EP0740194B1 - Matériau d'enregistrement à l'halogénure d'argent pour la préparation des images négatives ayant un contraste très haut - Google Patents

Matériau d'enregistrement à l'halogénure d'argent pour la préparation des images négatives ayant un contraste très haut Download PDF

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Publication number
EP0740194B1
EP0740194B1 EP96106510A EP96106510A EP0740194B1 EP 0740194 B1 EP0740194 B1 EP 0740194B1 EP 96106510 A EP96106510 A EP 96106510A EP 96106510 A EP96106510 A EP 96106510A EP 0740194 B1 EP0740194 B1 EP 0740194B1
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EP
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Prior art keywords
silver halide
group
light sensitive
recording material
material according
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EP96106510A
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German (de)
English (en)
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EP0740194A1 (fr
Inventor
Reinhold Dr. Rüger
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DuPont de Nemours Deutschland GmbH
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DuPont de Nemours Deutschland GmbH
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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
    • 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
    • G03C1/067—Additives for high contrast images, other than 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
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • 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
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G03C2001/03541—Cubic grains
    • 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
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G03C2001/0357—Monodisperse emulsion
    • 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
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G03C2001/03594—Size of the grains
    • 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
    • G03C2200/00—Details
    • G03C2200/44—Details pH value
    • 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
    • G03C5/30—Developers

Definitions

  • the invention relates to a silver halide photographic material to create black and white Negative images with ultra-partial contrast and a method for Using a black and white negative image of such material.
  • Halftone images can be converted into halftone dot images.
  • silver halide materials which one in special methods for ultra-partial contrast, d. H. to a maximum gradient of the density curve of more than 10, developed.
  • the lith process is also known, for example Low-sulfite, formaldehyde-containing hydroquinone developers. Development has recently become of particular practical importance in the presence of hydrazine compounds.
  • EP-A-02 03 521 can be salts of certain sulfonic or carboxylic acids as Solubilizers are used. The remaining However, problems addressed are caused by such additions unaffected.
  • the known developers usually have a pH above 11. Therefore, they are not sufficiently stable and in practice have a highly corrosive effect on the components of the development machines.
  • German patent application DE-A-43 10 327 there is a Process for the generation of negative images with ultra-partial Contrast described in which the development of the Silver halide recording material in the presence of Connections are made whose molecules have at least one quaternary nitrogen atom and at least one tertiary Have amine function.
  • EP-04 73 342-A1 there is a photographic Silver halide material described in a developer with a pH ⁇ 11 to be developed to ultra-partial contrast can.
  • the light sensitive coating of this material contains a hydrazine compound of a certain formula as well an amino or a quaternary onium compound and is on set a pH of at least 5.9.
  • EP 04 22 677 describes the use of tertiary Amino compounds with at least three oxyethylene units in the Molecule as a development accelerator in developer solutions, which also work in the presence of hydrazine compounds.
  • EP 05 39 998 claims silver halide materials, which besides Hydrazine compounds or thioether compounds with tertiary Amino group included.
  • the invention has for its object a silver halide recording material to propose that for generating Negative images with ultra-partial contrast at short Processing time with a stable, odorless and not Corrosive developer suitable and from those mentioned above Disadvantages is free, as well as a process for the production of Black and white negative images with ultra-partial contrast specify.
  • the tertiary amino group is replaced by a nitrogen atom realized, which with single bonds to two organic Remnants as well as via a divalent connecting group to the Nitri group is bound.
  • the contrast-increasing compound falls under one of the general formulas (A), (B) or (C) given below: RR 1 N - X - (CN) n NC - X - NR 2 - B - NR 2 - X - CN RR 1 N - X - N (CH 2 CN) 2
  • the radicals R and R 1 may be the same or different and each may be a straight-chain or branched alkyl group having 1 to 6 carbon atoms, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-hexyl.
  • Each of the groups R and R 1 can also be a benzyl group.
  • the groups R and R 1 and also the heterocyclic rings corresponding to these groups can be further substituted, preferably with hydroxyl, alkoxy, alkylthio or alkylamino groups, where the alkyl can have 1 to 6 carbon atoms. Examples of such substituents are methoxy, ethoxy, propoxy, butoxy, ethylamino, dimethylamino, butylthio.
  • R or R 1 can also connect to the connecting group X with their free end to form a ring which includes the nitrogen atom of the tertiary amino group.
  • a ring can be, for example, a piperidine ring or a morpholine ring.
  • the divalent connecting groups X and B are preferred straight-chain, branched or cyclic alkylene groups with 1 up to 20 carbon atoms, phenylene or aralkylene groups with 7 to 20 carbon atoms, or divalent chains from 1 to 20 methylene groups, in addition to these also oxygen, Sulfur, amino groups, alkene or alkyne groups or also Polyoxyalkylene groups, especially polyoxyethylene or Polyoxypropylene groups with 1 to 50 oxyalkyl units can be installed. An ethylene or Propylene group.
  • the groups mentioned can also continue be substituted, for example with alkyl, hydroxyl and further tertiary amino groups.
  • the connecting group X can also be trivalent and thus connect the tertiary amino group with two nitrile groups.
  • the groups mentioned in the previous paragraph are suitable if they contain a further free valence instead of a hydrogen atom. Examples include:
  • the radical R 2 in the general formula (B) denotes a saturated or unsaturated alkyl group, preferably having 1 to 12 carbon atoms, an aryl group, preferably having 6 to 14 carbon atoms or an aralkyl group, preferably having 7 to 15 carbon atoms. These groups can in turn be substituted, for example with hydroxyl, amino, alkylamino and alkoxy groups, the alkyl preferably having 1 to 6 carbon atoms. If it is an alkyl group, it can also be attached to a carbon atom of group B with its end facing away from the nitrogen, forming a ring. Such a ring can be, for example, a piperidine, pyrrolidine or hexahydroazepine ring.
  • the two radicals R 2 can also form together with B or with parts of B and with the two nitrogen atoms one or two saturated rings, preferably with 5 or 6 members, for example pyrrolidine or piperidine rings.
  • n is either 1 or 2.
  • contrast-increasing compounds according to the invention in have at least one tertiary amino group in their molecule, They can be in the form of the free amine as well as in the form a salt, i.e. an adduct of an acid and that free amine, produced, handled and used.
  • a preferred acid is hydrochloric acid.
  • Contrast-increasing compounds according to the invention can be from easily accessible and inexpensive raw materials produce.
  • the person skilled in the art can use the Find standard works on preparative organic chemistry, for example the introduction of a cyanomethyl group Chloroacetonitrile, the alkylation of cyanides (Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume 8 (1952), Pages 290 ff.) And the drainage of carboxamides (ibid., pages 330 ff.).
  • Other possibilities of synthesis are the alkylation of the anion of a suitable CH-azide Compound such as malononitrile with aminohalogen alkanes and the conversion of ketones with cyanides to cyanohydrins.
  • Several of the compounds of the invention are also reasonably priced in stores.
  • contrast-increasing compounds are: (C 2 H 5 ) 2 NC 3 H 6 ⁇ CN HCl (i - C 3 H 7 ) 2 NC 2 H 4 ⁇ CN HCl (C 4 H 9 ) 2 NC 2 H 4 ⁇ CN HCl (C 4 H 9 ) 2 NC 3 H 6 ⁇ N (CH 2 CN) 2 (C 2 H 5 ) 2 NC 2 H 4 ⁇ O ⁇ C 2 H 4 ⁇ CN (C 2 H 5 ) 2 NC 2 H 4 ⁇ S ⁇ C 2 H 4 ⁇ CN
  • the recording material according to the invention contains a Hydrazine compound.
  • This hydrazine compound can in itself known way either in one or more layers of Recording material can be incorporated.
  • This can be both Layers which are the photosensitive silver halide contain, as well as layers with the former in reactive connection, d. H. which are arranged so that Can diffuse substances from one layer to the other, if a concentration gradient through reactions is maintained.
  • Suitable hydrazine compounds are described, for example, in Research Disclosure 235 010 (November 1983), DE-27 25 743-A1, EP-00 32 456-B1, EP-01 26 000-A2, EP-01 38 200-A2, EP-02 03 521-A2, EP-02 17 310-A2, EP- 02 53 665-A2, EP-03 24 391-A2, EP-03 24 426-A2, EP-03 26 443-A2, EP-03 56 898-A2, EP-04 73 342-A1, EP-05 01 546-A1, EP-04 81 565-A, EP-05 98 315-A1, EP-04 44 506.
  • Preferred hydrazine compounds are described by the general formula (H): B - phenyl - NHNH - L - G
  • B is a ballast group
  • G is an activating group Group
  • L one of the groups -CO- and -CO-CO-.
  • Phenyl means a benzene ring on the B and the hydrazine group are bound, preferably in the para position.
  • Preferred ballast groups are those that are not are electron-attracting, for example straight or branched alkyl groups (e.g. methyl, ethyl, n-propyl, Isopropyl, n-butyl, isobutyl, n-hexyl, n-octyl, t-octyl, n-decyl, n-dodecyl and similar groups), also alkoxy groups, which contain one of the alkyl groups mentioned above as alkyl, as well as acylamino groups, such as acetylamino, propanoylamino, Butanoylamino, octanoylamino, benzoylamino, alkyl and Arylsulfonamido and similar groups.
  • alkyl groups e.g. methyl, ethyl, n-propyl, Isopropyl, n-butyl, isobutyl,
  • Ballast groups typically contain at least 8 Carbon atoms and can be made of relatively inert aliphatic or aromatic groups are selected, for example alkyl, alkoxy, phenyl, alkylphenyl, phenoxy, Alkylphenoxy, arylacyl, arylamido, alkylpyridinium-1-ylamido and similar groups.
  • the alkyl and alkoxy groups include any Ballast groups preferably 1 to 20, the acylamino groups preferably 2 to 21 carbon atoms. But it can be up to Contain 30 or more carbon atoms in these groups be. Methoxyphenyl, tolyl, ballasted butyramidophenyl, butylsulfonamido and Toluylsulfonamido.
  • Preferred hydrazine compounds include those whose Ballast group still contains an adsorption promoting group. Such groups promote the adsorption of the molecule on the Surface of the silver halide crystals and are in themselves known. They typically contain at least one sulfur or Nitrogen atom which can form a silver complex or otherwise has an affinity for the silver halide surface. Preferred examples are thiourea, thiuronium, heterocyclic thioamide and triazole groups.
  • G is preferably hydrogen, optionally substituted alkyl (e.g. methyl, hydroxymethyl, monofluoromethyl, pyridinomethyl, Phenoxymethyl, alkoxymethyl such as methoxymethyl), if appropriate substituted aralkyl (e.g. benzyl, o-hydroxybenzyl) and possibly substituted aryl (e.g. phenyl, 3,5-dichlorophenyl, o-methanesulfonamidophenyl, 4-methanesulfonylmethyl, 2-hydroxymethylphenyl), alkyl groups with electron-withdrawing substituents, for example cationic groups with quaternary nitrogen atom, such as Pyridinium and Imidazolium, are particularly preferred.
  • alkyl e.g. methyl, hydroxymethyl, monofluoromethyl, pyridinomethyl, Phenoxymethyl, alkoxymethyl such as methoxymethyl
  • substituted aralkyl e.g. benzyl
  • G can also be further substituted, e.g. B. with alkyl, Aralkyl, alkenyl, alkynyl, alkoxy, aryl, substituted amino, Ureido, urethane, aryloxy, sulfamoyl, carbamoyl, alkyl or Arylthio, alkyl- or arylsulfonyl, alkyl- or arylsulfinyl, Hydroxy, halogen, cyan, sulfo, aryloxycarbonyl, acyl, Alkoxycarbonyl, acyloxy, carbamide, sulfonamide, carboxyl, Phosphamide, diacylamino, imide.
  • G can also be chosen so that the L-G part of the molecule is separated to form a ring, as is e.g. in EP-B-02 53 665 is described.
  • OTS - is the anion of o-toluenesulfonic acid.
  • the light-sensitive silver halides of the invention recording materials used consist of Silver chloride, silver bromide, silver chlorobromide, Silver bromoiodide or silver chlorobromoiodide.
  • the silver halide grains can be spherical, polyhedral or tabular to have. Methods of making suitable photosensitive Silver halide emulsions are known to the person skilled in the art and for example in Research Disclosure 365 044, Chapter I to IV (September 1994).
  • Recording materials are silver halide emulsions that be produced by controlled double jet inlet and have a cubic grain shape. Emulsions are advantageous in which at least 80 percent by weight of the silver halide are available in cubic form. Are particularly preferred monodisperse emulsions, i.e. H. those where the Coefficient of variation (quotient of standard deviation and Mean) the grain size is less than 0.30. Under Grain size becomes the edge length of one with the real grain volume equal cube understood.
  • the grain volume of the silver halide grains in the emulsions depends on the required sensitivity and can for example the cubic grain from 0.1 to 0.7 ⁇ m Edge length. A preferred range is between 0.15 and 0.30 ⁇ m.
  • the emulsions are preferably chemically sensitized. Suitable processes are the sulfur, the reduction and the precious metal sensitization, also in combination can be applied. For the latter, for example Gold or iridium compounds can be used.
  • the Sensitization is preferred in the presence of salts organic thiosulfonic acids, such as p-toluenesulfonic acid, carried out.
  • the emulsions can be mixed with usual Sensitizing dyes are spectrally sensitized, such as in Research Disclosure 365 044, Chapter V (September 1994).
  • the emulsions can also be conventional antifoggants contain.
  • Substituted benzotriazole are preferred, 5-nitroindazole and 1-phenyl-5-mercaptotetrazole. This means can be used at any time during emulsion production be added or in an auxiliary layer of the photographic material may be included.
  • the photographic properties can before or the emulsion after chemical ripening an iodide, preferably a Alkali iodide, in an amount of about 0.5 to 5 mmol per mole Silver can be added.
  • the emulsions can also contain known polymer dispersions which, for example, improve the dimensional stability of the photographic material. These are generally latices of hydrophobic polymers in an aqueous matrix. Examples of suitable polymer dispersions are mentioned in Research Disclosure 176 043, Chapter IX B (December 1978). Polymers of esters of acrylic and methacrylic acid are preferred, particularly preferably of C 1 to C 6 esters. The particle size of these polymer latices is preferably between 20 and 100 nm.
  • the photosensitive layers of the photographic Materials can be hardened by adding a hardening agent be.
  • hardeners are in research Disclosure 365 044, Chapter II B (September 1994). This hardener can be added to the emulsion or via a Auxiliary layer, for example an outer protective layer, be introduced.
  • Suitable hardeners are, for example Aldehydes, such as formaldehyde or glutaraldehyde, vinyl sulfones, s-triazines, aziridines, carbodiimides, carbamoylpyridinium compounds, mono- and bifunctional carbamoylimidazolium compounds.
  • a preferred curing agent is Hydroxydichlorotriazine.
  • the photographic material can be further additives for the Generation of certain properties are known and common, contain. Such funds are, for example, in research Disclosure 365 044 (September 1994) in Chapter VI (Brightener), IX A (coating aid), IX B (Plasticizers and lubricants) and IX D (matting agents) listed.
  • the gelatin content of the emulsions is in general between 30 and 150 g per mole of silver; the is preferred Range between 40 and 100 g per mol of silver.
  • the invention also includes a method for the production black and white negative photographic images, which is characterized by having a preliminary described light-sensitive material exposed imagewise in an aqueous developer solution developed, fixed in the usual way, watered and dried.
  • the developer solutions used according to the invention contain preferably a dihydroxybenzene developer substance, for example hydroquinone, pyrocatechol, methylhydroquinone or chlorohydroquinone, and an antioxidant, preferably an alkali sulfite in a concentration of more than 0.3 mol per liter. Solutions with are particularly preferred pH values from 9 to a maximum of 11. Such developer solutions are also durable in use and largely result fog-free images.
  • Ascorbic acid type for example L-ascorbic acid, D-ascorbic acid, L-erythroascorbic acid, 6-deoxy-L-ascorbic acid, Imino-L-erythroascorbic acid or Sugar derivatives of these acids.
  • Developer solutions that both developer substances from Dihydroxybenzene type as well as those of the ascorbic acid type contain.
  • the developer solutions preferably contain known solutions super-additive auxiliary developer substances, for example N-methyl-p-aminophenol or 1-phenylpyrazolidinone-3 or derivatives of these compounds.
  • developers that consist of stabilizers contain the groups of benzotriazoles and mercaptotetrazoles.
  • Such stabilizers are, for example 1-phenyl-5-mercaptotetrazole, 1- (4-hydroxyphenyl) -5-mercaptotetrazole, 1- (1-naphthyl) -5-mercaptotetrazole, 1-cyclohexyl-5-mercaptotetrazole, 1- (4-chlorophenyl) -5- mercaptotetrazole, 1- (3-capramidophenyl) -5-mercaptotetrazole, benzotriazole, 5-chlorobenzotriazole, 5-bromobenzotriazole, 5-methylbenztriazole, 5-nitrobenztriazole, 5-benzoylaminobenztriazole, 1-hydroxymethylbenztriazole, 6-cyanobenztriazole.
  • the contrast-enhancing compounds according to the invention can added to the emulsion at every stage of manufacture will. Because of their molecular structure, they can both be surface active as well as with ionic polymers Interaction.
  • the nitrile group gives the Compounds hydrophilic properties. In contrast, in Molecule also present hydrocarbon groups hydrophobic and diffusion-inhibiting effect. It is therefore possible by selecting the number of nitrile groups, the number and type of hydrocarbon groups and possibly other hydrophilic groups such as ethylene oxide groups Water solubility, interfacial activity and Diffusibility of the connections on the respective To coordinate the application.
  • the compounds according to the invention are in the alkaline developer baths too photographically inactive secondary products are decomposed. she therefore do not enrich themselves - like other well-known in Recording material incorporated contrast-enhancing Connections - as a result of washing out in the developer. Therefore they affect the stability of developer activity not even if they are only slightly diffusion inhibited (ballasted).
  • the invention can be used to produce black and white Negative images with ultra-partial contrast, especially in the Reproduction in prepress for the black and white and Multi-color printing. It is through the following Embodiment explained in more detail.
  • a cubic silver chlorobromide emulsion (80 mole percent chloride) was produced by pAg-controlled two-jet inlet in the presence of a rhodium salt, the grains of which had an edge length of 0.21 ⁇ m. After the soluble salts had been removed by means of the flocking process, the total gelatin content was 55 g per mol of silver and chemical ripening was carried out using potassium thiotosylate, thiosulfate and gold salt.
  • potassium iodide (1.6 mmol / mol Ag), phenyl mercaptotetrazole, 5-nitroindazole, a polyethylene latex, a sensitizer for the green spectral range, two coating aids (Triton® X-102, Triton® X-200; manufacturer: Rohm & Haas ), 0.12 mmol of 1-pyridiniumacetyl-2- (4-benzyloxyphenyl) hydrazine bromide (compound H-9) per mol of silver and 0.10 mmol of dichlorohydroxytriazine sodium salt per g of gelatin were added.
  • Camera films were produced by applying the emulsion together with overcasts containing gelatin, matting agent, wetting agent (Triton® X-200) and additives according to Table 1.
  • the silver application was 4.2 g / m 2
  • the pouring application 0.9 g gelatin per m 2 .
  • Sample strips of the recording materials obtained were exposed to white light through an original from a density gradient wedge, which was partially underlaid with a contact grid.
  • the strips were developed, fixed, washed and dried in a developing machine (Dürr Graphica) at 36 ° C.
  • the development time was 28 s.
  • a commercially available fixing bath was used.
  • the developer had the following composition: water 500 g Sodium bisulfite 50 g KOH 27 g EDTA trisodium salt 3.7 g Hydroquinone 25 g Potassium bromide 4 g Benzotriazole 0.3 g Phenyl mercaptotetrazole 0.05 g 4-hydroxymethyl-4-methyl-1-phenylpyrazolidinone 1 g Boric acid 3 g Sodium hydroxide 24 g Diethylene glycol 40 g Water to 1 liter, pH to 10.5 at 22 ° C.
  • the rating 10 means optimal sharpness of the points, 4 - 5 is only of limited use and corresponds to the sharpness of a Rapid Access film without contrast enhancement, 1 - 3 is unusable.
  • Table 1 attempt additive Dmin Dmax S G1 G2 PQ Verb.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
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  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Claims (9)

  1. Surface d'enregistrement à l'halogénure d'argent photosensible, en particulier pour la préparation d'images négatives en noir et blanc à contraste extrêmement élevé, comprenant au moins une couche photosensible sur au moins l'une des faces d'un substrat et le cas échéant d'autres couches sur la même face du substrat, qui contient, dans la couche photosensible ou dans une couche associée réactivement à cette couche, au moins un dérivé d'hydrazine, caractérisé en ce qu'elle contient, dans cette couche ou dans ladite couche associés réactivement à celle-ci, au moins un dérivé augmentant le contraste qui a dans sa molécule au moins un groupe amine tertiaire et au moins un groupe nitrile.
  2. Surface d'enregistrement à l'halogénure d'argent photosensible, selon la revendication 1, caractérisée en ce que le dérivé augmentant le contraste répond à l'une des formules générales (A), (B) ou (C) RR1N - X - (CN)n NC - X - NR2 - B - NR2 - X - CN RR1N - X - N(CH2CN)2 dans lesquelles
    R, R1
    identiques ou différents, sont chacun un groupe alkyle éventuellement substitué comportant 1 à 6 atomes de carbone, ou un groupe benzyle éventuellement substitué, ou bien R et R1 forment avec l'atome d'azote auquel ils sont attachés et, le cas échéant, avec un atome d'oxygène supplémentaire, un cycle à 5 ou 6 éléments,
    R2
    est un groupe alkyle saturé ou insaturé, ou un groupe aryle, ces groupes pouvant être en outre substitués, en outre, un groupe alkyle peut être lié par son extrémité opposée à l'atome d'azote, à un atome de carbone du groupe B, pour former ainsi un cycle,
    X
    est un groupe de liaison divalent ou trivalent,
    B
    est un groupe de liaison divalent,
    n
    vaut 1 ou 2.
  3. Surface d'enregistrement photosensible à l'halogénure d'argent selon les revendications 1 ou 2, caractérisée en ce que le dérivé d'hydrazine répond à la formule générale (H) B - phényle - NHNH - L - G dans laquelle B est un groupe de lestage, B est un groupe activateur, et L représente CO ou CO-CO.
  4. Surface d'enregistrement photosensible à l'halogénure d'argent selon une quelconque des revendications 1 à 3, caractérisée en ce qu'elle contient le dérivé augmentant le contraste à raison de 0,05 à 5g par mole d'argent.
  5. Surface d'enregistrement photosensible à l'halogénure d'argent selon une quelconque des revendications 1 à 4, caractérisée en ce que 80% en poids de l'halogénure d'argent de l'émulsion consiste en grains cubiques.
  6. Surface d'enregistrement photosensible à l'halogénure d'argent selon une quelconque des revendications 1 à 5, caractérisée en ce que l'halogénure d'argent de l'émulsion présente une taille de grain moyenne de 0,15 à 0,30µm.
  7. Surface d'enregistrement photosensible à l'halogénure d'argent selon une quelconque des revendications 1 à 6, caractérisée en ce que l'halogénure d'argent de l'émulsion est monodisperse.
  8. Méthode d'obtention d'une image négative en noir et blanc présentant un contraste extrêmement élevé, caractérisée en ce qu'on expose et développe une surface d'enregistrement selon une quelconque des revendications 1 à 4, dans un révélateur ayant un pH compris entre 9 et 11.
  9. Méthode selon la revendication 8, caractérisée en ce que le révélateur contient plus de 0,30 mole de sulfite par litre.
EP96106510A 1995-04-28 1996-04-25 Matériau d'enregistrement à l'halogénure d'argent pour la préparation des images négatives ayant un contraste très haut Expired - Lifetime EP0740194B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19515619 1995-04-28
DE19515619A DE19515619A1 (de) 1995-04-28 1995-04-28 Silberhalogenid-Aufzeichnungsmaterial zur Erzeugung von Negativbildern mit ultrasteilem Kontrast

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EP0740194A1 EP0740194A1 (fr) 1996-10-30
EP0740194B1 true EP0740194B1 (fr) 1998-04-01

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EP (1) EP0740194B1 (fr)
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19618196A1 (de) * 1996-05-07 1997-11-13 Du Pont Deutschland Silberhalogenid-Aufzeichnungsmaterial mit verbesserter Lagerungsbeständigkeit zur Erzeugung von Negativbildern mit ultrasteilem Kontrast

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4269929A (en) * 1980-01-14 1981-05-26 Eastman Kodak Company High contrast development of photographic elements
JPS61267759A (ja) * 1985-05-22 1986-11-27 Fuji Photo Film Co Ltd ネガティブ画像の形成方法及び現像液
JPH0736076B2 (ja) * 1986-03-24 1995-04-19 富士写真フイルム株式会社 ハロゲン化銀写真感光材料およびそれを用いた画像形成方法
US4975354A (en) * 1988-10-11 1990-12-04 Eastman Kodak Company Photographic element comprising an ethyleneoxy-substituted amino compound and process adapted to provide high constrast development
JP2704453B2 (ja) * 1989-10-13 1998-01-26 富士写真フイルム株式会社 ハロゲン化銀感光材料
US5229248A (en) * 1990-08-16 1993-07-20 Konica Corporation Silver halide photographic light sensitive material
US5283158A (en) * 1991-10-31 1994-02-01 Konica Corporation Silver halide photographic light-sensitive material
DE4310327A1 (de) * 1993-03-30 1994-10-06 Du Pont Deutschland Verfahren zur Erzeugung von Negativbildern mit ultrasteilem Kontrast

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US5663034A (en) 1997-09-02
DE59600132D1 (de) 1998-05-07
DE19515619A1 (de) 1996-10-31
JPH08334856A (ja) 1996-12-17
JP3668554B2 (ja) 2005-07-06
EP0740194A1 (fr) 1996-10-30

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