EP1254768A2 - Imaging and erasure of a printing form made from a polymer having imide groups - Google Patents
Imaging and erasure of a printing form made from a polymer having imide groups Download PDFInfo
- Publication number
- EP1254768A2 EP1254768A2 EP02007336A EP02007336A EP1254768A2 EP 1254768 A2 EP1254768 A2 EP 1254768A2 EP 02007336 A EP02007336 A EP 02007336A EP 02007336 A EP02007336 A EP 02007336A EP 1254768 A2 EP1254768 A2 EP 1254768A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- printing
- printing form
- chemical treatment
- oxidizing agent
- areas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000007639 printing Methods 0.000 title claims abstract description 88
- 125000005462 imide group Chemical group 0.000 title claims description 9
- 229920000642 polymer Polymers 0.000 title description 6
- 238000003384 imaging method Methods 0.000 title description 5
- 239000000126 substance Substances 0.000 claims abstract description 36
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 28
- 239000007800 oxidant agent Substances 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 52
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000002861 polymer material Substances 0.000 claims description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000007645 offset printing Methods 0.000 claims description 5
- 239000012286 potassium permanganate Substances 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 150000004676 glycans Chemical class 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229920001282 polysaccharide Polymers 0.000 claims description 4
- 239000005017 polysaccharide Substances 0.000 claims description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 3
- 230000005855 radiation Effects 0.000 claims description 3
- 239000002563 ionic surfactant Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 abstract description 20
- 239000004642 Polyimide Substances 0.000 abstract description 18
- 239000000243 solution Substances 0.000 description 13
- 239000002585 base Substances 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 230000005670 electromagnetic radiation Effects 0.000 description 7
- 238000010306 acid treatment Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000007743 anodising Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 229920002312 polyamide-imide Polymers 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- RFSUNEUAIZKAJO-VRPWFDPXSA-N D-Fructose Natural products OC[C@H]1OC(O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-VRPWFDPXSA-N 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- ISQINHMJILFLAQ-UHFFFAOYSA-N argon hydrofluoride Chemical compound F.[Ar] ISQINHMJILFLAQ-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000012822 chemical development Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Images
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
- B41C1/1041—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by modification of the lithographic properties without removal or addition of material, e.g. by the mere generation of a lithographic pattern
Definitions
- the invention relates to a method for producing a structure from hydrophilic and hydrophobic areas on a surface, which in a first, essentially unstructured state has a polymer material with imide groups. Furthermore the invention relates to a printing form, in particular for use as a printing form in the Offset printing, with a surface for printing.
- lithographic printing is based on the exploitation of the Immiscibility of oil and water on a surface, the so-called printing form, wherein the lipophilic (hydrophobic) solution or the ink or color through the image-forming areas and the water or the hydrophilic solution through the non-image-forming areas of the printing surface.
- the in suitably prepared printing surface with hydrophilic and lipophilic substance or solution, especially water and ink or paint is wetted, so keep non-image areas preferably the hydrophilic substance or solution back and repel the lipophilic substances, while the pictorial areas repel the lipophilic solution or accept ink or paint and repel the hydrophilic substances.
- the lipophilic substance in a suitable manner on the surface of a material transferred, on which the image is to be fixed, for example paper, fabric, polymers and the same.
- Aluminum has been used as a material for printing forms for many years. Usually the aluminum is first a graining process and then a subsequent one Subjected to anodizing.
- the anodizing serves to be an anodizing To provide oxide layer, the adhesion of which is improved by the grain.
- Through the Grain size is the hydrophilic properties of the background of the printing plate strengthened.
- a strong acid, such as sulfur or Phosphoric acid used to subsequently by another method such as for example in a thermal siliconization process or the so-called Electrosiliconization to make the surface hydrophilic.
- a large number of radiation-sensitive materials known for generating images in the Use of the lithographic printing process are suitable insofar as they follow Exposure and any necessary development and fixation one Provide a pictorial area that can be used for printing.
- photopolymerizable substances can be used for this.
- the arrangement described above is subjected to imagewise exposure by energy is selectively supplied locally. This can be done, for example, by means of exposure through a mask with UV light or by writing directly with a laser respectively.
- lithographic printing plates of the type described above are usually included treated with a developer solution, which is typically an aqueous alkaline or basic solution with organic additives.
- a developer solution typically an aqueous alkaline or basic solution with organic additives.
- oxide ceramics for example in the form of Coatings are on a printing plate, find use.
- EP 0 911 154 A1 proposes titanium dioxide (TiO 2 ) and zirconium dioxide (ZnO 2 ) as materials for the plate surface, which can be present in ceramic form both in pure form and with other metallic additives in various mixing ratios.
- This surface is hydrophobic in the non-excited state and can be brought into a hydrophilic state by irradiation with ultraviolet light.
- the imaging is now done by illuminating the entire surface of the plate with ultraviolet light and areas which are supposed to lead to color during printing are covered by a mask or a film.
- titanium dioxide layers as the substrate it turns out to be a particular disadvantage that the titanium dioxide layers can be switched with UV light, but a small one Have stability with regard to the time course of the switchover. Furthermore With titanium dioxide layers it always turns out that sufficient Switching or sufficient stroke, d. H. a sufficient flip from hydrophilic to hydrophobic can only be achieved in insufficient strength. Furthermore, the complete cleaning of the substrate after printing is a not to be underestimated Problem in practice.
- the structuring of polymer surfaces or polymer films is known from US Pat. No. 4,568,632 known which at least one imide group in the corresponding monomer, be it in the main chain or a side chain of the polymer built up therefrom. It is a process for etching or removing polyimide without chemical Treatment steps revealed.
- the polyimide is exposed to ultraviolet light Wavelength shorter than 220 nm, for example from an argon fluoride excimer Exposed to lasers so that photocatalytic decomposition takes place, being volatile Products are removed by appropriate means.
- the process of reaction takes place in an atmosphere which Has oxygen.
- Structuring can be done, for example, by using a large-area illuminated mask or by scanning the surface with a Exposure beam for spatially selective reaction can be achieved. This structuring can without significant influence on the polyimide remaining on the surface can be achieved. Structuring the surface into hydrophobic and hydrophilic Areas that in particular use the structured surface for the Printing process using a lithographic process or an offset process enabled, can therefore not be achieved.
- the object of the present is Invention in a stable and easily switchable surface for printing processes propose.
- this object is achieved by a method for producing a structure from hydrophilic and hydrophobic areas on a surface with the characteristics according to claim 1 and by a printing form with the features according to claim 11 solved.
- the lithographic printing process creates hydrophobic and hydrophilic areas on a polyimide surface by that this may be illustrated after a chemical initialization or is structured by imaging by electromagnetic radiation and is completed by another chemical reaction. After printing can the illustrated structure is deleted by a further chemical reaction.
- the method according to the invention provides a printing form, which are used in a conventional wet offset process for printing can.
- the printing form according to the invention is also suitable for printing additive-free dampening solution, such as pure water, for example without the usual used isopropanol.
- the structured polyimide surface is covered by another chemical process can be deleted.
- the invention The process provides a surface that can be reversibly written on and erased again Available.
- polyimide is understood to mean a polymer material whose associated monomer is the functional group of an imide having. This group can occur in the main chain or in a side chain of the polyimide.
- the polyimide is referred to below as polybenzene diimide (PBDI) Use. This substance is marketed by Dupont under the name "Kapton”.
- PBDI polybenzene diimide
- polyamide imide is abbreviated as polyimide used.
- the physical behavior of the polyimides is essentially the same.
- the embodiments specified in detail are only examples.
- the process according to the invention can also be used with other substances having imide groups.
- the polymer used is very hydrophobic in its original state, so it is good in color.
- the method according to the invention for producing a structure from hydrophilic and hydrophobic areas on a surface, which in a first, essentially unstructured state has a polymer material with imide groups is characterized in that a locally selective exposure to electromagnetic radiation is local Energy subsequent chemical treatment of the surface with an oxidizing agent is carried out.
- the electromagnetic energy is preferably generated by a UV light source, which emits light with a wavelength between 200 and 440 nm, preferably 220 and 460 nm.
- Hydrogen peroxide (H 2 O 2 ), oxygen (O 2 ), ozone (O 3 ) or potassium permanganate (KMnO 4 ) or combinations of these oxidizing agents can preferably be used as the oxidizing agent.
- a liquid with ionic surfactants can also be used in subsequent chemical treatment.
- a large-area chemical treatment of the surface with a strong base can be carried out beforehand.
- the strong base is preferably an aqueous solution of potassium hydroxide (KOH) and / or sodium hydroxide (NaOH).
- a large-area chemical treatment of the surface is carried out with a strong acid.
- the strong acid is preferably an aqueous solution of sulfuric acid (H 2 SO 4 ) and / or hydrochloric acid (HCl) and / or nitric acid (HNO 3 ) and / or the like.
- the large-area chemical treatment of the surface can be carried out with a suitable, appropriate plate cleaner.
- a printing form according to the invention which is particularly suitable for use as a printing form is suitable in offset printing, comprises a surface for printing, which a Has polymer material with imide groups, preferably PBDI or PAI.
- a Has polymer material with imide groups preferably PBDI or PAI.
- Such Surface is with the inventive method, especially with the individual Options described above, structurable. Consequently, by the invention rewritable printing form created.
- the printing form according to the invention can be particularly advantageous in a printing unit or a printing press are used.
- a printing unit stands out characterized in that it is provided with a printing form according to the invention for printing.
- a printing press in particular an offset printing press, with at least one Feeder, a printing unit and a delivery then have at least one printing unit, which is provided with a printing form according to the invention for printing.
- FIG. 1 shows a flow chart of the method according to the invention with a chemical initialization step involving treatment with a basic substance includes.
- the flow chart serves to explain the individual process steps and their order.
- the polymer material used in the process according to the invention is a substance which in the first, original state is highly hydrophobic, ie at the same time it is good color-guiding.
- the polymer material is subjected to a base treatment 10. For example it will for a certain time interval in the minute range of an aqueous solution of a strong one Base such as potassium hydroxide or sodium hydroxide exposed. Through this Treatment makes the polymer material hydrophilic. Through a large area Base treatment 10 thus makes the surface hydrophilic over a large area. In this condition the actual structuring is carried out: it is the color-guiding and not color-guiding areas, that is to say image areas and not image areas. It will be one local exposure 12 by electromagnetic radiation, preferably in the UV range, performed. The next step is an oxidation 14.
- the oxidizing agent for example hydrogen peroxide, potassium permanganate or the like, switches or develops the property of the surface, that of electromagnetic radiation was exposed.
- hydrophilic areas now become hydrophobic.
- a polysaccharide or polysaccharide mixture preferably D-arbinose and / or D-fructose.
- This additional optional step improved a stabilization of the hydrophobic or hydrophilic areas.
- the thus structured surface is now ready for printing.
- After printing 16 can by means of a Acid treatment 18 the structure of the surface can be deleted.
- the Large surface of a strong acid for example an aqueous solution of Exposed to sulfuric acid, hydrochloric acid, nitric acid or the like or plate cleaners.
- the surface is again hydrophobic. It is possible to get one Iteration 110 of the specified sequence of procedural steps.
- a re-local exposure 12 can be a structure with another, generally deviating topography can be produced on the surface.
- FIG. 2 is a flowchart of the inventive method with direct Structuring of the polyimide surface by electromagnetic radiation.
- This Flow chart serves to explain the individual process steps and their Sequence.
- polymer material which is in a first, originally hydrophobic state is present, exposed to a local exposure 20.
- Oxidation 22 a structuring is achieved: the localized exposed areas are now hydrophilic.
- the thus structured surface can be used for printing 24 be used.
- An acid treatment 26 makes it possible to change the structure to delete hydrophilic and hydrophobic areas.
- the surface is covered by the Acid treatment 26 transferred to the first, hydrophobic state. So it is again possible to carry out an iteration 28 of the steps of the method according to the invention.
- FIG. 3 shows schematically the structuring of a printing form, its surface Has polyimide, by means of the inventive method including a chemical initialization step.
- the Printing form 30 has a surface which has a large-area hydrophobic area 32 represents.
- the surface becomes a hydrophilic area 34 over a large area converted.
- Selective exposure allows localized areas to be initialized first type 36 generated on the large-area hydrophilic surface 34.
- hydrophobic areas 32 arise in addition to hydrophilic Areas 34.
- a structuring of the surface of the printing form 30 is thus achieved.
- This structure can be deleted by printing form 30 over a large area Acid treatment is subjected.
- the printing form 30 lies again with a large area hydrophobic area 32.
- the polymer material preferably PBDI or PAI
- PBDI or PAI is applied in a thickness between a still manageable film of approximately 25 micrometers to a layer thickness of a few millimeters on a suitable carrier, for example on an aluminum plate.
- the surface of the applied polymer material is then subjected to a base treatment, sodium hydroxide (NaOH) and / or potassium hydroxide (KOH) preferably being used.
- NaOH sodium hydroxide
- KOH potassium hydroxide
- concentrations 0.5 to 1 molar solutions are used, for example, in the case of sodium hydroxide, it remaining to be noted that concentrations which are too high (of approximately 5 molar solution) can destroy the polymer material.
- the polymer material which is originally completely hydrophobic in its first state, is essentially completely hydrophilized by the base treatment, the duration of which is in the range of a few minutes, preferably about one minute.
- the imaging takes place either through a mask or through locally selective illumination by means of a light beam which is directed locally onto the printing surface.
- a UV laser is preferably used as the light source.
- the locally selective exposure is to be regarded as an initialization reaction, which is followed by a chemical treatment of the surface.
- the exposed surface is then exposed to an oxidizing agent, e.g. B. hydrogen peroxide (H 2 O 2 ), oxygen or ozone. Potassium permanganate (KMnO 4 ) can also be used in the liquid phase.
- the preferred concentration of hydrogen peroxide is a 15% solution of hydrogen peroxide in water.
- a 0.02 molar solution in water is preferably used.
- Treatment with an oxidizing agent makes the previously locally irradiated areas hydrophobic, while the remaining areas remain hydrophilic.
- the polymer printing form thus produced is used for printing. After printing, the printing form can be erased and cleaned at the same time, whereby all usual known mechanical cleaning options can be used:
- the surface is exposed to a strong acid, e.g. B. sulfuric acid (H 2 SO 4 ), hydrochloric acid (HCl) or nitric acid (HNO 3 ).
- the acids should preferably all be present in a concentration of a 1 molar solution.
- a can also be used to support a mechanical cleaning process chemical cleaning agent, especially commercially available plate cleaner, used become. Then the entire imaging process for a new one Printing process can be repeated.
- Figure 4 is a schematic representation of the structuring of a printing form, the Has surface polyimide, by means of the inventive method without chemical initialization step shown by treatment with a basic substance.
- Fig. 4 shows four states of the printing form 30, their chronological order by the arrows is indicated.
- the printing form 30 lies with a hydrophobic over a large area Area 32 before.
- initialized areas of the second type 38 are generated on the surface of the printing form 30.
- Oxidation turns them into hydrophilic areas 34.
- the surface thus has a Structure of hydrophobic areas 32 and hydrophilic areas 34, so that they to Printing can be used.
- After extensive treatment with a strong one Acid of the surface of the printing form 30 is achieved that the printing form has a large area is again hydrophobic.
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Printing Plates And Materials Therefor (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Materials For Photolithography (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Manufacture Or Reproduction Of Printing Formes (AREA)
- Rotary Presses (AREA)
- Liquid Developers In Electrophotography (AREA)
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Erzeugung einer Struktur aus hydrophilen und hydrophoben Bereichen auf einer Oberfläche, welche in einem ersten, im wesentlichen unstrukturierten Zustand ein Polymermaterial mit Imid-Gruppen aufweist. Des weiteren betrifft die Erfindung eine Druckform, insbesondere für den Einsatz als Druckform im Offsetdruck, mit einer Oberfläche zum Drucken.The invention relates to a method for producing a structure from hydrophilic and hydrophobic areas on a surface, which in a first, essentially unstructured state has a polymer material with imide groups. Furthermore The invention relates to a printing form, in particular for use as a printing form in the Offset printing, with a surface for printing.
Der lithographische Druck basiert, vereinfacht ausgedrückt, auf der Ausnutzung der Nichtmischbarkeit von Öl und Wasser auf einer Oberfläche, der sogenannten Druckform, wobei die lipophile (hydrophobe) Lösung oder die Tinte oder Farbe durch die bildaufbauenden Bereiche und das Wasser oder die hydrophile Lösung durch die nichtbildaufbauenden Bereiche der Druckoberfläche festgehalten werden. Wenn die in geeigneter Weise vorbereitete Druckoberfläche mit hydrophiler und lipophiler Substanz oder Lösung, insbesondere Wasser und Tinte oder Farbe, benetzt wird, so halten die nichtbildmäßigen Bereiche vorzugsweise die hydrophile Substanz oder Lösung zurück und stoßen die lipophilen Stoffe ab, während die bildmäßigen Bereiche die lipophile Lösung oder Tinte oder Farbe annehmen und die hydrophilen Stoffe abweisen. In der Folge wird dann die lipophile Substanz in geeigneter Weise auf die Oberfläche eines Materials übertragen, auf dem das Bild fixiert werden soll, beispielsweise Papier, Stoff, Polymere und dergleichen.To put it simply, lithographic printing is based on the exploitation of the Immiscibility of oil and water on a surface, the so-called printing form, wherein the lipophilic (hydrophobic) solution or the ink or color through the image-forming areas and the water or the hydrophilic solution through the non-image-forming areas of the printing surface. If the in suitably prepared printing surface with hydrophilic and lipophilic substance or solution, especially water and ink or paint, is wetted, so keep non-image areas preferably the hydrophilic substance or solution back and repel the lipophilic substances, while the pictorial areas repel the lipophilic solution or accept ink or paint and repel the hydrophilic substances. As a result then the lipophilic substance in a suitable manner on the surface of a material transferred, on which the image is to be fixed, for example paper, fabric, polymers and the same.
Seit vielen Jahren setzt man Aluminium als Material für Druckformen ein. Üblicherweise wird das Aluminium zuerst einem Körnungsverfahren und dann einem anschließenden Anodisierungsverfahren unterworfen. Die Anodisierung dient dazu, eine anodische Oxidschicht bereitzustellen, deren Haftung durch die Körnung verbessert wird. Durch die Körnung werden die hydrophilen Eigenschaften des Hintergrundes der Druckplatte verstärkt. Im Anodisierungsverfahren wird üblicherweise eine starke Säure, wie Schwefeloder Phosphorsäure eingesetzt, um anschließend durch ein weiteres Verfahren, wie beispielsweise in einem thermischen Silizierungsverfahren oder der sogenannten Elektrosilizierung, die Oberfläche hydrophil zu machen. Aluminum has been used as a material for printing forms for many years. Usually the aluminum is first a graining process and then a subsequent one Subjected to anodizing. The anodizing serves to be an anodizing To provide oxide layer, the adhesion of which is improved by the grain. Through the Grain size is the hydrophilic properties of the background of the printing plate strengthened. A strong acid, such as sulfur or Phosphoric acid used to subsequently by another method such as for example in a thermal siliconization process or the so-called Electrosiliconization to make the surface hydrophilic.
Zur Herstellung einer oben beschriebenen Druckform ist eine große Anzahl von strahlungsempfindlichen Materialien bekannt, die zur Generierung von Abbildungen im Einsatz des lithographischen Druckverfahrens geeignet sind, insofern als sie nach Belichtung und gegebenenfalls erforderlicher Entwicklung und Fixierung einen bildmäßigen Bereich zur Verfügung stellen, der zum Drucken verwendet werden kann. Beispielsweise können dazu fotopolymerisierbare Stoffe verwendet werden.To produce a printing form described above, a large number of radiation-sensitive materials known for generating images in the Use of the lithographic printing process are suitable insofar as they follow Exposure and any necessary development and fixation one Provide a pictorial area that can be used for printing. For example, photopolymerizable substances can be used for this.
Die oben beschriebene Anordnung wird einer bildmäßigen Belichtung unterworfen, indem örtlich selektiv Energie zugeführt wird. Dieses kann beispielsweise mittels der Belichtung durch eine Maske mit UV-Licht oder aber durch direktes Schreiben mit einem Laser erfolgen.The arrangement described above is subjected to imagewise exposure by energy is selectively supplied locally. This can be done, for example, by means of exposure through a mask with UV light or by writing directly with a laser respectively.
Die lithographischen Druckformen der oben beschriebenen Art werden üblicherweise mit einer Entwicklerlösung behandelt, welche typischerweise eine wässrige alkalische oder basische Lösung mit organischen Zusätzen ist.The lithographic printing plates of the type described above are usually included treated with a developer solution, which is typically an aqueous alkaline or basic solution with organic additives.
Es werden seit einiger Zeit Bemühungen unternommen, Druckformen herzustellen, bei denen zur Erzeugung des Bildes auf ein nasschemisches Entwicklungsverfahren verzichtet werden kann. Hierzu können Oxidkeramiken, welche beispielsweise in Form von Beschichtungen auf einer Druckplatte vorliegen, Verwendung finden.Efforts to manufacture printing forms have been made for some time at those who do not use a wet chemical development process to generate the image can be. For this purpose, oxide ceramics, for example in the form of Coatings are on a printing plate, find use.
In der EP 0 911 154 A1 wird als Materialien für die Plattenoberfläche Titandioxid (TiO2) und Zirkoniumdioxid (ZnO2) vorgeschlagen, welche in keramischer Form sowohl rein als auch mit anderen metallischen Zusätzen in verschiedenen Mischungsverhältnissen vorliegen können. Diese Oberfläche ist in nicht angeregtem Zustand hydrophob und kann durch Bestrahlung mit ultraviolettem Licht in einen hydrophilen Zustand versetzt werden. Die Bebilderung geschieht nun, indem die gesamte Oberfläche der Platte mit ultraviolettem Licht beleuchtet wird und Bereiche, die beim Druck Farbe führen sollen, durch eine Maske beziehungsweise einen Film abgedeckt werden. EP 0 911 154 A1 proposes titanium dioxide (TiO 2 ) and zirconium dioxide (ZnO 2 ) as materials for the plate surface, which can be present in ceramic form both in pure form and with other metallic additives in various mixing ratios. This surface is hydrophobic in the non-excited state and can be brought into a hydrophilic state by irradiation with ultraviolet light. The imaging is now done by illuminating the entire surface of the plate with ultraviolet light and areas which are supposed to lead to color during printing are covered by a mask or a film.
Zumindest bei Titandioxidschichten als Substrat stellt sich als besonderer Nachteil heraus, dass die Titandioxidschichten zwar mit UV-Licht schaltbar sind, jedoch eine geringe Stabilität hinsichtlich des zeitlichen Verlaufes der Umschaltung aufweisen. Darüber hinaus stellt es sich bei Titandioxidschichten immer wieder heraus, dass eine ausreichende Umschaltung oder ein ausreichender Hub, d. h. ein ausreichender Flip von hydrophil nach hydrophob nur in nicht ausreichender Stärke erzielt werden kann. Des weiteren stellt die vollständige Reinigung des Substrates nach erfolgtem Druck ein nicht zu unterschätzendes Problem in der Praxis dar.At least with titanium dioxide layers as the substrate it turns out to be a particular disadvantage that the titanium dioxide layers can be switched with UV light, but a small one Have stability with regard to the time course of the switchover. Furthermore With titanium dioxide layers it always turns out that sufficient Switching or sufficient stroke, d. H. a sufficient flip from hydrophilic to hydrophobic can only be achieved in insufficient strength. Furthermore, the complete cleaning of the substrate after printing is a not to be underestimated Problem in practice.
Aus der US 4,568,632 ist die Strukturierung von Polymeroberflächen oder Polymerfilmen bekannt, welche wenigstens eine Imid-Gruppe im korrespondierenden Monomer, sei es in der Hauptkette oder einer Seitenkette des daraus aufgebauten Polymers, aufweisen. Es wird ein Verfahren zur Ätzung oder Abtragung von Polyimid ohne chemische Behandlungsschritte offenbart. Das Polyimid wird ultraviolettem Licht mit einer Wellenlänge, die kürzer als 220 nm ist, beispielsweise von einem Argon-Fluorid Excimer Laser, ausgesetzt, so dass eine fotokatalytische Zersetzung stattfindet, wobei flüchtige Produkte durch geeignete Mittel entfernt werden. Zur Unterstützung, insbesondere zur Beschleunigung, des Prozesses findet die Reaktion in einer Atmosphäre statt, welche Sauerstoff aufweist. Eine Strukturierung kann beispielsweise durch die Verwendung einer großflächig ausgeleuchteten Maske oder durch eine Abtastung der Oberfläche mit einem Belichtungsstrahl zur räumlich selektiven Reaktion erreicht werden. Diese Strukturierung kann ohne eine wesentliche Beeinflussung des an der Oberfläche verbleibenden Polyimids erreicht werden. Eine Strukturierung der Oberfläche in hydrophobe und hydrophile Bereiche, welche insbesondere eine Einsatz der strukturierten Oberfläche für den Druckprozess nach einem lithographischen Verfahren oder einem Offset-Verfahren ermöglicht, kann daher nicht erreicht werden.The structuring of polymer surfaces or polymer films is known from US Pat. No. 4,568,632 known which at least one imide group in the corresponding monomer, be it in the main chain or a side chain of the polymer built up therefrom. It is a process for etching or removing polyimide without chemical Treatment steps revealed. The polyimide is exposed to ultraviolet light Wavelength shorter than 220 nm, for example from an argon fluoride excimer Exposed to lasers so that photocatalytic decomposition takes place, being volatile Products are removed by appropriate means. For support, especially for Acceleration, the process of reaction takes place in an atmosphere which Has oxygen. Structuring can be done, for example, by using a large-area illuminated mask or by scanning the surface with a Exposure beam for spatially selective reaction can be achieved. This structuring can without significant influence on the polyimide remaining on the surface can be achieved. Structuring the surface into hydrophobic and hydrophilic Areas that in particular use the structured surface for the Printing process using a lithographic process or an offset process enabled, can therefore not be achieved.
Vor dem Hintergrund dieses Stands der Technik besteht die Aufgabe der vorliegenden Erfindung darin, eine stabile und einfach schaltbare Oberfläche für Druckprozesse vorzuschlagen. Against the background of this prior art, the object of the present is Invention in a stable and easily switchable surface for printing processes propose.
Diese Aufgabe wird erfindungsgemäß durch ein Verfahren zur Erzeugung einer Struktur aus hydrophilen und hydrophoben Bereichen auf einer Oberfläche mit den Merkmalen gemäß Anspruch 1 sowie durch eine Druckform mit den Merkmalen gemäß Anspruch 11 gelöst.According to the invention, this object is achieved by a method for producing a structure from hydrophilic and hydrophobic areas on a surface with the characteristics according to claim 1 and by a printing form with the features according to claim 11 solved.
Erfindungsgemäß werden die für den lithographischen Druckprozess benötigten hydrophoben und hydrophilen Bereiche auf einer Polyimidoberfläche dadurch erzeugt, dass diese gegebenenfalls nach einer chemischen Initialisierung bebildert beziehungsweise strukturiert wird, indem die Bebilderung durch elektromagnetische Strahlung erfolgt und durch eine weitere chemische Reaktion abgeschlossen wird. Nach erfolgtem Drucken kann eine Löschung des bebilderten Struktur durch eine weitere chemische Reaktion erfolgen.According to the invention, they are required for the lithographic printing process creates hydrophobic and hydrophilic areas on a polyimide surface by that this may be illustrated after a chemical initialization or is structured by imaging by electromagnetic radiation and is completed by another chemical reaction. After printing can the illustrated structure is deleted by a further chemical reaction.
Durch das erfindungsgemäße Verfahren wird eine Druckform zur Verfügung gestellt, welche in einem konventionellen Naß-Offsetverfahren zum Drucken verwendet werden kann. Darüber hinaus eignet sich die erfindungsgemäße Druckform auch für den Druck mit zusatzfreiem Feuchtmittel, wie reines Wasser, also beispielsweise ohne den gängig verwendeten Isopropanol.The method according to the invention provides a printing form, which are used in a conventional wet offset process for printing can. In addition, the printing form according to the invention is also suitable for printing additive-free dampening solution, such as pure water, for example without the usual used isopropanol.
Besonders vorteilhaft ist, dass die strukturierte Polyimidoberfläche durch einen weiteren chemischen Prozess gelöscht werden kann. Mit anderen Worten: Das erfindungsgemäße Verfahren stellt eine reversibel beschreibbare und wieder löschbare Oberfläche zur Verfügung.It is particularly advantageous that the structured polyimide surface is covered by another chemical process can be deleted. In other words: the invention The process provides a surface that can be reversibly written on and erased again Available.
Im Zusammenhang des erfindungsgemäßen Verfahrens und der erfindungsgemäßen Druckform wird unter Polyimid ein Polymermaterial verstanden, dessen zugehöriges Monomer die funktionelle Gruppe eines Imids aufweist. Dabei kann diese Gruppe in der Hauptkette oder einer Seitenkette des Polyimids auftreten. In einer ersten bevorzugten Ausführungsform der Erfindung findet als Polyimid das im folgenden abgekürzt als Polybenzoldiimid (PBDI) bezeichnete Verwendung. Diese Substanz wird unter dem Namen "Kapton" von Dupont vertrieben. In einer zweiten Ausführungsform wird als Polyimid abgekürzt sogenanntes Polyamidimid eingesetzt. In Zusammenhang der Erfindung ist das physikalische Verhalten der Polyimide ist im Wesentlichen gleich. Die detailliert angegebenen Ausführungsformen stellen nur Beispiele dar. Das erfindungsgemäße Verfahren kann auch mit anderen Imid-Gruppen aufweisenden Substanzen eingesetzt werden. Das verwendete Polymer ist im ursprünglichen Zustand stark hydrophob, damit also gut farbführend.In the context of the method according to the invention and the printing form according to the invention, polyimide is understood to mean a polymer material whose associated monomer is the functional group of an imide having. This group can occur in the main chain or in a side chain of the polyimide. In a first preferred embodiment of the invention, the polyimide is referred to below as polybenzene diimide (PBDI) Use. This substance is marketed by Dupont under the name "Kapton". In a second embodiment, so-called polyamide imide is abbreviated as polyimide used. In the context of the invention, the physical behavior of the polyimides is essentially the same. The embodiments specified in detail are only examples. The process according to the invention can also be used with other substances having imide groups. The polymer used is very hydrophobic in its original state, so it is good in color.
Das erfindungsgemäße Verfahren zur Erzeugung einer Struktur aus hydrophilen und hydrophoben Bereichen auf einer Oberfläche, welche in einem ersten, im Wesentlichen unstrukturierten Zustand ein Polymermaterial mit Imid-Gruppen aufweist, zeichnet sich dadurch aus, dass eine sich an eine örtlich selektive Belichtung durch lokale Einstrahlung elektromagnetischer Energie zeitlich nachgehende chemische Behandlung der Oberfläche mit einem Oxidationsmittel durchgeführt wird. Die elektromagnetische Energie wird bevorzugt durch eine UV-Lichtquelle, welche Licht mit einer Wellenlänge zwischen 200 und 440 nm, bevorzugt 220 und 460 nm emittiert, erzeugt. Als Oxidationsmittel kann bevorzugt Wasserstoffperoxid (H2O2), Sauerstoff (O2), Ozon (O3) oder Kaliumpermanganat (KMnO4) oder Kombinationen dieser Oxidationsmittel verwendet werden. Neben dem Oxidationsmittel kann auch in der zeitlich nachgehenden chemischen Behandlung zusätzlich eine Flüssigkeit mit ionischen Tensiden eingesetzt werden. Der örtlich selektiven Belichtung kann zusätzlich zeitlich vorhergehend eine großflächige chemische Behandlung der Oberfläche mit einer starken Base ausgeführt werden. Bei der starken Base handelt es sich bevorzugt um eine wässrige Lösung von Kaliumhydroxid (KOH) und/oder Natriumhydroxid (NaOH).The method according to the invention for producing a structure from hydrophilic and hydrophobic areas on a surface, which in a first, essentially unstructured state has a polymer material with imide groups, is characterized in that a locally selective exposure to electromagnetic radiation is local Energy subsequent chemical treatment of the surface with an oxidizing agent is carried out. The electromagnetic energy is preferably generated by a UV light source, which emits light with a wavelength between 200 and 440 nm, preferably 220 and 460 nm. Hydrogen peroxide (H 2 O 2 ), oxygen (O 2 ), ozone (O 3 ) or potassium permanganate (KMnO 4 ) or combinations of these oxidizing agents can preferably be used as the oxidizing agent. In addition to the oxidizing agent, a liquid with ionic surfactants can also be used in subsequent chemical treatment. In addition to the locally selective exposure, a large-area chemical treatment of the surface with a strong base can be carried out beforehand. The strong base is preferably an aqueous solution of potassium hydroxide (KOH) and / or sodium hydroxide (NaOH).
Mit einem zusätzlichen, zeitlich nachgeordneten Verfahrensschritt ist es möglich, die Oberfläche in den ersten, im Wesentlichen unstrukturierten Zustand zu überführen. Dazu wird eine großflächige chemische Behandlung der Oberfläche mit einer starken Säure vorgenommen. Bei der starken Säure handelt es sich bevorzugt um eine wässrige Lösung von Schwefelsäure (H2SO4) und/oder Salzsäure (HCl) und/oder Salpetersäure (HNO3) und/oder dergleichen. Beispielweise kann die großflächige chemische Behandlung der Oberfläche mit einem geeigneten entsprechenden Plattenreiniger durchgeführt werden. Durch die Zurücksetzung der Oberfläche in den ersten, im Wesentlichen unstrukturierten Zustand ist es möglich, die Verfahrensschritte zu iterieren. Mit anderen Worten: eine Wiederbeschreibung der Fläche mit Strukturen wechselnder Topographie ist möglich.With an additional, temporally subordinate process step, it is possible to bring the surface into the first, essentially unstructured state. For this, a large-area chemical treatment of the surface is carried out with a strong acid. The strong acid is preferably an aqueous solution of sulfuric acid (H 2 SO 4 ) and / or hydrochloric acid (HCl) and / or nitric acid (HNO 3 ) and / or the like. For example, the large-area chemical treatment of the surface can be carried out with a suitable, appropriate plate cleaner. By resetting the surface to the first, essentially unstructured state, it is possible to iterate the process steps. In other words, it is possible to rewrite the surface with structures of changing topography.
Eine erfindungsgemäße Druckform, welche insbesondere für den Einsatz als Druckform im Offsetdruck geeignet ist, umfasst eine Oberfläche zum Drucken, welche ein Polymermaterial mit Imid-Gruppen, bevorzugt PBDI oder PAI aufweist. Eine derartige Oberfläche ist mit dem erfindungsgemäßen Verfahren, insbesondere mit den einzelnen oben beschriebenen Optionen, strukturierbar. Folglich wird durch die Erfindung eine wiederbeschreibbare Druckform geschaffen.A printing form according to the invention, which is particularly suitable for use as a printing form is suitable in offset printing, comprises a surface for printing, which a Has polymer material with imide groups, preferably PBDI or PAI. Such Surface is with the inventive method, especially with the individual Options described above, structurable. Consequently, by the invention rewritable printing form created.
Mit besonderem Vorteil kann die erfindungsgemäße Druckform in einem Druckwerk oder einer Druckmaschine zum Einsatz kommen. Ein derartiges Druckwerk zeichnet sich dadurch aus, dass es zum Drucken mit einer erfindungsgemäßen Druckform versehen ist. Eine Druckmaschine, insbesondere eine Offsetdruckmaschine, mit wenigstens einem Anleger, einem Druckwerk und einem Ausleger weist dann wenigstens ein Druckwerk, welches zum Drucken mit einer erfindungsgemäßen Druckform versehen ist, auf. The printing form according to the invention can be particularly advantageous in a printing unit or a printing press are used. Such a printing unit stands out characterized in that it is provided with a printing form according to the invention for printing. A printing press, in particular an offset printing press, with at least one Feeder, a printing unit and a delivery then have at least one printing unit, which is provided with a printing form according to the invention for printing.
Weitere Vorteile und vorteilhafte Ausführungsformen und Weiterbildungen der Erfindung werden anhand der nachfolgenden Figuren sowie deren Beschreibungen dargestellt. Es zeigt im Einzelnen:
- Figur 1
- ein Ablaufdiagramm des erfindungsgemäßen Verfahrens mit einem chemischen Initialisierungsschritt, der eine Behandlung mit einer basischen Substanz umfasst,
- Figur 2
- ein Ablaufdiagramm des erfindungsgemäßen Verfahrens mit direkter Strukturierung der Polyimidoberfläche durch elektromagnetische Strahlung,
- Figur 3
- eine schematische Darstellung der Strukturierung einer Druckform, deren Oberfläche Polyimid aufweist, mittels des erfindungsgemäßen Verfahrens einschließlich eines chemischen Initialisierungsschrittes, und
- Figur 4
- eine schematische Darstellung der Strukturierung einer Druckform, deren Oberfläche Polyimid aufweist, mittels des erfindungsgemäßen Verfahrens ohne chemischen Initialisierungsschritt durch Behandlung mit einer basischen Substanz.
- Figure 1
- 2 shows a flowchart of the method according to the invention with a chemical initialization step, which comprises treatment with a basic substance,
- Figure 2
- 1 shows a flowchart of the method according to the invention with direct structuring of the polyimide surface by electromagnetic radiation,
- Figure 3
- a schematic representation of the structuring of a printing form, the surface of which has polyimide, by means of the method according to the invention including a chemical initialization step, and
- Figure 4
- a schematic representation of the structuring of a printing form, the surface of which has polyimide, by means of the method according to the invention without a chemical initialization step by treatment with a basic substance.
Die Figur 1 zeigt ein Ablaufdiagramm des erfindungsgemäßen Verfahrens mit einem chemischen Initialisierungsschritt, der eine Behandlung mit einer basischen Substanz umfasst. Das Ablaufdiagramm dient zur Erläuterung der einzelnen Prozessschritte und deren Reihenfolge. Das im erfindungsgemäßen Verfahren verwendete Polymermaterial ist eine Substanz, welche im ersten, ursprünglichen Zustand stark hydrophob, also gleichzeitig gut farbführend, ist.FIG. 1 shows a flow chart of the method according to the invention with a chemical initialization step involving treatment with a basic substance includes. The flow chart serves to explain the individual process steps and their order. The polymer material used in the process according to the invention is a substance which in the first, original state is highly hydrophobic, ie at the same time it is good color-guiding.
Das Polymermaterial wird einer Basenbehandlung 10 unterzogen. Beispielsweise wird es
für ein gewisses Zeitintervall im Minutenbereich einer wässrigen Lösung einer starken
Base, wie beispielsweise Kaliumhydroxid oder Natriumhydroxid, ausgesetzt. Durch diese
Behandlung wird das Polymermaterial hydrophil. Durch eine großflächige
Basenbehandlung 10 wird somit die Oberfläche großflächig hydrophil. In diesem Zustand
wird die eigentliche Strukturierung durchgeführt: Es werden die farbführenden und nicht
farbführenden Bereiche, also Bildstellen und nicht Bildstellen, festgelegt. Es wird eine
lokale Belichtung 12 durch elektromagnetische Strahlung, bevorzugt im UV-Bereich,
vorgenommen. Als nächster Schritt erfolgt eine Oxidation 14. Das Oxidationsmittel,
beispielsweise Wasserstoffperoxid, Kaliumpermanganat oder dergleichen, schaltet oder
entwickelt die Eigenschaft der Oberfläche, welche der elektromagnetischen Strahlung
ausgesetzt war. Mit anderen Worten: vor Belichtung 12 und nachgehender Oxidation 14
hydrophile Bereiche werden nun hydrophob. Optional erfolgt nach dem Oxidationsprozess
eine Behandlung der Oberfläche mit einem Polysaccharid oder Polysaccharidgemisch,
bevorzugt D-Arbinose und/oder D-Fructose. Dieser zusätzliche optionale Schritt verbessert
eine Stabilisierung der hydrophoben respektive hydrophilen Bereiche. Die somit
strukturierte Oberfläche ist nun druckbereit. Nach dem Druck 16 kann mittels einer
Säurebehandlung 18 die Strukturierung der Oberfläche gelöscht werden. Dazu wird die
Oberfläche großflächig einer starken Säure, beispielsweise einer wässrigen Lösung von
Schwefelsäure, Salzsäure, Salpetersäure oder dergleichen oder Plattenreiniger ausgesetzt.
Durch diesen Verfahrensschritt ist die Oberfläche erneut hydrophob. Es ist möglich, eine
Iteration 110 der angegebenen Abfolge von Verfahrensschritten vorzunehmen. In einer
erneuten lokalen Belichtung 12 kann eine Struktur mit einer anderen, im Allgemeinen
abweichenden Topographie auf der Oberfläche hergestellt werden.The polymer material is subjected to a
Die Figur 2 ist ein Ablaufdiagramm des erfindungsgemäßen Verfahrens mit direkter Strukturierung der Polyimidoberfläche durch elektromagnetische Strahlung. Dieses Ablaufdiagramm dient zur Erläuterung der einzelnen Prozessschritte und deren Reihenfolge. In dieser Ausführungsform des erfindungsgemäßen Verfahrens wird das verwendete Polymermaterial, welches in einem ersten, ursprünglich hydrophoben Zustand vorliegt, einer lokalen Belichtung 20 ausgesetzt. Durch die zeitlich nachgeordnete Oxidation 22 wird eine Strukturierung erreicht: Die örtlich begrenzt belichteten Bereiche sind nunmehr hydrophil. Die somit strukturierte Oberfläche kann zum Drucken 24 verwendet werden. Durch eine Säurebehandlung 26 ist es möglich, die Struktur hydrophiler und hydrophober Bereiche zu löschen. Die Oberfläche wird durch die Säurebehandlung 26 in den ersten, hydrophoben Zustand überführt. Es ist also wiederum möglich, eine Iteration 28 der Schritte des erfindungsgemäßen Verfahrens auszuführen.Figure 2 is a flowchart of the inventive method with direct Structuring of the polyimide surface by electromagnetic radiation. This Flow chart serves to explain the individual process steps and their Sequence. In this embodiment of the method according to the invention used polymer material, which is in a first, originally hydrophobic state is present, exposed to a local exposure 20. By the temporally subordinate Oxidation 22 a structuring is achieved: the localized exposed areas are now hydrophilic. The thus structured surface can be used for printing 24 be used. An acid treatment 26 makes it possible to change the structure to delete hydrophilic and hydrophobic areas. The surface is covered by the Acid treatment 26 transferred to the first, hydrophobic state. So it is again possible to carry out an iteration 28 of the steps of the method according to the invention.
Die Figur 3 stellt schematisch die Strukturierung einer Druckform, deren Oberfläche
Polyimid aufweist, mittels des erfindungsgemäßen Verfahrens einschließlich eines
chemischen Initialisierungsschrittes dar. In der Fig. 3 sind fünf Zustände der Druckform 30
in der durch die Pfeile angedeuteten zeitlichen Ordnung gezeigt. Zunächst weist die
Druckform 30 eine Oberfläche auf, welche einen großflächigen hydrophoben Bereich 32
darstellt. Durch einen chemischen Initialisierungsschritt der Behandlung der Oberfläche
mit einer starken Base wird die Oberfläche großflächig in einen hydrophilen Bereich 34
umgewandelt. Durch selektive Belichtung werden lokal begrenzt initialisierte Bereiche
erster Art 36 auf der großflächig hydrophilen Fläche 34 erzeugt. Mittels der
nachgeordneten Oxidation entstehen hydrophobe Bereiche 32 neben hydrophilen
Bereichen 34. Damit ist eine Strukturierung der Oberfläche der Druckform 30 erreicht.
Diese Struktur kann gelöscht werden, indem die Druckform 30 großflächig einer
Säurebehandlung unterworfen wird. Nach diesem Schritt liegt die Druckform 30 wieder
mit einem großflächig hydrophoben Bereich 32 vor.Figure 3 shows schematically the structuring of a printing form, its surface
Has polyimide, by means of the inventive method including a
chemical initialization step. In FIG. 3 there are five states of the
Eine beispielhafte Ausführungsform des erfindungsgemäßen Verfahrens stellt sich damit wie folgt dar:An exemplary embodiment of the method according to the invention thus arises is as follows:
Das Polymermaterial, bevorzugt PBDI oder PAI, wird in einer Dicke zwischen einer noch handhabbaren Folie von etwa 25 Mikrometer bis zu einer Schichtdicke von einigen Millimetern auf einem geeigneten Träger, beispielsweise auf einer Aluminumplatte aufgebracht. Die Oberfläche des aufgebrachten Polymermaterials wird anschließend einer Basenbehandlung unterzogen, wobei bevorzugt Natriumhydroxid (NaOH) und/oder Kaliumhydroxid (KOH) eingesetzt wird. Im Hinblick auf die Konzentrationen werden beispielsweise bei Natriumhydroxid 0,5 bis 1 molarige Lösungen verwendet, wobei anzumerken bleibt, dass zu hohe Konzentrationen (von etwa 5molariger Lösung) das Polymermaterial zerstören können. Das in seinem ersten Zustand ursprünglich vollständig hydrophobe Polymermaterial wird durch die Basenbehandlung, deren Dauer im Bereich einiger Minuten, bevorzugt bei etwa einer Minute, im wesentlichen vollständig hydrophiliert. Anschließend erfolgt die Bebilderung entweder durch eine Maske oder durch örtlich selektive Beleuchtung durch einen Lichtstrahl, der lokal auf die Druckoberfläche gerichtet wird. Als Lichtquelle wird bevorzugt ein UV-Laser verwendet. Die örtlich selektive Belichtung ist als Initialisierungsreaktion anzusehen, an welche sich eine chemische Behandlung der Oberfläche anschließt. Die belichtete Oberfläche wird anschließend einem Oxidationsmittel ausgesetzt, z. B. Wasserstoffperoxid (H2O2), Sauerstoff oder Ozon. Weiterhin kann auch Kaliumpermanganat (KMnO4) in flüssiger Phase verwendet werden. Die bevorzugte Konzentration von Wasserstoffperoxid besteht in einer 15%igen Lösung von Wasserstoffperoxid in Wasser. Bei Kaliumpermanganat wird bevorzugt eine 0,02molare Lösung in Wasser benützt. Durch die Behandlung mit einem Oxidationsmittel werden die zuvor lokal bestrahlten Bereiche hydrophob, während die übrigen Bereiche hydrophil bleiben. Es ist vorteilhaft für eine verbesserte Stabilisierung der hydrophoben beziehungsweise hydrophilen Bereiche, die Oberfläche zusätzliche einer Behandlung beziehungsweise einer sogenannten Gummierung mit einem Polysaccharid zu unterwerfen.The polymer material, preferably PBDI or PAI, is applied in a thickness between a still manageable film of approximately 25 micrometers to a layer thickness of a few millimeters on a suitable carrier, for example on an aluminum plate. The surface of the applied polymer material is then subjected to a base treatment, sodium hydroxide (NaOH) and / or potassium hydroxide (KOH) preferably being used. With regard to the concentrations, 0.5 to 1 molar solutions are used, for example, in the case of sodium hydroxide, it remaining to be noted that concentrations which are too high (of approximately 5 molar solution) can destroy the polymer material. The polymer material, which is originally completely hydrophobic in its first state, is essentially completely hydrophilized by the base treatment, the duration of which is in the range of a few minutes, preferably about one minute. Subsequently, the imaging takes place either through a mask or through locally selective illumination by means of a light beam which is directed locally onto the printing surface. A UV laser is preferably used as the light source. The locally selective exposure is to be regarded as an initialization reaction, which is followed by a chemical treatment of the surface. The exposed surface is then exposed to an oxidizing agent, e.g. B. hydrogen peroxide (H 2 O 2 ), oxygen or ozone. Potassium permanganate (KMnO 4 ) can also be used in the liquid phase. The preferred concentration of hydrogen peroxide is a 15% solution of hydrogen peroxide in water. In the case of potassium permanganate, a 0.02 molar solution in water is preferably used. Treatment with an oxidizing agent makes the previously locally irradiated areas hydrophobic, while the remaining areas remain hydrophilic. For improved stabilization of the hydrophobic or hydrophilic areas, it is advantageous to additionally subject the surface to a treatment or a so-called gumming with a polysaccharide.
Die so hergestellte polymere Druckform wird zum Drucken verwendet. Nach dem Drucken kann die Druckform gleichzeitig gelöscht und gereinigt werden, wobei an sich alle üblichen bekannten mechanischen Reinigungsmöglichkeiten benutzt werden können: Die Oberfläche wird einer starken Säure ausgesetzt, z. B. Schwefelsäure (H2SO4), Salzsäure (HCl) oder Salpetersäure (HNO3). Die Säuren sollen dabei bevorzugt alle in einer Konzentration von einer 1molarigen Lösung vorliegen.The polymer printing form thus produced is used for printing. After printing, the printing form can be erased and cleaned at the same time, whereby all usual known mechanical cleaning options can be used: The surface is exposed to a strong acid, e.g. B. sulfuric acid (H 2 SO 4 ), hydrochloric acid (HCl) or nitric acid (HNO 3 ). The acids should preferably all be present in a concentration of a 1 molar solution.
Gegebenenfalls kann zur Unterstützung eines mechanischen Reinigungsprozesses auch ein chemisches Reinigungsmittel, insbesondere handelsüblicher Plattenreiniger, verwendet werden. Anschließend kann der gesamte Bebilderungsprozess für einen neuen Druckprozess wiederholt werden.If necessary, a can also be used to support a mechanical cleaning process chemical cleaning agent, especially commercially available plate cleaner, used become. Then the entire imaging process for a new one Printing process can be repeated.
In der Figur 4 ist eine schematische Darstellung der Strukturierung einer Druckform, deren Oberfläche Polyimid aufweist, mittels des erfindungsgemäßen Verfahrens ohne chemischen Initialisierungsschritt durch Behandlung mit einer basischen Substanz gezeigt. In Figure 4 is a schematic representation of the structuring of a printing form, the Has surface polyimide, by means of the inventive method without chemical initialization step shown by treatment with a basic substance.
Die Fig. 4 zeigt vier Zustände der Druckform 30, deren zeitliche Ordnung durch die Pfeile
angedeutet ist. Zunächst liegt die Druckform 30 mit einem großflächig hydrophoben
Bereich 32 vor. Durch lokale Belichtung, insbesondere mittels einer UV-Lichtquelle,
werden initialisierte Bereiche zweiter Art 38 auf der Oberfläche der Druckform 30 erzeugt.
Durch Oxidation werden daraus hydrophile Bereiche 34. Die Oberfläche weist damit eine
Struktur aus hydrophoben Bereichen 32 und hydrophilen Bereichen 34 auf, sodass sie zum
Drucken verwendet werden kann. Nach einer großflächigen Behandlung mit einer starken
Säure der Oberfläche der Druckform 30 wird erreicht, dass die Druckform großflächig
wieder hydrophob ist.Fig. 4 shows four states of the
In anderen Worten ausgedrückt: Ohne die Basenbehandlung 10, wie im Ablaufdiagramm
der Figur 1 gezeigt führt der anhand Figur 4 beschriebene Prozess der örtlich selektiven
Belichtung durch lokale Einstrahlung elektromagnetischer Energie zu einem umgekehrten
Hydophilierungs- respektive Hydrophobierungsergebnis, wenn die Druckform zeitlich
nachgehend einer chemischen Behandlung durch ein Oxidationsmittel ausgesetzt wird.In other words, without the
Es ist weiterhin anzumerken, dass mit besonderem Vorteil als Feuchtmittel für den Offsetdruck mit der erfindungsgemäßen Druckform Seifenwasser verwendet werden können. Die Tenside im Wasser lassen die bebilderten Bereiche beim Bedrucken stärker zur Geltung kommen.
- 10
- Basenbehandlung
- 12
- lokale Belichtung
- 14
- Oxidation
- 16
- Druck
- 18
- Säurebehandlung
- 110
- Iteration
- 20
- lokale Belichtung
- 22
- Oxidation
- 24
- Druck
- 26
- Säurebehandlung
- 28
- Iteration
- 30
- Druckform
- 32
- hydrophober Bereich
- 34
- hydrophiler Bereich
- 36
- initialisierter Bereich erster Art
- 38
- initialisierter Bereich zweiter Art
- 10
- base treatment
- 12
- local exposure
- 14
- oxidation
- 16
- 18
- acid treatment
- 110
- iteration
- 20
- local exposure
- 22
- oxidation
- 24
- 26
- acid treatment
- 28
- iteration
- 30
- printing form
- 32
- hydrophobic area
- 34
- hydrophilic area
- 36
- initialized area of the first kind
- 38
- initialized area of the second kind
Claims (15)
gekennzeichnet durch
eine sich an eine örtlich selektive Belichtung durch lokale Einstrahlung elektromagnetischer Energie zeitlich nachgehende chemische Behandlung der
Oberfläche mit einem Oxidationsmittel.Method for producing a structure from hydrophilic (34) and hydrophobic (32) areas on a surface which, in a first, essentially unstructured state, has a polymer material with imide groups,
marked by
a chemical treatment of the temporally subsequent exposure to locally selective exposure to local radiation of electromagnetic energy
Surface with an oxidizing agent.
gekennzeichnet durch
eine der örtlich selektiven Belichtung zeitlich vorhergehende großflächige chemische Behandlung der Oberfläche mit einer starken Base.Method according to claim 1,
marked by
a large-area chemical treatment of the surface with a strong base that precedes the locally selective exposure.
gekennzeichnet durch
eine großflächige chemische Behandlung der Oberfläche mit einer starken Säure.Method according to claim 1 or 2 with an additional, temporally subsequent method step of transferring the surface into the first, essentially unstructured state,
marked by
a large-area chemical treatment of the surface with a strong acid.
dadurch gekennzeichnet, dass die elektromagnetische Energie durch eine UV-Lichtquelle, welche Licht mit einer Wellenlänge zwischen 200 und 440 nm emittiert, erzeugt wird.Method according to one of the preceding claims,
characterized in that the electromagnetic energy is generated by a UV light source which emits light with a wavelength between 200 and 440 nm.
dadurch gekennzeichnet, dass das Oxidationsmittel Wasserstoffperoxid (H2O2) und/oder Sauerstoff (O2) und/oder Ozon (O3) und/oder Kaliumpermanganat (KMnO4) aufweist. Method according to one of the preceding claims,
characterized in that the oxidizing agent comprises hydrogen peroxide (H 2 O 2 ) and / or oxygen (O 2 ) and / or ozone (O 3 ) and / or potassium permanganate (KMnO 4 ).
dadurch gekennzeichnet, dass die starke Base eine wässrige Lösung von Kaliumhydroxid (KOH) und/oder Natriumhydroxid (NaOH) ist.Method according to one of claims 2 to 5,
characterized in that the strong base is an aqueous solution of potassium hydroxide (KOH) and / or sodium hydroxide (NaOH).
dadurch gekennzeichnet, dass die starke Säure eine wässrige Lösung von Schwefelsäure (H2SO4) und/oder Salzsäure (HCl) und/oder Salpetersäure (HNO3) ist.Method according to one of claims 3 to 6,
characterized in that the strong acid is an aqueous solution of sulfuric acid (H 2 SO 4 ) and / or hydrochloric acid (HCl) and / or nitric acid (HNO 3 ).
dadurch gekennzeichnet, dass neben dem Oxidationsmittel während der zeitlich nachgehenden chemischen Behandlung eine Flüssigkeit mit ionischen Tensiden eingesetzt wird.Method according to one of the preceding claims,
characterized in that, in addition to the oxidizing agent, a liquid with ionic surfactants is used during the subsequent chemical treatment.
dadurch gekennzeichnet, dass das Polymermaterial mit Imid-Gruppen PBDI oder PAI ist.Method according to one of the preceding claims,
characterized in that the polymer material with imide groups is PBDI or PAI.
dadurch gekennzeichnet, dass der chemischen Behandlung der Oberfläche mit einem Oxidationsmittel zeitlich nachgeordnet die Oberfläche mit einem Polysaccharid in Kontakt gebracht wird.Method according to one of the preceding claims,
characterized in that after the chemical treatment of the surface with an oxidizing agent, the surface is brought into contact with a polysaccharide.
dadurch gekennzeichnet, dass die Oberfläche ein Polymermaterial mit Imid-Gruppen aufweist.Printing form (30), in particular for use as a printing form (30) in offset printing, with a surface for printing,
characterized in that the surface has a polymer material with imide groups.
dadurch gekennzeichnet, dass die Oberfläche PBDI oder PAI aufweist.Printing form (30) with a surface according to claim 11,
characterized in that the surface has PBDI or PAI.
dadurch gekennzeichnet, dass die Oberfläche mit einem Verfahren gemäß Anspruch 1 bis 10 strukturierbar ist.Printing form (30) with a surface according to claim 11 or 12,
characterized in that the surface can be structured with a method according to claims 1 to 10.
dadurch gekennzeichnet, dass das Druckwerk zum Drucken mit einer Druckform gemäß Anspruch 11, 12 oder 13 versehen ist.Printing,
characterized in that the printing unit for printing is provided with a printing form according to claim 11, 12 or 13.
dadurch gekennzeichnet, dass die Druckmaschine wenigstens ein Druckwerk gemäß Anspruch 14 aufweist.Printing machine with at least one feeder, one printing unit and one delivery,
characterized in that the printing press has at least one printing unit according to claim 14.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DK02007336T DK1254768T3 (en) | 2001-05-03 | 2002-04-05 | Imaging and deletion from a printing material of polymer material with imide groups |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10121561 | 2001-05-03 | ||
DE10121561A DE10121561A1 (en) | 2001-05-03 | 2001-05-03 | Imaging and deletion of a printing form made of polymer material with imide groups |
Publications (3)
Publication Number | Publication Date |
---|---|
EP1254768A2 true EP1254768A2 (en) | 2002-11-06 |
EP1254768A3 EP1254768A3 (en) | 2003-09-03 |
EP1254768B1 EP1254768B1 (en) | 2005-02-09 |
Family
ID=7683521
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP02007336A Expired - Lifetime EP1254768B1 (en) | 2001-05-03 | 2002-04-05 | Imaging and erasure of a printing form made from a polymer having imide groups |
Country Status (9)
Country | Link |
---|---|
US (1) | US6919165B2 (en) |
EP (1) | EP1254768B1 (en) |
JP (1) | JP4657563B2 (en) |
CN (1) | CN1264676C (en) |
AT (1) | ATE288830T1 (en) |
CZ (1) | CZ300557B6 (en) |
DE (2) | DE10121561A1 (en) |
DK (1) | DK1254768T3 (en) |
HK (1) | HK1053087B (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1580595A2 (en) * | 2004-03-26 | 2005-09-28 | Fuji Photo Film Co., Ltd. | Pattern forming method, graft pattern material, conductive pattern forming method and conductive pattern material |
EP2236289A3 (en) * | 2009-04-01 | 2013-06-05 | Xerox Corporation | Imaging member |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10206938A1 (en) * | 2002-02-19 | 2003-09-04 | Oce Printing Systems Gmbh | Method and device for printing, wherein a hydrophilic layer is produced and structured |
US6566039B1 (en) * | 2002-06-04 | 2003-05-20 | Gary Ganghui Teng | Variable data lithographic printing device and method |
US6789478B1 (en) * | 2003-02-28 | 2004-09-14 | Heidelberger Druckmaschinen Ag | Device and method for controlling fluid delivery |
DE102005046863A1 (en) * | 2005-09-30 | 2007-06-14 | Man Roland Druckmaschinen Ag | printing form |
US7709185B2 (en) | 2006-03-24 | 2010-05-04 | Heidelberger Druckmaschinen Ag | Method for imaging a lithographic printing form |
CN112571697A (en) * | 2020-10-12 | 2021-03-30 | 安徽美阅文化发展股份有限公司 | Production process of deep embossing intaglio and relief plate of paper printed matter |
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EP0911154A1 (en) | 1997-10-24 | 1999-04-28 | Fuji Photo Film Co., Ltd. | Plate making device and printer and printing system using the plate making device |
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DE103977C (en) | ||||
DD103977A1 (en) * | 1973-04-11 | 1974-02-12 | ||
US4634659A (en) * | 1984-12-19 | 1987-01-06 | Lehigh University | Processing-free planographic printing plate |
US4693958A (en) * | 1985-01-28 | 1987-09-15 | Lehigh University | Lithographic plates and production process therefor |
US4999251A (en) * | 1989-04-03 | 1991-03-12 | General Electric Company | Method for treating polyetherimide substrates and articles obtained therefrom |
US5051312A (en) | 1990-03-29 | 1991-09-24 | E. I. Du Pont De Nemours And Company | Modification of polymer surfaces |
JPH04193956A (en) * | 1990-11-28 | 1992-07-14 | Sumitomo Metal Mining Co Ltd | Method for etching polyimide resin |
JPH04356387A (en) * | 1991-05-30 | 1992-12-10 | Shin Etsu Polymer Co Ltd | Eliminating method for adherent fragment |
US5288519A (en) * | 1992-04-27 | 1994-02-22 | General Electric Company | Method of producing modified polyimide layer having improved adhesion to metal layer thereon |
JP3405473B2 (en) * | 1994-03-31 | 2003-05-12 | 日立化成工業株式会社 | Laser processing of heat-resistant resin |
JPH08310148A (en) * | 1995-05-16 | 1996-11-26 | Nippon Paint Co Ltd | Laser direct engraving lithographic printing plate material requiring no liquid developing step, and printing method using the same |
DE69710867T2 (en) * | 1997-04-18 | 2002-10-31 | Eastman Kodak Co | Zirconia alloy cylinders and sleeves for lithographic imaging and printing processes |
DE19826377A1 (en) | 1998-06-12 | 1999-12-16 | Heidelberger Druckmasch Ag | Printing press and printing process |
US6162578A (en) * | 1998-12-18 | 2000-12-19 | Eastman Kodak Company | Imaging member containing heat sensitive hyperbranched polymer and methods of use |
US6410202B1 (en) * | 1999-08-31 | 2002-06-25 | Eastman Kodak Company | Thermal switchable composition and imaging member containing cationic IR dye and methods of imaging and printing |
-
2001
- 2001-05-03 DE DE10121561A patent/DE10121561A1/en not_active Withdrawn
-
2002
- 2002-04-05 CZ CZ20021199A patent/CZ300557B6/en not_active IP Right Cessation
- 2002-04-05 EP EP02007336A patent/EP1254768B1/en not_active Expired - Lifetime
- 2002-04-05 DE DE50202196T patent/DE50202196D1/en not_active Expired - Lifetime
- 2002-04-05 AT AT02007336T patent/ATE288830T1/en not_active IP Right Cessation
- 2002-04-05 DK DK02007336T patent/DK1254768T3/en active
- 2002-04-15 US US10/122,817 patent/US6919165B2/en not_active Expired - Fee Related
- 2002-04-27 CN CNB02118495XA patent/CN1264676C/en not_active Expired - Fee Related
- 2002-04-30 JP JP2002127910A patent/JP4657563B2/en not_active Expired - Fee Related
-
2003
- 2003-07-02 HK HK03104674.2A patent/HK1053087B/en not_active IP Right Cessation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US4568632A (en) | 1982-10-07 | 1986-02-04 | International Business Machines Corporation | Patterning of polyimide films with far ultraviolet light |
EP0911154A1 (en) | 1997-10-24 | 1999-04-28 | Fuji Photo Film Co., Ltd. | Plate making device and printer and printing system using the plate making device |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1580595A2 (en) * | 2004-03-26 | 2005-09-28 | Fuji Photo Film Co., Ltd. | Pattern forming method, graft pattern material, conductive pattern forming method and conductive pattern material |
EP2236289A3 (en) * | 2009-04-01 | 2013-06-05 | Xerox Corporation | Imaging member |
Also Published As
Publication number | Publication date |
---|---|
JP4657563B2 (en) | 2011-03-23 |
DE50202196D1 (en) | 2005-03-17 |
US6919165B2 (en) | 2005-07-19 |
EP1254768A3 (en) | 2003-09-03 |
CN1387998A (en) | 2003-01-01 |
HK1053087A1 (en) | 2003-10-10 |
DK1254768T3 (en) | 2005-04-11 |
DE10121561A1 (en) | 2002-11-07 |
EP1254768B1 (en) | 2005-02-09 |
HK1053087B (en) | 2007-01-12 |
ATE288830T1 (en) | 2005-02-15 |
CN1264676C (en) | 2006-07-19 |
CZ20021199A3 (en) | 2003-01-15 |
JP2003011316A (en) | 2003-01-15 |
US20020177053A1 (en) | 2002-11-28 |
CZ300557B6 (en) | 2009-06-17 |
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