EP0549976B1 - Bleachable antihalation system - Google Patents

Bleachable antihalation system Download PDF

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Publication number
EP0549976B1
EP0549976B1 EP92121574A EP92121574A EP0549976B1 EP 0549976 B1 EP0549976 B1 EP 0549976B1 EP 92121574 A EP92121574 A EP 92121574A EP 92121574 A EP92121574 A EP 92121574A EP 0549976 B1 EP0549976 B1 EP 0549976B1
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EP
European Patent Office
Prior art keywords
antihalation
bleaching agent
dye
oxathiadiazole
layer
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP92121574A
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German (de)
French (fr)
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EP0549976A1 (en
Inventor
Ingrid Dr. Gesing
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Sterling Diagnostic Imaging Deutschland GmbH
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Sterling Diagnostic Imaging Deutschland GmbH
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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
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/498—Photothermographic systems, e.g. dry silver
    • G03C1/49872—Aspects relating to non-photosensitive layers, e.g. intermediate protective layers
    • 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
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
    • G03C1/83—Organic dyestuffs therefor
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/156—Precursor compound
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/165—Thermal imaging composition

Definitions

  • the present application relates to a bleachable Anti-halation system, especially for use in thermal developable photographic materials, containing at least one antihalation dye and one Bleaching agent for antihalation dye, the Bleach consists of one or more compounds that when treated with heat and / or when irradiated with actinic radiation sulphurous acid and / or derivatives of form sulphurous acid.
  • photographic recording materials contain so-called screen or antihalation dyes to improve the resolution. These dyes can be contained in the emulsion layer, but the antihalation dyes are preferably contained in non-light-sensitive auxiliary layers which are located between the carrier material and the emulsion layer or on the back of the carrier material. In the case of multi-layer materials, these auxiliary layers can also lie between the different emulsion layers. Without these antihalation layers, radiation that has passed through the photographic emulsion layer would be reflected into this layer, reducing the sharpness of the images.
  • thermal active bleaching agents such as hexarylbisimidazoles (DE 28 40 634), Benzopinacolen (US 4,081,278), halogen compounds (DE 31 41 221), Sydnonen or iodonium salts (EP 01 19 830) and Oxidizing agents (US 4,336,323) is known, these but mostly only for a limited selection of dyes are applicable or no stable discoloration of the dyes can achieve, so that after a short time Background veil regresses the recording images adulterated.
  • bleachable dyes however often require high temperatures or additional ones Bleaching agents (US 3,745,009; EP 01 19 831, DE 28 17 408 and DE 27 22 044).
  • the object of the present invention is therefore to bleachable Antihalation systems for thermally developable photographic recording materials are available too make that at or with a simple procedural step can be decolorized after thermal development, whereby a variety of common antihalation dyes can be used should be.
  • a bleachable Anti-halation system containing at least one Antihalation dye and a bleach for the Antihalation dye characterized in that the bleaching agent consists of one or more compounds, those with heat treatment and / or with radiation sulphurous acid and / or derivatives with actinic radiation of sulfurous acid.
  • the bleachable antihalation protection system containing one or more compounds, the sulfurous Form acid and / or derivatives of sulfurous acid preferably in a process for the production of photographic records used, one thermally developable photographic material containing a layer support, at least one thermally developable photographic emulsion layer, a Top layer and a bleachable antihalation system containing at least one antihalation dye and one Bleaching agents imagewise irradiated with actinic radiation and then to form an image in the irradiated Areas of the emulsion layer or layers is thermally treated.
  • the energy required to Formation of sulphurous acid or derivatives of sulphurous Acid from the compounds essential to the invention can be pure can be supplied thermally or photochemically.
  • the bleaches essential to the invention in the Irradiation with actinic sulfurous acid and / or form sulfuric acid derivatives according to thermal treatment another irradiation step Activation of the bleaching agent carried out.
  • the kind of actinic radiation depends on the bleach.
  • Antihalation protection systems whose Bleach consists of one or more compounds that when treated with heat sulphurous acid and / or Form derivatives of sulfurous acid.
  • Such bleaches allow the thermal development of the photographic recording material and the decolorization of the Antihalation dyes directly in one process step perform together.
  • bleaches that are available at 85 are effective up to 150 ° C, preferably at 90 to 125 ° C, particularly preferably at 100 to 110 ° C, are advantageous for this.
  • the bleaches essential to the invention consist of one or several compounds preferred in the treatment with Heat, or even when irradiated with actinic Radiation, sulphurous acid and / or derivatives of sulphurous Form acid.
  • the bleach contains or forms still water and / or hydroxide ions.
  • Such bleach with Sulfur dioxide-releasing compounds in the presence of a water-containing or water-forming medium enable a high fading rate of antihalation dyes.
  • compounds 1 are particularly advantageous to 16. These compounds are characterized in that with bleachable antihalation systems are manufactured for them can, which have a high storage stability. At the same time but is also for a variety of common ones Antihalation dyes contribute to a high decolorization rate current processing conditions for thermally developable ensures photographic recording materials. Especially the compounds 1), 4), 6), 15) and 16) are by a high decolorization rate at processing temperatures between 100 and 110 ° C marked, the bleached Antihalation layers have an optical density of ⁇ 0.04 exhibit that does not increase even after prolonged storage.
  • the compounds essential to the invention are commercially available or can be produced by known methods.
  • Thiadiaziridine-1,1-oxides are e.g. by implementing Sulfuric acid dichloride with primary amines and subsequent ones Cyclization produced using hypochlorite.
  • the preferred Derivatives of 1,2,3,5-oxathiadiazole-2-oxide used e.g. by 1,3-dipolar cycloaddition of accordingly substituted aromatic nitrile oxides and aromatic N-sulfinylamines synthesized.
  • the production of nitrile oxides e.g. starting from the corresponding aldehydes Oximes and hydroxamic acid chlorides.
  • N-sulfinylamines are made from the corresponding amines by reaction with thionyl chloride produced.
  • a particular advantage of the bleaches essential to the invention is their broad applicability for a variety of common Antihalation dyes such as Oxazine, thiazine, azine, Xanthene, anthraquinone and methine dyes. Especially it is advantageous to use triphenylmethane, Quinonimine and oxonol dyes.
  • Malachite Green C.I. 42000B
  • C.I. Acid Green 3 C.I. Acid Green 5
  • C.I. Acid Blue 22 C.I. Acid Blue 93
  • C.I. Basic Violet 3 C.I.
  • the amount of antihalation dyes depends on the desired optical density. Usually this is Dye content 1 - 100 mmol per kg solids content of the Layer, preferably 25-95 for triphenylmethane dyes mmol / kg.
  • the amount of sulfurous essential to the invention Acid or derivatives of sulphurous acid, Compounds depends on the dye used desired process temperatures and times and to achieving color density reduction. Usually the compounds essential to the invention in approximately molar amounts or also in up to about 30 times excess (based on the Amount of dye), preferably in a 1.5 to 20-fold excess, in particular in a 2 to 10-fold excess.
  • the bleaches essential to the invention for Antihalation dyes can be used together with the Antihalation dyes in a layer of photographic recording material may be included or also in neighboring layers. Also applying the Bleach only at or after thermal development with subsequent activation is possible.
  • the preferred Embodiment of the antihalation system according to the invention but consists of a common layer for the Antihalation dye and the bleach between Carrier material and emulsion layer or particularly preferred on the back of the carrier material. At Multi-layer materials can also protect against antihalation can be used between the individual emulsion layers.
  • Binder can be essential for the invention Antihalation layers are used.
  • hydrophilic binders such as Polyvinyl alcohol, Polyacrylic acid, polysaccharides, polystyrene sulfonic acid, Maleic acid-methyl vinyl ether copolymers, cellulose or Cellulose derivatives. Mixtures of all of the binders mentioned can be used.
  • gelatin or gelatin derivatives as binders provides antihalation layers with high fading rates.
  • the bleaches essential to the invention can be dissolved or as Dispersions are processed. Usual additives like Pouring aids, stabilizers, wetting agents can be used. By adding water and / or Hydroxide ion binding or forming compounds such as e.g. Glycerin or polyethylene oxides can cause the bleaching reaction promoted, especially when using others Binders as the preferred used.
  • the production the antihalation protective layers essential to the invention can according to the usual casting processes from common solvents e.g. Ethanol, acetone. Aqueous are preferred Casting solutions used. The layers are usual Process conditions dried.
  • the discoloration of the Antihalation protective layers essential to the invention are preferred by heat treatment, e.g. by hanging on a hot one Metal plate.
  • the materials are preferred to 85 heated to 150 ° C, particularly preferably 90 to 125 ° C.
  • a heat treatment at 100 to is particularly advantageous 110 ° C.
  • thermally developable Silver films usually do not contain one photosensitive silver salt of an organic acid Silver halide and a reducing agent.
  • the silver halide can be used in very small quantities (0.1 to 20 percent by weight total silver salts).
  • Insensitive to light Silver salts are e.g. Silberbehenat, Silberlaurat, Silver palmitate, silver caprate, silver stearate and Silver saccharinate.
  • As reducing agents e.g. Hydroquinone, pyrocatechol, phenylenediamine, p-aminophenol, 1-phenyl-3-pyrazolidone or methyl gallate used.
  • binders e.g. Cellulose acetate, cellulose acetate butyrate, Polymethyl methacrylate, polyvinyl acetate or Polyvinyl butyral can be used.
  • the Dry silver films usual additives such as Sensitizers, Stabilizers, toners and wetting agents included.
  • Backing materials are all common supports such as e.g. Glass, paper or plastic films, such as polyamides and Polyester, suitable. Such dry silver films, their Manufacturing and processing are e.g. in Research Disclosure 17029, June 1978, pp. 9 - 15 and Research Disclosure 29963, March 1989, pp. 208 - 214 or in the in these two Publications cited literature described.
  • the casting solution was with a doctor knife applied to a polyester film (wet application approx. 70 ⁇ m) and Dried for 24 hours at room temperature.
  • the Anti-halation layer had an optical density of 0.6. To the The material became 90 when the antihalation dye faded sec by placing it on a hot metal plate at 120 ° C heated, the optical density was reduced to 0.03. The decolorization was stable for over 2 months.
  • a bleachable Anti-halation layer produced, instead of the Dye solution of Example 1 0.1 ml of a 10% solution of oxonol yellow in a 1: 1 mixture of water and ethanol was used. The optical density of the layer was 0.5. To bleach the antihalation dye that was Material 120 sec by placing it on a hot metal plate heated to 120 ° C, the optical density to 0.02 was reduced. The decolorization was stable for over 2 months.
  • N-sulfinylaniline prepared by reacting aniline with thionyl chloride in the warm or with N-sulfinyl-sulfonamide at room temperature and then distilling, in 50 ml of dry ether was added and then at room temperature for 2 to 8 hours with the exclusion of Humidity stirred. The end of the reaction was determined by thin layer chromatography. The solvent was removed in vacuo and the crude product was recrystallized from ether / n-hexane or ethyl acetate / n-hexane.
  • An antihalation layer I was produced and processed with the product thus produced, as described in Example 3b).
  • the optical density of the material was 0.6 and after a storage period of 26 weeks it was 0.32. After bleaching, the optical density was 0.03.
  • a second antihalation layer was produced and processed in accordance with Example 3c).
  • the optical density of the material was 0.45 and after a storage period of 10 weeks 0.35. After bleaching, the optical density was 0.03.
  • Analogous to example 3d a two-layer material was produced and processed.
  • the optical density of the material was 0.35 and after a storage period of 26 weeks 0.25. After bleaching, the optical density was 0.04.
  • the decolorization of all 3 layers was stable for 26 weeks.
  • Example 3a As described in Example 3a), starting from 2,4-dichlorobenzaldehyde and aniline, 3-phenyl-4- (2,4-dichlorophenyl) -1,2,3,5-oxathiadiazole-2-oxide was prepared.
  • An antihalation layer I was produced and processed with the product thus produced, as described in Example 3b).
  • the optical density of the material was 0.43 and after a storage period of 26 weeks 0.33. After bleaching, the optical density was 0.04.
  • a second antihalation layer was produced and processed in accordance with Example 3c).
  • the optical density of the material was 0.34 and after a storage period of 10 weeks 0.3. After bleaching, the optical density was 0.03.
  • Analogous to example 3d) a two-layer material was produced and processed.
  • the optical density of the material was 0.35 and after a storage period of 26 weeks 0.3. After bleaching, the optical density was 0.05.
  • the decolorization of all 3 layers was stable for 26 weeks.
  • Example 3b With the product so produced, as in Example 3b) described, an antihalation layer produced and processed.
  • the optical density of the material was 0.54 and after a storage period of 26 weeks 0.33. After fading the optical density was 0.02. The discoloration was over 26 Stable for weeks.
  • Example 3a As described in Example 3a), starting from 2,4-dichlorobenzaldehyde and 2,4-dichloroaniline 3- (2,4-dichlorophenyl) -4- (2,4-dichlorophenyl) -1,2,3,5-oxathiadiazole-2-oxide produced. With the product so produced, how described in Example 3b), an antihalation layer manufactured and processed. The optical density of the material was 0.54 and after a storage period of 26 weeks 0.34. After the optical density was 0.02 after bleaching. The Decolorization was stable for over 26 weeks.
  • Example 3a As described in Example 3a), starting from 2,6-dichlorobenzaldehyde and 2,4-dichloroaniline, 3- (2,4-dichlorophenyl) -4- (2,6-dichlorophenyl) -1,2,3,5-oxathiadiazole -2-oxide produced. An antihalation layer was produced and processed with the product thus produced, as described in Example 3b). The optical density of the material was 0.44 and after a storage period of 26 weeks it was 0.29. After bleaching, the optical density was 0.02. The decolorization was stable for 26 weeks.
  • Example 3a As described in Example 3a), starting from 4-trifluoromethylbenzaldehyde and 2,4-dichloroaniline 3- (2,4-dichlorophenyl) -4- (4-trifluoromethylphenyl) -1,2,3,5-oxathiadiazole-2-oxide produced.
  • Example 3b With the product so produced, as in Example 3b) described, an antihalation layer produced and processed.
  • the optical density of the material was 0.41 and after a storage period of 26 weeks 0.27. After fading the optical density was 0.02. The discoloration was over 26 Stable for weeks.
  • 3-phenyl-4- (4-nitrophenyl) -1,2,3,5-oxathiadiazole-2-oxide was prepared from 4-nitrobenzaldehyde and aniline.
  • An antihalation layer with Acid Blue 22 as antihalation dye was produced and processed with the product thus produced, as described in Example 3b).
  • the optical density of the material was 0.32 and after a storage period of 26 weeks 0.26. After bleaching, the optical density was 0.04 (130 ° C, 90 sec). The decolorization was stable for 26 weeks.
  • Example 3a As described in Example 3a), starting from terephthalaldehyde and 3-chloroaniline, 1,4-bis (2-oxo-3- (3-chlorophenyl) -1,2,3,5-oxathiadiazolyl) benzene was prepared, the last Reaction step 100 mmol of the N-sulfinyl-3-chloroaniline were used. An antihalation layer was produced and processed with the product thus produced, as described in Example 3c). The optical density of the material was 0.3 and after a storage period of 10 weeks it was 0.3. After bleaching, the optical density was 0.04 (130 ° C, 90 sec). The decolorization was stable for over 10 weeks.

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Description

Gegenstand der vorliegenden Anmeldung ist ein bleichbares Lichthofschutzsystem, insbesondere zur Verwendung in thermisch entwickelbaren photographischen Aufzeichnungsmaterialien, enthaltend mindestens einen Lichthofschutzfarbstoff und ein Bleichmittel für den Lichthofschutzfarbstoff, wobei das Bleichmittel aus einer oder mehreren Verbindungen besteht, die bei der Behandlung mit Wärme und/oder bei der Bestrahlung mit aktinischer Strahlung schweflige Säure und/oder Derivate der schwefligen Säure bilden.The present application relates to a bleachable Anti-halation system, especially for use in thermal developable photographic materials, containing at least one antihalation dye and one Bleaching agent for antihalation dye, the Bleach consists of one or more compounds that when treated with heat and / or when irradiated with actinic radiation sulphurous acid and / or derivatives of form sulphurous acid.

Photographische Aufzeichnungsmaterialien enthalten bekanntlich zur Verbesserung des Auflösungsvermögens sogenannte Schirm- oder Lichthofschutzfarbstoffe. Diese Farbstoffe können in der Emulsionsschicht enthalten sein, bevorzugt sind die Lichthofschutzfarbstoffe jedoch in nicht lichtempfindlichen Hilfsschichten enthalten, die sich zwischen Trägermaterial und Emulsionsschicht oder auf der Rückseite des Trägermaterials befinden. Bei Mehrschichtmaterialien können diese Hilfsschichten auch zwischen den verschiedenen Emulsionsschichten liegen.
Ohne diese Lichthofschutzschichten würde Strahlung, die durch die photographische Emulsionsschicht gelangt ist, in diese Schicht reflektiert werden und so die Schärfe der Bilder verringern.It is known that photographic recording materials contain so-called screen or antihalation dyes to improve the resolution. These dyes can be contained in the emulsion layer, but the antihalation dyes are preferably contained in non-light-sensitive auxiliary layers which are located between the carrier material and the emulsion layer or on the back of the carrier material. In the case of multi-layer materials, these auxiliary layers can also lie between the different emulsion layers.
Without these antihalation layers, radiation that has passed through the photographic emulsion layer would be reflected into this layer, reducing the sharpness of the images.

Da solche Lichthofschutzschichten aber aufgrund der Absorption der Farbstoffe im sichtbaren Bereich des Lichts das fertige Bild beeinträchtigen, ist es notwendig, sie nach der bildmäßigen Belichtung zu entfärben oder ganz zu entfernen. Since such antihalation layers are due to absorption of the dyes in the visible area of the light Affect image, it is necessary to post them to decolorize or completely remove imagewise exposure.

Bei wäßrig entwickelbaren photographischen Aufzeichnungsmaterialien stellt dies kein Problem dar, da bei oder nach der wäßrigen Entwicklung des photographischen Aufzeichnungsmaterials die Lichthofschutzfarbstoffe durch die Behandlungsbäder leicht entfärbt und/oder gelöst und entfernt werden können.In aqueous developable photographic This is not a problem with recording materials since or after the aqueous development of the photographic Antihalation dyes by the recording material Treatment baths are slightly discolored and / or dissolved and removed can be.

Bei thermisch entwickelbaren photographischen Aufzeichnungsmaterialien ist dieses Verfahren aber nicht anwendbar, da Verfahrensschritte mit Behandlungslösungen und die dadurch notwendigen Trocknungsschritte bei diesen Trockenentwicklungsverfahren ja gerade vermieden werden sollen.In thermally developable photographic However, this process is not recording materials applicable because process steps with treatment solutions and the drying steps required for this Dry development processes can be avoided should.

In der Vergangenheit wurden daher Lichthofschutzsysteme für thermisch entwickelbare photographische Aufzeichnungsmaterialien vorgeschlagen, die keine zusätzlichen Behandlungslösungen für die Bleichung der Lichthofschutzfarbstoffe benötigen. So wurden vollständig abziehbare Lichthofschutzschichten vorgeschlagen (EP 01 27 436), die jedoch die Lagerstabilität des photographischen Aufzeichnungsmaterials beeinträchtigen können, wenn sie sich vorzeitig ablösen. Auch der Zusatz verschiedener thermisch aktiver Bleichmittel wie Hexarylbisimidazolen (DE 28 40 634), Benzopinakolen (US 4,081,278), Halogenverbindungen (DE 31 41 221), Sydnonen oder Iodoniumsalzen (EP 01 19 830) und Oxidationsmitteln (US 4,336,323) ist bekannt, wobei diese jedoch meist nur für eine begrenzte Auswahl von Farbstoffen anwendbar sind oder keine stabile Entfärbung der Farbstoffe erzielen können, so daß sich nach kurzer Zeit ein Hintergrundschleier zurückbildet, der die Aufzeichnungsbilder verfälscht. Üblicherweise werden auch spezielle durch aktinische Strahlung bleichbare Farbstoffe verwendet, die jedoch oft hohe Temperaturen erfordern oder auch zusätzliche Bleichmittel (US 3,745,009; EP 01 19 831, DE 28 17 408 und DE 27 22 044). In the past, antihalation systems have therefore been used for thermally developable photographic Recording materials suggested that no additional Treatment solutions for bleaching the Antihalation dyes need. So were complete peelable antihalation layers proposed (EP 01 27 436), however, the storage stability of the photographic Recording material can affect if they are replace prematurely. Also the addition of various thermal active bleaching agents such as hexarylbisimidazoles (DE 28 40 634), Benzopinacolen (US 4,081,278), halogen compounds (DE 31 41 221), Sydnonen or iodonium salts (EP 01 19 830) and Oxidizing agents (US 4,336,323) is known, these but mostly only for a limited selection of dyes are applicable or no stable discoloration of the dyes can achieve, so that after a short time Background veil regresses the recording images adulterated. Usually there are also special ones actinic radiation uses bleachable dyes however often require high temperatures or additional ones Bleaching agents (US 3,745,009; EP 01 19 831, DE 28 17 408 and DE 27 22 044).

Es besteht demnach auch weiterhin ein Interesse an Lichthofschutzsystemen für thermisch entwickelbare Aufzeichnungsmaterialien, die ohne großen technischen Aufwand nach der bildmäßigen Belichtung entfärbt werden können.There is therefore still an interest in Antihalation protection systems for thermally developable Recording materials without much technical effort can be decolorized after the imagewise exposure.

Aufgabe der vorliegenden Erfindung ist es daher, bleichbare Lichthofschutzsysteme für thermisch entwickelbare photographische Aufzeichnungsmaterialien zur Verfügung zu stellen, die bei oder mit einem einfachen Verfahrensschritt nach der thermischen Entwicklung entfärbt werden können, wobei eine Vielzahl der üblichen Lichthofschutzfarbstoffe anwendbar sein sollen.The object of the present invention is therefore to bleachable Antihalation systems for thermally developable photographic recording materials are available too make that at or with a simple procedural step can be decolorized after thermal development, whereby a variety of common antihalation dyes can be used should be.

Diese Aufgabe wird gelöst durch ein bleichbares Lichthofschutzsystem enthaltend mindestens einen Lichthofschutzfarbstoff und ein Bleichmittel für den Lichthofschutzfarbstoff dadurch gekennzeichnet, daß das Bleichmittel aus einer oder mehreren Verbindungen besteht, die bei der Behandlung mit Wärme und/oder bei der Bestrahlung mit aktinischer Strahlung schweflige Säure und/oder Derivate der schwefligen Säure bilden.This problem is solved by a bleachable Anti-halation system containing at least one Antihalation dye and a bleach for the Antihalation dye characterized in that the bleaching agent consists of one or more compounds, those with heat treatment and / or with radiation sulphurous acid and / or derivatives with actinic radiation of sulfurous acid.

Das erfindungsgemäße bleichbare Lichthofschutzsystem enthaltend eine oder mehrere Verbindungen, die schweflige Säure und/oder Derivate der schwefligen Säure bilden, wird bevorzugt in einem Verfahren zur Herstellung von photographischen Aufzeichnungen verwendet, wobei ein thermisch entwickelbares photographisches Aufzeichnungsmaterial enthaltend einen Schichtträger, mindestens eine thermisch entwickelbare photographische Emulsionsschicht, eine Deckschicht und ein bleichbares Lichthofschutzsystem enthaltend mindestens einen Lichthofschutzfarbstoff und ein Bleichmittel bildmäßig mit aktinischer Strahlung bestrahlt und anschließend zur Ausbildung eines Bildes in den bestrahlten Bereichen der Emulsionsschicht oder der Emulsionsschichten thermisch behandelt wird. Die erforderliche Energie zur Bildung von schwefliger Säure oder Derivaten der schwefligen Säure aus den erfindungswesentlichen Verbindungen kann rein thermisch oder auch photochemisch zugeführt werden. Falls die erfindungswesentlichen Bleichmittel bei der Bestrahlung mit aktinischer Strahlung schweflige Säure und/oder Derivate der schwefligen Säure bilden, wird nach der thermischen Behandlung noch ein Bestrahlungsschritt zur Aktivierung des Bleichmittels durchgeführt. Die Art der aktinischen Strahlung richtet sich nach dem Bleichmittel.The bleachable antihalation protection system according to the invention containing one or more compounds, the sulfurous Form acid and / or derivatives of sulfurous acid preferably in a process for the production of photographic records used, one thermally developable photographic material containing a layer support, at least one thermally developable photographic emulsion layer, a Top layer and a bleachable antihalation system containing at least one antihalation dye and one Bleaching agents imagewise irradiated with actinic radiation and then to form an image in the irradiated Areas of the emulsion layer or layers is thermally treated. The energy required to Formation of sulphurous acid or derivatives of sulphurous Acid from the compounds essential to the invention can be pure can be supplied thermally or photochemically. If the bleaches essential to the invention in the Irradiation with actinic sulfurous acid and / or form sulfuric acid derivatives, according to thermal treatment another irradiation step Activation of the bleaching agent carried out. The kind of actinic radiation depends on the bleach.

Besonders vorteilhaft sind Lichthofschutzsysteme, deren Bleichmittel aus einer oder mehreren Verbindungen besteht, die bei der Behandlung mit Wärme schweflige Säure und/oder Derivate der schwefligen Säure bilden. Solche Bleichmittel ermöglichen es, die thermische Entwicklung des photographischen Aufzeichnungsmaterials und die Entfärbung der Lichthofschutzfarbstoffe direkt in einem Verfahrensschritt gemeinsam durchzuführen. Insbesondere Bleichmittel, die bei 85 bis 150°C wirksam sind, bevorzugt bei 90 bis 125°C, besonders bevorzugt bei 100 bis 110°C, sind hierfür vorteilhaft.Antihalation protection systems, whose Bleach consists of one or more compounds that when treated with heat sulphurous acid and / or Form derivatives of sulfurous acid. Such bleaches allow the thermal development of the photographic recording material and the decolorization of the Antihalation dyes directly in one process step perform together. In particular, bleaches that are available at 85 are effective up to 150 ° C, preferably at 90 to 125 ° C, particularly preferably at 100 to 110 ° C, are advantageous for this.

Die erfindungswesentlichen Bleichmittel bestehen aus einer oder mehreren Verbindungen, die bevorzugt bei der Behandlung mit Wärme, oder auch bei der Bestrahlung mit aktinischer Strahlung, schweflige Säure und/oder Derivate der schwefligen Säure bilden. Bevorzugt enthalten die erfindungswesentlichen Bleichmittel mindestens eine Verbindung, die bei der Behandlung mit Wärme Schwefeldioxid bildet. Insbesondere in diesem bevorzugten Fall enthält oder bildet das Bleichmittel noch Wasser und/oder Hydroxidionen. Solche Bleichmittel mit Schwefeldioxid abspaltenden Verbindungen in Gegenwart eines wasserhaltigen oder wasserbildenden Mediums ermöglichen eine hohe Ausbleichrate der Lichthofschutzfarbstoffe.The bleaches essential to the invention consist of one or several compounds preferred in the treatment with Heat, or even when irradiated with actinic Radiation, sulphurous acid and / or derivatives of sulphurous Form acid. Preferably contain those essential to the invention Bleach at least one compound used in the Treatment with heat forms sulfur dioxide. Especially in In this preferred case, the bleach contains or forms still water and / or hydroxide ions. Such bleach with Sulfur dioxide-releasing compounds in the presence of a water-containing or water-forming medium enable a high fading rate of antihalation dyes.

Geeignete Verbindungen im Sinne der Erfindung zur Bildung von schwefliger Säure bzw. Derivaten der schwefligen Säure, sei es durch direkte Abspaltung oder durch Abspaltung eines Zwischenproduktes, das mit in dem Bleichmittel vorhandenen oder gebildeten Wassermolekülen und/oder Hydroxidionen reagiert, sind z.B. Sulfone, Derivate der Schwefligsäure wie Diester, Halbester, Anhydride, Amidester und Amidsalze, oder auch cyclische Schwefelsäurehydrazide. Diese Verbindungen können sowohl gesättigt wie auch ungesättigt, offenkettig, ali- oder auch heterocyclisch und aromatisch bzw. heteroaromatisch sein. Bevorzugt werden heterocyclische und heteroaromatische Verbindungen verwendet. Insbesondere Sulfone, bevorzugt 3-Sulfolene (2,5-Dihydrothiophen-1,1-dioxide), 1,2,3,5-Oxathiadiazol-2-oxide und Thiadiaziridin-1,1,-dioxide sind in dem erfindungswesentlichen Bleichmitteln einsetzbar. Vor allem in 3- und 4-Stellung diarylsubstituierte 1,2,3,5-Oxathiadiazol-2-oxide sind besonders vorteilhaft. Die Arylgruppen dieser Verbindungen können unabhängig voneinander unsubstituiert sein oder je einen oder mehrere Substituenten tragen, die ausgewählt sein können aus einer Gruppe von Substituenten bestehend aus: Alkyl-, Aryl-, Ether-, Ester,- Halogen-, Hydroxy-, Cyano-, Amino-, Carbonyl-, Carboxyl-, Carbamoyl-, Sulfonylgruppen und carbocyclischen und heterocyclischen annelierten Ringen.
Als besonders geeignete Verbindungen seien beispielhaft genannnt:

  • 1) 3,4-Diphenyl-1,2,3,5-oxathiadiazol-2-oxid
  • 2) 3-Phenyl-4-(2-chlorphenyl)-1,2,3,5-oxathiadiazol-2-oxid
  • 3) 3-Phenyl-4-(4-chlorphenyl)-1,2,3,5-oxathiadiazol-2-oxid
  • 4) 3-Phenyl-4-(4-fluorphenyl)-1,2,3,5-oxathiadiazol-2-oxid
  • 5) 3-Phenyl-4-(2,6-dichlorphenyl)-1,2,3,5-oxathiadiazol-2-oxid
  • 6) 3-Phenyl-4-(2,4-dichlorphenyl)-1,2,3,5-oxathiadiazol-2-oxid
  • 7) 3-Phenyl-4-(4-bromphenyl)-1,2,3,5-oxathiadiazol-2-oxid
  • 8) 3-(3-Chlorphenyl)-4-(2-chlorphenyl)-1,2,3,5-oxathiadiazol-2-oxid
  • 9) 3-(2,4-Dichlorphenyl)-4-(4-fluorphenyl)-1,2,3,5-oxathiadiazol-2-oxid
  • 10) 3-(3-Chlorphenyl)-4-(4-trifluormethylphenyl)-1,2,3,5-oxathiadiazol-2-oxid
  • 11) 3-(3-Chlorphenyl)-4-(2,6-dichlorphenyl)-1,2,3,5-oxathiadiazol-2-oxid
  • 12) 3-(2,4-Dichlorphenyl)-4-(4-chlorphenyl)-1,2,3,5-oxathiadiazol-2-oxid
  • 13) 3-(3-Chlorphenyl)-4-(2,4-dichlorphenyl)-1,2,3,5-oxathiadiazol-2-oxid
  • 14) 3-(2,4-Dichlorphenyl)-4-(4-trifluormethylphenyl)-1,2,3,5-oxathiadiazol-2-oxid
  • 15) 3-(2,4-Dichlorphenyl)-4-(2,4-dichlorphenyl)-1,2,3,5-oxathiadiazol-2-oxid
  • 16) 3-(2,4-Dichlorphenyl)-4-(2,6-dichlorphenyl)-1,2,3,5-oxathiadiazol-2-oxid
  • 17) 1,4-Bis(2-oxo-3-phenyl-1,2,3,5-oxathiadiazolyl)-benzol
  • 18) 1,4-Bis(2-oxo-3-(3-chlorphenyl)-1,2,3,5-oxathiadiazolyl)-benzol
  • 19) 3-Phenyl-4-(4-nitrophenyl)-1,2,3,5-oxathiadiazol-2-oxid
  • 20) 3-(3-Chlorphenyl)-4-(4-nitrophenyl)-1,2,3,5-oxathiadiazol-2-oxid
  • 21) 2,5-Dihydrothiophen-1,1-dioxid
  • 22) 3-Methoxycarbonyl-2,5-dihydrothiophen-1,1-dioxid
  • 23) 2,3-Bis(1,1,3,3-tetramethyl-butyl)-thiadiaziridin-1,1-dioxid
    • Suitable compounds within the meaning of the invention for the formation of sulphurous acid or derivatives of sulphurous acid, be it by direct cleavage or by cleavage of an intermediate which reacts with water molecules and / or hydroxide ions present or formed in the bleaching agent are, for example, sulfones, derivatives of Sulfuric acid such as diesters, half esters, anhydrides, amide esters and amide salts, or cyclic sulfuric acid hydrazides. These compounds can be both saturated and unsaturated, open-chain, ali- or heterocyclic and aromatic or heteroaromatic. Heterocyclic and heteroaromatic compounds are preferably used. In particular, sulfones, preferably 3-sulfolenes (2,5-dihydrothiophene-1,1-dioxide), 1,2,3,5-oxathiadiazole-2-oxide and thiadiaziridine-1,1-dioxides, can be used in the bleaching agent essential to the invention. Diaryl-substituted 1,2,3,5-oxathiadiazole-2-oxides which are diaryl-substituted in the 3- and 4-positions are particularly advantageous. The aryl groups of these compounds can independently be unsubstituted or each carry one or more substituents, which can be selected from a group of substituents consisting of: alkyl, aryl, ether, ester, halogen, hydroxyl, cyano, Amino, carbonyl, carboxyl, carbamoyl, sulfonyl groups and carbocyclic and heterocyclic fused rings.
    Examples of particularly suitable compounds are:
  • 1) 3,4-Diphenyl-1,2,3,5-oxathiadiazole-2-oxide
  • 2) 3-phenyl-4- (2-chlorophenyl) -1,2,3,5-oxathiadiazole-2-oxide
  • 3) 3-phenyl-4- (4-chlorophenyl) -1,2,3,5-oxathiadiazole-2-oxide
  • 4) 3-phenyl-4- (4-fluorophenyl) -1,2,3,5-oxathiadiazole-2-oxide
  • 5) 3-phenyl-4- (2,6-dichlorophenyl) -1,2,3,5-oxathiadiazole-2-oxide
  • 6) 3-phenyl-4- (2,4-dichlorophenyl) -1,2,3,5-oxathiadiazole-2-oxide
  • 7) 3-Phenyl-4- (4-bromophenyl) -1,2,3,5-oxathiadiazole-2-oxide
  • 8) 3- (3-Chlorophenyl) -4- (2-chlorophenyl) -1,2,3,5-oxathiadiazole-2-oxide
  • 9) 3- (2,4-dichlorophenyl) -4- (4-fluorophenyl) -1,2,3,5-oxathiadiazole-2-oxide
  • 10) 3- (3-chlorophenyl) -4- (4-trifluoromethylphenyl) -1,2,3,5-oxathiadiazole-2-oxide
  • 11) 3- (3-Chlorophenyl) -4- (2,6-dichlorophenyl) -1,2,3,5-oxathiadiazole-2-oxide
  • 12) 3- (2,4-dichlorophenyl) -4- (4-chlorophenyl) -1,2,3,5-oxathiadiazole-2-oxide
  • 13) 3- (3-Chlorophenyl) -4- (2,4-dichlorophenyl) -1,2,3,5-oxathiadiazole-2-oxide
  • 14) 3- (2,4-dichlorophenyl) -4- (4-trifluoromethylphenyl) -1,2,3,5-oxathiadiazole-2-oxide
  • 15) 3- (2,4-dichlorophenyl) -4- (2,4-dichlorophenyl) -1,2,3,5-oxathiadiazole-2-oxide
  • 16) 3- (2,4-dichlorophenyl) -4- (2,6-dichlorophenyl) -1,2,3,5-oxathiadiazole-2-oxide
  • 17) 1,4-bis (2-oxo-3-phenyl-1,2,3,5-oxathiadiazolyl) benzene
  • 18) 1,4-bis (2-oxo-3- (3-chlorophenyl) -1,2,3,5-oxathiadiazolyl) benzene
  • 19) 3-Phenyl-4- (4-nitrophenyl) -1,2,3,5-oxathiadiazole-2-oxide
  • 20) 3- (3-chlorophenyl) -4- (4-nitrophenyl) -1,2,3,5-oxathiadiazole-2-oxide
  • 21) 2,5-Dihydrothiophene-1,1-dioxide
  • 22) 3-methoxycarbonyl-2,5-dihydrothiophene-1,1-dioxide
  • 23) 2,3-bis (1,1,3,3-tetramethylbutyl) thiadiaziridine-1,1-dioxide

    • Vorteilhaft ist insbesondere die Verwendung der Verbindungen 1 bis 16. Diese Verbindungen zeichnen sich dadurch aus, daß mit ihnen bleichbare Lichthofschutzsysteme hergestellt werden können, die eine hohe Lagerstabilität besitzen. Gleichzeitig ist aber auch für eine Vielzahl von üblichen Lichthofschutzfarbstoffen eine hohe Entfärbungsrate bei gängigen Verarbeitungsbedingungen für thermisch entwickelbare photographische Aufzeichnungsmaterialien gewährleistet. Speziell die Verbindungen 1),4),6),15) und 16) sind durch eine hohe Entfärbungsrate bei Verarbeitungstemperaturen zwischen 100 und 110°C gekennzeichnet, wobei die gebleichten Lichthofschutzschichten eine optische Dichte von ≤ 0.04 aufweisen, die auch nach längerer Lagerung nicht ansteigt. The use of compounds 1 is particularly advantageous to 16. These compounds are characterized in that with bleachable antihalation systems are manufactured for them can, which have a high storage stability. At the same time but is also for a variety of common ones Antihalation dyes contribute to a high decolorization rate current processing conditions for thermally developable ensures photographic recording materials. Especially the compounds 1), 4), 6), 15) and 16) are by a high decolorization rate at processing temperatures between 100 and 110 ° C marked, the bleached Antihalation layers have an optical density of ≤ 0.04 exhibit that does not increase even after prolonged storage.

    Die erfindungswesentlichen Verbindungen sind käuflich oder können nach bekannten Methoden hergestellt werden. Thiadiaziridin-1,1-oxide werden z.B. durch Umsetzung von Schwefelsäuredichlorid mit primären Aminen und anschließender Cyclisierung mittels Hypochlorit hergestellt. Die bevorzugt verwendeten Derivate des 1,2,3,5-Oxathiadiazol-2-oxids werden z.B. durch 1,3-dipolare Cycloaddition von entsprechend substituierten aromatisch Nitriloxiden und aromatischen N-Sulfinylaminen synthetisiert. Die Herstellung der Nitriloxide erfolgt z.B. ausgehend von den entsprechenden Aldehyden über Oxime und Hydroxamsäurechloride. N-Sulfinylamine werden aus den entsprechenden Aminen durch Umsetzung mit Thionylchlorid hergestellt.The compounds essential to the invention are commercially available or can be produced by known methods. Thiadiaziridine-1,1-oxides are e.g. by implementing Sulfuric acid dichloride with primary amines and subsequent ones Cyclization produced using hypochlorite. The preferred Derivatives of 1,2,3,5-oxathiadiazole-2-oxide used e.g. by 1,3-dipolar cycloaddition of accordingly substituted aromatic nitrile oxides and aromatic N-sulfinylamines synthesized. The production of nitrile oxides e.g. starting from the corresponding aldehydes Oximes and hydroxamic acid chlorides. N-sulfinylamines are made from the corresponding amines by reaction with thionyl chloride produced.

    Ein besonderer Vorteil der erfindungswesentlichen Bleichmittel ist ihre breite Anwendbarkeit für eine Vielzahl der gängigen Lichthofschutzfarbstoffe wie z.B. Oxazin-, Thiazin-, Azin-, Xanthen-, Anthrachinon- und Methinfarbstoffe. Besonders vorteilhaft ist die Verwendung von Triphenylmethan-, Chinonimin- und Oxonolfarbstoffen. Als Beispiele seien genannt: Malachit Grün (C.I. 42000B), C.I. Acid Green 3, C.I. Acid Green 5, C. I. Acid Blue 22, C.I. Acid Blue 93, C.I. Basic Violet 3, C.I. Basic Violet 14, 4-(4-Hydroxyphenylimino)-2,5-cyclohexadien-1-on Natriumsalz, 4-(4-Dimethylaminophenylimino)-2,5-cyclohexadien-1-on,4-(4-Hydroxyphenylimino)-2,6-dichlor-2,5-cyclohexadien-1-on Natriumsalz, Oxonolblau (4-(5-(5-Hydroxy-3-methyl-1-(4-sulfophenyl)-4-pyrazolyl)-2,4-pentadienyliden)-3-methyl-1-(4-sulfophenyl)-pyrazolon Dikaliumsalz), Oxonolgelb (4-(5-Hydroxy-3-methyl-1-(4-sulfophenyl)-4-pyrazolyl)-methin-3-methyl-1-(4-sulfophenyl)-pyrazolon Dikaliumsalz), Acid Violet (4-(3-(4-Dimethylaminophenyl)-2-propenyliden)-3-methyl-1-(4-sulfophenyl)-pyrazolon Triethylammmoniumsalz. Insbesondere die Verwendung von Triphenylmethanfarbstoffen in Kombination mit den besonders vorteilhaften erfindungswesentlichen Bleichmitteln ergibt Lichthofschutzsysteme mit sehr guter Lagerstabilität und hoher Ausbleichgeschwindigkeit bei niedrigen Prozeßtemperaturen. A particular advantage of the bleaches essential to the invention is their broad applicability for a variety of common Antihalation dyes such as Oxazine, thiazine, azine, Xanthene, anthraquinone and methine dyes. Especially it is advantageous to use triphenylmethane, Quinonimine and oxonol dyes. As examples called: Malachite Green (C.I. 42000B), C.I. Acid Green 3, C.I. Acid Green 5, C.I. Acid Blue 22, C.I. Acid Blue 93, C.I. Basic Violet 3, C.I. Basic Violet 14, 4- (4-hydroxyphenylimino) -2,5-cyclohexadien-1-one Sodium salt, 4- (4-dimethylaminophenylimino) -2,5-cyclohexadien-1-one, 4- (4-hydroxyphenylimino) -2,6-dichloro-2,5-cyclohexadien-1-one Sodium salt, oxonol blue (4- (5- (5-hydroxy-3-methyl-1- (4-sulfophenyl) -4-pyrazolyl) -2,4-pentadienylidene) -3-methyl-1- (4-sulfophenyl) - pyrazolone Dipotassium salt), oxonol yellow (4- (5-hydroxy-3-methyl-1- (4-sulfophenyl) -4-pyrazolyl) methine-3-methyl-1- (4-sulfophenyl) pyrazolone Dipotassium salt), Acid Violet (4- (3- (4-Dimethylaminophenyl) -2-propenylidene) -3-methyl-1- (4-sulfophenyl) pyrazolone Triethylammmonium salt. especially the Use of triphenylmethane dyes in combination with the particularly advantageous bleaching agents essential to the invention results in antihalation systems with very good storage stability and high bleaching speed at low Process temperatures.

    Die Menge der Lichthofschutzfarbstoffe richtet sich nach der gewünschten optischen Dichte. Üblicherweise beträgt der Farbstoffgehalt 1 - 100 mmol pro kg Feststoffgehalt der Schicht, bei Triphenylmethanfarbstoffen bevorzugt 25 - 95 mmol/kg. Die Menge der erfindungswesentlichen, schweflige Säure oder Derivate der schwefligen Säure abspaltenden, Verbindungen richtet sich nach dem eingesetzten Farbstoff, den gewünschten Prozeßtemperaturen und -zeiten und der zu erzielenden Farbdichtereduzierung. Üblicherweise werden die erfindungswesentlichen Verbindungen in ungefähr molaren Mengen oder auch in bis zu ungefähr 30fachem Überschuß (bezogen auf die Farbstoffmenge), bevorzugt in 1,5 bis 20fachem Überschuß, insbesondere in 2 bis 10fachem Überschuß, verwendet.The amount of antihalation dyes depends on the desired optical density. Usually this is Dye content 1 - 100 mmol per kg solids content of the Layer, preferably 25-95 for triphenylmethane dyes mmol / kg. The amount of sulfurous essential to the invention Acid or derivatives of sulphurous acid, Compounds depends on the dye used desired process temperatures and times and to achieving color density reduction. Usually the compounds essential to the invention in approximately molar amounts or also in up to about 30 times excess (based on the Amount of dye), preferably in a 1.5 to 20-fold excess, in particular in a 2 to 10-fold excess.

    Die erfindungswesentlichen Bleichmittel für Lichthofschutzfarbstoffe können gemeinsam mit den Lichthofschutzfarbstoffen in einer Schicht des photographischen Aufzeichnungsmaterials enthalten sein oder auch in benachbarten Schichten. Auch ein Aufbringen des Bleichmittels erst bei oder nach der thermischen Entwicklung mit anschließender Aktivierung ist möglich. Die bevorzugte Ausführungsform des erfindungsgemäßen Lichthofschutzsystems besteht jedoch aus einer gemeinsamen Schicht für den Lichthofschutzfarbstoff und das Bleichmittel zwischen Trägermaterial und Emulsionsschicht oder besonders bevorzugt auf der Rückseite des Trägermaterials. Bei Mehrschichtmaterialien können auch Lichthofschutzschichten zwischen den einzelnen Emulsionsschichten verwendet werden.The bleaches essential to the invention for Antihalation dyes can be used together with the Antihalation dyes in a layer of photographic recording material may be included or also in neighboring layers. Also applying the Bleach only at or after thermal development with subsequent activation is possible. The preferred Embodiment of the antihalation system according to the invention but consists of a common layer for the Antihalation dye and the bleach between Carrier material and emulsion layer or particularly preferred on the back of the carrier material. At Multi-layer materials can also protect against antihalation can be used between the individual emulsion layers.

    Eine Vielzahl der für Hilfsschichten üblichen polymeren Bindemittel kann für die erfindungswesentlichen Lichthofschutzschichten verwendet werden. Besonders geeignet sind hydrophile Bindemittel wie z.B. Polyvinylalkohol, Polyacrylsäure, Polysaccharide, Polystyrolsulfonsäure, Maleinsäure-Methylvinylether-Copolymere, Cellulose oder Cellulosederivate. Auch Gemische der gesamten genannten Bindemittel können verwendet werden. Insbesondere Gelatine oder Gelatinederivate als Bindemittel liefert Lichthofschutzschichten mit hohen Ausbleichraten. A large number of the polymers customary for auxiliary layers Binder can be essential for the invention Antihalation layers are used. Particularly suitable are hydrophilic binders such as Polyvinyl alcohol, Polyacrylic acid, polysaccharides, polystyrene sulfonic acid, Maleic acid-methyl vinyl ether copolymers, cellulose or Cellulose derivatives. Mixtures of all of the binders mentioned can be used. In particular gelatin or gelatin derivatives as binders provides antihalation layers with high fading rates.

    Die erfindungswesentlichen Bleichmittel können gelöst oder als Dispersionen verarbeitet werden. Übliche Zusätze wie Gießhilfsmittel, Stabilisatoren, Netzmittel können verwendet werden. Durch den Zusatz von Wasser und/oder Hydroxidionen bindenden oder bildenden Verbindungen wie z.B. Glycerin oder Polyethylenoxide kann die Ausbleichreaktion gefördert werden, insbesondere bei der Verwendung von anderen Bindemitteln als den bevorzugt eingesetzten. Die Herstellung der erfindungswesentlichen Lichthofschutzschichten kann nach den üblichen Gießverfahren aus den gängigen Lösungsmitteln z.B. Ethanol, Aceton, erfolgen. Bevorzugt werden wäßrige Gießlösungen verwendet. Die Schichten werden bei üblichen Prozeßbedingungen getrocknet. Die Entfärbung der erfindungswesentlichen Lichthofschutzschichten erfolgt bevorzugt durch eine Wärmebehandlung, z.B. durch Auflegen auf eine heiße Metallplatte. Hierbei werden die Materialien bevorzugt auf 85 bis 150° C, besonders bevorzugt auf 90 bis 125° C, erwärmt. Besonders vorteilhaft ist eine Wärmebehandlung bei 100 bis 110° C.The bleaches essential to the invention can be dissolved or as Dispersions are processed. Usual additives like Pouring aids, stabilizers, wetting agents can be used. By adding water and / or Hydroxide ion binding or forming compounds such as e.g. Glycerin or polyethylene oxides can cause the bleaching reaction promoted, especially when using others Binders as the preferred used. The production the antihalation protective layers essential to the invention can according to the usual casting processes from common solvents e.g. Ethanol, acetone. Aqueous are preferred Casting solutions used. The layers are usual Process conditions dried. The discoloration of the Antihalation protective layers essential to the invention are preferred by heat treatment, e.g. by hanging on a hot one Metal plate. The materials are preferred to 85 heated to 150 ° C, particularly preferably 90 to 125 ° C. A heat treatment at 100 to is particularly advantageous 110 ° C.

    Die erfindungsgemäßen bleichbaren Lichthofschutzsysteme lassen sich zur Herstellung der üblichen thermisch entwickelbaren photographischen Aufzeichnungsmaterialien verwenden. Besonders vorteilhaft ist ihre Verwendung in den sogenannten Trockensilberfilmen. Solche thermisch entwickelbaren Silberfilme enthalten üblicherweise ein nicht lichtempfindliches Silbersalz einer organischen Säure, ein Silberhalogenid und ein Reduktionsmittel. Das Silberhalogenid kann in sehr geringen Mengen (0.1 bis 20 Gewichtsprozent der gesamten Silbersalze) vorliegen. Lichtunempfindliche Silbersalze sind z.B. Silberbehenat, Silberlaurat, Silberpalmitat, Silbercaprat, Silberstearat und Silbersaccharinat. Als Reduktionsmittel werden z.B. Hydrochinon, Brenzkatechin, Phenylendiamin, p-Aminophenol, 1-Phenyl-3-pyrazolidon oder Gallussäuremethylester verwendet. Als Bindemittel können z.B. Celluloseacetat, Celluloseacetatbutyrat, Polymethylmethacrylat, Polyvinylacetat oder Polyvinylbutyral eingesetzt werden. Desweiteren können die Trockensilberfilme übliche Zusätze wie z.B. Sensibilisatoren, Stabilisatoren, Toner und Netzmittel enthalten. Als Trägermaterialien sind alle gebräuchlichen Schichtträger wie z.B. Glas, Papier oder Kunststoffolien, wie Polyamide und Polyester, geeignet. Solche Trockensilberfilme, ihre Herstellung und Verarbeitung sind z.B. in Research Disclosure 17029, Juni 1978, S. 9 - 15 und Research Disclosure 29963, März 1989, S. 208 - 214 oder auch in der in diesen beiden Veröffentlichungen zitierten Literatur beschrieben.The bleachable antihalation systems according to the invention leave themselves to produce the usual thermally developable Use photographic materials. Especially their use in the so-called Dry silver films. Such thermally developable Silver films usually do not contain one photosensitive silver salt of an organic acid Silver halide and a reducing agent. The silver halide can be used in very small quantities (0.1 to 20 percent by weight total silver salts). Insensitive to light Silver salts are e.g. Silberbehenat, Silberlaurat, Silver palmitate, silver caprate, silver stearate and Silver saccharinate. As reducing agents e.g. Hydroquinone, pyrocatechol, phenylenediamine, p-aminophenol, 1-phenyl-3-pyrazolidone or methyl gallate used. As binders e.g. Cellulose acetate, cellulose acetate butyrate, Polymethyl methacrylate, polyvinyl acetate or Polyvinyl butyral can be used. Furthermore, the Dry silver films usual additives such as Sensitizers, Stabilizers, toners and wetting agents included. As Backing materials are all common supports such as e.g. Glass, paper or plastic films, such as polyamides and Polyester, suitable. Such dry silver films, their Manufacturing and processing are e.g. in Research Disclosure 17029, June 1978, pp. 9 - 15 and Research Disclosure 29963, March 1989, pp. 208 - 214 or in the in these two Publications cited literature described.

    Die nachfolgenden Beispiele sollen die Erfindung veranschaulichen. Die angegebenen Teile und Prozente beziehen sich, falls nicht anders angegeben ist, auf das Gewicht. The following examples are intended to illustrate the invention illustrate. Obtain the specified parts and percentages unless otherwise stated, the weight.

    Beispiel 1example 1

    Zur Herstellung einer bleichbaren Lichthofschutzschicht wurde eine Gießlösung aus 1 g deionisierter Gelatine, 10 g deionisiertem Wasser, 0.55 g 3-Sulfolen, 0.8 ml einer 10%igen wäßrigen Lösung eines Netzmittels, 1 g einer 5%igen wäßrigen Polyvinylalkohollösung und 0.1 ml einer 10%igen Lösung von Acid Violet in einer 1:1 Mischung von Wasser und Ethanol hergestellt. Die Gießlösung wurde mit einem Abstreichmesser auf eine Polyesterfolie aufgetragen (Naßauftrag ca. 70 µm) und 24 Stunden bei Raumtemperatur getrocknet. Die Lichthofschutzschicht hatte eine optische Dichte von 0.6. Zum Ausbleichen des Lichthofschutzfarbstoffs wurde das Material 90 sec durch Auflegen auf eine heiße Metallplatte auf 120°C erhitzt, wobei die optische Dichte auf 0.03 reduziert wurde. Die Entfärbung war über 2 Monate lang stabil.To produce a bleachable antihalation layer a casting solution of 1 g deionized gelatin, 10 g deionized water, 0.55 g 3-sulfolene, 0.8 ml of a 10% aqueous solution of a wetting agent, 1 g of a 5% aqueous solution Polyvinyl alcohol solution and 0.1 ml of a 10% solution of Acid Violet in a 1: 1 mixture of water and ethanol produced. The casting solution was with a doctor knife applied to a polyester film (wet application approx. 70 µm) and Dried for 24 hours at room temperature. The Anti-halation layer had an optical density of 0.6. To the The material became 90 when the antihalation dye faded sec by placing it on a hot metal plate at 120 ° C heated, the optical density was reduced to 0.03. The decolorization was stable for over 2 months.

    Beispiel 2Example 2

    Wie in Beispiel 1 beschrieben, wurde eine bleichbare Lichthofschutzschicht hergestellt, wobei anstatt der Farbstofflösung des Beispiels 1 0.1 ml einer 10%igen Lösung von Oxonolgelb in einer 1:1 Mischung von Wasser und Ethanol verwendet wurde. Die optische Dichte der Schicht betrug 0.5. Zum Ausbleichen des Lichthofschutzfarbstoffs wurde das Material 120 sec durch Auflegen auf eine heiße Metallplatte auf 120°C erhitzt, wobei die optische Dichte auf 0.02 reduziert wurde. Die Entfärbung war über 2 Monate lang stabil.As described in Example 1, a bleachable Anti-halation layer produced, instead of the Dye solution of Example 1 0.1 ml of a 10% solution of oxonol yellow in a 1: 1 mixture of water and ethanol was used. The optical density of the layer was 0.5. To bleach the antihalation dye that was Material 120 sec by placing it on a hot metal plate heated to 120 ° C, the optical density to 0.02 was reduced. The decolorization was stable for over 2 months.

    Beispiel 3Example 3

  • a) Herstellung von 3-Phenyl-4-(4-chlorphenyl)-1,2,3,5-oxathiadiazol-2-oxid. Eine Lösung von 100 mmol 4-Chlorbenzaldehyd in 100 ml Methanol wurde innerhalb von 10 Minuten unter starkem Rühren zu einer Lösung von 110 mmol NH2OH·HCl und 50 mmol Na2CO3 in 100 ml deionisiertem Wasser getropft. Nach 2stündigem Rühren bei Raumtemperatur wurde das feste Oxim abfiltriert, mit Wasser gewaschen und über Nacht an der Luft getrocknet.100 mmol des so hergestellten Oxims wurden in 85 ml Dimethylformamid gelöst. Die Lösung wurde auf 40°C erwärmt, und 15 mmol N-Chlorsuccinimid wurden zugesetzt. Portionsweise wurden dann weitere 85 mmol N-Chlorsuccinimid zugesetzt, wobei die Temperatur unter 50°C gehalten wurde. Die Reaktionslösung wurde anschließend in Eiswasser geschüttet, und das Reaktionsprodukt durch 3maliges Ausschütteln mit Ether extrahiert. Die Etherextrakte wurden mit Wasser gewaschen, über CaSO4 getrocknet und der Ether entfernt.
    100 mmol des so hergestellten Hydroxamsäurechlorids wurden in wenig Ethanol gelöst und auf -10°C abgekühlt. Innerhalb von 2 Minuten wurden 110 mmol Triethylamin zugesetzt und weitere 5 Minuten gerührt. Durch Zugabe eines 5fachen Überschuß an Wasser wurde das Nitriloxid ausgefällt, anschließend mit Wasser gewaschen und über Nacht an der Luft getrocknet.
    50 mmol Nitriloxid und 50 mmol N-Sulfinylanilin, hergestellt durch Reaktion von Anilin mit Thionylchlorid in der Wärme oder mit N-Sulfinyl-Sulfonamid bei Raumtemperatur und anschließendes Destillieren wurden in 100 ml trockenem Ether gelöst und 2 bis 8 Stunden bei Raumtemperatur unter Ausschluß von Luftfeuchtigkeit gerührt. Das Ende der Reaktion wurde durch Dünnschichtchromatographie ermittelt. Das Lösungsmittel wurde im Vakuum entfernt und das Rohprodukt aus Ether/n-Hexan oder Essigsäureethylester/n-Hexan umkristallisiert.    a) Preparation of 3-phenyl-4- (4-chlorophenyl) -1,2,3,5-oxathiadiazole-2-oxide. A solution of 100 mmol of 4-chlorobenzaldehyde in 100 ml of methanol was added dropwise over 10 minutes with vigorous stirring to a solution of 110 mmol of NH 2 OH.HCl and 50 mmol of Na 2 CO 3 in 100 ml of deionized water. After stirring at room temperature for 2 hours, the solid oxime was filtered off, washed with water and air-dried overnight. 100 mmol of the oxime thus prepared were dissolved in 85 ml of dimethylformamide. The solution was warmed to 40 ° C and 15 mmol N-chlorosuccinimide was added. A further 85 mmol of N-chlorosuccinimide were then added in portions, the temperature being kept below 50.degree. The reaction solution was then poured into ice water and the reaction product extracted by shaking 3 times with ether. The ether extracts were washed with water, dried over CaSO 4 and the ether removed.
    100 mmol of the hydroxamic acid chloride thus prepared were dissolved in a little ethanol and cooled to -10 ° C. 110 mmol of triethylamine were added over the course of 2 minutes and the mixture was stirred for a further 5 minutes. The nitrile oxide was precipitated by adding a 5-fold excess of water, then washed with water and air-dried overnight.
    50 mmol of nitrile oxide and 50 mmol of N-sulfinylaniline, prepared by reaction of aniline with thionyl chloride in the warm or with N-sulfinyl-sulfonamide at room temperature and subsequent distillation, were dissolved in 100 ml of dry ether and for 2 to 8 hours at room temperature with the exclusion of atmospheric moisture touched. The end of the reaction was determined by thin layer chromatography. The solvent was removed in vacuo and the crude product was recrystallized from ether / n-hexane or ethyl acetate / n-hexane.
  • b) Lichthofschutzschicht I Zu einer Lösung aus 15 g 10%iger Gelatinelösung, 1 g 10%iger wäßriger Sorbitanmonolauratpolyglykolether-Lösung und 0.15 g C.I. Acid Blue 93 wurde eine Lösung von 0.25 g 3-Phenyl-4-(4-chlorphenyl)-1,2,3,5-oxathiadiazol-2-oxid und 0.25 g Triphenylphosphat in 1 g Essigsäureethylester gegeben. Diese Mischung wurde für 60 sec mit ca. 10.000 U/min gerührt. Die resultierende Dispersion wurde mit einem Abstreichmesser auf eine Polyesterfolie aufgetragen (Naßauftrag 75µm) und 24 Stunden bei Raumtemperatur getrocknet. Die Lichthofschutzschicht hatte eine optische Dichte von 0.55. Das Lichthofschutzmaterial wies auch nach einer Lagerungszeit von 26 Wochen noch eine ausreichende optische Dichte von 0.33 auf. Zum Ausbleichen des Lichthofschutzfarbstoffs wurde das Material 30 sec durch Auflegen auf eine heiße Metallplatte auf 105°C erhitzt, wobei die optische Dichte auf 0.03 reduziert wurde. Die Entfärbung war über 26 Wochen lang stabil.b) Antihalation layer I To a solution of 15 g of 10% gelatin solution, 1 g 10% aqueous sorbitan monolaurate polyglycol ether solution and 0.15 g C.I. Acid Blue 93 became a solution of 0.25 g 3-phenyl-4- (4-chlorophenyl) -1,2,3,5-oxathiadiazole-2-oxide and 0.25 g triphenyl phosphate in 1 g ethyl acetate given. This mixture was at 60,000 for 60 sec Stirred rpm. The resulting dispersion was mixed with a doctor knife on a polyester film (Wet application 75µm) and 24 hours at room temperature dried. The antihalation layer had an optical one Density of 0.55. The antihalation material also proved a storage period of 26 weeks is still sufficient optical density from 0.33. To fade the Antihalation dye was the material through 30 sec Placing on a hot metal plate heated to 105 ° C, the optical density was reduced to 0.03. The Decolorization was stable for over 26 weeks.
  • c) Lichthofschutzschicht II Zu einer Lösung aus 7.5 g 10%iger wäßriger Gelatinelösung, 1.5 g 10%iger wäßriger Netzmittellösung und 7 mg Oxonolblau wurde eine Lösung von 0.5 g 3-Phenyl-4-(4-chlorphenyl)-1,2,3,5-oxathiadiazol-2-oxid und 0.15 g Triphenylphosphat in 2 g Essigsäureethylester gegeben. Diese Mischung wurde für 60 sec mit ca. 7000 U/min gerührt. Die resultierende Dispersion wurde mit einem Abstreichmesser auf eine Polyesterfolie aufgetragen (Naßauftrag 75 µm) und 24 Stunden bei Raumtemperatur getrocknet. Die Lichthofschutzschicht hatte eine optische Dichte von 0.45. Das Lichthofschutzmaterial wies auch nach einer Lagerungszeit von 10 Wochen noch eine ausreichende optische Dichte von 0.35 auf. Zum Ausbleichen des Lichthofschutzfarbstoffs wurde das Material 30 sec durch Auflegen auf eine heiße Metallplatte auf 105°C erhitzt, wobei die optische Dichte auf 0.03 reduziert wurde. Die Entfärbung war über 10 Wochen lang stabil.c) Antihalation protection layer II To a solution of 7.5 g 10% aqueous Gelatin solution, 1.5 g 10% aqueous wetting agent solution and 7 mg of oxonol blue became a solution of 0.5 g of 3-phenyl-4- (4-chlorophenyl) -1,2,3,5-oxathiadiazole-2-oxide and 0.15 g Triphenyl phosphate in 2 g of ethyl acetate. This mixture was at about 7000 rpm for 60 sec touched. The resulting dispersion was washed with a Doctor knife applied to a polyester film (Wet application 75 µm) and 24 hours at room temperature dried. The antihalation layer had an optical one Density of 0.45. The antihalation material also proved a storage period of 10 weeks is still sufficient optical density from 0.35. To fade the Antihalation dye was the material through 30 sec Placing on a hot metal plate heated to 105 ° C, the optical density was reduced to 0.03. The Decolorization was stable for over 10 weeks.
  • d) Lichthofschutzschicht III 0.5 g 3-Phenyl-4-(4-chlorphenyl)-1,2,3,5-oxathiadiazol-2-oxid wurden in 9 g einer 5%igen Lösung eines Copolymers aus Methylvinylether und Maleinsäureanhydrid in Aceton gelöst. Die Gießlösung wurde mit einem Abstreichmesser auf eine Polyesterfolie aufgetragen (Naßauftrag 75 µm) und 24 Stunden bei Raumtemperatur getrocknet. Auf den so erhaltenen Unterguß trug man ein Gemisch aus 15 g 10%iger wäßriger Gelatinelösung, 0.03 g C.I. Acid Blue 22 und 0.1 g Netzmittel auf und trocknet bei Raumtemperatur. Die Lichthofschutzschicht hatte eine optische Dichte von 0.33. Das Lichthofschutzsystem wies auch nach einer Lagerzeit von 26 Wochen noch eine ausreichende optische Dichte von 0.32 auf. Zum Ausbleichen des Lichthofschutzfarbstoffs wurde das Material 30 sec durch Auflegen auf eine heiße Metallplatte auf 105°C erhitzt, wobei die optische Dichte auf 0.04 reduziert wurde. Die Entfärbung war über 26 Wochen lang stabil.d) antihalation layer III 0.5 g of 3-phenyl-4- (4-chlorophenyl) -1,2,3,5-oxathiadiazole-2-oxide were in 9 g of a 5% solution of a copolymer from methyl vinyl ether and maleic anhydride in acetone solved. The pouring solution was opened with a doctor knife applied a polyester film (wet application 75 µm) and 24 Dried for hours at room temperature. To that obtained casting was carried a mixture of 15 g of 10% aqueous gelatin solution, 0.03 g C.I. Acid Blue 22 and 0.1 g wetting agent and dries at room temperature. The Anti-halation layer had an optical density of 0.33. The antihalation system also indicated after a storage period sufficient optical density of 0.32 on. For bleaching the antihalation dye the material was placed on a hot one for 30 sec Metal plate heated to 105 ° C, the optical density was reduced to 0.04. The discoloration was over 26 Stable for weeks.

    • Beispiel 4Example 4

    Zur Herstellung von 3,4-Diphenyl-1,2,3,5-oxathiadiazol-2-oxid wurden 100 mmol Benzaldehydoxim wurden in 85 ml Dimethylformamid gelöst. Die Lösung wurde auf 40°C erwärmt und 15 mmol N-Chlorsuccinimid wurden zugesetzt. Portionsweise wurden dann weitere 85 mmol N-Chlorsuccinimid zugesetzt, wobei die Temperatur unter 50°C gehalten wurde. Die Reaktionslösung wurde anschließend in Eiswasser geschüttet, und das Reaktionsprodukt durch 3maliges Ausschütteln mit Ether extrahiert. Die Etherextrakte wurden mit Wasser gewaschen, über CaSO4 getrocknet und der Ether entfernt.
    50 mmol des so hergestellten Hydroxamsäurechlords wurde in 50 ml Ether gelöst. Die Lösung wurde mit Natronlauge ausgeschüttelt, und die organische Phase getrocknet. Eine Lösung von 50 mmol N-Sulfinylanilin, hergestellt durch Reaktion von Anilin mit Thionylchlorid in der Wärme oder mit N-Sulfinyl-Sulfonamid bei Raumtemperatur und anschließendes Destillieren, in 50 ml trockenem Ether wurde zugegeben und dann 2 bis 8 Stunden bei Raumtemperatur unter Ausschluß von Luftfeuchtigkeit gerührt. Das Ende der Reaktion wurde durch Dünnschichtchromatographie ermittelt. Das Lösungsmittel wurde im Vakuum entfernt und das Rohprodukt aus Ether/n-Hexan oder Essigsäureethylester/n-Hexan umkristallisiert.
    Mit dem so hergestellten Produkt wurde, wie in Beispiel 3b) beschrieben, eine Lichthofschutzschicht I hergestellt und verarbeitet. Die optische Dichte des Materials betrug 0.6 und nach einer Lagerzeit von 26 Wochen 0.32. Nach dem Ausbleichen betrug die optische Dichte 0.03.
    Eine zweite Lichthofschutzschicht wurde gemäß Beispiel 3c) hergestellt und verarbeitet. Die optische Dichte des Materials betrug 0.45 und nach einer Lagerzeit von 10 Wochen 0.35. Nach dem Ausbleichen betrug die optische Dichte 0.03.
    Analog Beispiel 3d) wurde ein Zweischichtmaterial hergestellt und verarbeitet. Die optische Dichte des Materials betrug 0.35 und nach einer Lagerzeit von 26 Wochen 0.25. Nach dem Ausbleichen betrug die optische Dichte 0.04. Die Entfärbung aller 3 Schichten war über 26 Wochen lang stabil.    To prepare 3,4-diphenyl-1,2,3,5-oxathiadiazole-2-oxide, 100 mmol of benzaldehyde oxime were dissolved in 85 ml of dimethylformamide. The solution was warmed to 40 ° C and 15 mmol N-chlorosuccinimide was added. A further 85 mmol of N-chlorosuccinimide were then added in portions, the temperature being kept below 50.degree. The reaction solution was then poured into ice water and the reaction product extracted by shaking 3 times with ether. The ether extracts were washed with water, dried over CaSO 4 and the ether removed.
    50 mmol of the hydroxamic acid chloride thus prepared was dissolved in 50 ml of ether. The solution was extracted with sodium hydroxide solution and the organic phase was dried. A solution of 50 mmol of N-sulfinylaniline, prepared by reacting aniline with thionyl chloride in the warm or with N-sulfinyl-sulfonamide at room temperature and then distilling, in 50 ml of dry ether was added and then at room temperature for 2 to 8 hours with the exclusion of Humidity stirred. The end of the reaction was determined by thin layer chromatography. The solvent was removed in vacuo and the crude product was recrystallized from ether / n-hexane or ethyl acetate / n-hexane.
    An antihalation layer I was produced and processed with the product thus produced, as described in Example 3b). The optical density of the material was 0.6 and after a storage period of 26 weeks it was 0.32. After bleaching, the optical density was 0.03.
    A second antihalation layer was produced and processed in accordance with Example 3c). The optical density of the material was 0.45 and after a storage period of 10 weeks 0.35. After bleaching, the optical density was 0.03.
    Analogous to example 3d), a two-layer material was produced and processed. The optical density of the material was 0.35 and after a storage period of 26 weeks 0.25. After bleaching, the optical density was 0.04. The decolorization of all 3 layers was stable for 26 weeks.

    Beispiel 5Example 5

    Wie in Beispiel 3a) beschrieben, wurde ausgehend von 2,4-Dichlorbenzaldehyd und Anilin 3-Phenyl-4-(2,4-dichlorphenyl)-1,2,3,5-oxathiadiazol-2-oxid hergestellt.
    Mit dem so hergestellten Produkt wurde, wie in Beispiel 3b) beschrieben, eine Lichthofschutzschicht I hergestellt und verarbeitet. Die optische Dichte des Materials betrug 0.43 und nach einer Lagerzeit von 26 Wochen 0.33. Nach dem Ausbleichen betrug die optische Dichte 0.04.
    Eine zweite Lichthofschutzschicht wurde gemäß Beispiel 3c) hergestellt und verarbeitet. Die optische Dichte des Materials betrug 0.34 und nach einer Lagerzeit von 10 Wochen 0.3. Nach dem Ausbleichen betrug die optische Dichte 0.03.
    Analog Beispiel 3d) wurde ein Zweischichtmaterial hergestellt und verarbeitet. Die optische Dichte des Materials betrug 0.35 und nach einer Lagerzeit von 26 Wochen 0.3. Nach dem Ausbleichen betrug die optische Dichte 0.05. Die Entfärbung aller 3 Schichten war über 26 Wochen lang stabil.    As described in Example 3a), starting from 2,4-dichlorobenzaldehyde and aniline, 3-phenyl-4- (2,4-dichlorophenyl) -1,2,3,5-oxathiadiazole-2-oxide was prepared.
    An antihalation layer I was produced and processed with the product thus produced, as described in Example 3b). The optical density of the material was 0.43 and after a storage period of 26 weeks 0.33. After bleaching, the optical density was 0.04.
    A second antihalation layer was produced and processed in accordance with Example 3c). The optical density of the material was 0.34 and after a storage period of 10 weeks 0.3. After bleaching, the optical density was 0.03.
    Analogous to example 3d), a two-layer material was produced and processed. The optical density of the material was 0.35 and after a storage period of 26 weeks 0.3. After bleaching, the optical density was 0.05. The decolorization of all 3 layers was stable for 26 weeks.

    Beispiel 6Example 6

    Wie in Beispiel 3a) beschrieben, wurde ausgehend von 4-Fluorbenzaldehyd und Anilin 3-Phenyl-4-(4-fluorphenyl)-1,2,3,5-oxathiadiazol-2-oxid hergestellt. As described in Example 3a), starting from 4-fluorobenzaldehyde and aniline 3-phenyl-4- (4-fluorophenyl) -1,2,3,5-oxathiadiazole-2-oxide produced.

    Mit dem so hergestellten Produkt wurde, wie in Beispiel 3b) beschrieben, eine Lichthofschutzschicht hergestellt und verarbeitet. Die optische Dichte des Materials betrug 0.54 und nach einer Lagerzeit von 26 Wochen 0.33. Nach dem Ausbleichen betrug die optische Dichte 0.02. Die Entfärbung war über 26 Wochen lang stabil.With the product so produced, as in Example 3b) described, an antihalation layer produced and processed. The optical density of the material was 0.54 and after a storage period of 26 weeks 0.33. After fading the optical density was 0.02. The discoloration was over 26 Stable for weeks.

    Beispiel 7Example 7

    Wie in Beispiel 3a) beschrieben, wurde ausgehend von 2,4-Dichlorbenzaldehyd und 2,4-Dichloranilin 3-(2,4-Dichlorphenyl)-4-(2,4-dichlorphenyl)-1,2,3,5-oxathiadiazol-2-oxid hergestellt. Mit dem so hergestellten Produkt wurde, wie in Beispiel 3b) beschrieben, eine Lichthofschutzschicht hergestellt und verarbeitet. Die optische Dichte des Materials betrug 0.54 und nach einer Lagerzeit von 26 Wochen 0.34. Nach dem Ausbleichen betrug die optische Dichte 0.02. Die Entfärbung war über 26 Wochen lang stabil.As described in Example 3a), starting from 2,4-dichlorobenzaldehyde and 2,4-dichloroaniline 3- (2,4-dichlorophenyl) -4- (2,4-dichlorophenyl) -1,2,3,5-oxathiadiazole-2-oxide produced. With the product so produced, how described in Example 3b), an antihalation layer manufactured and processed. The optical density of the material was 0.54 and after a storage period of 26 weeks 0.34. After the optical density was 0.02 after bleaching. The Decolorization was stable for over 26 weeks.

    Beispiel 8Example 8

    Wie in Beispiel 3a) beschrieben, wurde ausgehend von 2,6-Dichlorbenzaldehyd und 2,4-Dichloranilin 3-(2,4-Dichlorphenyl)-4-(2,6-dichlorphenyl)-1,2,3,5-oxathiadiazol-2-oxid hergestellt.
    Mit dem so hergestellten Produkt wurde, wie in Beispiel 3b) beschrieben, eine Lichthofschutzschicht hergestellt und verarbeitet. Die optische Dichte des Materials betrug 0.44 und nach einer Lagerzeit von 26 Wochen 0.29. Nach dem Ausbleichen betrug die optische Dichte 0.02. Die Entfärbung war über 26 Wochen lang stabil.    As described in Example 3a), starting from 2,6-dichlorobenzaldehyde and 2,4-dichloroaniline, 3- (2,4-dichlorophenyl) -4- (2,6-dichlorophenyl) -1,2,3,5-oxathiadiazole -2-oxide produced.
    An antihalation layer was produced and processed with the product thus produced, as described in Example 3b). The optical density of the material was 0.44 and after a storage period of 26 weeks it was 0.29. After bleaching, the optical density was 0.02. The decolorization was stable for 26 weeks.

    Beispiel 9Example 9

    Wie in Beispiel 3a) beschrieben, wurde ausgehend von 4-Trifluormethylbenzaldehyd und 2,4-Dichloranilin 3-(2,4-Dichlorphenyl)-4-(4-trifluormethylphenyl)-1,2,3,5-oxathiadiazol-2-oxid hergestellt. As described in Example 3a), starting from 4-trifluoromethylbenzaldehyde and 2,4-dichloroaniline 3- (2,4-dichlorophenyl) -4- (4-trifluoromethylphenyl) -1,2,3,5-oxathiadiazole-2-oxide produced.

    Mit dem so hergestellten Produkt wurde, wie in Beispiel 3b) beschrieben, eine Lichthofschutzschicht hergestellt und verarbeitet. Die optische Dichte des Materials betrug 0.41 und nach einer Lagerzeit von 26 Wochen 0.27. Nach dem Ausbleichen betrug die optische Dichte 0.02. Die Entfärbung war über 26 Wochen lang stabil.With the product so produced, as in Example 3b) described, an antihalation layer produced and processed. The optical density of the material was 0.41 and after a storage period of 26 weeks 0.27. After fading the optical density was 0.02. The discoloration was over 26 Stable for weeks.

    Beispiel 10Example 10

    Wie in Beispiel 3a) beschrieben, wurde ausgehend von 4-Nitrobenzaldehyd und Anilin 3-Phenyl-4-(4-nitrophenyl)-1,2,3,5-oxathiadiazol-2-oxid hergestellt.
    Mit dem so hergestellten Produkt wurde, wie in Beispiel 3b) beschrieben, eine Lichthofschutzschicht mit Acid Blue 22 als Lichthofschutzfarbstoff hergestellt und verarbeitet. Die optische Dichte des Materials betrug 0.32 und nach einer Lagerzeit von 26 Wochen 0.26. Nach dem Ausbleichen betrug die optische Dichte 0.04 (130°C, 90 sec). Die Entfärbung war über 26 Wochen lang stabil.    As described in Example 3a), 3-phenyl-4- (4-nitrophenyl) -1,2,3,5-oxathiadiazole-2-oxide was prepared from 4-nitrobenzaldehyde and aniline.
    An antihalation layer with Acid Blue 22 as antihalation dye was produced and processed with the product thus produced, as described in Example 3b). The optical density of the material was 0.32 and after a storage period of 26 weeks 0.26. After bleaching, the optical density was 0.04 (130 ° C, 90 sec). The decolorization was stable for 26 weeks.

    Beispiel 11Example 11

    Wie in Beispiel 3a) beschrieben, wurde ausgehend von Terephthaldialdehyd und 3-Chloranilin 1,4-Bis(2-oxo-3-(3-chlorphenyl)-1,2,3,5-oxathiadiazolyl)-benzol hergestellt, wobei im letzten Reaktionsschritt 100 mmol des N-Sulfinyl-3-chloranilins eingesetzt wurden.
    Mit dem so hergestellten Produkt wurde, wie in Beispiel 3c) beschrieben, eine Lichthofschutzschicht hergestellt und verarbeitet. Die optische Dichte des Materials betrug 0.3 und nach einer Lagerzeit von 10 Wochen 0.3. Nach dem Ausbleichen betrug die optische Dichte 0.04 (130°C, 90 sec). Die Entfärbung war über 10 Wochen lang stabil.    As described in Example 3a), starting from terephthalaldehyde and 3-chloroaniline, 1,4-bis (2-oxo-3- (3-chlorophenyl) -1,2,3,5-oxathiadiazolyl) benzene was prepared, the last Reaction step 100 mmol of the N-sulfinyl-3-chloroaniline were used.
    An antihalation layer was produced and processed with the product thus produced, as described in Example 3c). The optical density of the material was 0.3 and after a storage period of 10 weeks it was 0.3. After bleaching, the optical density was 0.04 (130 ° C, 90 sec). The decolorization was stable for over 10 weeks.

    Claims (10)

    1. Bleachable antihalation system comprising at least one antihalation dye and one bleaching agent for said antihalation dye, characterized in that the bleaching agent consists of one or several compounds, which yield sulfurous acid and/or derivatives of sulfurous acid under treatment with heat and/or irradiation with actinic radiation.
    2. Antihalation system according to claim 1, characterized in that the bleaching agent contains at least one compound, which yields sulphur dioxide under treatment with heat and/or under irradiation with actinic radiation, and the bleaching agent further contains or yields under treatment with heat and/or under irradiation with actinic radiation water and/or hydroxyl ions.
    3. Antihalation system according to one of claims 1 or 2, characterized in that the bleaching agent contains at least one 1,2,3,5-oxathiadiazole-2-oxide derivative, at least one heterocyclic or heteroaromatic sulphone and/or at least one thiadiaziridin-1,1-dioxide derivative.
    4. Antihalation system according to one of claims 1 to 3, characterized in that the bleaching agent contains 3,4-diaryl-substituted 1,2,3,5-oxathiadiazole-2-oxides, wherein the aryl groups are not substituted or are independently substituted with one or several substituents chosen from the group consisting of alkyl, aryl, ether, ester, halogen, hydroxy, cyano, amino, carbonyl, carboxyl, carbomoyl, sulfonyl groups and carbocyclic and heterocyclic annellated rings.
    5. Antihalation system according to one of claims 1 to 4, characterized in that it contains gelatin or gelatin derivatives as binders.
    6. Antihalation system according to one of claims 1 to 5, characterized in that triphenylmethan, quinonimine and/or oxonole dyes are used as antihalation dyes.
    7. Antihalation system according to one of claims 1 to 6, characterized in that the bleaching agent and the antihalation dye(s) are present together in one layer of a thermally developable photographic recording material.
    8. Antihalation dye according to one of claims 1 to 6, characterized in that the bleaching agent and the antihalation dye(s) are present in adjacent layers of a thermally developable photographic recording material.
    9. Thermally developable photographic recording material comprising
      A) a substrate,
      B) at least one thermally developable photographic emulsion layer,
      C) a cover layer and
      D) a bleachable antihalation system comprising at least one antihalation dye and one bleaching agent for the antihalation dye, characterized in that the bleaching agent consists of one or several compounds, which yield sulphurous acid and/or derivatives of sulphurous acid unter treatment with heat and/or under irradiation with actinic radiation.
    10. A method for producing photographic recordings comprising
      a) the imagewise irradiation with actinic radiation of thermally developable photographic recording materials comprising
      1) a substrate
      2) at least one thermally developable photographic emulsion layer
      3) a cover layer and
      4) a bleachable antihalation system comprising at least one antihalation dye and one bleaching agent for the antihalation dye and
      b) the thermal treatment of the imagewise irradiated recording material in order to generate an image in the irradiated regions of the emulsion layer(s), characterized in that the bleaching agent of the antihalation system consists of one or several compounds, which yield sulphurous acid and/or derivatives of sulphurous acid under treatment with heat and/or under irradiation with acitinic radiation.
    EP92121574A 1991-12-24 1992-12-18 Bleachable antihalation system Expired - Lifetime EP0549976B1 (en)

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    Application Number Priority Date Filing Date Title
    DE4142956 1991-12-24
    DE4142956A DE4142956C2 (en) 1991-12-24 1991-12-24 Bleachable antihalation system for photographic materials

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    EP0549976A1 EP0549976A1 (en) 1993-07-07
    EP0549976B1 true EP0549976B1 (en) 1998-02-04

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    EP0549976A1 (en) 1993-07-07
    DE4142956A1 (en) 1993-07-01

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