Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/76—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
  • G03C1/835—Macromolecular substances therefor, e.g. mordants
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
• • 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
  • G03C1/7614—Cover layers; Backing layers; Base or auxiliary layers characterised by means for lubricating, for rendering anti-abrasive or for preventing adhesion
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
  • C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
• • 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
  • Y10S430/16—Blocked developers

Definitions

• the present invention relates to a photographic element provided with an alkali soluble hydrophobic outer layer containing as the main constituent a layer-forming polymer, and more particularly to a photographic element provided with an antihalation backing or with a protective layer applied to the light-sensitive silver halide layer or to the layer bearing already a silver image or a color image.
• This layer generally consists of a binding agent such as gelatin or a synthetic polymer, and a substance absorbing the light rays of this region of the spectrum to which the silver halide emulsion (or, in the case of a multilayer film, the emulsion layernearest to the support) is sensitive.
• a protective layer e.g. an anti-abrasive layer or a layer which absorbs the ultraviolet radiations
• a protective layer e.g. an anti-abrasive layer or a layer which absorbs the ultraviolet radiations
• a layer-forming polymer e.g. an anti-abrasive layer or a layer which absorbs the ultraviolet radiations
• the polymeric products which are to be used as binding agents in outer layers must meet several severe requirements. Besides the particular function of these layers, they must in any case, on account of their position, possess special mechanical properties and show a resistance to outer influences such as friction, pression, water, moist air etc. so that the films, plates or photographic papers provided with such layers can be treated in the processing baths and/or in the apparatus, e.g. cameras or projection apparatus, without being damaged.
• the layer-forming polymers must moreover be chosen in such a way that the formed layers possess a sufiicient flexibility.
• Another requirement which particularly concerns the antihalation layers consists therein that neither thislayer nor a constituent thereof may be transferred onto the silver halide emulsionlayer if the emulsion layer and the backing layer come into contact e.g. when a photographic film is wound.
• the polymeric binding agent must moreover be sufiiciently soluble in the developers, which frequentlyare only slightly alkaline.
• the sensitivity to the alkali must not be too high since the contact of these layers e.g. with wet hands would damage the photographic element.
• the layers obtained from the polymeric binding agent must be become sticky in moist atmosphere.
• the antihalation coating or the protective layer contains as the main constituent a nitrated styrene-maleic acid copolymer.
• an organic dyestuff or a mixture of such dyestufis dissolved in an appropriated solvent can be incorporated in a solution of a nitrated styrene-maleic acid copolymer.
• Suitable antihalationdyestufis can be found e.g. among the styryl dyestuffs, the triand di-aryl methane dyestuffs and the azomethine dyestuffs.
• the antihalation layer can be applied to a usual support such as e.g. to a flexible light-transmitting film support or to a glass plate, which is to be provided on the other side with a light-sensitive silver halide emulsion layer.
• antihalation layers can be prepared by starting from pigment dispersions e.g. carbon black in the polymeric binding agent.
• pigment dispersions e.g. carbon black
• the nitrated styrenemaleic acid copolymers possess the great advantage to give stable dispersions by simply mixing, whilst stirring, the pigment with a solution of the polymer in an organic solvent such as a lower alcohol, without any addition of a dispersing agent.
• an organic solvent such as a lower alcohol
• styrene-maleic acid copolymers When the nitrated, styrene-maleic acid copolymers are i to be applied as a protective layer on a light-sensitive emulsion layer or on a photographic image-bearing layer, especially a color image-bearing layer, ultra-violet radiation absorbing substances, such as diaminostilbene derivatives, derivatives of coumarone, pyrazoline or imidazoline, may be incorporated in the solution of the polymer.
• the support for the emulsion layer or for the image bearing layer can be e.g. a flexible film or a barytacoated paper.
• the nitrated styrene-maleic acid copolymers are ob tained by action of nitric acid upon styrene-maleic acid copolymers.
• nitric acid hitherto was used therefor, a great part (up to 70%) of the fuming'nitric acid can be replaced by ordinary nitric acid. In the circumstances the reaction runs very smoothly at room temperature. Also a mixture of nitric acid and sulphuric acid can be used. In the event, the reaction is better carried out whilst heating e.g. between 50 and 70 C. Also the proportion nitric acid/ sulphuric acid is of importance and the best resultsare:
• the degree of polymerization of the starting products is only slightly influenced by the nitration. This degree of polymerization is not of particular importance in the preparation of ordinary antihalation layers with soluble dyestuffs; but must be taken into account in the preparation of antihalation backings containing carbon black. In this case, polymers with a relatively low molecular weight are preferably used so that strongly concentrated solutions (25 to 35%) can be prepared which do not show an excessive viscosity. 4
• PREPARATION l (a Styrene-maleic, acid copolymer i 41.6 parts by weight of styrene (previously washed with a solution of sodium hydroxide and water. respectively; dried upon calcium chloride and distilled in nitrogen atmosphere under reduced pressure) are copolyme'rized with 43.1 parts by weight of maleic acid anhydride' in 730 parts by volume of toluene, previously dried upon calcium chloride. The mixture is heated at'1l0 C. for 9 hours in the presence of 0.42 part by weight of azobisisobutyronitrile as initiator. The polymerization mixture is filtered and the deposited styrenemaleic acid copolymer is'washed with hexane and dried in a desiccator at '50? 'C.
• the clear solution is precipitated in distilled water.
• the precipitate is pulveriied and washed with distilled water to neutral reaction as can be controlled with indicator paper.
• the product is dried under vacuum at 40, C. It contains 5.6% of nitrogen.
• the product is dried under vacuum to constant weight. It contains 5.4% of nitrogen.
• a nitrated styrene-maleic acid copolyrner is prepared byv causing 1 kg. of the styrene-maleic acid copolymer to react withv 6.3 liter of strong nitric'acid (d l.42) and 9.95 liter of sulphuric acid (96%) for 8 hours at 60 C.
• the formed reaction product is separated in the same way. as in the previous examples. It contains 5.5% of nitrogen. a V
• a solution of 60 g. of a nitrated styrene-maleic acid copolymer in amixture of 300 crn. of ethanol and 300 c COf methal'l01 is prepared.
• This solution (hereinafter called A) is added to a solution of 22 g. of a green dyestufi (known under the denomination Bro 721 and described. in' BIOS comp. 146/2/ 382/ 30), in a mixture 015-209 cmfii of ethanol and200cm. of methanol (solution B).
• This solution is coated on the rear of a cellulose aceto-butyrate' film support, the front side of.which is to.
• panchromatic sensitized silver iodoare dissolved in a mixture of 200 cm. of ethanol and ns baths- ExaMPLE 2' 22 g. of a dyestufi of the following formula (IJH2-CH2QH are dissolved in a mixture of 200 cm. of ethanol and 200 cm. of methanol.
• This colored solution is added to solution A described in Example 1.
• a deep-red colored layer is ob 200 cm. of methanol.
• This solution is added to the solution A described in Example 1.
• an orange-colored layer is obtained which decoloriz es in the processing baths.
• EXAMPLE 4 22 g. of. a dyestuff described in PB report 74174, frame 820. (US. Government, Office of Technical Services, Washington), are dissolved together with 60 g. of nitrated styrene-maleic acid copolymer in a mixture of 500. cm. of ethanol and 500 cm. of methanol. After ap; plication to a flexible support which is to be provided with three, differentially sensitized silver halide emulsion layers contining color couplers, a violet layer is obtained. This layer d'ecolorizes and dissolves in the photographic processing baths. 7
• a photographic element eg a positive motion pic: ture color film, provided therewith, is free from halae tion.
• EXAMPLE 6 A solution of 9 g. of a nitrated styrene-maleic acid copolymerv in a mixture. of 700 cm. of ethanol and B QQ cm. -of m thanol is coated as an anti-abrasive layer onto a silver chloro-bjromide emulsion layer on a baryta-coated paper support.
• the photographic properties of the tlight sensitive lays .11 2 99;matlfidl she-na cremai s- 9 friction fog is periods of stockage, and moreover the light-reflection being almost completely. inhibited by considerably diminished in respect of those of a photographic emulsion without protective layer.
• EXAMPLE 7 75 g. of a nitrated styrene-maleic acid copolymer and 5 g. of Teregitol NP 35 (trademark for alkylphenylpolyethylene glycol ether) are dissolved in a mixture of 600 cm. of ethanol, 160 cm. of ether, 100 cm. of isopropylalcohol and 50 cm. of methylene-glycol. This solution is mechanically applied to the image-bearing layer of an exposed and developed motion picture film of the positive type. This layer protects the film against scratching, moisture and mishandling during the treatment.
• EXAMPLE 8 12 g. of Uvinul 400 (a substituted benzophenone) are added the solution of the copolymer described in Example 6. This solution is applied as protective layer on the emulsion layer of a photographic negative film. This layer protects the emulsion against ultra-violet rays.
• a photographic element comprising a support, at least one light-sensitive silver halide emulsion layer, and an alkali-soluble hydrophobic outer layer, said outer layer being mainly constituted by a nitrated copolymer consisting of 50 mol percent styrene monomeric units alternating with 50 mol percent maleic acid monomeric units, the copolymer containing 0.8 to 1.2 nitro groups per styrene monomeric unit.
• a photographic element comprising a flexible lighttransmitting support, at least one light-sensitive silver halide emulsion layer on one side of said support, and an alkali-soluble hydrophobic anti-halation layer on the other side of said support, said anti-halation layer comprising a copolymer and a light-absorbing substance, said copolymer consisting of 50 mol percent styrene monomen'c units alternating with 50 mol percent maleic acid monomeric units, the copolymer containing 0.8 to 1.2 nitro groups per styrene monomeric unit.
• a photographic element comprising a support, at least one light-sensitive silver halide emulsion layer on one side of said support, and an alkali-soluble hydrophobic protective layer coated on said emulsion layer, said protective layer being mainly constituted by a copolymer consisting of mol percent styrene monomeric units alternating with 50 mol percent maleic acid monomeric units, the copolymer containing 0.8 to 1.2 nitro groups per styrene monomeric unit.
• a photographic element comprising a support, at least one image-bearing layer, said image having been obtained by exposing to light a light-sensitive silver halide emulsion layer on one side of said support, said element further ocmprising a. protective layer coated on said image-bearing layer, said protective layer being mainly constituted by a copolymer consisting of 50 mol percent styrene monomeric units alternating with 50 mol percent maleic acid monomeric units, the copolymer containing 0.8 to 1.2 nitro groups per styrene monomeric unit.

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• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

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Citations (5)

• 0
  • BE BE552915D patent/BE552915A/xx unknown
  • DE DENDAT1071477D patent/DE1071477B/de active Pending
• 1957
  • 1957-11-25 GB GB36628/57A patent/GB852141A/en not_active Expired
  • 1957-11-26 US US698902A patent/US2984568A/en not_active Expired - Lifetime
  • 1957-11-26 FR FR1190631D patent/FR1190631A/fr not_active Expired

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