EP1423280B1 - Procede de production de formes flexographiques par gravure directe au laser - Google Patents

Procede de production de formes flexographiques par gravure directe au laser Download PDF

Info

Publication number
EP1423280B1
EP1423280B1 EP03759963A EP03759963A EP1423280B1 EP 1423280 B1 EP1423280 B1 EP 1423280B1 EP 03759963 A EP03759963 A EP 03759963A EP 03759963 A EP03759963 A EP 03759963A EP 1423280 B1 EP1423280 B1 EP 1423280B1
Authority
EP
European Patent Office
Prior art keywords
laser
relief
layer
flexographic printing
binder
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
Application number
EP03759963A
Other languages
German (de)
English (en)
Other versions
EP1423280A1 (fr
Inventor
Margit Hiller
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.)
Flint Group Germany GmbH
Original Assignee
BASF Drucksysteme GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BASF Drucksysteme GmbH filed Critical BASF Drucksysteme GmbH
Publication of EP1423280A1 publication Critical patent/EP1423280A1/fr
Application granted granted Critical
Publication of EP1423280B1 publication Critical patent/EP1423280B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • B41C1/02—Engraving; Heads therefor
    • B41C1/04—Engraving; Heads therefor using heads controlled by an electric information signal
    • B41C1/05—Heat-generating engraving heads, e.g. laser beam, electron beam

Definitions

  • the invention relates to a process for the production of flexographic printing plates by direct laser engraving, in which as starting material a flexographic printing element is used, which is a Relief layer with a combination of a styrene-butadiene block copolymer and 20 to 40 wt.% of a plasticizer.
  • the invention further relates to flexographic printing plates available according to this method and the use of flexographic printing plates for flexographic printing with water or alcohol based inks.
  • Lasers are now used both in the field of offset printing plates as in the field of relief printing forms for various Steps of the manufacturing process used.
  • the photosensitive layers of offset printing plates by means of suitable laser printers.
  • the photosensitive layer is chemically altered by the laser, for example crosslinked.
  • the finished offset printing plate is obtained from the imaged crude product by means of a suitable development process (see, for example, Imaging Technology, Chapter 3.4.1.2., Ullmann's Encyclopedia of Industrial Chemistry, 6 th Edt., 2000 Electronic Release).
  • the thickness of said photosensitive layers of offset printing plates is usually 0.3 to 5 ⁇ m.
  • IR ablative masks as disclosed for example in EP-A 654 150.
  • IR ablative masks as disclosed for example in EP-A 654 150.
  • the thickness of such IR ablative Layers is usually only a few microns.
  • the IR ablative Layer is pictorially described with an IR laser, i.e. removed at the places where they were hit by the laser beam becomes.
  • the actual relief will be on conventional Made way: Through the mask created is illuminated with actinic light and thus the relief layer selectively networked.
  • EP-A 640 043 and EP-A 640 044 disclose single-layered or multilayered ones Elastomeric laser-engravable flexographic printing elements for Production of flexographic printing plates by laser engraving.
  • the Elements consist of "reinforced" elastomeric layers.
  • the layer is used elastomeric binder. Due to the so-called reinforcement, the mechanical strength of the layer increased to allow flexographic printing.
  • the reinforcement is either by introducing suitable fillers, photochemical or thermochemical crosslinking or combinations thereof.
  • US 5,259,311 discloses a method in which in a first Step a commercial flexographic printing through full-surface Irradiation by UV / A photochemically crosslinked, then the release-layer with a flexo wash and removed in one second step engraved by means of a laser a printing relief becomes. Subsequently, a cleaning step by means of a flexo wash followed by final drying performed the plate.
  • the relief layers of flexographic printing plates are naturally soft and have relatively low melting or softening points. she In laser engraving, therefore, they have a strong tendency to melt edges around the to form engraved elements around. At the edge of the engraved Elements melts the layer under the influence of the laser beam Although on, but is no longer or no longer complete decomposed. Such melt edges can also be washed by rinsing usually not or at least not completely remove and lead to an unclean pressure. Unwanted melting The layer also has a reduced resolution of the print motif compared to the digital record result.
  • EP-A 1 136 254 proposes to solve this problem, relief layers with polyoxyalkylene / polyethylene glycol graft copolymers as a binder. But these copolymers are water-soluble are, such relief printing forms are disadvantageous only can be used to a limited extent. The relief layer swells in Water-based flexographic inks far too strong, so that when Print unwanted effects, such as a no longer tolerable dot gain. Such printing forms are therefore essentially used only for printing with UV inks. There is an urgent need for printing as well To provide water-soluble suitable laser-engravable relief printing elements, which are still without unwanted. melting engrave the layer with lasers.
  • Decomposition products who have reacted again with the surface can be even can not be removed and can therefore be seen in the print. It would be extreme desirable to be able to have a flexographic printing element, in which eventual Deposits are easily removed with water or aqueous cleaning agents can, without the plate swells.
  • WO 03/45693 discloses a flexographic printing element for the production of flexographic printing plates by laser engraving, the relief layer of a hydrophobic elastomer and a hydrophilic polymer as a primary or secondary binder.
  • the fastest possible engraving required depends on the one hand on the selected laser system.
  • the sensitivity should be the relief-forming layer with respect to the selected laser radiation as possible be high.
  • the relief layer of the flexographic printing plate both the elastomeric properties as gives the pressure typical properties. Measures to improve the sensitivity must therefore not impair the properties mentioned.
  • the object of the invention was therefore to provide a process for the production of flexographic printing plates by direct laser engraving, in which the occurrence of melt edges is significantly reduced, as few aerosols arise, possible deposits of decomposition products by simply treating the plate with water or aqueous cleaning agents can be removed, which a possible rapid high-resolution engraving, and the resulting flexographic printing plates in addition, suitable for printing with water-based flexographic inks.
  • flexographic printing plates were found, which according to the described method available, as well as the use of these flexographic printing plates for flexographic printing with Water-based and / or alcohol-based printing inks.
  • suitable dimensionally stable carriers for as starting material for the Process used flexographic printing elements are plates, films and conical and cylindrical tubes (sleeves) of metals such as steel, aluminum, copper or nickel or of plastics such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate, polyamide, polycarbonate, optionally also fabrics and nonwovens, such as glass fiber fabric and composite materials, e.g. made of glass fibers and plastics.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • polybutylene terephthalate polyamide
  • polycarbonate optionally also fabrics and nonwovens, such as glass fiber fabric and composite materials, e.g. made of glass fibers and plastics.
  • dimensionally stable carrier films such as polyester films, in particular PET or PEN foils or flexible metallic Carrier, such as thin sheets or metal foils made of steel, preferred made of stainless steel, magnetizable spring steel, Aluminum, zinc, magnesium, nickel, chromium or copper into consideration.
  • the flexographic printing element further comprises at least one laser engravable, crosslinkable relief-forming layer.
  • Die.vernetzbare Relief layer can be applied directly on the support. But also between the carrier and the relief layer can still other layers are, such as adhesive layers and / or elastic sublayers.
  • the crosslinkable relief-forming layer comprises at least one elastomeric binder, crosslinkable components and 20 to 40 % By weight of a plasticizer.
  • a plasticizer As a rule, already the crosslinkable relief layer as a whole elastomeric properties on; but it is sufficient for the invention, if only the networked relief layer typical of a flexographic printing plate having elastomeric properties.
  • the elastomeric binder is to a styrene-butadiene block copolymer. It can be about Two-block copolymers, triblock copolymers or multiblock copolymers act in which alternately several styrene and Butadiene blocks follow each other. It can be both linear, branched or star-shaped block copolymers act.
  • SBS block copolymers are commercially available, for example, under the name Kraton®, taking into account is that commercially available triblock copolymers usually one have a certain proportion of diblock copolymers. Of course may also be mixtures of different SBS block copolymers be used.
  • the elastomeric styrene-butadiene block copolymers used in the starting material according to the invention have an average molecular weight M w (weight average) of from 100,000 to 250,000 g / mol.
  • M w is preferably from 150 000 to 250 000 g / mol and very particularly preferably from 150 000 to 200 000 g / mol.
  • the styrene content of the styrene-butadiene block copolymer used is from 20 to 40% by weight with respect to the binder, preferably 25 to 35% by weight.
  • the Shore A hardness of the binder is determined according to the ISO 868 standard. According to the invention, the elastomeric styrene-butadiene block copolymer used a hardness of 55 to 85 Shore A on. The hardness of the binder is preferably 60 up to 80 Shore A and most preferably 65 to 75 Shore A.
  • the at least one styrene-butadiene block copolymer has the relief layer still one or more secondary binders on.
  • Such secondary binders are used by the expert for fine control of the properties of the relief layer used.
  • the choice of secondary binders is not limited in principle, as long as the properties of the relief layer are not affected thereby.
  • Prefers secondary binders are styrene-butadiene block copolymers which only the above-described requirements in terms of molecular weight, hardness and styrene content do not match. Of course it can also be about Chemically different polymers act.
  • the amount of secondary binder should as a rule 20% by weight, preferably 10% by weight, with respect to the total amount of all do not exceed the binder used. If it is the secondary binder is a styrene-butadiene block copolymer, up to about 30 % By weight, in special cases also up to about 40% by weight in relation to the total amount all used binders are
  • the total amount of binders, so styrene-butadiene block copolymers and existing secondary binders together, is usually 40 to 80 wt. % with respect to the sum of all constituents of the relief-forming layer, preferably 40 to 70% by weight, and more preferably 45 to 65% by weight.
  • the binder is mixed with at least used a plasticizer.
  • the amount of plasticizer is 20% by weight to 40% % By weight with respect to all constituents of the relief-forming layer, preferably 25 to 40 % By weight, and more preferably 30 to 40% by weight.
  • suitable plasticizers include modified and unmodified natural oils and resins, such as high-boiling paraffinic, naphthenic or aromatic mineral oils, synthetic oligomers or resins such as oligostyrene, oligomeric Styrene-butadiene copolymers, oligomeric ⁇ -methyl-oligomers ⁇ -methylstyrene / p-methylstyrene copolymers, liquid oligobutadienes, especially those with a molecular weight between 500 and 5000 g / mol, or liquid oligomeric acrylonitrile-butadiene copolymers or oligomeric ethylene-propylene-diene rubbers.
  • suitable plasticizers include modified and unmodified natural oils and resins, such as high-boiling paraffinic, naphthenic or aromatic mineral oils, synthetic oligomers or resins such as oligostyrene, oligomeric Styrene-butadiene copolymers, oli
  • inert plasticizer particularly suitable for the process according to the invention are so-called inert plasticizer.
  • "Inert” in the sense of this invention means that the plasticizers have no or at least essentially have no polymerizable groups in the course radical crosslinking of the relief-forming layer in such a way Can react that plasticizer in the polymeric network the relief layer are involved.
  • Inert plasticizers exhibit in particular substantially no ethylenically unsaturated Double bonds on.
  • inert plasticizers include high-boiling paraffinic, naphthenic and aromatic mineral oils. Preferred are in essential paraffinic and / or naphthenic mineral oils. Such mineral oils are also referred to as white oils, wherein the expert between technical white oils, which still a small Aromatic content, as well as medicinal white oils, which are essentially free of aromatics, differentiates.
  • mixtures of different plasticizers be used, provided the properties of the Relief layer are not adversely affected.
  • preferred Mixtures are those containing at least one inert plasticizer include.
  • a mixture of liquid oligobutadienes and white oil called.
  • the relief layer comprises at least one photoinitiator or a photoinitiator system as well suitable monomers or oligomers.
  • initiators for the photopolymerization are in a known manner and benzoin or benzoin derivatives such as ⁇ -methylbenzoin or Benzoin ethers, benzene derivatives, e.g. Benzil ketals, acylarylphosphine oxides, Acylarylphosphinic acid esters, multinuclear quinones suitable, without the list being limited to it.
  • the monomers have at least one polymerizable, olefinic unsaturated group on.
  • suitable monomers include butyl acrylate, 2-ethyl-hexyl acrylate, Lauryl acrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, Trimethylolpropane triacrylate, dioctyl fumarate, N-dodecylmaleimide. It is also possible to use suitable oligomers with olefinic groups be used. Of course, mixtures of different Monomer or oligomer can be used, provided There are no unwanted effects. The total amount the monomers are chosen by the skilled person depending on the desired properties the relief layer set. As a rule, but should 20 wt.% Regarding the amount of all components of the laser engravable relief-forming layer can not be exceeded.
  • Thermal crosslinking is preferred in analogy to the photochemical Networking done by instead of a photoinitiator a thermal polymerization initiator is used. in principle suitable commercial thermal initiators for the radical polymerization, such as peroxides, hydroperoxides or azo compounds.
  • the thermal crosslinking can also be carried out by thermally applying the layer curing resin such as an epoxy resin as crosslinking Adds component.
  • Crosslinking by means of electron radiation is preferred in analogy carried out for photochemical crosslinking by the already described photochemically crosslinkable relief layers be used and the UV radiation by electron radiation is replaced.
  • the addition of initiators is not necessarily required.
  • the crosslinkable relief layer may further comprise an absorber for laser radiation.
  • an absorber for laser radiation It can also be mixtures of different Absorbers are used for laser radiation.
  • suitable Absorbers for laser radiation have a high absorption in the Range of laser wavelength.
  • absorbers are suitable the high absorption in the near infrared and in the Have longer wavelength VIS range of the electromagnetic spectrum.
  • Such absorbers are particularly suitable for absorption the radiation of Nd-YAG lasers (1064 nm) and of IR diode lasers, the typically wavelengths between 700 and 900 nm as well between 1200 and 1600 nm.
  • suitable absorbers for the laser radiation are in infrared spectral strongly absorbing dyes such as for example phthalocyanines, naphthalocyanines, cyanines, Quinones, metal complex dyes such as dithiolenes or photochromic dyes.
  • Further suitable absorbers are inorganic pigments, in particular intensively colored inorganic Pigments such as chromium oxides, iron oxides, carbon black or metallic particles.
  • Particularly suitable as an absorber for laser radiation are finely divided carbon blacks with a primary particle size between 10 and 50 nm.
  • the amount of optionally added absorber is the expert ever according to the respective desired properties of the laser-engravable Flexo printing element selected.
  • the Specialists consider that the added absorber not only the engraving of the elastomeric layer is influenced by laser, but also the properties of the end product of the process obtained relief printing form such as their hardness, Elasticity, thermal conductivity or color transfer behavior. As a rule, it is therefore recommended that not more than 20 wt. %, preferably not more than 10% by weight of absorber for the laser radiation regarding the sum of all components of the layer.
  • the photochemical be crosslinked to add absorbers for laser radiation, which also absorb in the UV range, as a result of the photopolymerization at least severely impaired and possibly is made completely impossible. It is recommended regularly, such Thermally or by means of layers containing laser absorber To network electron beams.
  • the relief-forming layer may also contain additives and adjuvants such as dyes, dispersing aids or antistatic agents.
  • additives and adjuvants such as dyes, dispersing aids or antistatic agents.
  • the amount of such additives As a rule, however, it should be 5% by weight with respect to the amount of all components the crosslinkable, laser-engravable layer of the recording element do not exceed.
  • the crosslinkable relief-forming layer can also consist of several Sublayers are constructed. These crosslinkable sublayers may be of equal, approximately the same or different be material composition.
  • the thickness of the laser-engravable elastomeric layer is at least 0.2 mm.
  • the thickness is 0.3 to 7 mm, especially preferably 0.5 to 5 mm and most preferably 0.7 to 4 mm.
  • the thickness is determined by the person skilled in the art according to the intended use the flexographic printing suitable chosen.
  • the starting material comprises an additional, water-soluble or at least swellable laser-engravable Polymer layer on the laser-engravable relief-forming layer is arranged, and the at least one in aqueous solvents soluble, swellable or dispersible Polymer includes.
  • a layer serves to -optional To be performed Nachtherapies Republic to facilitate. in the As a result of laser engraving solid decomposition products formed Depositing on this auxiliary layer and easier detached become.
  • soluble in aqueous solvents or at least swellable polymers examples include polyvinyl alcohol, polyvinyl alcohol / polyethylene glycol graft copolymers, Polyvinylpyrrolidone and its derivatives or cellulose derivatives, in particular cellulose esters and cellulose ethers such as methyl cellulose, Ethylcellulose, benzylcellulose, hydroxyalkylcelluloses or nitrocelluloses. Of course, mixtures of several Polymer are used.
  • the additional laser-engravable polymer layer can also Contain additives and excipients, such as plasticizers or laser absorber. If provided, the laser engravable Photochemically crosslink relief layer, then should the additional Polymer layer in the UV range as transparent as possible be. For other meshing techniques this is not necessarily required.
  • the thickness of the additional polymer layer should be as small as possible be. It depends essentially on the depth of field of the used for engraving in the process laser. It is so limited that it does not become essential on the surface of the relief layer Broadening of focus comes.
  • the thickness of such an additional polymer layer should normally be Do not exceed 100 ⁇ m. As a rule, at larger thicknesses no longer achieves satisfactory results. Preferably, the thickness should not exceed 50 microns. Especially Preferably, the thickness is 1-40 microns and most preferably 2 - 25 ⁇ m.
  • the laser-engravable flexographic printing element can optionally have more Include layers.
  • Such layers include elastomeric sublayers from another wording that is between the wearer and the laser engravable layer (s) is located and not must necessarily be laser engravable. With such sublayers can the mechanical properties of the relief printing plates be changed without the properties of the actual to influence the printing relief layer.
  • the laser-engravable flexographic printing element against mechanical damage by, for example, made of PET Protective film, also known as a cover film, which is located on the topmost layer, and the must be removed before engraving with lasers.
  • PET Protective film also known as a cover film
  • the protective film may be used to facilitate stripping in a suitable manner and Be surface-treated, for example by siliconization, provided, by the surface treatment is the Relief upper layer not negatively influenced in their printing properties.
  • the flexographic printing element used as the starting material for the process can for example by dissolving or dispersing all components in a suitable solvent and pour be made on a carrier.
  • a suitable solvent for multi-layered elements can in principle known manner several layers be poured on each other.
  • the cover sheet After casting, if desired, the cover sheet to protect against damage Starting material are applied. It is also possible, conversely, to pour on the cover sheet and finally laminating the carrier.
  • the casting method is especially recommended when thermally crosslinked.
  • the production of the relief layer preferably takes place in principle known manner by melt extrusion between a carrier film and a cover sheet or a cover element and calendering the resulting composite, such as from EP-A 084 851 discloses. This way you can also make thick layers in a single operation.
  • multilayer For example, elements can be coextruded getting produced. Flexographic printing elements with metallic supports can preferably be obtained by looking at a temporary Carrier pours or extrudes, and then the layer on the metallic Carrier laminated.
  • the styrene-butadiene block copolymer with a part of the plasticizer in a suitable Mixing unit to process a homogeneous mass.
  • the mass obtained is then in a second step in the extruder along with the other components of the layer and the rest the plasticizer further processed.
  • This can also be advantageous incorporated a larger amount of plasticizer on a short extruder length and a particularly homogeneous incorporation of the plasticizer be achieved.
  • the residence times of the polymeric Mass be reduced in the hot zone of the extruder.
  • the application of the additional polymer layer can, for example by dissolving the ingredients in a suitable solvent and pouring onto the relief-forming layer.
  • the starting material in the first Process step (a) initially crosslinked over the entire surface.
  • the full-surface crosslinking of the crosslinkable relief layer can photochemically, in particular by irradiation with UV-A radiation with a wavelength between 320 and 400 nm, or UV-A / VIS radiation made with a wavelength of about 320 to about 700 nm become.
  • Full-surface thermochemical crosslinking takes place by as even, constant temperature heating of the Relief layer.
  • Electron beams are crosslinked. Particularly advantageous can the radiation dose required for cross-linking to several partial doses be split.
  • Photochemical crosslinking is particularly suitable for relief layers, which are not heavily colored absorbers for laser radiation contained and in the UV / VIS range transparent or at least largely are transparent.
  • transparent relief layers can of course also thermochemically or by electron radiation be networked.
  • Colored laser absorber containing relief layers can advantageously thermochemically or by means Electron radiation can be crosslinked.
  • Flexographic printing element usually from a printing plate manufacturer produced during the laser engraving of a cliché institution or printing company is made.
  • the full-surface networking (a) on the one hand by the cliché institution itself made become.
  • photochemical crosslinking in commercial Flexobelichtern be made.
  • the networking On the other hand, of course, synonymous of or the manufacturer take place of the flexographic printing element.
  • a printing is effected by means of a laser Relief engraved in the networked relief layer. If one Protective film is present, this is deducted before the engraving.
  • the term "laser engravable" is to be understood that the Relief layer has the property of laser radiation, in particular to absorb the radiation of an IR laser, so that in such places where they are more adequate for a laser beam Intensity is exposed, removed or at least detached becomes.
  • the layer is thereby without before melt evaporated or thermally or oxidatively decomposed, so their decomposition products in the form of hot gases, vapors, Smoke or small particles are removed from the layer.
  • IR laser For engraving are in particular IR laser.
  • a CO 2 laser with a wavelength of 10.6 microns can be used.
  • Nd-YAG lasers (1064 nm), IR diode lasers or solid-state lasers can be used. It is also possible to use lasers with shorter wavelengths, provided the laser has sufficient intensity. For example, it is also possible to use a frequency-doubled (532 nm) or frequency-tripled (355 nm) Nd-YAG laser or also excimer lasers (eg 248 nm).
  • absorbers for laser radiation depends essentially on the type of laser to be used for engraving.
  • the styrene-butadiene block copolymers used for the relief layer absorb the radiation of CO 2 lasers to a sufficient extent, so that when using this type of laser additional IR absorbers in the relief layer are generally not required.
  • UV lasers such as excimer lasers.
  • Nd-YAG lasers and IR diode lasers the addition of a laser absorber is generally required.
  • the image information to be engraved can be taken directly from the layout computer system be transferred to the laser apparatus.
  • the lasers can be operated either continuously or pulsed.
  • relief elements are engraved in which the Flanks of the elements initially fall vertically and only in the widen the lower area. This will be a good Versockelung the relief points achieved with still low dot gain. It but also differently shaped flanks can be engraved.
  • the depth of the elements to be engraved depends on the Total thickness of the relief and the type of elements to be engraved and will be chosen by the expert depending on the desired properties the printing form determined.
  • the depth of the engraved relief elements is at least 0.03 mm, preferably at least 0.05 mm - Here is the minimum depth between individual grid points. Pressure plates with too low relief depths are for the Printing by flexographic printing technology generally unsuitable, because the negative elements are filled up with printing ink. Individual negative points should usually have greater depths; for such of 0.2 mm diameter is usually a depth of at least 0.07 to 0.08 mm is recommended.
  • At weggrav convinced surfaces We recommend a depth of more than 0.15 mm, preferably more than 0.4 mm. The latter is of course only one thick relief possible.
  • the obtained flexographic printing plate is advantageous after the Laser engraving in a further process step (c) cleaned. In some cases this can be done by simply blowing off done with compressed air or brushing.
  • liquid detergent used to also polymer fragments completely removed. This is special, for example recommended when using the flexographic printing food packaging to be printed, where particularly severe Volatile component requirements apply.
  • aqueous Detergents consist essentially of water as well as optional small amounts of alcohols and can help the cleaning process aids, such as surfactants, Emulsifiers, dispersants or bases. It can Mixtures are also commonly used to develop conventional, water-developable flexographic printing plates be used. As the relief layer with styrene-butadiene block copolymers is not swellable in water, is by the Use of water or aqueous detergents time-consuming Drying the printing form avoided.
  • the post-cleaning for example, by simple immersion or spraying the relief printing form done or in addition by mechanical means, such as by brushing or plushes are supported. It can also usual Flexowascher be used.
  • wash-off agent for conventionally produced flexographic printing plates serve.
  • washout agents based on high-boiling, dearomatized petroleum fractions, such as from EP-A 332 070 or also "water-in-oil" emulsions, as disclosed by EP-A 463 016.
  • This variant can be especially be applied when no additional polymer layer is present is. If an additional polymer layer is present, but not removable with the organic solvent used, must be in addition with water or an aqueous cleaning agent getting cleaned.
  • the resulting flexographic printing plates are particularly suitable for printing with watercolors and alcohol colors. But they are self-evident also for printing with UV inks or flexographic inks, the Contain small amounts of esters, suitable.
  • a photochemically crosslinkable laser-engravable relief-forming layer was prepared with the following starting materials component description Quantity [weight%] Styrene-butadiene block copolymer SBS block copolymer, M w 125 000 g / mol, 29.5% styrene content, 70 ° Shore A (Kraton D-1102) 55% softener polybutadiene 32% Components for networking Monomer: hexanediol diacrylate 10% photoinitiator 2% additives Dye, thermal stabilizer 1 %
  • the components were processed with an extruder (ZSK 53) at 140 ° C, by means of a slot die between a dimensionally stable carrier film made of PET and a protective film PET introduced and then by means of a two-roll calender calendered.
  • the layer thickness of the crosslinkable, laser-engravable layer was 1.14 mm.
  • a photochemically crosslinkable laser-engravable relief-forming layer was prepared with the following starting materials component description Quantity [weight%] Styrene-butadiene block copolymer SBS block copolymer, M w 170 000 g / mol, 31% styrene content, 72 ° Shore A (Kraton D-1101) 38% Secondary binder Styrene-butadiene Zweiblockcpolymer, M w 230,000 g / mol (Kraton DX-1000) 10% softener Polybutadiene oil white oil 20% 18% Components for networking hexanediol 10% photoinitiator 2% additives Dye, thermal stabilizer 2%
  • the components were processed as in Example 1.
  • the Layer thickness of the obtained crosslinkable, laser-engravable Layer was 1.14 mm.
  • Example 2 The procedure was as in Example 1, only was an additional Polymer layer of a water-soluble polymer applied the relief layer (polyvinyl alcohol, Alcotex 4-86, Thickness: 3 ⁇ m). This was done in a separate process step the initially mentioned protective film made of PET with a solution Alcotex 4-86 coated in a water / alcohol mixture and the Solvent mixture evaporates. The coated PET film became too used the described extrusion process. The layer thickness the obtained crosslinkable, laser-engravable layer was 1.14 mm.
  • a photochemically crosslinkable laser-engravable relief-forming layer was prepared with the following starting materials component description Quantity [weight%] Elastomeric binder SIS block copolymer, M w 210 000 g / mol, 17% styrene content, 31 ° Shore A (Kraton D-1161) 48% softener White oil 6% Components for networking Hexanediol diacrylate, monoacrylate 13% photoinitiator 2% additives Dye, thermal stabilizer 4%
  • the components were processed as in Example 1.
  • the Layer thickness of the obtained crosslinkable, laser-engravable Layer was 1.14 mm.
  • the flexographic printing element on a cylinder became a test subject consisting of various, representative, engraved positive and negative elements in the flexographic printing element.
  • the subject In addition to completely weggrav convinced open spaces and 100% tone values, the subject also contains different grid areas with tonal values between 1% and 98% and 40 ⁇ m wide negative lines in the axial and transverse direction to the cylinder axis of rotation.
  • the rotational speed of the cylinder was 7 m / s.
  • the power setting The steel was: 1. Ray 40, 2. and 3. Ray 90.
  • the obtained flexographic printing plates were for two minutes with water while brushing the Surface washed.
  • a nyloprint® washer (device combination "CW 22 x 30", BASF Drucksysteme GmbH) used.
  • Figures 1 and 2 each show an image of the flexographic printing plate obtained according to Comparative Example 1 and according to Example 1.
  • Example no. Engraving depth T [ ⁇ m] Deposits (visual) Washability (visual) 1 410 Little Well 2 430 Little Well 3 410 little Very well V 1 300 much bad
  • the flexographic printing plates obtained according to the invention are well suited for printing with alcohol and water colors.
  • the "A” is 6 mm wide and 7 mm high.

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Plasma & Fusion (AREA)
  • Manufacturing & Machinery (AREA)
  • Manufacture Or Reproduction Of Printing Formes (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laser Beam Printer (AREA)
  • Laser Beam Processing (AREA)

Claims (13)

  1. Procédé de préparation de formes flexographiques par gravure directe au laser, dans lequel on met en oeuvre comme matériau de départ, un élément flexographique réticulable, pouvant être gravé par laser, qui comprend, disposés l'un sur l'autre, au moins :
    un support dimensionnellement stable,
    au moins une couche formant relief, réticulable, pouvant être gravée par laser, avec une épaisseur d'au moins 0,2 mm, comprenant au moins un liant élastomère, un plastifiant ainsi que des composants de réticulation,
       et le procédé comprend au moins les étapes suivantes :
    (a) réticulation sur toute la surface de la couche formant relief,
    (b) gravure d'un relief d'impression dans la couche de relief réticulée, à l'aide d'un laser, où la profondeur des éléments de relief gravés par le laser s'élève à au moins 0,03 mm,
       caractérisé en ce que le liant consiste en au moins des copolymères séquencés styrène-butadiène avec un poids moléculaire moyen Mw allant de 100 000 à 250 000 g/mole, une dureté Shore A de 55 à 85 ainsi qu'une teneur en styrène de 20-40% en poids par rapport au liant, ainsi qu'au moins un liant secondaire, où les polymères hydrophiles sont exclus comme liant secondaire, et où la quantité de plastifiant se situe dans l'intervalle allant de 20 à 40% en poids, sur base de la somme des constituants de la couche.
  2. Procédé selon la revendication 1, caractérisé en ce que le poids moléculaire moyen Mw du liant se situe dans l'intervalle allant de 150 000 à 250 000 g/mole.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que la teneur en styrène du liant se situe dans l'intervalle allant de 25 à 35% en poids.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que le plastifiant consiste en un plastifiant inerte.
  5. Procédé selon la revendication 4, caractérisé en ce que le plastifiant inerte consiste en au moins un choisi parmi le groupe des huiles minérales aromatiques, naphténiques et paraffiniques.
  6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que le liant secondaire consiste en un copolymère séquencé styrène-butadiène, qui se différencie du liant primaire par la dureté, la teneur en styrène et le poids moléculaire.
  7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que la quantité de liant secondaire n'est pas supérieure à 40% en poids, sur base de la somme de tous les liants mis en oeuvre.
  8. Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que la réticulation sur toute la surface (a) est réalisée de manière photochimique, à l'aide d'un rayonnement électronique, ou de manière thermique.
  9. Procédé selon l'une quelconque des revendications 1 à 8, caractérisé en ce que la couche de relief comprend en outre, un agent absorbant le rayonnement laser.
  10. Procédé selon l'une quelconque des revendications 1 à 9, caractérisé en ce que l'élément flexographique comprend une couche supplémentaire, soluble dans l'eau, pouvant être gravée par laser, qui est disposée sur la couche formant relief, pouvant être gravée par laser et qui comprend au moins un polymère soluble, gonflable ou dispersible dans un solvant aqueux, et qui est éliminé après l'étape de procédé (b), dans une étape supplémentaire de procédé (c), à l'aide d'eau ou d'un agent de nettoyage aqueux.
  11. Procédé selon la revendication 10, caractérisé en ce que le polymère consiste en au moins un choisi parmi le groupe du poly(alcool vinylique), les copolymères greffés poly(alcool vinylique)/polyéthylèneglycol, la polyvinylpyrrolidone ou des dérivés de la cellulose.
  12. Forme flexographique, pouvant être obtenue par un procédé selon l'une quelconque des revendications 1 à 11.
  13. Utilisation d'une forme flexographique selon la revendication 12, pour la flexographie avec des encres à base d'eau et/ou à base d'alcool.
EP03759963A 2002-06-18 2003-06-16 Procede de production de formes flexographiques par gravure directe au laser Expired - Lifetime EP1423280B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10227188 2002-06-18
DE10227188A DE10227188A1 (de) 2002-06-18 2002-06-18 Verfahren zur Herstellung von Flexodruckformen mittels Laser-Direktgravur
PCT/EP2003/006330 WO2003106172A1 (fr) 2002-06-18 2003-06-16 Procede de production de formes flexographiques par gravure directe au laser

Publications (2)

Publication Number Publication Date
EP1423280A1 EP1423280A1 (fr) 2004-06-02
EP1423280B1 true EP1423280B1 (fr) 2005-08-24

Family

ID=29719215

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03759963A Expired - Lifetime EP1423280B1 (fr) 2002-06-18 2003-06-16 Procede de production de formes flexographiques par gravure directe au laser

Country Status (7)

Country Link
US (1) US6880461B2 (fr)
EP (1) EP1423280B1 (fr)
JP (1) JP2005534524A (fr)
AT (1) ATE302687T1 (fr)
AU (1) AU2003246440A1 (fr)
DE (2) DE10227188A1 (fr)
WO (1) WO2003106172A1 (fr)

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE50211989D1 (de) * 2001-08-03 2008-05-08 Flint Group Germany Gmbh Verfahren zur Herstellung von Zeitungsflexodruckplatten
US6913794B2 (en) * 2002-01-14 2005-07-05 Coherent, Inc. Diode-laser curing of liquid epoxide encapsulants
CA2530223C (fr) 2003-06-23 2012-01-10 Bridgestone/Firestone North American Tire, Llc Procede et systeme pour marquer des pneus
US20070080146A1 (en) * 2003-11-10 2007-04-12 Werner Stockum Coloured laser marking
DE102004025364A1 (de) 2004-05-19 2005-12-08 Basf Drucksysteme Gmbh Verfahren zur Herstellung von Flexodruckformen mittels Laser-Direktgravur
JP2006001168A (ja) * 2004-06-18 2006-01-05 Toyobo Co Ltd 印刷版の製造方法およびレーザー彫刻カスの除去方法
US8501390B2 (en) 2006-06-27 2013-08-06 Xiper Innovations, Inc. Laser engravable flexographic printing articles based on millable polyurethanes, and method
DE102007007183A1 (de) * 2007-02-14 2008-08-21 Man Roland Druckmaschinen Ag Verfahren zur Herstellung von Druckformen
JP2008229875A (ja) * 2007-03-16 2008-10-02 Tokyo Ohka Kogyo Co Ltd フレキソ印刷原版及びフレキソ印刷版の製造方法
JP5150899B2 (ja) * 2007-06-04 2013-02-27 篠田商事株式会社 印刷用版材及びその製版方法
JP2009119810A (ja) * 2007-11-19 2009-06-04 Asahi Kasei Chemicals Corp レーザー彫刻用感光性樹脂組成物
JP5241252B2 (ja) * 2008-01-29 2013-07-17 富士フイルム株式会社 レーザー彫刻用樹脂組成物、レーザー彫刻用レリーフ印刷版原版、レリーフ印刷版及びレリーフ印刷版の製造方法
US7947426B2 (en) * 2008-02-25 2011-05-24 Eastman Kodak Company Laser-engraveable flexographic printing plate precursors
US20100215865A1 (en) 2009-02-26 2010-08-26 Xerox Corporation Preparation of flexographic printing masters using an additive process
US20110236705A1 (en) 2010-03-29 2011-09-29 Ophira Melamed Flexographic printing precursors and methods of making
US8820201B2 (en) * 2010-07-12 2014-09-02 Vistaprint Schweiz Gmbh Tear-away packaging for engraving
JP5174134B2 (ja) * 2010-11-29 2013-04-03 富士フイルム株式会社 レーザー彫刻用樹脂組成物、レーザー彫刻用レリーフ印刷版原版、レリーフ印刷版の製版方法及びレリーフ印刷版
JP5255100B2 (ja) * 2011-07-29 2013-08-07 富士フイルム株式会社 レーザー彫刻型フレキソ印刷版原版及びその製造方法、並びに、フレキソ印刷版及びその製版方法
US9156241B2 (en) 2011-12-12 2015-10-13 Eastman Kodak Company Laser-imageable flexographic printing precursors and methods of relief imaging
US20130196144A1 (en) 2012-01-31 2013-08-01 David H. Roberts Laser Engraveable Compositions for Relief Image Printing Elements
US8941028B2 (en) * 2012-04-17 2015-01-27 Eastman Kodak Company System for direct engraving of flexographic printing members
JP2015066853A (ja) * 2013-09-30 2015-04-13 富士フイルム株式会社 レーザー彫刻型フレキソ印刷版原版及びその製造方法、並びに、フレキソ印刷版の製版方法
DE102015007290A1 (de) * 2015-06-10 2016-12-15 Hell Gravure Systems Gmbh & Co. Kg Verfahren zur Herstellung einer Flexodruckform sowie Flexodruckform

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4427759A (en) 1982-01-21 1984-01-24 E. I. Du Pont De Nemours And Company Process for preparing an overcoated photopolymer printing plate
DE3807929A1 (de) 1988-03-10 1989-09-28 Basf Ag Verfahren zur herstellung von reliefformen
DE3831680A1 (de) * 1988-09-17 1990-03-22 Basf Ag Lichtempfindliches aufzeichnungsmaterial
DE3908764C2 (de) 1989-03-17 1994-08-11 Basf Ag Entwickler für die Herstellung photopolymerisierter flexographischer Reliefdruckformen
US5798202A (en) * 1992-05-11 1998-08-25 E. I. Dupont De Nemours And Company Laser engravable single-layer flexographic printing element
US5259311A (en) 1992-07-15 1993-11-09 Mark/Trece Inc. Laser engraving of photopolymer printing plates
US5679485A (en) * 1993-03-31 1997-10-21 Nippon Zeon Co., Ltd. Photosensitive composition, photosensitive rubber plate and process for producing same, and flexographic plate and process for producing same
CZ168896A3 (en) * 1995-06-27 1997-01-15 Egyt Gyogyszervegyeszeti Gyar Oxaindene derivatives and process for preparing thereof
US5919604A (en) * 1997-07-30 1999-07-06 Polyfibron Technologies, Inc. Rubber-based aqueous developable photopolymers and photocurable elements comprising same
DE69809682T2 (de) * 1997-09-16 2003-08-21 Asahi Chemical Ind Lichtempfindliches Element für den Flexodruck
US5894799A (en) * 1997-10-01 1999-04-20 E. I. Du Pont De Nemours And Company Element for cushioning a flexographic printing plate
DE19859623A1 (de) * 1998-12-23 2000-08-24 Basf Drucksysteme Gmbh Photopolymerisierbare Druckformen mit Oberschicht zur Herstellung von Reliefdruckformen
EP1136254B1 (fr) 2000-03-23 2003-05-28 BASF Drucksysteme GmbH Utilisation de copolymères greffés pour la fabrication d'éléments marquables au laser en relief
US20020018958A1 (en) * 2000-06-20 2002-02-14 Jsr Corporation Polymeric material for laser processing and a laminated body for laser processing thereof, flexographic printing plate and the method of producing the same, and a seal material
DE10061116A1 (de) * 2000-12-07 2002-06-13 Basf Drucksysteme Gmbh Fotoempfindliches flexographisches Druckelement mit mindestens zwei IR-ablativen Schichten
US6737216B2 (en) 2000-12-08 2004-05-18 E.I. Du Pont De Nemours And Company Laser engravable flexographic printing element and a method for forming a printing plate from the element
AU2002234587A1 (en) * 2000-12-19 2002-07-01 Basf Drucksysteme Gmbh Method for producing flexographic printing forms by means of laser gravure
DE10113926A1 (de) * 2001-03-21 2002-09-26 Basf Drucksysteme Gmbh Verfahren zur Herstellung von Flexodruckplatten mittels Lasergravur
DE50211989D1 (de) * 2001-08-03 2008-05-08 Flint Group Germany Gmbh Verfahren zur Herstellung von Zeitungsflexodruckplatten
JP2005510383A (ja) * 2001-11-27 2005-04-21 ビーエーエスエフ ドルクズュステーメ、ゲゼルシャフト、ミット、ベシュレンクテル、ハフツング 親水性重合体及び疎水性エラストマーのブレンドを含む、フレキソ印刷版製造用のレーザー彫刻可能なフレキソ印刷要素

Also Published As

Publication number Publication date
US6880461B2 (en) 2005-04-19
DE10227188A1 (de) 2004-01-08
JP2005534524A (ja) 2005-11-17
WO2003106172A1 (fr) 2003-12-24
US20040231540A1 (en) 2004-11-25
DE50301036D1 (de) 2005-09-29
ATE302687T1 (de) 2005-09-15
AU2003246440A1 (en) 2003-12-31
EP1423280A1 (fr) 2004-06-02

Similar Documents

Publication Publication Date Title
EP1423280B1 (fr) Procede de production de formes flexographiques par gravure directe au laser
EP1451014B1 (fr) Elements d'impression flexographique pouvant etre graves au laser, servant a la production de cliches flexographiques contenant des melanges de polymeres hydrophiles et d'elastomeres hydrophobes
EP1315617B1 (fr) Procede pour produire des plaques d'impression flexographique par gravure au laser
EP1613484B1 (fr) Element pour impression flexographique grave au laser, renfermant du noir de fumee de conductibilite, et procede de production de formes pour flexographie
EP1400857B1 (fr) Procédé de fabrication de plaques flexographiques par développement thermique
DE69721391T2 (de) Flexodruckelement mit einer Pulverschicht und Verfahren zur Herstellung einer Flexodruckplatte davon
EP1527373B1 (fr) Procede de production de formes flexographiques par gravure directe au laser
EP1311393B1 (fr) Procede pour produire des elements flexographiques pouvant etre graves par laser sur des supports metalliques flexibles
EP3304203B1 (fr) Plaque d'impression flexographique imageable de manière numérique pourvu d'une couche barrière intégrale
EP1381511B1 (fr) Element d'impression par flexographie pouvant etre grave au laser comprenant des couches elastomeres en relief renfermant du 1,2-polybutadiene syndiotactique
EP1460477A1 (fr) Elément d'impression flexographique photosensible pour l'enregistrement digitalisé et procédépour la fabrication d'une plaque d'impression flexographique pour des journaux
EP1213615A2 (fr) Elément d'impression flexographique photosensible ayant au moins deux couches décomposables par infrarouge
DE102007006378A1 (de) Fotopolymerisierbare zylindrische endlos-nahtlose Flexodruckelemente und daraus hergestellte harte Flexodruckformen
EP1414647B1 (fr) Procede de production de blocs d'impression flexographique par reticulation par faisceau electronique et par gravure laser
WO2004054803A1 (fr) Procede de fabrication de formes imprimantes flexographiques par gravure au laser a l'aide d'elements flexographiques photopolymeres et element flexographique photopolymerisable
DE10353762A1 (de) Verfahren zur Herstellung von Flexodruckformen durch thermische Entwicklung
DE19846529A1 (de) Photopolymerisierbare Druckformen zur Herstellung von Reliefdruckplatten für den Druck mit UV-härtbaren Druckfarben
EP3394672B1 (fr) Procede de fabrication generative de moules d'impression en relief a l'aide de diffusion de monomere par une couche de masque integrale
WO2002076738A1 (fr) Procede pour produire des plaques d'impression en relief par gravure au laser

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20040306

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK

17Q First examination report despatched

Effective date: 20040614

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050824

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050824

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050824

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050824

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050824

Ref country code: IE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050824

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050824

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REF Corresponds to:

Ref document number: 50301036

Country of ref document: DE

Date of ref document: 20050929

Kind code of ref document: P

DAX Request for extension of the european patent (deleted)
GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 20050917

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20051124

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20051124

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20051124

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20051124

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20051205

RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: XSYS PRINT SOLUTIONS DEUTSCHLAND GMBH

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060124

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060225

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

REG Reference to a national code

Ref country code: FR

Ref legal event code: CD

ET Fr: translation filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060630

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060630

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20060526

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060616

BERE Be: lapsed

Owner name: BASF DRUCKSYSTEME G.M.B.H.

Effective date: 20060630

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070630

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050824

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050824

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060616

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050824

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 13

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 14

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 15

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 16

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20190619

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20190626

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20190828

Year of fee payment: 17

Ref country code: GB

Payment date: 20190624

Year of fee payment: 17

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 50301036

Country of ref document: DE

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20200616

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200630

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200616

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210101

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200616