EP0733939B1 - Siver halide recording material for generation of negative images with ultrahigh contrast - Google Patents

Siver halide recording material for generation of negative images with ultrahigh contrast Download PDF

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Publication number
EP0733939B1
EP0733939B1 EP96104328A EP96104328A EP0733939B1 EP 0733939 B1 EP0733939 B1 EP 0733939B1 EP 96104328 A EP96104328 A EP 96104328A EP 96104328 A EP96104328 A EP 96104328A EP 0733939 B1 EP0733939 B1 EP 0733939B1
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EP
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Prior art keywords
group
silver halide
groups
recording material
contrast
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EP96104328A
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German (de)
French (fr)
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EP0733939A1 (en
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Reinhold Dr. Rüger
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Agfa Gevaert AG
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Agfa Gevaert AG
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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

Definitions

  • the invention relates to a silver halide photographic material to create black and white Negative images with ultra-partial contrast and its use.
  • 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 Low-sulfite, formaldehyde-containing hydroquinone developers. Development has recently become of particular practical importance in the presence of hydrazine compounds.
  • 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-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 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 Sulfonylurea or sulfonyl urethane group is bound.
  • the sulfonylurea and Sulfonyl urethane can be the divalent linking group both on the sulfonyl part and on the urea or Tie in urethane.
  • the contrast-increasing compound falls under one of the general formulas (A), (B) or (C) given below:
  • the radicals R 1 , R 2 , R 3 and R 4 can be the same or different and each can 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.
  • R1 and R 2 and R 3 and R 4 can also form a heterocyclic ring with 5 to 12 members, for example a piperidine, pyrrolidine, pyrrolidinone, pyrroline, including the nitrogen atom and optionally a further nitrogen atom, an oxygen atom or a carbonyl group -, oxazolidine, imidazoline, morpholine, pyrazane, azepine, oxazepine or azacyclodecane ring.
  • Each of the groups R 1 to R 4 can also be a benzyl group.
  • Each of the groups R 1 to R 4 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.
  • substituents are methoxy, ethoxy, propoxy, butoxy, ethylamino, dimethylamino, butylthio.
  • the divalent connecting groups X, X 1 and X 2 are preferably straight-chain, branched or cyclic alkylene groups with 1 to 20 carbon atoms, phenylene or aralkylene groups with 7 to 20 carbon atoms, or divalent chains from 1 to 20 methylene groups, in which, in addition to these, oxygen , Sulfur, amino groups, alkene or alkyne groups or also polyoxyalkylene groups, in particular polyoxyethylene or polyoxypropylene groups with 1 to 50 oxyalkyl units, can be incorporated.
  • An ethylene or propylene amino group is particularly preferred.
  • the radical R denotes a saturated or unsaturated one Alkyl group, preferably having 1 to 12 carbon atoms, one Aryl group, preferably having 6 to 14 carbon atoms or one Aralkyl group, preferably having 7 to 15 carbon atoms.
  • This Groups in turn can be substituted, for example with hydroxyl, amino, alkylamino and alkoxy groups, where herein the alkyl is preferably 1 to 6 carbon atoms having. If R is bound to nitrogen, it can too Mean hydrogen.
  • R 5 to R 7 which may be the same or different, each represent hydrogen or a C 1 to C 6 alkyl group or a benzyl group.
  • the alkyl and benzyl groups can be further substituted, preferably with hydroxyl, amino, alkylamino, alkoxy and alkylthio groups, the alkyl in these groups preferably having 1 to 6 carbon atoms.
  • the groups S can be incorporated into the molecule according to the general formula (A), (B) or (C) in the stated or in reverse order.
  • the radicals R and X 2 can therefore be bound both to the group SO 2 and to a nitrogen or oxygen atom.
  • contrast-increasing compounds are described by the general formulas (I), (II) or (III):
  • R 11 , R 12 , R 14 , R 15 which may be the same or different, each represent a straight-chain or branched alkyl group having 1 to 6 carbon atoms or a benzyl group, these groups having hydroxyl groups or having alkoxy, alkylthio or alkylamino groups can each be substituted with 1 to 6 carbon atoms, or R 11 and R 12 and / or R 14 and R 15 form together with the nitrogen atom, optionally including a further nitrogen or oxygen atom or a carbonyl group, a five- to eight-membered group heterocyclic ring, which in turn can be substituted as above, for example a piperidine, pyrrolidine, pyrrolidinone, pyrroline, oxazolidine, imidazoline, morpholine, pyrazane, azepine or oxazepine ring.
  • the divalent connecting groups X, X 1 and X 2 have the same meaning as described above.
  • Y means nitrogen or oxygen, depending on whether it is a sulfonylurea or sulfonyl urethane compound acts.
  • R 13 denotes hydrogen or a straight-chain or branched alkyl group with 1 to 6 carbon atoms or a benzyl group, optionally substituted with hydroxyl groups or with alkoxy, alkylthio or alkylamino groups each with 1 to 6 carbon atoms. If Y is oxygen, then R 13 is absent due to lack of further bonding.
  • R 19 denotes hydrogen or an optionally substituted alkyl group, which can also form a five- to eight-membered, optionally substituted, heterocyclic ring with R 13 , as described above for R 14 and R 15 .
  • R 18 is an optionally substituted phenyl, tolyl or alkyl group, preferably with 1-12 carbon atoms.
  • contrast-increasing compounds according to the invention in contain at least one tertiary amino group in their molecule, they can be used both in the form of the free amine and in the Form of a salt, that is, an adduct of an acid to that Amine, manufactured, handled and applied.
  • a preferred acid is hydrochloric acid.
  • the light-sensitive silver halide recording materials preferably contain the contrast-enhancing invention Compounds in an amount of 0.05 to 5 g each mol of silver.
  • Contrast-increasing compounds according to the invention with the grouping -SO 2 -NH-CO- can be produced from easily accessible and inexpensive starting materials.
  • the synthetic method is described in general and by way of example in: R. Graf, Reactions with N-Carbonyl-sulfamic Acid Chloride, Angewandte Chemie 80, 179 (1968) and in G. Anthony Benson et al., Sulfamic Acid and Its N-Substituted Derivatives, Chemical Reviews 80, 151 (1980).
  • the relatively complex compounds can be prepared in simple one-pot syntheses with very high yield and good purity.
  • the person skilled in the art can easily find analogy methods by varying the substituents.
  • the intermediates need not be isolated and the compounds can be added to the photographic layers without further purification.
  • the synthesis product can also be purified, for example by extraction with ether, by reprecipitation and / or by drying in vacuo.
  • contrast-enhancing invention Connections are made that meet multiple requirements correspond. For example, by selecting the hydrophobic, the hydrophilic and the ballast groups, that the compounds at for inclusion in the emulsion sufficient water miscibility at the same time a good one Diffusion resistance and a sufficient for the effect Have adsorption on silver halide. With this selection may also be compatible with that present in the emulsion Wetting agents and other components are taken into account.
  • contrast-increasing compounds according to the invention are:
  • 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-A1, EP-05 98 315-A1, EP-04 44 506-A1
  • Preferred hydrazine compounds are described by the general formula (VI): 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-.
  • 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 alkyox 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 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 could be up to Contain 30 or more carbon atoms in these groups be. Methoxyphenyl, tolyl, ballasted butyramidophenyl, butylsulfonamido and Toluylsulfonamido.
  • the 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, especially are preferred.
  • alkyl e.g. methyl, hydroxymethyl, monofluoromethyl, pyridinomethyl, Phenoxymethyl, alkoxymethyl such as methoxymethyl
  • substituted aralkyl e.g. benzyl, o-hydroxybenzyl
  • aryl
  • 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 in which the silver halide contains more than 80 Weight percent consisting of cubic grains are also prefers.
  • 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.
  • an iodide in an amount of about 0.5 to 5 mmol per mole of silver are 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 alkyl 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 with a known agent.
  • a known agent are, for example, 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 10 to a maximum of 11.5. 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.
  • contrast-enhancing compounds according to the invention can added to the emulsion at every stage of manufacture become. Because of their molecular structure, they can both be surface active as well as with ionic polymers Interaction. Therefore they can also be used as Coating aids and as emulsifiers, for example for photographically effective additives, and as flocculants for hydrophilic ionic colloids, such as gelatin, for example in a flocculation washing process for photographic Emulsions can be used.
  • 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 Examples explained in more detail.
  • a silver chlorobromide emulsion (20 mole percent bromide) with cubic grains with an edge length of 0.21 ⁇ m were controlled by pAg Two-jet inlet manufactured. After removing the soluble salts by means of the flocking process was gelatin up to a total gelatin content of 55 g per mol of silver added and chemical ripening in the presence of Thiosulfate, gold salt and thiotosylate performed.
  • the emulsion was mixed with a Protective layer solution, the gelatin, matting agent, Nonylphenyl diethoxysulfonate (Triton X-200, manufacturer: Rohm & Haas) and the additives listed in Table 1 contrast-increasing compounds according to the invention and the Comparative compounds.
  • a Protective layer solution the gelatin, matting agent, Nonylphenyl diethoxysulfonate (Triton X-200, manufacturer: Rohm & Haas) and the additives listed in Table 1 contrast-increasing compounds according to the invention and the Comparative compounds.
  • 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. The results are summarized in Table 1.

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Description

Die Erfindung betrifft ein photographisches Silberhalogenid-Aufzeichnungsmaterial zur Erzeugung von schwarz-weißen Negativbildern mit ultrasteilem Kontrast und seine Verwendung.The invention relates to a silver halide photographic material to create black and white Negative images with ultra-partial contrast and its use.

Bei der photomechanischen Reproduktion müssen häufig Halbtonbilder in Rasterpunktbilder umgewandelt werden. Hierzu verwendet man Silberhalogenidmaterialien, die man in besonderen Verfahren zu ultrasteilem Kontrast, d. h. zu einer maximalen Steigung der Schwärzungskurve von mehr als 10, entwickelt. Bekannt ist beispielsweise das Lithverfahren mit sulfitarmen, formaldehydhaltigen Hydrochinonentwicklern. Besondere praktische Bedeutung hat neuerdings die Entwicklung in Gegenwart von Hydrazinverbindungen.In photomechanical reproduction, often Halftone images can be converted into halftone dot images. For this one uses 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. For example, the lith process is also known Low-sulfite, formaldehyde-containing hydroquinone developers. Development has recently become of particular practical importance in the presence of hydrazine compounds.

Bei diesem Verfahren werden häufig gewisse Aminoverbindungen zur weiteren Steigerung des Kontrastes angewendet. So wird in der EP-00 32 456-B1 ein Verfahren beansprucht, bei dem man ein Aufzeichnungsmaterial in Gegenwart einer Hydrazinverbindung mit einem Hydrochinon-3-Pyrazolidinon-Entwickler verarbeitet, der eine kontraststeigernde Menge einer Aminoverbindung enthält.Certain amino compounds are often used in this process applied to further increase the contrast. So in EP-00 32 456-B1 claims a method in which one Recording material in the presence of a hydrazine compound processed with a hydroquinone-3-pyrazolidinone developer, which is a contrast increasing amount of an amino compound contains.

In der EP-04 73 342-A1 ist ein photographisches Silberhalogenidmaterial beschrieben, das in einem Entwickler mit einem pH < 11 zu ultrasteilem Kontrast entwickelt werden kann. Die lichtempfindliche Beschichtung dieses Material enthält eine Hydrazinverbindung einer bestimmten Formel sowie eine Amino- oder eine quaternäre Oniumverbindung und ist auf einen pH von mindestens 5,9 eingestellt.In 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.

Entwickler, die eine kontraststeigernde Menge einer Aminoverbindung enthalten, sind nicht frei von Nachteilen. Die erforderliche Konzentration der Aminoverbindung ist beträchtlich und liegt häufig in der Nähe der Löslichkeitsgrenze. Infolge der Temperaturerhöhung oder von geringen Konzentrationsänderungen durch Wasserverdunstung während des Gebrauchs kann die Löslichkeitsgrenze leicht überschritten werden und die Aminoverbindung scheidet sich aus. Dies kann zu ungleichmäßiger Entwicklung und zur Verunreinigung der Aufzeichnungsmaterialien und der Entwicklungsmaschine führen. Wegen ihrer Wasserdampfflüchtigkeit können die ausgeschiedenen Aminoverbindungen auch an entfernte Stellen der Entwicklungsmaschine gelangen und unerwünschte Verunreinigungen sowie Korrosion hervorrufen.Developers who have a contrast increasing amount of one Containing amino compounds are not free from disadvantages. The required concentration of the amino compound is considerable and is often close to the Solubility limit. As a result of the temperature increase or of low concentration changes due to water evaporation during use the solubility limit can be easily exceeded and the amino compound separates out. This can lead to uneven development and Contamination of the recording materials and the Lead development machine. Because of their water vapor volatility the excreted amino compounds can also get to remote parts of the processor and cause unwanted contamination and corrosion.

Bei der Verwendung von Entwicklern, welche bekannte Aminoverbindungen enthalten, tritt ein auch sehr unangenehmer Geruch auf, der auf die hohe erforderliche Konzentration und die Flüchtigkeit dieser Verbindungen zurückzuführen ist.When using developers who are known Containing amino compounds occurs also very uncomfortable Smell based on the high concentration and required the volatility of these connections is due.

Da die Aminoverbindungen nur begrenzt löslich sind ist es schwierig, die als wirtschaftliche Handelsform üblichen Entwicklerkonzentrate zu formulieren. Nach der EP-A-02 03 521 können zwar Salze gewisser Sulfo- oder Carbonsäuren als Lösungsvermittler eingesetzt werden. Die übrigen angesprochenen Probleme werden jedoch durch solche Zusätze nicht beeinflußt.Since the amino compounds are only soluble to a limited extent, it is difficult, the usual as an economic form of trading Formulate developer concentrates. According to 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.

Die bekannten Entwickler haben in der Regel einen pH über 11. Daher sind sie für die Praxis nicht hinreichend stabil und wirken stark korrosiv auf die Bauteile der Entwicklungsmaschinen.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.

Obgleich mit diesen bekannten Verfahren auch bei kurzer Verarbeitungszeit Negativbilder mit ultrasteilem Kontrast erzeugt werden können, sind sie noch mit gewissen Nachteilen verbunden. So sind die benötigten Mengen der kontrasterhöhenden Zusätze so groß, daß sie zu unerwünschten Veränderungen der Filmeigenschaften führen, beispielsweise der Lagerungsstabilität, der Trocknungseigenschaften nach der Verarbeitung und der Naßkratzfestigkeit.Although with these known methods even with a short Processing time negative images with ultra-partial contrast can be generated, they are still with certain disadvantages connected. So the quantities needed are the contrast enhancing additives so large that they become undesirable Changes in film properties lead, for example Storage stability, the drying properties after the Processing and wet scratch resistance.

In der deutschen Offenlegungsschrift DE-A-43 10 327 ist ein Verfahren zur Erzeugung von Negativbildern mit ultrasteilem Kontrast beschrieben, bei dem die Entwicklung des Silberhalogenid-Aufzeichnungsmaterials in Gegenwart von Verbindungen erfolgt, deren Moleküle mindestens ein quaternäres Stickstoffatom und mindestens eine tertiäre Aminfunktion aufweisen.In the 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.

US 4,975,354 schlägt vor, den Silberhalogenidmaterialien neben Hydrazinverbindungen noch bestimmte sekundäre oder tertiäre Aminoverbindungen, die außerdem mindestens drei Oxyethylenenheiten in ihrem Molekül enthalten, als Kontrastverstärker ("booster") zu inkorporieren.US 4,975,354 suggests the silver halide materials alongside Hydrazine compounds still certain secondary or tertiary Amino compounds that also have at least three Oxyethylene units contained in their molecule as Incorporating contrast enhancers ("boosters").

EP 04 22 677 beschreibt die Anwendung von tertiären Aminoverbindungen mit mindestens drei Oxyethyleneinheiten im Molekül als Entwicklungsbeschleuniger in Entwicklerlösungen, die auch in Gegenwart von Hydrazinverbindungen wirken.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 beansprucht Silberhalogenidmaterialien, die neben Hydrazinverbindungen noch Thioetherverbindungen mit tertiärer Aminogruppe enthalten.EP 05 39 998 claims silver halide materials, which besides Hydrazine compounds or thioether compounds with tertiary Amino group included.

Auch mit diesen kontraststeigernden Zusätzen kann man nur dann befriedigende Bilder erhalten, wenn man sie in relativ großen Mengen anwendet. Damit sind nachteilige Einflüsse auf die Eigenschaften des Aufzeichnungsmaterials, zum Beispiel auf die Lagerbeständigkeit, die Naßdruckempfindlichkeit und das Trocknungsverhalten, verbunden.Even with these contrast-enhancing additives you can only then get satisfactory pictures if you put them in relatively large Applies quantities. So that are adverse influences on the Properties of the recording material, for example on the Shelf life, the wet pressure sensitivity and that Drying behavior, connected.

Die Erfindung stellt sich die Aufgabe, ein Silberhalogenid-Aufzeichnungsmaterial vorzuschlagen, das zum Erzeugen von Negativbildern mit ultrasteilem Kontrast bei kurzer Verarbeitungszeit mit einem stabilen, geruchfreien und nicht korrosiven Entwickler geeignet und von den oben erwähnten Nachteilen frei ist, sowie ein Verfahren zur Herstellung von Schwarz-Weiß-Negativbildern mit ultrasteilem Kontrast anzugeben.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.

Diese Aufgaben werden gelöst durch Silberhalogenid-Aufzeichnungsmaterialien nach dem Hauptanspruch und durch ein Verfahren nach Anspruch 9. These objects are achieved with silver halide recording materials according to the main claim and by a The method of claim 9.

Es wurde nämlich überraschenderweise gefunden, daß Verbindungen, die in ihrem Molekül eine Sulfonylharnstoff- oder Sulfonylurethangruppe sowie eine tertiäre Aminogruppe enthalten, wenn sie gemeinsam mit Hydrazinverbindungen in Silberhalogenid-Aufzeichnungsmaterialien inkorporiert werden, die Herstellung von Bildern mit ultrasteilem Kontrast auch bei relativ niedrigem Entwickler-pH und bei kurzer Entwicklungszeit ermöglichen.Surprisingly, it was found that Compounds that have a sulfonylurea or Sulfonyl urethane group and one contain tertiary amino group when used together with Hydrazine compounds in silver halide recording materials be incorporated, manufacturing of images with ultra-partial contrast even at relative low developer pH and short development time enable.

Die tertiäre Aminogruppe wird durch ein Stickstoffatom realisiert, welches mit Einfachbindungen an zwei organische Reste sowie über eine zweiwertige verbindende Gruppe an die Sulfonylharnstoff- oder Sulfonylurethangruppe gebunden ist. Im Falle des Sulfonylharnstoffs und Sulfonylurethans kann die zweiwertige verbindende Gruppe sowohl an den Sulfonylteil als auch an den Harnstoff- bzw. Urethanteil anknüpfen.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 Sulfonylurea or sulfonyl urethane group is bound. In the case of the sulfonylurea and Sulfonyl urethane can be the divalent linking group both on the sulfonyl part and on the urea or Tie in urethane.

In einer bevorzugten Ausführungsform der Erfindung fällt die kontraststeigernde Verbindung unter eine der nachstehend angegebenen allgemeinen Formeln (A), (B) oder (C):

Figure 00040001
Figure 00040002
Figure 00040003
In a preferred embodiment of the invention, the contrast-increasing compound falls under one of the general formulas (A), (B) or (C) given below:
Figure 00040001
Figure 00040002
Figure 00040003

Die Reste R1, R2, R3 und R4 können gleich oder verschieden sein und je eine geradkettige oder verzweigte Alkylgruppe mit 1 bis 6 Kohlenstoffatomen sein, beispielsweise Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, Isobutyl, n-Hexyl. R1 und R2 sowie R3 und R4 können auch unter Einschluß des Stickstoffatoms und ggf. eines weiteren Stickstoffatoms, eines Sauerstoffatoms oder einer Carbonylgruppe einen heterozyklischen Ring mit 5 bis 12 Gliedern bilden, beispielsweise einen Piperidin-, Pyrrolidin-, Pyrrolidinon-, Pyrrolin-, Oxazolidin-, Imidazolin-, Morpholin-, Pyrazan-, Azepin-, Oxazepin- oder Azacyclodecanring. Jede der Gruppen R1 bis R4 kann auch eine Benzylgruppe sein. Sowohl jede der Gruppen R1 bis R4 als auch die diesen Gruppen entsprechenden heterozyklischen Ringe können weiter substituiert sein, bevorzugt mit Hydroxyl-, Alkoxy-, Alkylthio- oder Alkylaminogruppen, wobei das Alkyl 1 bis 6 Kohlenstoffatome aufweisen kann. Beispiele solcher Substituenten sind Methoxy, Ethoxy, Propoxy, Butoxy, Ethylamino, Dimethylamino, Butylthio.The radicals R 1 , R 2 , R 3 and R 4 can be the same or different and each can 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. R1 and R 2 and R 3 and R 4 can also form a heterocyclic ring with 5 to 12 members, for example a piperidine, pyrrolidine, pyrrolidinone, pyrroline, including the nitrogen atom and optionally a further nitrogen atom, an oxygen atom or a carbonyl group -, oxazolidine, imidazoline, morpholine, pyrazane, azepine, oxazepine or azacyclodecane ring. Each of the groups R 1 to R 4 can also be a benzyl group. Each of the groups R 1 to R 4 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.

Die zweiwertigen verbindenden Gruppen X, X1 und X2 sind bevorzugt gradkettige, verzweigte oder cyclische Alkylengruppen mit 1 bis 20 Kohlenstoffatomen, Phenylen- oder Aralkylengruppen mit 7 bis 20 Kohlenstoffatomen, oder zweiwertige Ketten aus 1 bis 20 Methylengruppen, in die neben diesen auch Sauerstoff, Schwefel, Aminogruppen, Alken- oder Alkingruppen oder auch Polyoxyalkylengruppen, insbesondere Polyoxyethylen oder Polyoxypropylengruppen mit 1 bis 50 Oxyalkyleinheiten eingebaut sein können. Besonders bevorzugt ist eine Ethylen- oder Propylenaminogruppe.The divalent connecting groups X, X 1 and X 2 are preferably straight-chain, branched or cyclic alkylene groups with 1 to 20 carbon atoms, phenylene or aralkylene groups with 7 to 20 carbon atoms, or divalent chains from 1 to 20 methylene groups, in which, in addition to these, oxygen , Sulfur, amino groups, alkene or alkyne groups or also polyoxyalkylene groups, in particular polyoxyethylene or polyoxypropylene groups with 1 to 50 oxyalkyl units, can be incorporated. An ethylene or propylene amino group is particularly preferred.

Der Rest R bedeutet eine gesättigte oder ungesättigte Alkylgruppe, bevorzugt mit 1 bis 12 Kohlenstoffatomen, eine Arylgruppe, bevorzugt mit 6 bis 14 Kohlenstoffatomen oder eine Aralkylgruppe, bevorzugt mit 7 bis 15 Kohlenstoffatomen. Diese Gruppen können ihrerseits substituiert sein, beispielsweise mit Hydroxyl-, Amino-, Alkylamino- und Alkoxygruppen, wobei hierin das Alkyl vorzugsweise 1 bis 6 Kohlenstoffatome aufweist. Wenn R an Stickstoff gebunden ist, kann es auch Wasserstoff bedeuten.The radical R denotes a saturated or unsaturated one Alkyl group, preferably having 1 to 12 carbon atoms, one Aryl group, preferably having 6 to 14 carbon atoms or one Aralkyl group, preferably having 7 to 15 carbon atoms. This Groups in turn can be substituted, for example with hydroxyl, amino, alkylamino and alkoxy groups, where herein the alkyl is preferably 1 to 6 carbon atoms having. If R is bound to nitrogen, it can too Mean hydrogen.

S steht für eine der Gruppen - SO2 - NR5 - CO - NR6 - oder - SO2 - NR7 - CO - O -. Hierin bedeuten R5 bis R7, die gleich oder verschieden sein können, jeweils Wasserstoff oder eine C1- bis C6-Alkylgruppe oder eine Benzylgruppe. Die Alkyl- und Benzylgruppen können weiter substituiert sein, vorzugsweise mit Hydroxyl-, Amino-, Alkylamino-, Alkoxy- und Alkylthiogruppen, wobei das Alkyl in diesen Gruppen vorzugsweise 1 bis 6 Kohlenstoffatome aufweist. Die Gruppen S können in der angegebenen oder in umgekehrter Reihenfolge in das Molekül nach der allgemeinen Formel (A), (B) oder (C) eingebaut sein. Daher können beispielsweise die Reste R und X2 sowohl an die Gruppe SO2 als auch an ein Stickstoff- oder Sauerstoffatom gebunden sein.S stands for one of the groups - SO 2 - NR 5 - CO - NR 6 - or - SO 2 - NR 7 - CO - O -. Herein, R 5 to R 7 , which may be the same or different, each represent hydrogen or a C 1 to C 6 alkyl group or a benzyl group. The alkyl and benzyl groups can be further substituted, preferably with hydroxyl, amino, alkylamino, alkoxy and alkylthio groups, the alkyl in these groups preferably having 1 to 6 carbon atoms. The groups S can be incorporated into the molecule according to the general formula (A), (B) or (C) in the stated or in reverse order. For example, the radicals R and X 2 can therefore be bound both to the group SO 2 and to a nitrogen or oxygen atom.

Besonders bevorzugte kontraststeigernde Verbindungen werden durch die allgemeinen Formeln (I), (II) oder (III) beschrieben:

Figure 00060001
Figure 00060002
Figure 00060003
Particularly preferred contrast-increasing compounds are described by the general formulas (I), (II) or (III):
Figure 00060001
Figure 00060002
Figure 00060003

Hierin bedeuten R11, R12, R14, R15, die gleich oder verschieden sein können, je eine geradkettige oder verzweigte Alkylgruppe mit 1 bis 6 Kohlenstoffatomen oder eine Benzylgruppe, wobei diese Gruppen mit Hydroxylgruppen oder mit Alkoxy-, Alkylthio- oder Alkylaminogruppen mit jeweils 1 bis 6 Kohlenstoffatomen substituiert sein können, oder R11 und R12 und/oder R14 und R15 bilden gemeinsam mit dem Stickstoffatom, ggf. unter Einschluß eines weiteren Stickstoff- oder eines Sauerstoffatoms oder einer Carbonylgruppe, einen fünf- bis achtgliedrigen heterozyklischen Ring, der seinerseits wie vorstehend substituiert sein kann, beispielsweise einen Piperidin-, Pyrrolidin-, Pyrrolidinon-, Pyrrolin-, Oxazolidin-, Imidazolin-, Morpholin-, Pyrazan-, Azepin- oder Oxazepinring.Herein R 11 , R 12 , R 14 , R 15 , which may be the same or different, each represent a straight-chain or branched alkyl group having 1 to 6 carbon atoms or a benzyl group, these groups having hydroxyl groups or having alkoxy, alkylthio or alkylamino groups can each be substituted with 1 to 6 carbon atoms, or R 11 and R 12 and / or R 14 and R 15 form together with the nitrogen atom, optionally including a further nitrogen or oxygen atom or a carbonyl group, a five- to eight-membered group heterocyclic ring, which in turn can be substituted as above, for example a piperidine, pyrrolidine, pyrrolidinone, pyrroline, oxazolidine, imidazoline, morpholine, pyrazane, azepine or oxazepine ring.

Die zweiwertigen verbindenden Gruppen X, X1 und X2 haben die gleiche Bedeutung wie oben beschrieben.The divalent connecting groups X, X 1 and X 2 have the same meaning as described above.

Y bedeutet Stickstoff oder Sauerstoff, je nachdem, ob es sich um eine Sulfonylharnstoff- oder eine Sulfonylurethanverbindung handelt.Y means nitrogen or oxygen, depending on whether it is a sulfonylurea or sulfonyl urethane compound acts.

R13 bedeutet Wasserstoff oder eine geradkettige oder verzweigte Alkylgruppe mit 1 bis 6 Kohlenstoffatomen oder eine Benzylgruppe, gegebenenfalls substituiert mit Hydroxylgruppen oder mit Alkoxy-, Alkylthio- oder Alkylaminogruppen mit jeweils 1 bis 6 Kohlenstoffatomen. Wenn Y Sauerstoff ist, dann ist R13 mangels einer weiteren Bindung nicht vorhanden.R 13 denotes hydrogen or a straight-chain or branched alkyl group with 1 to 6 carbon atoms or a benzyl group, optionally substituted with hydroxyl groups or with alkoxy, alkylthio or alkylamino groups each with 1 to 6 carbon atoms. If Y is oxygen, then R 13 is absent due to lack of further bonding.

R19 bedeutet Wasserstoff oder eine ggf. substituierte Alkylgruppe, die auch mit R13 einen fünf- bis achtgliedrigen, gegebenenfalls substituierten, heterozyklischen Ring bilden kann, wie oben für R14 und R15 beschrieben.R 19 denotes hydrogen or an optionally substituted alkyl group, which can also form a five- to eight-membered, optionally substituted, heterocyclic ring with R 13 , as described above for R 14 and R 15 .

R18 ist eine gegebenenfalls substituierte Phenyl, Tolyl- oder Alkylgruppe, bevorzugt mit 1-12 Kohlenstoffatomen.R 18 is an optionally substituted phenyl, tolyl or alkyl group, preferably with 1-12 carbon atoms.

Da die erfindungsgemäßen kontraststeigernden Verbindungen in ihrem Molekül mindestens eine tertiäre Aminogruppe enthalten, können sie sowohl in der Form des freien Amins als auch in der Form eines Salzes, das heißt eines Adduktes einer Säure an das Amin, hergestellt, gehandhabt und angewendet werden. Eine bevorzugte Säure ist Salzsäure. Since the contrast-increasing compounds according to the invention in contain at least one tertiary amino group in their molecule, they can be used both in the form of the free amine and in the Form of a salt, that is, an adduct of an acid to that Amine, manufactured, handled and applied. A preferred acid is hydrochloric acid.

Bevorzugt enthalten die lichtempfindlichen Silberhalogenid-Aufzeichungsmaterialien die erfindungsgemäßen kontraststeigernden Verbindungen in einer Menge von 0,05 bis 5 g je mol Silber. The light-sensitive silver halide recording materials preferably contain the contrast-enhancing invention Compounds in an amount of 0.05 to 5 g each mol of silver.

Erfindungsgemäße kontraststeigernde Verbindungen mit der Gruppierung -SO2-NH-CO- lassen sich aus leicht zugänglichen und kostengünstigen Ausgangsstoffen herstellen. Insbesondere geht man von Chlorsulfonylisocyanat sowie von Alkyl- oder Arylsulfonylisocyanaten aus. Die synthetische Methode ist allgemein und beispielhaft beschrieben in: R. Graf, Umsetzungen mit N-Carbonyl-sulfamidsäurechlorid, Angewandte Chemie 80, 179 (1968) sowie in G. Anthony Benson et al., Sulfamic Acid and Its N-Substituted Derivatives, Chemical Reviews 80, 151 (1980). Durch Umsetzung der Ausgangsstoffe mit den geeigneten Alkoholen oder Aminen lassen sich in einfachen Eintopfsynthesen die relativ komplex aufgebauten Verbindungen mit sehr hoher Ausbeute und in guter Reinheit herstellen. Der Fachmann kann leicht Analogieverfahren durch Variation der Substituenten auffinden. In den meisten Fällen braucht man die Zwischenprodukte nicht zu isolieren und kann die Verbindungen ohne weitere Reiningung den photographischen Schichten zusetzen. Falls erforderlich kann das Syntheseprodukt auch gereinigt werden, beispielsweise durch Extrahieren mit Ether, durch Umfällen und/oder durch Trocknen im Vakuum.Contrast-increasing compounds according to the invention with the grouping -SO 2 -NH-CO- can be produced from easily accessible and inexpensive starting materials. In particular, one starts from chlorosulfonyl isocyanate and from alkyl or arylsulfonyl isocyanates. The synthetic method is described in general and by way of example in: R. Graf, Reactions with N-Carbonyl-sulfamic Acid Chloride, Angewandte Chemie 80, 179 (1968) and in G. Anthony Benson et al., Sulfamic Acid and Its N-Substituted Derivatives, Chemical Reviews 80, 151 (1980). By reacting the starting materials with the appropriate alcohols or amines, the relatively complex compounds can be prepared in simple one-pot syntheses with very high yield and good purity. The person skilled in the art can easily find analogy methods by varying the substituents. In most cases, the intermediates need not be isolated and the compounds can be added to the photographic layers without further purification. If necessary, the synthesis product can also be purified, for example by extraction with ether, by reprecipitation and / or by drying in vacuo.

Da diese Ausgangsstoffe in beträchtlicher Vielfalt kommerziell angeboten werden, können erfindungsgemäße kontraststeigernde Verbindungen hergestellt werden, die mehreren Anforderungen entsprechen. So läßt sich beispielsweise durch Auswahl der hydrophoben, der hydrophilen und der Ballastgruppen erreichen, daß die Verbindungen bei für das Einbringen in die Emulsion ausreichender Wassermischbarkeit gleichzeitig eine gute Diffusionsfestigkeit und eine für die Wirkung ausreichende Adsorption am Silberhalogenid aufweisen. Bei dieser Auswahl kann auch die Verträglichkeit mit in der Emulsion vorhandenen Netzmitteln und anderen Komponenten berücksichtigt werden.Because these raw materials are commercially available in considerable variety can be offered, contrast-enhancing invention Connections are made that meet multiple requirements correspond. For example, by selecting the hydrophobic, the hydrophilic and the ballast groups, that the compounds at for inclusion in the emulsion sufficient water miscibility at the same time a good one Diffusion resistance and a sufficient for the effect Have adsorption on silver halide. With this selection may also be compatible with that present in the emulsion Wetting agents and other components are taken into account.

Beispiele für erfindungsgemäße kontraststeigernde Verbindungen sind:

Figure 00100001
Figure 00110001
Figure 00120001
Examples of contrast-increasing compounds according to the invention are:
Figure 00100001
Figure 00110001
Figure 00120001

Das erfindungsgemäße Aufzeichnungsmaterial enthält eine Hydrazinverbindung. Diese Hydrazinverbindung kann in an sich bekannter Weise entweder in eine oder mehrere Schichten des Aufzeichnungsmaterials inkorporiert werden. Dies können sowohl Schichten sein, welche das lichtempfindliche Silberhalogenid enthalten, als auch Schichten, die mit den erstgenannten in reaktiver Verbindung stehen, d. h. die so angeordnet sind, daß Stoffe von einer in die andere Schicht diffundieren können, wenn durch Reaktionen ein Konzentrationsgefälle aufrechterhalten wird.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.

Geeignete Hydrazinverbindungen sind beispielsweise beschrieben 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-A1, EP-05 98 315-A1, EP-04 44 506-A1Suitable 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-A1, EP-05 98 315-A1, EP-04 44 506-A1

Bevorzugte Hydrazinverbindungen sind durch die allgemeine Formel (VI) beschrieben: B - Phenyl - NHNH - L - G Preferred hydrazine compounds are described by the general formula (VI): B - phenyl - NHNH - L - G

Hierin bedeuten B eine Ballastgruppe, G eine aktivierende Gruppe und L eine der Gruppen -CO- und -CO-CO-.Here B is a ballast group, G is an activating group Group and L one of the groups -CO- and -CO-CO-.

Bevorzugte Ballastgruppen sind jene, die nicht elektronenanziehend sind, beispielsweise gerade oder verzweigte Alkylgruppen, (z. B. Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, Isobutyl, n-Hexyl, n-Octyl, t-Octyl, n-Decyl, n-Dodecyl und ähnliche Gruppen), auch Alkyoxgruppen, die als Alkyl eine der oben genannten Alkylgruppen enthalten, sowie Acylaminogruppen, wie Acetylamino, Propanoylamino, Butanoylamino, Octanoylamino, Benzoylamino, Alkyl- und Arylsulfonamido- und ähnliche Gruppen.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 alkyox 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.

Die genannten Gruppen können ihrerseits mit herkömmlichen photographischen Ballastgruppen substituiert sein, wie sie von inkorporierten diffusionsfesten Kupplern und anderen immobilisierten photographischen Zusätzen bekannt sind. Solche Ballastgruppen enthalten typischerweise mindestens 8 Kohlenstoffatome und können aus relativ reaktionsträgen aliphatischen oder aromatischen Gruppen ausgewählt werden, beispielsweise Alkyl, Alkoxy, Phenyl, Alkylphenyl, Phenoxy, Alkylphenoxy und ähnlichen Gruppen. The groups mentioned can in turn be used with conventional photographic ballast groups as substituted by incorporated diffusion-proof couplers and others immobilized photographic additives are known. Such 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 and similar groups.

Die Alkyl- und Alkoxygruppen enthalten einschließlich etwaiger Ballastgruppen vorzugsweise 1 bis 20, die Acylaminogruppen vorzugsweise 2 bis 21 Kohlenstoffatome. Es könne aber bis zu 30 oder mehr Kohlenstoffatome in diesen Gruppen enthalten sein. Besonders bevorzugt sind Methoxyphenyl, Tolyl, ballastiertes Butyramidophenyl, Butylsulfonamido und Toluylsulfonamido.The alkyl and alkoxy groups include any Ballast groups preferably 1 to 20, the acylamino groups preferably 2 to 21 carbon atoms. But it could be up to Contain 30 or more carbon atoms in these groups be. Methoxyphenyl, tolyl, ballasted butyramidophenyl, butylsulfonamido and Toluylsulfonamido.

Zu den bevorzugten Hydrazinverbindungen gehören solche, deren Ballastgruppe noch eine adsorptionsfördernde Gruppe enthält. Solche Gruppen fördern die Adsorption des Moleküls an der Oberfläche der Silberhalogenidkristalle und sind an sich bekannt. Sie enthalten typischerweise wenigstens ein Schwefel- oder Stickstoffatom, das einen Silberkomplex bilden kann oder sonst eine Affinität zur Silberhalogenidoberfläche hat. Bevorzugte Beispiele sind Thioharnstoff-, Thiuronium-, heterozyklische Thioamid- und Triazolgruppen.The 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 ist vorzugsweise Wasserstoff, ggf. substituiertes Alkyl (z.B. Methyl, Hydroxymethyl, Monofluoromethyl, Pyridinomethyl, Phenoxymethyl, Alkoxymethyl wie Methoxymethyl), ggf. substituiertes Aralkyl (z.B. Benzyl, o-Hydroxybenzyl) und ggf. substituiertes Aryl (z.B. Phenyl, 3,5-Dichlorphenyl, o-Methansulfonamidophenyl, 4-Methansulfonylmethyl, 2-Hydroxymethylphenyl), wobei Alkylgruppen mit elektronenanziehenden Substituenten, beispielsweise kationischen Gruppen mit quaternärem Stickstoffatom, besonders bevorzugt sind.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, especially are preferred.

G kann auch weiter substituiert sein, z. B. mit Alkyl, Aralkyl, Alkenyl, Alkinyl, Alkoxy, Aryl, substituiertem Amino, Ureido, Urethan, Aryloxy, Sulfamoyl, Carbamoyl, Alkyl- oder Arylthio, Alkyl- oder Arylsulfonyl, Alkyl- oder Arylsulfinyl, Hydroxy, Halogen, Cyan, Sulfo, Aryloxycarbonyl, Acyl, Alkoxycarbonyl, Acyloxy, Carbamid, Sulfonamid, Carboxyl, Phosphamid, Diacylamino, Imid. 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 kann auch so gewählt werden, daß das L-G-Teil des Moleküls unter Ringbildung abgetrennt wird, wie dies z.B. in EP-B-02 53 665 beschrieben ist.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.

Beispiele geeigneter Hydrazinverbindungen sind

Figure 00150001
Figure 00150002
Figure 00150003
Figure 00150004
Figure 00150005
Figure 00150006
Figure 00150007
Figure 00150008
Figure 00160001
Figure 00160002
Figure 00160003
Figure 00160004
Examples of suitable hydrazine compounds are
Figure 00150001
Figure 00150002
Figure 00150003
Figure 00150004
Figure 00150005
Figure 00150006
Figure 00150007
Figure 00150008
Figure 00160001
Figure 00160002
Figure 00160003
Figure 00160004

OTS- ist das Anion der o-Toluolsulfonsäure.OTS - is the anion of o-toluenesulfonic acid.

Die lichtempfindlichen Silberhalogenide der erfindungsgemäß verwendeten Aufzeichnungsmaterialien bestehen aus Silberchlorid, Silberbromid, Silberchlorobromid, Silberbromoiodid oder Silberchlorobromoiodid. Sie können monodispers oder polydispers sein, eine einheitliche Zusammensetzung haben aber auch Körner mit Kern-Schale-Aufbau aufweisen, sowie auch Gemische von Körnern verschiedener Zusammensetzung und Korngrößenverteilung sein. Sie werden unter Verwendung eines hydrophilen kolloidalen Bindemittels, bevorzugt Gelatine, hergestellt. Die Silberhalogenidkörner können sphärische, polyedrische oder tafelförmige Gestalt haben. Methoden zur Herstellung geeigneter lichtempfindlicher Silberhalogenidemulsionen sind dem Fachmann bekannt und beispielsweise in der Research Disclosure 365 044, Kapitel I bis IV (September 1994) zusammengefaßt.The light-sensitive silver halides of the invention recording materials used consist of Silver chloride, silver bromide, silver chlorobromide, Silver bromoiodide or silver chlorobromoiodide. You can be monodisperse or polydisperse, a uniform Grains with a core-shell structure also have a composition have, as well as mixtures of grains of different Composition and grain size distribution. you will be using a hydrophilic colloidal binder, preferably gelatin. 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).

Bevorzugt für die erfindungsgemäß verwendeten Aufzeichnungsmaterialien werden Silberhalogenidemulsionen, die durch kontrollierten Doppelstrahleinlauf hergestellt werden und eine kubische Kornform haben. Besonders bevorzugt sind monodisperse Emulsionen, d. h. solche, bei denen der Variationskoeffizient (Quotient aus Standardabweichung und Mittelwert) der Korngröße kleiner als 0,30 ist.Preferred for those used according to the invention Recording materials are silver halide emulsions that be produced by controlled double jet inlet and have a cubic grain shape. 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.

Emulsionen, bei denen das Silberhalogenid zu mehr als 80 Gewichtsprozent aus kubischen Körnern besteht, sind ebenfalls bevorzugt.Emulsions in which the silver halide contains more than 80 Weight percent consisting of cubic grains are also prefers.

Das Kornvolumen der Silberhalogenidkörner in den Emulsionen richtet sich nach der erforderlichen Empfindlichkeit und kann beispielsweise dem kubischer Körner von 0,1 bis 0,7 µm Kantenlänge entsprechen. Ein bevorzugter Bereich liegt zwischen 0,15 und 0,30 µm. Bei der Emulsionsherstellung können Edelmetallsalze, besonders Salze von Rhodium oder Iridium, zur Steuerung der photographischen Eigenschaften in den üblichen Mengen anwesend sein.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 µm Edge length. A preferred range is between 0.15 and 0.30 µm. When making emulsions Precious metal salts, especially salts of rhodium or iridium, for Control of photographic properties in the usual Be present in large quantities.

Die Emulsionen werden bevorzugt chemisch sensibilisiert. Geeignete Verfahren sind die Schwefel-, die Reduktions- und die Edelmetallsensibilisierung, die auch in Kombination angewendet werden können. Für letztere können beispielsweise Gold- oder Iridiumverbindungen benutzt werden. Die Sensibilisierung wird bevorzugt in Gegenwart von Salzen organischer Thiosulfonsäuren, wie der p-Toluolthiosulfonsäure, durchgeführt.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.

Die Emulsionen können mit üblichen Sensibilisierungsfarbstoffen spektral sensibilisiert werden, wie beispielsweise in Research Disclosure 365 044, Kapitel V (September 1994) beschrieben.The emulsions can be mixed with usual Sensitizing dyes are spectrally sensitized, such as in Research Disclosure 365 044, Chapter V (September 1994).

Die Emulsionen können auch übliche Antischleiermittel enthalten. Bevorzugt sind ggf. substituiertes Benztriazol, 5-Nitroindazol und 1-Phenyl-5-mercaptotetrazol. Diese Mittel können zu jedem Zeitpunkt bei der Emulsionsherstellung zugesetzt werden oder in einer Hilfsschicht des photographischen Materials enthalten sein. Zur Verbesserung der photographischen Eigenschaften kann der Emulsion vor oder nach der chemischen Reifung ein Jodid in einer Menge von etwa 0,5 bis 5 mmol je Mol Silber zugesetzt werden. 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. For improvement the photographic properties can before or the emulsion after chemical ripening, an iodide in an amount of about 0.5 to 5 mmol per mole of silver are added.

Die Emulsionen können auch bekannte Polymerdispersionen enthalten, durch die beispielsweise die Dimensionsstabilität des photographischen Materials verbessert wird. Es handelt sich dabei in der Regel um Latices hydrophober Polymere in wäßriger Matrix. Beispiele für geeignete Polymerdispersionen sind in der Research Disclosure 176 043, Kapitel IX B (Dezember 1978) genannt. Bevorzugt werden Polymere von Estern der Acryl- und der Methacrylsäure, besonders bevorzugt von C1-bis C6-Alkylestern. Die Teilchengröße dieser Polymerlatices liegt bevorzugt zwischen 20 und 100 nm.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 alkyl esters. The particle size of these polymer latices is preferably between 20 and 100 nm.

Die lichtempfindlichen Schichten der photographischen Materialien können mit einem bekannten Mittel gehärtet sein. Solche bekannten Mittel sind beispielsweise in der Research Disclosure 365 044, Kapitel II B (September 1994) genannt. Dieses Härtemittel kann der Emulsion zugesetzt oder über eine Hilfsschicht beispielsweise eine äußere Schutzschicht, eingebracht werden. Geeignete Härtemittel sind beispielsweise Aldehyde, wie Formaldehyd oder Glutaraldehyd, Vinylsulfone, s-Triazine, Aziridine, Carbodiimide, Carbamoylpyridiniumverbindungen, mono- und bifunktionelle Carbamoylimidazoliumverbindungen. Ein bevorzugtes Härtungsmittel ist Hydroxydichlorotriazin.The photosensitive layers of the photographic Materials can be hardened with a known agent. Such known agents are, for example, 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.

Das photographische Material kann weitere Zusätze, die für die Erzeugung bestimmter Eigenschaften bekannt und üblich sind, enthalten. Solche Mittel sind zum Beispiel in der Research Disclosure 365 044 (September 1994) in den Kapiteln VI (Aufheller), IX A (Beschichtungshilfsmittel), IX B (Weichmacher und Gleitmittel) und IX D (Mattierungsmittel) aufgeführt.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.

Der Gelatinegehalt der Emulsionen liegt im allgemeinen zwischen 30 und 150 g je mol Silber; bevorzugt wird der Bereich zwischen 40 und 100 g je mol Silber.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.

Zur Erfindung gehört auch ein Verfahren für die Herstellung schwarz-weißer negativer photographischer Bilder, welches dadurch gekennzeichnet ist, daß man ein vorgehend beschriebenes lichtempfindliches Aufzeichnungsmaterial bildmäßig belichtet, in einer wäßrigen Entwicklerlösung entwickelt, in üblicher Weise fixiert, wässert und trocknet.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.

Die erfindungsgemäß verwendeten Entwicklerlösungen enthalten bevorzugt eine Dihydroxybenzol-Entwicklersubstanz, beispielsweise Hydrochinon, Brenzkatechin, Methylhydrochinon oder Chlorhydrochinon, und ein Oxydationsschutzmittel, bevorzugt ein Alkalisulfit in einer Konzentration von mehr als 0,3 mol je Liter. Besonders bevorzugt werden Lösungen mit pH-Werten von 10 bis höchstens 11,5. Solche Entwicklerlösungen sind auch im Gebrauch gut haltbar und ergeben weitgehend schleierfreie Bilder. Ebenfalls verwendbar sind Entwicklerlösungen mit einer Entwicklersubstanz vom Ascorbinsäuretyp, beispielsweise L-Ascorbinsäure, D-Ascorbinsäure, L-Erythroascorbinsäure, 6-Desoxy-L-ascorbinsäure, Imino-L-erythroascorbinsäure oder Zuckerderivate dieser Säuren. Geeignet sind auch Entwicklerlösungen, die sowohl Entwicklersubstanzen vom Dihydroxybenzol-Typ als auch solche vom Ascorbinsäuretyp enthalten.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 10 to a maximum of 11.5. Such developer solutions are also durable in use and largely result fog-free images. Are also usable Developer solutions with a developer substance from 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. Are also suitable Developer solutions that both developer substances from Dihydroxybenzene type as well as those of the ascorbic acid type contain.

Bevorzugt enthalten die Entwicklerlösungen bekannte superadditiv wirkende Hilfsentwicklersubstanzen, beispielsweise N-Methyl-p-aminophenol oder 1-Phenylpyrazolidinon-3 oder Derivate dieser Verbindungen.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.

Ebenfalls bevorzugt sind Entwickler, die Stabilisatoren aus den Gruppen der Benztriazole und Mercaptotetrazole enthalten. Solche Stabilisatoren sind beispielsweise 1-Phenyl-5-mercaptotetrazol, 1-(4-Hydroxyphenyl)-5-mercaptotetrazol, 1-(1-Naphthyl)-5-mercaptotetrazol, 1-Cyclohexyl-5-mercaptotetrazol, 1-(4-Chlorphenyl)-5-mercaptotetrazol, 1-(3-Capramidophenyl)-5-mercaptotetrazol, Benztriazol, 5-Chlorbenztriazol, 5-Brombenztriazol, 5-Methylbenztriazol, 5-Nitrobenztriazol, 5-Benzoylaminobenztriazol, 1-Hydroxymethylbenztriazol, 6-Cyanobenztriazol. Also preferred are 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.

Bei dem erfindungsgemäßen Verfahren ist die Verwendung von Alkanolaminen nach dem Stand der Technik entweder völlig entbehrlich oder ihre Menge kann auf einen geringen Bruchteil vermindert werden. Dadurch arbeitet das Verfahren ohne störende oder schädliche Geruchsbelästigung und die Korrosion durch aus dem Entwickler sich verflüchtigende Aminoverbindungen wird vermieden.In the method according to the invention, the use of State of the art alkanolamines either completely dispensable or their amount can be a small fraction can be reduced. As a result, the process works without annoying or harmful smell and the corrosion by evaporating from the developer Amino compounds are avoided.

Die erfindungsgemäßen kontraststeigernden Verbindungen können der Emulsion in jedem Stadium der Herstellung zugesetzt werden. Aufgrund ihrer Molekülstruktur können sie sowohl oberflächenaktiv sein als auch mit ionischen Polymeren in Wechselwirkung treten. Daher können sie auch als Beschichtungshilfsmittel und als Emulgatoren, beispielsweise für photographisch wirksame Zusätze, und als Flockmittel für hydrophile ionische Kolloide, wie Gelatine, beispielsweise in einem Flockungs-Wasch-Verfahren für photographische Emulsionen, eingesetzt werden.The contrast-enhancing compounds according to the invention can added to the emulsion at every stage of manufacture become. Because of their molecular structure, they can both be surface active as well as with ionic polymers Interaction. Therefore they can also be used as Coating aids and as emulsifiers, for example for photographically effective additives, and as flocculants for hydrophilic ionic colloids, such as gelatin, for example in a flocculation washing process for photographic Emulsions can be used.

Die Erfindung kann zur Erzeugung von schwarz-weißen Negativbildern mit ultrasteilem Kontrast, insbesondere bei der Reproduktion in der Druckvorstufe für den Schwarz-Weiß- und Mehrfarbdruck, angewendet werden. Sie wird durch die folgenden Beispiele näher erläutert.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 Examples explained in more detail.

Beispiel 1 (Synthesebeispiel)Example 1 (synthesis example) Herstellung von N-(3-Dibutylaminopropylsulfamoyl)-isopropylurethanhydrochlorid (Verbindung 3)Preparation of N- (3-dibutylaminopropylsulfamoyl) isopropyl urethane hydrochloride (Connection 3)

Zu einer Lösung von 7,13 g (0,05 mol) Chlorsulfonylisocyanat in 30 ml Diethylether werden unter Rühren bei -5 °C 4 ml Isopropanol getropft. Die Mischung wird 1 Stunde weitergerührt und dabei auf Raumtemperatur gebracht. Dann werden 19,5 ml Dibutylaminopropylamin (0,05 mol), gelöst in 20 ml Diethylether, zugetropft. Die Mischung wird noch 8 Stunden bei Raumtemperatur gerührt, wobei sich zwei Phasen bilden. Das hellgelbe ölige Produkt wird von der Etherphase abgetrennt, zweimal mit Ether ausgeschüttelt und im Vakuum getrocknet Ausbeute 19 g eines hochviskosen Öls. To a solution of 7.13 g (0.05 mol) of chlorosulfonyl isocyanate in 30 ml of diethyl ether with stirring at -5 ° C 4 ml Dropped isopropanol. The mixture is further stirred for 1 hour and brought to room temperature. Then 19.5 ml Dibutylaminopropylamine (0.05 mol), dissolved in 20 ml Diethyl ether, added dropwise. The mixture is left at 8 hours Stirred at room temperature, forming two phases. The light yellow oily product is separated from the ether phase, Shaken twice with ether and dried in vacuo Yield 19 g of a highly viscous oil.

Beispiel 2 (Anwendungsbeispiel)Example 2 (application example)

Eine Silberchlorobromidemulsion (20 Molprozent Bromid) mit kubischen Körnern der Kantenlänge 0,21 µm wurde durch pAggeregelten Zweistrahleinlauf hergestellt. Nach Entfernen der löslichen Salze mittels des Flockverfahrens wurde Gelatine bis auf einen Gesamtgelatinegehalt von 55 g je mol Silber zugesetzt und eine chemische Reifung in Gegenwart von Thiosulfat, Goldsalz und Thiotosylat durchgeführt. Danach wurden zur Emulsion noch Kaliumiodid (1,6 millimol je mol Silber), Phenylmercaptotetrazol, 5-Nitroindazol, eine wäßrige Polyethylendispersion, ein Sensibilisator für den grünen Spektralbereich, Netzmittel, 1-Pyridiniumacetyl-2-(4-benzyloxyphenyl)hydrazin (0,12 millimol je mol Silber) und Natriumsalz des Dichlorhydroxytriazins (0,10 millimol je g Gelatine) zugefügt. Die Emulsion wurde gemeinsam mit einer Schutzschichtlösung, die Gelatine, Mattierungsmittel, Nonylphenyldiethoxysulfonat (Triton X-200, Hersteller: Rohm & Haas) und die in Tabelle 1 angegebenen Zusätze der erfindungsgemäßen kontraststeigernden Verbindungen und der Vergleichsverbindungen.A silver chlorobromide emulsion (20 mole percent bromide) with cubic grains with an edge length of 0.21 µm were controlled by pAg Two-jet inlet manufactured. After removing the soluble salts by means of the flocking process was gelatin up to a total gelatin content of 55 g per mol of silver added and chemical ripening in the presence of Thiosulfate, gold salt and thiotosylate performed. After that Potassium iodide (1.6 millimoles per mol Silver), phenyl mercaptotetrazole, 5-nitroindazole, an aqueous Polyethylene dispersion, a sensitizer for the green Spectral range, wetting agent, 1-pyridiniumacetyl-2- (4-benzyloxyphenyl) hydrazine (0.12 millimoles per mole of silver) and sodium salt of dichlorohydroxytriazine (0.10 millimoles per g Gelatin) added. The emulsion was mixed with a Protective layer solution, the gelatin, matting agent, Nonylphenyl diethoxysulfonate (Triton X-200, manufacturer: Rohm & Haas) and the additives listed in Table 1 contrast-increasing compounds according to the invention and the Comparative compounds.

Als Vergleichsverbindungen wurden verwendet:

Figure 00220001
Figure 00220002
Figure 00220003
Figure 00220004
The following were used as comparison compounds:
Figure 00220001
Figure 00220002
Figure 00220003
Figure 00220004

Probestreifen der erhaltenen Aufzeichnungsmaterialien wurden durch eine Vorlage aus einem Dichteverlaufskeil, der teilweise mit einem Kontaktraster unterlegt war, mit Weißlicht belichtet. Die Streifen wurden in einer Entwicklungsmaschine (Dürr Graphica) bei 36 °C entwickelt, fixiert, gewässert und getrocknet. Die Entwicklungszeit betrug 28 s. Es wurde ein handelsübliches Fixierbad verwendet. Der Entwickler hatte folgende Zusammensetzung: Wasser 500 g Natriumbisulfit 50 g KOH 27 g EDTA Trinatriumsalz 3,7 g Hydrochinon 25 g Kaliumbromid 4 g Benzotriazol 0,3 g Phenylmercaptotetrazol 0,05 g 4-Hydroxymethyl-4-methyl-1-phenylpyrazolidinon 1 g Borsäure 3 g Natriumhydroxid 24 g Diethylenglykol 40 g Wasser auf 1 Liter, pH auf 10,5 bei 22 °C. 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.

Die verarbeiteten Streifen wurden nach folgenden Kriterien ausgewertet: Minimaldichte Dmin, Maximaldichte Dmax, Empfindlichkeit S als Dichte des Vorlagen-Verlaufskeils an der Stelle, die im Rasterbild den Tonwert 50% ergab, Fußgradation G1 zwischen den Dichtewerten D = 0,1 und 0,4 im Halbtonbild, Hauptgradation G2 zwischen D = 1,0 und 2,5 sowie eine visuelle Bewertung der Punktqualität PQ der Rasterpunkte. Die Bewertung 10 bedeutet optimale Schärfe der Punkte, 4 - 5 ist nur bedingt brauchbar und entspricht der Schärfe eines Rapid Access Films ohne Kontrastverstärkung, 1 - 3 ist unbrauchbar. Die Ergebnisse sind in Tabelle 1 zusammengefaßt. Versuch Zusatz Dmin Dmax S G1 G2 PQ Verbindung mg/m2 1 ---- 0,04 5,2 1,20 4,0 9,0 5 2 V1 40 0,04 5,2 1,24 4,2 8,9 5 3 V2 40 0,04 5,2 1,24 5,5 12 5 4 V3 40 0,04 5,2 1,22 4,4 9 5 5 V4 40 0,04 5,2 1,44 9,5 >25 9 6 4 20 0,04 5,2 1,35 9,4 >25 9 7 4 40 0,04 5,2 1,40 9,2 >25 9 8 9 40 0,04 5,2 1,35 9,6 >25 9 9 11 20 0,04 5,2 1,33 8,8 >25 9 10 14 20 0,04 5,2 1,35 9 >25 9 11 10 20 0,04 5,3 1,50 8 25 9 12 23 20 0,04 5,3 1,50 8 25 9 13 21 20 0,04 5,3 1,47 9,6 >25 9 14 21 10 0,04 5,3 1,44 7,3 17 8 15 22 20 0,04 5,3 1,50 7,5 23 9 The processed strips were evaluated according to the following criteria: minimum density Dmin, maximum density Dmax, sensitivity S as the density of the original wedge at the point that gave the tone value 50% in the raster image, foot gradation G1 between the density values D = 0.1 and 0.4 in the halftone image, main gradation G2 between D = 1.0 and 2.5 and a visual assessment of the dot quality PQ of the halftone dots. 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. The results are summarized in Table 1. attempt additive Dmin Dmax S G1 G2 PQ connection mg / m2 1 ---- 0.04 5.2 1.20 4.0 9.0 5 2nd V1 40 0.04 5.2 1.24 4.2 8.9 5 3rd V2 40 0.04 5.2 1.24 5.5 12th 5 4th V3 40 0.04 5.2 1.22 4.4 9 5 5 V4 40 0.04 5.2 1.44 9.5 > 25 9 6 4th 20th 0.04 5.2 1.35 9.4 > 25 9 7 4th 40 0.04 5.2 1.40 9.2 > 25 9 8th 9 40 0.04 5.2 1.35 9.6 > 25 9 9 11 20th 0.04 5.2 1.33 8.8 > 25 9 10th 14 20th 0.04 5.2 1.35 9 > 25 9 11 10th 20th 0.04 5.3 1.50 8th 25th 9 12th 23 20th 0.04 5.3 1.50 8th 25th 9 13 21 20th 0.04 5.3 1.47 9.6 > 25 9 14 21 10th 0.04 5.3 1.44 7.3 17th 8th 15 22 20th 0.04 5.3 1.50 7.5 23 9

Die Ergebnisse zeigen, daß Filmproben, welche die erfindungsgemäßen Verbindungen enthalten, schon bei pH 10,5 ultrasteile Gradation ergeben, selbst wenn sie in einem Entwickler ohne kontrasterhöhende Aminoverbindung entwickelt werden. Vergleichsverbindungen V1 bis V3 ergeben hingegen nur eine geringfügige Steigerung der Empfindlichkeit und der Gradation.The results show that film samples containing the Contain compounds of the invention, already at pH 10.5 result in ultra-gradation even if they are in one Developer developed without a contrast-enhancing amino compound become. Comparative compounds V1 to V3, however, only result a slight increase in sensitivity and Gradation.

Claims (10)

  1. Photosensitive silver halide recording material, in particular for the production of black-&-white negative images with ultra-steep contrast, having at least one photosensitive layer on at least one side of a film support and optionally further layers on the same side of the film support, which material contains in the photosensitive layer or in a layer reactively associated therewith at least one hydrazine compound,
    characterised in that
    it contains in this layer or in another layer reactively associated therewith at least one contrast-promoting compound, the molecule of which contains at least one tertiary amino group and at least one sulfonylurea or sulfonylurethane group.
  2. Photosensitive silver halide recording materials,
    characterised in that the contrast-promoting compound is of one of the general formulae (A), (B) or (C)
    Figure 00300001
    Figure 00300002
    Figure 00300003
    in which
    R1 to R4
    identically or differently each mean an optionally substituted alkyl group having 1 to 6 carbon atoms or an optionally substituted benzyl group, or R1 and R2 and/or R3 and R4 together with the nitrogen atom and optionally a further oxygen or nitrogen atom or a carbonyl group mean a five- to twelve-membered ring,
    X, X1, X2
    mean a divalent linking group,
    R
    means a saturated or unsaturated alkyl group, an aralkyl group or an aryl group, this group may be further substituted if it is attached to a nitrogen atom, also hydrogen,
    S
    means one of the groups
    - SO2 - NR5 - CO - NR6 - or
    - SO2- NR7- CO - O -
    in which R5 to R7 may be identical or different and mean hydrogen or an optionally substituted C1 to C6 alkyl group or benzyl group
    and wherein these groups S may be incorporated into the molecule of the formula (A), (B) or (C) in the stated or reverse sequence.
  3. Photosensitive silver halide recording material according to claim 2,
    characterised in that
    the compound of the formula (A), (B) or (C) belongs to one of the groups described by the following general formulae (I), (II) or (III):
    Figure 00320001
    Figure 00320002
    Figure 00320003
    in which
    R11, R12, R14, R15
    identically or differently each mean a linear or branched alkyl group having 1 to 6 carbon atoms or a benzyl group, wherein these groups may be substituted with hydroxyl groups or with alkoxy, alkylthio or alkylamino groups each having 1 to 6 carbon atoms, or R11 and R12 and/or R14 and R15 together with the nitrogen atom, optionally with the inclusion of a further nitrogen or an oxygen atom or a carbonyl group, mean a five- to eight-membered heterocyclic ring, which may in turn be substituted,
    X, X1, X2
    each mean a divalent linking group,
    Y
    means nitrogen or oxygen,
    R13
    means hydrogen or a linear or branched alkyl group having 1 to 6 carbon atoms or a benzyl group, optionally substituted with hydroxyl groups or with alkoxy, alkylthio or alkylamino groups each having 1 to 6 carbon atoms, R13 is not present if Y is oxygen,
    R19
    means hydrogen or an optionally substituted alkyl group, which may also form with R13 a five- to eight-membered, optionally substituted, heterocyclic ring,
    R18
    means an optionally substituted phenyl, tolyl or alkyl group.
  4. Photosensitive silver halide recording material according to claim 1,
    characterised in that
    the hydrazine compound is of the general formula (VI) B - phenyl - NHNH - L - G wherein B is a ballast group, G is an activating group and L equals CO or CO-CO.
  5. Photosensitive silver halide recording material according to one of claims 1 to 4,
    characterised in that
    it contains the contrast-promoting compound in a quantity of 0.05 to 5 g per mol. of silver.
  6. Photosensitive silver halide recording material according to one of claims 1 to 5,
    characterised in that
    more than 80 wt.% of the silver halide of the silver halide emulsion consists of cubic grains.
  7. Photosensitive silver halide recording material according to one of claims 1 to 6,
    characterised in that
    the silver halide of the silver halide emulsion has an average grain size of 0.15 to 0.30 µm.
  8. Photosensitive silver halide recording material according to one of claims 1 to 7,
    characterised in that
    the silver halide of the silver halide emulsion is monodisperse.
  9. Process for the production of a black-&-white negative image having ultra-steep contrast,
    characterised in that
    a recording material according to one of claims 1 to 4 is exposed and developed in a developer having a pH of between 10 and 11.5.
  10. Process according to claim 9,
    characterised in that
    the developer contains more than 0.30 mol. of sulfite per litre.
EP96104328A 1995-03-23 1996-03-19 Siver halide recording material for generation of negative images with ultrahigh contrast Expired - Lifetime EP0733939B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19510614 1995-03-23
DE19510614A DE19510614A1 (en) 1995-03-23 1995-03-23 Silver halide recording material for producing negative images with ultra-contrast contrast

Publications (2)

Publication Number Publication Date
EP0733939A1 EP0733939A1 (en) 1996-09-25
EP0733939B1 true EP0733939B1 (en) 1999-06-30

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EP96104328A Expired - Lifetime EP0733939B1 (en) 1995-03-23 1996-03-19 Siver halide recording material for generation of negative images with ultrahigh contrast

Country Status (4)

Country Link
US (1) US5783357A (en)
EP (1) EP0733939B1 (en)
JP (1) JP2782703B2 (en)
DE (2) DE19510614A1 (en)

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 (en) * 1985-05-22 1986-11-27 Fuji Photo Film Co Ltd Formation of negative image
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 (en) * 1989-10-13 1998-01-26 富士写真フイルム株式会社 Silver halide photosensitive material
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
JP2775560B2 (en) * 1992-11-12 1998-07-16 富士写真フイルム株式会社 Silver halide photographic material
DE4310327A1 (en) * 1993-03-30 1994-10-06 Du Pont Deutschland Method of producing negative images with ultra-contrast contrast

Also Published As

Publication number Publication date
JP2782703B2 (en) 1998-08-06
DE19510614A1 (en) 1996-09-26
US5783357A (en) 1998-07-21
DE59602310D1 (en) 1999-08-05
JPH08304947A (en) 1996-11-22
EP0733939A1 (en) 1996-09-25

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