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
  • G03C1/675—Compositions containing polyhalogenated compounds as photosensitive substances
• • 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
  • Y10S430/153—Multiple image producing on single receiver

Definitions

• Photographic systems wherein photosensitive colloid or polymer layers are applied which are adapted to the duplication of drawings, line and halftone copies, to the reproduction of colour wiring and circuit printing, cartography and colour proofing are generally known.
• dichromated gelatin is used as light-sensitive substance that'on exposure to activating electromagnetic radiation is tanned and on subsequent wash-off yields a relief image of the recorded radiation pattern.
• the formation of a polymer resist is based on the use of normally liquid to solid monomers containing the grouping e.g., acrylamide, methacrylamide, vinyl acetate, methyl methacrylate and acrylonitrile in the presence of a photocatalyst, such as, e.g. iron(III) ammonium citrate, iron(III) oxalate, iron(III) tartrate and the like.
• a photocatalyst such as, e.g. iron(III) ammonium citrate, iron(III) oxalate, iron(III) tartrate and the like.
• relief images are produced by means of a photographic process in which the imagewise exposure is of fairly low intensity.
• the recording material applied in the present invention comprises a photosensitive dispersed phase in the form of discrete particles of an intimate mixture of N- vinylcarbazole and carbon tetrabromide in a hydrophilic colloid medium.
• the hydrophilic film-forming binder or binder mixture into which the combination of said aromatic N- vinyl compound and photosensitive organic polyhalogen compound is dispersed consists of or mainly contains a water-soluble film-forming colloid containing active hydrogen atoms as are present, e.g., in hydroxyl groups and amino groups. Both qualitative characterization and quantitative determination of active hydrogen can be carried out by the procedure known as the Zerewitinoff active hydrogen determination.
• Hardenable hydrophilic colloids containing active hydrogen atoms are, e.g., polyvinyl alcohol, polyacrylamide or gelatin, and other film or stratum-forming protein type colloids.
• aldehyde-hardenable hydrophilic water-soluble colloids e.g. gelatin which possess the property of sol-gel transformation.
• the present invention provides two modes of operation, a negative working mode, according to which a relief image having reversed image values with respect to the original is formed, and a positive working mode, according to which a relief image having the same image values with respect to the original is obtained.
• the recording layer is overall exposed to UV. radiation of a higher intensity (more lux.sec) than applied in the image-wise exposure. This results in the formation of a visible image corresponding with the initially non-exposed portions.
• the recording layer is overall heated, preferably in the range of to C, to intensify the colour in the initially non-exposed portions.
• the recording layer portions that have been struck by light in the image-wise exposure obtain a decrease in water-permeability and wash-off removability
• the heated recording material is subsequently overall exposed to very intensive ultra-violet radiation. This exposure results in the colouration of the initially image-wise exposed portions of the recording layer.
• the recording layer incorporates colouring matter e.g. already applied in the coating stage in the form of dyes or coloured pigments said very intensive ultra-violet radiation exposure is not necessary for obtaining a coloured negative relief image in thesubsequent wash-off step.
• the recording layer portions which correspond with the areas that initially have not been struck by the weak radiation, are washed off selectively by means of an aqueous liquid, e.g., tap water having a temperature in the range of 2050C.
• an aqueous liquid e.g., tap water having a temperature in the range of 2050C.
• the recording layer in a first step is given an image-wise exposure with ultra-violet radiation of an intensity sufficient to produce'a visible print-out colour image.
• the recording layer is overall heated thereby effecting an intensification of the colour image in the initially exposed portions and a reduction of the water-permeability and wash-off removability of the portions of the recording layer that have not been struck image-wise by U.V.-radiation.
• the recording layer is subjected to a very intensive overall exposure to ultra-violet radiation effecting a colouration in the portions of the recording layer that initially have not been struck by said radiation.
• the recording layer portions that initially have been struck by the light of the image-wise exposure are removed by an aqueous wash-off treatment so that a positive relief colour image of the original remains.
• the recording layer composition contains the N-vinylcarbazole and carbon tetrabromide in a preferred molar range of 40:60 to 75:25.
• the hardenable hydrophilic colloid binder is present for preferably 60 parts by weight with respect to 100 parts by weight of the mixture of N-vinylcarbazole and carbon tetrabromide.
• the above described photosensitive composition is inherently sensitive to near ultraviolet radiation and to blue light.
• Suitable spectral sensitizing agents are compounds that have the property of absorbing electromagnetic energy and that can convert such energy and transfer it through an active contact with a phototransformable substance to said substance.
• a survey of suitable sensitizing agents for the photosensitive compositions used according to the present invention is given in the French Patent Specification 1,574,740 and the US. Pat. No. 3,503,745.
• spectrally sensitizing dye bases more particularly those of the styryl and azastyryl type, e.g. 4-(p-dimethylaminostyryl)-quinoline and Z-(p-dimethylaminostyryl)- quinoline.
• dye bases yield dyes that are good red sensitizers for the photopolymerization of aromatic N-vinyl compounds (see Yamada et al.; Camera Speed Photopolymerization System Part II, Dye-Sensitization and Latensification in the Basic Photopolymerization Emulsion Preprints SPSE Congress Los Angeles May 12-16, 1969).
• the molar ratio of dye base to photosensitive carbon tetrabromide is preferably in the range of 0.0001 to 0.01.
• the photosensitive recording layer containing the dye base is given a weak image-wise exposure to visible light
• the recording layer is overall exposed to visible light of an intensity high enough to produce a colouration in the initially non-exposed areas of the recording layer
• the photosensitive composition is overall heated, preferably between a temperature of ll50C, to intensify the colour in the initially non-exposed areas and to effect a selective decrease in water-permeability of the initially image-wise exposed areas,
• the photosensitive composition is overall exposed to intensive ultra-violet radiation, resulting in a colouration of the initially image-wise exposed areas of the recording layer, and
• the already described process for forming positive relief images may proceed with an image-wise exposure to visible light instead of an image-wise exposure to ultra-violet radiation.
• the carbon tetrabromide before its incorporation into the coating composition is first dissolved in a high-boiling organic liquid, e.g. ethylene glycol monomethyl ether, and in that state dispersed in the hydrophilic colloid medium, in which it comes in intimate contact with the aromatic N-vinyl compound.
• a high-boiling organic liquid e.g. ethylene glycol monomethyl ether
• the spectral sensitizing agent is preferably incorporated into the recording layer composition in the fonn of a solution in a solvent that is miscible with water, so that it becomes very homogeneously distributed throughout the hydrophilic colloid and can come in intimate contact with the complex formed by the polyhalogen and N-vinyl compound.
• the photosensitive coating composition can be applied to any type of support known from the photographic art, e. g. a transparent resin support and a transparent or opaque paper support.
• a transparent resin support e. g. a transparent resin support and a transparent or opaque paper support.
• the support is provided with a subbing layer known in the art for hydrophilic colloid layers such as gelatin-containing layers.
• the light sources used for exposure in the present invention may be any light source of the commercial type emitting in the wavelength range indicated in the preceding exposure modes.
• the heating step before the final overall ultraviolet exposure may proceed with the common means suited for that purpose, e.g. heated rollers, hot glazing plate, hot air current and the like.
• the wash-off treatment of the water-permeable colloid portions may proceed advantageously with running water (tap water at a temperature of 20'60C) with the application of some mechanical friction.
• Example 1 Preparation of the recording material A photographic paper support was covered with a subbing layer of the following composition:
• the high speed mixing was continued for 2 min., during which period of time the temperature reached 72C.
• the dispersion obtained was cooled down to 40C and then mixed by low speed stirring with the following ingredients:
• the light-sensitive recording layer held in contact with a transparent line original was exposed for 2 sec. through said original with a 1,000 W ultra-violet lamp held at a distance of 10 cm. A negative blue-print-out image was formed.
• the image-wise exposed recording material was heated for 10 sec. at 140C by keeping it on a hot glazing plate.
• the heated material was then exposed to ultra-violet radiation with the same radiation source as applied in the image-wise exposure but now for 10 sec.
• the thus exposed recording layer was then held under a jet of water having a temperature of 30C whereby the initially image-wise exposed portions of the recording layer were removed and a black positive copy of the original on a white image background was obtained.
• Example 2 The recording material was the same as that of Example 1.
• the photosensitive recording layer held in contact with a transparent line original was exposed for 15 sec. through said original with a 1,000 W incandescent lamp held at a distance of 5 cm.
• the image-wise exposed recording material was heated for 15 sec. at 140C by conveying it between a pair of heated rollers.
• the heated recording material was then overall exposed for 10 sec to an ultraviolet radiation source of 1,000 W held at a distance of 10 cm.
• a wash-off treatment with running water having a temperature of 40C was applied, whereby a black positive copy of the original on a white image background was obtained.
• Example 3 The composition of the recording material was the same as that described in Example 1.
• the light-sensitive recording layer was contactexposed for 3 see through a positive silver image line transparency in a THERMOFAX (type Secretary) copying apparatus of Minnesota Mining and Manufacturing Co., St. Paul, Minn., USA.
• the recording layer that was image-wise exposed to infrared radiation was overall heated for 10 sec. at 140C by contacting it with a hot glazing plate.
• the overall heating was followed by an overall exposure of 10 sec. to ultra-violet radiation with a 1000 W ultra-violet lamp held at a distance of 10 cm.
• the thus exposed recording layer was then treated with a jet of tap water having a temperature of 30C whereby the initially image-wise exposed portions of the recording layer were removed and a black positive copy of the original on a white image background was obtained.
• Example 4 The recording material was the same as that described in Example 1.
• the photosensitive recording layer while being in contact with a transparent line original was exposed for 0.1 sec. with a W high pressure mercury vapour ultra-violet lamp (type HPR PhilipsGloeilampenfabrieken, Eindhoven, Netherlands).
• the image-wise exposure was followed by an overall exposure for 2 sec. with the same light source.
• the thus exposed recording material was overall heated for 10 sec. at C by conveying it over a heated drum.
• the heated recording material was then overall exposed for 10 sec. with an ultra-violet lamp of 1000 W placed at a distance of 10 cm.
• Example 5 The recording material was the same as that described in Example 1. Recording and Processing The photosensitive recording layer while being in contact with a transparent line original was exposed for 1 sec. with a 1000 W incandescent lamp placed at a distance of 5 cm.
• the image-wise exposed recording layer was then overall exposed with the same incandescent lamp for 5 sec.
• the further processing was the same as that described in Example 4.
• the obtained result was the same as that described in Example 4.
• Example 6 The recording material was the same as that described in Example 1. Recording and Processing The photosensitive recording layer was exposed in an enlarging apparatus (type reader-printer)-through a transparent microfilm image of a line original. The exposure lasted 10 sec. and was effected with a W incandescent lamp placed at a distance of 30 cm and emitting 1000 lux.
• an enlarging apparatus type reader-printer
• the enlargement was 10 times.
• the image-wise exposed recording material was overall exposed for sec with an incandescent lamp of lOOOW placed at a distance of 30 cm or overall exposed for 1 sec. with an ultra-violet high pressure mercury vapour lamp of 125 W type HPR.
• the thus exposed recording material was overall heated at 140C for sec. on a hot glazing plate.
• the heated recording material was overall exposed for 10 sec. with an ultra-violet source of 1000 W held at a distance of 10 cm.
• a wash-off treatment with running water having a temperature of 50C was applied, whereby a black copy enlarged 10 times and having reversed image values with respect to the microfilm original was obtained.
• Example 7 The recording material was the same as that described in Example 1.
• the recording material was exposed reflectographically for 1 sec. to infra-red radiation in a thermographic copier THERMOFAX type secretary copying apparatus using a line original (printed text on opaque paper base).
• the recording material was then overall exposed for 2 sec. with an ultra-violet lamp of 125 W placed at a distance of 30 cm or overall exposed for 3 sec. with an incandescent lamp of 1000 W placed at a distance of 5 cm from the recording layer.
• the thus overall exposed recording material was then overall heated for 10 sec. at 140C on a hot glazing plate.
• the heated recording material was then overall exposed for 10 sec. with an ultra-violet lamp of 1000 W.
• a wash-off treatment in running water of 30C yielded a negative reflex copy (mirror image) suited for yielding positive direct copies of the initially used original in contact-printing e.g., on silver halide emulsion paper.
• a negative reflex copy mirror image
• Example 8 The recording material was the same as that described in Example 1.
• the recording material containing the print-out image was overall heated for 10 sec. at 140C on a hot glazing plate.
• Example 9 Preparation of the recording material An unsubbed polyethylene terephthalate film was first covered with a precoat at a ratio of 33 g per sq.m with the following composition:
• the resulting precoat was covered with a subbing layer and a photosensitive layer as described in Example 1.
• the photosensitive recording layer was contactexposed for 5 sec. through a positive line transparency with a 1000 W ultra-violet lamp.
• the image-wise exposed recording material was overall heated for 3 sec. at C by conveying it between hot rollers.
• the heated recording material was overall exposed for 10 sec. to the ultra-violet radiation of a 1000 W lamp placed at a distance of 10 cm.
• a wash-off treatment in running water of 30C yielded a black-positive copy of the original.
• the copy was suited for use as an intermediate original in diamtype copying.
• Example 10 The recording material was the same as that described in Example 9.
• the photosensitive recording layer was exposed in an enlarging apparatus (type reader-printer) through a transparent microfilm image of a line original.
• the exposure lasted 10 sec. and was effected with a 150 W incandescent lamp emitting 1000 lux.
• the enlargement was 10 times.
• the image-wise exposed recording material was overall exposed for 5 sec. with an incandescent lamp of 1000 W or for 1 sec. with an ultraviolet lamp of W (type HPR).
• the thus overall exposed recording material was then overall heated for 3 sec. at 90C on a hot glazing plate.
• the overall-heated recording material was then overall exposed for 10 sec. with an ultra-violet lamp of 1000 W.
• a wash-off treatment with running water of 30C resulted in the production of a 10 times enlarged copy having reversed image values with respect to the microfilm original.
• a photographic process for forming a relief image in a photographic material including a recording layer comprising a photosensitive dispersed phase in the form of discrete particles of an intimate mixture of N- vinylcarbazole and carbon tetrabromide in a hardenable hydrophilic colloid medium, said colloid containing active hydrogen atoms, by
• hydrophilic hardenable colloid is a protein
• the recording layer composition contains N-vinyl-carbazole and carbon tetrabromide in a molar range of 40:60 to 75:25.
• the recording layer contains 60 parts by weight of hardenable hydrophilic colloid binder with respect to parts by weight of the mixture of N-vinylcarbazole and carbon tetrabromide.
• said negative mode (A) includes between said uniform heating and selective washing off steps the additional step of uniformly exposing the recording layer to strong UV.- radiation to effect coloration of the initially exposed layer regions.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Photosensitive Polymer And Photoresist Processing (AREA)
• Materials For Photolithography (AREA)
• Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)

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Citations (6)

• 0
  • BE BE788208D patent/BE788208A/xx unknown
• 1971
  • 1971-09-08 GB GB4194171A patent/GB1395329A/en not_active Expired
• 1972
  • 1972-08-14 IT IT7286271A patent/IT968386B/it active
  • 1972-08-15 JP JP47081756A patent/JPS4837142A/ja active Pending
  • 1972-08-22 CA CA149,973A patent/CA973749A/en not_active Expired
  • 1972-08-25 DE DE2241957A patent/DE2241957A1/de active Pending
  • 1972-09-04 FR FR7231338A patent/FR2152622B3/fr not_active Expired
  • 1972-09-07 US US00286935A patent/US3833373A/en not_active Expired - Lifetime

Patent Citations (6)

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