EP1315617A1 - Procede pour produire des plaques d'impression flexographique par gravure au laser - Google Patents

Procede pour produire des plaques d'impression flexographique par gravure au laser

Info

Publication number
EP1315617A1
EP1315617A1 EP02722235A EP02722235A EP1315617A1 EP 1315617 A1 EP1315617 A1 EP 1315617A1 EP 02722235 A EP02722235 A EP 02722235A EP 02722235 A EP02722235 A EP 02722235A EP 1315617 A1 EP1315617 A1 EP 1315617A1
Authority
EP
European Patent Office
Prior art keywords
laser
layer
flexographic printing
filler
relief
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP02722235A
Other languages
German (de)
English (en)
Other versions
EP1315617B1 (fr
Inventor
Margit Hiller
Jens Schadebrodt
Jürgen Kaczun
Dieter Niederstadt
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 EP1315617A1 publication Critical patent/EP1315617A1/fr
Application granted granted Critical
Publication of EP1315617B1 publication Critical patent/EP1315617B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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 present invention relates to a method for producing flexographic printing plates by engraving a printing relief into a laser-engravable flexographic printing element which is photochemically
  • the relief layer 10 has cross-linked relief layer, the relief layer being transparent and comprising an oxidic, silicate or zeolitic solid with a particle size between 1 and 400 nm in an amount of 0.1 to 8% by weight with respect to the amount of all components of the relief layer.
  • Direct laser engraving has several advantages over the conventional production of flexographic printing plates.
  • flank shape of the individual relief elements can be designed individually using the laser engraving technique. While the flanks of a relief point in photopolymer plates continuously diverge from the surface to the base of the relief, one can also be laser engraved in the upper one
  • EP-B 640 043 and EP-B 640 044 disclose single-layer or multi-layer elastomeric laser-engravable recording elements for the production of flexographic printing plates.
  • the elements consist of
  • elastomeric binders in particular thermoplastic elastomers, stomers such as SBS, SIS or SEBS block copolymers used.
  • the so-called reinforcement increases the mechanical strength of the layer.
  • the reinforcement is achieved either through certain fillers, photochemical or thermochemical crosslinking or combinations thereof.
  • the purpose of the reinforcing fillers is to improve the mechanical properties of the laser-engravable recording elements, for example tensile strength, rigidity or abrasiveness. Larger amounts of fillers are required for this.
  • the examples of EP-B 640 043 disclose the addition of 10 to 25% by weight of carbon black with respect to the sum of all components of the layer as reinforcing filler.
  • the recording materials mentioned can moreover also have strongly colored pigments or dyes as IR absorbers to increase the sensitivity to laser radiation.
  • Carbon black has a double function and acts both as an IR absorber and as a reinforcing filler.
  • EP-B 640 043 therefore proposes as a solution to produce a thick layer by casting a multiplicity of thin layers, each followed by photochemical crosslinking of each individual layer.
  • this procedure is cumbersome, expensive and also requires other production facilities.
  • the relief layers of laser-engravable flexographic printing elements should not melt in the course of laser engraving, but rather a direct transition of the degradation products into the gas phase should take place.
  • the previous melting of the layer is disadvantageous: melting edges can form around engraved depressions, and the edges of the relief elements become blurred. With flexographic printing plates that have such irregularities, prints of poorer quality are obtained than with printing plates without such irregularities.
  • the object of the present invention was to provide an improved method for producing flexographic printing plates by means of laser engraving, with which the occurrence of melting edges can be avoided and a significantly higher resolution can be achieved.
  • the flexographic printing elements used as the starting material for the process should be able to be produced on the same production lines as conventional flexographic printing elements.
  • a method for producing transparent flexographic printing plates by engraving a printing relief in a laser-engravable flexographic printing element which has a transparent relief layer, which was obtained by photochemical crosslinking, the relief layer 0.1 to 8 wt .-%, preferably 0.2 to 5 wt .-% of an oxidic, silicate or zeolitic solid with a particle size between 1 and 400 nm.
  • a flexographic printing element which has at least one transparent and laser-engravable elastomer layer which is applied to a dimensionally stable support and has been photochemically crosslinked.
  • 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 such that the relief layer of the laser-engravable element is largely transparent, as is the case with conventional photopolymerizable flexographic printing plates, i.e. that structures underneath can be recognized with the naked eye. This does not rule out that the plate can be colored to a certain extent.
  • suitable dimensionally stable supports are, in particular, films made from metals such as steel, aluminum, copper or nickel or from plastics such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate, polyamide or polycarbonate.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • polybutylene terephthalate polyamide or polycarbonate.
  • Dimensionally stable polyester films, in particular PET or PEN films, or thin, flexible carriers made of aluminum or stainless steel are particularly suitable as dimensionally stable supports.
  • Conical or cylindrical tubes made of the said materials, so-called sleeves, can also be used as supports. Glass fibers or composite materials made from glass fibers and suitable polymeric materials are also suitable for sleeves.
  • the dimensionally stable support can be coated with a suitable adhesive layer.
  • the transparent, laser-engravable layer comprises at least one elastomeric binder.
  • Polymers which contain 1,3-diene monomers such as isoprene or butadiene in polymerized form are particularly suitable as elastomeric binders for the laser-engravable layer.
  • such binders have crosslinkable olefin groups as part of the main chain (1,4-incorporation) or as a side group (1,2-incorporation).
  • Examples include natural rubber, polybutadiene, polyisoprene, styrene-butadiene rubber, nitrile-butadiene rubber, butyl rubber, styrene-isoprene rubber, polynorbornene rubber or ethylene-propylene-diene rubber (EPDM) ,
  • ethylene-propylene, ethylene-acrylic ester, ethylene-vinyl acetate or acrylate rubbers can also be used.
  • Hydrogenated rubbers or elastomeric polyurethanes are also suitable.
  • Modified binders can also be used in which crosslinkable groups are introduced into the polymeric molecule by grafting reactions. Binders soluble in organic solvents are particularly preferred because these binders usually have only a slight swelling with aqueous printing inks or alcoholic / aqueous printing inks.
  • thermoplastic elastomeric block copolymers made of alkenyl aromatics and
  • the block copolymers can be linear block copolymers or radial block copolymers. Usually it is a three-block copolymers of the A-BA type, but it can also be a two-block polymer of the AB type, or those with several alternating elastomeric and thermoplastic blocks, for example ABABA. Mixtures of two or more different block copolyers can also be used. Commercially available three-block copolymers often contain certain proportions of two-block copolymers.
  • the diene units can be linked with 1, 2 or 1, 4. They can also be fully or partially hydrogenated.
  • Both block copolymers of styrene-butadiene and of the styrene-isoprene type can be used. They are commercially available, for example, under the name Kraton ® . Furthermore possible to employ thermoplastic-elastomeric block copolymers having end blocks of styrene and a random styrene-butadiene middle block, which are available under the name Styroflex ®.
  • the type and the amount of the binder used are chosen by the person skilled in the art depending on the desired properties of the relief layer. As a rule, an amount of 45 to 95% by weight of the binder with respect to the amount of all components of the la- proven engravable layer. Mixtures of different binders can also be used.
  • an inorganic solid is added to the relief layer.
  • the particle size of the solid added according to the invention is between 1 and 400 nm.
  • the particle size is preferably between 2 and 200 nm and very particularly preferably between 5 and 100 nm. It is thus smaller than the wavelength of the visible light.
  • the laser-engravable layer, which contains the filler appears accordingly transparent.
  • the specification of the particle size relates to the diameter, in the case of irregularly shaped particles, such as for example in the case of needle-shaped particles, to the longest axis.
  • Particle size is to be understood as the primary particle size. It goes without saying for the person skilled in the art that solid particles tend to agglomerate more and more with decreasing primary particle size, and accordingly form larger secondary particles. For this reason, they usually have to be dispersed very intensively in a particular matrix.
  • Fillers with a specific surface area between 30 and 300 m 2 / g and very particularly those with 100 to 200 m 2 / g have proven particularly useful for carrying out the method according to the invention.
  • the fillers are generally colorless. However, the invention also includes the use of colored fillers for special applications, provided the relief layer remains transparent and the photochemical crosslinking of the relief layer is not impaired thereby.
  • the filler added is selected from the group of the oxidic, silicate or zeolite solids.
  • suitable filler examples include Tikel finely divided Mikroglaspar- such as Spheriglass ® (Fa. Potters-Ballotini).
  • suitable filler finely divided Mikroglaspar- such as Spheriglass ® (Fa. Potters-Ballotini).
  • finely divided bentonite or aluminosilicates such as finely divided feldspar can be used as silicate.
  • Oxides or mixed oxides of the elements silicon, aluminum, magnesium, titanium or calcium are particularly suitable as oxidic solids. These can also contain additional dopants. It goes without saying for the person skilled in the art that finely divided inorganic solids have always either adsorbed certain amounts of water on the surface or have chemically bound them. Oxides obtained through the precipitation process can be used. such as precipitated silica. Pyrogenic oxides, that is to say compounds obtained by thermal decomposition of suitable starting products, are very particularly suitable. In particular, pyrogenic silicon dioxide, pyrogenic aluminum oxide, pyrogenic aluminum-doped silicon dioxide or pyrogenic titanium dioxide can be used. Such oxides are available, for example under the name Aerosil ® (Messrs. Degussa.) Commercially. The fillers can also be coated with suitable dispersing aids, adhesion promoters or water repellents. Mixtures of two or more fillers can also be used.
  • 0.1 to 8% by weight of the finely divided filler is used for the process.
  • the quantity is based on the sum of all components of the laser-engravable relief layer.
  • the layer preferably comprises 0.2 to 5% by weight of the filler and very particularly preferably 1 to 5% by weight.
  • the laser-engravable layer is cross-linked photochemically.
  • monomeric or oligomeric compounds which have polymerizable groups are generally added to the laser-engravable recording layer.
  • polymerizable or crosslinkable groups can also be constituents of the elastomeric binder itself, which can be crosslinkable groups in the main chain, terminal groups and / or pendant groups.
  • the monomers should be compatible with the binders and have at least one polymerizable, olefinically unsaturated group.
  • Esters or amides of acrylic acid or methacrylic acid with mono- or polyfunctional alcohols, amines, amino alcohols or hydroxy ethers and esters, styrene or substituted styrenes, esters of fumaric or maleic acid or alkyl compounds have proven to be particularly advantageous.
  • Suitable monomers are butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate, 1, 6-hexanediol dimethacrylate, 1, 9-nonanediol diacrylate, trimethylolpropane triacrylumate, dioctyl dylctyl fumarate, dioctyl nyl dylctyl dylctyl fumarate, dioctyl dylctyl fumarate, dioctyl dimethyl diumctyl fumarate, dioctyl fumarate, dioctyl fumarate.
  • Suitable oligomers with olefinic groups can also be used. Mixtures of different monomers or oligomers can of course also be used, provided these are compatible with one another.
  • the total amount of any monomers used is determined by the person skilled in the art depending on the desired properties of the recording layer. Among other things, it depends on whether the polymeric binder itself already has polymerizable groups. As a rule, however, 45% by weight with regard to the amount of all components of the laser-engravable layer must not be exceeded.
  • Photoinitiators such as benzoin or benzoin derivatives such as ⁇ -methylbenzoin or benzoin ether, benzene derivatives such as benzil ketals, acylarylphosphine oxides, acylarylphosphinic acid esters, multinuclear quinones can be used in a known manner for photochemical crosslinking, without the enumeration being intended to be limited thereto.
  • the crosslinking is carried out in a manner known per se by irradiation with actinic, that is to say chemically active, radiation.
  • UV-A radiation with a wavelength between 320 and 400 nm or UV-A / VIS radiation with a wavelength of 320 to approx. 700 nm is particularly suitable.
  • the type and amount of the photoinitiator is chosen by the person skilled in the art depending on the desired Layer properties set. For example, when using Ti0 2 as filler, he will take care to use an initiator that does not absorb below 415 nm. As a rule, the amount of photoinitiator is between 0.1 and 5% by weight.
  • the laser-engravable layer can additionally contain plasticizers.
  • suitable plasticizers are modified and unmodified natural oils and resins, alkyl, alkenyl, arylalkyl or arylalkenyl esters of acids, such as alkanoic acids, arylcarboxylic acids or phosphoric acid; synthetic oligomers or resins such as oligostyrene, oligomeric styrene-butadiene copolymers, oligomeric ⁇ -methylstyrene / p-methylstyrene copolymers, liquid oligobutadienes, or liquid oligomeric acrylonitrile-butadiene copolymers; as well as polyterpenes, polyacrylates, polyesters or polyurethanes, polyethylene, ethylene-propylene-diene rubbers or ⁇ -methyl
  • Oligo ethylene oxide
  • plasticizers are paraffinic mineral oils; Esters of dicarboxylic acids such as dioctyl adipate or terephthalic acid dioctyl ester; naphthenic plasticizers or polybutadienes with a molecular weight between 500 and 5000 g / mol. Mixtures of different plasticizers can also be used.
  • the amount of the plasticizer which may be present is selected by the person skilled in the art in accordance with the desired hardness of the printing plate. It is generally less than 40% by weight, preferably less than 20% by weight and particularly preferably less than 10% by weight, based on the sum of all components of the photopolymerizable mixture.
  • the laser-engravable layer can also contain additives and auxiliaries such as dyes, dispersing aids or antistatic agents.
  • additives and auxiliaries such as dyes, dispersing aids or antistatic agents.
  • the amount of such additives should generally be 10% by weight with respect to the amount Do not exceed all components of the cross-linkable, laser-engravable layer of the recording element.
  • the flexographic printing element used as the starting material can also have a plurality of laser-engravable layers one above the other. These laser-engravable, cross-linkable partial layers can be of the same, approximately the same or different material composition. Such a multilayer structure, in particular a two-layer structure, is sometimes advantageous because it allows surface properties and layer properties to be changed independently of one another in order to achieve an optimal printing result.
  • the laser-engravable recording element can, for example, have a thin laser-engravable top layer, the composition of which was selected with a view to optimal color transfer, while the composition of the layer below was selected with regard to optimum hardness or elasticity of the relief layer. It is essential to the invention that at least the top layer contains the filler described. However, it is recommended that all layers contain the filler, at least all layers up to the maximum relief depth.
  • the laser-engravable layer can be produced, for example, by dissolving or dispersing all components in a suitable solvent and pouring them onto a carrier.
  • a carrier for example, a suitable solvent, a solvent, or a solvent, or a suitable solvent, or a suitable solvent, or a suitable solvent.
  • several layers can be cast onto one another in a manner known in principle.
  • the individual layers can be cast onto temporary supports, for example, and the layers can then be connected to one another by lamination.
  • the laser-engravable recording elements are preferably produced in a known manner in principle by melt extrusion followed by calendering.
  • twin screw extruders can be used. In principle, the person skilled in the art knows what type of screws he has to use in order to ensure a very uniform distribution of the filler in the mass.
  • the thickness of the laser-engravable layer or all layers together is generally between 0.1 and 7 mm.
  • the thickness is suitably chosen by the person skilled in the art depending on the intended use of the printing plate.
  • the crosslinkable, laser-engravable flexographic printing element used as the starting material can optionally comprise further layers.
  • layers include an elastomeric underlayer made of another formulation, which is located between the carrier and the laser-engravable layer (s) and which does not necessarily have to be laser-engravable. With such lower layers, the mechanical properties of the relief printing plates can be changed without influencing the properties of the actual printing relief layer.
  • So-called elastic substructures which are located under the dimensionally stable support of the laser-engravable recording element, that is to say on the side of the support facing away from the laser-engravable layer, serve the same purpose.
  • adhesive layers that connect the support with layers above or different layers to one another.
  • the laser-engravable flexographic printing element can be protected against mechanical damage by a protective film, for example made of PET, which is located on the top layer in each case and which must be removed before laser engraving.
  • the protective film can also be siliconized to make it easier to remove or provided with a suitable adhesive layer.
  • a printing relief is engraved into the cross-linked, laser-engravable layer by means of a laser.
  • Image elements are advantageously engraved in which the flanks of the image elements initially drop vertically and only widen in the lower region of the image element. This achieves a good base of the pixels with a slight increase in tone value.
  • flanks of the pixels with different designs can also be engraved, e.g. a staircase relief.
  • C0 lasers with a wavelength of 10640 nm are particularly suitable for laser engraving.
  • the image information to be engraved is transferred directly from the layout computer system to the laser apparatus.
  • the laser can either be operated continuously or pulsed.
  • the added finely divided fillers bring about a very significant improvement in the printing properties of the printing form obtained, while without the addition of fillers, the laser-engravable layer still tends to melt under the influence of the laser radiation and melt edges can be observed, as can be seen from the Addition of 1% the Eliminate melting edges completely. At the same time, the achievable resolution is significantly improved.
  • the flexographic printing plate obtained can be used directly. If desired, the flexographic printing plate obtained can still be cleaned. Such a cleaning step removes layer components which have been detached but which may not yet be completely removed from the plate surface. As a rule, simple treatment with water or alcohol is completely sufficient.
  • the flexographic printing elements used as the starting material for laser engraving can also be conventionally exposed and developed imagewise using photographic negatives without the filler content adversely affecting this process. This double usability enables particularly economical production.
  • a laser system with a rotating outer drum (Meridian Finesse, ALE) was used for the engraving tests, which is equipped with a C0 laser with a 250 W output line.
  • the laser beam was focused on a 20 ⁇ m diameter.
  • the flexographic printing elements to be engraved were stuck to the drum with adhesive tape and the drum was accelerated to 250 rpm (web speed on the surface of the drum: 240 cm / s).
  • a light-sensitive mixture of 78% by weight of a SIS block copolymer (Kraton ® 1161, 12.5% by weight of acrylates, 1% by weight of photoinitiator and 8.5% by weight of auxiliaries) was mixed in a two-screw extruder at a melt temperature of 130 ° C and discharged through a slot die.
  • the melt emerging from the nozzle was introduced into the nip of a two-roll calender, both rolls were heated to 80 ° C.
  • a PET film coated with an adhesive varnish was introduced as the base film into the calender gap via one calender roll and a PET protective film was inserted over the other.
  • the sandwich composite obtained was cooled and made up.
  • the photosensitive flexographic printing element obtained was crosslinked in its entirety with UV-A light by exposure for 30 minutes from the front and exposure for 30 minutes from the rear.
  • the plate was transparent.
  • the procedure was as in the comparative example, except that 1% by weight (based on the sum of all components of the layer) of a finely divided pyrogenic silicon dioxide with a specific surface area of 160 m 2 / g and an average primary particle size of 10 to 20 was used during the production of the flexographic printing element nm (Aerosil ® R 8200, degussa.) added as filler.
  • a finely divided pyrogenic silicon dioxide with a specific surface area of 160 m 2 / g and an average primary particle size of 10 to 20 was used during the production of the flexographic printing element nm (Aerosil ® R 8200, degussa.) added as filler.
  • the negative element is also much easier to see in the case of the filled plate.

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  • 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)

Abstract

L'invention concerne un procédé pour produire des formes d'impression flexographique par gravure d'un relief d'impression dans un élément d'impression flexographique gravable au laser, ledit élément comportant une couche en relief à réticulation photochimique. Cette couche en relief est transparente et comprend une substance solide oxydique, silicique ou zéolitique présentant une taille de particules comprise entre 1 et 400 nm dans une quantité comprise entre 0,1 et 8 % en poids par rapport à la quantité de tous les composants de la couche en relief.
EP02722235A 2001-03-21 2002-03-16 Procede pour produire des plaques d'impression flexographique par gravure au laser Expired - Lifetime EP1315617B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10113926A DE10113926A1 (de) 2001-03-21 2001-03-21 Verfahren zur Herstellung von Flexodruckplatten mittels Lasergravur
DE10113926 2001-03-21
PCT/EP2002/002954 WO2002076739A1 (fr) 2001-03-21 2002-03-16 Procede pour produire des plaques d'impression flexographique par gravure au laser

Publications (2)

Publication Number Publication Date
EP1315617A1 true EP1315617A1 (fr) 2003-06-04
EP1315617B1 EP1315617B1 (fr) 2003-12-17

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Application Number Title Priority Date Filing Date
EP02722235A Expired - Lifetime EP1315617B1 (fr) 2001-03-21 2002-03-16 Procede pour produire des plaques d'impression flexographique par gravure au laser

Country Status (5)

Country Link
US (1) US6935236B2 (fr)
EP (1) EP1315617B1 (fr)
JP (1) JP2004533343A (fr)
DE (2) DE10113926A1 (fr)
WO (1) WO2002076739A1 (fr)

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US6935236B2 (en) 2005-08-30
WO2002076739A1 (fr) 2002-10-03
EP1315617B1 (fr) 2003-12-17
US20040089180A1 (en) 2004-05-13
JP2004533343A (ja) 2004-11-04
DE50200155D1 (de) 2004-01-29
DE10113926A1 (de) 2002-09-26

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