EP1136254B1 - Utilisation de copolymères greffés pour la fabrication d'éléments marquables au laser en relief - Google Patents

Utilisation de copolymères greffés pour la fabrication d'éléments marquables au laser en relief Download PDF

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Publication number
EP1136254B1
EP1136254B1 EP01106885A EP01106885A EP1136254B1 EP 1136254 B1 EP1136254 B1 EP 1136254B1 EP 01106885 A EP01106885 A EP 01106885A EP 01106885 A EP01106885 A EP 01106885A EP 1136254 B1 EP1136254 B1 EP 1136254B1
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EP
European Patent Office
Prior art keywords
laser
engravable
relief
layer
graft copolymers
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP01106885A
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German (de)
English (en)
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EP1136254A3 (fr
EP1136254A2 (fr
Inventor
Margit Dr. Hiller
Alfred Leinenbach
Uwe Dr. Stebani
Wolfgang Wenzl
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Flint Group Germany GmbH
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BASF Drucksysteme GmbH
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Publication of EP1136254A3 publication Critical patent/EP1136254A3/fr
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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
    • 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
    • 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 invention relates to a method for producing flexographic printing plates by engraving a printing relief with the help of a laser in at least one on a dimensionally stable carrier applied cross-linked layer, the cross-linked layer comprises at least one graft copolymer, which by radical polymerization of vinyl esters in the presence of Polyalkylene oxides and subsequent, at least partial saponification of the ester function of graft copolymers available is.
  • the conventional technique for the production of flexographic printing plates starting from photopolymerizable raw panels comprises several Process steps such as back exposure, imagewise exposure with actinic light, washing out, drying, post-treatment as well as drying at room temperature and is overall a relative time-consuming process. Depending on the thickness of the plate, pass usually up to 24 hours to get from a raw photopolymer plate to produce a print-ready flexographic printing plate.
  • IR lasers such as, for example, CO 2 lasers or Nd-YAG lasers.
  • indentations are engraved directly into a suitable plate, which in principle forms a relief suitable for printing.
  • direct laser engraving has a number of other advantages.
  • the shape of the relief can be chosen freely. While the sides of a relief point in photopolymer plates continuously diverge from the surface to the base of the relief, the side shape of laser-engraved plates can be freely selected. For example, a flank that slopes vertically or almost vertically in the upper region and that only widens in the lower region is common.
  • a typical flexographic printing plate is between, for example 0.5 and 7 mm thick and the non-printing depressions in the The plate is between 300 ⁇ m and 3 mm deep.
  • Sufficiently powerful lasers must therefore be available stand in order to be able to engrave as economically as possible.
  • the lasers must be able to be focused as well as possible in order to to ensure high resolution.
  • elastomeric binders such as SIS or SBS block copolymers are in principle sensitive to Laser radiation. Recording elements containing such binders for the production of flexographic printing plates by laser engraving are disclosed, for example, by EP-A 640 043 and EP-A 640 044.
  • the sensitivity to laser radiation is only moderate. There is therefore still a need for higher binders To provide sensitivity to laser radiation.
  • the relief layers Laser radiation absorbing materials add to the sensitivity to increase compared to laser radiation, for example DE-A 196 25 749, EP-A 710 573 or EP-A 640 043.
  • absorbent In particular, carbon black has been suggested for materials.
  • the laser-engravable layer also important application properties for relief printing plates such as For example, elasticity, hardness, roughness, color acceptance or low Must show swellability in printing inks due to fillers u.U. could be adversely affected. Optimizing the Materials with a view to optimal laser engraving there are limits to this by adding absorbent materials. Common photopolymer flexographic printing plates also lose through these fillers their transparency, what the exact registration Assembly difficult because of assembly crosses or similar markings are no longer visible through the plate. For filled Plates must be used with special assembly devices.
  • polyvinyl alcohols or polyvinyl alcohol derivatives for the production of water-based developable photopolymer relief printing plates is also known.
  • Laser engraving of relief printing plates with such polymers is also known.
  • DE-A 198 38 315 discloses a laser-engravable recording element which contains polyvinyl alcohol or polyvinyl alcohol derivatives in the relief layer.
  • the recording elements disclosed therein contain particulate, polymeric fillers with a low ceiling temperature, ie fillers which can be depolymerized at comparatively low temperatures, in order to improve the sensitivity to lasers.
  • polyvinyl alcohols can be engraved using CO 2 lasers without the addition of fillers, the speed of laser engraving is slow.
  • the object of the invention was to develop a manufacturing process for flexographic printing plates by laser engraving laser-engravable marking elements, which has a very high sensitivity to Have laser radiation, and which are without melting edges have it engraved with lasers, to shafts.
  • a method for making flexographic printing forms has been developed by engraving a printing relief with the help of a laser in at least one on a dimensionally stable carrier applied, crosslinked layer found, the crosslinked Layer comprises at least one graft copolymer, which by radical polymerization of vinyl esters in the presence of Polyalkylene oxides and subsequent, at least partial saponification of the ester function of graft copolymers available is.
  • graft copolymers In the manufacture of the graft copolymers used it is preferred to graft onto the polyalkylene oxides. However, mechanisms other than grafting are also conceivable.
  • graft copolymers used are both pure graft copolymers and mixtures of Graft copolymers with residues of ungrafted polyalkylene oxides as well as at least partially saponified polyvinyl esters.
  • the graft copolymers used are in one first reaction stage by polymerization of vinyl esters in Presence of polyalkylene oxides and an initiator for radical Polymerization produced.
  • a second reaction stage at least the ester groups in the graft copolymer obtained are partially saponified to form vinyl alcohol structural units.
  • Such graft copolymers, their preparation and their properties are disclosed, for example, in EP-A 224 164 We explicitly refer to their statements at this point.
  • Particularly suitable polyalkylene oxides are polymers based on Ethylene oxide, propylene oxide and butylene oxide as well as statistical Copolymers or block copolymers thereof in question.
  • the copolymers Preferably included the copolymers have at least 50 mol% ethylene oxide.
  • Especially polyethylene oxide is preferred.
  • the OH end groups of the polyalkylene oxides can also be modified, for example esterified or etherified.
  • Branched polyalkylene oxides can be obtained by, for example, polyalcohols such as glycerol, ethylene oxide and / or other alkylene oxides attaches. Polyalkylene oxides can also be used still contain small amounts of other chain building blocks.
  • carbonate groups which are formed by the reaction of polyalkylene oxides are available with phosgene or urethane groups, which by reacting polyalkylene oxides with aliphatic or aromatic diisocyanates are available.
  • chain building blocks should generally 5 mol% with regard to the total amount of chain building blocks.
  • the molecular weights M n (number average) of the polyalkylene oxides used are generally between 5000 and 100000 g / mol, preferably between 10000 g / mol and 50000 g / mol.
  • the vinyl esters of aliphatic C 1 -C 24 monocarboxylic acids may be mentioned in particular as vinyl esters for the synthesis of the grafted-on side groups.
  • Vinyl acetate and vinyl propionate are preferred; vinyl acetate is particularly preferred.
  • one or more additional ethylenically unsaturated monomers be used in addition to the vinyl esters.
  • the amount of these additional monomers should, however, 20 mol% based on. do not exceed the total amount of monomers used. 0 to 5 mol% are preferred.
  • Acidic monomers are exemplary such as acrylic acid or methacrylic acid and basic monomers such as Called vinylformamide or 1-vinylimidazole.
  • initiators for radical polymerization the the usual peroxo and / or azo compounds are used for this, for example dibenzoyl peroxide, t-butyl perbenzoate or azobisisobutyronitrile.
  • the amounts of initiator or initiator mixtures used are between 0.01 and 10% by weight, preferred between 0.5 and 2% by weight, based on the vinyl ester or others Monomers.
  • the polymerization of the vinyl esters and optionally further monomers in the presence of polyalkylene oxides is advantageous at 50 to 150 ° C, preferably carried out at 80 to 120 ° C. You can after methods known to the person skilled in the art in solvents or in the absence be carried out by solvents. Particularly advantageous can polymerize in the absence of one Solvents are carried out in molten polyalkylene oxide. Suitable embodiments of the polymerization are in EP-A 224 164.
  • the amount of grafted vinyl ester and optionally more Monomers is generally 30 to 400 mol% based on the sum all monomeric units in the graft copolymer, preferably 30 to 80 mol%.
  • the ester groups in the obtained graft copolymer at least in a known manner are partially saponified to form vinyl alcohol structural units.
  • the ester groups in the obtained graft copolymer at least in a known manner are partially saponified to form vinyl alcohol structural units.
  • the reaction step can be, for example, sodium hydroxide solution or potassium hydroxide solution be used. It is also possible to use the carboxyl groups by transesterification, for example with a methanolic NaOH solution being vinyl alcohol groups and methyl acetate arise.
  • the degree of saponification is determined by the person skilled in the art depending on the desired properties of the polymer chosen. As a rule, however, at least 50 mol% of the vinyl ester structural units in the graft copolymer saponified, preferably at least 65 mol%. Especially the degree of saponification is preferably 80 to 98%.
  • the vinyl alcohol groups obtained with the ester function Compounds are implemented that contain olefinic groups.
  • graft copolymers are formed which contain additional contain pendant polymerizable groups.
  • the implementation can in a known manner with esters, chlorides or preferably anhydrides of olefinically unsaturated carboxylic acids, such as, for example, acrylic acid, methacrylic acid or maleic acid become.
  • esters, chlorides or preferably anhydrides of olefinically unsaturated carboxylic acids such as, for example, acrylic acid, methacrylic acid or maleic acid become.
  • olefinic content Side groups of about 2 to 20 mol% based on the total amount the vinyl ester or vinyl alcohol units advantageous.
  • the properties of the graft copolymers used can for example by selecting the type and Amount of additional ethylenically unsaturated monomers or changed by said additional functionalization, and on be adapted to the intended use in each case. So for example, graft copolymers can also be obtained have elastomeric properties.
  • the graft copolymers are made in pasgravable elements for the production of flexographic printing forms and especially of transparent ones Flexographic printing forms or flexographic printing forms on metallic supports used.
  • the laser-engravable elements include a laser-engravable one Layer with an adhesive layer on one if necessary Dimensionally stable carrier applied.
  • suitable Dimensionally stable supports are plates, foils as well as conical and cylindrical sleeves made of metals such as steel, aluminum, Copper or nickel or from plastics such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate, Polyamide, polycarbonate, optionally also fabric and nonwovens, such as glass fiber fabrics and composite materials Glass fibers and plastics.
  • dimensionally stable carrier films especially for transparent flexographic printing plates - come especially dimensionally stable carrier films such as for example polyester films, in particular PET or PEN films in question.
  • Flexible metallic supports are particularly advantageous. Under flexible in the sense of this invention should be understood that the carriers are so thin that they are bent around the impression cylinder can. On the other hand, they are also dimensionally stable and such thick that the carrier in the production of the laser-engravable Elementes or the assembly of the finished printing plate on the Printing cylinder is not kinked.
  • thin sheets come as flexible metallic supports or metal foils made of steel, preferably made of stainless steel, magnetizable spring steel, aluminum, zinc, magnesium, nickel, Chromium or copper into consideration, whereby the metals are also alloyed could be.
  • Combined metallic supports can also be used such as with tin, zinc, chrome, aluminum, nickel or also combination of different metals coated steel sheets are used, or also such metal supports, which are produced by lamination identical or different types of metal sheets can be obtained.
  • Pre-treated sheets such as, for example, can also be used phosphated or chromated steel sheets or anodized Aluminum sheets are used. As a rule, will degrease the sheets or foils before inserting them.
  • Carriers made of steel or aluminum are used, particularly preferred is magnetizable spring steel.
  • the thickness of such flexible metallic supports is usually between 0.025 mm and 0.4 mm and aligns next to the desired one Degree of flexibility also depending on the type of used Metal.
  • Steel beams usually have a thickness between 0.025 and 0.25 mm, in particular between 0.14 and 0.24 mm.
  • Aluminum supports usually have a thickness between 0.25 and 0.4 mm.
  • laser-engravable is to be understood to mean that the relief layer has the property of absorbing laser radiation, in particular the radiation from an IR laser, so that it is removed or at least removed at those locations where it is exposed to a laser beam of sufficient intensity is replaced.
  • the layer is preferably vaporized or thermally or oxidatively decomposed without melting beforehand, so that its decomposition products are removed from the layer in the form of hot gases, vapors, smoke or small particles.
  • transparent is to be understood in such a way that the relief layer of the laser-engravable element, like conventional photopolymerizable flexographic printing plates, is largely transparent, that is to say that structures underneath can be recognized with the naked eye.
  • a laser-engravable element on a metallic carrier can also be transparent in this sense, ie can have a transparent relief layer, although such a laser-engravable element is of course not transparent as a whole.
  • the laser-engravable elements can also be several, one above the other arranged laser-engravable layers of different Have composition. Contains at least one of the layers at least one of said graft copolymers. It can too Mixtures of different graft copolymers are used. It however, it is preferred that each of the layers has at least one or contains several of said graft copolymers.
  • the laser-engravable layer can also have other, different from the graft copolymers used contain polymeric binders.
  • additional Binders can be used, for example, to control the properties the layer can be used. Requirement for the Addition of other binders is that they are with the graft copolymer are tolerated.
  • other polyvinyl alcohols are suitable or polyvinyl alcohol derivatives or water-soluble Polyamides. The amount is determined by the expert depending on the desired Properties of the layer selected.
  • the speed laser engraving not, at least not in excess should be reduced. As a rule, therefore, should not more than 20% by weight of the total amount of binders used, preferably no more than 10% by weight of such additional ones Binders are used.
  • the laser-engravable layers are preferably cross-linked.
  • the networking the laser-engravable layer can be replaced by a chemical Reaction, e.g. radical or ionic polymerization, by polycondensation or polyaddition, depending on Suitable crosslinkers are added to the crosslinking reaction. she can also be carried out using an ion beam.
  • the crosslinking can be polymerized without the addition of further Connections are made when the graft copolymers described above used with olefinically polymerizable groups become.
  • the graft copolymers are preferred in a mixture with polymerizable ethylenically unsaturated, compatible with the binder Connections used.
  • Monomer can be used, or several can be mixed with one another be used.
  • Suitable compatible monomers are for example mono- and di (meth) acrylates of di- or polyalcohols, such as ethylene glycol, di-, tri-, tetra- or polyethylene glycols. Examples include ethylene glycol monoacrylate, ethylene glycol dimethacrylate or called methyl polyethylene glycol monoacrylate.
  • the amount of monomers mixed can depend on the person skilled in the art according to the desired application properties such as for example hardness and elasticity of the layer can be selected.
  • graft copolymers with olefinic side groups are used, as a rule, no more than 15% by weight of additional Monomers required.
  • graft copolymers without olefinic side groups are used, so larger quantities, in general, however, not more than 50% by weight and preferably 15 to 45% by weight used.
  • thermal polymerization for example, typical peroxides or hydroperoxides are used become.
  • the thermal crosslinking is usually done by heating of the laser-engravable element.
  • acyloins and their derivatives such as For example, benzoin or vicinal diketones such as, for example, benzil are used become.
  • the photopolymerization can be carried out in a known manner be triggered by actinic light.
  • the laser-engravable recording layer can also still include auxiliaries and additives.
  • auxiliaries and additives are dyes, color pigments, plasticizers, Dispersing agents or adhesion promoters.
  • plasticizers for Use with the graft copolymers used Glycerol or polyethylene glycols are particularly suitable.
  • the present invention also includes the use of such additives.
  • aluminum oxide or hydrated oxide, iron oxides or soot can be used.
  • the plate loses its transparency and becomes opaque.
  • the easily depolymerizable polymer particles described above, for example made of polymethyl methacrylate (for example Agfaperl®), can also be used.
  • fillers that serve other purposes can also be used.
  • Fine SiO 2 particles for example Aerosil®, from Degussa
  • the latter have a particle size that is smaller than the wavelength of visible light, so that the plate remains transparent if the filler is sufficiently well dispersed.
  • the thickness of the laser-engravable recording layer or all Recording layers together is usually between 0.1 and 7 mm. The thickness is determined by the expert depending on the desired Appropriately chosen for the intended use of the printing plate.
  • the recording element can also be a thin top layer on the laser-engravable recording layer include.
  • Such an upper layer can contribute to the printing behavior and color transfer essential parameters such as roughness, Abrasiveness, surface tension, surface stickiness or Solvent resistance on the surface are changed, without the relief-typical properties of the printing form such as for example, to influence hardness or elasticity. surface properties and layer properties can therefore be independent be changed from one another to achieve an optimal printing result to reach.
  • the composition of the upper class is only insofar limited than the laser engraving of those below laser-engravable layer must not be impaired and the top layer must be removable together with this.
  • the Top layer should be thin compared to the laser-engravable layer his.
  • the thickness of the top layer does not exceed 100 ⁇ m, preferably the thickness is between 1 and 80 ⁇ m, particularly preferably between 3 and 10 microns.
  • the upper class should be preferred be easily laser-engravable, and includes as a polymeric binder therefore preferably also one used Graft copolymer.
  • Graft copolymers are used whose side chains through Copolymerization of vinyl esters with other monomers targeted were modified, for example by the color acceptance of the plate to improve.
  • other polymeric binders as well Auxiliaries used to set the desired properties become.
  • the laser-engravable element can also have an underlayer include that between the carrier and the laser-engravable Layer.
  • the lower layer can be laser-engravable; she but can also not be laser-engravable. With such lower layers can change the mechanical properties of the relief printing plates be changed without the characteristics typical of the relief to influence the printing form.
  • the laser-engravable recording element can be optional against mechanical damage from, for example Protective film made of PET, which is located on the each top layer, each before engraving must be removed with lasers.
  • the laser-engravable elements can be removed by loosening the components in suitable solvents and pouring onto the carrier followed by evaporating the solvent. Several Layers can be poured on top of each other.
  • the laser-engravable layer on a temporary Pouring and drying supports, for example onto a PET film, and then in a second step the dried, laser-engravable layer with the layer facing away from the temporary support Laminated side on the flexible metallic carrier.
  • An optionally available upper layer can either be known per se Way to be poured or laminated, or it can be co-extruded simultaneously with the laser-engravable one Layer.
  • the photochemical crosslinking can advantageously be carried out immediately after shaping the laser-engravable printing form by irradiation done with actinic light. But it is also possible that Only carry out networking at a later point in time.
  • the Exposure can only be from one side or from both sides.
  • the thermal crosslinking takes place by heating the laser-engravable Element.
  • Laser-engravable elements serve as the starting material for the production of flexographic printing plates.
  • the process includes that the cover film - if present - is first removed. in the following process step is a printing relief in the Recording material engraved with a laser.
  • Advantageous picture elements are engraved in which the flanks of the Image elements initially drop vertically and only in the lower one Widen the area of the picture element. This will be a good one Socking of the pixels with a slight increase in tone value reached. However, flanks of different design can also be used Pixels can be engraved.
  • CO 2 lasers with a wavelength of 10640 nm are CO 2 lasers with a wavelength of 10640 nm, but also Nd-YAG lasers (1064 nm) and IR diode lasers or solid-state lasers, which typically have wavelengths between 700 and 900 nm and between 1200 and 1600 nm ,
  • lasers with shorter wavelengths can also be used, provided the laser is of sufficient intensity.
  • a frequency-doubled (532 nm) or frequency-tripled (355 nm) Nd-YAG laser can also be used, or an excimer laser (eg 248 nm).
  • the image information to be engraved is transferred directly from the lay-out computer system to the laser apparatus.
  • the lasers can either be operated continuously or pulsed.
  • the method has the great advantage that the Relief layer is removed very completely by the laser, so that intensive post-cleaning is usually not necessary is. If desired, the printing plate obtained can still be cleaned. Through such a cleaning step detached, but possibly not completely from the Removed layer components removed from the plate surface. As a rule simply hosing down with water is sufficient.
  • graft copolymer Recording elements are characterized by an extraordinary high sensitivity to laser radiation. she can be considerably faster than conventional, SIS or Engrave flexographic printing plates containing SBS block copolymers with lasers. Alternatively, consider the same speed the engravings get deeper reliefs.
  • a mixture of the following components was prepared in water / n-propanol (volume ratio 6: 4): feedstock source Part by weight [%] Graft copolymer approx. 70000 g / mol, based on polyethylene glycol 35000 g / mol, 42 mol% proportion of vinyl alcohol / ester groups, degree of saponification 97% Alcotex 975 (Harco Chemical) 36 Graft copolymer approx. 62000 g / mol, based on polyethylene glycol approx.
  • the manufactured, laser-engravable plate was glued to the cylinder of an ALE laser machine (type Meridian Finesse) using an adhesive tape and the PET protective film was removed.
  • This machine is equipped with a CO 2 laser with an output of 200 W.
  • the plate was exposed to the laser radiation at a rotation speed of 266 rpm and a feed of 20 ⁇ m.
  • a test motif consisting of solid areas and various grid elements the size of a DIN A4 page was engraved within 30 minutes.
  • the depth of the relief obtained was 800 ⁇ m.
  • the resolution was 60 lines / cm (determined by counting the number under a microscope).
  • Photoinitiator, inhibitor and dye were dissolved in the monomer and incorporated into the melt.
  • the homogeneous melt was run into a calender heated to 100 ° C. between the cover and carrier film.
  • the types described in Example 1 were used as films.
  • the photopolymerization was carried out as described in Example 1. A plate with a total thickness of 2.84 mm was obtained.
  • the plate thus produced was engraved in the same manner as described in Example 1 using a CO 2 laser.
  • the depth of the relief obtained was 800 ⁇ m.
  • the resolution was 60 lines / cm.
  • the PET film was removed and the laser-engravable element was engraved as described in Example 1 using a CO 2 laser.
  • a plate of a crosslinked, carbon black-filled natural rubber (rubber 85% by weight, carbon black 9.5% by weight, 5.5% by weight plasticizer and crosslinking agent) was engraved in the same manner as described in Example 1 using a CO 2 laser.
  • the depth of the relief obtained was 650 ⁇ m.
  • the resolution was only 54 lines / cm.
  • the engraved plate also had enamel edges around the depressions.
  • a laser-engravable element was produced from a high-temperature crosslinking two-component silicone rubber and engraved in the same manner as described in Example 1 using a CO 2 laser.
  • the depth of the relief obtained was 600 ⁇ m.
  • the resolution was only 48 lines / cm.
  • the edges of line elements were not sharp but frayed.
  • the examples and comparative examples show that printing plates with excellent sensitivity to laser radiation are obtained using the graft copolymers according to the invention.
  • the laser-engravable elements obtained can be easily engraved in the infrared using a CO 2 laser or in the ultraviolet using an excimer laser.

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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)
  • Graft Or Block Polymers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Claims (10)

  1. Procédé de fabrication de formes imprimantes pour flexographie par gravure d'un relief imprimant à l'aide d'un laser dans au moins une couche réticulée, appliquée sur un support dimensionnellement stable, caractérisé en ce que la couche réticulée comporte au moins un copolymère greffé, qui peut être obtenu par polymérisation radicalaire d'esters vinyliques en présence de poly(oxydes d'alkylène), puis saponification au moins partielle de la fonction ester des copolymères greffés formés.
  2. Procédé selon la revendication 1, caractérisé en ce que, lors de la polymérisation radicalaire, on utilise, en plus des esters vinyliques, au moins un autre monomère polymérisable par polymérisation radicalaire.
  3. Procédé selon la revendication 1, caractérisé en ce que les groupes hydroxyle obtenus par saponification de la fonction ester sont mis au moins partiellement à réagir avec des composés comportant des groupes oléfiniques.
  4. Procédé selon l'une des revendications 1 à 3, caractérisé en ce que, pour ce qui concerne le copolymère greffé, il s'agit d'un copolymère greffé élastomère.
  5. Procédé selon l'une des revendications 1 à 4, caractérisé en ce que, pour ce qui concerne le support dimensionnellement stable, il s'agit d'un support métallique.
  6. Procédé selon l'une des revendications 1 à 4, caractérisé en ce que la couche réticulée appliquée sur le support est transparente.
  7. Procédé selon l'une des revendications 1 à 4, caractérisé en ce que la couche réticulée contient des additifs qui absorbent le rayonnement laser.
  8. Procédé selon l'une des revendications 1 à 4, caractérisé en ce que la couche réticulée est obtenue par réticulation photochimique.
  9. Procédé selon l'une des revendications 1 à 4, caractérisé en ce que la couche réticulée est obtenue par réticulation thermochimique.
  10. Procédé selon l'une des revendications 1 à 4, caractérisé en ce que l'élément gravable par laser comporte une couche superficielle supplémentaire sur la couche réticulée.
EP01106885A 2000-03-23 2001-03-20 Utilisation de copolymères greffés pour la fabrication d'éléments marquables au laser en relief Expired - Lifetime EP1136254B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE10014049 2000-03-23
DE10014049 2000-03-23
DE10040926 2000-08-18
DE10040926 2000-08-18

Publications (3)

Publication Number Publication Date
EP1136254A2 EP1136254A2 (fr) 2001-09-26
EP1136254A3 EP1136254A3 (fr) 2002-09-11
EP1136254B1 true EP1136254B1 (fr) 2003-05-28

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CN101535900B (zh) * 2006-08-30 2013-09-04 斯蒂茨丁荷兰聚合物学会 一种制备聚合浮雕结构的方法

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JP2001328365A (ja) 2001-11-27
US6627385B2 (en) 2003-09-30
EP1136254A3 (fr) 2002-09-11
EP1136254A2 (fr) 2001-09-26
JP4808322B2 (ja) 2011-11-02
DE50100265D1 (de) 2003-07-03
US20010044076A1 (en) 2001-11-22

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