EP1375136B1 - Reusable printing plate - Google Patents

Reusable printing plate Download PDF

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Publication number
EP1375136B1
EP1375136B1 EP03011112A EP03011112A EP1375136B1 EP 1375136 B1 EP1375136 B1 EP 1375136B1 EP 03011112 A EP03011112 A EP 03011112A EP 03011112 A EP03011112 A EP 03011112A EP 1375136 B1 EP1375136 B1 EP 1375136B1
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EP
European Patent Office
Prior art keywords
printing
reusable
metal oxide
organic compound
printing forme
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.)
Expired - Lifetime
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EP03011112A
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German (de)
French (fr)
Other versions
EP1375136A1 (en
Inventor
Martin Gutfleisch
Gerald Erik Dr. Hauptmann
Harald Dr. Latzel
Gerhard Dr. Peiter
Wolfgang Dr. Eck
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Heidelberger Druckmaschinen AG
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Heidelberger Druckmaschinen AG
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Publication of EP1375136A1 publication Critical patent/EP1375136A1/en
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
    • B41N1/00—Printing plates or foils; Materials therefor
    • B41N1/006—Printing plates or foils; Materials therefor made entirely of inorganic materials other than natural stone or metals, e.g. ceramics, carbide materials, ferroelectric materials
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
    • B41N3/00—Preparing for use and conserving printing surfaces
    • B41N3/006—Cleaning, washing, rinsing or reclaiming of printing formes other than intaglio formes

Definitions

  • the invention relates to a reusable printing forme, especially for use in offset printing, with a printing surface, and a method for imaging a reusable printing forme.
  • Printing forms are used in printing units of printing presses to apply a predetermined print pattern, a given subject or image to a substrate.
  • Typical substrates are paper, cardboard, cardboard, organic polymers, textiles or the like.
  • printing forms are used, on the printing surface of which, part of the surface of the printing form, the pattern to be printed is permanently applied, structured or described.
  • Such printing forms can only be used easily.
  • printing surfaces are of particular interest, which can be deleted after structuring into a first image and later structured into a second image.
  • a reusable printing form is understood to mean a printing form having a printing surface, which can be patterned several times into different images.
  • Offset printing a structuring of the printing surface is present in regions of different wetting properties, in particular hydrophilic / lipophobic and hydrophobic / lipophilic regions.
  • Offset printing is based on exploiting the immiscibility of lipophilic substances, particularly oily fluids or liquids, and hydrophilic substances, especially aqueous fluids or liquids, on the printing form, the lipophilic substance or ink being colored by the image-forming areas and hydrophilic ones Substance or water are held by the non-image forming areas of the printing surface.
  • the non-image areas preferentially retain the hydrophilic substance and repel the lipophilic substance while the imagewise areas accept the lipophilic substance and repel the hydrophilic substance.
  • the lipophilic substance is then suitably transferred to the surface of a material on which the image is to be fixed.
  • a structuring of the printing surface is present in regions of different wetting properties.
  • This surface is hydrophobic when unexcited and can be rendered hydrophilic by irradiation with ultraviolet light. By heating, this switching process can be reversed again. Imaging is now done by illuminating the entire surface of the plate with ultraviolet light and masking areas of ink which are to be printed. For deletion, the image areas are then thermally, z. B. with a laser beam, switched back.
  • the hydrophobicity of such a metal oxide surface is particularly based on a surface contaminated with hydrocarbons in air, such as Fourier Transform Infrared Spectroscopy (FTIR), X-ray Photoelectron Spectroscopy (XPS), Atomic Force Microscopy (AFM) or the like can be determined.
  • FTIR Fourier Transform Infrared Spectroscopy
  • XPS X-ray Photoelectron Spectroscopy
  • AFM Atomic Force Microscopy
  • the surface can be hydrophilized with the aid of UV radiation or wet chemistry, it is hydrophobized again in an uncontrolled manner within a few hours when stored in air. So there is no defined, permanent hydrophobicity as initial state.
  • EP 0 962 333 A1 it is known to use printing forms whose printing pattern is changeable.
  • hydrophobic or hydrophilic materials are applied to the printing plate surface, then wetted the printing plate surface with water and then applied to the printing plate surface color. Due to the hydrophilic or hydrophobic properties, the water is attracted to the wetting process with water in the hydrophilic surface areas, so that the hydrophilic surface areas no longer absorb printing ink during the subsequent coating with printing ink.
  • the applied print pattern is removed again. Subsequently, the printing form can be structured or described with a new printing pattern.
  • a thiol compound as the material for the coating of the printing plate surface. The thiol compound is removed again under the action of heat from the printing plate surface.
  • the object of the present invention is to provide a reusable printing plate whose printing surface allows multiple image creation and deletion.
  • a reusable, in particular rewriteable or re-imageable printing form having a printing surface which has a metal oxide surface treated with at least one amphiphilic organic compound whose polar region has an acidic character
  • the amphiphilic organic Compound may be a surfactant-like compound.
  • the amphiphilic organic compound may be an aliphatic or aromatic radical-substituted inorganic or organic acid which comprises at least one element of IV, V or VI. Main group of the Periodic Table, in particular carbon (C), phosphorus (P), sulfur (S) or nitrogen (N), having.
  • the radical may be an unsubstituted or a substituted aliphatic or an unsubstituted or substituted aromatic.
  • the rest may in particular be partially or completely halogenated, in particular fluorinated.
  • the remainder has a carbon chain wherein the number of carbons is greater than or equal to 12 and less than or equal to 25.
  • the amphiphilic organic compound may in one embodiment be a hydroxamic acid or a phosphonic acid.
  • the amphiphilic organic compound may be n-heptadecane hydroxamic acid ⁇ CH3- (CH2) 16-C (O) NH-OH ⁇ or n-octadecane phosphonic acid ⁇ CH3- (CH2) 17-P (O) - (OH) 2 ⁇ .
  • the metal oxide surface may be a native oxidized titanium surface, native oxidized stainless steel surface, e.g., Hastelloy, or natively oxidized aluminum surface.
  • the invention is therefore based, inter alia, on the idea of treating technically rough metal oxide surfaces with amphiphilic, surfactant-like organic compounds, in particular applying or coating amphiphilic, surfactant-like organic on technically rough metal oxide surfaces.
  • the reusable printing form can thus also be referred to in particular as a (in the nano range) re-coatable printing form.
  • the printing form according to the invention has a surface which is obtained by the action of an amphiphilic organic compound on a metal oxide surface. Details of the underlying method of providing a printing form according to the invention are described below.
  • the rewritable printing form according to the invention is particularly advantageously in an offset printing process, in particular in direct or in indirect planographic printing, used. It can therefore also be referred to in particular as a rewritable offset printing form or as a (in the nano range) recoatable offset printing form.
  • amphiphilic, surfactant-like organic compounds it is possible to produce reproducibly defined hydrophobic metal oxide surfaces, in particular titanium oxide surfaces.
  • the pressure surface treated by an amphiphilic organic compound may be hydrophobic.
  • hydrophilically substituted or terminated amphiphilic surfactant-like compounds A printing surface treated by a hydrophilic substituted amphiphilic surfactant-like compound may be hydrophilic.
  • the amphiphilic, surfactant-like organic compounds n-heptadecane-hydroxamic acid (CH3- (CH2) 16-C (O) -NH-OH) -also tautomeric form and / or n-octadecane-phosphonic acid (CH3- (CH2 ) of 17-P (O) - (OH) 2).
  • the metal oxide surface is brought into a hydrophobic, ink-bearing state, which can serve as the starting state for imaging for an offset printing process.
  • the contact angles, measured against water, of these hydrophobic metal oxide surfaces are values from the set of numbers of the real number interval between 80 and 120 degrees.
  • the metal oxide surface can then be brought into a hydrophilic, ink-carrying state by controlled energy input.
  • the contact angles, measured against water, in the hydrophilic state are values from the number of times the interval of real numbers between 0 and 10 degrees.
  • the stroke between the two states is thus sufficiently large for offset printing.
  • the printing form according to the invention is switchable, in particular between a hydrophilic and a hydrophobic state. After structuring the rewritable printing form according to the invention into regions in the hydrophilic and hydrophobic state, an offset printing process can be carried out.
  • the reusable printing form according to the invention can be embodied in various embodiments with different topological and geometric properties.
  • the printing form according to the invention can be realized as the surface of a solid cylinder or as the surface of a hollow cylinder.
  • the cylinder, full or hollow, can in particular be a straight circular cylinder. Under surface is to be understood in particular the lateral surface.
  • the printing form according to the invention may also be formed as a sleeve or as a plate.
  • a sleeve has two surfaces (inner surface and outer surface) and has two edges.
  • the sleeve may be cylindrical with a uniform diameter, in particular inner diameter or outer diameter, (circular hollow cylindrical) or conical, that is with variable, in particular uniformly increasing or decreasing diameter, in particular inner diameter or outer diameter.
  • Inner diameter and outer diameter can vary differently. It is thus in the topological sense a not simply coherent object.
  • a plate has two surfaces (top and bottom) and has an edge. It is thus in the topological sense a simply coherent object.
  • the plate may in particular be cuboid or rectangular.
  • the reusable printing form according to the invention can be used in a printing unit, in particular in an offset printing unit. It may form the surface of a printing cylinder or be received on the surface of a cylinder.
  • An inventive printing unit is therefore characterized by at least one reusable printing form according to the invention.
  • the printing unit according to the invention may be part of a printing press, in particular an offset printing press.
  • the printing press may be a sheet-fed or a web-processing press.
  • a sheet-fed printing machine may include a feeder, a number of printing units, and a cantilever.
  • a printing press according to the invention has at least one printing unit according to the invention.
  • the reusable printing form according to the invention is also an inventive method for imaging a reusable, in particular rewriteable or creamybercisbaren, printing form with various advantageous developments.
  • the inventive method is based on the desire to provide a cyclic process in which a printing form according to the invention can be repeatedly imaged and erased, so that the printing form is particularly suitable for offset printing.
  • the inventive method for imaging can be carried out both inside and outside a printing unit or a printing press.
  • the printing surface can be processed imagewise by exposure through a mask-like template. But preferred is the pointwise direct exposure with digital information.
  • the method according to the invention for imaging a reusable printing form comprises the following steps: A reusable, in particular rewriteable or reproducible printing form having a printing surface which has a metal oxide surface treated with at least one amphiphilic organic compound is provided.
  • the rewritable printing form can in particular be designed as described in greater detail above in this illustration.
  • An image is generated by selective, in particular spatially and temporally selective, pointwise energy supply to the printing surface. In other words, a digital imaging is performed.
  • the imaging transforms the printing form from a hydrophobic to a hydrophilic state. After printing on a printing material, in particular in an offset printing process, the image is erased by large-area energy supply.
  • the printing surface of the printing form is treated with a solution of an amphiphilic organic compound.
  • the provision of the printing form is iterated or repeated.
  • the steps of imaging and deleting can thus be carried out several times with different print patterns or subjects.
  • the method according to the invention allows a cyclic process.
  • the step of providing the reusable printing plate may advantageously comprise the treatment of the printing surface with an amphiphilic organic compound whose polar region has an acidic character:
  • the printing surface is treated with an aqueous solution (also pure water) or with an alcoholic Solution, in particular ethanol, which contains at least one amphiphilic organic compound in a suitable concentration, close to the saturation limit, preferably in the concentration of 1 mmol / l.
  • an alcoholic Solution in particular ethanol
  • the metal oxide surface is exposed to an amphiphilic organic compound.
  • the amphiphilic organic compound is applied. This application or termination can take place in an advantageous embodiment in an ultrasonic bath.
  • the application, termination or coating of the metal oxide surface, in particular titanium dioxide surface, with the molecules of the amphiphilic organic compound takes place in a few seconds when the metal oxide surface is exposed to the solution, for example immersed in the solution, to cause a macroscopically detectable change in the wetting property.
  • the step of providing the reusable printing plate may advantageously comprise the following steps:
  • the printing surface is cleaned by irradiating the metal oxide surface with a UV light source.
  • Non-adherent compounds are removed from the treated metal oxide surface.
  • This cleaning of the treated metal oxide surface can be carried out in particular with an alcoholic solution, preferably with ethanol.
  • the treated, cleaned metal oxide surface is dried with an anhydrous process gas, in particular with nitrogen.
  • the method according to the invention may comprise the following steps for the preparation of the metal oxide surface.
  • the metal oxide surface may be a surface of the amount of the following surfaces: native oxidized titanium surface, native oxidized stainless steel surface, native oxidized aluminum surface, titanate and zirconate. More specifically, a first provision of the reusable printing form may be preceded by the following steps for preparation.
  • the metal oxide surface is prepurified. Purification may include the step of rinsing with acetone, ethanol, isopropanol, ethyl acetate or other suitable organic solvent. One purpose is in particular the degreasing of the surface.
  • the metal oxide surface can then be an aqueous solution of the composition a volume of 25% NH 4 OH solution and a volume of 30% H 2 O 2 solution in four volumes of H 2 O at a temperature of about 60 ° C for about 10 minutes get abandoned.
  • This step is particularly advantageous for a native oxidized titanium surface.
  • One purpose is, in particular, oxidation of hydrocarbons located on the metal oxide surface.
  • a main cleaning can be done by etching the metal oxide surface. The etching may be performed by a solution of the composition comprising 40% HF solution by volume and three volumes of 30% H 2 O 2 in twenty volumes of H 2 O at room temperature for about 1 minute.
  • One purpose is, in particular, the removal of a few individual metal oxide layers and the setting of a defined roughness of the metal oxide surface.
  • a defined oxide film, in particular a hydrophilic surface can be achieved by oxidation of the cleaned and etched surface.
  • the surface of a solution of the composition may be exposed to a volume fraction of 25% NH 4 OH solution and a volume fraction of 30% H 2 O 2 solution in four volumes of H 2 O at a temperature of about 60 ° C.
  • the steps of etching and producing a defined oxide film is particularly advantageous for a native oxidized titanium surface.
  • an image is generated on the printing surface by selective pointwise energy supply for hydrophilizing with the aid of electromagnetic radiation.
  • the electromagnetic radiation can be in the range of 150 to 1200 nanometers wavelength.
  • the energy can be supplied in the infrared spectral range.
  • the digital imaging can be done by a laser, preferably with about 1100 nanometers wavelength.
  • the image is erased in the preferred embodiment by large-scale energy supply to the hydrophobing by means of an irradiation of the printing surface with electromagnetic radiation.
  • the large-area irradiation can be carried out in the ultraviolet spectral range.
  • a preferred light source is an excimer radiator.
  • the printing surface of printing ink is cleaned or freed after printing of the printing material.
  • a cleaning can be carried out using a conventional color cleaner or a conventional detergent, a surfactant-containing aqueous solution, for example the detergent sold under the name EUROSTAR.
  • the structured pressure surface treated with at least one hydrophilic substituted or terminated amphiphilic organic compound after the formation of an image by selective pointwise energy supply for hydrophilization on the pressure surface of the treated with an amphiphilic organic compound metal oxide surface, in particular titanium dioxide surface, the structured pressure surface treated with at least one hydrophilic substituted or terminated amphiphilic organic compound.
  • the substituent may form a head group on the molecule of the compound.
  • the amphiphilic organic compound may be a compound as described in this presentation.
  • Substituents may in particular be one or more NH.sub.2 groups, one or more COOH groups or one or more OH groups.
  • the areas formed by the selective point-wise energy supply can be occupied or terminated in this way with molecules of the substituted or terminated amphiphilic organic compound. This additional process step advantageously leads to a reinforcement and / or stabilization of the hydrophilicity of the dot-wise imaged areas.
  • the invention provides a reusable, especially rewriteable or re-imageable, printing form with reliably reproducible behavior with regard to the imaging and erasing process.
  • the creation of an image or structure on the printing surface is simple and reliable. It is not necessary for a monolayer of the amphiphilic organic compound to self-assemble on the metal oxide surface.
  • the process for imaging thus requires a short provision time of the printing form according to the invention.
  • the application of above-mentioned compounds within a period of a few minutes, is sufficient to achieve a sufficiently strong hydrophobing of the metal oxide surfaces, in particular for use in an offset printing process.
  • the process according to the invention enables the hydrophobing of rough metal oxide surfaces, as are produced in current industrial production processes.
  • an advantageous embodiment of the reusable printing form according to the invention and an advantageous embodiment of a method according to the invention for imaging a reusable printing form using a natively oxidized titanium surface and n-octadecane-phosphonic acid are exemplified.
  • the FIG. 1 shows a flowchart of an advantageous embodiment of the method according to the invention for imaging a reusable printing form according to the invention.
  • Titanium surface samples can be purchased from Goodfellow. In order to first clean the titanium surface to be treated, it is irradiated with a light in the ultraviolet wavelength range.
  • the step of providing a reusable printing plate comprises applying the amphiphilic surfactant-like organic compounds: The titanium surface is wetted with a solution containing the above-mentioned compounds in suitable concentration. The titanium surface is immersed in 1 mM ethanolic solution of n-octadecane phosphonic acid (stearic phosphonic acid) at room temperature for about 5 minutes.
  • a cleaning of the treated titanium surface is effected by rinsing with ethanol, which removes the non-adherent compounds from the n-octadecane-phosphonic acid solution.
  • the cleaned, treated titanium surface is completely dried with an anhydrous, a so-called dry process gas, here nitrogen.
  • Such prepared or prepared titanium surfaces are hydrophobic and can be imaged with intense UV or IR light sources. By means of imaging hydrophilic areas are generated.
  • a diode-pumped yttrium-doped fiber laser from SDL is used as the light source.
  • Local, selective, digital imaging can be done using 30 micron spots of light (spots, 1 / e 2 waste). The wavelength is 1100 nanometers, the power 3 watts and the intensity or fluence 15 to 30 joules / square centimeter.
  • a visible structure or pattern is formed.
  • variable v denotes the scanning speed (scanning speed) of the printing surface.
  • a pattern can be imaged over the entire area (full-length) or pixel-area (pixel area) be.
  • the pixel size is 40 microns.
  • the color impressions are due to oxides of titanium, which are not necessarily stoichiometric composition.
  • XPS measurements have shown that after the one-time wet-chemical preparation, in particular as described in detail above, at a depth of 6 nanometers at the titanium surface, there are different oxidation states of the titanium. For example, TiO, TiO2, Ti2O3 and metallic Ti are present in these first 6 nanometers of surface. After a single laser irradiation, the oxide film on the surface is already thicker than 6 nanometers; the XPS-detectable 6 nanometers consist of 100% or 100% TiO2 in terms of measurement accuracy.
  • a one-time, full-surface laser treatment after the one-time wet-chemical preparation is a very advantageous initial state for the reversible (erasable) imaging on this titanium surface.
  • Repeated imaging with IR laser at the same areas of the surface although resulting in slight color changes, but have no influence on the wetting properties of these areas.
  • the irradiation of the hydrophobic surface always results in hydrophilic areas.
  • a functional printing form can be obtained at irradiation of more than 15 joules / square centimeter. Particularly good quality is achieved from 30 joules / square centimeter.
  • the reproduction of the subject on a printing substrate by an offset printing process takes place.
  • the titanium surface may be cleaned of ink by contact with a solution of suitable composition.
  • color cleaner EUROSTAR is used.
  • the titanium surface is extensively exposed to ultraviolet light of the wavelength of approximately 172 nanometers for approximately 5 minutes Minutes exposed.
  • the light source is a Xenon Excimerstrahler the company Xeradex (OSRAM) with an optical power of 5 watts with electrical power of 20 watts.
  • the FIG. 2 is a schematic representation of the structuring of a reusable printing form according to the invention, the pressure surface having a treated with at least one amphiphilic organic compound whose polar region has an acidic character, treated metal surface by means of the inventive method.
  • the FIG. 2 shows three states of the printing plate 30, whose temporal order is indicated by the arrows.
  • the printing form 30 is present with a large area of hydrophobic printing surface 32.
  • By local, pointwise, selective imaging hydrophilic region 34 are generated on the surface of the printing plate 30.
  • the surface thus has a structure of hydrophobic regions 32 and hydrophilic regions 34, so that they can be used for printing, in particular in an offset printing process.

Abstract

A reusable printing form comprises a printing area having a metal oxide surface that is treated with amphiphilic organic compound having a polar region with an acidic character. Independent claims are also included for: (a) a printing unit or printing machine having at least reusable printing form; (b) a method for imaging a reusable printing form comprising producing an image on the printing area by selectively inputting energy on a dot-by-dot basis, and erasing the image through large-surface input of energy subsequent to printing on a printing substrate; and (c) a method for creating an imageable printing area comprising treating the metal oxide surface with amphiphilic organic compound(s) having a polar region with an acidic character.

Description

Die Erfindung betrifft eine wiederverwendbare Druckform, insbesondere für den Einsatz im Offsetdruck, mit einer Druckfläche, und ein Verfahren zur Bebilderung einer wiederverwendbaren Druckform.The invention relates to a reusable printing forme, especially for use in offset printing, with a printing surface, and a method for imaging a reusable printing forme.

Druckformen werden in Druckwerken von Druckmaschinen eingesetzt, um ein vorgegebenes Druckmuster, ein vorgegebenes Sujet oder Bild, auf einen Bedruckstoff aufzubringen. Typische Bedruckstoffe sind Papier, Pappe, Karton, organische Polymere, Textilien oder dergleichen. Im überwiegenden Maße kommen dabei Druckformen zum Einsatz, auf deren Druckfläche, ein Teil der Oberfläche der Druckform, dauerhaft das zu druckende Muster aufgebracht, strukturiert oder beschrieben ist. Derartige Druckformen können nur einfach genutzt werden. Aus verschiedenen Gründen ist es wünschenswert, Druckformen einzusetzen, welche mehrfach verwendet, insbesondere mehrfach beschrieben oder mehrfach bebildert, werden können. Anders ausgedrückt, von besonderem Interesse sind Druckflächen, welche nach einer Strukturierung in ein erstes Bild gelöscht und später in ein zweites Bild strukturiert werden können. Im Zusammenhang dieser Darstellung sei unter einer wiederverwendbaren Druckform eine Druckform mit einer Druckfläche verstanden, welche mehrfach in verschiedene Bilder strukturiert werden kann.Printing forms are used in printing units of printing presses to apply a predetermined print pattern, a given subject or image to a substrate. Typical substrates are paper, cardboard, cardboard, organic polymers, textiles or the like. For the most part, printing forms are used, on the printing surface of which, part of the surface of the printing form, the pattern to be printed is permanently applied, structured or described. Such printing forms can only be used easily. For various reasons, it is desirable to use printing forms which can be used several times, in particular multiply written or multiply imaged. In other words, printing surfaces are of particular interest, which can be deleted after structuring into a first image and later structured into a second image. In the context of this illustration, a reusable printing form is understood to mean a printing form having a printing surface, which can be patterned several times into different images.

Beim Offsetdruck liegt eine Strukturierung der Druckfläche in Bereiche unterschiedlicher Benetzungseigenschaften, insbesondere hydrophile/lipophobe und hydrophobe/lipophile Bereiche, vor. Der Offsetdruck basiert auf der Ausnutzung der Nichtmischbarkeit von lipophilen Substanzen, insbesondere von öligen Fluiden oder Flüssigkeiten, und hydrophilen Substanzen, insbesondere von wässrigen Fluiden oder Flüssigkeiten, auf der Druckform, wobei die lipophile Substanz oder die Tinte oder Druckfarbe durch die bildaufbauenden Bereiche und die hydrophile Substanz oder Wasser durch die nichtbildaufbauenden Bereiche der Druckfläche festgehalten werden. Wenn die in geeigneter Weise vorbereitete Druckfläche mit hydrophiler und lipophiler Substanz benetzt wird, so halten die nichtbildmäßigen Bereiche vorzugsweise die hydrophile Substanz zurück und stoßen die lipophilen Substanz ab, während die bildmäßigen Bereiche die lipophile Substanz annehmen und die hydrophilen Substanz 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. Entsprechend liegt auch beim wasserlosen Offsetdruck eine Strukturierung der Druckfläche in Bereiche unterschiedlicher Benetzungseigenschaften vor.In offset printing, a structuring of the printing surface is present in regions of different wetting properties, in particular hydrophilic / lipophobic and hydrophobic / lipophilic regions. Offset printing is based on exploiting the immiscibility of lipophilic substances, particularly oily fluids or liquids, and hydrophilic substances, especially aqueous fluids or liquids, on the printing form, the lipophilic substance or ink being colored by the image-forming areas and hydrophilic ones Substance or water are held by the non-image forming areas of the printing surface. When the appropriately prepared printing surface wets with hydrophilic and lipophilic substance Thus, the non-image areas preferentially retain the hydrophilic substance and repel the lipophilic substance while the imagewise areas accept the lipophilic substance and repel the hydrophilic substance. As a result, the lipophilic substance is then suitably transferred to the surface of a material on which the image is to be fixed. Correspondingly, even in the case of waterless offset printing, a structuring of the printing surface is present in regions of different wetting properties.

In der Literatur werden verschiedene Konzepte für wiederverwendbare, insbesondere wiederbeschreibbare Druckformen vorgestellt und diskutiert.Various concepts for reusable, especially rewritable printing forms are presented and discussed in the literature.

In der EP 0 911 154 A1 werden als Materialen für eine Oberfläche einer Druckform. Titandioxid, Zinkoxid, welche in keramischer Form sowohl rein als auch mit anderen metallischen Zusätzen in verschiedenen Mischungsverhältnissen vorliegen können, oder Zirkonkeramik vorgeschlagen. Diese Oberfläche ist in nicht angeregtem Zustand hydrophob und kann durch Bestrahlung mit ultraviolettem Licht in einen hydrophilen Zustand versetzt werden. Durch Erwärmung kann dieser Schaltvorgang wieder rückgängig gemacht 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. Zur Löschung werden anschließend die Bildbereiche thermisch, z. B. mit einem Laserstrahl, zurückgeschaltet.In the EP 0 911 154 A1 are used as materials for a surface of a printing plate. Titanium dioxide, zinc oxide, which may be present in ceramic form, both pure and with other metallic additives in different mixing ratios, or zirconium ceramics proposed. This surface is hydrophobic when unexcited and can be rendered hydrophilic by irradiation with ultraviolet light. By heating, this switching process can be reversed again. Imaging is now done by illuminating the entire surface of the plate with ultraviolet light and masking areas of ink which are to be printed. For deletion, the image areas are then thermally, z. B. with a laser beam, switched back.

Die Hydrophobie einer derartigen Metalloxidoberfläche basiert insbesondere auf einer mit Kohlenwasserstoffen kontaminierten Oberfläche an Luft, wie durch Messungen mittels Fourier-Transform-Infrarot-Spektroskopie (FTIR), mittels Röntgen-Photoelektronen-Spektroskopie (XPS), mittels Atomic Force Microscopy (AFM) oder dergleichen festgestellt werden kann. Zwar lässt sich die Oberfläche mit Hilfe von UV-Strahlung oder Nasschemie hydrophilieren, jedoch wird sie wieder binnen weniger Stunden bei Lagerung an Luft unkontrolliert hydrophobiert. Es liegt also keine definierte, dauerhafte Hydrophobie als Ausgangszustand vor.The hydrophobicity of such a metal oxide surface is particularly based on a surface contaminated with hydrocarbons in air, such as Fourier Transform Infrared Spectroscopy (FTIR), X-ray Photoelectron Spectroscopy (XPS), Atomic Force Microscopy (AFM) or the like can be determined. Although the surface can be hydrophilized with the aid of UV radiation or wet chemistry, it is hydrophobized again in an uncontrolled manner within a few hours when stored in air. So there is no defined, permanent hydrophobicity as initial state.

Weiterhin ist beispielsweise aus EP 0 962 333 A1 bekannt, Druckformen zu verwenden, deren Druckmuster veränderbar ist. Dabei werden auf die Druckformoberfläche hydrophobe oder hydrophile Materialien aufgebracht, anschließend die Druckformoberfläche mit Wasser benetzt und daraufhin auf die Druckformoberfläche Farbe aufgebracht. Aufgrund der hydrophilen oder hydrophoben Eigenschaften wird beim Benetzungsvorgang mit Wasser in den hydrophilen Flächenbereichen das Wasser angezogen, so dass die hydrophilen Flächenbereiche bei der anschließenden Beschichtung mit Druckfarbe keine Druckfarbe mehr aufnehmen. Nach einer vorgegebenen Anzahl von Druckvorgängen wird das aufgebrachte Druckmuster wieder entfernt. Anschließend kann die Druckform mit einem neuen Druckmuster strukturiert oder beschrieben werden. Dabei ist es bekannt, als Material für die Beschichtung der Druckformoberfläche eine Thiolverbindung einzusetzen. Die Thiolverbindung wird unter Einwirkung von Wärme wieder von der Druckformoberfläche entfernt.Furthermore, for example EP 0 962 333 A1 it is known to use printing forms whose printing pattern is changeable. In this case, hydrophobic or hydrophilic materials are applied to the printing plate surface, then wetted the printing plate surface with water and then applied to the printing plate surface color. Due to the hydrophilic or hydrophobic properties, the water is attracted to the wetting process with water in the hydrophilic surface areas, so that the hydrophilic surface areas no longer absorb printing ink during the subsequent coating with printing ink. After a predetermined number of printing operations, the applied print pattern is removed again. Subsequently, the printing form can be structured or described with a new printing pattern. It is known to use a thiol compound as the material for the coating of the printing plate surface. The thiol compound is removed again under the action of heat from the printing plate surface.

Beim Vorgehen gemäß der technischen Lehre des Dokumentes EP 0 962 333 A1 ist es sehr aufwendig und zeitintensiv, eine definierte und hochgeordnete monomolekulare Schicht auf beliebigen, unbehandelten Oberflächen herzustellen. Einer möglichen technologischen Anwendung stehen insbesondere auch die Kosten des Goldsubstrates und der verwendeten selbstorganisierenden Moleküle mit Thiolgruppen (-SH) entgegen.In the procedure according to the technical teaching of the document EP 0 962 333 A1 It is very complicated and time-consuming to produce a defined and highly ordered monomolecular layer on any untreated surfaces. In particular, the costs of the gold substrate and the self-organizing molecules with thiol groups (-SH) used also stand in the way of a potential technological application.

Des Weiteren ist aus dem Dokument JP 2002-001899 bekannt, dass der Benetzungsunterschied zwischen hydrophilen und hydrophoben Bereichen auf einer in derartige Bereiche strukturierte Metalloxidoberfläche, insbesondere eine Titanoxide aufweisenden Oberfläche, durch Aufbringen einer hydrophilen Substanz verstärkt werden kann. Als Ausführungsbeispiele werden unter Anderem amphiphile organische Verbindungen, deren polare Bereiche säureartig sind, genannt.Furthermore, from the document JP 2002-001899 It is known that the wetting difference between hydrophilic and hydrophobic regions on a metal oxide surface structured in such regions, in particular a surface containing titanium oxides, can be enhanced by applying a hydrophilic substance. Examples of amphiphilic organic compounds whose polar regions are acidic are mentioned as examples.

Aufgabe der vorliegenden Erfindung ist es, eine wiederverwendbare Druckform zu schaffen, deren Druckfläche ein mehrfache Erzeugen und Löschen von Bildern gestattet.The object of the present invention is to provide a reusable printing plate whose printing surface allows multiple image creation and deletion.

Diese Aufgabe wird erfindungsgemäß durch eine wiederverwendbare Druckform mit den Merkmalen gemäß Anspruch 1 gelöst. Vorteilhafte Weiterbildungen der Erfindung sind in den abhängigen Ansprüchen charakterisiert.This object is achieved by a reusable printing forme with the features of claim 1. Advantageous developments of the invention are characterized in the dependent claims.

Erfindungsgemäß wird eine wiederverwendbare, insbesondere wiederbeschreibbare oder wiederbebilderbare, Druckform mit einer Druckfläche, welche eine mit wenigstens einer amphiphilen organischen Verbindung deren polarer Bereich einen säureartigen Charakter hat, behandelte Metalloxidoberfläche aufweist, vorgeschlagen. Die amphiphile organische Verbindung kann eine tensidartige Verbindung sein. Die amphiphile organische Verbindung kann eine mit einem aliphatischen oder aromatischen Rest substituierte anorganische oder organische Säure sein, welche wenigstens ein Element aus der IV., V. oder VI. Hauptgruppe des Periodensystems, insbesondere Kohlenstoff (C), Phosphor (P), Schwefel (S) oder Stickstoff (N), aufweist. Der Rest kann ein unsubstituiertes oder ein substituiertes Aliphat oder ein unsubstituiertes oder substituiertes Aromat sein. Der Rest kann insbesondere teilweise oder vollständig halogeniert, insbesondere fluoriert sein. Der Rest weist eine Kohlenstoffkette auf, wobei die Anzahl der Kohlenstoffe größer oder gleich 12 und kleiner oder gleich 25 ist.According to the invention, a reusable, in particular rewriteable or re-imageable printing form having a printing surface which has a metal oxide surface treated with at least one amphiphilic organic compound whose polar region has an acidic character has been proposed. The amphiphilic organic Compound may be a surfactant-like compound. The amphiphilic organic compound may be an aliphatic or aromatic radical-substituted inorganic or organic acid which comprises at least one element of IV, V or VI. Main group of the Periodic Table, in particular carbon (C), phosphorus (P), sulfur (S) or nitrogen (N), having. The radical may be an unsubstituted or a substituted aliphatic or an unsubstituted or substituted aromatic. The rest may in particular be partially or completely halogenated, in particular fluorinated. The remainder has a carbon chain wherein the number of carbons is greater than or equal to 12 and less than or equal to 25.

Die amphiphile organische Verbindung kann in einer Ausführungsform eine Hydroxamsäure oder eine Phosphonsäure sein. Insbesondere kann die amphiphile organische Verbindung in einer bevorzugten Ausführungsform der erfindungsgemäßen wiederverwendbaren Druckform n-Heptadecan-Hydroxamsäure {CH3-(CH2)16-C(O) NH-OH} oder n-Octadecan-Phosphonsäure {CH3-(CH2)17-P(O)-(OH)2} sein. Die Metalloxidoberfläche kann eine nativ oxidierte Titanoberfläche, nativ oxidierte Edelstahloberfläche, beispielsweise Hastelloy, oder nativ oxidierte Aluminimnoberfläche sein. Der Erfindung liegt damit unter anderem der Gedanke zugrunde, technisch rauhe Metalloxidoberflächen mit amphiphilen, tensidartigen organische Verbindungen, zu behandeln, insbesondere amphiphile, tensidartige organische auf technischen rauhen Metalloxidoberflächen aufzubringen oder zu beschichten. Die wiederverwendbare Druckform kann damit auch insbesondere als (im Nanobereich) wiederheschichtbare Druckform bezeichnet werden.The amphiphilic organic compound may in one embodiment be a hydroxamic acid or a phosphonic acid. In particular, in a preferred embodiment of the reusable printing form according to the invention, the amphiphilic organic compound may be n-heptadecane hydroxamic acid {CH3- (CH2) 16-C (O) NH-OH} or n-octadecane phosphonic acid {CH3- (CH2) 17-P (O) - (OH) 2}. The metal oxide surface may be a native oxidized titanium surface, native oxidized stainless steel surface, e.g., Hastelloy, or natively oxidized aluminum surface. The invention is therefore based, inter alia, on the idea of treating technically rough metal oxide surfaces with amphiphilic, surfactant-like organic compounds, in particular applying or coating amphiphilic, surfactant-like organic on technically rough metal oxide surfaces. The reusable printing form can thus also be referred to in particular as a (in the nano range) re-coatable printing form.

In anderen Worten ausgedrückt, die erfindungsgemäße Druckform weist eine Oberfläche auf, welche durch Einwirkung einer amphiphilen organischen Verbindung auf eine Metalloxidoberfläche erhalten wird. Details des zugrundeliegenden Verfahrens der Bereitstellung einer erfindungsgemäßen Druckform sind weiter unten beschrieben.In other words, the printing form according to the invention has a surface which is obtained by the action of an amphiphilic organic compound on a metal oxide surface. Details of the underlying method of providing a printing form according to the invention are described below.

Die erfindungsgemäße wiederbeschreibbare Druckform ist mit besonderem Vorteil in einem Offsetdruckverfahren, insbesondere in direktem oder in indirektem Flachdruck, einsetzbar. Sie kann daher auch insbesondere als wiederbeschreibbare Offsetdruckform oder als (im Nanobereich) wiederbeschichtbare Offsetdruckform bezeichnet werden.The rewritable printing form according to the invention is particularly advantageously in an offset printing process, in particular in direct or in indirect planographic printing, used. It can therefore also be referred to in particular as a rewritable offset printing form or as a (in the nano range) recoatable offset printing form.

Mit Hilfe von amphiphilen, tensidartigen organischen Verbindungen ist es möglich, reproduzierbar definiert hydrophobe Metalloxidoberflächen, insbesondere Titanoxidoberflächen, herzustellen. Die durch eine amphiphile organische Verbindung behandelte Druckfläche kann hydrophobiert sein. Alternativ dazu ist es auch möglich, mittels hydrophil substituierten oder terminierten amphiphilen, tensidartigen Verbindungen reproduzierbar definiert hydrophile Metalloxidoberflächen herzustellen. Eine durch eine hydrophil substituierte amphiphile, tensidartige Verbindung behandelte Druckfläche kann hydrophil sein. In bevorzugter Ausführungsform sind die amphiphilen, tensidartigen organischen Verbindungen n-Heptadecan-Hydroxamsäure (CH3-(CH2)16-C(O)-NH-OH)-auch deren Tautomerieform- und/oder n-Octadecan-Phosphonsäure (CH3-(CH2)17-P(O)-(OH)2). Die Metalloxidoberfläche wird in einen hydrophoben, farbführenden Zustand gebracht, welcher als Ausgangszustand für eine Bebilderung für ein Offsetdruckverfahren dienen kann. Die Kontaktwinkel, gemessen gegen Wasser, dieser hydrophoben Metalloxidoberflächen sind Werte aus der Zahlenmenge des Intervalls reeller Zahlen zwischen 80 und 120 Grad. Die Metalloxidoberfläche kann dann durch kontrollierte Energiezufuhr in einen hydrophilen, farbführenden Zustand gebracht werden. Die Kontaktwinkel, gemessen gegen Wasser, im hydrophilen Zustand sind Werte aus der Zahlemnenge des Intervalls reeller Zahlen zwischen 0 und 10 Grad. Der Hub zwischen den beiden Zuständen ist damit hinreichend groß für Offsetdruck. Die erfindungsgemäße Druckform ist schaltbar, insbesondere zwischen einem hydrophilen und einem hydrophoben Zustand. Nach einer Strukturierung der erfindungsgemäßen wiederbeschreibbaren Druckform in Bereiche im hydrophilen und Bereich im hydrophoben Zustand kann ein Offsetdruckverfahren durchgeführt werden.With the help of amphiphilic, surfactant-like organic compounds, it is possible to produce reproducibly defined hydrophobic metal oxide surfaces, in particular titanium oxide surfaces. The pressure surface treated by an amphiphilic organic compound may be hydrophobic. Alternatively, it is also possible to reproducibly produce hydrophilic metal oxide surfaces by means of hydrophilically substituted or terminated amphiphilic surfactant-like compounds. A printing surface treated by a hydrophilic substituted amphiphilic surfactant-like compound may be hydrophilic. In a preferred embodiment, the amphiphilic, surfactant-like organic compounds n-heptadecane-hydroxamic acid (CH3- (CH2) 16-C (O) -NH-OH) -also tautomeric form and / or n-octadecane-phosphonic acid (CH3- (CH2 ) of 17-P (O) - (OH) 2). The metal oxide surface is brought into a hydrophobic, ink-bearing state, which can serve as the starting state for imaging for an offset printing process. The contact angles, measured against water, of these hydrophobic metal oxide surfaces are values from the set of numbers of the real number interval between 80 and 120 degrees. The metal oxide surface can then be brought into a hydrophilic, ink-carrying state by controlled energy input. The contact angles, measured against water, in the hydrophilic state are values from the number of times the interval of real numbers between 0 and 10 degrees. The stroke between the two states is thus sufficiently large for offset printing. The printing form according to the invention is switchable, in particular between a hydrophilic and a hydrophobic state. After structuring the rewritable printing form according to the invention into regions in the hydrophilic and hydrophobic state, an offset printing process can be carried out.

Die erfindungsgemäße wiederverwendbare Druckform kann in verschiedenen Ausführungsformen mit unterschiedlichen topologischen und geometrischen Eigenschaften ausgeführt sein. Die erfindungsgemäße Druckform kann als Oberfläche eines Vollzylinders oder als Oberfläche eines Hohlzylinders realisiert sein. Der Zylinder, voll oder hohl, kann insbesondere ein gerader Kreiszylinder sein. Unter Oberfläche ist insbesondere die laterale Oberfläche zu verstehen. Alternativ dazu kann die erfindungsgemäße Druckform auch als eine Hülse oder als eine Platte ausgebildet sein. Eine Hülse weist zwei Oberflächen (Innenfläche und Außenfläche) auf und hat zwei Ränder. Die Hülse kann zylinderförmig mit gleichmäßigem Durchmesser, insbesondere Innendurchmesser oder Außendurchmesser, (kreishohlzylinderförmig) oder konisch, das heißt mit variablen, insbesondere gleichförmig zu- oder abnehmendem Durchmesser, insbesondere Innendurchmesser oder Außendurchmesser, sein. Innendurchmesser und Außendurchmesser können unterschiedlich variieren. Sie ist damit im topologischen Sinn ein nichteinfach zusammenhängendes Objekt. Eine Platte weist zwei Oberflächen (Oberseite und Unterseite) auf und hat einen Rand. Sie ist damit im topologischen Sinn ein einfach zusammenhängendes Objekt. Die Platte kann insbesondere quaderförmig oder rechteckig sein.The reusable printing form according to the invention can be embodied in various embodiments with different topological and geometric properties. The printing form according to the invention can be realized as the surface of a solid cylinder or as the surface of a hollow cylinder. The cylinder, full or hollow, can in particular be a straight circular cylinder. Under surface is to be understood in particular the lateral surface. Alternatively, the printing form according to the invention may also be formed as a sleeve or as a plate. A sleeve has two surfaces (inner surface and outer surface) and has two edges. The sleeve may be cylindrical with a uniform diameter, in particular inner diameter or outer diameter, (circular hollow cylindrical) or conical, that is with variable, in particular uniformly increasing or decreasing diameter, in particular inner diameter or outer diameter. Inner diameter and outer diameter can vary differently. It is thus in the topological sense a not simply coherent object. A plate has two surfaces (top and bottom) and has an edge. It is thus in the topological sense a simply coherent object. The plate may in particular be cuboid or rectangular.

Die erfindungsgemäße wiederverwendbare Druckform kann in einen Druckwerk, insbesondere in einem Offsetdruckwerk, zum Einsatz kommen. Sie kann die Oberfläche eines Druckzylinders bilden oder auf der Oberfläche eines Zylinders aufgenommen sein. Ein erfindungsgemäßes Druckwerk zeichnet sich daher durch wenigstens eine erfindungsgemäße wiederverwendbare Druckform aus. Das erfindungsgemäße Druckwerk kann Teil einer Druckmaschine, insbesondere einer Offsetdruckmaschine, sein. Die Druckmaschine kann eine bogenverarbeitende oder eine bahnverarbeitende Druckmaschine sein. Eine bogenverarbeitende Druckmaschine kann einen Anleger, eine Anzahl von Druckwerken und einen Ausleger aufweisen. Eine erfindungsgemäße Druckmaschine weist wenigstens ein erfindungsgemäßes Druckwerk auf.The reusable printing form according to the invention can be used in a printing unit, in particular in an offset printing unit. It may form the surface of a printing cylinder or be received on the surface of a cylinder. An inventive printing unit is therefore characterized by at least one reusable printing form according to the invention. The printing unit according to the invention may be part of a printing press, in particular an offset printing press. The printing press may be a sheet-fed or a web-processing press. A sheet-fed printing machine may include a feeder, a number of printing units, and a cantilever. A printing press according to the invention has at least one printing unit according to the invention.

Im erfinderischen Zusammenhang mit der erfindungsgemäßen wiederverwendbaren Druckform steht auch ein erfindungsgemäßes Verfahren zur Bebilderung einer wiederverwendbaren, insbesondere wiederbeschreibbaren oder wiederbebilderbaren, Druckform mit diversen vorteilhaften Weiterbildungen. Dem erfindungsgemäßen Verfahren liegt das Bestreben zugrunde, einen Kreisprozess zu schaffen, in welchem eine erfindungsgemäße Druckform mehrfach bebildert und gelöscht werden kann, so dass sich die Druckform insbesondere für den Offsetdruck eignet. Das erfindungsgemäße Verfahren zur Bebilderung kann sowohl innerhalb als auch außerhalb eines Druckwerks oder einer Druckmaschine durchgeführt werden. Die Druckfläche kann bildmäßig durch Belichtung durch eine maskenartige Vorlage verarbeitet werden. Bevorzugt ist aber die punktweise direkte Belichtung mit digitaler Information.In the inventive context with the reusable printing form according to the invention is also an inventive method for imaging a reusable, in particular rewriteable or wiederbebilderbaren, printing form with various advantageous developments. The inventive method is based on the desire to provide a cyclic process in which a printing form according to the invention can be repeatedly imaged and erased, so that the printing form is particularly suitable for offset printing. The inventive method for imaging can be carried out both inside and outside a printing unit or a printing press. The printing surface can be processed imagewise by exposure through a mask-like template. But preferred is the pointwise direct exposure with digital information.

Das erfindungsgemäße Verfahren zur Bebilderung einer wiederverwendbaren Druckform umfasst die folgenden Schritte: Es wird eine wiederverwendbare, insbesondere wiederbeschreibbare oder wiederbebilderbare Druckform mit einer Druckfläche, welche eine mit wenigstens einer amphiphilen organischen Verbindung behandelte Metalloxidoberfläche aufweist, bereitgestellt. Die wiederbeschreibbare Druckform kann insbesondere so ausgeführt sein, wie es oben in dieser Darstellung näher beschrieben ist. Ein Bild wird durch selektive, insbesondere räumlich und zeitlich selektive, punktweise Energiezufuhr auf der Druckfläche erzeugt. Anders ausgedrückt, es wird eine digitale Bebilderung ausgeführt. Durch die Bebilderung wird die Druckform von einem hydrophoben in einen hydrophilen Zustand überführt. Nach einem Bedrucken eines Bedruckstoffes, insbesondere in einem Offsetdruckverfahren, wird das Bild durch großflächige Energiezufuhr gelöscht. Um die wiederverwendbare Druckform für eine neue Bebilderung vorzubereiten, wird die Druckfläche der Druckform mit einer Lösung einer amphiphilen organischen Verbindung behandelt. Anders ausgedrückt, das Bereitstellen der Druckform wird iteriert oder wiederholt. Die Schritte des Bebilderns und Löschens können somit mehrfach mit verschiedenen Druckmustern oder Sujets durchgeführt werden. Das erfindungsgemäße Verfahren ermöglicht einen Kreisprozess.The method according to the invention for imaging a reusable printing form comprises the following steps: A reusable, in particular rewriteable or reproducible printing form having a printing surface which has a metal oxide surface treated with at least one amphiphilic organic compound is provided. The rewritable printing form can in particular be designed as described in greater detail above in this illustration. An image is generated by selective, in particular spatially and temporally selective, pointwise energy supply to the printing surface. In other words, a digital imaging is performed. The imaging transforms the printing form from a hydrophobic to a hydrophilic state. After printing on a printing material, in particular in an offset printing process, the image is erased by large-area energy supply. To prepare the reusable printing form for a new imaging, the printing surface of the printing form is treated with a solution of an amphiphilic organic compound. In other words, the provision of the printing form is iterated or repeated. The steps of imaging and deleting can thus be carried out several times with different print patterns or subjects. The method according to the invention allows a cyclic process.

Im erfindungsgemäßen Verfahren kann in vorteilhafter Weise der Schritt des Bereitstellens der wiederverwendbaren Druckform die Behandlung der Druckfläche mit einer amphiphilen organischen Verbindung, deren polarer Bereich einen säureartigen Charakter hat, umfassen: Die Druckfläche wird mit einer wässrigen Lösung (auch reines Wasser) oder mit einer alkoholischen Lösung, insbesondere Ethanol, benetzt, welche wenigstens eine amphiphile organische Verbindung in geeigneter Konzentration, nahe an der Sättigungsgrenze, bevorzugt in der Konzentration 1mMol/l, enthält. Durch diesen Schritt wird die Metalloxidoberfläche einer amphiphilen organischen Verbindung ausgesetzt. In anderen Worten, die amphiphile organische Verbindung wird aufgebracht. Dieses Aufbringen oder Terminieren kann in vorteilhafter Weiterbildung in einem Ultraschallbad erfolgen. Das Aufbringen, Terminieren oder Belegen der Metalloxidoberfläche, insbesondere Titandioxidoberfläche, mit den Molekülen der amphiphilen organischen Verbindung erfolgt bereits in einigen Sekunden, wenn die Metalloxidoberfläche der Lösung ausgesetzt, beispielsweise in die Lösung eingetaucht wird, um eine makroskopisch feststellbare Änderung der Benetzungseigenschaft hervorzurufen.In the method according to the invention, the step of providing the reusable printing plate may advantageously comprise the treatment of the printing surface with an amphiphilic organic compound whose polar region has an acidic character: The printing surface is treated with an aqueous solution (also pure water) or with an alcoholic Solution, in particular ethanol, which contains at least one amphiphilic organic compound in a suitable concentration, close to the saturation limit, preferably in the concentration of 1 mmol / l. Through this step The metal oxide surface is exposed to an amphiphilic organic compound. In other words, the amphiphilic organic compound is applied. This application or termination can take place in an advantageous embodiment in an ultrasonic bath. The application, termination or coating of the metal oxide surface, in particular titanium dioxide surface, with the molecules of the amphiphilic organic compound takes place in a few seconds when the metal oxide surface is exposed to the solution, for example immersed in the solution, to cause a macroscopically detectable change in the wetting property.

Im erfindungsgemäßen Verfahren kann in vorteilhafter Weise der Schritt des Bereitstellens der wiederverwendbaren Druckform die folgenden Schritte umfassen: Die Druckfläche wird durch Bestrahlung der Metalloxidoberfläche mit einer UV-Lichtquelle gereinigt. Nicht anhaftende Verbindungen von der behandelten Metalloxidoberfläche werden entfernt. Diese Reinigung der behandelten Metalloxidoberfläche kann insbesondere mit einer alkoholischen Lösung, bevorzugt mit Ethanol, erfolgen. Die behandelte, gereinigte Metalloxidoberfläche wird mit einem wasserfreien Prozessgas, insbesondere mit Stickstoff, getrocknet.In the method according to the invention, the step of providing the reusable printing plate may advantageously comprise the following steps: The printing surface is cleaned by irradiating the metal oxide surface with a UV light source. Non-adherent compounds are removed from the treated metal oxide surface. This cleaning of the treated metal oxide surface can be carried out in particular with an alcoholic solution, preferably with ethanol. The treated, cleaned metal oxide surface is dried with an anhydrous process gas, in particular with nitrogen.

In vorteilhafter Weise kann das erfindungsgemäße Verfahren, insbesondere das Bereitstellen der widerverwendbaren Druckform, die folgenden Schritte zur Präparation der Metalloxidoberfläche umfassen. Die Metalloxidoberfläche kann eine Oberfläche aus der Menge der folgenden Oberflächen sein: Nativ oxidierte Titanoberfläche, nativ oxidierte Edelstahloberfläche, nativ oxidierte Aluminiumoberfläche, Titanat und Zirkonat. Genauer gesagt, einer ersten Bereitstellung der wiederverwendbaren Druckform können folgende Schritte zur Präparation vorgeordnet sein. Die Metalloxidoberfläche wird vorgereinigt. Eine Reinigung kann den Schritt des Abspülens mit Aceton, Ethanol, Isopropanol, Ethylacetat oder einem anderen geeigneten organischen Lösungsmittel umfassen. Ein Zweck ist insbesondere die Entfettung der Oberfläche. Die Metalloxidoberfläche kann dann einer wässrigen Lösung der Zusammensetzung ein Volumenanteil 25%ige NH4OH Lösung und ein Volumenanteil 30%ige H2O2 Lösung in vier Volumenanteilen H2O bei einer Temperatur von etwa 60°C etwa für die Dauer von 10 Minuten ausgesetzt werden.Advantageously, the method according to the invention, in particular the provision of the reusable printing form, may comprise the following steps for the preparation of the metal oxide surface. The metal oxide surface may be a surface of the amount of the following surfaces: native oxidized titanium surface, native oxidized stainless steel surface, native oxidized aluminum surface, titanate and zirconate. More specifically, a first provision of the reusable printing form may be preceded by the following steps for preparation. The metal oxide surface is prepurified. Purification may include the step of rinsing with acetone, ethanol, isopropanol, ethyl acetate or other suitable organic solvent. One purpose is in particular the degreasing of the surface. The metal oxide surface can then be an aqueous solution of the composition a volume of 25% NH 4 OH solution and a volume of 30% H 2 O 2 solution in four volumes of H 2 O at a temperature of about 60 ° C for about 10 minutes get abandoned.

Dieser Schritt ist insbesondere vorteilhaft für eine nativ oxidierte Titanoberfläche. Ein Zweck ist insbesondere eine Oxidation von sich auf der Metalloxidoberfläche befindlichen Kohlenwasserstoffe. Eine Hauptreinigung kann durch ein Ätzen der Metalloxidoberfläche erfolgen. Das Ätzen kann durch eine Lösung der Zusammensetzung ein Volumenanteil 40%ige HF Lösung und drei Volumenanteile 30%ige H2O2 in zwanzig Volumenanteilen H2O bei Zimmertemperatur für die Dauer von etwa 1 Minute durchgeführt werden. Ein Zweck ist insbesondere das Abtragen einiger einzelner Metalloxidlagen und das Einstellen einer definierten Rauigkeit der Metalloxidoberfläche. Ein definierter Oxidfilm, insbesondere eine hydrophile Oberfläche kann durch eine Oxidation der gereinigten und geätzten Oberfläche erreicht werden. Für die Oxidation kann die Oberfläche einer Lösung der Zusammensetzung ein Volumenanteil 25%ige NH4OH Lösung und ein Volumenanteil 30%ige H2O2 Lösung in vier Volumenanteilen H2O bei einer Temperatur von etwa 60°C ausgesetzt werden. Die Schritte des Ätzens und des Erzeugens eines definierten Oxidfilms ist insbesondere vorteilhaft für eine nativ oxidierte Titanoberfläche.This step is particularly advantageous for a native oxidized titanium surface. One purpose is, in particular, oxidation of hydrocarbons located on the metal oxide surface. A main cleaning can be done by etching the metal oxide surface. The etching may be performed by a solution of the composition comprising 40% HF solution by volume and three volumes of 30% H 2 O 2 in twenty volumes of H 2 O at room temperature for about 1 minute. One purpose is, in particular, the removal of a few individual metal oxide layers and the setting of a defined roughness of the metal oxide surface. A defined oxide film, in particular a hydrophilic surface, can be achieved by oxidation of the cleaned and etched surface. For the oxidation, the surface of a solution of the composition may be exposed to a volume fraction of 25% NH 4 OH solution and a volume fraction of 30% H 2 O 2 solution in four volumes of H 2 O at a temperature of about 60 ° C. The steps of etching and producing a defined oxide film is particularly advantageous for a native oxidized titanium surface.

In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens wird ein Bild auf der Druckfläche durch selektive punktweise Energiezufuhr zum Hydrophilieren mit Hilfe von elektromagnetischer Strahlung erzeugt. Die elektromagnetische Strahlung kann im Bereich von 150 bis 1200 Nanometern Wellenlänge liegen. Insbesondere kann die Energiezufuhr im infraroten Spektralbereich erfolgen. Die digitale Bebilderung kann durch einen Laser, bevorzugt mit ca. 1100 Nanometern Wellenlänge, erfolgen. Das Bild wird in der bevorzugten Ausführungsform durch großflächige Energiezufuhr zum Hydrophobieren mittels einer Bestrahlung der Druckfläche mit elektromagnetischer Strahlung gelöscht. Insbesondere kann die großflächige Bestrahlung im ultravioletten Spektralbereich erfolgen. Eine bevorzugte Lichtquelle ist ein Excimerstrahler.In a preferred embodiment of the method according to the invention, an image is generated on the printing surface by selective pointwise energy supply for hydrophilizing with the aid of electromagnetic radiation. The electromagnetic radiation can be in the range of 150 to 1200 nanometers wavelength. In particular, the energy can be supplied in the infrared spectral range. The digital imaging can be done by a laser, preferably with about 1100 nanometers wavelength. The image is erased in the preferred embodiment by large-scale energy supply to the hydrophobing by means of an irradiation of the printing surface with electromagnetic radiation. In particular, the large-area irradiation can be carried out in the ultraviolet spectral range. A preferred light source is an excimer radiator.

In einer vorteilhaften Ausführungsform des erfindungsgemäßen Verfahrens wird nach dem Bedrucken des Bedruckstoffes die Druckfläche von Druckfarbe gereinigt oder befreit. Insbesondere kann eine Reinigung unter Verwendung eines konventionellen Farbreinigers oder eines konventionellen Waschmittels, einer tensidhaltigen wässrigen Lösung, beispielsweise dem unter dem Namen EUROSTAR vertriebenen Waschmittel, vorgenommen werden.In an advantageous embodiment of the method according to the invention, the printing surface of printing ink is cleaned or freed after printing of the printing material. In particular, a cleaning can be carried out using a conventional color cleaner or a conventional detergent, a surfactant-containing aqueous solution, for example the detergent sold under the name EUROSTAR.

In einer vorteilhaften Weiterbildung des erfindungsgemäßen Verfahrens wird nach der Erzeugung eines Bildes durch selektive punktweise Energiezufuhr zum Hydrophilieren auf der Druckfläche der mit einer amphiphilen organischen Verbindung behandelten Metalloxidoberfläche, insbesondere Titandioxidoberfläche, die strukturiere Druckfläche mit wenigstens einer hydrophil substituierten oder terminierten amphiphilen, organischen Verbindung behandelt. Der Substituent kann eine Kopfgruppe am Molekül der Verbindung bilden. Die amphiphile, organische Verbindung kann eine Verbindung, wie sie in dieser Darstellung beschrieben ist, sein. Substituenten können insbesondere eine oder mehrere NH2-Gruppen, eine oder mehrere COOH-Gruppen oder eine oder mehrere OH-Gruppen sein. Die durch die selektive punktweise Energiezufuhr entstandenen Bereiche können auf diese Weise mit Molekülen der substituierten oder terminierten amphiphilen, organischen Verbindung belegt oder terminiert werden. Dieser zusätzliche Verfahrensschritt führt in vorteilhafter Weise zu einer Verstärkung und/oder Stabilisierung der Hydrophilie der punktweise bebilderten Bereiche.In an advantageous development of the method according to the invention, after the formation of an image by selective pointwise energy supply for hydrophilization on the pressure surface of the treated with an amphiphilic organic compound metal oxide surface, in particular titanium dioxide surface, the structured pressure surface treated with at least one hydrophilic substituted or terminated amphiphilic organic compound. The substituent may form a head group on the molecule of the compound. The amphiphilic organic compound may be a compound as described in this presentation. Substituents may in particular be one or more NH.sub.2 groups, one or more COOH groups or one or more OH groups. The areas formed by the selective point-wise energy supply can be occupied or terminated in this way with molecules of the substituted or terminated amphiphilic organic compound. This additional process step advantageously leads to a reinforcement and / or stabilization of the hydrophilicity of the dot-wise imaged areas.

Die Erfindung stellt eine wiederverwendbare, insbesondere wiederbeschreibbare oder wiederbebilderbare, Druckform mit verlässlich reproduzierbarem Verhalten bezüglich des Bebilderungs- sowie Löschvorgangs zur Verfügung. Die Erzeugung eines Bildes oder einer Struktur auf der Druckfläche ist einfach und verlässlich. Es ist nicht notwendig, dass sich eine Monolage der amphiphilen organischen Verbindung auf der Metalloxidoberfläche selbstorganisierend aufbaut. Das Verfahren zur Bebilderung erfordert damit eine geringe Bereitstellungszeit der erfindungsgemäßen Druckform. Das Aufbringen von oben erwähnten Verbindungen innerhalb eines Zeitraums von wenigen Minuten, reicht aus, um eine genügend starke Hydrophobierung der Metalloxidoberflächen, insbesondere für einen Einsatz im einem Offsetdruckverfahren, zu erreichen. Insbesondere ermöglicht das erfindungsgemäße Verfahren die Hydrophobierung von rauen Metalloxidoberflächen, wie sie in gängigen industriellen Produktionsverfahren hergestellt werden.The invention provides a reusable, especially rewriteable or re-imageable, printing form with reliably reproducible behavior with regard to the imaging and erasing process. The creation of an image or structure on the printing surface is simple and reliable. It is not necessary for a monolayer of the amphiphilic organic compound to self-assemble on the metal oxide surface. The process for imaging thus requires a short provision time of the printing form according to the invention. The application of above-mentioned compounds within a period of a few minutes, is sufficient to achieve a sufficiently strong hydrophobing of the metal oxide surfaces, in particular for use in an offset printing process. In particular, the process according to the invention enables the hydrophobing of rough metal oxide surfaces, as are produced in current industrial production processes.

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 einer vorteilhaften Ausführungsform des erfindungsgemäßen Verfahrens zur Bebilderung einer erfindungsgemäßen wiederverwendbaren Druckform, und
Figur 2
eine schematische Darstellung der Strukturierung einer erfindungsgemäßen wiederverwendbaren Druckform, deren Druckfläche eine mit wenigstens einer amphiphilen organischen Verbindung behandelte Metalloberfläche aufweist, mittels des erfindungsgemäßen Verfahrens.
Further advantages and advantageous embodiments and developments of the invention will be described with reference to the following figures and their descriptions. It shows in detail:
FIG. 1
a flow diagram of an advantageous embodiment of the method according to the invention for imaging a reusable printing form according to the invention, and
FIG. 2
a schematic representation of the structuring of a reusable printing form according to the invention, the pressure surface has a treated with at least one amphiphilic organic compound metal surface, by means of the method according to the invention.

Ohne eine Einschränkung der Allgemeinheit hinsichtlich der amphiphilen organischen Verbindungen und hinsichtlich der Metalloxidoberflächen wird eine vorteilhafte Ausführungsform der erfindungsgemäßen wiederverwendbaren Druckform und eine vorteilhafte Ausführungsform eines erfindungsgemäßen Verfahren zur Bebilderung einer wiederverwendbaren Druckform anhand einer nativ oxidierten Titanoberfläche und anhand n-Octadecan-Phosphonsäure beispielhaft erläutert.Without restricting the general public in terms of the amphiphilic organic compounds and with respect to the metal oxide surfaces, an advantageous embodiment of the reusable printing form according to the invention and an advantageous embodiment of a method according to the invention for imaging a reusable printing form using a natively oxidized titanium surface and n-octadecane-phosphonic acid are exemplified.

Die Figur 1 zeigt ein Ablaufdiagramm einer vorteilhaften Ausführungsform des erfindungsgemäßen Verfahrens zur Bebilderung einer erfindungsgemäßen wiederverwendbaren Druckform. Proben mit Titanoberflächen können von der Unternehmung Goodfellow erworben werden. Um die zu behandelnde Titanoberfläche zunächst zu reinigen, wird diese mit einer Licht im ultravioletten Wellenlängenbereich bestrahlt. Der Verfahrensschritt der Bereitstellung 10 einer wiederverwendbaren Druckform umfasst das Aufbringen der amphiphilen, tensidartigen organischen Verbindungen: Die Titanoberfläche wird mit einer Lösung benetzt, die oben genannte Verbindungen in geeigneter Konzentration enthält. Die Titanoberfläche wird in 1mM ethanolische Lösung aus n-Octadecan-Phosphonsäure (Stearin-Phosphonsäure) bei Zimmertemperatur für die Dauer von etwa 5 Minuten getaucht. Eine Reinigung der behandelten Titanoberfläche wird durch Spülen mit Ethanol bewirkt, welches die nichtanhaftende Verbindungen aus der n-Octadecan-Phosphonsäure Lösung entfernt. Die gereinigten, behandelten Titanoberfläche wird mit einem wasserfreien, einem sogenannten trockenen Prozessgas, hier Stickstoff, vollständig getrocknet.The FIG. 1 shows a flowchart of an advantageous embodiment of the method according to the invention for imaging a reusable printing form according to the invention. Titanium surface samples can be purchased from Goodfellow. In order to first clean the titanium surface to be treated, it is irradiated with a light in the ultraviolet wavelength range. The step of providing a reusable printing plate comprises applying the amphiphilic surfactant-like organic compounds: The titanium surface is wetted with a solution containing the above-mentioned compounds in suitable concentration. The titanium surface is immersed in 1 mM ethanolic solution of n-octadecane phosphonic acid (stearic phosphonic acid) at room temperature for about 5 minutes. A cleaning of the treated titanium surface is effected by rinsing with ethanol, which removes the non-adherent compounds from the n-octadecane-phosphonic acid solution. The cleaned, treated titanium surface is completely dried with an anhydrous, a so-called dry process gas, here nitrogen.

Derartig präparierte oder bereitgestellte Titanoberflächen sind hydrophob und können mit intensiven UV- oder IR-Lichtquellen bebildert werden. Mittels Bebilderung werden hydrophile Bereiche erzeugt. Als Lichtquelle wird in einer vorteilhaften Ausführungsform ein diodengepumter Yttrium-dotierter Faserlaser der Firma SDL eingesetzt. Lokale, selektive, digitale Bebilderung kann mittels 30 Mikrometer großen Lichtflecken (spots, 1/e2 Abfall) vorgenommen werden. Die Wellenlänge beträgt 1100 Nanometer, die Leistung 3 Watt und die Intensität oder Fluenz 15 bis 30 Joule/Quadratzentimeter. Im Verfahrensschritt der Bebilderung 12 von Titanoberflächen mit einer Infrarotlaser entsteht eine sichtbare Struktur oder ein sichtbares Muster.Such prepared or prepared titanium surfaces are hydrophobic and can be imaged with intense UV or IR light sources. By means of imaging hydrophilic areas are generated. In an advantageous embodiment, a diode-pumped yttrium-doped fiber laser from SDL is used as the light source. Local, selective, digital imaging can be done using 30 micron spots of light (spots, 1 / e 2 waste). The wavelength is 1100 nanometers, the power 3 watts and the intensity or fluence 15 to 30 joules / square centimeter. In the step of imaging titanium surfaces with an infrared laser, a visible structure or pattern is formed.

Beispiele für diese sichtbaren Strukturen mit unterschiedlichem Farbeindruck sind in der folgenden Tabelle für eine mit einer amphiphilen organischen Vebindung, deren polarer Bereich einen säureartigen Charakter hat, behandelte Titanoberfläche zusammengestellt: Farbeindruck Muster v [cm/s] Einstrahldauer [µs] Diodenstrom I [A] Leistung P [W] Fluenz [J/cm2] Energie pro Pixel W[mJ] messing vollfl. 25 72 16 1,95 17,7 0,13 dunkelblau vollfl. 25 72 22 3,0 27,2 0,19 kupfer vollfl. 25 72 25 3,7 33,5 0,24 graukupfer pixelfl. 25 72 25 3,7 33,5 0,24 grauviolett pixelfl. 25 72 22 3,0 27,2 0,19 beige pixelfl. 25 72 25 1,95 17,7 0,13 Examples of these visible structures with different color impressions are listed in the following table for a titanium surface treated with an amphiphilic organic compound whose polar region has an acid-like character: color impression template v [cm / s] Irradiation duration [μs] Diode current I [A] Power P [W] Fluence [J / cm 2 ] Energy per pixel W [mJ] Brass vollfl. 25 72 16 1.95 17.7 0.13 dark blue vollfl. 25 72 22 3.0 27.2 0.19 copper vollfl. 25 72 25 3.7 33.5 0.24 gray copper pixelfl. 25 72 25 3.7 33.5 0.24 gray violet pixelfl. 25 72 22 3.0 27.2 0.19 beige pixelfl. 25 72 25 1.95 17.7 0.13

Für eine einfache Titanoberfläche wurden dagegen folgende Farbeindrücke beobachtet: Farbeindruck v [cm/s] Einstrahldauer [µs] Diodenstrom I[A] Leistung P [W] Fluenz [J/cm2] Energie/ Pixel W [mJ] kupfer 25 72 25 3,7 33,5 0,24 dunkelblau 25 72 22 3,0 27,2 0,19 blauviolet 25 72 19 2,5 22,6 0,16 messing 25 72 16 1,95 17,7 0,13 bronze 25 72 17 2,1 19,0 0,14 dunkelblau 25 72 22 3,0 27,2 0,19 blau 12,5 144 22 3,0 54,4 0,38 goldfarben 25 72 32 5,0 45,3 0,32 For a simple titanium surface, however, the following color impressions were observed: color impression v [cm / s] Irradiation duration [μs] Diode current I [A] Power P [W] Fluence [J / cm 2 ] Energy / Pixel W [mJ] copper 25 72 25 3.7 33.5 0.24 dark blue 25 72 22 3.0 27.2 0.19 blue violet 25 72 19 2.5 22.6 0.16 Brass 25 72 16 1.95 17.7 0.13 bronze 25 72 17 2.1 19.0 0.14 dark blue 25 72 22 3.0 27.2 0.19 blue 12.5 144 22 3.0 54.4 0.38 gold 25 72 32 5.0 45.3 0.32

Für eine mehrfach behandelte Titanoberfläche - ohne Behandlung mit amphiphiler chemischer Verbindung, deren polarer Bereich einen säureartigen Charakter hat, wurden folgende Beispiele beobachtet: Farbeindruck Muster [mm x mm] v [cm/s] Einstrahldauer [µs] Diodenstrom I[A] Leistung P [W] Fluenz [J/cm2] Energie/ Pixel W[mJ] dunkelblau vollfl. 3x7 25 72 22 3,0 27,2 0,19 dunkelblau glänzend vollfl. 3x7 25 2 x 72 22 3,0 2 x 27,2 2 x 0,19 schwarzblau vollfl. 3x 7 25 3 x 72 25 3,0 3 x 27,2 3 x 0,19 grau-blau pixelfl* 3x7 25 72 25 3,0 27,2 0,19 graudunklblau pixelfl* 1,5x7 12 144 25 3,0 54,4 0,38 For a multi-treated titanium surface - without treatment with an amphiphilic chemical compound whose polar region has an acid-like character, the following examples were observed: color impression Pattern [mm x mm] v [cm / s] Irradiation duration [μs] Diode current I [A] Power P [W] Fluence [J / cm 2 ] Energy / Pixel W [mJ] dark blue vollfl. 3x7 25 72 22 3.0 27.2 0.19 dark blue shiny vollfl. 3x7 25 2 x 72 22 3.0 2 x 27.2 2 x 0.19 black blue vollfl. 3x 7 25 3 x 72 25 3.0 3 x 27.2 3 x 0.19 gray-blue pixelfl * 3x7 25 72 25 3.0 27.2 0.19 graudunklblau pixelfl * 1,5x7 12 144 25 3.0 54.4 0.38

Die Variable v bezeichnet die Abtastgeschwindigkeit (Scangeschwindigkeit) der Druckfläche. Ein Muster kann vollflächig (vollfl.) oder pixelflächig (pixelfl.) bebildert sein. Die Pixelgröße beträgt 40 Mikrometer.The variable v denotes the scanning speed (scanning speed) of the printing surface. A pattern can be imaged over the entire area (full-length) or pixel-area (pixel area) be. The pixel size is 40 microns.

Verschiedene Laserenergien führen zu unterschiedlichen Farbeindrücken auf der Oberfläche. Die Farbeindrücke sind auf Oxide des Titans zurückzuführen, die nicht unbedingt stöchiometrische Zusammensetzung haben. XPS-Messungen haben gezeigt, dass nach der einmaligen nasschemischen Präparation, insbesondere wie sie oben näher beschrieben wurde, in einer Tiefe von 6 Nanometern an der Titanoberfläche verschiedene Oxidationsstufen des Titans vorliegen. Zum Beispiel sind TiO, TiO2, Ti2O3 und metallisches Ti sind in diesen ersten 6 Nanometern der Oberfläche vorhanden. Nach einmaliger Laserbestrahlung wird der Oxidfilm an der Oberfläche schon dicker als 6 Nanometer, die mittels XPS-Methode detektierbaren 6 Nanometer bestehen im Rahmen der Messgenauigkeit zu 100% oder vollständig aus TiO2. Eine einmalige, vollflächige Laserbehandlung ist nach der einmaligen nasschemischen Präparation ein sehr vorteilhafter Anfangszustand für die reversible (löschbare) Bebilderung an dieser Titanoberfläche. Mehrmalige Bebilderungen mit IR-Laser an denselben Bereichen der Oberfläche resultieren zwar in leichten Farbänderungen, haben aber keinen Einfluss auf die Benetzungseigenschaften dieser Bereiche. In anderen Worten ausgedrückt, durch die Bestrahlung der hydrophoben Oberfläche entstehen immer hydrophile Bereiche.Different laser energies lead to different color impressions on the surface. The color impressions are due to oxides of titanium, which are not necessarily stoichiometric composition. XPS measurements have shown that after the one-time wet-chemical preparation, in particular as described in detail above, at a depth of 6 nanometers at the titanium surface, there are different oxidation states of the titanium. For example, TiO, TiO2, Ti2O3 and metallic Ti are present in these first 6 nanometers of surface. After a single laser irradiation, the oxide film on the surface is already thicker than 6 nanometers; the XPS-detectable 6 nanometers consist of 100% or 100% TiO2 in terms of measurement accuracy. A one-time, full-surface laser treatment after the one-time wet-chemical preparation is a very advantageous initial state for the reversible (erasable) imaging on this titanium surface. Repeated imaging with IR laser at the same areas of the surface, although resulting in slight color changes, but have no influence on the wetting properties of these areas. In other words, the irradiation of the hydrophobic surface always results in hydrophilic areas.

Eine funktionsfähige Druckform kann bei Einstrahlung von mehr als 15 Joule/Quadratzentimeter erhalten werden. Besonders gute Qualität wird ab 30 Joule/Quadratzentimeter erreicht.A functional printing form can be obtained at irradiation of more than 15 joules / square centimeter. Particularly good quality is achieved from 30 joules / square centimeter.

Im dritten Verfahrensschritt des Druckens 14 erfolgt die Vervielfältigung des Sujets auf einen Bedruckstoff nach einem Offsetdruckverfahren. Optional kann nach dem Drucken die Titanoberfläche durch Kontakt mit einer Lösung geeigneter Zusammensetzung von Druckfarbe gereinigt werden. In der vorteilhaften Ausführungsform wird Farbreiniger der Firma EUROSTAR benutzt.In the third method step of printing 14, the reproduction of the subject on a printing substrate by an offset printing process takes place. Optionally, after printing, the titanium surface may be cleaned of ink by contact with a solution of suitable composition. In the advantageous embodiment, color cleaner EUROSTAR is used.

Im vierten Verfahrensschritt des Löschens 18 wird die Titanoberfläche großflächig ultraviolettem Licht der Wellenlänge von etwa 172 Nanometern etwa für die Dauer von 5 Minuten ausgesetzt. Als Lichtquelle dient ein Xenon-Excimerstrahler der Firma Xeradex (OSRAM) mit einer optischen Leistung von 5 Watt bei elektrischer Leistung von 20 Watt.In the fourth method step of the erasing 18, the titanium surface is extensively exposed to ultraviolet light of the wavelength of approximately 172 nanometers for approximately 5 minutes Minutes exposed. The light source is a Xenon Excimerstrahler the company Xeradex (OSRAM) with an optical power of 5 watts with electrical power of 20 watts.

Nun ist eine Wiederholung 110 der einzelnen Schritte, beginnend mit dem Schritt der Bereitstellung 10 der wiederverwendbaren Druckform, möglich. Der Kreisprozess lässt sich innerhalb von weniger als 30 Minuten durchführen.Now a repetition 110 of the individual steps, starting with the step of providing the reusable printing plate 10, is possible. The cycle can be completed in less than 30 minutes.

Die Figur 2 ist eine schematische Darstellung der Strukturierung einer erfindungsgemäßen wiederverwendbaren Druckform, deren Druckfläche eine mit wenigstens einer amphiphilen organischen Verbindung, deren polarer Bereich einen säureartigen Charakter hat, behandelte Metalloberfläche aufweist, mittels des erfindungsgemäßen Verfahrens. Die Figur 2 zeigt drei Zustände der Druckform 30, deren zeitliche Ordnung durch die Pfeile angedeutet ist. Zunächst liegt die Druckform 30 mit einem großflächig hydrophoben Druckfläche 32 vor. Durch lokale, punktweise, selektive Bebilderung werden hydrophile Bereich 34 auf der Oberfläche der Druckform 30 erzeugt. Die Oberfläche weist damit eine Struktur aus hydrophoben Bereichen 32 und hydrophilen Bereichen 34 auf, so dass sie zum Drucken, insbesondere in einem Offsetdruckverfahren verwendet werden kann. Nach einer großflächigen Bestrahlung der Oberfläche der Druckform 30 und Behandlung mit einer amphiphilen organischen Verbindung, deren polarer Bereich einen säureartigen Charakter hat, wird erreicht, dass die Druckform großflächig wieder eine hydrophobe Druckfläche 32 aufweist.The FIG. 2 is a schematic representation of the structuring of a reusable printing form according to the invention, the pressure surface having a treated with at least one amphiphilic organic compound whose polar region has an acidic character, treated metal surface by means of the inventive method. The FIG. 2 shows three states of the printing plate 30, whose temporal order is indicated by the arrows. First, the printing form 30 is present with a large area of hydrophobic printing surface 32. By local, pointwise, selective imaging hydrophilic region 34 are generated on the surface of the printing plate 30. The surface thus has a structure of hydrophobic regions 32 and hydrophilic regions 34, so that they can be used for printing, in particular in an offset printing process. After a large-area irradiation of the surface of the printing plate 30 and treatment with an amphiphilic organic compound whose polar region has an acid-like character, it is achieved that the printing plate has a hydrophobic printing surface 32 over a large area.

BEZUGSZEICHENLISTELIST OF REFERENCE NUMBERS

1010
Verfahrensschritt der BereitstellungStep of providing
1212
Verfahrensschritt der BebilderungProcess step of the illustration
1414
Verfahrensschritt des DruckensProcess step of printing
1616
Verfahrensschritt des LöschensProcess step of deleting
110110
Wiederholung der SchritteRepeat the steps
3030
Druckformprinting form
3232
hydrophobe Druckflächehydrophobic printing surface
3434
hydrophile Bereichehydrophilic areas

Claims (17)

  1. Reusable printing forme, in particular for use in offset printing, including a printing surface that has a metal oxide surface to which at least one amphiphilic organic compound whose polar region has an acidic character is applied,
    characterized in
    that the amphiphilic organic compound is an acid substituted by a group including a carbon chain, the number of carbons being greater than or equal to 12 and smaller than or equal to 25, so that the printing surface is hydrophobized by the amphiphilic organic compound.
  2. Reusable printing forme according to Claim 1,
    characterized in
    that the anorganic or organic acid substituted with the group of the amphiphilic organic compound includes at least one element of main group IV, V, or VI of the periodic table.
  3. Reusable printing forme according to Claim 1 or 2,
    characterized in
    that the amphiphilic organic compound is a hydroxamic acid or a phosphonic acid.
  4. Reusable printing forme according to Claim 3,
    characterized in
    that the amphiphilic organic compound is n-heptadecan-hydroxamic acid {CH3-(CH2)16-C(O)-NH-OH} and/or n-octadecan-phosphonic acid {CH3-(CH2)17-P(O)-(OH)2}.
  5. Reusable printing forme according to any one of the preceding claims,
    characterized in
    that the group is partially or completely halogenated.
  6. Reusable printing forme according to any one of the preceding claims,
    characterized in
    that the metal oxide surface is a surface of one of the following surfaces: native oxidized titanium surface, native oxidized stainless steel surface, native oxidized aluminium surface.
  7. Reusable printing forme according to any one of the preceding claims,
    characterized in
    that the printing forme is embodied as the surface of a solid cylinder, the surface of a hollow cylinder, a sleeve, or a plate.
  8. Printing unit,
    characterized by
    at least one reusable printing forme in accordance with any one of the preceding claims.
  9. Printing press,
    characterized by
    at least one printing unit in accordance with Claim 8.
  10. Method of imaging a reusable printing forme,
    characterized by
    - providing (10) a reusable printing forme having a printing surface surface in accordance with any one of the preceding claims 1 to 7;
    - producing (12) an image on the printing surface by selective, dot-by-dot input of energy;
    - erasing (16) the image after printing on a printing stock, in particular in an offset printing process, by large-area input of energy.
  11. Method according to Claim 10,
    characterized in
    that the provision of the reusable printing forme comprises wetting the printing surface with a solution that includes at least one amphiphilic organic compound whose polar region has an acidic character.
  12. Method according to Claim 10 or 11,
    characterized in
    that the provision of the reusable printing forme comprises the following steps:
    - cleaning the printing surface by irradiation of the metal oxide surface using an UV light source;
    - removing nonadhering compounds from the treated metal oxide surface; and
    - drying the metal oxide surface using a waterless process gas, in particular nitrogen.
  13. Method according to Claim 10, 11, or 12;
    characterized in
    that the provision of the reusable printing forme comprises a step for preparing the metal oxide surface in which the metal oxide surface is pre-cleaned.
  14. Method according to any one of Claims 10 to 13,
    characterized in
    that the provision of the reusable printing forme comprises the following steps for preparing a native oxidized titanium surface:
    - etching the native oxidized titanium surface; and
    - producing a defined oxide film, in particular a hydrophilic surface.
  15. Method according to any one of Claims 10 to 14,
    characterized in
    that the production of an image on the printing surface is carried out by selective, dot-by-dot input of energy for the purpose of hydrohpilization with the aid of electromagnetic radiation, in particular in the infrared spectral range, and that the erasing of the image is carried out by large-area input of energy for the purpose of hydrophobization by means of a radiation of the printing surface with electromagnetic radiation, in particular in the ultraviolet spectral range.
  16. Method according to any one of Claims 10 to 15,
    characterized in
    that, after production (12) of an image on the printing surface, the printing surface is treated with at least one hypophilic substituted or terminated amphiphilic, organic compound.
  17. Method according to any one of Claims 10 to 16,
    characterized in
    that, after printing on the printing stock, the printing surface is cleaned to remove printing ink, in particular using a conventional ink cleaner.
EP03011112A 2002-06-17 2003-05-22 Reusable printing plate Expired - Lifetime EP1375136B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10227054 2002-06-17
DE10227054A DE10227054B4 (en) 2002-06-17 2002-06-17 Reusable printing form, printing unit and printing machine with it as well as methods for imaging the printing form

Publications (2)

Publication Number Publication Date
EP1375136A1 EP1375136A1 (en) 2004-01-02
EP1375136B1 true EP1375136B1 (en) 2008-02-13

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Application Number Title Priority Date Filing Date
EP03011112A Expired - Lifetime EP1375136B1 (en) 2002-06-17 2003-05-22 Reusable printing plate

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EP (1) EP1375136B1 (en)
JP (1) JP4679806B2 (en)
CN (2) CN1329212C (en)
AT (1) ATE385894T1 (en)
DE (2) DE10227054B4 (en)
DK (1) DK1375136T3 (en)
HK (1) HK1062662A1 (en)

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Also Published As

Publication number Publication date
DE10227054B4 (en) 2013-01-03
CN1470396A (en) 2004-01-28
JP2004042633A (en) 2004-02-12
HK1062662A1 (en) 2004-11-19
DE50309140D1 (en) 2008-03-27
DK1375136T3 (en) 2008-06-02
CN101121351B (en) 2012-02-22
ATE385894T1 (en) 2008-03-15
CN101121351A (en) 2008-02-13
DE10227054A1 (en) 2003-12-24
CN1329212C (en) 2007-08-01
EP1375136A1 (en) 2004-01-02
JP4679806B2 (en) 2011-05-11

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