EP1414647B1 - Procede de production de blocs d'impression flexographique par reticulation par faisceau electronique et par gravure laser - Google Patents

Procede de production de blocs d'impression flexographique par reticulation par faisceau electronique et par gravure laser Download PDF

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Publication number
EP1414647B1
EP1414647B1 EP02791422A EP02791422A EP1414647B1 EP 1414647 B1 EP1414647 B1 EP 1414647B1 EP 02791422 A EP02791422 A EP 02791422A EP 02791422 A EP02791422 A EP 02791422A EP 1414647 B1 EP1414647 B1 EP 1414647B1
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EP
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Prior art keywords
laser
flexographic printing
relief layer
relief
energy
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EP02791422A
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German (de)
English (en)
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EP1414647A1 (fr
Inventor
Jürgen Kaczun
Jens Schadebrodt
Margit Hiller
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Flint Group Germany GmbH
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BASF Drucksysteme GmbH
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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
    • B41N1/12—Printing plates or foils; Materials therefor non-metallic other than stone, e.g. printing plates or foils comprising inorganic materials in an organic matrix
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/145—Infrared
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/146—Laser beam

Definitions

  • the present invention relates to a process for the preparation of flexographic printing plates by laser engraving by applying at least one elastomeric relief layer on a dimensionally stable Carrier, wherein the relief layer at least one elastomeric Binder and at least one absorber for laser radiation comprises, full-surface crosslinking of the relief layer by means of electron radiation in a minimum total dose of 40 kGy and engrave a relief in the networked relief layer by means of a laser.
  • the invention further relates to flexographic printing plates, which are obtainable by the method.
  • the direct laser engraving has opposite the conventional production of flexographic printing plates several advantages.
  • the flank shape of the individual can be Customize relief elements in laser engraving technology. While in photopolymer plates the flanks of a relief point continuous from the surface to the relief ground diverge, can also laser engraved one in the top Area perpendicular or almost vertical sloping flank, extending widened, engraved only in the lower area. Consequently It also comes with increasing wear of the plate during the Printing process to no or at most a slight dot gain. Further details on the technique of laser engraving are For example, shown in "Technique of flexographic printing", p. 173 ff., 4. Ed., 1999, Coating Verlag, St. Gallen, Switzerland.
  • EP-A 640 043 and EP-A 640 044 disclose single-layered or multilayered ones Elastomeric laser engravable recording elements for Production of flexographic printing plates.
  • the elements consist of "reinforced" elastomeric layers.
  • elastomeric binders in particular thermoplastic elastomers such as SBS, SIS or SEBS block copolymers used. Due to the so-called reinforcement, the mechanical Strength of the layer increased to allow flexographic printing.
  • the Reinforcement is achieved either by introducing suitable fillers, photochemical or thermochemical crosslinking or combinations reached from it.
  • CO 2 lasers with a wavelength of 10640 nm can be used.
  • Very powerful CO 2 lasers are commercially available.
  • the elastomeric binders commonly used for flexographic printing plates typically absorb radiation having a wavelength in the range of about 10 ⁇ m. They can thus be engraved with CO 2 lasers (wavelength of 10640 nm) in principle, as disclosed for example by US 5,259,311, even if the speed of the engraving is not always optimal.
  • the achievable resolution and thus the quality of the printing plate when engraving with CO 2 lasers is limited. In addition to existing physical boundaries, the beam becomes increasingly difficult to focus with increasing power.
  • solid-state lasers with wavelengths in the range of around 1 ⁇ m can also be used.
  • powerful Nd / YAG lasers (wavelength 1064 nm) can be used.
  • Nd / YAG lasers have the advantage over CO 2 lasers that significantly higher resolutions are possible due to the significantly shorter wavelength.
  • elastomeric binders of flexographic printing plates do not or only poorly absorb the wavelength of solid-state lasers.
  • Laser-engravable flexographic printing elements that have an opaque relief layer can also be prepared by adding the layer pours and then thermally, e.g. using monomers and thermal polymerization initiators crosslinked. But also by casting only layers with limited thickness can be made be, because with increasing layer thickness at Evaporation of the solvent also increasingly causes coating defects.
  • Flexographic printing plates have layer thicknesses of up to 7 mm on. Such layer thicknesses are usually only by means of multiple Achieve one another when high quality Layers are to be obtained, and the procedure is accordingly cumbersome and expensive. Many still have many Carrier films at the temperatures of thermal crosslinking no longer adequate dimensional stability.
  • the object of the invention was therefore to provide a process for the preparation of flexographic printing plates in which the printing relief by means of a laser in relief layers, the absorber for Laser radiation is included, engraved, and in which too thicker layers and other layers that may be present can be networked in a single operation.
  • an elastomeric Relief layer containing at least one elastomeric binder and includes at least one absorber for laser radiation, on one dimensioned stable support applied.
  • the relief layer opaque.
  • suitable dimensionally stable carriers include films polyethylene terephthalate (PET), polyethylene naphthalate (PEN), Polybutylene terephthalate, polyamide or polycarbonate, preferably PET or PEN films.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • Polybutylene terephthalate polyamide or polycarbonate
  • PET or PEN films preferably PET or PEN films.
  • a carrier may also be conical or cylindrical Tubes made of said materials, so-called sleeves, be used.
  • fiberglass fabrics are suitable or composites of glass fibers and suitable polymers Materials.
  • Metallic supports are for carrying out the process generally unsuitable because they are under electron beam radiation too much heat, which is their use in special cases but not to exclude.
  • the dimensionally stable carrier can for better adhesion of the relief layer optionally coated with an adhesive layer.
  • the relief layer comprises at least one elastomeric binder.
  • the selection of the binder is limited only insofar as For flexographic printing suitable relief layers must be obtained. Suitable binders are chosen by the skilled person depending on the desired Properties of the relief layer, for example, in terms of hardness, elasticity or color transfer behavior selected.
  • Suitable elastomers include essentially 3 groups, without the invention being limited thereto.
  • the first group includes those elastomeric binders which are over ethylenically unsaturated groups.
  • the ethylenically unsaturated Groups can be crosslinked by means of electron radiation.
  • Such binders are, for example, those which are 1,3-diene monomers as isoprene or butadiene in copolymerized form.
  • the ethylenically unsaturated group can be used as chain building block of the polymer (1,4-incorporation), or it may be considered Side group (1,2-incorporation) to be bound to the polymer chain.
  • Examples are natural rubber, polybutadiene, polyisoprene, styrene-butadiene rubber, Nitrile butadiene rubber, acrylate butadiene rubber, Acrylonitrile-isoprene rubber, butyl rubber, Styrene-isoprene rubber, polynorbornene rubber or ethylene-propylene-diene rubber Called (EPDM).
  • natural rubber polybutadiene, polyisoprene, styrene-butadiene rubber, Nitrile butadiene rubber, acrylate butadiene rubber, Acrylonitrile-isoprene rubber, butyl rubber, Styrene-isoprene rubber, polynorbornene rubber or ethylene-propylene-diene rubber Called (EPDM).
  • thermoplastic elastomeric block copolymers from alkenylaromatics and 1,3-dienes include thermoplastic elastomeric block copolymers from alkenylaromatics and 1,3-dienes.
  • block copolymers It may be either linear block copolymers or um radial block copolymers act. Usually it is about It is also possible to use triblock copolymers of the A-B-A type Two-block polymers of the A-B type act, or to those with several alternating elastomeric and thermoplastic blocks, e.g. A-B-A-B-A. It can also be mixtures of two or more different Block copolymers are used.
  • commercial Triblock copolymers often contain certain proportions of diblock copolymers.
  • the diene units can be 1,2- and / or 1,4-linked.
  • Both block copolymers of styrene and butadiene may be used as used by the styrene-isoprene type. you are for example, under the name Kraton® commercially available. Farther It is also possible to use thermoplastic elastomeric block copolymers with styrene endblocks and a random styrene-butadiene midblock, available under the name Styroflex® are.
  • binder with ethylenically unsaturated Groups include modified binders in which crosslinkable Groups introduced by grafting reactions in the polymeric molecule become.
  • the second group includes those elastomeric binders having functional groups that are crosslinkable by electron beams. These are preferably lateral functional groups. But they can also be groups that are integrated into the polymer chain. Examples of suitable functional groups include -OH, -NH 2 , -NHR, -NCO, -CN, -COOH, -COOR, -CONH 2 , -CONHR, -CO-, -CHO or -SO 3 H, where R is generally aliphatic and aromatic radicals. Particularly advantageous for the production of flexographic printing plates by means of electron beam crosslinking and laser engraving have protic functional groups, such as -OH, -NH 2 , -NHR, -COOH or -SO 3 H proved.
  • binders include acrylate rubbers, ethylene-acrylate rubbers, ethylene-acrylic acid rubbers or ethylene-vinyl acetate rubbers and their partially hydrolyzed derivatives, thermoplastic elastomeric polyurethanes, sulfonated polyethylenes or thermoplastic elastomeric polyesters.
  • elastomeric binders can also be used which are both ethylenically unsaturated over like functional groups.
  • examples include copolymers of Butadiene with (meth) acrylates, (meth) acrylic acid or acrylonitrile, and also copolymers or block copolymers of butadiene or Isoprene with functionalized styrene derivatives, For example, block copolymers of butadiene and 4-hydroxystyrene.
  • Unsaturated thermoplastic elastomeric polyester and unsaturated Thermoplastic elastomeric polyurethanes are also suitable.
  • the third group of elastomeric binders includes those neither ethylenically unsaturated groups nor functional Groups.
  • elastomeric binders includes those neither ethylenically unsaturated groups nor functional Groups.
  • Ethylene / propylene elastomers ethylene / 1-alkylene elastomers or products obtained by hydrogenation of diene units, such as SEBS rubbers.
  • mixtures of two or more elastomeric binder can be used, which it is both binders from each one of the described Groups can act or even to mixtures of binders two or all three groups.
  • the combination options are limited only insofar as the suitability of the relief layer for the flexographic printing is not adversely affected by the binder combination may be.
  • a mixture of at least one elastomeric binder which does not having functional groups, with at least one other Binder having functional groups used become.
  • the amount of elastomeric binder (s) in the relief layer is usually 40 wt.% To 99 wt.% Regarding the sum of all components, preferably 50 to 95 wt.%, and most preferably 60 to 90 wt.%.
  • the relief layer further comprises at least one absorber for Laser radiation. It can also be mixtures of different absorbers be used for laser radiation. Suitable absorber for laser radiation have a high absorption in the range of the laser wavelength on. In particular, absorbers are suitable, the high Absorption in the near infrared as well as in the longer wavelength VIS range of the electromagnetic spectrum. Such absorbers are particularly suitable for absorbing the radiation of powerful Nd-YAG lasers (1064 nm) and IR diode lasers, the typically wavelengths between 700 and 900 nm as well as 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.
  • suitable absorbers are inorganic pigments, in particular intensively colored inorganic pigments such as Chromium oxides, iron oxides, iron oxide hydrates or carbon black.
  • Particularly suitable as absorber for laser radiation are finely divided Carbon blacks with a particle size between 10 and 50 nm.
  • the added absorber not only the speed and efficiency of the engraving of the influence elastomeric layer by laser, but also others Properties of the flexographic printing element, such as its Hardness, elasticity, thermal conductivity or ink acceptance.
  • the amount of the absorber for laser radiation 1 to 30 wt .-% and particularly preferably 5 to 20% by weight.
  • the elastomeric relief layer also by means of Electron radiation crosslinkable low molecular weight or oligomeric Compounds include.
  • Oligomeric compounds generally have a molecular weight of not more than 20,000 g / mol. low molecular weight and oligomeric compounds are the following For the sake of simplicity, they are referred to as monomers.
  • monomers can be added to increase the speed increase the networking, if desired by the skilled person becomes.
  • elastomeric binders from the Groups 1 and 2 is the addition of monomers for acceleration generally not mandatory.
  • elastomeric binders from Group 3 is the addition of monomers as a rule recommended, without this being mandatory in any case necessary would.
  • Monomers also for controlling the crosslinking density in the course of Electron beam hardening and to set the desired Hardness of the crosslinked material can be used. Depending on the type and Amount of added low molecular weight compounds are more or get closer networks.
  • the known ethylenically unsaturated Monomers are used, which are also used for the production of conventional photopolymer flexographic printing plates are used can.
  • the monomers should be compatible with the binders be and have at least one ethylenically unsaturated group. They should not be volatile.
  • the Boiling point of suitable monomers not lower than 150 ° C.
  • amides and esters of acrylic acid or methacrylic acid with mono- or polyfunctional alcohols, amines, amino alcohols or hydroxy ethers and esters, styrene or substituted ones Styrenes, esters of fumaric or maleic acid or allyl compounds prove.
  • Examples include butyl acrylate, 2-ethylhexyl 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.
  • monomers which have at least one functional group which can be crosslinked under the influence of electron beam curing.
  • the functional group is a protic group. Examples include -OH, -NH 2 , -NHR, -COOH or -SO 3 H. With particular preference it is also possible to use di- or polyfunctional monomers in which terminal functional groups are connected to one another via a spacer.
  • Examples of such monomers include dialcohols such as 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, diamines such as 1,6-hexanediamine, 1,8-hexanediamine, dicarboxylic acids such as oxalic acid, malonic acid, Adipic acid, 1,6-hexanedicarboxylic acid, 1,8-octanedicarboxylic acid, 1,10-decanedicarboxylic acid, phthalic acid, terephthalic acid, maleic acid or fumaric acid.
  • dialcohols such as 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol
  • diamines such as 1,6-hexanediamine, 1,8-hexanediamine
  • monomers which are both ethylenic have unsaturated groups such as functional groups.
  • ⁇ -hydroxyalkyl acrylates such as Ethylene glycol mono (meth) acrylate, 1,4-butanediol mono (meth) acrylate or 1,6-hexanediol mono (meth) acrylate.
  • the amount of monomer added is 0 to 30 % By weight with respect to the amount of all components of the relief layer, preferably 0 to 20 wt .-%.
  • the elastomeric relief layer may also contain additives and auxiliaries such as, for example, dyes, dispersing aids, Antistatic agents, plasticizers or abrasive particles include.
  • additives and auxiliaries such as, for example, dyes, dispersing aids, Antistatic agents, plasticizers or abrasive particles include.
  • the amount of such additives should, however, usually 20 wt .-% with respect to the amount of all components of the elastomeric Do not exceed the relief layer of the recording element.
  • the elastomeric relief layer may also consist of several relief layers being constructed. These elastomeric sublayers can be of same, approximately the same or of different material Be composition.
  • the thickness of the elastomeric relief layer or all relief layers together is generally between 0.1 and 7 mm, preferably 0.4 to 7 mm. The thickness is determined by the expert depending on the desired Purpose of the flexographic printing form chosen suitably.
  • the flexographic printing element used as the starting material may be optional still a top layer with a thickness of not have more than 100 microns.
  • the composition of such a top layer may be in terms of optimal printing properties like For example, color transfer can be selected while the composition the underlying relief layer in terms of is selected for optimum hardness or elasticity.
  • the upper class must either be laser engravable, or at least in the course of the laser engraving along with the underneath lying relief layer be removable. It includes at least a polymeric binder which is not necessarily elastomeric have to be. It can also be an absorber for laser radiation or also comprise monomers or auxiliaries.
  • the starting material for the process can, for example, by Dissolve or disperse all components in a suitable solvent and pouring onto a carrier.
  • at multilayer elements can in principle known type and Way several layers are poured on each other. Since wet-innass worked, the layers combine well with each other. Even an upper class can be infused.
  • the individual layers can be on temporary supports poured and then the layers by laminating with each other get connected. After casting can still optional one Cover film for protection against damage to the starting material be applied.
  • thermoplastic elastomeric binders and the preparation is carried out in a known manner by extrusion between a carrier film and a cover sheet or a Cover element followed by calendering, such as from EP-A-084 851. This way you can also make thick layers in a single operation. multilayer Elements can be made by coextrusion.
  • the relief layer is produced by means of electron radiation fully networked. If the flexographic printing element still has a protective film, this should be before crosslinking usually be deducted. But this is just in networking not necessarily compelling by means of electron beams.
  • Suitable devices for electron beam crosslinking are the person skilled in principle known.
  • the irradiation with electrons can be both inline directly following the continuous Making the relief layer, e.g. immediately after to the calendering.
  • the irradiation with electrons can but advantageously also be done in a separate process step.
  • the flexographic printing elements in usually irradiated only from the top of the elements.
  • the invention also includes the procedure that you irradiated the element from the top and from the bottom.
  • the maximum irradiation dose will vary according to the professional the desired properties such as hardness or restoring force the flexographic printing set. As a rule, it is recommended but not to use more than 200 kGy for networking and especially it is preferable not to crosslink more than 150 kGy use. Has proven to be a total dose for irradiation of 60 to 120 kGy.
  • the energy of the electron beam is depending on the expert Thickness and composition of the flexographic printing element determined.
  • the Energy of electron radiation is decisive for the maximum Penetration depth of the electron beam in the relief layer.
  • the absorber For laser radiation it has but usually proven, electron beams with an energy of at least 2 Use MeV.
  • the irradiation with electrons can be made such that administered the entire dose in a single irradiation procedure becomes.
  • the dose rate should be as high as possible to achieve the shortest possible irradiation times.
  • she is allowed not be so high that the flexographic printing element too Heavily heated because otherwise the dimensional stability of the flexographic printing element could be affected.
  • a warm up above 80 ° C should be avoided.
  • it is regularly advantageous, especially temperature-stable Carrier films, such as those from PEN use.
  • the irradiation is usually done in air, but the Irradiation can of course also in special cases under protective gases such as argon or nitrogen. if desired
  • the plates to be irradiated can also be encapsulated to exclude air become.
  • the flexographic printing element during the Irradiation is also advantageous to use to cool, for example by an air flow, the is transferred, or by placing on a chilled surface.
  • Procedure is the total dose of electron radiation distributed over two or more subdoses.
  • the partial doses can be the same size or different sizes, the electron beams can the same energy or different energy or the have the same or a different dose rate.
  • the individual sub-cans can follow each other directly. But they can also be advantageous for the same length or different long breaks have been interrupted.
  • the Irradiation can be interrupted only briefly or even longer become. Irradiation breaks of more than 60 min between the individual Cans should be avoided, however. Have proven Irradiation breaks between 1 and 30 min.
  • the electron beam crosslinking step is the energy of electron radiation administered at all Partial doses equal or approximately equal. After every partial dose a radiation break is taken. It is preferred with irradiated a relatively high dose rate, causing the relief layer strongly heated. Temperatures of more than 100 ° C should but be avoided. During irradiation breaks, the relief layer can abreact and cool off again.
  • the energy is the electron beam at least one of the administered partial doses of that of the other sub-cans different.
  • the Energy of the electron beams of the first administered partial doses be chosen so that the flexographic printing element throughout the Depth of the relief is networked while the energy of the electron beams the last administered partial dose is measured that continues only in a thin layer on the surface is networked.
  • a flexographic printing plate can be obtained which a relatively soft underlayer and harder by comparison Upper layer has.
  • the energy of the electron beams can also be applied to all partial doses be different.
  • a printing relief by means of a Laser engraved in the crosslinked by electron beam layer is engraved.
  • pixels are engraved in which the flanks of the picture elements initially fall vertically and down widen only in the lower part of the picture element.
  • Laser engraving is especially suitable for IR lasers. It can but also lasers with shorter wavelengths can be used, provided the laser has sufficient intensity. For example can also be a frequency doubled (532 nm) or frequency tripled (355 nm) Nd-YAG laser can be used or also excimer lasers (e.g., 248 nm). If needed for material removal, must each be adapted to the laser wavelength accordingly Absorber can be used for laser radiation.
  • a CO 2 laser with a wavelength of 10640 nm can be used.
  • Particularly advantageous lasers are used with a wavelength between 600 and 2000 nm.
  • Nd-YAG lasers (1064 nm), IR diode lasers or solid-state lasers can be used.
  • Particularly preferred for carrying out the method according to the invention are Nd / YAG lasers.
  • the image information to be engraved is transmitted directly from the lay-out computer system to the laser apparatus.
  • the lasers can be operated either continuously or pulsed.
  • the flexographic printing plate obtained can be used directly become. If desired, however, the resulting flexographic printing plate can still to be cleaned. By such a cleaning step will be detached, but may not be complete yet Plate surface removed removed layer components. As a rule is easy to handle with water, water / surfactant or Alcohol sufficient.
  • the process according to the invention can be carried out in a single production cycle be performed, in which all process steps in succession be executed.
  • the method but also be interrupted after process step (b).
  • the networked, Laser-engraved recording element can be assembled and stored at a later date by means of Laser engraved to a flexographic printing plate or flexo sleeve be further processed.
  • the flexographic printing element e.g. with a temporary cover sheet, for example to protect from PET, which of course deducted again before the laser engraving must become.
  • the thermal load of the flexographic printing element in the course of crosslinking can be compared to thermal crosslinking significantly be reduced or even avoided altogether. This leads to Flexographic printing plates with significantly improved dimensional stability and thus significantly better print quality.
  • a relief layer with a binder having ethylenically unsaturated groups was prepared.
  • the following components were used.
  • components feedstocks Amount [wt%] binder Polybutadiene rubber (high vinyl content) 68.5 Absorber for laser radiation finely divided carbon black 10.0 monomers lauryl 10.0 additives Polybutadiene oil (plasticizer) 10.0 therm. stabilizer 1.5
  • Binders, additives and absorbers for laser radiation were used in a laboratory kneader at a melt temperature of 150 ° C mixed. After 15 minutes, the absorber for laser radiation was homogeneously dispersed. The compound thus obtained was together with the monomer dissolved in toluene at 80 ° C, cooled to 60 ° C and to a uncoated, 125 ⁇ m thick PET film poured. After 24 hours Flash off at room temperature and dry for 3 hours 60 ° C, the resulting relief layer (layer thickness 900 microns) on a second, adhesive-coated, 125 ⁇ m thick PET film laminated. Before further treatment, the item was 1 week stored at room temperature.
  • a relief layer was prepared with a binder mixture having ethylenically unsaturated groups.
  • the following components were used.
  • components feedstocks Amount [wt%] binder EPDM rubber with 5% by weight of ethylidene norbornene as a termonomer 75.5
  • Polybutadiene rubber high vinyl content 4.0
  • Absorber for laser radiation finely divided carbon black 10.0 monomers lauryl 7.5 trimethacrylate 1.5 additives therm. stabilizer, dispersing agent 1.5
  • Binders, additives and absorbers for laser radiation were used in a laboratory kneader at a melt temperature of 170 ° C mixed. After 15 minutes, the absorber for laser radiation was homogeneously dispersed. The compound thus obtained was together with the monomers dissolved in toluene at 80 ° C, cooled to 60 ° C and to a uncoated, 125 ⁇ m thick PET film poured. After 24 hours Flash off at room temperature and dry for 3 hours 60 ° C, the resulting relief layer (layer thickness 800 microns) on a second, adhesive-coated, 175 ⁇ m thick PET film laminated. Before further treatment, the item was 1 week stored at room temperature.
  • the components were in a twin-screw extruder at a Melt temperature of 140 - 160 ° C mixed intensively, extruded through a slot die and then between a cover sheet and a carrier sheet calendered.
  • the thickness of the Relief layer was 860 microns. Before further treatment the element was stored for 1 week at room temperature.
  • a relief layer with a binder having ethylenically unsaturated groups was prepared by extrusion and subsequent calendering between a cover film and a carrier film.
  • the following components were used.
  • components feedstocks Amount [wt%] binder SIS triblock copolymer with 15% by weight of styrene (Kraton D-1161, Kraton Polymers) 79.0
  • the components were in a twin-screw extruder at a Melt temperature of 140 - 160 ° C mixed intensively, extruded through a slot die and then between a cover sheet and a carrier sheet calendered.
  • the thickness of the Relief layer was 850 microns. Before further treatment the element was stored for 1 week at room temperature.
  • an electron irradiation apparatus (rated power about 150 kW), which electron beams with Can generate electron energies of 2.5 - 4.5 MeV.
  • the transport the electron-radiating elements through the zone of electron irradiation carried out by means of vertically freely suspended Aluminum pallets, which have a movable suspension with a guided conveyor belt were connected, so by the Control of conveyor belt speed uniform transport aluminum pallets through the zone of electron irradiation could be done.
  • Example 1 A total of 6 elements according to Example 1 were used, of which 1 element was retained as reference (Sample No. 0).
  • the Energy of electron radiation was about 3.0 MeV.
  • the waiting time between 2 partial doses was every 20 minutes. After each partial dose, one element was taken out taken from the radiation circuit, the rest were taken before administration the next partial dose turned by 180 °.
  • Example 2 A total of 9 elements according to Example 2 were used, of which 1 element was retained as reference (Sample No. 0).
  • the Energy of electron radiation was about 3.0 MeV. there has been a successive irradiation series with 8 z.T. different partial doses carried out.
  • the partial doses were in detail successively 23, 22, 22, 35, 42, 30, 30 and 29 kGy.
  • the waiting time between 2 partial doses was 20 minutes each. After every partial dose an element was taken from the radiation circuit, the remainder were reversed before administration of the next partial dose 180 ° turned.
  • Example 3 A total of 9 elements according to Example 3 were used, of which 1 element was retained as reference (Sample No. 0).
  • the Energy of electron radiation was about 3.0 MeV. there has been a successive irradiation series with 8 z.T. different partial doses carried out.
  • the partial doses were in detail successively 23, 22, 22, 35, 42, 30, 30 and 29 kGy.
  • the waiting time between 2 partial doses was 20 minutes each. After every partial dose an element was taken from the radiation circuit, the remainder were reversed before administration of the next partial dose 180 ° turned.
  • Example 4 A total of 6 elements according to Example 4 were used, of which 1 element was retained as reference (Sample No. 0). It was a series of irradiation with UVA light as described above with the following single irradiation times: 1, 5, 15, 30, 60 min.
  • the following table shows the properties of the flexographic printing element obtained as a function of the UVA irradiation time.
  • No. Duration of UVA irradiation [min] Swelling in toluene [Wt .-%] gel [Wt .-%] Mech. Hardness (DIN 53505) [Shore A] 0 0 ⁇ 0 1 1 ⁇ 0 32 2 5 ⁇ 0 33 3 15 ⁇ 1 35 4 30 ⁇ 3 36 5 60 ⁇ 2 34
  • a test motif consisting of solid surfaces and various line elements was engraved into the respective flexographic printing element.
  • Each 1 cm x 1 cm line elements consisted of parallel, individual negative lines with per line element of the same line width and the same line spacing.
  • a list of the engraved line elements is given in the following table. Line element no. Width of the negative lines [ ⁇ m] Distance of the negative lines [ ⁇ m] 1 20 20 2 40 40 3 60 60 4 80 80 5 100 100 6 200 200 7 500 500 8th 1000 1000
  • the quality of the laser-engraved flexographic printing elements was with Assessed the help of a light microscope, which has a device for measuring distances or heights and depths.
  • the engraving depth was based on the entire area engraved area measured. Furthermore, each of the finest line element determined, in which the engraved individual lines under the microscope were still completely separated from each other. The individual lines were considered completely separate from each other assessed resolved when the surface of the between the negative lines remaining positive line elements have a width of had at least 5 microns and this surface except for a difference of 20 microns the same height possessed as the non-engraved areas the positive full surface. In this type of assessment means a low number of the number of the finest still pictured Line element therefore a good engraving quality while a high number of lower resolution and thus one worse engraving quality corresponds.
  • melt edges and deposits in the peripheral zones of the negative elements and solid surfaces were assessed visually.
  • Example no. Cure type crosslinking conditions laser type Melt edges (visual) Engraving depth [ ⁇ m] Finest line element [No.] 5 IT 60 kGy CO 2 Little 760 3 5 IT 80 kGy CO 2 None 830 1 5 IT 60 kGy Nd-YAG Little 810 2 5 IT 80 kGy Nd-YAG None 830 1 6 IT 67 kGy CO 2 medium 640 3 6 IT 102 kGy CO 2 Little 700 2 6 IT 67 kGy Nd-YAG medium 660 3 6 IT 102 kGy Nd-YAG Little 690 2 7 IT 102 kGy CO 2 medium 650 2 7 IT 144 kGy CO 2 None 710 2 7 IT 102 kGy Nd-YAG medium 660 2 7 IT 144 kGy Nd-YAG None 680 1 8th UVA 15 minutes CO 2 Very strong 390 7 8th UVA 15

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Plasma & Fusion (AREA)
  • Manufacturing & Machinery (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Manufacture Or Reproduction Of Printing Formes (AREA)
  • Laser Beam Processing (AREA)
  • Lasers (AREA)

Claims (27)

  1. Procédé de fabrication de blocs d'impression flexographique par gravure au laser, comprenant les étapes suivantes:
    a) application d'au moins une couche élastomère en relief sur un support dimensionnellement stable, la couche en relief comprenant au moins un liant élastomère et au moins un agent absorbant pour le rayonnement laser;
    b) réticulation sur toute la surface de la couche en relief ;
    c) gravure d'un relief d'impression dans la couche en relief au moyen d'un laser;
    caractérisé en ce que la réticulation sur toute la surface est effectuée au moyen d'un rayonnement électronique en dose totale minimale de 40 kGy.
  2. Procédé selon la revendication 1, caractérisé en ce que l'on applique en outre, dans une étape (a'), une couche supérieure d'une épaisseur ne dépassant pas 100 µm, la couche supérieure comprenant au moins un liant polymère.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que les rayonnements électroniques présentent une énergie d'au moins 2 MeV.
  4. Procédé selon la revendication 1 ou 2, caractérisé en ce que l'on répartit la dose totale du rayonnement électronique en deux doses partielles ou plus.
  5. Procédé selon la revendication 4, caractérisé en ce que le rayonnement est interrompu après l'administration d'une telle dose partielle pendant une pause de rayonnement.
  6. Procédé selon la revendication 4 ou 5, caractérisé en ce que l'énergie du rayonnement électronique est identique à chacune des doses partielles administrées.
  7. Procédé selon la revendication 4 ou 5, caractérisé en ce que l'énergie du rayonnement électronique est, pour au moins une des doses partielles administrées, différente de celle des autres doses partielles.
  8. Procédé selon la revendication 4 ou 5, caractérisé en ce que l'énergie du rayonnement électronique est différente pour toutes les doses partielles administrées.
  9. Procédé selon la revendication 8, caractérisé en ce que l'on commence par la dose partielle dans laquelle les rayons électroniques présentent l'énergie la plus élevée et l'on réduit progressivement l'énergie à chaque autre dose partielle.
  10. Procédé selon l'une quelconque des revendications 4 à 8, caractérisé en ce qu'au moins une des doses partielles présente une énergie d'au moins 2 MeV.
  11. Procédé selon l'une quelconque des revendications 1 à 10, caractérisé en ce que l'on ne dépasse pas une dose totale de 200 kGy.
  12. Procédé selon l'une quelconque des revendications 1 à 10, caractérisé en ce que l'on ne dépasse pas une dose totale de 150 kGy.
  13. Procédé selon l'une quelconque des revendications 1 à 12, caractérisé en ce que l'on effectue l'exposition au rayonnement électronique à l'air.
  14. Procédé selon l'une quelconque des revendications 1 à 13, caractérisé en ce que le liant élastomère présente des groupes à insaturation éthylénique.
  15. Procédé selon l'une quelconque des revendications 1 à 13, caractérisé en ce que le liant élastomère présente des groupes fonctionnels réticulables sous l'influence du rayonnement électronique.
  16. Procédé selon la revendication 15, caractérisé en ce que les groupes fonctionnels sont des groupes protiques.
  17. Procédé selon l'une quelconque des revendications 1 à 13, caractérisé en ce que le liant élastomère présente des groupes à insaturation éthylénique et des groupes fonctionnels réticulables sous l'influence du rayonnement électronique.
  18. Procédé selon l'une quelconque des revendications 1 à 13, caractérisé en ce que l'on utilise un mélange d'au moins un liant élastomère, qui ne présente aucun groupe fonctionnel, avec au moins un autre liant qui présente des groupes fonctionnels.
  19. Procédé selon l'une quelconque des revendications 1 à 18, caractérisé en ce que la couche en relief comprend en outre au moins un composé réticulable au moyen du rayonnement électronique, de faible poids moléculaire ou oligomère.
  20. Procédé selon la revendication 19, caractérisé en ce que le composé de faible poids moléculaire est un monomère à insaturation éthylénique.
  21. Procédé selon la revendication 19, caractérisé en ce que le composé de faible poids moléculaire ou oligomère est un composé présentant des groupes fonctionnels.
  22. Procédé selon la revendication 21, caractérisé en ce que les groupes fonctionnels sont des groupes protiques.
  23. Procédé selon l'une quelconque des revendications 1 à 22, caractérisé en ce que le liant élastomère est un liant élastomère thermoplastique et en ce que l'on fabrique la couche en relief par extrusion suivie d'un calandrage.
  24. Procédé selon l'une quelconque des revendications 1 à 23, caractérisé en ce que la couche en relief est opaque.
  25. Procédé selon l'une quelconque des revendications 1 à 24, caractérisé en ce que l'on effectue la gravure au laser (c) avec un laser ayant une longueur d'onde de 600 à 2000 nm.
  26. Procédé selon la revendication 25, caractérisé en ce que l'on effectue la gravure au laser (c) avec un laser Nd/YAG.
  27. Bloc d'impression flexographique qui peut être obtenu selon l'une quelconque des revendications 1 à 26.
EP02791422A 2001-07-27 2002-07-18 Procede de production de blocs d'impression flexographique par reticulation par faisceau electronique et par gravure laser Expired - Lifetime EP1414647B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10136477A DE10136477A1 (de) 2001-07-27 2001-07-27 Verfahren zur Herstellung von Flexodruckformen mittels Elektronenstrahlvernetzung und Lasergravur
DE10136477 2001-07-27
PCT/EP2002/008013 WO2003011596A1 (fr) 2001-07-27 2002-07-18 Procede de production de blocs d'impression flexographique par reticulation par faisceau electronique et par gravure laser

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EP1414647A1 EP1414647A1 (fr) 2004-05-06
EP1414647B1 true EP1414647B1 (fr) 2005-04-13

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US (1) US6921625B2 (fr)
EP (1) EP1414647B1 (fr)
JP (1) JP2004535962A (fr)
AT (1) ATE293041T1 (fr)
DE (2) DE10136477A1 (fr)
WO (1) WO2003011596A1 (fr)

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DE10318039A1 (de) 2003-04-17 2004-11-04 Basf Drucksysteme Gmbh Lasergravierbares Flexodruckelement enthaltend einen Leitfähigkeitsruß sowie Verfahren zur Herstellung von Flexodruckformen
JP2007524722A (ja) 2003-06-20 2007-08-30 サイメッド ライフ システムズ インコーポレーティッド 末端キャップポリマー鎖およびその産物
US7226979B2 (en) 2004-02-11 2007-06-05 University Of Massachusetts Lowell Copolymers comprising olefin and protected or unprotected hydroxystyrene units
US7056985B2 (en) 2004-02-11 2006-06-06 University Of Massachusetts Lowell End-capped polymer chains and products thereof
US8501390B2 (en) * 2006-06-27 2013-08-06 Xiper Innovations, Inc. Laser engravable flexographic printing articles based on millable polyurethanes, and method
WO2008002980A2 (fr) * 2006-06-27 2008-01-03 Stork Prints America, Inc. article d'impression flexographique gravable AU laser
US20080057295A1 (en) * 2006-09-01 2008-03-06 Fina Technology, Inc. Engravable board
DE102008024214A1 (de) * 2008-05-19 2009-11-26 Flint Group Germany Gmbh Fotopolymerisierbare Flexodruckelemente für den Druck mit UV-Farben
US20110014573A1 (en) * 2009-07-14 2011-01-20 Eynat Matzner System for engraving flexographic plates
US9197736B2 (en) 2009-12-31 2015-11-24 Digimarc Corporation Intuitive computing methods and systems
DE102010027728A1 (de) * 2010-04-14 2011-10-20 Manroland Ag Walzenaufzug oder Zylinderaufzug einer Druckmaschine
US9311640B2 (en) 2014-02-11 2016-04-12 Digimarc Corporation Methods and arrangements for smartphone payments and transactions
JP6403107B2 (ja) * 2013-03-22 2018-10-10 パナソニックＩｐマネジメント株式会社 車載充電装置
CN112876623B (zh) * 2021-01-18 2023-04-07 万华化学(四川)有限公司 一种abs接枝胶乳的制备方法及制备的abs树脂

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JPS5756259A (en) * 1980-09-19 1982-04-03 Dainippon Printing Co Ltd Manufacture of gravure plate
US5798202A (en) 1992-05-11 1998-08-25 E. I. Dupont De Nemours And Company Laser engravable single-layer flexographic printing element
US5804353A (en) 1992-05-11 1998-09-08 E. I. Dupont De Nemours And Company Lasers engravable multilayer flexographic printing element
US5259311A (en) 1992-07-15 1993-11-09 Mark/Trece Inc. Laser engraving of photopolymer printing plates
DE19918363A1 (de) * 1999-04-22 2000-10-26 Dlw Ag Druckform für Flexodruck auf Basis nachwachsender Rohstoffe
ATE270191T1 (de) * 2000-12-19 2004-07-15 Basf Drucksysteme Gmbh Verfahren zur herstellung von flexodruckformen mittels lasergravur
WO2003045693A1 (fr) * 2001-11-27 2003-06-05 Basf Drucksysteme Gmbh 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

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WO2003011596A1 (fr) 2003-02-13
JP2004535962A (ja) 2004-12-02
EP1414647A1 (fr) 2004-05-06
DE50202790D1 (de) 2005-05-19
US20040197711A1 (en) 2004-10-07
ATE293041T1 (de) 2005-04-15
DE10136477A1 (de) 2003-02-06
US6921625B2 (en) 2005-07-26

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