EP1381511B1 - Element d'impression par flexographie pouvant etre grave au laser comprenant des couches elastomeres en relief renfermant du 1,2-polybutadiene syndiotactique - Google Patents

Element d'impression par flexographie pouvant etre grave au laser comprenant des couches elastomeres en relief renfermant du 1,2-polybutadiene syndiotactique Download PDF

Info

Publication number
EP1381511B1
EP1381511B1 EP02740469A EP02740469A EP1381511B1 EP 1381511 B1 EP1381511 B1 EP 1381511B1 EP 02740469 A EP02740469 A EP 02740469A EP 02740469 A EP02740469 A EP 02740469A EP 1381511 B1 EP1381511 B1 EP 1381511B1
Authority
EP
European Patent Office
Prior art keywords
relief
laser
weight
component
elastomeric
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP02740469A
Other languages
German (de)
English (en)
Other versions
EP1381511A1 (fr
Inventor
Jürgen Kaczun
Jens Schadebrodt
Margit Hiller
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Flint Group Germany GmbH
Original Assignee
BASF Drucksysteme GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF Drucksysteme GmbH filed Critical BASF Drucksysteme GmbH
Publication of EP1381511A1 publication Critical patent/EP1381511A1/fr
Application granted granted Critical
Publication of EP1381511B1 publication Critical patent/EP1381511B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • B41C1/02—Engraving; Heads therefor
    • B41C1/04—Engraving; Heads therefor using heads controlled by an electric information signal
    • B41C1/05—Heat-generating engraving heads, e.g. laser beam, electron beam
    • 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
    • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055—Radiation sensitive composition or product or process of making
    • Y10S430/106—Binder containing
    • 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
    • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055—Radiation sensitive composition or product or process of making
    • Y10S430/106—Binder containing
    • Y10S430/108—Polyolefin or halogen containing
    • 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
    • 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
    • Y10S430/165—Thermal imaging composition

Definitions

  • the invention relates to laser-engravable flexographic printing elements with relief-forming elastomeric layers containing syndiotactic 1,2-polybutadiene, process for Production of relief printing elements from the laser-engravable flexographic printing elements.
  • WO 93/23252 discloses laser-engravable flexographic printing elements comprising a carrier a laser-engravable, elastomeric layer containing at least one thermoplastic elastomer as a binder and process for the preparation of flexographic printing plates. This is the laser-engravable elastomeric layer thermochemically by heating or photochemically by irradiation with actinic Light amplified and then the printing relief engraved with a laser.
  • Binder calls the font copolymers of butadiene and styrene, copolymers of Isoprene and styrene, styrene-diene-styrene triblock copolymers such as polystyrene-polybutadiene-polystyrene (SBS), polystyrene-polyisoprene-polystyrene (SIS) or polystyrene-poly (ethylene-butylene) -polystyrene (SEBS).
  • SBS polystyrene-polybutadiene-polystyrene
  • SIS polystyrene-polyisoprene-polystyrene
  • SEBS polystyrene-poly (ethylene-butylene) -polystyrene
  • SEBS polystyrene-poly (ethylene-butylene) -polystyrene
  • EP-A 0 076 588 discloses photocrosslinkable flexographic printing elements comprising a Mixture of 30 to 70% syndiotactic 1,2-polybutadiene with a degree of crystallinity from 5 to 20%, a content of 1,2-linked units of 85% and a molecular weight above 100,000 g / mol and 70 to 30% cis-1,4-polyisoprene.
  • the printing elements will be exposed imagewise with UV light and by washing the uncrosslinked areas with developed an organic solvent.
  • US Pat. No. 4,517,278 discloses a flexographic printing plate which is melt-pressed from a photosensitive molding composition, the molding composition containing syndiotactic 1,2-polybutadiene (I) swollen with the solution of an ethylenically unsaturated monomer (II) and a photoinitiator (III).
  • (I) has an average molecular weight of 10,000 to 300,000 g / mol, a content of 1,2-linked polybutadiene units of at least 80% and a degree of crystallinity of 10 to 30%.
  • (II) is an ester of methacrylic acid with a C 4 -C 20 alkanol and (III) is benzoin or a benzoin alkyl ether.
  • pellets of (I) are swollen in a solution of (II) and then melt pressed into 0.1 to 10 mm thick plates. This method is only discontinuous feasible and expensive.
  • the printing plates prepared in the examples require xylene as a leaching agent for development. Shore A hardnesses of 60 to 65 are achieved only with the use of larger amounts of non-crosslinking plasticizers such as vinyl ethers or phthalates. These form melt edges during laser engraving.
  • Disadvantages of the known binders include the sometimes long exposure times Photochemical crosslinking of the elastomeric relief-forming layers as well as not always satisfactory resolution and sharpness of the engraved printing reliefs.
  • the object of the invention is improved, laser-engravable flexographic printing elements provide.
  • a laser-engravable flexographic printing element comprising a flexible support an elastomeric relief-forming, laser-engravable, thermal or Photochemically crosslinkable layer containing at least 5% by weight as binder syndiotactic 1,2-polybutadiene containing 1,2-linked butadiene units from 80 to 100%, a degree of crystallinity of 5 to 30% and a mean Molar mass from 20,000 to 300,000 g / mol.
  • the elastomeric relief forming Layer has the property of laser radiation, in particular the radiation of an IR laser, absorb, leaving them in those places where they receive a laser beam is exposed to sufficient intensity, removed or at least replaced.
  • the layer is thereby, without first melting, evaporated or thermally or oxidatively decomposed, and their decomposition products in the form of hot Gases, vapors, smoke or small particles from the layer.
  • elastomeric relief-forming layers result in the laser engraving very sharp and high-resolution relief elements. There are no laser engravings Melt edges, but only weak deposits, mechanically or by simple post-treatment with water or alcohol can be removed. Further are the elastomeric relief-forming layers by irradiation with UV-A light extremely fast photocrosslinkable.
  • the elastomeric relief-forming layer contains syndiotactic 1,2-polybutadiene containing from 80 to 100% of 1,2-linked butadiene units, a degree of crystallinity of 5 to 30% and an average molecular weight of 20,000 to 300 000 g / mol.
  • the content of 1,2-linked butadiene units is preferably 90 to 95 %, more preferably 90 to 92%, the degree of crystallinity from 10 to 30%, especially preferably 15 to 30% and the average molecular weight of 80,000 to 200,000 g / mol, more preferably from 100,000 to 150,000 g / mol.
  • the elastomeric relief-forming layer optionally contains further Binder.
  • elastomeric binder as well as thermoplastic elastomeric binder suitable.
  • suitable binders are the known ones Triblock copolymers of the SIS or SBS type, which are also fully or partially hydrogenated can. It is also possible to use ethylene / propylene / diene elastomeric polymers, Ethylene / acrylic acid rubbers or elastomeric polymers based on acrylates or Acrylate copolymers are used. Further examples of suitable polymers are in DE-A 22 15 090, EP-A 084 851, EP-A 819 984 or EP-A 553 662. It can also two or more different further binders are used.
  • the elastomeric relief-forming layer contains crosslinking oligomers Plasticizers, the main chain reactive groups and / or reactive pendants and / or terminal groups.
  • Suitable plasticizers are, for example Polybutadiene oils, polyisoprene oils, allyl citrates and other allyl groups synthetic plasticizers having a viscosity of 500 to 150,000 mPas at 25 ° C, the may have functional end groups such as OH groups.
  • Preferred crosslinking oligomeric plasticizers are the polybutadiene oils mentioned and polyisoprene oils. These preferably have a viscosity of 500 to 100,000 mPas, more preferably from 500 to 10,000 mPas at 25 ° C.
  • crosslinking acting oligomeric plasticizer Smelting during laser engraving avoided particularly efficiently. Furthermore, a achieved particularly good color transfer of the printing relief layers, for example with water-based or alcohol-based inks or UV-curable inks.
  • the elastomeric relief-forming layer optionally contains ethylenically unsaturated monomers.
  • the ethylenically unsaturated monomers are advantageous, but not necessary, since the elastomeric relief-forming layer also in their Absence can network.
  • the monomers should be compatible with the binders and at least one polymerizable, ethylenically unsaturated double bond. Suitable monomers generally have a boiling point of more than 100 ° C at Atmospheric pressure and a molecular weight of up to 3,000 g / mol, preferably up to 2,000 g / mol.
  • Suitable monomers are Butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, isobornyl methacrylate, Isodecyl methacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, trimethylolpropane triacrylate, Dioctyl fumarate and N-dodecylmaleimide. It can also be mixtures of different Monomers can be used.
  • the elastomeric relief-forming layer optionally contains Photoinitiators and / or thermally decomposing initiators.
  • the presence of Photoinitiators is not necessary, but advantageous because the elastomeric relief-forming Layer can be photochemically crosslinked even in the absence of photoinitiators. If the elastomeric relief-forming layer to be thermally crosslinked, then the Presence of thermally decomposing initiators in amounts of 0.1 to 5 wt .-%, based on the sum of components A to F, generally required.
  • the elastomeric relief-forming layer can also be crosslinked photochemically and thermally be as component D photoinitiators and / or thermally decomposing Initiators may be included.
  • Suitable photoinitiators are benzoin or benzoin derivatives, such as methylbenzoin or Benzoin ethers, benzil derivatives such as benzil ketals, acylarylphosphine oxides, acylarylphosphinic acid esters and multinucleated quinones without being limited to the list. Preference is given to using those photoinitiators which have a high absorption between Have 3 00 and 450 nm.
  • Suitable thermally decomposing initiators are, for example, peroxyesters, such as t-butyl peroctoate, t-amyl peroctoate, t-butyl peroxy isobutyrate, t-butyl peroxymaleic acid, t-amyl perbenzoate, Di-t-butyl diperoxyphthalate, t-butyl perbenzoate, t-butyl peracetate or 2,5-di (benzoylperoxy) -2,5-dimethylhexane, certain diperoxyketals such as 1,1-di (tamylperoxy) cyclohexane, 1,1-di (t-butylperoxy) cyclohexane, 2,2-di (t-butylperoxy) butane or ethyl 3,3-di (t-butylperoxy) butyrate, certain dialkyl peroxides such as di-t-butyl peroxide, t-
  • azo compounds such as for example 1- (t-butylazo) formamide, 2- (t-butylazo) isobutyronitrile, 1- (t-butylazo) cyclohexanecarbonitrile, 2- (t-butylazo) -2-methylbutanenitrile, 2,2'-azobis (2-acetoxypropane), 1,1'-azobis (cyclohexanecarbonitrile), 2,2'-azobis (isobutyronitrile) or 2,2'-azobis (2-methylbutanenitrile).
  • the elastomeric relief-forming layer may contain absorbers for laser radiation.
  • the presence of the absorbers is advantageous, but not necessary, if the binders already absorb laser radiation of a suitable wavelength, for example that of a CO 2 laser.
  • Suitable absorbers for laser radiation have a high absorption in the range of the laser wavelength.
  • absorbers are suitable which have a high absorption in the near infrared, as well as in the longer-wave VIS range of the electromagnetic spectrum.
  • Such absorbers are particularly suitable for absorbing the radiation of high-performance Nd-YAG lasers (1064 nm) and of IR diode lasers, which typically have wavelengths between 700 and 900 nm and between 1200 and 1600 nm.
  • Suitable absorbers for laser radiation are in the infrared spectral range strongly absorbing dyes such as phthalocyanines, naphthalocyanines, Cyanines, quinones, metal complex dyes such as dithiolenes or photochromes Dyes.
  • suitable absorbers are inorganic pigments, in particular intensively colored inorganic pigments such as chromium oxides, iron oxides, carbon black or metallic Particle.
  • Particularly suitable as an absorber for laser radiation are finely divided carbon blacks with a Particle size between 10 and 50 nm.
  • suitable absorbers for laser radiation are iron-containing solids, in particular intensively colored iron oxides.
  • iron oxides are commercially available and are commonly used as color pigments or as pigments for magnetic recording.
  • Suitable absorbers for laser radiation are, for example, FeO, goethite (alpha-FeOOH), akaganeite (beta-FeOOH), lepidocrocite (gamma-FeOOH), hematite (alpha-Fe 2 O 3 ), maghemite (gamma-Fe 2 O 3 ), magnetite (Fe 3 O 4 ) or Berthollide.
  • doped iron oxides or mixed oxides of iron with other metals can be used.
  • Examples of mixed oxides are Umbra Fe 2 O 3 xn MnO 2 or Fe x Al (1-x) OOH, in particular various spinel black pigments such as Cu (Cr, Fe) 2 O 4 , Co (Cr, Fe) 2 O 4 or Cu (Cr, Fe, Mn) 2 O 4 .
  • Examples of dopants are, for example, P, Si, Al, Mg, Zn or Cr. Such dopants are usually added in small amounts in the course of the synthesis of the oxides to control particle size and particle shape.
  • the iron oxides can also be coated. Such coatings can be applied, for example, to improve the dispersibility of the particles. These coatings may, for example, consist of inorganic compounds such as SiO 2 and / or AlOOH.
  • organic coatings for example organic adhesion promoters such as aminopropyl (trimethoxy) silane.
  • organic adhesion promoters such as aminopropyl (trimethoxy) silane.
  • absorbers for laser radiation are FeOOH, Fe 2 O 3 and Fe 3 O 4 , very particularly preferably Fe 3 O 4 .
  • the elastomeric relief-forming layer may contain further additives.
  • Further additives are non-crosslinking plasticizers, fillers, dyes, compatibilizers or dispersing agent.
  • the flexographic printing elements according to the invention have the usual layer structure and consist of a flexible dimensionally stable support, optionally an elastomeric Underlayer, one or more elastomeric relief-forming, laser-engravable layers, wherein the different layers can be connected by adhesive layers, and one optionally with a detackifying layer (release layer) coated protective film.
  • the flexographic printing elements according to the invention comprise a flexible, dimensionally stable Carrier.
  • suitable flexible dimensionally stable supports for laser engravable Flexographic printing elements are plates, films as well as conical and cylindrical tubes made of metals such as steel, aluminum, copper or nickel or of plastics such as Polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate, Polyamide, polycarbonate, if appropriate also fabrics and nonwovens, such as glass fiber fabric and composite materials, e.g. made of glass fibers and plastics.
  • PET Polyethylene terephthalate
  • PEN polyethylene naphthalate
  • Polyamide polycarbonate
  • fabrics and nonwovens such as glass fiber fabric and composite materials, e.g. made of glass fibers and plastics.
  • dimensionally stable Carriers are above all dimensionally stable carrier films, such as polyester films, for example. in particular PET or PEN films in question.
  • the elastomeric relief-forming, laser-engravable layer may also have a multilayer structure be.
  • These laser-engravable, crosslinkable partial layers can be of the same, approximately same or of different material composition.
  • Such a multilayer construction, especially a two-layered construction, is sometimes advantageous because thereby surface properties and layer properties independently can be optimized to achieve an optimal print result.
  • a laser-engravable flexographic printing element may be a thin laser-engravable one Upper layer whose composition in terms of optimal Color transfer was selected while the composition of the underlying Layer was selected for optimum hardness or elasticity.
  • the thickness of the elastomeric relief-forming, laser-engravable layer or all As a rule, relief-forming layers together are between 0.1 and 7 mm.
  • the Thickness is determined by the person skilled in the art according to the intended use of the printing plate selected.
  • the laser-engravable flexographic printing elements according to the invention can optionally be further Include layers.
  • the carrier and the or laser-engravable layer (s) have an elastomeric sublayer that is not must necessarily be laser engravable. With such a lower layer, the mechanical properties of the relief printing plates are changed without the Properties of the actual printing relief layer are influenced. the serve the same purpose so-called elastic substructures, which are based on the laser-engravable layer opposite side of the dimensionally stable support are located.
  • Further layers may be adhesive layers which overlay the carrier Connect layers or different layers with each other.
  • the protective film may be used to facilitate peeling also be siliconized or provided with a suitable Entklebe harsh.
  • the laser-engravable flexographic printing element for example, by solving or Disperse all components in a suitable solvent and pour on one Carriers are produced.
  • multilayer elements can in a conventional manner and several layers are poured on top of each other.
  • the Single layers for example, poured onto temporary support and the layers then be joined together by laminating.
  • Photochemically crosslinkable systems can be extruded and / or calendered getting produced. This technique can in principle also for thermally crosslinkable systems be used, provided that only those components are used in the Do not cross-link the process temperature yet.
  • the elastomeric relief-forming, laser-engravable layer is photochemical and / or thermally crosslinkable.
  • the photochemical crosslinking is carried out in particular by Irradiate with shortwave visible or longwave ultraviolet light. Naturally, however, radiation of higher energy, such as short-wave UV light or X-radiation, or - with appropriate sensitization - also longer-wave light in principle suitable. In particular, electron radiation is also suitable for crosslinking.
  • the thermal crosslinking is generally by heating the Flexographic printing element to temperatures of generally 80 to 220 ° C, preferably 120 to 200 ° C over a period of 2 to 30 minutes causes.
  • Laser engraving is particularly suitable for CO 2 lasers having a wavelength of 10,640 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 1,200 and 1,600 nm , However, it is also possible to use lasers with shorter wavelengths, provided the laser has sufficient intensity. For example, it is also possible to use a frequency-doubled (532 nm) or frequency-tripled (355 nm) Nd-YAG laser or eximer lasers (eg 248 nm).
  • 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 relief layer is very completely removed by the laser, so that an intense Post-cleaning is usually not necessary. If desired, the obtained Pressure plate but still to be cleaned. By such a cleaning step are detached, but may not yet completely from the disk surface removed removed layer components. As a rule, simple treatment with water or methanol completely sufficient.
  • JSR RB 810 16 g of Lithene PH, 16 g of lauryl acrylate, 2.4 g of Lucirin® BDK and 1.6 g Kerobit® TBK are dissolved at 110 ° C in 240 g of toluene.
  • the obtained homogeneous solution is cooled to 70 ° C and with the help of a doctor blade so on several transparent PET films applied that a homogeneous dry film thickness of 1.20 mm each is obtained.
  • the layers thus prepared are first for 18 hours at 25 ° C and finally dried at 50 ° C for 3 hours. Then the dried ones Layers each laminated on an equal piece of a second PET film. To For one day storage, the layer is photochemically crosslinked as explained below and characterized as described below.
  • JSR RB 810 16 g Plastomoll® DNA, 16 g Lithene PH and 1.6 g Kerobit® TBK and 16 g of Printex® A in a laboratory kneader at a given temperature kneaded at 100 ° C for 15 minutes.
  • the compound thus obtained (158.4 g) is dissolved at 110 ° C in 240 g of toluene. After this Cool the solution to 60 ° C and add 1.6 g of dicumyl peroxide. To Homogenization by stirring, the resulting solution using a doctor blade so applied to several transparent PET films that a homogeneous dry film thickness each of 1.20 mm is obtained. The layers thus produced become dried first for 18 hours at 25 ° C and finally for 3 hours at 50 ° C. Subsequently, the dried layers are each on an equal piece of a laminated second PET film. After a storage period of one day, the layer becomes 15 Thermally crosslinked at 160 ° C and characterized as described below.
  • the photochemical crosslinking of the example layers described was with a nyloflex® F III platesetter of BASF Drucksysteme GmbH made by first the transparent PET protective film was removed and then for the respective duration the exposure series was irradiated with UVA light over the entire surface without vacuum.
  • the transparent PET protective film was first removed and then the layer for the duration of the crosslinking at the selected temperature heated without inertization.
  • a laser system with rotating outer drum was used (Meridian Finesse, ALE), which was equipped with a CO 2 laser with 250 W output power.
  • the laser beam was focused to a diameter of 20 ⁇ m.
  • the flexographic printing elements to be engraved were taped to the drum and the drum was accelerated to 250 rpm.
  • the letter A (font Helvetica, font size 24 pt) as a positive engraved in the cross-linked material.
  • the Resolution was 1270 dpi.
  • To assess the quality was a section of the Engraved letter A through a light microscope at 32x magnification Photographed. Furthermore, two lines of 20 ⁇ m width were spaced apart engraved of 20 microns in the respective material. From the negative line pairs were made by scanning electron micrographs.
  • Figures 1.1 - 1.8 and 2.1 - 2.8 show the underlying evaluation photographic and scanning electron micrographs.
  • Table 2 summarizes the assessments of the above characteristics and the arithmetic mean of all the characteristics.
  • the superior quality of the Laser engraving produced relief elements in flexographic printing elements based on syndiotactic 1,2-polybutadiene (examples) compared to conventional Recognize flexographic printing elements (comparative examples).
  • examples can finest relief elements as the negative-line pairs shown in high quality be imaged.
  • the quality of larger engraved relief elements as shown by way of example on the section of the letter A, in the case of flexographic printing elements Basis of syndiotactic 1,2-polybutadiene significantly better, as strong melting phenomena or avoid material deposits on the printing surface become.

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Plasma & Fusion (AREA)
  • Manufacturing & Machinery (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Laminated Bodies (AREA)
  • Adhesive Tapes (AREA)

Claims (5)

  1. Elément d'impression flexographique qui peut être gravé au laser et qui comporte, sur un substrat flexible, de dimensions stables, une couche élastomère qui forme un relief, peut être gravée au laser, et est réticulable par voie thermique et/ou photochimique, cette couche contenant
    (a) 50 à 99,9% en poids d'un ou plusieurs liants, comme composant A, constitués
    (a1) de 5 à 100% en poids de 1,2-polybutadiène syndiotactique ayant une teneur en unités de butadiène reliées en 1,2 de 80 à 100%, un degré de cristallinité de 5 à 30% et une masse molaire moyenne de 20.000 à 300.000 g/mole, comme composant A1, et
    (a2) de 0 à 95% en poids d'un autre liant, comme composant A2,
    la somme des composants A1 et A2 donnant 100% en poids,
    (b) 0,1 à 30% en poids d'agents plastifiants oligomères réticulants, qui présentent des groupes réactifs dans la chaíne principale et/ou des groupes réactifs qui se trouvent en position latérale et/ou terminale, comme composant B,
    (c) 0 à 25% en poids de monomères éthyléniquement insaturés, comme composant C,
    (d) 0 à 10% en poids de photo-initiateurs et/ou d'initiateurs qui se décomposent thermiquement, comme composant D,
    e) 0 à 20% en poids d'absorbeurs pour rayonnement laser, comme composant E, et
    (f) 0 à 30% en poids d'autres additifs courants, comme composant F,
    la somme des composants A à F donnant 100% en poids.
  2. Elément d'impression flexographique qui peut être gravé au laser suivant la revendication 1, caractérisé en ce que le composant B est choisi parmi le groupe constitué d'agents plastifiants contenant des huiles de polybutadiène, des huiles de polyisoprène ou des groupes allyle, qui peuvent présenter des groupes terminaux fonctionnels, avec une viscosité de 500 à 150.000 mPas à 25°C.
  3. Elément d'impression flexographique qui peut être gravé au laser suivant la revendication 2, caractérisé en ce que le composant B est une huile de polybutadiène ayant une viscosité de 500 à 100.000 mPas à 25°C.
  4. Procédé de préparation d'un élément d'impression en relief comprenant les étapes
    (i) de réticulation thermique ou photochimique de la couche élastomère formant relief d'un élément d'impression flexographique, tel que défini dans l'une des revendications 1 à 3, et
    (ii) de gravure d'un relief d'impression dans la couche réticulée, élastomère, formant relief, au moyen d'un laser.
  5. Procédé de préparation d'un élément d'impression en relief comprenant les étapes
    (i) de réticulation thermique ou photochimique de la couche élastomère formant relief d'un élément d'impression flexographique, comportant, sur un substrat flexible, de dimensions stables, une couche élastomère formant relief, qui peut être gravée au laser et être réticulée par voie thermique et/ou photochimique et qui contient, comme liant, au moins 5% en poids de 1,2-polybutadiène syndiotactique ayant une teneur en unités de butadiène reliées en 1,2 de 80 à 100%, un degré de cristallinité de 5 à 30% et une masse molaire moyenne de 20.000 à 3.000.000 g/mole, et
    (ii) de gravure d'un relief d'impression dans la couche réticulée, élastomère, formant relief, au moyen d'un laser.
EP02740469A 2001-04-18 2002-04-15 Element d'impression par flexographie pouvant etre grave au laser comprenant des couches elastomeres en relief renfermant du 1,2-polybutadiene syndiotactique Expired - Lifetime EP1381511B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10118987A DE10118987A1 (de) 2001-04-18 2001-04-18 Lasergravierbare Flexodruckelemente mit reliefbildenden elastomeren Schichten enthaltend syndiotaktisches 1,2,-Polybutadien
DE10118987 2001-04-18
PCT/EP2002/004162 WO2002083418A1 (fr) 2001-04-18 2002-04-15 Element d'impression par flexographie pouvant etre grave au laser comprenant des couches elastomeres en relief renfermant du 1,2-polybutadiene syndiotactique

Publications (2)

Publication Number Publication Date
EP1381511A1 EP1381511A1 (fr) 2004-01-21
EP1381511B1 true EP1381511B1 (fr) 2005-02-02

Family

ID=7681841

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02740469A Expired - Lifetime EP1381511B1 (fr) 2001-04-18 2002-04-15 Element d'impression par flexographie pouvant etre grave au laser comprenant des couches elastomeres en relief renfermant du 1,2-polybutadiene syndiotactique

Country Status (6)

Country Link
US (1) US7101653B2 (fr)
EP (1) EP1381511B1 (fr)
JP (1) JP2004523401A (fr)
AT (1) ATE288358T1 (fr)
DE (2) DE10118987A1 (fr)
WO (1) WO2002083418A1 (fr)

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10258668A1 (de) * 2002-12-13 2004-06-24 Basf Ag Verfahren zur Herstellung von Flexodruckformen mittels Lasergravur unter Verwendung von fotopolymeren Flexodruckelementen und fotopolymerisierbares Flexodruckelementen
DE10355991A1 (de) 2003-11-27 2005-06-30 Basf Drucksysteme Gmbh Verfahren zur Herstellung von Flexodruckplatten mittels Lasergravur
DE102004025364A1 (de) 2004-05-19 2005-12-08 Basf Drucksysteme Gmbh Verfahren zur Herstellung von Flexodruckformen mittels Laser-Direktgravur
DE102004050277A1 (de) * 2004-10-14 2006-04-27 Basf Drucksysteme Gmbh Verfahren und Vorrichtung zur Herstellung von fotopolymerisierbaren, zylindrischen, endlos-nahtlosen Flexodruckelementen
JP4982988B2 (ja) * 2004-12-28 2012-07-25 Ｊｓｒ株式会社 レーザー加工用組成物、レーザー加工用シート、及びフレキソ印刷版
US20100141724A1 (en) * 2005-02-24 2010-06-10 Atsushi Nakajima Ink-Jet Recording Apparatus, Ink-Jet Recording Method and Ultraviolet Ray Curable Ink
US20070084369A1 (en) * 2005-09-26 2007-04-19 Jsr Corporation Flexographic printing plate and process for production thereof
EP1958968A4 (fr) * 2005-12-09 2011-03-30 Jsr Corp Composition de polymere durcissable aux ultraviolets, article moule en resine et son procede de fabrication
US8501390B2 (en) * 2006-06-27 2013-08-06 Xiper Innovations, Inc. Laser engravable flexographic printing articles based on millable polyurethanes, and method
JP4958571B2 (ja) * 2006-07-20 2012-06-20 富士フイルム株式会社 レーザー分解性樹脂組成物及びそれを用いるパターン形成材料
DE102006037415A1 (de) * 2006-08-10 2008-02-14 Basf Ag Matrizen mit einer Kennzeichnung zur Herstellung von Dekor-Zurichtungen
US8795950B2 (en) * 2010-06-30 2014-08-05 Jonghan Choi Method of improving print performance in flexographic printing plates
US20120129097A1 (en) * 2010-11-18 2012-05-24 Jonghan Choi Photopolymer Printing Plates with In Situ Non-Directional Floor Formed During Extrusion
US8920692B2 (en) 2011-03-22 2014-12-30 Eastman Kodak Company Method for recycling relief image elements
US20120240802A1 (en) 2011-03-22 2012-09-27 Landry-Coltrain Christine J Laser-engraveable flexographic printing precursors
DE102012013532B4 (de) * 2012-07-05 2017-01-12 Martin, Prof. Dr. Dreher Einrichtung zum Drucken mit weich-elastischen Druckformen
US20140366759A1 (en) * 2013-06-12 2014-12-18 Maria Celeste Tria Patterned materials and methods of making them
WO2015115599A1 (fr) * 2014-01-31 2015-08-06 富士フイルム株式会社 Composition de résine pour gravure au laser, plaque originale d'impression flexographique pour gravure au laser, procédé de production d'une plaque originale d'impression flexographique pour gravure au laser, plaque d'impression flexographique, et procédé de fabrication de plaque pour plaque d'impression flexographique
JP6383598B2 (ja) * 2014-03-26 2018-08-29 住友理工株式会社 フレキソ印刷版原版
JP7200605B2 (ja) * 2018-11-02 2023-01-10 富士フイルムビジネスイノベーション株式会社 三次元形状データの生成装置、三次元造形装置、及び三次元形状データの生成プログラム

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1099435A (fr) 1971-04-01 1981-04-14 Gwendyline Y. Y. T. Chen Traduction non-disponible
FR2318441A1 (fr) 1975-07-17 1977-02-11 Nippon Paint Co Ltd Composition
JPS5632534A (en) * 1979-08-27 1981-04-02 Japan Synthetic Rubber Co Ltd Thermoplastic elastomer composition
US4517278A (en) 1981-01-13 1985-05-14 Nippon Paint Co., Ltd. Flexographic printing plates and process for making the same
US4394435A (en) 1981-10-01 1983-07-19 Uniroyal, Inc. Syndiotactic polybutadiene composition for a photosensitive printing plate
US4427759A (en) 1982-01-21 1984-01-24 E. I. Du Pont De Nemours And Company Process for preparing an overcoated photopolymer printing plate
CA2019824A1 (fr) 1989-06-28 1990-12-28 Seiji Arimatsu Derives de l'acrylamide polyetheres et composition de resine durcissable par des rayonnements d'energie active
DE4202332A1 (de) 1992-01-29 1993-08-05 Basf Lacke & Farben Lichtempfindliches gemisch zur herstellung von relief- und druckformen
US5804353A (en) * 1992-05-11 1998-09-08 E. I. Dupont De Nemours And Company Lasers engravable multilayer flexographic printing element
US5798202A (en) 1992-05-11 1998-08-25 E. I. Dupont De Nemours And Company Laser engravable single-layer flexographic printing element
DE19628541A1 (de) 1996-07-16 1998-01-22 Du Pont Deutschland Strahlungsempfindliche Zusammensetzung und ein diese enthaltendes strahlungsempfindliches Aufzeichnungsmaterial
DE19814839A1 (de) * 1998-04-02 1999-10-07 Bayer Ag Hydrophobierte oxidische oder silikatische Füllstoffe enthaltende Emulsionskautschukmischungen sowie deren Verwendung zur Herstellung von Reifen

Also Published As

Publication number Publication date
US20040115562A1 (en) 2004-06-17
DE50202172D1 (de) 2005-03-10
DE10118987A1 (de) 2002-10-24
ATE288358T1 (de) 2005-02-15
WO2002083418A1 (fr) 2002-10-24
EP1381511A1 (fr) 2004-01-21
US7101653B2 (en) 2006-09-05
JP2004523401A (ja) 2004-08-05

Similar Documents

Publication Publication Date Title
EP1381511B1 (fr) Element d'impression par flexographie pouvant etre grave au laser comprenant des couches elastomeres en relief renfermant du 1,2-polybutadiene syndiotactique
EP1343632B1 (fr) Procede de fabrication de blocs d'impression flexographique par gravure laser
EP1311393B1 (fr) Procede pour produire des elements flexographiques pouvant etre graves par laser sur des supports metalliques flexibles
EP1353802B1 (fr) Procede de production d'elements flexographiques a reticulation thermique et pouvant etre graves par laser et composites multicouches
EP1315617B1 (fr) Procede pour produire des plaques d'impression flexographique par gravure au laser
EP1613484B1 (fr) Element pour impression flexographique grave au laser, renfermant du noir de fumee de conductibilite, et procede de production de formes pour flexographie
EP1423280B1 (fr) Procede de production de formes flexographiques par gravure directe au laser
EP1451014B1 (fr) Elements d'impression flexographique pouvant etre graves au laser, servant a la production de cliches flexographiques contenant des melanges de polymeres hydrophiles et d'elastomeres hydrophobes
EP1136254B1 (fr) Utilisation de copolymères greffés pour la fabrication d'éléments marquables au laser en relief
EP0982124B1 (fr) Procédé de fabrication d'une plaque d'impression en relief par gravure utilisant des rayons actiniques cohérents et plaque d'impression préparé l'utilisant
EP1527373B1 (fr) Procede de production de formes flexographiques par gravure directe au laser
EP1213615A2 (fr) Elément d'impression flexographique photosensible ayant au moins deux couches décomposables par infrarouge
EP1414647B1 (fr) Procede de production de blocs d'impression flexographique par reticulation par faisceau electronique et par gravure laser
WO2005050327A1 (fr) Procede de realisation de formes flexographiques par developpement thermique
DE19846529A1 (de) Photopolymerisierbare Druckformen zur Herstellung von Reliefdruckplatten für den Druck mit UV-härtbaren Druckfarben
WO2002076738A1 (fr) Procede pour produire des plaques d'impression en relief par gravure au laser
EP3394672B1 (fr) Procede de fabrication generative de moules d'impression en relief a l'aide de diffusion de monomere par une couche de masque integrale

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20031118

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

AX Request for extension of the european patent

Extension state: AL LT LV MK RO SI

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

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

Ref country code: NL

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

Effective date: 20050202

Ref country code: TR

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

Effective date: 20050202

Ref country code: IE

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

Effective date: 20050202

Ref country code: FI

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

Effective date: 20050202

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: GERMAN

REF Corresponds to:

Ref document number: 50202172

Country of ref document: DE

Date of ref document: 20050310

Kind code of ref document: P

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

Ref country code: AT

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

Effective date: 20050415

Ref country code: LU

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

Effective date: 20050415

Ref country code: CY

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

Effective date: 20050415

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 20050406

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

Ref country code: MC

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

Effective date: 20050430

Ref country code: BE

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

Effective date: 20050430

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

Ref country code: GR

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

Effective date: 20050502

Ref country code: DK

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

Effective date: 20050502

Ref country code: SE

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

Effective date: 20050502

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

Ref country code: ES

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

Effective date: 20050513

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

BERE Be: lapsed

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

Effective date: 20050430

REG Reference to a national code

Ref country code: FR

Ref legal event code: CD

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

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

ET Fr: translation filed
26N No opposition filed

Effective date: 20051103

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

Ref country code: LI

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

Effective date: 20060430

Ref country code: CH

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

Effective date: 20060430

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

BERE Be: lapsed

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

Effective date: 20050430

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

Ref country code: PT

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

Effective date: 20050702

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 15

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 16

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 17

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

Ref country code: IT

Payment date: 20190419

Year of fee payment: 18

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

Ref country code: FR

Payment date: 20190423

Year of fee payment: 18

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

Ref country code: GB

Payment date: 20190424

Year of fee payment: 18

Ref country code: DE

Payment date: 20190628

Year of fee payment: 18

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 50202172

Country of ref document: DE

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

Ref country code: DE

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

Effective date: 20201103

Ref country code: FR

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

Effective date: 20200430

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

Effective date: 20200415

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

Ref country code: GB

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

Effective date: 20200415

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

Ref country code: IT

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

Effective date: 20200415