Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
  • G03C5/29—Development processes or agents therefor
  • G03C5/305—Additives other than developers
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/061—Hydrazine compounds

Definitions

• the present invention relates to a developer composition capable of forming a ultra high-contrast photographic image and a method for the formation of an image which uses the developer composition.
• a photomechanical process includes a process of transforming an original continuous-tone image into a halftone-dot image; i.e., transforming the continuous tone's density changes into a gathering of dots in different sizes corresponding to the densities.
• This process employs a ultra high-contrast-image-reproducible photographic technique, in which a graphic arts film is exposed through a contact screen to an original image and then subjected to an infectious development to form a halftone-dot image.
• a lithographic silver halide light-sensitive material for use in the infectious development must be processed in an infectious developer (lith developer) for obtaining a sufficiently contrasty image; for example, if it is processed in a MQ or PQ developer, its gamma value comes to 5 or 6 at the most and produces much fringe that must be avoided in the halftone image formation, and thus it is essential to process the light-sensitive material in an infectious developer, which is not preservable.
• lith developer infectious developer
• the above silver halide photographic light-sensitive material makes it possible to obtain a ultra high-contrast photographic image even when processed in a developer well-preservable and suitable for rapid processing.
• This silver halide light-sensitive material has the disadvantage that sandy dots, so-called black spots, appear among the half-tone dots in the halftone image formation to impair the half-tone image quality.
• the hydrazine derivative used in the invention is preferable to be of a structure having the following Formula H, described in Japanese Patent Application No. 327402/1990, pp.13 to 72.
• A represents an aryl group or a heterocyclic group containing at least one sulfur atom or oxygen atom
• G is a group, a sulfonyl group, a sulfoxy group, a group or an iminomethylene group
• n is an integer of 1 or 2
• A1 and A2 each represent a hydrogen atom, or either one of them is a hydrogen atom, while the other is a substituted or unsubstituted alkylsulfonyl group or a substituted or unsubstituted acyl group
• R is a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a carbamoyl group, an oxycarbonyl group or a -O-R3
• the hydrazine derivative used in the invention is further preferred to be of structures of the following Formulas A and B: wherein A is an aryl group or a heterocyclic group containing at least one sulfur or oxygen atom; n is an integer of 1 or 2, provided that when n is equal to 1, R1 and R2 each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkinyl group, an aryl group, a heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkinyloxy group, an aryloxy group or a heterocycloxy group, and R1 and R2 together with a nitrogen atom may form a ring, while when n is equal to 2, R1 and R2 each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkinyl group, an aryl group, a saturated or unsaturated heterocyclic ring, a hydroxy group, an alkoxy group, an al
• Compounds represented by Formulas [A] and [B] include those in which at least either one of the hydrogen atoms of the -NHNH- group thereof is substituted by a substituent.
• A represents an aryl group, such as phenyl or naphthyl, or a heterocyclic group containing a sulfur or oxygen atom, such as thiophene, furan, benzothiophene, pyrane or the like.
• R1 and R2 each represent a hydrogen atom, an alkyl group such as methyl, ethyl, methoxyethyl, cyanoethyl, hydroxyethyl, benzyl or trifluoroethyl, an alkenyl group such as allyl, butenyl, pentenyl or pentadienyl, an alkynyl group such as propargyl, butynyl or pentynyl, an aryl group such as phenyl, naphthyl, cyanophenyl or methoxyphenyl, a heterocyclic group including a saturated heterocyclic group such as pyridine, thiophene or furan and a unsaturated heterocyclic group such as tetrahydrofuran or sulforan, a hydroxy group, an alkoxy group such as methoxy, ethoxy, benzyloxy or cyanomethoxy, an alkenyloxy group such as
• R1 and R2 represents an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group or a heterocycloxy group.
• Examples of the alkynyl group and saturated heterocyclic group represented by R3 include what have been described earlier.
• any of various substituents may be introduced to the aryl group or heterocyclic group having at least one sulfur or oxygen atom represented by A.
• the introducible substituent include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an alkylthio group, arylthio group, a sulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, an acyl group, an amino group, an alkylamino group, an arylamino group, an acylamino group, a sulfonamido group, an arylaminothiocarbonylamino group, a hydroxy group, a carboxy group, a sulfo group and a cyano group.
• the preferred among these is a sulfonamido
• the group represented by A is preferable to contain at least one nondiffusible group or silver halide adsorption-accelerating group.
• the nondiffusible group is a ballast group that is usually used in stationary photographic additives such as couplers.
• the ballast group is a group which has not less than eight carbon atoms and which is relatively inert photographically, and may be selected from the group consisting of an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group and an alkylphenoxy group.
• Preferred as the silver halide adsorption-accelerating group are those groups described in U.S. Patent No. 4,385,1098, such as thiourea, thiourethane, heterocyclic thioamido, mercaptoheterocyclic and triazole groups.
• the hydrogen atoms for the hydrazine group -NHNH- may be replaced by a substituent such as a sulfonyl group such as methanesulfonyl or toluenesulfonyl, an acyl group such as acetyl, trifluoroacetyl or ethoxycarbonyl, an oxalyl group such as ethoxalyl or pyruvoyl.
• a substituent such as a sulfonyl group such as methanesulfonyl or toluenesulfonyl, an acyl group such as acetyl, trifluoroacetyl or ethoxycarbonyl, an oxalyl group such as ethoxalyl or pyruvoyl.
• R1 and R2 each are a hydrogen atom, an alkyl, alkenyl, alkynyl, aryl, saturated or unsaturated heterocyclic, hydroxy or alkoxy group, provided at least either one of R1 and R2 is an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxyl group or an alkoxy group.
• the photographic light-sensitive material according to the invention contains a hydrazine derivative in an amount of preferably 5x10 ⁇ 7 to 5x10 ⁇ 1 mol and more preferably 5x10 ⁇ 6 to 1x10 ⁇ 2 mol per mol of silver halide.
• the adding amount of the above compound depends on the type of an object into which it is to be incorporated and on its kind, but is usually in the range of from 0.1 to 100g, and preferably from 0.5 to 20g per liter of a developer.
• the hydroxybenzene developing agent used in the developer of the invention is, e.g., hydroquinone, chlorohydroquinone, methylhydroquinone, or the like, but is preferably hydroquinone.
• 1-phenyl-3-pyrazolidone-type developing agent used in the invention include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4--hydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone and 1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone. Of these the most preferred is the 1-phenyl-3-pyrazolidone.
• the p-aminophenol-type developing agent used in the invention there are N-methyl-p-aminophenol, p-aminophenol, N-( ⁇ -hydroxyethyl)-p-aminophenol and p-benzylaminophenol. Of these the most preferred is the N-methyl-p-aminophenol.
• the dihydroxybenzene is used preferably in a concentration of 0.05 mol to 0.5 mol per liter, while the 1-phenyl-3-pyrazolidone and/or the p-aminophenol preferably in a concentration of not more than 0.06 mol per liter of a developer solution.
• the sulfite to be used in the invention can be any sulfite as long as it liberates sulfurous acid ions (SO32 ⁇ ) in a developer solution; e.g., sodium sulfite, potassium sulfite or potassium hydrogensulfite.
• SO32 ⁇ sulfurous acid ions
• the sulfurous acid ion concentration in a developer solution is preferably not less than 0.3 mol per liter of a developer solution, but exceeding 1.2 moles per liter is impractical for manufacture.
• the suitable concentration range for manufacture is 0.4 to 0.7 mol per liter.
• the pH range of the developer solution of the invention is preferably from 10 to about 13, and more preferably 10 to 12. If the pH value is less than 10, the developer solution is unable to provide any sufficiently contrasty image.
• a preferred embodiment of the invention is such that the foregoing developer solution contains a phosphate in a concentration of preferably not less than 0.05 mol, more preferably 0.2 to 1 mol per liter of the developer solution.
• a more preferred embodiment is the processing being made in the presence of an organic antifoggant.
• Still another preferred embodiment is the use of an antioxidant in addition to the sulfite.
• a still further preferred embodiment is the use of a developer solution whose sodium ion concentration is higher than potassium ion concentration.
• the developer solution should contain a carbonate as a pH buffer in a concentration of preferably not less than 0.05 mol, more preferably not less than 0.2 mol per liter.
• the silver halide for the silver halide emulsion used in the invention may be any discretionary silver halide for ordinary silver halide emulsions, such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloride, or the like, but is preferably silver chlorobromide, silver bromide, or silver iodobromide containing silver iodide below 2 mol%.
• the silver halide is preferably of monodisperse grains having a variation coefficient of not more than 15%, which is defined by Standard deviation of grain diameters Average value of grain diameters x 100
• the silver halide photographic emulsion and backing layer of the invention there may be incorporated various additives such as chemical sensitizers, toning agents, hardeners, surfactants, viscosity increasing agents, plasticizers, lubricants, development restrainers, UV absorbents, antiirradation agents, heavy metals, matting agents and the like, in accordance with various methods.
• various additives such as chemical sensitizers, toning agents, hardeners, surfactants, viscosity increasing agents, plasticizers, lubricants, development restrainers, UV absorbents, antiirradation agents, heavy metals, matting agents and the like, in accordance with various methods.
• the silver halide photographic emulsion and backing layer of the invention may also contain a polymer latex.
• Materials usable as the support of the silver halide photographic light-sensitive material of the invention include cellulose acetate, cellulose nitrate, a polyester such as polyethylene terephthalate, a polyolefin such as polyethylene, polystyrene, baryta paper, polyolefin-coated paper, glass and metals.
• the support may be subjected to subbing treatment if necessary.
• a silver iodobromide emulsion (containing 2 mol% silver iodide per mol of silver) was prepared in accordance with a double-jet process.
• K2IrCl6 was added in an amount of 8x10 ⁇ 7 mol per mol of silver.
• the obtained emulsion was an emulsion of cubic monodisperse silver halide grains (variation coefficient: 9%) having an average grain diameter of 0.20 ⁇ m.
• This emulsion after adding thereto a denatured gelatin (exemplified compound G-8 in Japanese Patent Application no. 180787/1989), was washed to be desalted in the same manner as in Example 1 described in Japanese Patent Application No. 180787/1989.
• Emulsion A was obtained.
• a silver halide emulsion layer of the following prescription (1) so as to have a gelatin coating weight of 2.0g/m2 and a silver coating weight of 3.2g/m2, and further coated on the emulsion layer an emulsion protective layer of the following prescription (2) so as to have a gelatin coating weight of 1.0g/m2, and on the other side of the support was coated a backing layer of the following prescription (3) so as to have a gelatin coating weight of 2.4g/m2, and further thereon coated a backing protective layer of the following prescription (4) so as to have a gelatin coating weight of 1g/m2, whereby a sample was obtained.
• the obtained sample was exposed through an optical step-wedge in close contact therewith to a 3200K tungsten light for 5 seconds, and then processed under the following conditions in a rapid processing automatic processor GR-26SR, manufactured by KONICA Corp, using developer and fixer solutions of the following compositions: Developer Sodium hydrogensulfite 40 g EDTA 1.0g Potassium hydroxide (45%) 0.07ml Sodium chloride 4.7g Potassium bromide 1.2h Potassium phosphate 27g 5-Methylbenzotriazole 0.25g 2-Mercaptobenzotriazole 23mg Benzotriazole 83mg Hydroquinone 29g 1-Phenyl-3-pyrazolidone 0.5g Diisopropylaminoethanol 2.25ml Invention's Compound [1] 1g Water to make 1 liter pH was adjusted to 11.6 with potassium hydroxide.
• compositions A and B were dissolved in the described order into 500ml of water, and then water was added to make the whole 1 liter. pH of the fixer bath was adjusted to 4.8 with acetic acid. Processing conditions Step Temperature Time Developing 38°C 20 seconds Fixing 35°C 20 seconds Washing 30°C 15 seconds Drying 50°C 15 seconds
• Each of the obtained samples was subjected to density measurement by means of an optical densitometer KONICA PDA-65 to thereby provide photographic characteristics, wherein the sensitivity of each sample is shown in terms of a relative speed to the speed at a density of 2.5 of Sample No.1 set at 100, while the gamma is given at a tangential slope formed between the points at densities of 0.1 and 2.5.
• a gamma value of less than 6 is totally unacceptable, that of more than 6 and less than 10.0 is still insufficient for high-contrast characteristic and that of 10 or more can form a ultra high-contrast image which is considered practically usable.
• Black spots in unexposed areas were examined for evaluation by being observed through a 40-power magnifying glass.
• An unexposed area with no black spots at all was ranked top '5', followed by being ranked down as '4', '3', '2' and '1' as the number of black spots increases. Those ranked '1' and '2' are on undesirable black spot levels.
• Table 1 Sample N°. Hydrazine derivative [H] Compound [I] of invention Gamma Black spots Remarks 1 - - 5.5 3 Comparative 2 - 3 6.2 3 '' 3 1 - 8.7 1 '' 4 '' 3 13.9 4 Invention 5 '' 4 12.7 4 '' 6 '' 8 13.3 5 '' 7 '' 12 14.1 5 '' 8 4 2 15.3 4 '' 9 '' 5 16.1 4 '' 10 '' 8 14.8 5 '' 11 '' 13 16.6 4 '' 12 '' 14 15.5 4 '' 13 12 2 11.4 4 '' 14 '' 8 12.2 4 '' 15 '' 14 11.9 5 '''
• Example 2 Experiments were made in the same manner as in Example 1 except that the developer solution used in Example 1 was replaced by a developer solution according to the following prescription 3: Developer prescription 3 Sodium hydrogen sulfite 40 g EDTA 1.0g Potassium hydroxide (45%) 0.07ml Sodium chloride 4.7g Potassium bromide 1.2g Potassium phosphate 27g 5-Methylbenzotriazole 0.25g 2-Mercaptobenzothiazole 23 mg Benzotriazole 83 mg Hydroquinone 29 g N-methyl-p-aminophenol 0.5g Diisopropylaminoethanol 2.25ml Invention's Compound [1] 1g Water to make 1 liter pH was adjusted to 10.6 with potassium hydroxide.
• Developer prescription 3 Sodium hydrogen sulfite 40 g EDTA 1.0g Potassium hydroxide (45%) 0.07ml Sodium chloride 4.7g Potassium bromide 1.2g Potassium phosphate 27g 5-Methyl

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• 1992
  • 1992-11-13 EP EP92310374A patent/EP0543576A1/fr not_active Withdrawn

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