EP0382455A1 - Matériau photographique de haut contraste à l'halogénure d'argent - Google Patents

Matériau photographique de haut contraste à l'halogénure d'argent Download PDF

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Publication number
EP0382455A1
EP0382455A1 EP90301187A EP90301187A EP0382455A1 EP 0382455 A1 EP0382455 A1 EP 0382455A1 EP 90301187 A EP90301187 A EP 90301187A EP 90301187 A EP90301187 A EP 90301187A EP 0382455 A1 EP0382455 A1 EP 0382455A1
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EP
European Patent Office
Prior art keywords
group
silver halide
iii
optionally substituted
photographic material
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP90301187A
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German (de)
English (en)
Inventor
Kazuhiko Hirabayashi
Takeshi Sampei
Yoji Hara
Miho Sai
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Konica Minolta Inc
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Konica Minolta Inc
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Publication of EP0382455A1 publication Critical patent/EP0382455A1/fr
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    • 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
    • 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
    • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
    • G03C1/043—Polyalkylene oxides; Polyalkylene sulfides; Polyalkylene selenides; Polyalkylene tellurides

Definitions

  • the present invention relates to a silver halide photographic material. More particularly, the present invention relates to a silver halide photographic material capable of providing a high-contrast and sensitivity photographic image in a rapid and consistent way.
  • High-contrast photographic image is usually employed in forming characters or halftone image in photomechanical processes, or forming fine-line image in ultra-high-­precision photomechanical processes.
  • Certain kinds of silver halide photographic materials are known to be capable of forming photographic image with very high contrast.
  • a light-sensitive material composed of a silver chlorobromide emulsion that has an average grain size of 0.2 ⁇ m, that has a narrow grain size distribution, that comprises uniformly shaped grains and that has a high silver chloride content (at least 50 mol%) is processed with an alkaline hydroquinone developer of low sulfite ion concentration to form an image of high sharpness and high resolution, for example, a halftone image or a fine-line image.
  • Silver halide light-­sensitive materials of a type to be processed by this method are known as "lithographic" light-sensitive materials.
  • the photomechanical process involves a step of converting the original of continuous tone to be reproduced into a halftone image, or a step in which the continuous change in the density of the original is converted to a set of dots having areas proportional to the varying densities.
  • the original is imaged onto a "lithographic" light-sensitive material via a crossline screen or a contact screen and subsequently developed.
  • a lith-type light-sensitive material i.e., a silver halide photographic material containing a silver halide emulsion consisting of fine grains of uniform size and shape
  • an ordinary black-­and-white developer results in the formation of a lower quality image than when it is developed with a lith-type developer.
  • the lith-type light-sensitive material is conventionally processed with a lith-type developer that has a very low concentration of sulfite ions and which contains hydroquinone as the sole developing agent.
  • developers of the lith type are very low in storage stability because they are highly sensitive to autooxidation. Hence, there is a strong need for controlling them to provide consistent quality of development in their continuous use and substantial efforts have been made to improve the storage stability of lith-­type developers.
  • One of the methods proposed so far to attain object is replenishment with two separate liquids, one being a replenisher intended to compensate for the deterioration in developer's activity during development (compensation for process fatigue) and the other being a replenisher intended to compensate for the oxidative deterioration over time (compensation for aging fatigue).
  • This method of using two types of replenishers is commonly adopted with automatic processors in photomechanical processes.
  • this method suffers the problem of complexity in both equipment and operations.
  • lith-type developers Another problem with the use of lith-type developers is that they have a long induction period (i.e., the time required for an image to appear upon development) and hence are incapable of providing rapid access to image.
  • a first object, therefore, of the present invention is to provide a silver halide photographic material that is capable of producing a contrasty image in a rapid and consistent way.
  • a second object of the present invention is to provide a silver halide photographic material that is capable of consistent production of a contrasty image with minimum loss in sensitivity.
  • a third object of the present invention is to provide a silver halide photographic image capable of producing a contrasty and low-fog image.
  • a fourth object of the present invention is to provide a silver halide photographic image capable of producing a contrasty halftone image of high quality.
  • a silver halide photographic material having at least one light-sensitive silver halide emulsion layer and which contains at least one of the compounds represented by the general formulas (I), (II) and (III) shown below and at least one compound represented by the general formula (IV) also shown below:
  • R1 and R2 each represents an aryl group or a heterocyclic group; R is an organic linkage; n is 0 - 6; and m is 0 or 1, provided that when n is 2 or more, R may be the same or different
  • R1 is an aliphatic, aromatic or heterocyclic group
  • R2 is a hydrogen atom or an optionally substituted alkoxy, heterocyclicoxy, amino or aryloxy group
  • P1 and P2 each represents a hydrogen atom, an acyl group or a sulfinic acid group
  • Ar is an aryl group containing at least one of a non-diffusible group or a silver
  • Examples of the aryl group represented by R1 and R2 include phenyl, naphthyl, etc.
  • Examples of the heterocyclic group represented by R1 and R2 include pyridyl, benzothiazolyl, quinolyl, thienyl, etc.
  • a preferred example of R1 and R2 is an aryl group.
  • substituents can be introduced into the aryl or heterocyclic group represented by R1 and R2.
  • Exemplary substituents include a halogen atom (e.g. chlorine or fluorine), an alkyl group (e.g. methyl, ethyl or dodecyl), an alkoxy group (e.g.
  • an acylamino group e.g. acetylamino, pivalylamino, benzoylamino, tetradecanoylamino or ⁇ -(2,4-di-t-amylphenoxy) butyrylamino
  • a sulfonylamino group e.g. methanesulfonylamino, butanesulfonylamino, dodecanesulfonylamino or benzenesulfonylamino
  • a urea group e.g.
  • phenylurea or ethylurea a thiourea group (e.g. phenylthiourea or ethylthiourea), a hydroxy group, an amino group an alkylamino group (e.g. methylamino or dimethylamino), a carboxyl group, an alkoxycarbonyl group (e.g. ethoxycarbonyl), a carbamoyl group and a sulfo group.
  • the divalent organic group represented by R include an alkylene group (e.g. methylene, ethylene, trimethylene and tetramethylene), an arylene group (e.g.
  • the alkylene group may contain in the bond an oxy group, a thio group, a seleno group, a carbonyl group, group (where R3 is a hydrogen atom, an alkyl group or an aryl group), a sulfonyl group, etc.
  • R3 is a hydrogen atom, an alkyl group or an aryl group
  • Various substituents may be introduced into the group represented by R.
  • Exemplary substituents include -CONHNHR4 (R4 has the same meaning as R1 and R2 described above), an alkyl group, an alkoxy group, a halogen atom, a hydroxy group, a carboxyl group, an acyl group, an aryl group, etc.
  • a preferred example of R is an alkylene group.
  • R1 is an aliphatic, aromatic or heterocyclic group
  • R2 is a hydrogen atom or an optionally substituted alkoxy, heterocyclicoxy, amino or aryloxy group
  • P1 and P2 each represents a hydrogen atom, an acyl group or a sulfinic acid group.
  • the aliphatic group represented by R1 is preferably one having at least 6 carbon atoms, with a straight-­chained, branched or cyclic alkyl group having 8 - 50 carbon atoms being particularly preferred.
  • the branched alkyl group may be cyclized to form a saturated hetero ring containing one or more hetero atoms.
  • the alkyl group represented by R1 may contain a substituent such as an aryl, alkoxy or sulfoxy group.
  • the aromatic group represented by R1 is a monocyclic or bicycyclic aryl group or an unsaturated heterocyclic group, which may be condensed with a mono- or bicyclic aryl group to form a hetero aryl group.
  • Examples of the aromatic group represented by R1 included those which contain a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, a benzothiazole ring, etc. and an aromatic group containing a benzene ring is particularly preferred.
  • a particularly preferred example of R1 is an aryl group.
  • the aryl group or unsaturated heterocyclic group represented by R1 may be substituted and typical substituents include, for example, a straight-chained, branched or cyclic alkyl group (preferably one in which the alkyl portion is mono- or bicyclic with 1 - 20 carbon atoms), an alkoxy group (preferably one having 1 - 20 carbon atoms), a substituted amino group (preferably one which is substituted with an alkyl group having 1 - 20 carbon atoms), an acylamino group (preferably one having 2 - 30 carbon atoms), a sulfonamido group (preferably one having 1 - 30 carbon atoms) and a ureido group (preferably one having 1 - 30 carbon atoms).
  • substituents include, for example, a straight-chained, branched or cyclic alkyl group (preferably one in which the alkyl portion is mono- or bicyclic with 1 - 20 carbon atoms), an alkoxy group (preferably one
  • the optionally substituted alkoxy group represented by R2 in the general formula (II) is one having 1 - 20 carbon atoms which may have a substituent such as a halogen atom or an aryl group.
  • the optionally substituted aryloxy or heterocyclic oxy group which is represented by R2 in the general formula (II) is preferably monocyclic and exemplary substituents include a halogen atom, an alkyl group, an alkoxy group, a cyano group, etc.
  • R2 is an optionally substituted alkoxy or amino group.
  • an amino group it is group where A1 and A2 are each an optionally substituted alkyl or alkoxy group, or they may combine to form a cyclic structure containing an -O-, -S- or -N- bond. It should however be noted that R2 is in no case a hydrazino group.
  • a ballast group commonly employed in couplers and other immobilized photographic additives may be incorporated into R1 or R2 in the general formula (II).
  • a ballast group is a group having at least 8 carbon atoms which is fairly innert to photographic properties and may be selected from among, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group, an amino group, an amido group and an ureido group.
  • a group that enhances adsorption onto the surface of silver halide grains may be incorporated into R1 or R2 in the general formula (II).
  • adsorption enhancing group include those which are described in U.S. Patent 4,355,105 such as a thiourea group, a heterocyclic thioamido group, a mercapto heterocyclic group and a triazole group.
  • R3 and R4 each represents a hydrogen atom, an optionally substituted alkyl group (e.g.
  • R5 represents a hydrogen atom or an optionally substituted benzyl, alkoxy or alkyl group (e.g. benzyl, p-methylbenzyl, methoxy, ethoxy, ethyl or butyl);
  • R6 and R7 each represents a divalent aromatic group (e.g.
  • R8 represents -NR′R ⁇ or -OR9 [where R′, R ⁇ and R9 each represents a hydrogen atom or an optionally substituted alkyl (methyl, ethyl or dodecyl), phenyl (e.g. phenyl, p-methylphenyl or p-methoxyphenyl) or naphthyl (e.g. ⁇ -naphthyl or ⁇ -naphthyl) group; and m and a n each represents 0 or 1, provided that when R8 is OR9, Y is preferably a sulfur atom.
  • a portion (30 g) of the compound (D) is hydrogenated by the same procedure as described above to obtain 20 g of compound (E).
  • the general formula (III) is as follows: where Ar is an aryl group containing at least one of a non-­diffusible group or a silver halide adsorption accelerating group; R1 is an optionally substituted alkyl, alkoxy or amino group.
  • a preferred non-diffusible group is a ballast group which is commonly employed in couplers and other immobilized photographic additives.
  • a ballast group is a group having at least 8 carbon atoms which is fairly inert to photographic properties and may be selected from among, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group, an amino group, an amido group and an ureido group.
  • the silver halide adsorption accelerating group include those which are described in U.S. Patent 4,385,108 such as a thiourea group, a thiourethane group, a heterocyclic thioamido group, a mercapto heterocyclic group and a triazole group.
  • An alkyl group is represented by R1 in the general formula (III) and it is a straight-chained, branched or cyclic alkyl group as exemplified by methyl, ethyl, propyl, butyl, isopropyl, pentyl, cyclohexyl, etc.
  • substituents that is introduced into these alkyl groups include: an alkoxy group e.g. methoxy or ethoxy; an aryloxy group e.g. phenoxy or or p-chlorophenoxy; a heterocyclic oxy group e.g. pyridyloxy; a mercapto group; an alkylthio group e.g.
  • methylthio or ethylthio an arylthio group e.g. phenylthio or p-chlorophenylthio; a heterocyclic thio group e.g. pyridylthio, pyrimidylthio or thiazolylthio; an alkylsulfonyl e.g. methanesulfonyl or butanesulfonyl; an arylsulfonyl group e.g. benzenesulfonyl; a heterocyclic sulfonyl group e.g.
  • pyridylsulfonyl or morpholinosulfonyl e.g. acetyl or benzoyl; a cyano group; a chlorine atom; a bromine atom; an alkoxycarbonyl group e.g. ethoxycarbonyl or methoxycarbonyl; an aryloxycarbonyl group e.g. phenoxycarbonyl; a carboxy group; a carbamoyl group; an alkylcarbamoyl group e.g. N-methylcarbamoyl or N,N-­dimethylcarbamoyl; an arylcarbamoyl group e.g.
  • N-­ phenylcarbamoyl an amino group; an alkylamino group e.g. methylamino or N,N-dimethylamino; an arylamino group e.g. phenylamino or naphthylamino; an acylamino group e.g. acetylamino or benzoylamino; an alkoxycarbonylamino group e.g. ethyoxycarbonylamino; an aryloxycarbonylamino group e.g. phenoxycarbonylamino; an acyloxy group e.g. acetyloxy or benzoyloxy; an alkylaminocarbonyloxy group e.g.
  • methylaminocarbonyloxy an arylaminocarbonyloxy group e.g. phenyl-aminocarbonyloxy; a sulfo group; a sulfamoyl group; an alkylsulfamoyl group e.g. methylsulfamoyl; and an arylsulfamoyl group e.g. phenylsulfamoyl.
  • R′ examples include sulfonyl group (e.g. methanesulfonyl or toluenesulfonyl), an acyl group (e.g. acetyl or trifluoroacetyl) or an oxalyl group (e.g. ethoxalyl).
  • sulfonyl group e.g. methanesulfonyl or toluenesulfonyl
  • acyl group e.g. acetyl or trifluoroacetyl
  • oxalyl group e.g. ethoxalyl
  • R2, R3 and R4 each represents a hydrogen atom, an optionally substituted aliphatic group, e.g. an alkyl group such as methyl, ethyl, buthyl, 3-aryloxypropyl or cyclohexyl; an optionally substituted aromatic group, e.g. a phenyl or naphthyl group; an optionally substituted heterocyclic group, e.g. a pyridyl or pyrrolidyl group; an optionally substituted alkoxy group, e.g. a methoxy, ethoxy or buthoxy group; or an optionally substituted aryloxy group, e.g. a phenoxy or 4pmethylphenoxy group.
  • R2, R3 and R4 each represents a hydrogen atom, an optionally substituted aliphatic group, e.g. an alkyl group such as methyl, ethyl, buthyl, 3-aryloxypropyl or cyclo
  • R2 and R3 are an alkoxy group and a substituted alkyl group, the substituent being an alkoxy or aryl group or the like.
  • R4 is a hydrogen atom or an alkyl group.
  • R5 represents a divalent aromatic group, e.g. a phenylene or naphthylene group, and Y represents a sulfur atom or an oxygen atom.
  • R6 represents an optionally substituted alkyl, alkoxy or amino group, the substituent being an alkoxy, cyano or aryl group or the like.
  • Compound III-5 can be synthesized as in the case of synthesis of compound II-45.
  • One or more of the compounds (I), (II) and (III) are contained in the silver halide photographic material of the present invention in a total amount which preferably ranges from 5 ⁇ 10 ⁇ 7 to 5 ⁇ 10 ⁇ 1 moles, more preferably from 5 ⁇ 10 ⁇ 5 to 1 ⁇ 10 ⁇ 2 mole, per mole of silver halide contained in said photographic material.
  • Hydrazide compounds may be incorporated in either the light-sensitive material or a developer or both in accordance with the present invention. If they are to be incorporated in the light-sensitive material, it may be contained in a light-sensitive silver halide emulsion layer containing a 3-pyrazolidone compound and/or a trihydroxybenzene compound and/or in at least one of other layers coated on the support in such a way that the incorporated hydrazide compounds will have diffused into said emulsion layer by the time development starts.
  • hydrazide compounds are to be incorporated in the light-­sensitive material, they are suitably used in amounts ranging from 10 ⁇ 6 to 10 ⁇ 1 mole per mole of silver halide, preferably from 10 ⁇ 4 to 10 ⁇ 2 mole per mole of silver halide.
  • a suitable amount can be determined in consideration of the balance with other factors such as the silver halide composition, the size of silver halide grains, the degree of their chemical ripening, the amount of a hydrophilic colloid used as a binder, and the amounts of other additives such as a stabilizer, a restrainer and an accelerator.
  • hydrazide compounds are to be incorporated in a developer, they are usually added in amounts ranging from 10 ⁇ 5 to 10 ⁇ 2 mole, preferably from 10 ⁇ 4 to 10 ⁇ 3 mole, per liter of the developer. A suitable amount is determined in consideration of the balance with other factors such as the amino compound used, pH and fog restrainer used.
  • the general formula (IV) is as follows: R1 - 0 ( ⁇ CH2CH2O) n H (IV) Where R1 is a hydrogen atom or a substituted or unsubstituted aromatic ring; and n is an integer of 10 -­200.
  • These compounds are readily available from the commercial market. They are preferably added in an amount of 0.01 - 4.0 moles, more preferably from 0.02 to 2 moles, per mole of silver halide. Two or more compounds having different values of n may be used in admixture.
  • the silver halide emulsion to be used in the light-­sensitive material of the present invention may employ various silver halides such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide and silver chloroiodobromide.
  • the present invention proves effective with silver bromide and silver iodobromide, with particular advantage being exhibited with a high-­sensitivity light-sensitive material having a small content ( ⁇ 5 mol%, particularly 1.5 to 3 mol%) of silver iodide.
  • the present invention proves particularly effective with an emulsion obtained by adding a water-soluble iodide at the stage of adjustment.
  • the silver halide emulsion to be used in the present invention may be such that silver halide grains are suspended in a hydrophilic colloid by a known method such as the neutral method, ammoniacal method, single-jet method or double-jet method.
  • the silver halide emulsion layer in the light-­sensitive material of the present invention preferably contains a silver halide composed of grains having an average size of 0.1 - 1.0 ⁇ m, more preferably 0.1 - 0.7 ⁇ m, with at least 75%, preferably at least 80%, of the total grains having a grain size ranging from 0.7 - 1.3 times the average grain size.
  • a silver halide emulsion having polyvalent metallic ions (e.g. iridium or rhodium) occluded therein may also be used and examples of such emulsion are described in U.S. Patent 3,271,157, 3,447,927 and 3,531,291.
  • Silver halide emulsions used in the present invention may be chemically sensitized by a common method such as the use of sulfur compounds or gold compounds exemplified by chloroaurates and gold trichloride.
  • the silver halide emulsion to be used in the present invention may be treated with spectral sensitizers to have sensitivity to colors in desired spectral ranges of wavelength.
  • spectral sensitizers may be used for this purpose and they include methine and styryl dyes such as cyanine, hemicyanine, rhodacyanine, merocyanine, exanole and hemioxonole.
  • methine and styryl dyes such as cyanine, hemicyanine, rhodacyanine, merocyanine, exanole and hemioxonole.
  • spectral sensitizers reference may be made to various prior patents such as U.S. Patent Nos.
  • the silver halide photographic emulsion in the light-­sensitive material of the present invention may be used with common hardeners such as aldehydes (e.g. formaldehyde, glyoxal, glutaraldehyde and mucochloric acid), N-methylol compounds (e.g. dimethylolurea and methylol dimethyl hydantoin), dioxane derivatives (e.g. 2,3-­dihydroxydioxane), active vinyl compounds (e.g. 1,3,5-­triacryloylhexahydro-s-triazine and bis (vinylsulfonyl) methyl ether), and active halide (e.g.
  • aldehydes e.g. formaldehyde, glyoxal, glutaraldehyde and mucochloric acid
  • N-methylol compounds e.g. dimethylolurea and methylol dimethyl hydanto
  • 2,4-dichloro-6-­hydroxy-s-triazine which may be used either on their own or as admixtures.
  • the emulsion may also be used with common thickeners, matting agents and coating aids.
  • Suitable binders are hydrophilic binders that work as protective colloids and which are commonly used in the art.
  • the light-sensitive material of the present invention may further contain various other additives such as couplers, ultraviolet absorbers, brighteners, image stabilizers, antioxidants, lubricants, metallic ion sequestering agents and emulsifying/dispersing agents, which are selected in accordance with the specific object of interest.
  • additives such as couplers, ultraviolet absorbers, brighteners, image stabilizers, antioxidants, lubricants, metallic ion sequestering agents and emulsifying/dispersing agents, which are selected in accordance with the specific object of interest.
  • the light-­sensitive material of the present invention may have other photographic layers such as a protective layer, an intermediate layer, a filter layer, an anti-halation layer, a subbing layer, an auxiliary layer, an anti-irradiation layer and a backing layer.
  • Various supports may be employed as selected from among, for example, baryta paper, polyethylene-coated paper, cellulose acetate, cellulose nitrate and polyethylene terephthalate, in accordance with the specific use of the light-sensitive material.
  • Polymer latices made of homo- or copolymers of monomeric compounds such as alkyl acrylates, alkyl methacrylates, acrylic acid or glycidyl acrylate may be contained in the light-sensitive silver halide emulsion layer or some other layers coated on the support in order to attain certain purposes such as improvements in the dimensional stability of the photographic material and in its film properties.
  • a stabilizer or an anti-foggant may be contained in the light-sensitive silver halide emulsion, with a suitable one being selected from among many compounds including 4-­hydroxy-6-methyl-1,3,3a, 7-tetraazaindene, 1-phenyl-5-­mercaptotetrazole, resorcinol oxime and hydroquinone aldoxime. These compounds can be incorporated in amounts ranging from 10 ⁇ 4 to 10 ⁇ 1 mole per mole of silver halide.
  • a polyethylene terephthalate film with a thickness of 100 ⁇ m that had a subbing layer (see Example 1 of JP-A-59-­19941) on each sides in a thickness of 0.1 ⁇ m was used as a support.
  • the subbing layer on one side was coated with a silver halide emulsion layer (for its composition, see recipe (1) below) to give a gelatin and a silver deposit of 2.0 g/m2 and 3.5 g/m2, respectively.
  • the resulting emulsion layer was coated with a protective layer according to recipe (2) shown below, to give a gelatin deposit of 1.5 g/m2.
  • the subbing layer on the other side was coated with a backing layer according to recipe (3) shown below, to give a gelatin deposit of 2.7 g/m2.
  • the backing layer was coated with a protective layer according to recipe (4) shown below, to give a gelatin deposit of 1 g/m2.
  • the samples prepared were subjected to a halftone dot quality test by the following method.
  • a contact screen (50% dot area; 150 lines per inch) was partly attached to a step wedge and a sample placed in close proximity with the contact screen was exposed to light from a xenon lamp for 5 seconds. The exposed sample was then developed with a rapid access automatic processor supplied with a developer having the formulation shown below.
  • the quality of halftone dots in the processed samples was observed with a magnifier (X 100) and rated by a five-score method, with the best sample (having the highest quality of halftone dots) being given score 5 and followed by 4, 3, 2 and 1 in the decreasing order of quality. Samples rated "1" and "2" were unacceptable for practical purposes.
  • Example 1 The results of Example 1 are shown in Table 1.
  • sample Nos. 6 - 15 and 17 according to the present invention had higher sensitivity and formed more contrasty image with better quality of halftone dots and fewer black peppers than the comparative samples.
  • Example 2 The procedure of Example 1 was repeated except that the samples prepared in it were processed with a developer having the formulation described below. The results are shown in Table 2.
  • Formulation of developer Hydroquinone 45.0 g N-Methyl-p-aminophenol hemisulfate 0.8 g Sodium hydroxide 18.0 g Potassium hydroxide 55.0 g 5-Sulfosalicylic acid 45.0 g Boric acid 25.0 g Potassium sulfite 110.g g Ethylenediaminetetraacetic acid disodium salt 1.0 g Potassium bromide 6.0 g 5-Methylbenzotriazole 15.0 g n-Butyl diethanolamine 15.
  • Table 2 shows that sample Nos. 6 - 15 and 17 according to the present invention had higher sensitivity and formed more contrasty image with better quality of halftone dots and fewer black peppers than the comparative samples.
  • Silver halide (90 mol% AgCl and 10 mol% AgBr) grains having an average size of 0.08 ⁇ m and containing rhodium in an amount of 2 ⁇ 10 ⁇ 6 mole per mole of silver halide were sulfur-sensitized in the usual manner. Thereafter, a stabilizer or 6-methyl-4-hydroyx-1,3,31,7-tetraazaindene (570 mg per mole of silver halide) and gelatin (25 g) were added.
  • the coating solutions for the necessary layers had the following formulations.
  • the emulsion layer was applied to give a silver deposit of 3.5 g/m2.
  • Dioctyl sulfosuccinate ester 300 mg/m2 Matting agent (particulate methyl methacrylate with an average grain size of 4.0 ⁇ m) 100 mg/m2 Ossein gelatin (isoelectric point, 4.9) 1.1 g/m2 Fluorinated sodium dodecylbenzenesulfonate 50 mg/m2
  • the samples prepared in accordance with the recipes shown above were exposed under a quartz iodine light source (halogen lamp) at 1.5 kW for 10 seconds.
  • the discharge tube was a light source having a substantial energy intensity at 400 nm and longer wavelengths.
  • the samples as prepared were such that they could be handled under illumination with an ordinary fluorescent lamp at 300 lux.
  • the exposed samples were developed and subsequently processed as in Example 1 and subjected to similar tests.
  • the test results are shown in Table 3, from which one can see that sample Nos. 6 - 15 and 17 according to the present invention had higher sensitivity and formed more contrasty image with better quality of halftone dots and fewer black peppers than the comparative samples.
  • Table 3 Sample No.
  • Silver halide (98 mole% AgCl and 2 mol% AgBr) grains having an average size of 0.17 pm and containing rhodium in an amount of 1.0 ⁇ 10 ⁇ 4 mole per mole of silver halide were sulfur-sensitized in the usual manner. Thereafter, 6-­methyl-4-hydroxyl,3,3a, 7-tetraazaindene was added as a stabilizer.
  • the coating solutions for the necessary layers had the following formulations.
  • the emulsion layer was applied to give a silver deposit of 3.0 g/mz.
  • Recipe (1) (formulation of silver halide emulsion layer) Compound (S) (as used in Example 3) 1 mg/m2 Sodium hydroxide 14 mg/m2 Compound according to the present invention [as represented by the general formula (I), (II), (III) or (IV)] or comparative compound (see Table 4)
  • emulsions were prepared as in Example 1 except that compounds within the scope of the present invention or comparative compounds were added as shown in Table 5.
  • the silver halide grains used were cubic, monodispersed silver iodobromide grains (grains A) having an average size of 0.3 ⁇ m and containing 1 mol% AgI and 10 ⁇ 7 mole of iridium per mole of AgI, and sulfur-sensitized cubic, monodispersed silver iodobromide grains (grains B) having an average size of 0.15 ⁇ m and containing 0.1 mol% AgI.
  • the two types of grains were mixed at a ratio of 1:1 to prepare emulsions.
  • sample Nos. 6 - 15 and 17 according to the present invention had higher sensitivity and formed more contrasty image with better quality of halftone dots and fewer black peppers than the comparative samples.
  • Emulsions were prepared as in Example 5 except that grains A were replaced by tabular grains (grains C), which were made from Emulsion 1 described on page 13 of JP-A-58-­113926.
  • This emulsion was a silver iodobromide emulsion having an average diameter of 2.8 ⁇ m and an average thickness of 0.095 ⁇ m, with an average aspect ratio being 29.5:1.
  • Grains B used in Example 5 and grains C were mixed at a ratio of 5:1.
  • light-­sensitive materials were fabricated as in Example 4 except that compounds within the scope of the present invention or comparative compounds were used as shown in Table 6. The samples were exposed, developed and subsequently processed.
  • Emulsions were prepared as in Example 1.
  • the composition of the silver halide emulsion layer used in this example was the same as what was employed in Example 1 except that the cyanine dye and spectral sensitizer were replaced by the following dye and compound, respectively, with each being added in an amount of 1 mg/m2;
  • the samples of light-sensitive material prepared were exposed for 10 ⁇ 5 second with an apparatus using as a light source an infrared semiconductor laser emitting light having a main peak at 780 nm.
  • the exposed samples were developed and subsequently processed as in Example 1.
  • the processed samples were subjected to similar tests and the test results are shown in Table 7.
  • Table 7 Sample No. Hydrazide compound Compound formula (IV) Relative sensitivity Gamma Quality of halftone dots Black pepper Remarks Identification Amount, mg/m2 Identification Amount, mg/m2 1 a 35 - - 100 7.7 3 2 comparison 2 b 35 - - 101 7.3 2 3 do. 3 c 35 - - 88 8.1 2 2 do. 4 c 35 IV-4 100 99 7.7 2 2 do.
  • sample Nos. 6 - 15 and 17 according to the present invention had higher sensitivity and formed image with better quality of dots and fewer black peppers.
  • the present invention provides a silver halide photographic material that has high sensitivity and forms a contrasty image with good quality of halftone dots and few black peppers.

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  • Spectroscopy & Molecular Physics (AREA)
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  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP90301187A 1989-02-07 1990-02-05 Matériau photographique de haut contraste à l'halogénure d'argent Withdrawn EP0382455A1 (fr)

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JP2938589 1989-02-07
JP29385/89 1989-02-07

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EP0539925A1 (fr) * 1991-11-01 1993-05-05 Konica Corporation Matériau photographique à l'halogénure d'argent sensible à la lumière
EP0554856A1 (fr) * 1992-02-06 1993-08-11 Fuji Photo Film Co., Ltd. Matériau photographique à l'halogénure d'argent

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US8326903B2 (en) * 2008-01-04 2012-12-04 International Business Machines Corporation System and method for improved vector analysis

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EP0217310B1 (fr) * 1985-09-26 1992-11-04 International Paper Company Composés et composition utiles comme agents de promotion de points

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JPS589412B2 (ja) 1977-08-30 1983-02-21 富士写真フイルム株式会社 ハロゲン化銀写真感光材料の現像方法
DE3023099A1 (de) 1979-06-21 1981-01-08 Fuji Photo Film Co Ltd Verfahren zur bildung eines negativen punktbildes
US4816373A (en) 1986-01-31 1989-03-28 Mitsubishi Paper Mills, Ltd. Method of producing images
JPS63128338A (ja) 1986-11-18 1988-05-31 Fuji Photo Film Co Ltd 画像形成方法
US4914002A (en) 1987-11-04 1990-04-03 Fuji Photo Film Co., Ltd. Silver halide photographic material
US4988603A (en) 1988-01-11 1991-01-29 Konica Corporation Method for the formation of high-contrast images using a developer comprising a hydrazine derivative
JP2683796B2 (ja) 1988-03-03 1997-12-03 コニカ株式会社 高コントラストな画像を得ることができるハロゲン化銀写真感光材料
JP2639984B2 (ja) 1988-10-14 1997-08-13 コニカ株式会社 ピンホールの改良されたハロゲン化銀写真感光材料

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DE2941428A1 (de) * 1978-10-12 1980-04-30 Fuji Photo Film Co Ltd Lichtempfindliches photographisches silberhalogenidmaterial und dessen verwendung in einem verfahren zur erzeugung von photographischen bildern
EP0217310B1 (fr) * 1985-09-26 1992-11-04 International Paper Company Composés et composition utiles comme agents de promotion de points

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0539925A1 (fr) * 1991-11-01 1993-05-05 Konica Corporation Matériau photographique à l'halogénure d'argent sensible à la lumière
US5279920A (en) * 1991-11-01 1994-01-18 Konica Corporation Silver halide photographic light sensitive material
EP0554856A1 (fr) * 1992-02-06 1993-08-11 Fuji Photo Film Co., Ltd. Matériau photographique à l'halogénure d'argent
US5340694A (en) * 1992-02-06 1994-08-23 Fuji Photo Film Co., Ltd. Silver halide photographic material

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