EP0816095A1 - Tête d'impression par jet d'encre à base de composés organosiliciques - Google Patents

Tête d'impression par jet d'encre à base de composés organosiliciques Download PDF

Info

Publication number
EP0816095A1
EP0816095A1 EP97110589A EP97110589A EP0816095A1 EP 0816095 A1 EP0816095 A1 EP 0816095A1 EP 97110589 A EP97110589 A EP 97110589A EP 97110589 A EP97110589 A EP 97110589A EP 0816095 A1 EP0816095 A1 EP 0816095A1
Authority
EP
European Patent Office
Prior art keywords
compound
group
lacquer
ink jet
ink
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
EP97110589A
Other languages
German (de)
English (en)
Other versions
EP0816095B1 (fr
Inventor
Jürgen Dr. Kappel
Michael Dr. Popall
Jochen Dr. Schulz
Adelheid Martin
Birke-E. Olsowski
Karl Bühler
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.)
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Original Assignee
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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 Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV filed Critical Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Publication of EP0816095A1 publication Critical patent/EP0816095A1/fr
Application granted granted Critical
Publication of EP0816095B1 publication Critical patent/EP0816095B1/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
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B41J2/135—Nozzles
    • B41J2/16—Production of nozzles
    • B41J2/1621—Manufacturing processes
    • B41J2/1631—Manufacturing processes photolithography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B41J2/135—Nozzles
    • B41J2/16—Production of nozzles
    • B41J2/1601—Production of bubble jet print heads

Definitions

  • the present invention relates to ink jet printheads which consist at least in part of a polymeric material that is produced using organosilicon compounds with polycondensable and polymerizable groups.
  • Inkjet printheads now have to be sold in increasing numbers to be produced. This printing technology is now one time extremely widespread, on the other hand it is desirable to have one To develop "cheap printhead", each together with the Ink cartridge can be replaced.
  • Inkjet printheads exist next to the actuator (heating element, Piezo element, electrodynamic transducer, etc.) made of structures for liquid management (channel walls, covers, nozzle walls, -covers, ink supply), ink filters and one not wetting nozzle outlet side (e.g. nozzle plate).
  • Modern Ink printheads have the planar structure in common that with the means of semiconductor manufacturing a relatively inexpensive Manufacture with high accuracy in large numbers enables. There are differences in the structure: “Edge shooter arrangement” the droplet is ejected tangentially to the heating element surface, while the so-called “Side shooter arrangement” of the drops normal to the heating element surface is delivered.
  • the layered structure of the "edge shooter variant” (substrate, Thin film structure, channel structure, channel cover, glass tub with Ink reservoir) requires nozzles that come from different Materials with different wetting properties be formed (thin film layer, photoresist channel wall, Photoresist adhesive layer, channel cover). This different wetting properties can be negative affect drop formation. Therefore, with “edge shooter arrangements” additionally the coating on the nozzle outlet side with a hydrophobic material.
  • the nozzle outlet of the side-shooter arrangement nozzle plate exists but from only one material. Thereby lie in the nozzle area same wetting properties.
  • an additional one only Coating (anti-slide coating) required, if the hydrophobic properties of the material are not suffice.
  • the channel structures of today's printheads are usually made Acrylic-based photoresists through photolithographic Processes generated.
  • photo glass is used that structured after the exposure of the mask can be etched.
  • the object of the present invention is a universally applicable To provide material for inkjet printheads, with the channel structures, substrates, nozzle plates, nozzles, ink reservoirs, Ink filters and the like for color and mono ink jet print heads can be completely manufactured, and whose hydrophobic properties are sufficient to respond to the To be able to dispense with an anti-triel coating.
  • the Material should be inexpensive, and structuring should with little effort and / or with high precision can.
  • Polymer materials of the type used according to the invention belong to the material class of the so-called ORMOCERE (ORganically MOdified CERamics). You can choose between inorganic and organic polymers are classified. The production is based on alkoxides of silicon and, if necessary, in addition other metals wholly or partly through organic polymerizable substituents are modified. By hydrolysis and condensation becomes the inorganic part of the network built up by polymerization, polyaddition or others organic coupling reactions the organic part from reactive organic substituents.
  • ORMOCERE ORganically MOdified CERamics
  • layers to be structured can be produced as follows: First of all, within a polycondensation reaction (eg in the sol-gel process), a pre-condensate (here usually referred to as "lacquer") is produced from the selected starting materials, which, depending on the chemical compounds used, is usually stable in storage for a few months.
  • the solids content of the lacquer can be varied, for example by removing solvent or water or by adding an additional solvent.
  • the lacquer is then applied to the desired substrate material as a layer by dipping, spin coating or spraying or the like, the substrate not only consisting of foreign material such as glass, ceramic, metal or foreign polymer, but also of the identical material.
  • the lacquer By structuring exposure (mostly UV light), the lacquer can be photopolymerized at the desired positions using any technology, whereupon in a so-called “development step” the part not exposed to the light is removed (negative resist behavior), which is done with the help of solvents such as acetone or an alkaline aqueous medium. Finally, the already structured material is thermally crosslinked. Mechanical embossing with simultaneous or subsequent exposure and subsequent thermal post-crosslinking is also possible.
  • the polymeric material be both photopolymerizable groups as well as thermally cross-linkable Contains groups. Furthermore, it is of course preferred a photoinitiator and possibly an accelerator, for example based on amine added.
  • FIG. 1 shows an example of the formation of a polymeric "ORMOCER" hybrid material:
  • the inorganic oxide network is built up by polycondensation of alkoxysilanes, in a subsequent step the methacrylic groups of 3-methacryloxypropyltrimethoxysilane (MEMO) are photochemically crosslinked and finally the epoxy groups of 3-glycidoxypropyltrimethoxysilane (GLYMO) are thermally polymerized, so that an organic network value also arises .
  • MEMO 3-methacryloxypropyltrimethoxysilane
  • GLYMO 3-glycidoxypropyltrimethoxysilane
  • the use of the GMP2T system is very particularly preferred.
  • the paint is preferably made by first the desired silanes, if necessary with further additives (e.g. Network formers or modifying substances), mixed and, if necessary under heat, hydrolyzed by adding water.
  • further additives e.g. Network formers or modifying substances
  • the Water addition can be done slowly, so the system first substoichiometric amounts are supplied.
  • the liquid lacquer produced as described above becomes possibly brought to a desired solids content, what preferably by spinning in or distilling off Solvent or water happens. If necessary, additional or alternatively diluted with a suitable solvent (e.g. with ethanol, acetone, propyl acetate or the like).
  • a suitable solvent e.g. with ethanol, acetone, propyl acetate or the like.
  • a Solids content in the range from 50% to 85%, especially from about 75% is desirable. However, it should be clear that depending on the type of order and the one you want Structure height also worked with other solids contents can be.
  • the varnish can then be applied as a layer on one or different Substrate (s) are applied.
  • the substrate or substrates can it be made of another material like glass, Ceramic, metal, silicon or polymer or the like. Act it can also be an order on the used according to the invention Material take place, which should then already be hardened.
  • the varnish can be applied by spin-on application (for example at a rotation speed of about 300 to 800 rpm and a period of about 30 to 80 seconds).
  • spin-on application for example at a rotation speed of about 300 to 800 rpm and a period of about 30 to 80 seconds.
  • Doctor blade dipping, spraying, embossing or similar
  • the components 1. to 4. are submitted and at Room temperature stirred for 18 h. Then within The suspension was heated to about 70 ° C. for 90 minutes. after the Suspension has become clear, is 1/4 of the amount of water Maintenance of heating added. At intervals of approx. The remaining amount of water is added for 20 min 1/4). After all the water has been added, the mixture is stirred at 70 ° C. for 1 h continued stirring. Then the heater is removed, and after the paint is ready to use after cooling.
  • the system GMPT2 is used for the generation of channel structures, which has very good adhesion to the various substrate materials, even after ink storage.
  • the solvent is distilled off until a solids content of 75% is reached.
  • 1.5% by mass of photoinitiator (Quantacure ITX, Shell Chemie) and 1.5% by mass of accelerator (N-methyldiethanolamine and diethylenetriamine, ratio 1: 1) are dissolved in the lacquer and this system is carried out on substrates (glass, Si) Spin-on application applied (600 rpm for 60 sec.).
  • the photostructuring is carried out using a mask aligner (Karl-Süss MA 45) at a wavelength of 360 nm and an exposure intensity of 14 mW / cm 2 . Exposure times of approximately 10 seconds have proven to be optimal under these conditions.
  • the exposed structures are developed by spraying with ethanol (duration: 10 seconds).
  • the structures obtained are cured at 120 ° C. for 10 h. These structures are characterized in FIGS. 2 to 4 (SEM and profilometer measurements). With the described method, crack-free structure heights of up to 30 ⁇ m can be achieved in one step. These structures have a high edge steepness, have good substrate adhesion and the required ink storage stability. For this reason and due to their temperature stability up to 270 ° C (thermogravimetric determination in air), they are very well suited for use as channel structures for inkjet printheads.
  • the concentration on Photoinitiator is 0.05% by weight (Irgacure 184, company Ciba-Geigy or Quantacure ITX)
  • the laser wavelength is included 360 nm
  • the laser power before focusing is 1.41 - 2.28 mW (variable; 1 mm beam diameter).
  • the laser beam is focused on approx. 10 - 15 ⁇ m. It is written with a Speed of 1 mm / sec.
  • Figures 5 and 6 is one such laser-written structuring and the associated Profilometer measurement shown.
  • the thickening on the corners is on the persistence of the laser beam when changing direction attributed.
  • the structure height is 20 ⁇ m.
  • the GMP2T system is also used for embossing channel structures (see example 2).
  • Application conditions glass substrates
  • curing photochemical and thermal post-curing
  • the embossing process requires thermal pretreatment of the applied coating.
  • the most favorable pre-hardening conditions are thermal pre-treatments at approx. 80 ° C (5 min). Increasing the temperature leads to strong pre-crosslinking (bad penetration of the embossing mask as a result), while shorter thermal pre-treatment leads to the mask and layer sticking together.
  • Structured glass or Si masks with structure heights of up to 40 ⁇ m are used as masks. After the pre-hardening of the layer, these masks are placed on it and pressed with a pressure of approx. 1 kg / cm 2 , exposure being carried out (approx. 10 sec, 14 mW / cm 2 at 360 nm). Then the pressure is released again, the mask is removed and the structure obtained is post-cured at 120 ° C. for 10 hours.

Landscapes

  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Particle Formation And Scattering Control In Inkjet Printers (AREA)
  • Paints Or Removers (AREA)
EP97110589A 1996-06-28 1997-06-27 Tête d'impression par jet d'encre à base de composés organosiliciques Expired - Lifetime EP0816095B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19626053 1996-06-28
DE19626053 1996-06-28
PCT/DE1997/001340 WO1998000296A1 (fr) 1996-06-28 1997-06-26 Tete d'impression a jet d'encre avec des elements constitues de composes organosiliciques
WOPCT/DE97/01340 1997-06-26

Publications (2)

Publication Number Publication Date
EP0816095A1 true EP0816095A1 (fr) 1998-01-07
EP0816095B1 EP0816095B1 (fr) 2001-05-16

Family

ID=7798351

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97110589A Expired - Lifetime EP0816095B1 (fr) 1996-06-28 1997-06-27 Tête d'impression par jet d'encre à base de composés organosiliciques

Country Status (4)

Country Link
EP (1) EP0816095B1 (fr)
CA (1) CA2230636A1 (fr)
DE (1) DE59703535D1 (fr)
WO (1) WO1998000296A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1136520A2 (fr) * 2000-03-17 2001-09-26 nanoFILM, Ltd. Materiau polymère hybride organique-inorganique et procédé de préparation de celui-ci

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58224761A (ja) * 1982-06-25 1983-12-27 Canon Inc インクジエツト記録ヘツド
DE4400315C1 (de) * 1994-01-07 1995-01-12 Kernforschungsz Karlsruhe Verfahren zum stufenweisen Aufbau von Mikrostrukturkörpern und damit hergestellter Mikrostrukturkörper
EP0658430A1 (fr) * 1993-11-26 1995-06-21 Canon Kabushiki Kaisha Tête d'impression à jet d'encre ne représentant pas de détachement entre un substrat et les canaux d'écoulement de l'encre formés sur ce substrat
JPH08174845A (ja) * 1994-12-26 1996-07-09 Canon Inc 液流路形成用樹脂材料、これを用いた液体噴射記録ヘッド、及びその製造方法
EP0734866A2 (fr) * 1995-03-31 1996-10-02 Canon Kabushiki Kaisha Procédé de fabrication d'une tête à jet d'encre
DE19613650C1 (de) * 1996-04-04 1997-04-10 Fraunhofer Ges Forschung Hydrolisierbare, fluorierte Silane, Verfahren zu deren Herstellung und deren Verwendung zur Herstellung von Kieselsäurepolykondensaten und Kieselsäureheteropolykondensaten

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58224761A (ja) * 1982-06-25 1983-12-27 Canon Inc インクジエツト記録ヘツド
EP0658430A1 (fr) * 1993-11-26 1995-06-21 Canon Kabushiki Kaisha Tête d'impression à jet d'encre ne représentant pas de détachement entre un substrat et les canaux d'écoulement de l'encre formés sur ce substrat
DE4400315C1 (de) * 1994-01-07 1995-01-12 Kernforschungsz Karlsruhe Verfahren zum stufenweisen Aufbau von Mikrostrukturkörpern und damit hergestellter Mikrostrukturkörper
JPH08174845A (ja) * 1994-12-26 1996-07-09 Canon Inc 液流路形成用樹脂材料、これを用いた液体噴射記録ヘッド、及びその製造方法
EP0734866A2 (fr) * 1995-03-31 1996-10-02 Canon Kabushiki Kaisha Procédé de fabrication d'une tête à jet d'encre
DE19613650C1 (de) * 1996-04-04 1997-04-10 Fraunhofer Ges Forschung Hydrolisierbare, fluorierte Silane, Verfahren zu deren Herstellung und deren Verwendung zur Herstellung von Kieselsäurepolykondensaten und Kieselsäureheteropolykondensaten

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE INSPEC INSTITUTE OF ELECTRICAL ENGINEERS, STEVENAGE, GB; ROSCHER C: "perfluoroaryl substituted inorganic-organic hybrid materials", XP002044420 *
PATENT ABSTRACTS OF JAPAN vol. 008, no. 080 (M - 289) 12 April 1984 (1984-04-12) *
PATENT ABSTRACTS OF JAPAN vol. 096, no. 011 29 November 1996 (1996-11-29) *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1136520A2 (fr) * 2000-03-17 2001-09-26 nanoFILM, Ltd. Materiau polymère hybride organique-inorganique et procédé de préparation de celui-ci
EP1136520A3 (fr) * 2000-03-17 2001-12-19 nanoFILM, Ltd. Materiau polymère hybride organique-inorganique et procédé de préparation de celui-ci
US6451420B1 (en) 2000-03-17 2002-09-17 Nanofilm, Ltd. Organic-inorganic hybrid polymer and method of making same
US6607590B2 (en) 2000-03-17 2003-08-19 Nanofilm, Ltd. Organic-inorganic hybrid polymer and method of making same

Also Published As

Publication number Publication date
CA2230636A1 (fr) 1998-01-08
WO1998000296A1 (fr) 1998-01-08
DE59703535D1 (de) 2001-06-21
EP0816095B1 (fr) 2001-05-16

Similar Documents

Publication Publication Date Title
DE69815189T2 (de) Strahlungshärtbare Harzschicht enthaltender Tintenstrahldruckkopf
DE3507338C2 (fr)
DE3222874C2 (fr)
DE3108206C2 (fr)
DE60100914T2 (de) Tintenstrahldruckkopf
DE19730245B4 (de) Beschichtungsmaterial, beschichtetes Material und Verfahren zu deren Herstellung
DE60315205T2 (de) Epoxidharzzusammensetzung, Verfahren zur Oberflächenbehandlung, Flüssigkeitsstrahlaufzeichnungskopf und ein Flüssigkeitsstrahlaufzeichnungsgerät
DE602005004675T2 (de) Optischer Wellenleiter und Herstellungsmethode
DE69934532T2 (de) Tintenstrahlaufzeichnungskopf und tintenstrahlaufzeichnungsapparat enthaltend fluor-enthaltende epoxidharzzusammensetzung
EP0816094B1 (fr) Revêtement hydrophobe pour tête d'impression à jet d'encre
EP0101586B1 (fr) Procédé pour la fabrication de clichés pour l'impression en creux avec des plaques d'impression en matière plastique
DE19919794A1 (de) Polymer und dessen Verwendung in einem Verfahren zur Bildung eines Mikromusters
DE102006033280A1 (de) Kompositzusammensetzung für mikrostrukturierte Schichten
DE102005028240A1 (de) Abdecklack zum Ausbilden eines Musters und Verfahren zum Ausbilden des Musters unter Verwendung desselben
DE60126736T2 (de) Strahlungsempfindliche polysilazan-zusammensetzung, daraus erzeugte muster sowie ein verfahren zur veraschung eines entsprechenden beschichtungsfilms
DE60015884T2 (de) Alkylsiloxanenthaltende Epoxidharzzusammensetzung, Verwendung als Oberflächenmodifizierungsmittel, Tintenstrahldruckkopf und Flüssigkeitsstrahlaufzeichnungsgerät
EP0141389A2 (fr) Procédé pour la fabrication de réserves structurées selon une image et réserve à sec pour ce procédé
DE60202012T2 (de) Epoxidharzzusammensetzung, Verfahren zur Verbesserung der Oberfläche eines Substrats, eines Tintenstrahlaufzeichnungskopfs und eines Tintenstrahlaufzeichnungsgeräts
WO2003086959A2 (fr) Procede de transfert destine a la fabrication de substrats microstructures
EP0816095B1 (fr) Tête d'impression par jet d'encre à base de composés organosiliciques
DE2350211A1 (de) Verfahren zur herstellung einer vorsensibilisierten trockenen flachdruckplatte
DE60306212T2 (de) Epoxidharzzusammensetzung, Verfahren zur Oberflächenbehandlund, Tintenstrahlaufzeichnungskopf und Tintenstrahlaufzeichnungsaparat
DE3322647C2 (fr)
US10265960B2 (en) Method for manufacturing liquid ejection head
DE3543961C2 (fr)

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

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): CH DE FR GB IT LI

17P Request for examination filed

Effective date: 19980706

AKX Designation fees paid

Free format text: CH DE FR GB IT LI

RBV Designated contracting states (corrected)

Designated state(s): CH DE FR GB IT LI

17Q First examination report despatched

Effective date: 19990618

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): CH DE FR GB IT LI

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: PA ALDO ROEMPLER

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 59703535

Country of ref document: DE

Date of ref document: 20010621

ITF It: translation for a ep patent filed

Owner name: IPSER S.R.L.

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

Effective date: 20010801

ET Fr: translation filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

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

26N No opposition filed
REG Reference to a national code

Ref country code: CH

Ref legal event code: PFA

Owner name: FRAUNHOFER-GESELLSCHAFT ZUR FOERDERUNG DER ANGEWA

Free format text: FRAUNHOFER-GESELLSCHAFT ZUR FOERDERUNG DER ANGEWANDTEN FORSCHUNG E.V.#LEONRODSTRASSE 54#80636 MUENCHEN (DE) -TRANSFER TO- FRAUNHOFER-GESELLSCHAFT ZUR FOERDERUNG DER ANGEWANDTEN FORSCHUNG E.V.#HANSASTRASSE 27 C#80686 MUENCHEN (DE)

REG Reference to a national code

Ref country code: CH

Ref legal event code: PCAR

Free format text: ALDO ROEMPLER PATENTANWALT;BRENDENWEG 11 POSTFACH 154;9424 RHEINECK (CH)

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

Ref country code: CH

Payment date: 20110623

Year of fee payment: 15

Ref country code: FR

Payment date: 20110630

Year of fee payment: 15

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

Ref country code: GB

Payment date: 20110621

Year of fee payment: 15

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

Ref country code: DE

Payment date: 20110826

Year of fee payment: 15

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

Ref country code: IT

Payment date: 20110627

Year of fee payment: 15

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Effective date: 20120627

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: 20120627

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20130228

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 59703535

Country of ref document: DE

Effective date: 20130101

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: 20130101

Ref country code: CH

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

Effective date: 20120630

Ref country code: LI

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

Effective date: 20120630

Ref country code: GB

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

Effective date: 20120627

Ref country code: FR

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

Effective date: 20120702