Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
  • B41C1/00—Forme preparation
  • B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
  • B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
  • B41C1/1025—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials using materials comprising a polymeric matrix containing a polymeric particulate material, e.g. hydrophobic heat coalescing particles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
  • B41M5/36—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using a polymeric layer, which may be particulate and which is deformed or structurally changed with modification of its' properties, e.g. of its' optical hydrophobic-hydrophilic, solubility or permeability properties
  • B41M5/368—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using a polymeric layer, which may be particulate and which is deformed or structurally changed with modification of its' properties, e.g. of its' optical hydrophobic-hydrophilic, solubility or permeability properties involving the creation of a soluble/insoluble or hydrophilic/hydrophobic permeability pattern; Peel development
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
  • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
  • B41C2210/04—Negative working, i.e. the non-exposed (non-imaged) areas are removed
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
  • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
  • B41C2210/08—Developable by water or the fountain solution
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
  • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
  • B41C2210/22—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by organic non-macromolecular additives, e.g. dyes, UV-absorbers, plasticisers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
  • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
  • B41C2210/24—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions involving carbon-to-carbon unsaturated bonds, e.g. acrylics, vinyl polymers

Definitions

• the present invention relates to a heat-sensitive material for preparing lithographic printing plates.
• the invention is related to a processless heat-sensitive material which yields lithographic printing plates with a high endurance.
• Lithographic printing is the process of printing from specially prepared surfaces, some areas of which are capable of accepting ink, whereas other areas will not accept ink.
• a photographic material is made imagewise receptive to oily or greasy ink in the photo-exposed (negative working) or in the non-exposed areas (positive working) on a ink-repelling background.
• lithographic plates also called surface litho plates or planographic printing plates
• a support that has affinity to water or obtains such affinity by chemical treatment is coated with a thin layer of a photosensitive composition.
• Coatings for that purpose include light-sensitive polymer layers containing diazo compounds, dichromate-sensitized hydrophilic colloids and a large variety of synthetic photopolymers. Particularly diazo-sensitized systems are widely used.
• the exposed image areas become insoluble and the unexposed areas remain soluble.
• the plate is then developed with a suitable liquid to remove the diazonium salt or diazo resin in the unexposed areas.
• thermoplastic polymer particles By image-wise exposure to an infrared laser, the thermoplastic polymer particles are image-wise coagulated thereby rendering the surface of the imaging element at these areas ink accepting without any further development.
• a disadvantage of this method is that the printing plate obtained is easily damaged since the non-printing areas may become ink-accepting when some pressure is applied thereto. Moreover, under critical conditions, the lithographic performance of such a printing plate may be poor and accordingly such printing plate has little lithographic printing latitude.
• EP-A- 770 494, 770 495, 770 496 and 770 497 disclose a method for making a lithographic printing plate comprising the steps of (1) image-wise exposing to light a heat-sensitive imaging element comprising (i) on a hydrophilic surface of a lithographic base an image-forming layer comprising hydrophobic thermoplastic polymer particles dispersed in a hydrophilic binder and (ii) a compound capable of converting light to heat, said compound being comprised in said image-forming layer or a layer adjacent thereto; (2) and developing a thus obtained image-wise exposed element by rinsing it with plain water.
• a heat-sensitive material for making lithographic printing plates comprising on a lithographic support an image-forming layer comprising a hydrophilic binder, a cross-linking agent for said hydrophilic binder, metal oxide particles with a mean diameter of at least 100 nm and dispersed hydrophobic thermoplastic polymer particles, characterized in that said image-forming layer has a ratio of specific surface (in m 2 per g) over mean roughness( in ⁇ m) of more than 0.75 and that the mean pore width is less than 15 nm.
• the specific surface of the coating (in m 2 per g) is measured by a Micromeritics ASAP2400-apparatus. Therefore the material, including the support, is cut in small pieces and introduced into the apparatus, then a sorption/desorption isotherm of the material is measured with nitrogen-gas as adsorbate.
• the specific surface is calculated, following the sorption/desorption approximation corresponding with BET. Also the mean pore diameter is calculated by the method of Barett, Joyner and Hallender.
• the average surface roughness of the plate (in ⁇ m) is measured with a perthometer MAHR PERTHEN S6P containing a measuring head RTK50 (tradename of Feinprüf Perthen GmbH, Goettingen, Germany) equipped with a diamond stylus with a diameter of 50 ⁇ m under a pressure of 1.0 mN according to techniques well known in the art.
• the sampling length Ls which is the reference length for roughness evaluation measures 0.25 mm.
• the evaluation length Lm being that part of the travelling length Lt which is evaluated for acquiring the roughness profile R contains standard 5 consecutive sampling lengths.
• the traversing length Lt is the overall length travelled by the tracing system when acquiring the roughness profile.
• the average roughness Ra is the measured roughness averaged over the evaluation length Lm.
• the ratio of specific surface over mean roughness is more than 0.75, more preferably more than 0.85.
• the mean pore width is preferably less than 10 nm, more preferably less than 7 nm.
• an imaging element comprising preferably hydrophobic thermoplastic polymer particles with an average particle size between 40nm and 150nm. More preferably the hydrophilic thermoplastic polymer particles are used with an average particle size of 40nm to 80nm. Furthermore the hydrophobic thermoplastic polymer particles used in connection with the present invention preferably have a coagulation temperature above 50°C and more preferably above 70°C. Coagulation may result from softening or melting of the thermoplastic polymer particles under the influence of heat. There is no specific upper limit to the coagulation temperature of the thermoplastic hydrophobic polymer particles, however the temperature should be sufficiently below the decomposition temperature of the polymer particles.
• the coagulation temperature is at least 10°C below the temperature at which the decomposition of the polymer particles occurs.
• said polymer particles are subjected to a temperature above the coagulation temperature they coagulate to form a hydrophobic agglomerate in the hydrophilic layer so that at these parts the hydrophilic layer becomes hydrophobic and oleophilic.
• hydrophobic polymer particles for use in connection with the present invention have a Tg above 80°C.
• the polymer particles are selected from the group consisting of polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polyvinyl carbazole etc., copolymers or mixtures thereof. Most preferably used are polystyrene, polymethylmethacrylate or copolymers thereof.
• the weight average molecular weight of the polymers may range from 5,000 to 5,000,000g/mol.
• the polymer particles are present as a dispersion in the aqueous coating liquid of the image-forming layer and may be prepared by the methods disclosed in US-P- 3 476 937 .
• Another method especially suitable for preparing an aqueous dispersion of the thermoplastic polymer particles comprises:
• the amount of hydrophobic thermoplastic polymer particles contained in the image-forming layer is preferably at least 10% by weight and more preferably at least 15% by weight and most preferably at least 20% by weight of the total weight of said layer.
• Suitable hydrophilic binders for use in an image-forming layer in connection with this invention are water soluble (co)polymers for example synthetic homo- or copolymers such as polyvinylalcohol, a poly(meth)acrylic acid, a poly(meth)acrylamide, a polyhydroxyethyl(meth)acrylate, a polyvinylmethylether or natural binders such as gelatin, a polysaccharide such as e.g. dextran, pullulan, cellulose, arabic gum, alginic acid, inuline or chemically modified inuline.
• water soluble (co)polymers for example synthetic homo- or copolymers such as polyvinylalcohol, a poly(meth)acrylic acid, a poly(meth)acrylamide, a polyhydroxyethyl(meth)acrylate, a polyvinylmethylether or natural binders such as gelatin, a polysaccharide such as e.g. dextran,
• a cross-linked hydrophilic binder in the heat-sensitive layer used in accordance with the present embodiment also contains substances that increase the mechanical strength and the porosity of the layer e.g. metal oxide particles having an average diameter of at least 100 nm which are particles of titanium dioxide or other metal oxides. Incorporation of these particles gives the surface of the cross-linked hydrophilic layer a uniform rough texture consisting of microscopic hills and valleys.
• metal oxide particles having an average diameter of at least 100 nm which are particles of titanium dioxide or other metal oxides. Incorporation of these particles gives the surface of the cross-linked hydrophilic layer a uniform rough texture consisting of microscopic hills and valleys.
• titanium dioxide used in 50 to 95 % by weight of the heat-sensitive layer, more preferably in 60 to 90% by weight of the heat-sensitive layer.
• the image-forming layer also comprises crosslinking agents.
• crosslinking agents such as formaldehyde, glyoxal, polyisocyanate or a hydrolysed tetraalkylorthosilicate. The latter is particularly preferred.
• the imaging element can further include a compound capable of converting light to heat.
• Suitable compounds capable of converting light into heat are preferably infrared absorbing components although the wavelength of absorption is not of particular importance as long as the absorption of the compound used is in the wavelength range of the light source used for image-wise exposure.
• Particularly useful compounds are for example dyes and in particular infrared dyes and pigments and in particular infrared pigments such as carbon black, metal carbides, borides, nitrides, carbonitrides, bronze-structured oxides and oxides structurally related to the bronze family but lacking the A component e.g. WO 2.9 .
• conductive polymer dispersion such as polypyrrole or polyaniline-based conductive polymer dispersions.
• the lithographic performance and in particular the print endurance obtained depends i.a.on the heat-sensitivity of the imaging element. In this respect it has been found that carbon black yields very good and favorable results.
• a light-to-heat converting compound in connection with the present invention is most preferably added to the image-forming layer but at least part of the light-to-heat converting compound may also be comprised in a neighbouring layer.
• the imaging layer preferably contains surfactants which can be anionic, cationic, non-ionic or amphoteric.
• Perfluoro surfactants are preferred. Particularly preferred are non-ionic perfluoro surfactants. Said surfactants can be used alone or preferably in combination.
• the weight of the imaging layer ranges preferably from 1 to 12 g/m 2 , more preferably from 3 to 9 g/m 2 .
• the lithographic base according to the present invention can be aluminum e.g. electrochemically and/or mechanically grained and anodised aluminum.
• the lithographic base can be a flexible support.
• flexible support in connection with the present embodiment it is particularly preferred to use a plastic film e.g. substrated polyethylene terephthalate film, polyethylene naphthalate film, cellulose acetate film, polystyrene film, polycarbonate film, polyethylene film, polypropylene film, polyvinyl chloride film, polyether sulphone film.
• the plastic film support may be opaque or transparent.
• paper or glass of a thickness of not more than 1.2 mm can also be used.
• the imaging element is image-wise exposed. During said exposure, the exposed areas are converted to hydrophobic and oleophilic areas while the unexposed areas remain hydrophilic.
• Said image-forming can be realized by direct thermal recording wherein the thermal transfer is effected by heat radiation, heat conductivity or inductive heat transport.
• the thermal transfer is effected by heat radiation, heat conductivity or inductive heat transport.
• the hydrophobic polymer particles coagulate and forms a hydrophobic area while on the non-heated areas the hydrophobic polymer particles remain unchangedand said area remains hydrophilic.
• Said image-forming can also effected by irradiation with high intensity light.
• the heat-sensitive material should then comprise a compound capable of converting light into heat.
• Image-wise exposure in connection with the present invention is preferably an image-wise scanning exposure involving the use of a laser or L.E.D.
• a laser or L.E.D Preferably used are lasers that operate in the infrared or near-infrared, i.e. wavelength range of 700-1500 nm. Most preferred are laser diodes emitting in the near-infrared.
• the plate is then ready for printing without an additional development and can be mounted on the printing press.
• the imaging element is first mounted on the printing cylinder of the printing press and then image-wise exposed directly on the press. Subsequent to exposure, the imaging element is ready for printing.
• the printing plate of the present invention can also be used in the printing process as a seamless sleeve printing plate.
• the printing plate is soldered in a cylindrical form by means of a laser.
• This cylindrical printing plate which has as diameter the diameter of the print cylinder is slid on the print cylinder instead of mounting a conventional printing plate. More details on sleeves are given in "Grafisch Nieuws" , 15, 1995, page 4 to 6.
• aqueous dispersion comprising 25% by weight of TiO 2 with average particle size between 0.3 and 0.5 ⁇ m and 2.5% by weight of polyvinylalcohol (hydrolysed polyvinylacetate, marketed by Wacker Chemie GmbH, F.R. Germany, under the trademark POLYVIOL WX)
• 218 g of an aqueous dispersion of hydrolysed tetramethoxysilane (22% by weight of hydrolysed tetramethoxysilane) was added.
• AKYPO OP80 TM was added.
• Akypo OP80 is a commercial available surfactant from Chemy.
• 2 g of a 5% by weight solution of a fluorosurfactant N-polyoxyethyleneethyl-perfluorooctane acid amide was added.
• the volume was adjusted to 1000 ml with distilled water.
• the pH was adjusted to 4.0 with NaOH.
• the solution was applied to a heat-set, biaxially oriented polyethylene terephtalate film with a thickness of 175 ⁇ m, so that a total thickness of 6.83 g/m 2 of the coating was present.
• the coating was applied at a wet thickness of 50 ⁇ m and the film was dried under impingement drying with air from 50°C and a moisture content of 4 g/m 3 .
• aqueous dispersion comprising 25% by weight of TiO2 with an average particle size between 0.3 and 0.5 ⁇ m and 2.5% by weight of polyvinylalcohol (hydrolysed polyvinylacetate, marketed by Wacker Chemie GmbH, F.R. Germany, under the trademark POLYVIOL WX)
• 170 g of an aqueous dispersion of hydrolysed tetramethoxysilane (22% by weight of hydrolysed tetramethoxysilane) was added.
• AKYPO OP80 TM was added to this mixture.
• Akypo OP80 is a commercial available surfactant from Chemy.
• 2 g of a 5% by weight solution of a fluorosurfactant N-polyoxyethyleneethyl-perfluorooctane acid amide was added.
• the volume was adjusted to 1000 ml with distilled water.
• the pH was adjusted to 4.0 with NaOH.
• the solution was applied to a heat-set, biaxially oriented polyethylene terephtalate film with a thickness of 175 ⁇ m, so that a total thickness of 6.83 g/m 2 of the coating was present.
• the coating was applied at a wet thickness of 50 ⁇ m and the film was dried under impingement drying with air from 50°C and a moisture content of 4 g/m 3 .
• aqueous dispersion comprising 25% by weight of TiO 2 with an average particle size between 0.3 and 0.5 ⁇ m and 2.5% by weight of polyvinylalcohol (hydrolysed polyvinylacetate, marketed by Wacker Chemie GmbH, F.R. Germany, under the trademark POLYVIOL WX)
• 152 g of an aqueous dispersion of hydrolysed tetramethoxysilane (22% by weight of hydrolysed tetramethoxysilane) was added.
• AKYPO OP80 TM was added to this mixture.
• Akypo OP80 is a commercial available surfactant from Chemy.
• 2 g of a 5% by weight solution of a fluorosurfactant N-polyoxyethyleneethyl-perfluorooctane acid amide was added.
• the volume was adjusted to 1000 ml with distilled water.
• the pH was adjusted to 4.0 with NaOH.
• the solution was applied to a heat-set, biaxially oriented polyethylene terephtalate film with a thickness of 175 ⁇ m, so that a total thickness of 6.83 g/m 2 of the coating was present.
• the coating was applied with a wet thickness of 50 ⁇ m and the film was dried under impingement drying with air from 50°C and a moisture content of 4 g/m 3 .
• an aqueous dispersion comprising 25% by weight of TiO 2 with an average particle size between 0.3 and 0.5 ⁇ m and 2.5% by weight of polyvinylalcohol (hydrolysed polyvinylacetate, marketed by Wacker Chemie GmbH, F.R. Germany, under the trademark POLYVIOL WX), 79.1 g of an aqueous dispersion of hydrolysed tetramethoxysilane (22% by weight of hydrolysed tetramethoxysilane) was added. To this mixture 10g of a 4.1% by weight solution of AKYPO OP80 TM was added. Akypo OP80 is a commercial available surfactant from Chemy. Also 2 g of a 5% by weight solution of a fluorosurfactant, N-polyoxyethyleneethyl-perfluorooctane acid amide was added.
• a fluorosurfactant N-polyoxyethyleneethyl-perfluorooctane
• the volume was adjusted to 1000 ml with distilled water.
• the pH was adjusted to 4.0 with NaOH.
• the solution was applied to a heat-set, biaxially oriented polyethylene terephtalate film with a thickness of 175 ⁇ m, so that a total thickness of 6.83 g/m 2 of the coating was present.
• the coating was applied at a wet thickness of 50 ⁇ m and the film was dried under impingement drying with air from 50°C and a moisture content of 4 g/m 3 .
• an aqueous dispersion comprising 25% by weight of TiO 2 with average particle size between 0.3 and 0.5 ⁇ m and 2.5% by weight of polyvinylalcohol (hydrolysed polyvinylacetate, marketed by Wacker Chemie GmbH, F. R. Germany, under the trademark POLYVIOL WX)
• 73.5 g of an aqueous dispersion of hydrolysed tetramethoxysilane (22% by weight of hydrolysed tetramethoxysilane) was added.
• 175 g of a 5% by weight of a polyvinylalcohol solution was added.
• the used polyvinylalcohol is POLYVIOL WX 48/20, commercially available from Wacker, Burghausen, Germany.
• AKYPO OP80 TM a 4.1% by weight solution of AKYPO OP80 TM was added.
• Akypo OP80 is a commercially available surfactant from Chemy.
• the volume was adjusted to 1000 ml with distilled water.
• the pH was adjusted to 4.0 with NaOH.
• the solution was applied to a heat-set, biaxially oriented polyethylene terephtalate film with a thickness of 175 ⁇ m, so that a total thickness of 6.83 g/m 2 of the coating was present.
• the coating was applied with a wet thickness of 50 ⁇ m and the film was dried under impingement drying with air from 50°C and a moisture content of 4 g/m 3 .
• aqueous dispersion comprising 25% by weight of TiO 2 with average particle size between 0.3 and 0.5 ⁇ m and 2.5% by weight of polyvinylalcohol (hydrolysed polyvinylacetate, marketed by Wacker Chemie GmbH, F.R. Germany, under the trademark POLYVIOL WX)
• 74.6 g of an aqueous dispersion of hydrolysed tetramethoxysilane (22% by weight of hydrolysed tetramethoxysilane) and 7.4 g of glycerol was added.
• AKYPO OP80 TM was added to this mixture.
• Akypo OP80 is a commercial available surfactant from Chemy.
• 2 g of a 5% by weight solution of a fluorosurfactant N-polyoxyethyleneethyl-perfluorooctane acid amide was added.
• the volume was adjusted to 1000 ml with distilled water.
• the pH was adjusted to 4.0 with NaOH.
• the solution was applied to a heat-set, biaxially oriented polyethylene terephtalate film with a thickness of 175 ⁇ m, so that a total thickness of 6.83 g/m 2 of the coating was present.
• the coating was applied with a wet thickness of 50 ⁇ m and the film was dried under impingement drying with air from 50°C and a moisture content of 4 g/m 3 .
• the specific surface and the pore diameter of the coating was measured by a Micromeritics ASAP2400-apparatus.
• the average surface roughness of the plate is measured with a perthometer MAHR PERTHEN S6P containing a measuring head RTK50 (tradename of Feinprüf Perthen GmbH, Goettingen, Germany) equipped with a diamond stylus with a diameter of 5 ⁇ m under a pressure of 1.0 mN.
• a perthometer MAHR PERTHEN S6P containing a measuring head RTK50 (tradename of Feinprüf Perthen GmbH, Goettingen, Germany) equipped with a diamond stylus with a diameter of 5 ⁇ m under a pressure of 1.0 mN.
• the lithographic properties of the thermal imaging element was tested on a Heidelberg GTO 52 with a Van Son Rubberbase RB2329 ink and Rotamatic fountain. Before testing the lithographic properties, the press was ran during 3000 prints to obtain 'equilibrium'-conditions. Then the test plates were mounted on the press without wetting. The press was then rotated 10 times with contact from the plates with the Dahlgren dampening system. Then contact was made with the ink rollers and after 5 rotations, contact was made with paper. Staining on the printed papers was given a visual quotation.
• the physical properties of the imaging element were evaluated by measuring the scratch resistance. In this test, the mechanical properties and the adhesion are quantified.
• scratches are formed by displacing needles at a speed of 96 cm/min, under well defined loads.
• the needles are of ruby type with a radius of 1.5 mm.
• 15 scratches are formed under following loads: 57 - 85 - 114 - 142 - 170 - 113 - 169 - 225 - 282 - 338 - 400 - 600 - 800 - 1000 en 1200 mN.
• Ratio MPW Linisoft Staining Image quality/print length Comparative 0.339 3.9 0 very good not thermally sensitive Ex 1 0.892 1.6 0 very good very good Ex 2 0.775 4.1 0 good good Ex 3 0.720 19 59 bad bad Ex 4 0.591 4.0 29 bad bad Ex 5 1.256 17 38 bad bad Ratio: Ratio of specific surface on mean roughness (g/m 2 . ⁇ m) MPW: mean pore width (nm).

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• Physics & Mathematics (AREA)
• Optics & Photonics (AREA)
• Thermal Sciences (AREA)
• Engineering & Computer Science (AREA)
• Manufacturing & Machinery (AREA)
• Printing Plates And Materials Therefor (AREA)
• Materials For Photolithography (AREA)
• Photosensitive Polymer And Photoresist Processing (AREA)

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Cited By (5)

Citations (1)

• 1998
  • 1998-07-31 DE DE69818659T patent/DE69818659T2/de not_active Expired - Lifetime
  • 1998-07-31 EP EP19980202576 patent/EP0976549B1/de not_active Expired - Lifetime
• 1999
  • 1999-07-29 JP JP21523999A patent/JP2000079771A/ja active Pending

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