EP1718473B1 - Positiv arbeitende thermische bilderzeugungsanordnung und verfahren zu deren herstellung - Google Patents

Positiv arbeitende thermische bilderzeugungsanordnung und verfahren zu deren herstellung Download PDF

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Publication number
EP1718473B1
EP1718473B1 EP03819081A EP03819081A EP1718473B1 EP 1718473 B1 EP1718473 B1 EP 1718473B1 EP 03819081 A EP03819081 A EP 03819081A EP 03819081 A EP03819081 A EP 03819081A EP 1718473 B1 EP1718473 B1 EP 1718473B1
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Prior art keywords
layer
thermal imaging
compound
positive working
substrate
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English (en)
French (fr)
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EP1718473A1 (de
Inventor
André Luiz ARIAS
Luiz Nei Arias
Marjorie Arias
Mario Italo Provenzano
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IBF Industria Brasileira de Filmes S/A
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Ibf - Industria Brasileira De Filmes S/a
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    • 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
    • B41C1/1016—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 characterised by structural details, e.g. protective layers, backcoat layers or several imaging layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2201/00—Location, type or constituents of the non-imaging layers in lithographic printing formes
    • B41C2201/04—Intermediate layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2201/00—Location, type or constituents of the non-imaging layers in lithographic printing formes
    • B41C2201/14—Location, type or constituents of the non-imaging layers in lithographic printing formes characterised by macromolecular organic compounds, e.g. binder, adhesives
    • 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
    • B41C2210/02—Positive working, i.e. the exposed (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
    • B41C2210/06—Developable by an alkaline 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
    • B41C2210/14—Multiple imaging layers
    • 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
    • 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
    • B41C2210/26—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 not involving carbon-to-carbon unsaturated bonds
    • B41C2210/262—Phenolic condensation polymers, e.g. novolacs, resols

Definitions

  • the invention relates to new positive working thermal imaging assembly or structure and a process for preparing a positive working thermal imaging assembly, especially suitable as lithographic printing plates, color proofing films and photoresists produced with aluminum or polyester substrates.
  • compositions used for heat sensitive lithographic printing plates are well-known in the art. Imaging on such plates occurs through the action of infrared radiation which, upon striking on the radiation sensitive composition, changes its solubility in the developer, the non-exposed area solubility remaining unchanged. In the case of a positive plate, the area exposed to radiation becomes developer-soluble while in a negative plate the exposed area becomes insoluble.
  • US patent 5,491,046 describes an example of printing plate containing a radiation sensitive composition, such composition containing a novolak phenolic resin, a resol phenolic resin, a Broensted acid, and an infrared absorber.
  • a resin for such radiation sensitive composition requires a combination of a resol resin and a novolak resin. If, for example, novolak resin is omitted, there will be no imaging and when the layer is put into contact with the developer it will be removed together with that portion which was not exposed. Accordingly, the plate thus processed is no good for use.
  • the area exposed to radiation in order to imaging requires a heating step before it can be developed.
  • such plates require highly alkali developers which are subject to react with carbon dioxide.
  • WO 97 39894 disclose a composition for use with a printing plate comprised of an alkali developer-insoluble complex, made up from a phenolic resin and quinoline, benzothiazole, pyridine and imidazoline. When this complex is exposed to infrared radiation, its solubility changes because of the heat absorbed, the non-exposed area remaining unaffected.
  • the agents making insoluble the polymer mentioned in that patent are dyes which formulae are described therein.
  • WO 9620429 is another example of imaging from a composition for positive plates containing naphthoquinone diazide ester and a phenolic resin.
  • the photo-sensitive composition is firstly uniformly exposed to ultraviolet radiation in order to make the composition soluble in an alkali developer.
  • the plate is placed on a device where it receivers infrared radiation so as to image and changes the composition solubility on those areas. The areas not exposed to radiation are then removed by the developing alkali solution.
  • WO002/096649 of the own applicant also discloses compositions and structures for radiation sensitive plates.
  • EP1270218 , EP1262318 , WO02/096649 and EP1256444 each discloses a lithographic printing plate precursor comprising a substrate, a first layer deposited onto the substrate and a further layer deposited onto the first layer.
  • the further layer comprises a recording layer which contains an infra-red absorbent, an alkali-soluble resin and an inhibitor for inhibiting the alkali-soluble resin from dissolving in an alkali aqueous developer.
  • the further layer comprising a recording layer which contains alkali-soluble resin and an infra-red absorbent.
  • the further layer comprises an amphiphilic polymer.
  • the present invention also includes a process for preparing a positive working thermal imaging assembly according to claim 17.
  • the invention refers to positive working thermal imaging assembly used as graphic arts material such as lithographic printing plates, films and proofing materials.
  • the positive working thermal imaging assembly of the invention comprises:
  • the first layer is applied to the substrate and thereafter it is treated with solutions at elevated temperatures that contain an active compound or compounds capable of rendering said first polymeric material insoluble to aqueous alkali developer at the point of contact.
  • the alkali-soluble polymer of the first layer is rendered alkali-insoluble by the application of the active compound or compounds which are usually applied in a non-solvent for the first layer, for example, using toluene.
  • the Image-wise exposure of the whole assembly resulted in an increase in alkali-developer solubility where the incident radiation had been absorbed relative to the alkali-insolubility of the unexposed regions.
  • Application of an appropriate alkali developer dissolved the exposed regions leaving the unexposed regions intact to create a positive image.
  • the exposed and developed plate can be suitably an efficiently employed as a printing plate, films and proofing materials.
  • TIE Thermally Imageable Element
  • the weight of the thin layer formed from the treatment with the active compound over the first layer is very low (preferably 10-100mg/m 2 ) which means its dry film thickness is likely to be between 0.1 to 0.005 ⁇ m.
  • the coating from solvents and drying to a solvent-free or low solvent-content film is standard practice in the manufacture of graphic arts materials such as lithographic printing plates, film and proofing materials.
  • the controlled application of such thin films as 0.1 to 0.005 ⁇ m over such large surface areas (thousands of square meters) requires expensive specialist equipment and skilful process control.
  • the treatment of the surface of the first layer after application on the substrate is critical for successful imaging and developing according to the invention.
  • the application of alkali, normal positive developers in practice, to an area of low or no coverage by the active compound(s) will result in discontinuity of the TIE rendering it useless in application due to developer attack.
  • the treatment of the first surface is preferably performed by immersing the substrate coated with the first layer coating into a solution at elevated temperature. Thereafter, the structure (substrate / first layer treated with the active compound(s)) thus treated is subjected to rinsing in the immersion solvent and drying.
  • immersion techniques for the treatment with the active compound(s) is preferred over other alternative coating process since it furnishes some advantages as for example:
  • the treatment of the surface of the first layer is preferably performed by immersing techniques, the treatment can also be performed by using coating rolls in which the active compound/compounds are applied on the first layer in the substrate.
  • the in-line conventional coating devices which would no longer be used for treating the first layer, for example, the No Pre-Heat positive thermal plates are renowned for a susceptibility to scratching, scuffing and marking created by general handling and especially by the automatic loading devices where rollers and suction cups create surface damage.
  • the additional coating device could be used to apply a further coating which acts to protect the TIE from scratching and marking.
  • An example is a 'methacryloxy-functional silicone polyether copolymer' supplied by Dow Coming under the product name '31 Additive' which has a low coefficient of friction or a silicone glycol copolymer product known as '11 additive' from the same company.
  • the visible dye in the additional layers or optional layers and not using it in the first layer.
  • Typical visible dyes used in the art are triarylmethane dyes [such as Crystal Violet, Victoria Blue] as they are bright and soluble in typical coating solvents.
  • triarylmethane dyes such as Crystal Violet, Victoria Blue
  • the 'complex' formed that is responsible for this affect can be reversibly broken down by heat. There are two disadvantages to this type of system. The nature and strength of the complex changes over time and with ambient conditions.
  • the amount of energy (for example from a thermal laser) required to break down the complex [and create a change in alkali developer solubility thereby forming an image after development in alkali developer] is proportional to the strength of the complex. This means that the optimum exposure energy will change over time possibly imiting the usefulness of a derived product. Therefore, one advantage is that by removing the visible dye from the resin layer the coating can be rendered more stable over time.
  • the photographic speed of the coating is limited since increasing the inhibitor level increase alkali developer resistance but will increase the amount of energy required to image i.e. the coating is photographically slower.
  • the inhibitor level we reduce the energy required to break down the complex but resistance to alkali developer reduces to a point of uselessness in application. Therefore, one advantage of not using the dye in the first resin layer is that it breaks the 'photographic speed/alkali developer resistance' constraint and allows a faster assembly to be formulated without compromise to alkali developer resistance.
  • the energy absorbed by the infrared-absorbing dye is transferred as heat and destroys the phenolic resin protection, allowing dissolution thereof in an alkali solution.
  • the positive working thermal imaging assembly of the present invention has many advantages as compared to the conventional printing plates made from other compositions.
  • One of the advantages of the present invention is that preheating of the binding polymer system so to image prior to development is not required.
  • Another advantage of this invention is that pre-exposure to ultraviolet radiation prior to infrared image is not needed.
  • Still another advantage of this invention is that low concentration of infrared sensitive dye is used since the treatment of the first layer interacts with and protects and insolubilize the resin of the first layer, allowing development thereof in high pH developers, about 14, of the kind used for conventional positive plates (PD2 IBF developer), after exposure.
  • TIE Thermally Imageable Element
  • the positive working thermal imaging assembly containing the Thermally Imageable Element (TIE) of the present invention may be processed in different radiating devices, at wavelengths such as from 830 nm to 1064 nm.
  • the coating compositions of the present invention do not emit particles or vapors (ablation), avoiding the formation of precipitates on the infrared-emitting devices and the evolution of harmful vapors to the environment during exposure.
  • the positive working thermal imaging assembly of the invention can, optionally, comprises a first intermediate layer between the substrate and the first layer with a second polymeric material which is soluble or dispersible in aqueous solution optionally containing compounds that absorb and convert light or radiation to heat and/or a coloured dye or pigment coated from a solvent that does not substantially dissolve the first layer.
  • a third or top layer over the converted first layer (over the TIE structure) and composed of a second polymeric material which is soluble or dispersible in aqueous solution optionally containing compounds that absorb and convert light or radiation to heat and/or a visible coloured dye or pigment; the first intermediate layer and the third layer being applied with a solvent that does not substantially dissolve the converted first layer.
  • the optional intermediate and third layers can be mutually exclusive regarding IR absorbing/converting compounds and visible coloured dye or pigment.
  • the first intermediate layer or third layer may contain both IR absorbing/converting compounds and visible dyes and, by using this combination, the other layers (TIE) is absent from them.
  • TIE the other layers
  • Another possibility is to use both the IR absorbing compounds and visible dyes in the first layer on the substrate, whereby these components would be absent from the intermediate and third layers.
  • the first layer is applied to the substrate and thereafter the upper surface of the first layer (surface not contacting the substrate) is treated by contact with a solution of a compound that renders the surface of said layer insoluble to aqueous alkaline developer.
  • the treatment is preferably by immersion for 1 to 120 seconds at a temperature of 50 to 120°C. More particularly, the contact process is for 10 to 90 seconds at a temperature of 60 to 100°C and most preferably for 20 to 60 seconds at a temperature of 70 to 90°C.
  • the contact process is carried out by using a solution containing a non-solvent for the first layer.
  • a solution containing a non-solvent for the first layer Preferably it is performed by using toluene or water.
  • the active compound used for the treatment of the first layer may be in a solution containing from 0.001 to 0.25 weight % thereof, preferably from 0.005 to 0.10 weight % thereof and most preferably from 0.01 to 0.075 weight % thereof.
  • compositions employed for coating the imaging assembly of the present invention are not limited to the use of only one resin as the binding polymer; they are sensitive to radiation in the range from 700 to 1200 nm of the radiation spectrum and can be manipulated in the visible region; they can be used in commercially available infrared image setters and with different wavelengths; and they employ developers for conventional positive plates. Therefore, the radiation sensitive assembly of the present invention provides a wide range of processing (e.g., temperature, dip time etc.) and a high degree of adequacy of the printing plates to the printer real needs.
  • the positive working thermal imaging assembly of the invention provides printing plates containing the compositions of the present invention exhibit a large number of prints in the printing process, about 100,000 copies in regular processing and over 600,000 copies if they are subject to heat (cure).
  • the positive working thermal imaging assembly encompasses not only the combination of layer(s) with the substrate as defined herein but also any related product manufactured from the corresponding structure disclosed herein.
  • the new positive working thermal imaging assembly of the present invention essentially comprises a first layer duly treated as disclosed herein on an aluminum surface (most preferred substrate), as known to one skilled in the art of forming a substrate for a printing plate, the first layer being applied onto the substrate and thereafter the upper surface of the first layer is treated with the active compound. The treated structure is then rinsed and dried.
  • the substrate is a polyester support, it may be used as a color proofing film or for printing.
  • the assembly When used as a printing plate, the assembly is sensitive to energy in the infrared region and is not sensitive in the visible region of the spectrum. Depending on the infrared absorber selected, a composition may be made to respond in the region between 700 and 1200 nm.
  • the layers of the positive working thermal imaging assembly of the present invention may contain one or more infrared-absorbing dye, even of different wavelengths.
  • a printing plate containing infrared absorbers of different wavelengths has the advantage of making possible the use thereof in different commercially available devices for receiving radiation and imaging. Presently, two wavelengths are used.
  • An array of laser diodes emitting at 830 nm is commercially available, which is manufactured and sold by Creo, Vancouver, Canada.
  • the other is the YAG laser outputting at the range of 1064 nm also in the market, which is manufactured and sold by Gerber, a Barco division, Gent, Belgium.
  • Each wavelength has its advantages and disadvantages and both are able to generate acceptable images according to the specific manufacturing mode. Digital information is then used for modulating the laser output.
  • the positive working thermal imaging assembly can be developed using a developing composition, which is aqueous and alkaline. Developers typically used for positive printing plates may be employed in the present invention. Developer takes advantage from the differentiation created with the radiation exposure, to remove the coating from the non-image area and allow the image area to remain. At this point, the plate is able of performance on the printing machines, and may print 100,000 copies. If necessary, such performance may be enhanced by subjecting the coating to heat cure. The step of full cure completes the polymers cross-linking resulting in an image able to provide over 600,000 copies. The curing time usually employed is in the range of 1 to 10 minutes and the temperature is from 180 to 260°C. Curing is usually carried out with conveyor oven such as those sold by Wisconsin Oven.
  • TIE Thermally imageable Element
  • the binding polymer is a condensation product of phenol, orthochlorophenol, o-, m- or p-cresol, p-hydroxy benzoic acid, 2 naphthol or other aromatic monohydroxy monomer with an aldehyde such as formaldehyde, acetaldehyde, fural, benzaldehyde, or any other aliphatic or aromatic aldehyde.
  • This polymer is preferred to have a molecular weight in the range from 2,000 to 80,000, more preferably in the range of 4,000 to 40,000 and most preferably in the range of 7,000 to 20,000.
  • the binding polymer of the first layer is preferably phenolic resin, polyvinylphenol or mixture thereof, most particularly a novolac resin.
  • the binding phenolic polymer is preferably used in the range from about 85% to about 99%, more preferably in the range from about 90% to about 95%, based on the total solids in the composition used to form the first layer.
  • polymers can be optionally added to the system above, such as the condensation polymer of methylated melamine formaldehyde - Resimene 735 manufactured by Monsanto, polymer of butylated urea formaldehyde - Cymel U216-8 - manufactured by Cytec Industries, copolymer of vinyl pirridone/ vinyl acetate - Luviskol Va - manufactured by BASF Fine Chemicals. These polymers can be added in the ratio of 0,5 to 20% based on the total weight of the binding polymer, preferably from 2.0 to 10%.
  • the infrared absorber may be one or more dye or insoluble material such as carbon black.
  • Preferred dyes are those from the classes including, but not limited to, pyridyl, quinolinyl, benzoxazolyl, thiazolyl, benzothiazolyl, oxazolyl and selenazolyl.
  • Carbon black is useful in that it is a panchromatic absorber and works well with energy sources in the full infrared spectrum used for the application of imaging coating films and it is inexpensive and readily available. This region begins in the near infrared (nir) at 700 nm and goes up to 1200 nm. The disadvantage of the carbon black is that it is unable to participate in an image differentiation.
  • dyes are just appearing as commercial products and are very expensive. They must be carefully selected so that the maximum absorption ( ⁇ max) closely matches the output wavelength of the laser used in the image setter. Dyes will advantageously improve differentiation between image and non-image areas created when laser images in the medium being employed.
  • the infrared-absorbing medium is preferably used in the composition in the range of 0,5% to 10% by weight based on the total weight of solids in the composition. More preferably is ranges from about 2.0% to about 5.0%.
  • a dye can be desirable to add to the layers.
  • the purpose of using dyes in the layers is to distinguish an image area after development and increasing the layer oleophily thus enabling a higher amount of printing paint to be received.
  • the amount of dye to be added ranges from 0.5 to 3.0% by weight based on the total weight of solids in the composition.
  • Dyes which may be employed are Malachita green, methylene blue, Victoria Blue, Crystal Violet and Rhodamine B.
  • Other types of dyes that can be used are Orasol Blue, Orasol Red and Orasol Violet, manufactured by Ciba-Geigy.
  • composition to form the first layer is dissolved in a suitable solvent (or suitable solvents).
  • suitable solvents include, but are not limited to: 1-methoxy-2-ethanol, 1-methoxy-2-propanol, acetone, methyl ethyl ketone, diisobutyl ketone, methyl isobutyl ketone, n-propanol, isopropanol, tetrahydrofuran, butyrolactone and methyl lactate.
  • the active compound for the treatment of the first layer of the binding polymer, making it developer-resistant may be one or more polymers including polymeric amines, polyacetals (polyvinyl butyral, polyvinyl formal etc.), polyethylene glycol, butylated urea formaldehyde, copolymers of vinyl pyrrolidone and vinyl acetate, methylated melamine formaldehyde, cellulose esters, or mixtures thereof.
  • This second layer is preferably dissolved in solvents not dissolving the binding polymer of the first layer, which form a film evenly adhered to the first layer, and which are readily evaporated, such as in methylene chloride, toluene and xylene.
  • the dry coating weight must range between 5 and 200 mg/m 2 , preferably 10-100 mg/m 2 .
  • the following commercially available polymers may be mentioned:
  • surfactants may be added to the compositions so as to obtain characteristics required by positive working thermal imaging assembly.
  • Surfactants are employed in order to enhance the coating application to aluminum or polyester supports.
  • Surfactants to be employed include fluorocarbonated surfactants such as FC-430 by 3M Corporation or Zonyl Ns by DuPont, block polymers of ethylene oxide and propylene oxide known as Pluronic and manufactured by Basf and silicone surfactants such as BYK 307 manufactured by BYK Chemie. These surfactants improve the composition cosmetics during application thereof to the substrate, avoiding imperfections and the appearance of voids on the layer.
  • the amount of surfactant employed ranges from 0.01 to 0.5% by weight base on the total weight of solids in the composition.
  • the coating components may be added at several solids levels depending on the technique used to apply the coating to the substrate being coated. Therefore, the ratios of components may be the same, but percentages can differ. The disclosure of the percentage ranges of the components as that of the solution is not significant. As an example, some amounts of each coating component will be cited herein as a percentage of total solids.
  • the coating components are dissolved in a desired solvent system.
  • the solution of the first coating layer is applied to the selected substrate.
  • the coating is applied such as to have a dry coating weight in the range from about 0.5 g/m2 to about 2.0 g/m2. More preferably, from about 0.8 g/m2 to about 1.4 g/m2 is used.
  • the coating is dried under conditions which will effectively remove all solvent therein, but not so harmful to cause degradation of the polymers with themselves or with others. Then, the second coating layer is applied so as to have a dry coating weight from 5 to 200 mg/m 2 , preferably from 10 to 100 mg/m 2 .
  • a coating solution was prepared by dissolving 8.0 g Bakelite 6564 (a novolak resin sold by Bakelite), 0.25 g laser dye 830 A (manufactured by Siber Hegner, Zurich, Switzerland), 0.02 g Zonyl Ns (manufactured by DuPont) and 0.20 g Orasol Violet (manufactured by Ciba Geigy) in 58 g 1-methoxy-2-propanol and 19 g methyl ethyl ketone.
  • An aluminum substrate which has been previously degreased, electrochemically grained, anodized and made hydrophilic with a polyvinyl phosphonic acid treatment, as is well-known to one skilled in the art, was coated with the above composition. After properly dried, a toluene solution of 2% CAB-551-0.1 (manufactured by Eastman Chemical) was applied onto the plate and dried forming a 50 mg/m 2 film.
  • the plate was placed on a Creo Trendsetter image setter and imaging is carried out in the "write-the-non-image-area" mode using 120 mJ/cm2 energy density at 830 nm. After exposure, the areas exposed to radiation were observed not to have suffered ablation.
  • the plate was developed through a processing machine charged with positive developer IBF-PD2. The developed plate was observed to have a good resolution positive image. Based on a UGRA scale, halftone dot resolution was 2.0 - 98%. Under standard printing conditions, the plate was observed to print about 80,000 good copies.
  • Another plate was prepared as described in example 1 except that after imaging and development the plate was protected with an IBF oven solution and subjected to a heat curing treatment over 5 minutes at 230°C. The plate was washed for removing the oven solution, dried and placed in a printing machine. Under standard printing conditions, the plate was observed to print about 600,000 good copies.
  • a coating solution was prepared by dissolving 9.6 g HRJ 2606 (a novolak resin sold by Schenectady), 0.34 g laser dye 830 A (manufactured by Siber Hegner, Zurich, Switzerland), 1.2 g Cymel U216-8 (manufactured by Cytec), 0.02 g Fluorad FC-430 (manufactured by 3M), and 0.12 g flexo blue (a dye manufactured by BASF Corporation) in 81.6 g 1-methoxy-2-propanol and 20 g methyl ethyl ketone.
  • An aluminum substrate which has been previously degreased, electrochemically grained, anodized and made hydrophilic with a polyvinyl phosphonic acid treatment, as is well-known to one skilled in the art, was coated with the above composition.
  • a solution containing 1,5% Solsperse 20.000 (a polymeric amine manufactured by AVECIA Pigments and Additives USA) was applied onto the plate, dried forming a 75 mg/m2 film, and placed on a Creo Trendsetter image setter. Imaging is carried out in the "write-the-non-image-area" mode adjusting the energy density to 120 mJ/cm2 at 830 nm. After exposure, the areas exposed to radiation were observed not to have suffered ablation.
  • the plate was developed through a processing machine charged with positive developer IBF-PD2. Positive image resolution was very good. Based on a UGRA scale, halftone dot resolution was 2.0 - 98%. Under standard printing conditions, the plate was observed to print about 150.000 good copies.
  • a coating solution was prepared by dissolving 8.6 g Bakelite 744 (a novolak resin sold by Bakelite), 0.80 g Luviskol VA 64 (manufactured by BASF Fine Chemical), 0.27 g laser dye 830 A (manufactured by Siber Hegner, Zurich, Switzerland), 0.015 g of a mixture of 1:2 Fluorad FC 430 and BYK 370 (manufactured by BYK Chemie), and 0.15 g Malachita Green in 81.6 g 1-methoxy-2-propanol and 20 g methyl ethyl ketone.
  • the plate was developed through an automatic processing machine charged with positive developer IBF-PD2, and the positive image formed was observed to belong to the area not exposed to radiation. Image resolution was very good and based on a UGRA scale, halftone dot resolution was 2.0 - 98%. Under standard printing conditions, the plate was observed to print about 80,000 good copies.
  • a coating solution was prepared by dissolving 12.0 g HRJ 2606 (a novolak resin sold by Schenectady), 0.17 g laser dye ADS 830 A (sold by ADS American Dye Source, Inc.), 0.04 g Pluronic PE 4300 (manufactured by Basf) and 0.10 g Malachita green in 81.6 g 1-methoxy-2-propanol and 20 g methyl ethyl ketone.
  • An aluminum substrate which has been previously degreased, electrochemically grained, anodized and made hydrophilic with a polyvinyl phosphonic acid treatment, as is well-known to one skilled in the art, was coated with the above composition.
  • a 2% Cymel U 216-Y solution was coated onto the plate which, after it is dried, formed a 50 mg/m2 film.
  • the plate is placed on a Creo Trendsetter image setter and imaging is carried out in the "write-the-non-image-area" mode adjusting the energy density to 120 mJ/cm 2 at 830 nm. After exposure, the areas exposed to radiation were observed not to have suffered ablation.
  • the plate was developed through a processing machine charged with positive developer IBF-PD2. The developed plate was observed to have a strong positive image with good resolution. Based on a UGRA scale, halftone dot resolution was 2.0 - 98%. Under standard printing conditions, the plate was observed to print about 120,000 good copies.
  • a coating solution was prepared by dissolving 4.6 g Bakelite 744 (a novolak resin sold by Bakelite), 5.0 g HRJ 2606 (a novolak resin sold by Schenectady), 0.26 g laser dye ADS 1064 (sold by ADS American Dye Source), 0.15 g Malachita green, and 0.85 g Resimene 735 (manufactured by Monsanto) in 81.6 g 1-methoxy-2-propanol and 20 g methyl ethyl ketone.
  • An aluminum substrate which has been previously degreased, electrochemically grained, anodized and made hydrophilic with a polyvinyl phosphonic acid treatment, as is well-known to one skilled in the art, was coated with the above composition.
  • a toluene solution of 1% CAB 551-0.1 and 1% Solsperse 27000 (manufactured by AVECIA Pigments and Additives USA) was applied onto the plate, forming a 55 mg/m2 film.
  • the plate was placed on a heat image setter, Gerber Crescent 42T, with laser YAG at a wavelength about 1064 nm. Imaging is carried out in the "write-the-non-image-area" mode, adjusting the energy density to 100 mJ/cm 2 . After exposure, the areas exposed to radiation were observed not to have suffered ablation.
  • the plate was developed through an automatic processing machine charged with positive developer IBF-PD2, and the positive image formed exhibits a good resolution. Based on a UGRA scale, halftone dot resolution was 2.0 - 98%. Under standard printing conditions, the plate was observed to print about 130,000 good copies.
  • a coating solution was prepared by dissolving 8.6 g Bakelite 6564 (a novolak resin sold by Bakelite), 0.19 g dye 1064 (sold by Epolin NJ USA), 0.20 g laser dye 830 A (manufactured by Siber Hegner, Zurich, Switzerland), 0.12 g triphenyl phosphate and 0.15 g Malachita Green in 81.6 g 1-methoxy-2-propanol and 20 g methyl ethyl ketone.
  • An aluminum substrate which has been previously degreased, electrochemically grained, anodized and made hydrophilic with a polyvinyl phosphonic acid treatment, as is well-known to one skilled in the art, was coated with the above composition.
  • a xylene solution of 2.0% Carbowax 2000 (Union Carbide) was applied onto the plate which, after dried, formed an about 75 mg/m2 coating. Then, the plate was placed on a heat image setter at 830 nm, with the energy density adjusted to 120 mJ/cm 2 in the "write-the-non-image-area" mode. After exposure, the areas exposed to radiation were observed not to have suffered ablation.
  • the plate was developed through an automatic processing machine charged with positive developer IBF-PD2. Positive image resolution was very good and based on a UGRA scale, halftone dot resolution was 2.0 - 98%. Under standard printing conditions, the plate was observed to print about 80,000 good copies.
  • a plate was prepared as described in example 7 and placed on a heat image setter Gerber Crescent 42 T with the energy density adjusted to 100 mJ/m 2 at 1064 nm in the "write-the-non-image-area" mode. After exposure, the areas exposed to radiation were observed not to have suffered ablation.
  • the plate was developed through an automatic processing machine charged with positive developer IBF-PD2. Image resolution based on a UGRA scale was about 2 to 98% and the plate printed about 80,000 good copies.
  • This example shows the possibility of treating by immersion technique the aluminium substrate coated with the first layer of the invention.
  • the active compound Solsperse was applied by immersion onto a substrate coated with novolac. The assembly was thereafter rinsed and dried (sample S-Oct-01 and 02). 9.1.
  • test 9.2 was repeated by substituting water in place of toluene and achieved the following results (S-Nov-IA-3) Time/s 20 30 40 50 60 Density/% 37 38.75 40 41 44
  • This example shows the use of different active components for treating (by immersion) the substrate coated with the first layer of Novolac.
  • This example shows the use Polyvinylphenol resin (sample S-Dec-III-2) as the polymer for the first layer on an aluminum substrate.
  • the conditions were the preferred process conditions used for the previous examples related to novolac in the first layer.
  • Solsperse was then applied by immersion as tin the previous examples.
  • the effectiveness of Solsperse as the active component in toluene was evaluated to change the dissolution behaviour of the materials.
  • the Make up a first coating comprising a high molecular weight Polyvinylphenol (Marukar Lyncur, CBA [styrene: butylmethacrylate copolymer] from Japan) in place of current resin system but containing current IR and visible dyes.
  • Figure 1 attached illustrates an structure of the invention, in which the bottom is the substrate; layer 1 is the optional intermediate layer; layer 2 means the first layer of binding polymer; T means the thin layer formed by the treatment with the active component and 3 means the optional third layer.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Thermal Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials For Photolithography (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Measurement Of The Respiration, Hearing Ability, Form, And Blood Characteristics Of Living Organisms (AREA)
  • Manufacture Or Reproduction Of Printing Formes (AREA)

Claims (38)

  1. Positiv arbeitende thermische Bilderzeugungsanordnung, umfassend
    A - einen Träger; und
    B - ein thermisch empfindliches Bilderzeugungselement aus einer Verbundschichtstruktur, umfassend
    eine erste Schicht auf dem Träger aus einem Novolakharz, das in einer wässrigen Alkalilösung löslich ist, das optional eine Verbindung enthält, die Licht absorbiert und in Wärme umwandelt, und/oder einen farbigen Farbstoff oder Pigment;
    wobei die erste Schicht umgewandelt wurde auf einer Oberfläche davon durch Behandlung mit einer Lösung bei einer erhöhten Temperatur, die eine aktive Verbindung enthält, die in der Lage ist, das Novolakharz unlöslich in einem wässrigen, alkalischen Entwickler bei dem Berührungspunkt zu machen; wobei die erste Schicht oleophil ist, wobei die erste Schicht behandelt wurde durch Kontakt mit der Lösung über 1 bis 120 Sekunden bei einer Temperatur von 50 bis 120 °C, und wobei die aktive Verbindung ein polymeres Amin ist;
    optional eine erste Zwischenschicht zwischen dem Träger und der ersten Schicht, wobei die erste Zwischenschicht aus einem polymeren Material zusammengesetzt ist, das in einer wässrigen Lösung löslich oder dispergierbar ist und das optional eine Verbindung enthält, die Licht oder Strahlung absorbiert und in Wärme umwandelt, und/oder einen farbigen Farbstoff oder Pigment, beschichtet aus einem Lösungsmittel, das nicht wesentlich die erste Schicht auflöst; und
    optional eine dritte oder Außenschicht über der umgewandelten ersten Schicht und die aus einem polymeren Material zusammengesetzt ist, das in einer wässrigen Lösung löslich oder dispergierbar ist und das optional eine Verbindung enthält, die Licht oder Strahlung absorbiert und in Wärme umwandelt, und/oder einen farbigen Farbstoff oder Pigment, wobei die erste Zwischenschicht und die dritte Schicht mit einem Lösungsmittel aufgetragen werden, das nicht wesentlich die umgewandelte erste Schicht auflöst.
  2. Positiv arbeitende thermische Bilderzeugungsanordnung nach Anspruch 1, wobei die erste Zwischenschicht und die dritte Schicht vorhanden sind und sich einander ausschließen im Hinblick auf eine Verbindung, die Licht oder Strahlung absorbiert und in Wärme umwandelt, und einen farbigen Farbstoff oder Pigment.
  3. Positiv arbeitende thermische Bilderzeugungsanordnung nach Anspruch 1, wobei eine von entweder der ersten Zwischenschicht oder der dritten Schicht vorhanden ist und sowohl eine Verbindung, die Licht oder Strahlung absorbiert und in Wärme umwandelt, als auch einen farbigen Farbstoff oder Pigment enthält, und die andere Schicht in der Anordnung fehlt.
  4. Positiv arbeitende thermische Bilderzeugungsanordnung nach Anspruch 1, wobei die erste Schicht sowohl eine Verbindung, die Licht oder Strahlung absorbiert und in Wärme umwandelt, als auch einen farbigen Farbstoff oder Pigment enthält, und sie in der Zwischenschicht und der dritten Schicht fehlen.
  5. Positiv arbeitende thermische Bilderzeugungsanordnung nach Anspruch 1, wobei das Kontaktverfahren über 10 bis 90 Sekunden bei einer Temperatur von 60 bis 100 °C stattfindet.
  6. Positiv arbeitende thermische Bilderzeugungsanordnung nach Anspruch 5, wobei das Kontaktverfahren über 20 bis 60 Sekunden bei einer Temperatur von 70 bis 90 °C stattfindet.
  7. Positiv arbeitende thermische Bilderzeugungsanordnung nach Anspruch 1, wobei das Kontaktverfahren ausgeführt wird, indem eine Lösung verwendet wird, die ein Nichtlösungsmittel für die erste Schicht enthält.
  8. Positiv arbeitende thermische Bilderzeugungsanordnung nach Anspruch 7, wobei das Kontaktverfahren unter Verwendung von Toluol oder Wasser ausgeführt wird.
  9. Positiv arbeitende thermische Bilderzeugungsanordnung nach Anspruch 1, wobei die aktive Verbindung in einer Lösung ist, die von 0,001 bis 0,25 Gew.-% davon enthält.
  10. Positiv arbeitende thermische Bilderzeugungsanordnung nach Anspruch 9, wobei die aktive Verbindung in einer Lösung ist, die von 0,005 bis 0,10 Gew.-% davon enthält.
  11. Positiv arbeitende thermische Bilderzeugungsanordnung nach Anspruch 9, wobei die aktive Verbindung in einer Lösung ist, die von 0,01 bis 0,075 Gew.-% davon enthält.
  12. Positiv arbeitende thermische Bilderzeugungsanordnung nach Anspruch 1, wobei die Verbindung, die Licht oder Strahlung absorbiert und in Wärme umwandelt, ein Pigment oder Farbstoff ist, das bzw. der Strahlung zwischen den Wellenlängen von 700 und 1200 nm absorbiert.
  13. Positiv arbeitende thermische Bilderzeugungsanordnung nach Anspruch 12, wobei die Verbindung ein Pigment ist und Miloriblau oder Kohleschwarz ist.
  14. Positiv arbeitende thermische Bilderzeugungsanordnung nach Anspruch 12, wobei die Verbindung ein Farbstoff ist.
  15. Positiv arbeitende thermische Bilderzeugungsanordnung nach Anspruch 1, die ausschließlich nur die erste Schicht auf dem Träger umfasst, wobei die erste Schicht auf der Oberfläche nicht in Kontakt mit dem Träger behandelt wird.
  16. Positiv arbeitende thermische Bilderzeugungsanordnung nach Anspruch 1, umfassend den Träger, die erste Schicht, die erste Zwischenschicht und die dritte Schicht.
  17. Verfahren zur Herstellung einer positiv arbeitenden thermischen Bilderzeugungsanordnung, umfassend
    A - einen Träger; und
    B - ein thermisch empfindliches Bilderzeugungselement aus einer Verbundschichtstruktur, wobei das Verfahren umfasst
    (i) das Auftragen auf einem Träger einer ersten Schicht aus einem ersten polymeren Material, das in wässriger Alkalilösung löslich ist, das optional eine Verbindung enthält, die Licht absorbiert und in Wärme umwandelt, und/oder einen farbigen Farbstoff oder Pigment, wobei die erste Schicht oleophil ist;
    (ii) das Behandeln der ersten Schicht auf einer Oberfläche davon mit einer Lösung bei einer erhöhten Temperatur, die eine aktive Verbindung oder Verbindungen enthält, die in der Lage ist bzw. sind, das erste polymere Material unlöslich in einem wässrigen, alkalischen Entwickler bei dem Berührungspunkt zu machen, wobei die erste Schicht behandelt wird durch Kontakt mit der Lösung über 1 bis 120 Sekunden bei einer Temperatur von 50 bis 120 °C, und wobei die aktive Verbindung oder Verbindungen polymere Amine, Polyacetale, Polyethylenglycol, butylierter Harnstoffformaldehyd, Copolymere von Vinylpyrrolidon und Vinylacetat, methylierter Melaminformaldehyd, Celluloseester oder Mischungen davon sind;
    optional und vor Schritt (i) das Auftragen einer ersten Zwischenschicht zwischen dem Träger und der ersten Schicht, wobei die erste Zwischenschicht aus einem polymeren Material zusammengesetzt ist, das in einer wässrigen Lösung löslich oder dispergierbar ist und das optional eine Verbindung enthält, die Licht oder Strahlung absorbiert und in Wärme umwandelt, und/oder einen farbigen Farbstoff oder Pigment, beschichtet aus einem Lösungsmittel, das nicht wesentlich die erste Schicht auflöst; und
    optional das Auftragen einer dritten oder Außenschicht über der behandelten ersten Schicht aus Schritt (ii), wobei die dritte oder Außenschicht aus einem polymeren Material zusammengesetzt ist, das in einer wässrigen Lösung löslich oder dispergierbar ist und das optional eine Verbindung enthält, die Licht oder Strahlung absorbiert und in Wärme umwandelt, und/oder einen farbigen Farbstoff oder Pigment, wobei die
    erste Zwischenschicht und die dritte Schicht mit einem Lösungsmittel aufgetragen werden, das nicht wesentlich die behandelte oder umgewandelte erste Schicht auflöst.
  18. Verfahren nach Anspruch 17, wobei der Schritt (ii) durchgeführt wird, indem der Träger, der die erste Schicht enthält, in eine Lösung bei einer erhöhten Temperatur eingetaucht wird,
    wobei die Lösung eine aktive Verbindung oder Verbindungen enthält, die in der Lage ist bzw. sind, das erste polymere Material unlöslich in einem wässrigen, alkalischen Entwickler bei dem Berührungspunkt zu machen.
  19. Verfahren nach Anspruch 18, wobei der Schritt (ii) über 10 bis 90 Sekunden bei einer Temperatur von 60 bis 100 °C durchgeführt wird.
  20. Verfahren nach Anspruch 19, wobei der Schritt (ii) über 20 bis 60 Sekunden bei einer Temperatur von 70 bis 90 °C durchgeführt wird.
  21. Verfahren nach Anspruch 17, wobei der Schritt (ii) durchgeführt wird, indem der Träger, der die erste Schicht enthält, in eine Lösung eingetaucht wird, die ein Nichtlösungsmittel für die erste Schicht enthält.
  22. Verfahren nach Anspruch 21, wobei der Schritt (ii) durchgeführt wird, indem der Träger, der die erste Schicht enthält, in eine Lösung eingetaucht wird, die Toluol oder Wasser enthält.
  23. Verfahren nach Anspruch 17, wobei die aktive Verbindung in einer Lösung ist, die von 0,001 bis 0,25 Gew.-% davon enthält.
  24. Verfahren nach Anspruch 23, wobei die aktive Verbindung in einer Lösung ist, die von 0,005 bis 0,10 Gew.-% davon enthält.
  25. Verfahren nach Anspruch 17, wobei die aktive Verbindung in einer Lösung ist, die von 0,01 bis 0,075 Gew.-% davon enthält.
  26. Verfahren nach Anspruch 17, wobei das polymere Material der ersten Schicht ein Phenolharz, ein Polyvinylphenol oder eine Mischung davon ist.
  27. Verfahren nach Aspruch 17, wobei das polymere Material der ersten Schicht ein Novolakharz ist.
  28. Verfahren nach Anspruch 17, wobei die erste Zwischenschicht und die dritte Schicht aufgetragen werden und das' polymere Material der ersten Zwischenschicht und der dritten Schicht ausgewählt wird aus der Gruppe, bestehend aus Polyvinylalkohol, Polyvinylpyrrolidon, Polyvinylmethylether und Polyvinylethylether.
  29. Verfahren nach Anspruch 17, wobei die Verbindung, die Licht oder Strahlung absorbiert und in Wärme umwandelt, ein Pigment oder Farbstoff ist, das bzw. der Strahlung zwischen den Wellenlängen von 700 und 1200 nm absorbiert.
  30. Verfahren nach Anspruch 29, wobei die Verbindung ein Pigment ist und Miloriblau oder Kohleschwarz ist.
  31. Verfahren nach Anspruch 29, wobei die Verbindung ein Farbstoff ist.
  32. Verfahren nach Anspruch 17, wobei nur die Schritte (i) und (ii) durchgeführt werden und die erste Schicht auf ihrer oberen Oberfläche davon behandelt wird.
  33. Verfahren nach Anspruch 17, wobei die Vorrichtung die erste Schicht auf dem Träger, die erste Zwischenschicht und die dritte Schicht umfasst, wobei die erste Schicht auf ihrer oberen Oberfläche davon behandelt wird.
  34. Verfahren nach Anspruch 17, wobei der Schritt (ii) durchgeführt wird, indem eine Beschichtung auf die erste Schicht unter Verwendung von Beschichtungsrollen aufgetragen wird;
    wobei die Beschichtung aus einer Beschichtungslösung gebildet wird, die eine aktive Verbindung oder Verbindungen enthält, die in der Lage ist bzw. sind, das erste polymere Material der ersten Schicht unlöslich in einem wässrigen, alkalischen Entwickler bei dem Berührungspunkt zu machen.
  35. Vorrichtung nach Anspruch 1, wobei das Polymer ein Molekulargewicht im Bereich von 2.000 bis 80.000 hat.
  36. Vorrichtung nach Anspruch 1, wobei andere Polymere zu dem Polymer hinzugefügt werden, um dessen Plattenverhalten zu verbessern; wobei die anderen Polymere ein methylierter Melaminformaldehyd, ein butylierter Harnstoffformaldehyd oder ein Copolymer von Vinylpyrrolidon und Vinylacetat sind.
  37. Vorrichtung nach Anspruch 1, wobei die Schichten einen Farbstoff, der bei 830 nm absorbiert, und einen weiteren Farbstoff, der bei 1064 nm absorbiert, enthalten.
  38. Vorrichtung nach Anspruch 1, wobei der Farbstoff ein Pyridyl-, Quinolinyl-, Benzaxazolyl-, Thiazolyl-, Benzothiazolyl-, Oxazolyl- oder Selenazolyl-Farbstoff ist.
EP03819081A 2003-12-04 2003-12-04 Positiv arbeitende thermische bilderzeugungsanordnung und verfahren zu deren herstellung Expired - Lifetime EP1718473B1 (de)

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US4708925A (en) 1984-12-11 1987-11-24 Minnesota Mining And Manufacturing Company Photosolubilizable compositions containing novolac phenolic resin
US5286612A (en) 1992-10-23 1994-02-15 Polaroid Corporation Process for generation of free superacid and for imaging, and imaging medium for use therein
US5340699A (en) 1993-05-19 1994-08-23 Eastman Kodak Company Radiation-sensitive composition containing a resole resin and a novolac resin and use thereof in lithographic printing plates
US5466557A (en) 1994-08-29 1995-11-14 Eastman Kodak Company Radiation-sensitive composition containing a resole resin, a novolac resin, a latent bronsted acid, an infrared absorber and terephthalaldehyde and use thereof in lithographic printing plates
GB9426206D0 (en) 1994-12-23 1995-02-22 Horsell Plc Lithographic plate
US5491046A (en) 1995-02-10 1996-02-13 Eastman Kodak Company Method of imaging a lithographic printing plate
ATE183136T1 (de) 1996-04-23 1999-08-15 Kodak Polychrome Graphics Co Vorläufer einer lithographischen druckform und ihre verwendung bei der bebilderung durch wärme
US6060218A (en) 1997-10-08 2000-05-09 Agfa-Gevaert, N.V. Method for making positive working printing plates from a heat mode sensitive image element
EP1256444B1 (de) * 2001-04-09 2004-06-30 Agfa-Gevaert Positivarbeitende lithographische Druckplattenvorläufer
BR0102218B1 (pt) 2001-05-31 2012-10-16 produto sensìvel à radiação, e processo de impressão ou revelação de imagem utilizando o referido produto.
JP2002357894A (ja) * 2001-06-01 2002-12-13 Fuji Photo Film Co Ltd 平版印刷版用原版およびその処理方法
JP2003005354A (ja) * 2001-06-20 2003-01-08 Fuji Photo Film Co Ltd 平版印刷版用原版および平版印刷版の製版方法

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EP1718473A1 (de) 2006-11-08
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ATE403552T1 (de) 2008-08-15
BR0318606A (pt) 2006-10-24
DE60322753D1 (de) 2008-09-18

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