1-269936. Preferred examples thereof include the following groups.

[0038] In the following formulas, (*) represents a position where (̵Time

-PUG is bonded to V in general formula (I) and (*)(*) represents a position where (̵Time)̵_t is bonded to PUG.

































































        T - (33)    (∗) - O - CH₂ - (∗) (∗)

[0039] PUG represents a group having a development-restraining effect as (̵Time

-PUG or PUG.

[0040] Development restrainers represented by PUG or (̵Time

-PUG are conventional development restrainers having hetero-atom and are bonded through hetero-atom. For example, these development restrainers are described in C.E.K. Mees and T.H. James, The Theory of the Photographic Process, third edition, pages 344-346 (1966 Macmillan). The development restrainers include concretely mercaptotetrazoles, mercaptotriazoles, mercaptoimidazoles, mercaptopyrimidines, mercaptobenzimidazoles, mercaptobenzthiazoles, mercaptobenzoxazoles, mercaptothidiazoles, benztriazoles, benzimidazoles, indazoles, adenines, guanines, tetrazoles, tetraataindenes, triazaindenes and mercaptoaryls.

[0041] The development restrainers represented by PUG may have one or more substituent groups which may be further substituted.

[0042] Examples of the substituent groups include an alkyl group, an aralkyl group, an alkenyl group, an alkinyl group, an alkoxy group, an aryl group, a substituted amino group, an acylamino group, a sulfonylamino group, a ureido group, a urethane group, an aryloxy group, a sulfamoyl group, a carbamoyl group, an alkylthio group, an arylthio group, a sulfonyl group, a sulfinyl group, hydroxyl group, a halogen atom, cyano group, sulfo group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an acyl group, an acyloxy group, a carbonamido group, a sulfonamido group, carboxyl group, sulfoxy group, a phosphono group, a phosphinyl group, a phosphoric amido group and nitro group.

[0043] Preferred substituent groups are nitro group, sulfo group, carboxyl group, a sulfamoyl group, a phosphono group, a phosphinyl group and a sulfonamido group.

[0044] Typical development restrainers include the following compounds.

1. Mercaptotetrazole Derivatives

[0045] 

(1) 1-Phenyl-5-mercaptotetrazole

(2) 1-(4-Hydroxyphenyl)-5-mercaptotetrazole

(3) 1-(4-Aminophenyl)-5-mercaptotetrazole

(4) 1-(4-Carboxyphenyl)-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

(10) 1-(3,5-Dicarboxyphenyl)-5-mercaptotetrazole

(11) 1-(4-Methoxyphenyl)-5-mercaptotetrazole

(12) 1-(2-Methoxyphenyl)-5-mercaptotetrazole

(13) 1-[4-(2-Hydroxyethoxy)phenyl]-5-mercaptotetrazole

(14) 1-(2,4-Dichlorophenyl)-5-mercaptotetrazole

(15) 1-(4-Dimethylaminophenyl)-5-mercaptotetrazole

(16) 1-(4-Nitrophenyl)-5-mercaptotetrazole

(17) 1,4-Bis(5-mercapto-1-tetrazolyl)benzene

(18) 1-(a-Naphthyl)-5-mercaptotetrazole

(19) 1-(4-Sulfophenyl)-5-mercaptotetrazole

(20) 1-(3-Sulfophenyl)-5-mercaptotetrazole

(21) 1-(β-Naphthyl)-5-mercaptotetrazole

(22) 1-Methyl-5-mercaptotetrazole

(23) 1-Ethyl-5-mercaptotetrazole

(24) 1-Propyl-5-mercaptotetrazole

(25) 1-Octyl-5-mercaptotetrazole

(26) 1-Dodecyl-5-mercaptotetrazole

(27) 1-Cyclohexyl-5-mercaptotetrazole

(28) 1-Palmityl-5-mercaptotetrazole

(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) 3-(5-Mercapto-1-tetrazole)ethyltrimethylammonium chloride

(34) 1-(3-Phenoxycarbonylphenyl)-5-mercaptotetrazole

(35) 1-(3-Maleinimidophenyl)-6-mercaptotetrazole

2. Mercaptotriazole Derivatives

[0046] 

(1) 4-Phenyl-3-mercaptotriazole

(2) 4-Phenyl-5-methyl-3-mercaptotriazole

(3) 4,5-Diphenyl-3-mercaptotriazole

(4) 4-(4-Carboxyphenyl)-3-mercaptotriazole

(5) 4-Methyl-3-mercaptotriazole

(6) 4-(2-Dimethylaminoethyl)-3-mercaptotriazole

(7) 4-(a-Naphthyl)-3-mercaptotriazole

(8) 4-(4-sulfophenyl)-3-mercaptotriazole

(9) 4-(3-Nitrophenyl)-3-mercaptotriazole

3. Mercaptoimidazole Derivatives

[0047] 

(1) 1-Phenyl-2-mercaptoimidazole

(2) 1,5-Diphenyl-2-mercaptoimidazole

(3) 1-(4-Carboxyphenyl)-2-mercaptoimidazole

(4) 1-(4-Hexylcarbamoyl)-2-mercaptoimidazole

(5) 1-(3-Nitrophenyl)-2-mercaptoimidazole

(6) 1-(4-Sulfophenyl)-2-mercaptoimidazole

4. Mercaptopyrimidine Derivatives

[0048] 

(1) Thiouracil

(2) Methylthiouracyl

(3) Ethylthiouracil

(4) Propylthiouracil

(5) Nonylthiouracil

(6) Aminothiouracil

(7) Hydroxythiouracil

5. Mercaptobenzimidazole Derivatives

[0049] 

(1) 2-Mercaptobenzimidazole

(2) 5-Carboxy-2-mercaptobenzimidazole

(3) 5-Amino-2-mercaptobenzimidazole

(4) 5-Nitro-2-mercaptobenzimidazole

(5) 5-Chloro-2-mercaptobenzimidazole

(6) 5-Methoxy-2-mercaptobenzimidazole

(7) 2-Mercaptonaphthoimidazole

(8) 2-Mercapto-5-sulfobenzimidazole

(9) 1-(2-Hydroxyethyl)-2-mercaptobenzimidazole

(10) 5-Caproamido-2-mercaptobenzimidazole

(11) 5-(2-Ethylhexanoylamino)-2-mercaptobenzimidazole

6. Mercaptothiadiazole Derivatives

[0050] 

(1) 5-Methylthio-2-mercapto-1,3,4-thiadiazole

(2) 5-Ethylthio-2-mercapto-1,3,4-thiadiazole

(3) 5-(2-Dimethylaminoethylthio)-2-mercapto-1,3,4-thiadiazole

(4) 5-(2-Carboxypropylthio)-2-mercapto-1,3,4-thiadiazole

(5) 2-Phenoxycarbonylmethylthio-2-mercapto-1,3,4-thiadiazole

7. Mercaptobenzthiazole Derivatives

[0051] 

(1) 2-Mercaptobenzthiazole

(2) 5-Nitro-2-mercaptobenzthiazole

(3) 5-Carboxy-2-mercaptobenzthiazole

(4) 5-Sulfo-2-mercaptobenzthiazole

8. Mercaptobenzoxazole Derivatives

[0052] 

(1) 2-Mercaptobenzoxazole

(2) 5-Nitro-2-mercaptobenzoxazole (3) 5-Carboxy-2-mercaptobenzoxazole

(4) 5-Sulfo-2-mercaptobenzoxazole

9. Benztriazole Derivatives

[0053] 

(1) 5,6-Dimethylbenztriazole

(2) 5-Butylbenztriazole

(3) 5-Methylbenztriazole

(4) 5-Chlorobenztriazole

(5) 5-Bromobenztriazole

(6) 5,6-Dichlorobenztriazole

(7) 4,6-Dichlorobenztriazole

(8) 5-Nitrobenztriazole

(9) 4-Nitro-6-chlorobenztriazole

(10) 4,5,6-Trichlorobenztriazole

(11) 5-Carboxybenztriazole

(12) Na salt of 5-sulfobenztriazole

(13) 5-Methoxycarbonylbenztriazole

(14) 5-Aminobenztriazole

(15) 5-Butoxybenztriazole

(16) 5-Ureidobenztriazole

(17) Benztriazole

(18) 5-Phenoxycarbonylbenztriazole

(19) 5-(2,3-Dichloropropyloxycarbonyl)benztriazole

10. Benzimidazole Derivatives

[0054] 

(1) Benzimidazole

(2) 5-Chlorobenzimidazole

(3) 5-Nitrobenzimidazole

(4) 5-n-Butylbenzimidazole

(5) 5-Methylbenzimidazole

(6) 4-Chlorobenzimidazole

(7) 5,6-Dimethylbenzimidazole

(8) 5-Nitro-2-(trifluoromethyl)benzimidazole

11. Indazole Derivatives

[0055] 

(1) 5-Nitroindazole

(2) 6-Nitroindazole

(3) 5-Aminoindazole

(4) 6-Aminoindazole

(5) Indazole

(6) 3-Nitroindazole

(7) 5-Nitro-3-chloroindazole

(8) 3-Chloro-5-nitroindazole

(9) 3-Carboxy-5-nitroindazole

12. Tetrazole Derivatives

[0056] 

(1) 5-(4-Nitrophenyl)tetrazole

(2) 5-Phenyltetrazole

(3) 5-(3-Carboxyphenyl)tetrazole

13. Tetraazaindene Derivatives

[0057] 

(1) 4-Hydroxy-6-methyl-5-nitro-1,3,3a,7-tetraazaindene

(2) 4-Mercapto-6-methyl-5-nitro-1,3,3a,7-tetraazaindene

14. Mercaptoaryl Derivatives

[0058] 

(1) 4-Nitrothiophenol

(2) Thiophenol

(3) 2-Carboxythiophenol

[0059] V is carbonyl group,

a sulfonyl group, a sulfoxy group,

(wherein R₁ is an alkoxy group or an aryloxy group), an iminomethylene group or a thiocarbonyl group. Preferably, V is carbonyl group.

[0060] The aliphatic group represented by R is a straight-chain, branched or cyclic alkyl, alkenyl or alkinyl group having preferably 1 to 30 carbon atoms, particularly preferably 1 to 20 carbon atoms. The branched alkyl group may be cyclized so as to form a saturated heterocyclic ring having one or more heteroatoms as the members of the ring.

[0061] Examples of the aliphatic group include methyl group, t-butyl group, n-octyl group, t-octyl group, cyclohexyl group, hexenyl group, pyrrolidyl group, tetrahydrofuryl group and n-dodecyl group.

[0062] The aromatic group is a monocyclic or bicyclic aryl group such as phenyl group and naphthyl group.

[0063] The heterocyclic group is preferably a 3-membered to 10-membered saturated or unsaturated heterocyclic ring containing at least one atom of N, O and S atoms and may be a monocyclic ring or a condensed ring with other aromatic ring or heterocyclic ring. Preferably, the heterocyclic ring is a 5-membered or 6-membered aromatic heterocyclic ring such as pyridine ring, imidazolyl group, quinolinyl group, benzimidazolyl group, pyrimidinyl group, pyrazolyl group, isoquinolinyl group, benzthiazolyl group and thiazolyl group.

[0064] R may have one or more substituent groups which may be further substituted.

[0065] Examples of the substituent groups include an alkyl group, an aralkyl group, an alkenyl group, an alkinyl group, an alkoxy group, an aryl group, a substituted amino group, an acylamino group, a sulfonylamino group, a ureido group, a urethane group, an aryloxy group, a sulfamoyl group, a carbamoyl group, an alkylthio group, an arylthio group, a sulfonyl group, a sulfinyl group, hydroxyl group, a halogen atom, cyano group, sulfo group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an acyl group, an acyloxy group, a carbonamido group, a sulfonamido group, carboxy group and phosphoric amido group.

[0066] In general formula (I), R or (̵Time

-PUG may have a ballast group conventionally used in non-mobile photographic additives such as couplers or a group which accelerate the adsorption of the compounds of general formula (I) on silver halide.

[0067] The ballast group is an organic group which give sufficient molecular weight so that the compounds of general formula (I) are substantially not allowed to be diffused in other layers or processing solutions. The ballast group is composed of an alkyl group, an aryl group, a heterocyclic group, an ether group, a thioether group, an amido group, a ureido group, a urethane group or a sulfonamido group singly or in combination. Preferred ballast group is a ballast group having a substituted benzene ring. Ballast groups having a branched alkyl group-substituted benzene ring are particularly preferred.

[0068] Concrete examples of the group which accelerate the adsorption of the compounds on silver halide include cyclic thioamido groups such as 4-thiazoline-2-thione, 4-imidazoline-2-thione, 2-thiohydantoin, rhodanine, thiobarbituric acid, tetrazoline-5-thione, 1,2,4-triazoline-3-thione, 1,3,4-oxazoline-2-thione, benzimidazoline-2-thione, benzoxazoline-2-thione, benzothiazoline-2-thione, thiotriazine and 1,3-imidazoline-2-thione, chain thioamido groups, aliphatic mercapto groups, aromatic mercapto groups, heterocyclic mercapto groups (when atom adjacent to carbon atom to which -SH group is bonded is nitrogen group, the group and said cyclic thioamido group exist in a tautomeric form and examples thereof include those described above), groups having disulfide bond, 5-membered to 6-membered nitrogen-containing heterocyclic groups comprising nitrogen, oxygen and/or sulfur and carbon atoms such as benztriazole, triazole, tetrazole, indazole, benzimidazole, imidazole, benzthiazole, thiazole, thiazoline, benzoxazole, oxazole, oxazoline, thiadiazole, oxathiazole, triazine and azaindene and heterocyclic quaternary salts such as benzimidazolium.

[0069] These groups may be substituted by one or more appropriate substituent groups.

[0070] Examples of the substituent groups include those already described above in the definition of the substituent groups for R.

[0071] Concrete examples of the compounds which can be used in the present invention include the following compounds.

[0072] The redox compounds used in the present invention are preferably used in an amount of 1.0×10^-7 to 1.0×10^-3 mol/m², preferably 1.0×10^-6 to 1.0×10^-4 mol/m².

[0073] The redox compounds can be used by dissolving them in appropriate water-miscible organic solvents such as alcohols (e.g., methanol, ethanol, propanol, fluorinated alcohols), ketones (e.g., acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide or methyl cellosolve.

[0074] The redox compounds may be used in the form of emulsified dispersions prepared by dissolving them in oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate with an auxiliary solvent such as ethyl acetate or cyclohexanone and forming mechanically the emulsified dispersions by well-known emulsifying dispersion method. Alternatively, the redox compounds may be used by dispersing the powder thereof in water by using a ball mill, a colloid mill or ultrasound by well-known emulsifying dispersion method.

[0075] A layer containing the redox compound used in the present invention may be provided above or under a light-sensitive emulsion layer containing a hydrazine nucleating agent. The layer containing the redox compound may contain further light-sensitive or light-insensitive silver halide emulsion grains. An interlayer containing gelatin or a synthetic polymer (e.g., polyvinyl acetate, polyvinyl alcohol) may be provided between the layer containing the redox compound and the light-sensitive emulsion layer containing the hydrazine nucleating agent.

[0076] The hydrazine nucleating agent (hereinafter referred to as hydrazine derivative) used in the present invention is a compound which exhibits a function capable of fogging silver halide by a nucleophilic reaction, a hydrolysis reaction or an elimination reaction after the compound is oxidized by the oxidation product of a developing agent. Concretely, compounds represented by the following general formula (II) are preferred.

wherein R₁ represents an aliphatic group or an aromatic group; R₂ represents hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a carbamoyl group or an oxycarbonyl group; G₁ represents carbonyl group, a sulfonyl group, a sulfoxy group, a group of

or an iminomethylene group; and both A₁ and A₂ are hydrogen atom or one of A₁ and A₂ represents hydrogen atom and the other represents a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group or a substituted or unsubstituted acyl group.

[0077] In general formula (II), the aliphatic group represented by R₁ is preferably a straight-chain, branched or cyclic alkyl group having preferably 1 to 30 carbon atoms, particularly preferably 1 to 20 carbon atoms. The branched alkyl group may be cyclized so as to form a saturated heterocyclic ring having one or more heteroatoms as the members of the ring. The alkyl group may have one or more substituent groups such as an aryl group, an alkoxy group, a sulfoxy group, a sulfonamido group and a carbonamido group.

[0078] The aromatic group represented by R₁ in general formula (II) is preferably a monocyclic or bicyclic aryl or unsaturated heterocyclic group. The unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a hetero-aryl group.

[0079] Examples of the aromatic group include benzene ring, naphthalene ring, pyridine ring, pyrimidine ring, imidazole ring, pyrazole ring, quinoline ring, isoquinoline ring, benzimidazole ring, thiazole ring and benzthiazole ring. Among them, groups having benzene ring are preferred.

[0080] Particularly preferably, R₁ is an aryl group.

[0081] The aryl group or the unsaturated heterocyclic represented by R₁ may be substituted. Typical examples of substituent groups include an alkyl group, an aralkyl group, an alkenyl group, an alkinyl group, an alkoxy group, an aryl group, a substituted amino group, an acylamino group, a sulfonylamino group, a ureido group, a urethane group, an aryloxy group, a sulfamoyl group, a carbamoyl group, an alkylthio group, an arylthio group, a sulfonyl group, a sulfinyl group, hydroxyl group, a halogen atom, cyano group, sulfo group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an acyl group, an alkoxycarbonyl group, an acyloxy group, a carbonamido group, a sulfonamido group, carboxyl group, phosphoric amido group, a diacylamino group and an imido group. Preferred substituent groups are a straight-chain, branched or cyclic alkyl group (having preferably 1 to 20 carbon atoms), an aralkyl group (preferably, a monocyclic or bicyclic group having an alkyl portion of 1 to 3 carbon atoms), an alkoxy group (having preferably 1 to 20 carbon atoms), a substituted amino group (preferably an amino group substituted by an alkyl group having 1 to 20 carbon atoms), an acylamino group (having preferably 2 to 30 carbon atoms), a sulfonamido group (having preferably 1 to 30 carbon atoms), a ureido group (having preferably 1 to 30 carbon atoms), a phosphoric amido group (having preferably 1 to 30 carbon atoms), etc.

[0082] The alkyl group represented by R₂ in general formula (II) is preferably an alkyl group having 1 to 4 carbon atoms which may be substituted. Examples of the substituent groups include a halogen atom, cyano group, carboxy group, sulfo group, an alkoxy group, phenyl group and a sulfonyl group.

[0083] The aryl group is preferably a monocyclic or bicyclic group such as a group having benzene ring. The aryl group may be substituted. Examples of substituent groups include a halogen atom, an alkyl group, cyano group, carboxyl group, sulfo group and a sulfonyl group.

[0084] The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms and may be substituted by a halogen atom or an aryl group.

[0085] The aryloxy group is preferably a monocyclic group and may be substituted by e.g. a halogen atom.

[0086] The amino group is preferably unsubstituted amino group, an alkylamino group having 1 to 10 carbon atoms or an arylamino group. The amino group may be substituted by an alkyl group, a halogen atom, cyano group, nitro group or carboxy group.

[0087] The carbamoyl group is preferably unsubstituted carbamoyl group, an alkylcarbamoyl group having 1 to 10 carbon atoms or an arylcarbamoyl group. The carbamoyl group may be substituted by an alkyl group, a halogen atom, cyano group or carboxy group.

[0088] The oxycarbonyl group is preferably an alkoxycarbonyl group having 1 to 10 carbon atoms or aryloxycarbonyl group. The oxycarbonyl group may be substituted by an alkyl group, a halogen atom, cyano group or nitro group.

[0089] Among the groups represented by R₂, there are preferred hydrogen atom, an alkyl group (e.g., methyl group, trifluoromethyl group, 3-hydroxypropyl group, 3-methanesulfonamidopropyl group, phenylsulfonylmethyl group), an aralkyl group (e.g., o-hydroxybenzyl group) and an aryl group (e.g., phenyl group, 3,5-dichlorophenyl group, o-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group), with hydrogen atom being particularly preferred when G₁ is carbonyl group.

[0090] When G₁ is sulfonyl group, R₂ is preferably an alkyl group (e.g., methyl group), an aralkyl group (e.g., o-hydroxyphenylmethyl group), an aryl group (e.g., phenyl group) or a substituted amino group (e.g., dimethylamino group).

[0091] When G₁ is sulfoxy group, R₂ is preferably diaminobenzyl group or methylthiobenzyl group. When G₁ is a group of

R₂ is preferably methoxy group, ethoxy group, butoxy group, phenoxy group or phenyl group with phenoxy group being most preferred.

[0092] When G₁ is an N-substituted or unsubstituted iminomethylene group, R₂ is preferably methyl group, ethyl group or a substituted or unsubstituted phenyl group.

[0093] Examples of substituent groups for R₂ include those already described above in the definition of the substituent groups for R₁.

[0094] Most preferably, G₁ in general formula (II) is carbonyl group.

[0095] R₂ may be a group which cause the cleavage of G₁-R₂ moiety from the remainder of the molecule and allow a cyclization reaction to take place to thereby form a cyclic structure containing the atoms of the -G₁-R₂ moiety. Concretely, such a group can be represented, for example, by the following general formula (a).

        General Formula (a)    -R₃-Z₁

wherein Z₁ is a group which nucleophilically attacks G₁ to cause the cleavage of a G₁-R₂-Z₁ moiety from the remainder of the molecule, and R₃ is a group which is formed by removing one hydrogen atom from R₂ and enables the nucleophilic attack of Z₁ on G₁ to be made whereby a ring structure can be formed by G₁, R₃ and Z₁.

[0096] In more detail, Z₁ is a group which easily cause a nucleophilic reaction with G₁ and enables a group of R₁-N=N to be cleaved from G₁ when the following reaction intermediate R₁-N=N-G₁-R₃-Z₁ is formed by the oxidation of the hydrazine compound of e.g. general formula (II). Concretely, Z₁ may be a functional group such as OH, SH, NHR₄ (wherein R₄ is hydrogen atom, an alkyl group, an aryl group, -COR₅ or -SO₂R₅, and R₅ is hydrogen atom, an alkyl group, an aryl group, a heterocyclic group) or COOH which can be directly reacted with G₁ (OH, SH, NHR₄ and -COOH may be temporarily protected with an alkyl group so as to allow these groups to be reformed by hydrolysis), or a functional group such as

(wherein R₆ and R₇ are each hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group) which can be reacted with G₁ in the presence of a nucleophilic reagent such as hydroxyl ion or a sulfite ion.

[0097] The ring formed by G₁, R₃ and Z₁ is preferably a 5-membered or 6-membered ring.

[0098] Among the groups represented by general formula (a), groups represented by the following general formulas (b) and (c) are preferred.

wherein R_b¹ to R_b⁴ may be the same or different groups and each is hydrogen atom, an alkyl group (having preferably 1 to 12 carbon atoms), an alkenyl group (having preferably 2 to 12 carbon atoms) or an aryl group (having preferably 6 to 12 carbon atoms); B is an atomic group required for the formation of a 5-membered or 6-membered ring which may be substituted; and m and n are each 0 or 1 and (n+m) is 1 or 2.

[0099] Examples of the 5-membered or 6-membered ring formed by B include cyclohexene ring, cycloheptene ring, benzene ring, naphthalene ring, pyridine ring and quinoline ring.

[0100] Z₁ is as defined above in general formula (a).

wherein R_c¹ and R_c² may be the same or different groups and each is hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a halogen atom; R_c³ is hydrogen atom, an alkyl group, an alkenyl group or an aryl group; p is 0, 1 or 2; q is 1 to 4; and R_c¹, R_c² and R_c³ may be combined together to form a ring, so long as the ring has a structure which allows the intramolecular nucleophilic attack of Z₁ on G₁ to be made.

[0101] R_c¹ and R_c² are each preferably hydrogen atom, a halogen atom or an alkyl group, and R_c³ is preferably an alkyl group or an aryl group.

[0102] Preferably, q is 1 to 3. When q is 1, p is 1 or 2. When q is 2, p is 0 or 1 and when q is 3, p is 0 or 1. When q is 2 or 3, CR_c¹R_c² may be the same or different groups.

[0103] Z₁ is as defined above in general formula (a).

[0104] A₁ and A₂ are preferably each hydrogen atom, an alkylsulfonyl group having not more than 20 carbon atoms, an arylsulfonyl group having not more than 20 carbon atoms (preferably phenylsulfonyl group or a substituted phenylsulfonyl group wherein the sum of Hammett's substituent constant is at least -0.5) or an acyl group having not more than 20 carbon atoms [preferably benzoyl group, a substituted benzoyl group wherein the sum of Hammett's substituent constant is at least -0.5 or a straight-chain, branched or cyclic unsubstituted or substituted aliphatic acyl group (examples of substituent groups include a halogen atom, an ether group, a sulfonamido group, a carbonamido group, hydroxyl group, carboxy group and sulfo group)].

[0105] Most preferably, A₁ and A₂ preferably are each hydrogen atom.

[0106] R₁ or R₂ in general formula (II) may have a ballast group therein conventionally used in non-mobile photographic additives such as couplers. The ballast group is a group having at least 8 carbon atoms which is relatively inert to photographic characteristics. The ballast group can be chosen from among an alkyl group, an alkoxy group, phenyl group, an alkylphenyl group, phenoxy group and an alkylphenoxy group.

[0107] A group which increases adsorption on the surfaces of silver halide grains may be incorporated into the structure of R₁ or R₂ in general formula (II). Examples of such adsorption groups include groups such as a thiourea group, a heterocyclic group, a thioamido group, a mercaptoheterocyclic group and a triazole group described in U.S. Patents 4,385,108 and 4,459,347, JP-A-59-195233, JP-A-59-200231, JP-A-59-201045, JP-A-59-201046, JP-A-59-201407, JP-A-59-201048, JP-A-59-201049, JP-A-61-170733, JP-A-61-270744, JP-A-62-948, JP-A-63-234244 and JP-A-63-234246.

[0108] Concrete examples of the compounds represented by general formula (II) include the following compounds.

[0109] In addition to the above-described hydrazine derivatives, there can be used in the present invention compounds described in Research Disclosure, item 23516 (page 346, November 1983) and the literature cited therein, U.S. Patents 4,080,207, 4,269,929, 4,276,364, 4,278,748, 4,385,108, 4,459,347, 4,560,638 and 4,478,928, U.K. Patent 2,011,391B, JP-A-60-179734, JP-A-62-270948, JP-A-63-29751, JP-A-61-170733, JP-A-61-270744, JP-A-62-948, European Patent 217,310, U.S. Patent 4,686,167, JP-A-62-178246, JP-A-63-234244, JP-A-63-234245, JP-A-63-234246, JP-A-63-294552 and JP-A-63-306438.

[0110] It is preferred that the hydrazine derivatives are contained in silver halide emulsion layers of the photographic material. If desired, the hydrazine derivatives may be contained in light-insensitive hydrophilic colloid layers (e.g., protective layer, interlayer, filter layer, antihalation layer). Concretely, when the compounds to be used are water-soluble, they in the form of an aqueous solution are added to a hydrophilic colloid solution, and when the compounds are difficultly soluble in water, a solution thereof in a water-miscible organic solvent such as an alcohol, an ester or a ketone is added to the hydrophilic colloid solution. When the compounds are to be added to the silver halide emulsion layers, the addition may be made at any stage before coating after the commencement of chemical ripening, but it is preferred that the addition is made before coating after the completion of chemical ripening. It is particularly preferred that the compounds are added to coating solutions prepared for coating.

[0111] It is desirable that the optimum amount of the hydrazine derivative content is chosen according to the grain size and halogen composition of the silver halide emulsion, the method and degree of chemical sensitization, the relationship between the layer in which the compound is contained and the silver halide emulsion layer or the type of anti-fogging agent. Test methods for choosing the optimum amount are well known by those skilled in the art. The hydrazine derivatives are used in an amount of preferably 10^-6 to 1×10^-1 mol, particularly preferably 10^-5 to 4×10^-2 mol per mol of silver halide.

[0112] Silver halide emulsions which are used in the present invention may have any composition of e.g. silver chloride, silver bromide, silver chlorobromide, silver iodobromide or silver iodochlorobromide. However, silver iodobromide is preferred. The content of silver iodide is preferably not higher than 10 mol%, particularly preferably 0.1 to 3.5 mol%.

[0113] The mean grain size of silver halide used in the present invention is preferably fine grain size (e.g., not larger than 0.7 µm) and particularly preferably not larger than 0.5 µm. Though there is basically no limitation with regard to grain size distribution, monodisperse system is preferable. The term "monodisperse system" as used herein means that it is composed of grains at least 95% (in terms of weight or the number of grains) of which have a grain size of within mean grain size ±40%.

[0114] The silver halide grains in the photographic emulsions may have regular crystal form such as cube, octahedron, tetradecahedron or rhombic dodecahedron, particularly preferably cube or tetradecahedron, irregular crystal form such as sphere, plate or tabular form having an aspect ratio of 3 to 20 or a composite form of these crystal forms.

[0115] The interior and surface layer of the silver halide grain may be composed of a uniform phase or separate phases. Two or more kinds of silver halide emul sions separately prepared may be mixed and used.

[0116] Cadmium salt, sulfite, lead salt, thallium salt, rhodium salt or complex salt thereof, iridium salt or complex salt thereof may be allowed to coexist during the course of the formation of silver halide grains used in the present invention or the physical ripening thereof.

[0117] Silver halide particularly suitable for use in the present invention is a silver haloiodide which is prepared by allowing an iridium salt or a complex salt thereof in an amount of 10^-3 to 10^-5 mol per mol of silver to coexist and in which the silver iodide content on the surface of grain is higher than the average silver iodide content of grain. When an emulsion containing such a silver haloiodide is used, photographic characteristics having further higher sensitivity and high gamma value can be obtained.

[0118] It is preferred that an iridium salt in an amount described above is added before the completion of physical ripening, particularly during the course of the formation of grains in the above-described preparation of the silver halide emulsion.

[0119] The iridium salt used above is a water-soluble iridium salt or iridium complex salt. Examples thereof include iridium trichloride, iridium tetrachloride, potassium hexachloroiridate(III), potassium hexachloroiridate(IV) and ammonium hexachloroiridate(III).

[0120] The emulsion used in the present invention may not be subjected to chemical sensitization or may be subjected to chemical sensitization. Examples of chemical sensitization methods include conventional methods such as sulfur sensitization, reduction sensitization and gold sensitization. These methods may be used either alone or in combination. Preferred chemical sensitization method is sulfur sensitization.

[0121] Examples of sulfur sensitizing agents which can be used include sulfur compounds contained in gelatin and various sulfur compounds such as thiosulfates, thioureas, thiozoles and rhodanines. Concrete examples thereof are those described in U.S. Patents 1,574,944, 2,278,947, 2,410,689, 2,728,668, 3,501,313 and 3,656,955. Preferred sulfur compounds are thiosulfates and thiourea compounds. During chemical sensitization, pAg is preferably 8.3 or below, more preferably in the range of 7.3 to 8.0.

[0122] Good results can be obtained by a method using polyvinyl pyrrolidone in combination with thiosulfates as reported by Moisar, Klein Gelatione. Proc. Symp. 2nd, 301-309 (1970).

[0123] Typical example of noble metal sensitization method is gold sensitization method using gold compounds, particularly gold complex salts. In addition to gold compounds, other noble metal complex salts such as complex salts of platinum, palladium and iridium may be contained. Concrete examples thereof are described in U.S. Patent 2,448,060 and U.K. Patent 618,061.

[0124] Examples of reduction sensitizing agents which can be used include stannous salts, amines, formaminedisulfinic acid and silane compounds. Concrete examples of these compounds are described in U.S. Patents 2,487,850, 2,518,698, 2,983,609, 2,983,610 and 2,694,637.

[0125] Silver halide emulsion in the light-sensitive material used in the present invention may be composed of one kind of an emulsion or a combination of two or more kinds of emulsions (e.g., emulsions which are different in mean grain size, halogen composition or crystal habit or which are prepared under different chemical sensitization conditions).

[0126] When two kinds of emulsions are used, it is preferred from the viewpoint of rise in maximum density (Dmax) that two kinds of monodisperse emulsions which are different in mean grain size from each other are contained and smaller-size monodisperse grains are chemical-sensitized as described in JP-A-61-223734 and JP-A-62-90646. Sulfur sensitization is most preferred as the chemical sensitization method. The larger-size monodisperse emulsion may not be chemical-sensitized or may be chemical-sensitized. Since the larger-size monodisperse emulsion is generally liable to form black pepper, chemical sensitization is not conducted. When chemical sensitization is conducted, it is particularly desirable that chemical sensitization is slightly conducted to such an extent that black pepper is not formed. The term "slightly conducted" as used herein means that chemical sensitization time is shortened, temperature is lowered or the amount of the chemical sensitizing agent to be added is reduced in comparison with the chemical sensitization of the smaller-size grains. Though there is no particular limitation with regard to a difference in sensitivity between the larger-size monodisperse emulsion and the smaller-size monodisperse emulsion, the difference in terms of Alog E is 0.1 to 1.0, preferably 0.2 to 0.7 and it is preferred that the larger-size monodisperse emulsion has higher sensitivity.

[0127] The silver halide emulsion layer may be composed of a single layer or a multi-layer (e.g. two layers or three layers). When the emulsion layer is a multi-layer, different silver halide emulsions may be used, or the same emulsions may be used.

[0128] Gelatin can be advantageously used as a binder or protective colloid for photographic emulsions. However, other hydrophilic colloid can be used. Examples of usable hydrophilic colloid include protein such as gelatin derivatives, gelatin-grafted polymers, albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfate; saccharide derivatives such as sodium alginate and starch derivatives; and various synthetic hydrophilic high-molecular materials such as homopolymers, for example, polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole and polyvinyl pyrazole and copolymers thereof.

[0129] Examples of usable gelatin include lime-processed gelatin, acid-processed gelatin, gelatin hydrolyzate and enzymatic decomposate of gelatin.

[0130] Sensitizing dyes (e.g., cyanine dyes or merocyanine dyes) having absorption maximum in the visible region as described in JP-A-55-52050 (pages 45-53) can be added in the present invention, whereby the emulsions can be spectral-sensitized to longer wavelength side than sensitivity region inherent in silver halide.

[0131] These sensitizing dyes may be used either alone or in combination. A combination of sensitizing dyes are often used for the purpose of supersensitization. In addition to the sensitizing dyes, the emulsions may contain dyes which themselves do not have any spectral sensitization effect or substances which do substantially not absorb visible light, but exhibit supersensitization activity.

[0132] Useful sensitizing dyes, the combination of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in Research Disclosure, Vol. 176, No. 17643 (December 1978), item IV-J of page 23.

[0133] The light-sensitive materials used in the present invention may contain various compounds to prevent fogging from being caused during the course of the manufacturing, storage or processing of the light-sensitive materials or to stabilize photographic performance. Examples of the compounds which are known as anti-fogging agents or stabilizers include azoles such as benzthiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptotetrazoles, mercaptothiazoles, mercaptobenzthiazoles, mercaptothiazoles, aminotriazoles, benzthiazoles and nitrobenztriazoles; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as triazaindenes, tetraazaindenes (particularly, 4-hydroxy-substituted(1,3,3a,7)tetraazaindenes) and pantaazaindenes; and benzenethiosulfonic acid, benzenesulfinic acid and benzenesulfonamide. Among these compounds, benztriazoles (e.g., 5-methyl-benztriazole) and nitroindazoles (e.g., 5-nitroindazole) are preferred. These compounds may be contained in processing solutions. Further, compounds which release an inhibitor during development as described in JP-A-62-30243 may be contained as stabilizers or to inhibit black pepper from being formed.

[0134] The photographic materials used in the present invention may contain developing agents such as hydroquinone derivatives and phenidone derivatives for the purpose of using them as stabilizers, accelerators, etc.

[0135] The photographic emulsion layers and other hydrophilic colloid layers of the photographic materials used in the present invention may contain inorganic or organic hardening agents. Examples of the hardening agents include chromium salts (e.g., chromium alum, chromium acetate), aldehydes (e.g., formaldehyde, glutaraldehyde), N-methylol compounds (e.g., dimethylol urea), dioxane derivatives, active vinyl compounds (e.g., 1,3,5-triacrylol-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol), active halogen compounds (e.g., 2,4-dichloro-6-hydroxy-s-triazine) and mucohalogenic acids (e.g., mucochloric acid). These compounds may be used either alone or in combination.

[0136] The photographic emulsion layers and other hydrophilic colloid layers of the photographic materials used in the present invention may contain various surfactants as coating aid or for the purpose of imparting antistatic properties, improving slipperiness or emulsifying dispersion, preventing sticking from being caused or improving photographic characteristics (e.g., development acceleration, high contrast, sensitization).

[0137] Examples of the surfactants include nonionic surfactants such as saponin (steroid), alkylene oxide derivatives (e.g., polyethylene glycol, polyethylene glycol/polypropylene glycol condensate, polyethylene glycol alkyl ethers, polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides and polyethylene oxide adducts of silicone), glycidol derivatives (e.g., alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides) and alkyl esters such as fatty acid esters of polyhydric alcohols; anionic surfactants having an acid group such as carboxy group, sulfo group, phospho group, sulfuric ester group or phosphoric ester group such as salts of alkylcarboxylic acids, salts of alkylsulfonic acids, salts of alkylbenzenesulfonic acids, salts of alkylnaphthalenesulfonic acids, alkylsulfuric esters, alkylphosphoric esters, N-acyl-N-alkyltaurines, sulfosuccinic esters, sulfoalkylpolyoxyethylene alkylphenyl ethers and polyoxyethylene alkylphosphoric esters; amphoteric surfactants such as amino acids, aminoalkylsulfonic acids, aminoalkylsulfuric or phosphoric esters, alkylbetaines and amine oxides; and cationic surfactants such as alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium salts and imidazolium salts and aliphatic or heterocyclic phosphonium or sulfonium salts.

[0138] Surfactants which can be preferably used in the present invention are polyalkylene oxides having a molecular weight of not less than 600 described in JP-B-58-9412 (the term "JP-B" as used herein means an "examined Japanese patent publication").

[0139] It is preferred that fluorine-containing surfactants described in JP-A-60-80849 are used for the purpose of imparting antistatic properties.

[0140] The photographic emulsion layers and other hydrophilic colloid layers of the photographic materials used in the present invention may contain hydroquinone derivatives (called DIR-hydroquinone) which release a development restrainer according to the density of image during development.

[0141] Examples of the hydroquinone derivatives include compounds described in U.S. Patents 3,379,529, 3,620,746 4,377,634 and 4,332,878, JP-A-49-129536, JP-A-54-67419, JP-A-56-153336, JP-A-56-153342, JP-A-59-278853, JP-A-59-90435, JP-A-59-90436 and JP-A-59-138808.

[0142] The photographic emulsion layers and other hydrophilic colloid layers of the photographic materials used in the present invention may contain matting agents such as silica, magnesium oxide and polymethyl methacrylate to prevent sticking from being caused.

[0143] The photographic materials used in the present invention may contain a dispersion of a water-insoluble or difficultly soluble synthetic polymer for the purpose of dimensional stabilization. Examples of the polymer include polymers of one or more monomers of alkyl (meth)acrylates, alkoxyacryl (meth)acrylates or glycidyl (meth)acrylates, and polymers of one or more monomer components thereof with acrylic acid or methacrylic acid.

[0144] It is preferred that the silver halide emulsion layers and other layers of the photographic materials used in the present invention contain compounds having an acid radical. Examples of the compounds having an acid radical include organic acids such as salicylic acid, acetic acid and ascorbic acid and polymers and copolymers having a repeating unit derived from an acid monomer such as acrylic acid, maleic acid and phthalic acid. These compounds are described in the specifications of JP-A-61-223834, JP-A-61-228437, JP-A-62-25745 and JP-A-62-55642. Among these compounds, the particularly preferred low-molecular compound is ascorbic acid and the particularly preferred high-molecular compounds are water-dispersible latexes of copolymers of an acid monomer such as acrylic acid with a crosslinking monomer having at least two unsaturated groups such as divinylbenzene.

[0145] The above-described silver halide emulsions are coated on an appropriate support such as glass, a plastic film (e.g., cellulose acetate film or polyethylene terephthalate film), paper, baryta paper or polyolefin-coated paper. Among them, plastic films are preferred.

[0146] Development accelerators or nucleating infectious development accelerators suitable for use in the present invention include compounds described in JP-A-53-77616, JP-A-54-37732, JP-A-53-137133, JP-A-60-140340, and JP-A-60-14959. In addition thereto, compounds containing N or S atom are effective.

[0147] Examples of the accelerators include the following compounds.































        n-C₄H₉N(C₂H₄OH)₂

[0148] The optimum amounts of these accelerators to be added vary depending on the types of the compounds, but they are used in an amount of generally 1.0×10^-3 to 0.5 g/m², preferably 5.0×10^-3 to 0.1 g/m². These accelerators are dissolved in an appropriate solvent (e.g., H₂O, an alcohol such as methanol or ethanol, acetone, dimethylformamide, methyl cellosolve) and then added to the coating solution.

[0149] These additives may be used in combination of two or more kinds of them.

[0150] Stable developing solutions can be used to obtain ultra-high-contrast photographic characteristics by using the silver halide light-sensitive materials without necessity of the use of conventional infectious developing solutions or high-alkali developing solutions having a pH of nearly 13 described in U.S. Patent 2,419,975.

[0151] Namely, when the silver halide light-sensitive materials are processed with developing solutions containing a sulfite ion as a preservative in an amount of at least 0.15 mol/ℓ and having a pH of 10.5 to 12.3, particularly 11.0 to 12.0, sufficiently ultra-high-contrast negative image can be obtained.

[0152] The phenols having an acid dissociation constant of 1×10^-11 to 3×10^-13 which are used in the developing solutions include the following compounds.

wherein R₅, R₆, R₇ and R₈ may be the same or different groups and each is hydrogen atom, amino group, carboxyl group, sulfo group, an alkyl group having 1 to 4 carbon atoms (which may be substituted) or an alkoxy group (which may be substituted).

[0153] Examples of the compounds represented by general formula (IV) include the following compounds.

[0154] Among these phenols, the compound of IV-11 is particularly preferred.

[0155] Most of these compounds are commercially available and other compounds are known and can be easily synthesized.

[0156] The following compounds can be used for the developing solutions without particular limitations except that the developing solutions contain the above phenol compounds in an amount of at least 0.05 mol/ℓ.

[0157] Though there is no particular limitation with regard to developing agents used in the developing solutions, it is preferred from the viewpoint of easily obtaining good halftone dot quality that the developing solutions contain dihydroxybenzenes. Combinations of dihydroxybenzenes with 1-phenyl-3-pyrazolidones or combinations of dihydroxybenzenes with p-aminophenols are optionally used. Examples of the dihydroxybenzene developing agents used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone and 2,5-dimethylhydroquinone. Among them, hydroquinone is particularly preferred.

[0158] Examples of 1-phenyl-3-pyrazolidone or derivatives thereof which can be used as developing agents in the present invention include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4,4-dimethyl-3-pyrazolidone and 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone.

[0159] The p-aminophenol developing agents which can be used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N-(β-hydroxyethyl)-p-aminophenol, N-(4-hydroxyphenyl)glycine, 2-methyl-p-aminophenol and p-benzylaminophenol. Among them, N-methyl-p-aminophenol is preferred.

[0160] The developing agents are generally used in an amount of preferably 0.05 to 0.8 mol/ℓ. When the combinations of the dihydroxybenzenes with the 1-phenyl-3-pyrazolidones or p-aminophenols are used, it is preferred that the former is used in an amount of 0.05 to 0.5 mol/ℓ and the latter is used in an amount of not more than 0.06 mol/ℓ.

[0161] Sulfites used as preservatives in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite and formaldehyde sodium bisulfite. The sulfites are used in an amount of preferably at least 0.3 mol/ℓ, particularly preferably at least 0.4 mol/ℓ. It is desirable that the upper limit is 2.5 mol/ℓ, particularly 1.2 mol/ℓ.

[0162] Alkali agents used for setting pH include pH adjustors and buffering agents such as sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.

[0163] Examples of additives which may be used in addition to the above-described components include compounds such as boric acid and borax, development restrainers such as sodium bromide, potassium bromide and potassium iodide; organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol and methanol; and anti-fogging agents or black pepper inhibitors such as mercapto compounds (e.g., 1-phenyl-5-mercaptotetrazole and sodium 2-mercaptobenzimidazole-5-sulfonate), indazole compounds (e.g., 5-nitroindazole) and benztriazole compounds (e.g., 5-methylbenztriazole). Further, toning agents, surfactants, anti-foaming agents, water softeners, hardening agents, amino compounds described in JP-A-56-106244, JP-A-61-267759 and Japanese Patent Application No. 1-29418 may be optionally contained.

[0164] The developing solutions used in the present invention may contain compounds as silver stain inhibitors described in JP-A-56-24347, compounds as development blurs inhibitors described in JP-A-62-212651 and compounds as dissolution aids described in JP-A-61-267759.

[0165] The developing solutions used in the present invention contain, as buffering agents, boric acids described in JP-A-62-186259 and saccharide (e.g., saccharose), oximes (e.g., acetoxime) and phenols (e.g., 5-sulfosalicylic acid) described in JP-A-60-93433.

[0166] Fixing solutions are acidic aqueous solutions containing water-soluble aluminum compounds as hardening agents in addition to fixing agents and optionally acetic acid and dibasic acids (e.g., tartaric acid, citric acid or a salt thereof) and having a pH of not lower than 3.8, more preferably 4.0 to 5.5.

[0167] The fixing agents include sodium thiosulfate and ammonium thiosulfate. Ammonium thiosulfate is particularly preferred from the viewpoint of the rate of fixing. The amounts of the fixing agents to be used can be properly changed and are generally in the range of 0.1 to 5 mol/ℓ.

[0168] The water-soluble aluminum salts which function mainly as hardening agents in the fixing solutions are compounds which are known as hardening agents for acid hardening fixers. Examples thereof include aluminum chloride, aluminum sulfate and potassium alum.

[0169] The water-soluble aluminum salts are used in an amount of 0.005 mol/ℓ to 0.1 mol/ℓ, preferably 0.01 mol/ℓ to 0.07 mol/ℓ.

[0170] As the aforesaid dibasic acids, tartaric acid or derivatives thereof and citric acid or derivatives thereof singly or in combination of two or more can be used. The effective amounts of these compounds are at least 0.005 mol per liter of the fixing solution, and an amount of 0.01 mol/ℓ to 0.03 mol/ℓ is particularly effective.

[0171] Concrete examples include tartaric acid, potassium tartrate, sodium tartrate, sodium potassium tartrate, ammonium tartrate and potassium ammonium tartrate.

[0172] Examples of citric acid or derivatives thereof which can be effectively used in the present invention include citric acid, sodium citrate and potassium citrate.

[0173] If desired, the fixing solutions may contain preservatives (e.g., sulfite, bisulfite), pH buffering agents (e.g., acetic acid, boric acid), pH adjustors (e.g., ammonia, sulfuric acid), image storage improvers (e.g., potassium iodide) and chelating agents. The pH adjustors are used in an amount of 10 to 40 g/ℓ, more preferably 18 to 25 g/ℓ, because the pH of the developing solutions is high.

[0174] Fixing temperature and time are preferably 20°C to 50°C and 10 seconds to one minute as in development.

[0175] Rinsing water may contain mildew proofing agents (e.g., compounds described in Germicidal and Antifungal Chemistry, written by Horiguchi and JP-A-62-115154), rinsing accelerators (e.g., sulfite) and chelating agents.

[0176] According to the above-described method, photographic materials after development and fixing are rinsed and dried. Rinsing is carried out to remove nearly completely silver salt dissolved by fixing and is preferably conducted at 20°C to 50°C for 10 seconds to 3 minutes. Drying is carried out at 40°C to 100°C, and drying time varies properly depending on environmental conditions, but is generally 5 seconds to 3.5 minutes.

[0177] Roller conveying type automatic processors are described in the specifications of U.S. Patents 3,025,779 and 3,545,971, and are herein referred to simply as roller conveying type processor. The roller conveying type processor comprises four stages of development, fixing, rinsing and drying. It is most preferred that the method of the present invention follows these four stages, though other stages (e.g., stop stage) is not removed.

[0178] The replenishment rate of rinsing water may be not more than 1200 ml/m² (including 0). The description "the case where the replenishment rate of rinsing water (or stabilizing solution) is 0" means a rinsing method by means of called a standing water rinse system.

[0179] Multi-stage countercurrent systems (e.g., two-stage, three-stage) are known for a long time as a means for reducing replenishment rate.

[0180] Good processing performance can be obtained by combining the following techniques to solve problems which are caused by the less replenishment rate of rinsing water.

[0181] Rinsing bath or stabilizing bath may contain, as microbiocides, isothiazoline compounds described in R.T. Kreiman, J. Imaging Tech., Vol. 10, No. 6, 242 (1984), isothiazoline compounds described in Research Disclosure (RD), Vol. 205, No. 20526 (May 1981) and ibid., Vol. 228, No. 22845 (April 1983) and compounds described in JP-A-61-115154 and JP-A-62-209532. In addition thereto, the rinsing bath or the stabilizing bath may contain compounds described in Germicidal and Antifungal Chemistry, written by Hiroshi Horiguchi (Sankyo Shuppan 1982), Microcial Antifungal Technical Handbook, edited by Nippon Microcidal Antifungal Society (Hakuhodo 1986) and L.E. West Water Quality Criteria, Photo. Sci. & Eng., Vol. 9, No. 6 (1965), M.W. Beach, Microbiological Growths in Motion Picture Processing, SMPTE Journal Vol. 85 (1976), R.O. Deegan Photo Processing Wash Water Biocides, J. Imaging Tech., Vol. 10, No. 6 (1984).

[0182] When rinsing is carried out with a small amounts of rinsing water in the method of the present invention, it is more preferred to provide squeezing rollers and cross-over rack washing tank described in JP-A-63-18350 and JP-A-62-287252.

[0183] Further, a part or the whole of overflow solution from the rinsing bath or the stabilizing bath can be utilized as a processing solution having an ability of fixing which is used in the processing stage prior to the rinsing or stabilizing stage as described in JP-A-60-235133 and JP-A-63-129343, said overflow solution being formed by replenishing water provided with an antifungal means corresponding to the rate of processing in the rinsing or stabilizing bath used according to the present invention. Further, water-soluble surfactants or anti-foaming agents may be added to prevent treating agent components deposited on the squeezing rollers from being transferred to films and/or to prevent unevenness in foams which is liable to be caused when rinsing is carried out with a small amount of rinsing water.

[0184] Dye adsorbents described in JP-A-63-163456 may be used in the rinsing tank to prevent the light-sensitive materials from being stained by dyes dissolved out from the light-sensitive materials.

[0185] It is preferred that the developing solutions used in the present invention are kept in packaging materials having low oxygen permeability and low moisture permeability described in JP-A-61-73147. Replenishment system described in JP-A-62-91939 can be preferably used for the developing solutions used in the present invention.

[0186] The silver halide photographic materials used in the present invention give high Dmax. Hence, when they are subjected to reduction treatment after image formation, high density can be kept even when dot area is reduced.

[0187] Any of reducers described in The Theory of the Photographic Process, pages 738-744, written by Mees (Macmillan 1954), Theory and Practice of Photographic Processing, pages 166-169, written by Tetsuo Yano (Kyoritsu Shuppan 1978), JP-A-50-27543, JP-A-52-68429, JP-A-55-17123, JP-A-55-79444, JP-A-57-10140, JP-A-57-142639 and JP-A-61-61155 can be used in the present invention without particular limitation.

[0188] Namely, there can be used reducers containing, as oxidizing agent, e.g. permanganate, persulfate, ferric salt, cupric salt, ceric salt, red prussiate or dichromate, singly or in combination and optionally inorganic acids such as sulfuric acid and alcohols and reducers containing oxidizing agents such as red prussiate and ethylenediaminetetraacetic acid iron(III) salt, silver halide solvent, such as thiosulfate, rhodanate, thiourea or their derivatives and optionally inorganic acids such as sulfuric acid.

[0189] Typical examples of the reducers which can be used in the present invention include Farmer's reducer, ethylenediaminetetraacetic acid iron(III) salt, potassium permanganate, ammonium persulfate reducer (Kodak R-5) and ceric salt reducer.

[0190] It is preferred that reduction processing is completed generally at a temperature of 10°C to 40°C, preferably 15°C to 30°C in a period of several seconds to several tens of minutes, particularly several minutes. When the light-sensitive materials for plate making are used, sufficiently wide reduction margin can be obtained under the above-described conditions.

[0191] The reducer is allowed to act on silver image formed in the emulsion layer through the upper light-insensitive layer containing the compound used in the present invention.

[0192] Concretely, there are various methods for carrying out reduction. Examples of the methods include a method wherein the light-sensitive material for plate making is immersed in the reducer and the liquid is stirred and a method wherein the reducer is applied to the surface of the light-sensitive material for plate making by means of brush or roller.

[0193] Preferred embodiments of the present invention are as follows.

(1) A processing method as in claim 1, wherein said redox compound has hydroquinones, catechols, naphthohydroquinones, amidophenols, pyrazolidones, hydrazines, hydroxylamines or reductones as redox group.

(2) A processing method as in claim 1, wherein said redox compound has hydrazines as redox group.

(3) A processing method as in claim 1, wherein said redox compound is represented by the following general formula (I),

wherein both A₁ and A₂ represent hydrogen atom, or one of A₁ and A₂ represents hydrogen atom and the other represents a residue of a sulfinic acid or

(wherein R₀ represents an alkyl group, an alkenyl group, an aryl group, an alkoxy group or an aryloxy group and ℓ represents 1 or 2); A₁ may be combined together with (̵Time

to form a ring; Time represents a divalent linking group; t represents 0 or 1; PUG represents a development restrainer; V represents carbonyl group,

a sulfonyl group, a sulfoxy group,

(wherein R₁ represents an alkoxy group or an aryloxy group), an iminomethylene group or a thiocarbonyl group; and R represents an aliphatic group, an aromatic group or a heterocyclic group.

BRIEF DESCRIPTION OF THE DRAWING

[0194] Figure 1 shows an embodiment during exposure when superimposed letter image is formed by overlay contact work wherein each sign represents the following member.

(a) Transparent or semitransparent laminating base.

(b) The line original (black portions show line works).

(c) Transparent or semitransparent laminating base.

(d) The halftone original (black portions show halftone dots).

(e) Light-sensitive material for dot to dot work (the shaded portion shows the light-sensitive layer).

BEST MODE FOR CARRYING OUT THE INVENTION

EXAMPLE 1

Preparation of Light-Sensitive Emulsion

[0195] To an aqueous gelatin solution kept at 50°C, there were simultaneously added an aqueous solution of silver nitrate and an aqueous solution containing potassium iodide and potassium bromide in the presence of 4×10^-7 mol of potassium iridium(III) hexachloride per mol of silver and ammonia over a period of 60 minutes while keeping pAg at 7.8 to prepare a cubic monodisperse emulsion having a mean grain size of 0.28 µm and an average silver iodide content of 0.3 mol%. After the emulsion was desalted by flocculation method, 40 g of inert gelatin per mol of silver was added thereto. The temperature thereof was kept at 50°C, and 5,5'-dichloro-9-ethyl-3,3'-bis(3-sulfopropyl)oxacarbocyanine as a sensitizing dye and 10^-3 mol of a KI solution per mol of silver were added thereto. After a lapse of 15 minutes, the temperature was lowered.

Coating of Light-Sensitive Emulsion Layer

[0196] The emulsion was re-dissolved and the following hydrazine derivative was added thereto at 40°C.

[0197] The compound of general formula (I) was added as indicated in Table 1. Further, 5-methylbenztriazole, 4-hydroxy-1,3,3a,7-tetraazaindene, the following compounds (a) and (b), 30 wt% (based on the weight of gelatin) of polyethyl acrylate and the following compound (c) as a hardening agent for gelatin were added thereto. The resulting emulsion was coated on polyethylene terephthalate film (150 µm) having an undercoat layer (0.5 µm) composed of a vinylidene chloride copolymer in such an amount as to give a coating weight of 3.4 g/m² in terms of silver.

Coating of Protective Layer

[0198] A protective layer comprising gelatin (1.5 g/m²) and polymethyl methacrylate particles (average particle size: 2.5 µm, 0.3 g/m²) was coated thereon by using the following surfactants.

[0199] The resulting samples were exposed to tungsten light (3200°K) through an optical wedge and 150 line contact screen. The exposed samples were developed with the following developing solutions A and B at 38°C for 20 seconds, fixed with the following fixing solutions A and B, washed with water and dried by using an automatic processor FG680A (manufactured by Fuji Photo Film Co., Ltd.). In this case, 100 sheets of 20 × 24 inch films (50.8 cm × 61.0 cm) an area of which should be blackened to an extent of 50%, were processed with a replenishment rate of 100 ml per sheet of each of the developing solution and the fixing solution. The results are shown in Table 1.

	Developing Solution A	Developing Solution B
Hydroquinone	50.0 g	50.0 g
N-Methyl-p-aminophenol	0.3 g	0.3 g
Sodium hydroxide	18.0 g	18.0 g
Boric acid	20.0 g	20.0 g
Potassium sulfite	110.0 g	110.0 g
Disodium ethylenediamine	1.0 g	1.0 g
tetraacetate
Potassium bromide	10.0 g	10.0 g
5-Methylbenztriazole	0.4 g	0.4 g
2-Mercaptobenzimidazole-5-sulfonic acid	0.3 g	0.3 g
Sodium 3-(5-mercaptotetrazole)benzenesulfonate	0.2 g	0.2 g
6-Dimethylamino-l-hexanol	4.0 g	4.0 g
Sodium p-toluenesulfonate	15.0 g	15.0 g
5-Sulfosalicylic acid	30.0 g (0.14 mol/ℓ)	-
Add water	to make 1 liter
pH was adjusted to 11.7 by adding potassium hydroxide.

	Fixing Solution A	Fixing Solution B
Ammonium thiosulfate	160.0 g	160.0 g
Sodium thiosulfate	30.0 g	30.0 g
Sodium sulfite	22.0 g	22.0 g
Disodium ethylenediaminetetraacetate	0.1 g	0.1 g
Tartaric acid	3.0 g	3.0 g
Ammonia water (27%)	10.0 g	10.0 g
Acetic acid (90%)	30.0 g	30.0 g
Aluminum sulfate (27%)	35.0 g	-
Add water	to make 1 liter
pH was adjusted to 4.8 by sodium hydroxide.

[0200] The results are shown in Table 1.

[0201] The reciprocal of exposure amount giving a blacking density of 1.5 when the film No. 1 was processed with the developing solution A and the fixing solution B, was referred to as sensitivity of 100. The sensitivity in terms of the relative sensitivity is shown.

[0202] Halftone gradation is represented by the following equation.

[0203] Halftone dot quality was visually evaluated by five ranks. In five rank evaluation, a rank of 5 indicates the best quality and a rank of 1 indicates the worst quality. As the halftone original plate, the ranks of 5 and 4 indicate a quality which is practically usable, the rank of 3 indicates a quality which is practically usable limit level and the ranks of 2 and 1 indicate a quality which is practically unusable.

[0204] Drying characteristics were evaluated by the dryness of films when two sheets of films were put upon each other immediately after the completion of development, fixing, rinsing and drying in the automatic processor as mentioned above. The mark × of drying characteristics means that the water contents of the films are high, and films have poor slipperiness and are hard to handle. The mark ○ of drying characteristics means that the films have a lower water content and good slipperiness and are easy to handle.

[0205] It is clear from Table 1 that the films containing the compounds of general formula (I) have long halftone gradation and wide tone reproduction exposure range and give good halftone dot quality. When the films are processed with the developing solution containing the compound IV-11 such as the developing solution A, a lowering in sensitivity is not caused after processing 100 sheets of the films. When the films are processed with the fixing solution containing the water-soluble aluminum such as the fixing solution A, drying characteristics are good.

[0206] There can be achieved the processing method which give long halftone gradation and good halftone dot quality, does not cause a change in sensitivity even after film processing and gives good drying characteristics by processing the silver halide light-sensitive materials containing a hydrazine nucleating agent and the redox compounds of e.g. general formula (I) with the developing solution containing the compound of e.g. general formula IV and then processing it with an acid hardening fixer containing the water-soluble aluminum compound.

EXAMPLE 2

[0207] An aqueous solution of silver nitrate and an aqueous solution of sodium chloride were simultaneously mixed with an aqueous gelatin solution kept at 50°C in the presence of 5.0×10^-6 mol of (NH₄)₃RhCl₆ per mol of silver. After soluble salts were removed by a method well known by those skilled in the art, gelatin was added thereto, and 2-methyl-4-hydroxy-1,3,3a,7-tetraazaindene as a stabilizer was then added thereto without carrying out chemical ripening. The resulting emulsion was a cubic system monodisperse emulsion having a mean grain size of 0.15 µm.

[0208] The following hydrazine compound was added to the emulsion.

[0209] Further, the compound used in the present invention indicated in Table 2 was added, 30 wt% (on a solid basis; based on the weight of gelatin) of polyethyl acrylate latex was added and 1,3-vinylsulfonyl-2-propanol as a hardening agent was added thereto. The resulting emulsion was coated on a polyester support in such an amount as to give a coating weight of 3.8 g/m² in terms of Ag. The coating weight of gelatin was 1.8 g/m². Further, a protective layer comprising gelatin (1.5 g/m²), polymethyl methacrylate particles having an average particle size of 2.5 µm (0.3 g/m²) as a matting agent, the following surfactants as coating aids, the following stabilizer and the following ultraviolet light-absorbing dye was coated thereon and dried.

Stabilizer
Thioctic acid	2.1 mg/m2

[0210] The samples were subjected to imagewise exposure through the original as shown in Fig. 1 by using a daylight printer p-607 (manufactured by Dainippon Screen KK). The exposed samples were developed with the developing solutions A and B at 38°C for 20 seconds, fixed with the fixing solutions A and B, washed with water and dried by using the automatic processor FG680A (manufactured by Fuji Photo Film Co., Ltd.), said developing solutions A and B and said fixing solutions being the same as those used in Example 1. In this case, 100 sheets of 20 × 24 inch films an area of which should be blackened to an extent of 50%, were processed with a replenishment rate of 80 ml per sheet of each of the developing solution and the fixing solution. The results are shown in Table 2.

[0211] A rank of superimposed letter image quality 5 means an image quality which shows the reproduction of 30 µm wide letter when exposure is properly carried out so that 50% dot area becomes 50% dot area in the light-sensitive material for dot to dot work with using the original as shown in Fig. 1, and the rank of 5 is very good superimposed letter image quality. On the other hand, a rank of superimposed letter image quality 1 means an image quality which shows only the reproduction of letters of 150 µm wide or above when the same proper exposure is conducted, and the rank of 1 is bad superimposed letter image quality. The ranks of 4 to 2 are set between the superimposed letter image quality 5 and the superimposed letter image quality 1 by organoleptic evaluation. The rank 3 or higher is practically usable level.

[0212] It is clear from Table 2 that the films containing the compounds of general formula (I) provide good superimposed letter image quality. When the films are processed with the developing solution containing the compound IV-11 such as the developing solution A, a lowering in sensitivity is not caused after processing 100 sheets of the films. When the films are processed with the fixing solution containing the water-soluble aluminum such as the fixing solution A, drying characteristics are good.

[0213] There can be achieved the processing method which provides good superimposed letter image quality, does not cause a change in sensitivity even after film processing and gives good drying characteristics by processing the silver halide light-sensitive materials containing a hydrazine nucleating agent and the redox compounds of e.g. general formula (I) with the developing solution containing the compound of e.g. general formula IV and then processing it with an acid hardening fixer containing the water-soluble aluminum compound.

POSSIBILITY OF UTILIZATION IN INDUSTRY

[0214] The method for processing stably and rapidly the silver halide photographic materials having excellent original reproducibility in the photographing of the letter original and the halftone original is made possible by the present invention.

Claims

1. A processing method of a silver halide photographic material characterized by processing a light-sensitive silver halide photographic material containing a hydrazine nucleating agent and a redox compound capable of releasing a development restrainer when oxidized, with a developing solution containing a phenol having an acid dissociation constant of 1x10^-11 to 3x10^-13 in an amount of at least 0.05 mol/l and then processing it with an acid hardening fixer containing a water-soluble aluminum compound.

2. The processing method according to claim 1, wherein said redox compound has hydroquinones, catechols, naphthohydroquinones, aminophenols, pyrazolidones, hydrazines, hydroxylamines or reductones as redox group.

3. The processing method according to claim 1, wherein said redox compound is represented by the following general formula (I),

wherein both A₁ and A₂ represent hydrogen atom, or one of A₁ and A₂ represents hydrogen atom and the other represents a residue of a sulfinic acid or

wherein R₀ represents an alkyl group, an alkenyl group, an aryl group, an alkoxy group or an aryloxy group and ℓ represents 1 or 2; A₁ may be combined together with (̵Time)̵_t to form a ring; Time represents a divalent linking group; t represents 0 or 1; PUG represents a development restrainer; V represents carbonyl group,

a sulfonyl group, a sulfoxy group,

wherein R₁ represents an alkoxy group or an aryloxy group , an iminomethylene group or a thiocarbonyl group; and R represents an aliphatic group, an aromatic group or a heterocyclic group.

4. The processing method according to any of claims 1 to 3, wherein the phenol is a compound of the general formula (IV)

wherein R₅, R₆, R₇ and R₈ may be the same or different and each is a hydrogen atom, an amino group, a carboxyl group, a sulfo group, substituted or unsubstituted alkyl group having 1 to 4 carbon atoms substituted or unsubstituted alkoxy group.

5. The processing method according to claim 4, wherein the phenol is a compound of the formula

6. The process according to any of claims 1 to 5, wherein the hydrazine nucleating agent is a compound of the general formula (II)

wherein R₁ 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; G₁ represents a carbonyl group, a sulfonal group, a sulfoxy group, a group of

or an iminomethylene group; and both A₁ and A₂ are hydrogen atom or one of A₁ and A₂ represents hydrogen atom and the other represents a Substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group or a substituted or unsubstituted acyl group.

7. The processing method according to any of claims 1 to 6, wherein the water soluble aluminum compound is a aluminum chloride, aluminum sulfate or a potassium alum.

Ansprüche

1. Verfahren zur Verarbeitung eines photographischen Silberhalogenidmaterials, gekennzeichnet durch die Verarbeitung eines lichtempfindlichen photographischen Silberhalogenidmaterials, enthaltend einen Hydrazin-Keimbildner und eine Redoxverbindung, die bei ihrer Oxidation einen Entwicklungsverzögerer freisetzen kann, mit einer Entwicklerlösung, enthaltend eine Phenolverbindung mit einer Säuredissoziationskonstante im Bereich von 1x10^-11 bis 3x10^-13 in einer Menge von mindestens 0,05 Mol/l, und die nachfolgende Verarbeitung des Materials mit einer sauren Fixierlösung, die eine wasserlösliche Aluminiumverbindung als Härtungsmittel enthält.

2. Verarbeitungsverfahren nach Anspruch 1, wobei die Redoxgruppe der Redoxverbindung ausgewählt ist aus Hydrochinon-, Catechol-, Naphthohydrochinon-, Aminophenol-, Pyrazolidon-, Hydrazin-, Hydroxylamin- und Reduktongruppen.

3. Verarbeitungsverfahren nach Anspruch 1, wobei die Redoxverbindung durch die folgende allgemeine Formel (I) dargestellt ist:

worin sowohl A₁ als auch A₂ ein Wasserstoffatom bedeuten, oder eine der Gruppen A₁ und A₂ ist ein Wasserstoffatom und die andere Gruppe ist ein Sulfinsäurerest oder

worin R₀ eine Alkylgruppe, eine Alkenylgruppe, eine Arylgruppe, eine Alkoxygruppe oder eine Aryloxygruppe bedeutet, und ℓ bedeutet 1 oder 2; A₁ kann mit (̵Time)̵_t verbunden sein, um einen Ring zu bilden; Time ist eine zweiwertige Verbindungsgruppe; t bedeutet 0 oder 1; PUG ist ein Entwicklungsverzögerer; V ist eine Carbonylgruppe,

eine Sulfonylgruppe, eine Sulfoxygruppe,

worin R₁ eine Alkoxygruppe oder eine Aryloxygruppe bedeutet, eine Iminomethylengruppe oder eine Thiocarbonylgruppe; und R ist eine aliphatische Gruppe, eine aromatische Gruppe oder eine heterocyclische Gruppe.

4. Verarbeitungsverfahren nach einem der Ansprüche 1 bis 3, wobei die Phenolverbindung eine Verbindung ist, die durch die allgemeine Formel (IV) dargestellt ist:

worin R₅, R₆, R₇ und R₈ gleich oder verschieden sein können und jeweils ein Wasserstoffatom, eine Aminogruppe, eine Carboxylgruppe, eine Sulfogruppe, eine substituierte oder unsubstituierte Alkylgruppe mit 1 bis 4 Kohlenstoffatomen oder eine substituierte oder unsubstituierte Alkoxygruppe bedeuten.

5. Verarbeitungsverfahren nach Anspruch 4, wobei die Phenolverbindung durch die Formel

dargestellt ist.

6. Verarbeitungsverfahren nach einem der Ansprüche 1 bis 5, wobei der Hydrazin-Keimbildner eine Verbindung ist, die durch die allgemeine Formel (II) dargestellt ist:

worin R₁ eine aliphatische Gruppe oder eine aromatische Gruppe bedeutet; R₂ ist ein Wasserstoffatom, eine Alkylgruppe, eine Arylgruppe, eine Alkoxygruppe, eine Aryloxygruppe, eine Aminogruppe, eine Carbamoylgruppe oder eine Oxycarbonylgruppe; G₁ ist eine Carbonylgruppe, eine Sulfonylgruppe, eine Sulfoxygruppe,

oder eine Iminomethylengruppe; und sowohl A₁ als auch A₂ bedeuten ein Wasserstoffatom, oder eine der Gruppen A₁ und A2 ist ein Wasserstoffatom und die andere Gruppe ist eine substituierte oder unsubstituierte Alkylsulfonylgruppe, eine substituierte oder unsubstituierte Arylsulfonylgruppe oder eine substituierte oder unsubstituierte Acylgruppe.

7. Verarbeitungsverfahren nach einem der Ansprüche 1 bis 6, wobei die wasserlösliche Aluminiumverbindung Aluminiumchlorid, Aluminiumsulfat oder Kaliumalaun ist.

Revendications

1. Procédé de traitement d'un matériau photographique à l'halogénure d'argent, caractérisé par le traitement d'un matériau photographique à l'halogénure d'argent photosensible contenant un agent de formation de germes cristallins hydrazine et un composé redox capable de dégager un retardateur de développement quand il est oxydé, avec une solution de développement contenant un phénol ayant une constante de dissociation acide de 1x10^-11 à 3 x 10^-13 en une quantité d'au moins 0,05 mole/litre et ensuite son traitement avec un fixateur durcissant acide contenant un composé d'aluminium soluble dans l'eau.

2. Procédé de traitement selon la revendication 1, caractérisé en ce que ledit composé redox possède comme groupe redox des hydroquinones, catéchols, naphtohydroquinones, aminophénols, pyrazolidones, hydrazines, hydroxylamines ou réductones.

3. Procédé de traitement selon la revendication 1, caractérisé en ce que ledit composé redox est représenté par la Formule générale suivante (I):

dans laquelle les deux A₁ et A₂ représentent un atome d'hydrogène, ou l'un de A₁ et A₂ représente un atome d'hydrogène et l'autre représente un reste d'un acide sulfinique ou

dans laquelle R₀ représente un groupe alkyle, un groupe alcényle, un groupe aryle, un groupe alcoxy ou un groupe aryloxy et ℓ représente 1 ou 2; A₁ peut être combiné ensemble avec -(-Temps-)_t pour former un cycle; Temps représente un groupe de liaison divalent, t représente 0 ou 1; PUG représente un retardateur de développement; V représente un groupe carbonyle;

un groupe sulfonyle, un groupe sulfoxy,

dans lequel R₁ représente un groupe alcoxy ou un groupe aryloxy, un groupe iminométhylène ou un groupe thiocarbonyle; et R représente un groupe aliphatique, un groupe aromatique ou un groupe hétérocyclique.

4. Procédé de traitement selon l'une quelconque des revendications 1 à 3, caractérisé en ce que le phénol est un composé de Formule générale (IV):

dans laquelle R₅, R₆, R₇ et R₈ peuvent être semblables ou différents et chacun est un atome d'hydrogène, un groupe amino, un groupe carboxyle, un groupe sulfo, un groupe alkyle substitué ou non substitué ayant de 1 à 4 atomes de carbone, un groupe alcoxy substitué ou non substitué.

5. Procédé de traitement selon la revendication 4, caractérisé en ce que le phénol est un composé de formule:

6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que l'agent de formation de germes cristallins hydrazine est un composé de Formule générale (II):

dans laquelle R₁ représente un groupe aliphatique ou un groupe aromatique; R₂ représente un atome d'hydrogène, un groupe alkyle, un groupe aryle, un groupe alcoxy, un groupe aryloxy, un groupe amino, un groupe carbamoyle ou un groupe oxycarbonyle; G₁ représente un groupe carbonyle, un groupe sulfonyle, un groupe sulfoxy, un groupe

ou un groupe iminométhylène; et les deux A₁ et A₂ sont un atome d'hydrogène ou l'un de A₁ et A₂ représente un atome d'hydrogène et l'autre représente un groupe alkylsulfonyle substitué ou non substitué, un groupe arylsulfonyle substitué ou non substitué ou un groupe acyle substitué ou non substitué.

7. Procédé de traitement selon l'une quelconque des revendications 1 à 6, caractérisé en ce que le composé d'aluminium soluble dans l'eau est un chlorure d'aluminium, un sulfate d'aluminium ou un alun de potassium.

Drawing