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
  • G03C1/775—Photosensitive materials characterised by the base or auxiliary layers the base being of paper
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/16—X-ray, infrared, or ultraviolet ray processes
  • G03C5/164—Infrared processes
• • 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
• • 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
  • G03C1/95—Photosensitive materials characterised by the base or auxiliary layers rendered opaque or writable, e.g. with inert particulate additives

Definitions

• This invention relates to photographic elements sensitive to light emitted in the near-infrared portion of the spectrum, from 750 nm and above, especially 750 to 1500 nm, and in particular to photographic elements adapted to provide a high quality recording medium for laser diode scanning systems.
• a widely used image processing technique is to convert a visible image into electronic data by encoding the brightness of adjacent small areas of the visible image.
• Such electronic encoding is advantageous for manipulation, transmission and storage of images. It is known to reconvert electronic data into visible images by means of a so-called "scanner system" whereby a finely focussed beam of light is rapidly scanned across a light sensitive medium in a succession of abutting raster lines, whilst modulating the intensity of light so as to reproduce the required image densities, based on the electronic signals.
• Lasers especially those using argon, krypton, helium-neon or helium-cadmium mixtures as the gas lasing media, have been used as sources of high intensity light for this imaging technique.
• the lasers all suffer the disadvantage of requiring an additional, complex device to modulate the intensity of light emitted, and to a greater or lesser extent, from large physical bulk, mechanical fragility and expense of manufacture.
• Semiconductor laser diodes are potentially highly suitable as light sources for scanner systems in that their light output can be directly modulated by the electrical signal input, and that they are very compact and physically durable.
• NIR near-infrared
• NIR sensitised photographic films especially those having silver halide grains of mean diameter less than 0.4 um, when supported by the edges in a glassless holder, to prevent contact with other surfaces, and given a uniform overall exposure from a laser diode scanner system emitting at 820 nm, produce images covered with broad swirling interference patterns, referred to hereinafter as "non-contact scanner fringes". These fringes are believed to arise as a result of the reflection of the exposing light from the two interfaces of the film element with surrounding air.
• the path difference between the rays reflected from the top surface of the film and the bottom surface is controlled by the thickness of the film at a given point, and the net phase diference causes either destructive or constructive interference, causing either diminished or increased exposure to be transmitted into the light sensitive emulsion layer at that given point.
• the fringes therefore follow contours of microscopic thickness variation in the film element itself, and cover the whole of the image area with broad lines usually about 1 mm apart and often several centimetres in length.
• Non-contact interference fringes have not previously been reported in the literature in relation to silver halide emulsion materials. This phenomenon does not occur under the normal conditions of exposure with visible light because the turbidity of the photosensitive emulsion layer is sufficient to scatter the reflections from the back of the film element. However, because of its longer wavelength, infrared light is able to pass without serious scattering through small-grained photographic emulsions, and the coherence of the laser diode output enhances the tendency to form interference patterns. Thus, a photographic emulsion having silver halide grains of mean diameter 0.28um, with a coating weight of silver of 3 g/m 2 , shows detectable fringes. Lowering the grain size to 0.23 um or reducing the coating weight causes more noticeable patterns, whilst emulsions of mean grain diameter 0.20 um or less exhibit severe fringes after non-contact laser diode scanning.
• Non-contact scanner fringes seriously degrade the quality of scanner images, especially those having continuous tone gradation. They are not only aesthetically displeasing but they also obscure important information conveyed by small density differences in the image. It is desirable to be able to use photographic emulsions having grains of mean diameter less than 0.4 um preferably less than 0.30 um. Fine grain emulsions having a grain size of 0.4 um or less are advantageous in permitting high spatial resolution, and in having high covering power, permitting a lower coating weight of silver to produce a given maximum optical density after development. Accordingly, photographic elements for use with laser diode scanning systems must be capable of suppressing non-contact interference fringes.
• matting particles in the outer surface of films.
• matting particles include silica, poly-methyl methacrylate (PMMA), other polyvinyl compounds including copolymers, starch or inorganic salts.
• PMMA poly-methyl methacrylate
• the density of matting coverage varies from a relatively small number (e.g. applied at less than 0.1 g/m 2 ) of fairly large particles usually 5 to 10 ⁇ m in diameter as disclosed in United States Patent Specification Nos. 4 235 959, 4 022 622, 3 754 924 and 2 322 037, to a particle weight of greater than up to 1 g/m 2 or 50% of the topcoat binders as disclosed in British Patent Specification Nos. 2 077 935 and 2 033 596 and United States Patent Specification Nos. 3 507 678 and 2 992 101 utilizing smaller particle sizes.
• United States Patent Specification No. 4 343 873 discloses a photographic element designed to minimise such fringes which includes a light-scattering layer through which the light-sensitive layer is exposed to laser light.
• the light-scattering particles have a diameter of from 50 to 150% of the wavelength of the illuminating laser.
• the light scattering layer may be coated as an outer layer on the photographic element or beneath other layers.
• matting agents in photographic elements for non-optical properties, such as resistance to adhesion, abrasion resistance, retouchability, good draw-down in vacuum frames, and reduced static effects.
• An example of the use of a matting agent is an infrared sensitive film is disclosed in United States Patent Specification No. 4 266 010 which describes an emulsion topcoat containing PMMA of size in the range 0.2 to 10 pm in an acid-processed gelatin binder, stating this to be suitable for all types of photographic materials including infrared films.
• a further example is disclosed in United States Patent Specification No.
• 3 695 888 which describes a photographic emulsion sensitised to infrared light by cyanine dyes with mesoalkylamino substituents and specific supersensitisers, stating that such elements can contain matting agents such as starch, titanium dioxide, zinc oxide, silica, polymeric beads, including 1 to 4 ⁇ m beads of a methacrylic acid-methyl methacrylate copolymer disclosed in United States Patent Specification No. 2 992 101 and 1 to 20 ⁇ .Lm poly-methyl methacrylate beads formed by emulsion polymerisation as disclosed in United States Patent Specification No. 2 701 245.
• matting agents such as starch, titanium dioxide, zinc oxide, silica, polymeric beads, including 1 to 4 ⁇ m beads of a methacrylic acid-methyl methacrylate copolymer disclosed in United States Patent Specification No. 2 992 101 and 1 to 20 ⁇ .Lm poly-methyl methacrylate beads formed by emulsion polymerisation as disclosed in United States
• a photographic element comprising a support transparent to near infrared radiation above 750 nm, generally in the range 750 to 1500 nm, one or more layers of a silver halide emulsion having grains of an average diameter of not more than 0.4 pm, sensitised to near infrared radiation, characterised in that the element comprises one or more of:
• a photographic element in accordance with the invention is resistant to the formation of internal optical interference patterns which cause unprotected fine grain near-infrared films to become covered in broad swirling fringes when processed after scanning with a laser diode NIR light source, despite non-contact of the film with other surfaces during exposure.
• a microscopic surface roughness having 200,000 protrusions per square millimetre provides a marked reduction in the formation of interference fringes and a surface roughness on the backside of the film having 250,000 protrusions per square millimetre will substantially completely eliminate interference fringes, as will a surface roughness of more than 250,000, preferably, 450,000 protrusions per square millimetre on the top surface.
• a second technique of inhibiting the formation of interference fringes is to provide a backing or subbing layer containing a dye absorbing light in the wavelength range of the exposing source.
• a layer is used alone as fringe suppression layers of the invention means the layer should have a peak transmission optical density of at least 0.75; when such a layer is used in combination with other fringe suppression means an optical density of at least 0.3 will make a significant contribution to the fringe reduction.
• the third technique for reducing fringe formation employs a backing and/or topcoat layer comprising a binder containing particles having a high refractive index substantially preferably greater than 0.3 larger than that of the binder, e.g., desensitised silver halide particles in gelatin.
• the use of silver halide particles is advantageous as the halide may be removed during the processing of the photographic element.
• the high refractive index layer may desirably be removed subsequent to exposure, such as by applying a solvent for the binder.
• non-contact interference fringes may be suppressed in such photographic elements incorporating one or more of the methods in the following constructions:
• the microscopic roughness of the photographic element markedly affects the propensity of the element to form non-contact interference fringes when imaged with a scanning laser.
• an outer backing layer providing a microscopic roughness having at least 250,000 protrusions per square millimetre above the average level of the surface will prevent fringe formation, assuming irradiation takes place from the other side of the element.
• fringe formation can be prevented by provision of a topcoat layer the microscopic surface roughness providing at least 250,000 preferably 450,000 protrusions per square millimetre assuming the element is irradiated from the same side as this layer.
• Combinations of surface roughening layers and antihalation layers may be employed as described above in which case the critical parameters of surface roughening and optical density for each individual layer may be reduced compared to that required when such layers are used as the only means for reducing fringe formation since the effect of the combination of layers is additive. It has been found that a suitable microscopic surface roughness for an outer layer to be used in combination with a further fringe suppressing layer is 200,000 protrusions per square millimetre. The optical density required by an antihalation layer to be used in combination with a surface roughening layer is at least 0.3.
• Particle-containing surface layers described above are preferably used on the back surfaces of the elements, or on both outermost surfaces, rather than as topcoats on the photosenstive emulsion side only, since, surprisingly, the suppression of non-contact laser scanner fringes by surface roughened backings is superior to that by similar topcoats on the emulsion side assuming the exposure is from the emulsion side.
• Advantageous surface roughening agents for use in such layers are particles of organic polymers, particularly of polymethyl methacrylate or developer-soluble polymers such as methacrylic acid- methacrylic ester copolymers, e.g. as described in United States Patent Specification No. 2 992 101.
• suitable organic polymers when used in the particle size range, and loading needed to give the matting properties specified above, are other polyvinyl compounds or vinyl compound copolymers, e.g. as described in British Patent Specification Nos. 2 078 992 and 2 033 596 and United States Patent Specification Nos. 4 287 299 and 3 079 257.
• Other suitable materials include silicaa or composites of silica with polymer, e.g.
• matting agent known in the art consists of very small particles of silica, typically of diameter 0.1 um or less. On dispersion in coating binders such as aqueous gelatine, these small particles form tightly-bound aggregates, typically of 1 pm or greater in diameter, which behave as though they were a single particle.
• the matting properties required for the purposes of this invention may be obtained either by the use of single particles in the required size range, or equally by use of aggregates, the overall size of which falls in the same required range.
• Suitable materials of high refractive index include non-photosensitive silver halide crystals, which are readily produced in uniform sizes and removed by photographic fixers. Silver halides generally have a refractive index in the range 2.0 to 2.2. Other suitable materials of high refractive index include zinc oxide and calcium carbonate.
• Gelatin is a suitable binder for all these layers and has a refractive index of about 1.5.
• the photographic element can contain small quantities (less than 0.1 g/m 2 ) of larger polymer, silica or other matting agent with particles of mean diameter 5 pm and greater, to improve mechanical properties such as adhesion and abrasion resistance.
• Silver halide emulsions useful in the photographic elements of this invention may comprise silver bromide, silver chloride, silver chlorobromide silver bromoiodide or silver chlorobromiodide, and can be prepared by any of the well known procedures, e.g. as described in Research Disclosure 17643, December 1978, par. II and III.
• the emulsions have a particle size of not more than 0.4 um, generally in the range 0.05 to 0.4 pm.
• the emulsions can be sensitised to near-infrared using the dyes disclosed in European Patent Application Publication No. 0 088 595, or using any of the other spectral sensitising dyes known in the art to give sensitivity to radiation of wavelength 750 to 1500 nm, preferably 750 to 900 nm, e.g. as described in Mees and James, The Theory of the Photographic Process, 3rd Ed., pp. 198-199.
• Silver halide emulsions present in the photographic element of this invention can be protected against the production of fog and can be stabilised against loss of sensitivity during keeping.
• Suitable antifoggants and stabilisers are described, for example, in Research Disclosure 17643, December 1978, par. VI.
• Silver halide emulsions present in the photographic elements of this invention can employ optical brightening agents as described, for example, in Research Disclosure 17643, December 1978, par. V.
• the spectrally sensitised silver halide emulsions used in the invention can contain speed increasing compounds, e.g. those described in Research Disclosure 17643, December 1978, par. XXI.
• the layers of the photographic elements can contain various colloids as vehicles or binding agents, e.g. those described in Research Disclosure 17643, December 1978, par. IX. Such colloids can be hardened by various organic and inorganic hardeners, e.g. those described in Research Disclosure 17643, December 1978, par. X.
• the photographic elements of the invention can contain antistatic or conducting layers, plasticisers and lubricants, surfactants, as described, for example, in Research Disclosure 17643, December 1978, par. XI, XII and XIII.
• Photographic emulsions used in the invention can be coated on a wide variety pftransparentsupports, e.g. those described in Research Disclosure 17643, December 1978, par. XVIII.
• the sensitising dyes and other emulsion addenda can be incorporated into the layers of the photographic elements by various methods known in the photographic elements by various methods known in the art, e.g. those described in Research Disclosure 17643, December 1978, par. XIV.
• the photographic elements can be coated on photographic supports by various procedures. Supports and coating procedures are described, for example, in Research Disclosure 17643, December 1978, par. XVV and XVII.
• the sensitised silver halide emulsions used in this invention can be processed after exposure to form a visible silver and/or dye image by associating the silver halide with an aqueous alkaline medium in the presence of a developing agent as described, for example, in Research Disclosure 17643, December 1978, par. XIX.
• the invention Whilst the invention is described in detail for elements containing silver halide grains below 0.4 pm in diameter; the methods for fringe suppression are equally applicable to elements containing other photosensitive silver halide crystals which may permit formation of scanner fringes due to low turbidity.
• the invention is applicable to elements containing tabular grains of silver halide exceeding 0.4 um in diameter, but of high aspect ratio, especially if these are present as a low overall fraction of the silver halide grains in the element, the remainder being comprised of fine grains.
• the photographic elements of this invention can be useful in physical development systems, image transfer systems, dry development systems, diffusion transfer systems, printing and lithography, print-out and direct-print systems as, described, for example, in Research Disclosure 17643, December 1978, par. XXII, XXIII, XXIV, XXV, XXVI and XXVII.
• the invention will now be illustrated by the following Examples.
• Samples were evaluated by uniform exposure in a scanner system in which the radiation from a Hitachi HLP 1400 laser diode emitting at 815 nm was focused to a circular spot of 50 um diameter on the surface of the sample.
• the focused spot was scanned in raster pattern of 200 lines/cm over the sample by means of an oscillating galvanometer mirror in path of the infrared beam.
• the intensity of the exposure was increased stepwise to produce after processing a scale from minimum to maximum density on the sample.
• the samples were then developed using an automatic roller processor 3M type XP507 utilising Eastman Kodak RP X-Omat processing solutions. A visual inspection for fringe patterns was made, and these assessed using the following ranking order:
• the fringe patterns were quantitatively evaluated by tracing with a Joyce-Loebl MDM6 microdensitometer using a small (2.0 x 0.25 mm) slit aperture.
• the maximum transmission optical density difference (O.D.) thus measured between light and dark fringes is given in the Examples.
• the O.D. was measured in areas scanned to mean optical density of between 1.0 and 2.0, in which region the emulsion had contrast values of from 2.5 to 3.5.
• Samples were prepared prior to testing by physical removal of the photosensitive emulsion layer, and by application of a densely I.R. absorbing, non-reflective layer in its place.
• the untreated side of the samples was then irradiated at an angle of 10° to the normal with a collimated beam of known energy, of 5 mm diameter, from a laser diode emitting at 815 nm.
• a radiometric detector was used to monitor the reflected energy at a total angle of 20° to the incident beam (Optronics model 730A). This detector was sited at a distance of 30 cm from the test surface, and admitted light through a circular aperture of 1 cm diameter.
• a sample (approximately 1 cm 2 ) of the film was bonded to a pin stub, with the surface to be examined uppermost.
• a gold coating, approximately 25 nm thick, was applied, using an International Scientific Instruments Inc. (ISI) PS-2 coating unit, at 1.2 kVand 10 mA for 2 minutes.
• the samples were examined in an ISI Super IIIA scanning electron microscope, operating at 10 kV.
• the samples were angled at +20°. In each case a photograph was taken at a print magnification of 5000X, using an internal calibration marker. Particle counts were made within a grid representing an area of 10 um x 10 ⁇ m.
• Particles were counted if they appeared to extend above the average surface level by at least 30% of their diameter, or 0.2 um, whichever was smaller. In samples where only large, infrequent particles were present, photographs at 2000X or lower magnification were taken, and counts made over a more extensive area.
• the back surface of the film base was left uncoated.
• Superamide L9C is a high activity lauric acid-diethanolamine condensate commercially available from Millmaster-Onyx UK.
• Teepol 610 is a sodium salt of a secondary alkyl sulphate commercially available from Shell Chemicals UK Ltd.
• This Example demonstrates the increasing severity of scanner fringes with decreasing silver halide grain size.
• Photographic elements according to the invention having backing layers containing PMMA particles, and resistant to scanner fringes
• Emulsions were prepared, NIR sensitised and coated as in Example 1, but using an 0.18 mm subbed polyester base provided with a backing layer containing 0.3 g/m 2 of poly(methyl methacrylate) particles of mean diameter 0.5 pm in a gelatin binder (1.3 g/m 2 ), which was coated from an aqueous solution also containing as in Example 1 Superamide L9C and Teepol 610 wetting agents, and formaldehyde hardener. Immediately after coating onto the film base, the wet backing layer was passed briefly through a chill zone, at 13°C and 30% relative humidity, causing the gel to set, drying was then brought about at 30°C and 30% relative humidity, and appeared to be complete within 1 minute. The samples were tested in the laser diode scanner system as described above and the results reported in Table 2.
• the coatings of the same grain size emulsions in Example 1 act as control standards.
• Photographic elements according to the invention having backing layers containing non-photosensitive silver halide grains
• Example 3 An 0.16 ⁇ m chlorobromide emulsion was coated as in Example 1, but using a 0.18 mm polyester base provided with a backing layer containing silver halide grains, insensitive to NIR light, in a gelatin binder (1.3 g/m 2 ). The effect on scanner fringes of different sizes and loadings of backing grains is reported in Table 3.
• a 0.16 um chlorobromide emulsion was coated as in Example 1, but on a 0.18 mm subbed polyester base having a backing containing particles (mean grain size of 0.5 to 2.0 pm) of alkali-soluble methacrylic acid-ethyl methacrylate copolymer, in a gelatin binder (1.3 g/m 2 ), which was coated from an aqueous solution containing as in example 1 Superamide L9C or Teepol 610 wetting agents, and formaldehyde hardener as in Example 1.
• An otherwise identical sample was prepared in which the polymer particles were replaced by a lower loading of silica particles of mean diameter 5 um. These samples were tested in comparison with an unbacked one, and the results are reported in Table 4.
• a 0.16 um chlorobromide emulsion was coated as in Example 1, but on a 0.18 mm subbed polyester base having a backing consisting of gelatin 5 g/m 2 , containing an antihalation dye absorbing strongly between 750 and 900 nm, (Dye 29 in European Patent Application Publication No. 0 01 646) with an optical density of 0.40 at 820 nm.This was tested in comparison with an unbacked sampled in the laser diode scanner system, and the results are reported in Table 5.
• a 3% iodobromide emulsion of average grain size 0.21 um was prepared, chemically sensitized, stabilised, spectrally sensitised, and coated on transparent 0.18 mm subbed polyester base, in accordance with Example 17A of European Patent Application Publication No 0 088 595.
• a topcoat of 1.3 g/m 2 of gelatin was simultaneously applied.
• the antihalation layers clearly aid the suppression of fringes.
• Example 2 A 0.16 ⁇ m chlorobromide emulsion was coated as in Example 1, but using 0.18 ⁇ m subbed polyester bases provided with backing layers containing a series of concentrations of PMMA particles of mean diameter 0.5 pm, coated in a gelatin binder (1.3 g/m 2 ) as in Example 2. These samples were tested in a laser diode scanner system and the effect on fringe formation is reported in Table 6.
• a chlorobromide emulsion of grain size 0.26 um was prepared and sensitized using the methods of Example 1.
• the emulsion was coated on a 0.18mm polyester base, at 2.4 g/m 2 silver coverage, simultaneously applying a thin gelatin (1.3 g/m 2 ) topcoat containing 0.036 g/m 2 of PMMA particles of 2.5 ⁇ m mean diameter.
• the opposite side of the base was provided with a layer of gelatin (5 g/m 2 ) containing an infrared absorbing dye (Dye 17 in European Patents Application Publication No.
• Sample (a) was found to give distinctly visible, non-contact scanner fringes whereas Sample (b) did not give any non-contact scanner fringes under the most stringent conditions a laser diode scanner testing.
• Photographic elements having outer matting layers containing particles of an alkali-soluble copolymer
• a 0.16 ⁇ m chlorobromide emulsion was coated as in Example 1, but on a 0.18 mm polyester base having a backing containing particles of alkali-soluble methacrylic acid-ethyl methacrylate copolymer, in a gelatin binder (1.3g/m 2 ), which was coated from an aqueous solution containing Superamide L9C and Teepol 610 wetting agents, and formaldehyde hardener as in Example 1.
• the copolymer particles were of mean diameter 0.75 pm but included a broad range of diameters up to 2 pm. Samples containing different densities of this matting agent were tested for fringe formation in comparison with an unbacked one, and the results are reported in Table 8.
• the degree to which fringes are suppressed is dependent on the type of construction, and on the surface density of protruding particles produced by the matting agent. Further coatings were made in a similar manner using the same 0.16 pm chlorobromide emulsion and suspensions of copolymer matting agent, but using a 0.18 mm polyester base having applied to one side an infra-red absorbing antihalation layer, as in Example 5. The matting layers were applied directly over the antihalation layer, and the photosensitive emulsion to the opposite side of the film base.
• a third set of coatings has made of the same chlorobromide emulsion on an unbacked 0.18 mm polyester base, as in Example 1, except that the usual emulsion supercoat was replaced by the matting suspensions of copolymer particles as described above.

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• 1984
  • 1984-08-31 GB GB848422069A patent/GB8422069D0/en active Pending
• 1985
  • 1985-08-06 AU AU45832/85A patent/AU575983B2/en not_active Ceased
  • 1985-08-12 CA CA000488545A patent/CA1294478C/en not_active Expired - Lifetime
  • 1985-08-12 ZA ZA856085A patent/ZA856085B/xx unknown
  • 1985-08-22 MX MX206386A patent/MX159941A/es unknown
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  • 1985-08-28 ES ES546480A patent/ES8800759A1/es not_active Expired
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