WO2001009230A1 - Matiere pouvant etre marquee au laser - Google Patents

Matiere pouvant etre marquee au laser Download PDF

Info

Publication number
WO2001009230A1
WO2001009230A1 PCT/EP2000/007304 EP0007304W WO0109230A1 WO 2001009230 A1 WO2001009230 A1 WO 2001009230A1 EP 0007304 W EP0007304 W EP 0007304W WO 0109230 A1 WO0109230 A1 WO 0109230A1
Authority
WO
WIPO (PCT)
Prior art keywords
laser
radiation
pigment
marking
absorption band
Prior art date
Application number
PCT/EP2000/007304
Other languages
English (en)
Inventor
Tang Yung Lee
Zheng Hong Yu
Zhao Jian Hong
Lim Gnian Cher
Original Assignee
Nokia Mobile Phones Limited
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 Nokia Mobile Phones Limited filed Critical Nokia Mobile Phones Limited
Priority to AU74075/00A priority Critical patent/AU7407500A/en
Publication of WO2001009230A1 publication Critical patent/WO2001009230A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/267—Marking of plastic artifacts, e.g. with laser

Definitions

  • This invention relates to material that is capable of being marked by a laser and in particular to laser-markable thermoplastic elastomer material.
  • Laser marking technology is also widely used in industry because of its superior mark quality and flexibility to traditional marking techniques. Examples of such applications include laser marking on IC chips, aircraft cables and metal surfaces of various products.
  • the current technique of laser marking on polymers such as thermoplastic elastomer, polyethylene, polypropylene and polycarbonates is through a thermal process.
  • the laser beam heats up the materials and causes melting and vaporisation of the surface material. Grooves are produced with re-solidified material particles. As articles such as keymats have high cosmetic requirements, the laser marking quality through thermal processes is not acceptable.
  • Infrared lasers such as C02 and Nd:YAG lasers produce colour changes through thermal processes, which result in material melting and vaporisation.
  • a material comprising a thermoplastic elastomer and a pigment additive, the pigment additive having an absorption band in a band of e.m. radiation which results in a photochemical reaction taking place when the material is subjected to e.m. radiation in the absorption band.
  • the invention results in a material which may be subjected to laser marking by photo-chemical transformation rather than thermal changes.
  • the photochemical reaction leads to clearly visible colour changes with no apparent surface damage. This is achieved by adding pigments to the thermoplastic elastomer (TPE) substrate material.
  • thermoplastic elastomer is injection mouldable.
  • the thermoplastic elastomer may be a KratonTM-based polymer and the pigment additive may be Ti0 2 .
  • the pigment additive comprises 0.5 - 5.0% by weight of the material. Most advantageously for applications which require back lighting the pigment additive comprises 1.5% by weight of the material.
  • the material may further comprise up to 5% by weight of a thermoplastic polymer to enhance the mechanical and/or thermal properties of the material.
  • the absorption band of the pigment lies in the invisible band of the e.m. spectrum and in particular the UV band.
  • thermoplastic elastomer material said material comprising a thermoplastic elastomer and a pigment additive, the pigment additive having an absorption band within a band of e.m. radiation which results in a photo-chemical reaction when the material is subjected to e.m radiation in the absorption band
  • the method comprising: subjecting the material to a laser beam having a wavelength of radiation in the absorption band such that the pigment undergoes a photochemical reaction.
  • the wavelength of radiation of the laser beam is in the range 300- 400 nm, and most advantageously in the range 350-360 nm.
  • the laser beam may be provided by a pulsed third harmonic YAG laser.
  • a method of making a laser-markable material comprising: adding pigment additive to a thermoplastic elastomer, said pigment additive having an absorption band in a band of e.m. radiation which results in a photo-chemical reaction taking place when the material is subjected to e.m. radiation in the absorption band, mixing the pigment additive and the thermoplastic elastomer, melting the mixed pigment additive and thermoplastic elastomer to form a molten material and forming the molten material into pellets or the like.
  • the invention also extends to an article made from the material according to the invention and in particular to keymats for use with portable devices such as radio telephones, personal digital assistants (PDAs), portable computers, palm tops, lap tops and the like.
  • portable devices such as radio telephones, personal digital assistants (PDAs), portable computers, palm tops, lap tops and the like.
  • PDAs personal digital assistants
  • portable computers palm tops, lap tops and the like.
  • a laser- markable material comprising a thermoplastic elastomer and 0.5- 5.0% by weight of Ti0 2 .
  • the material contains 1.5% by weight of Ti0 2 .
  • Such a material has been found to be particular suitable for keymats for portable devices such as mobile phones.
  • the material can be injection mouldable, which is a significant improvement over silicon rubber which has to be compression moulded.
  • the material and manufacturing process according to the invention uses a thermoplastic elastomer as the raw material.
  • the thermoplastic material is preferably injection-mouldable.
  • the laser marking process is used for marking of texts and graphics.
  • the invention also allows the use of an automated inspection system for quantitative evaluation of laser-marked keymats.
  • the developed manufacturing process is expected to have the following advantages over the current process: TPE materials are recyclable economically; the production cycle time is reduced from around 65 minutes to 1 minute; component cost can be reduced by 25%; and high flexibility in customisation of a component is possible since the laser marking process is programmable. Additionally the resulting method is less labour intensive due to automation. The quality of resulting articles is also more consistent compared with known techniques.
  • the new laser marking technique uses a photo-chemical process, hereinafter referred to as laser colour-change marking.
  • the characteristics of the laser colour-change marking include: no or minimal thermal effects; no or minimal surface material removal; no or minimal surface structural changes; and good marking contrast due to colour changes.
  • laser sensitive pigments are incorporated into the substrate materials. Under an appropriate laser wavelength, pulse energy and peak power, a photo-chemically induced colour change occurs.
  • TPEs Thermoplastic elastomers
  • TPEs are considered to be the most suitable thermoplastic material to be used.
  • TPEs can be injection-moulded which is more productive than the compression moulding process used for silicon rubber keymats.
  • Laser marking contrast is an important quality criteria. Apart from the laser parameters, the types of pigments and their weight percentage ratios in the substrate materials play a major role in achieving adequate marking contrast. In general, higher pigment contents will lead to high laser marking contrast.
  • Translucency is another important quality criteria.
  • the keymat must be sufficiently translucent to allow back-lights to transmit through so that texts and graphics can be seen in a dark environment. In general, lower pigment contents will lead to higher translucency.
  • Commercial TPEs have different grades of translucency. This is one of the selection criteria of TPEs.
  • the contradictory effects of pigments on the laser marking contrast and on the keymat translucency require a compromised solution.
  • the aim is to achieve the highest contrast with sufficient translucency.
  • Figure 1 shows an example of laser positive marking
  • Figure 2 shows an example of laser reverse marking
  • Figure 3 shows an example of an arrangement for laser mask marking
  • Figure 4 shows an example of an arrangement for laser beam marking
  • Figure 5 shows the parameters of a focussed laser beam.
  • a laser beam directly writes the texts or graphics on a material surface.
  • marking refers to "positive marking” unless otherwise stated.
  • Figure 1 shows a substrate forming a keymat 2 for a portable device such as a mobile telephone.
  • graphics and text 4 are produced by photochemical reaction of the substrate in the areas representing the graphics/text.
  • FIG. 2 shows a substrate forming a keymat 2 for a portable device such as a mobile telephone.
  • a colour change is produced in the areas 6 surrounding the desired graphics and text 4 by photo-chemical reaction of the substrate in these areas 6.
  • the buttons of the keypad are highlighted.
  • mask marking There are two basic methods for laser marking: mask marking and beam scanning marking.
  • mask marking a mask 30 showing the desired texts and graphics is positioned above the sample 32 of material.
  • a lens 34 is provided to focus the laser beam 36.
  • the laser beam transmits through the mask 30 and the lens 34 and an image 38 of the mask pattern 34 is produced on the sample surface.
  • laser beam scanning marking may be used, in which a laser beams write directly on the surface of a sample of material.
  • Figure 4 shows an exemplary arrangement for laser beam scanning marking.
  • the movement of the laser beams 46 are controlled through two beam scanners 40, 41.
  • Beam scanner 40 controls movement in the x-axis and beam scanner 41 controls movement in the y-axis.
  • a lens focuses the controlled laser beams
  • Mask marking is more suitable for high volume production with a fixed mask pattern, whereas beam scanning marking is more flexible in terms of pattern selection and size control.
  • C0 2 , Nd:YAG & excimer lasers Three major types of lasers are used in laser marking: C0 2 , Nd:YAG & excimer lasers.
  • C0 2 and Nd:YAG lasers have their wavelengths in the infrared range, the marking process by these lasers is conventionally a thermal process.
  • the Nd:YAG laser can be frequency-tripled to achieve a wavelength of 355nm in the ultra-violet range.
  • a KrF excimer laser has a wavelength of 248nm in the deep UV range. These UV lasers generate photo-chemical reactions and thus have minimum thermal effects on substrate materials.
  • Laser marking contrast is achieved through colour change in the material.
  • the marking contrast is a function of many parameters, which include laser parameters (e.g., laser wavelength, pulse duration, peak power), material composition (e.g. pigments) and properties, and interaction parameters (such as marking speed and overlap).
  • laser parameters e.g., laser wavelength, pulse duration, peak power
  • material composition e.g. pigments
  • interaction parameters such as marking speed and overlap
  • Pigments are chemical compounds widely used for colouring plastics.
  • White pigments achieve a white appearance by reflecting all wavelengths of light equally.
  • Black pigments absorb all wavelengths equally.
  • a specific coloured pigment imparts a desired colour by selectively absorbing and reflecting different wavelengths of the visible light spectrum. In selection of a pigment, the following characteristics should be considered.
  • Tinting strength the ability of whitening a base material
  • the pigment titanium dioxide TiO 2 is colourless and appears white in powdered form. No absorption bands are present in the visible region for crystalline TiO 2 .
  • Ti0 2 has a strong absorption band in the near UV band (below 400 nm).
  • Transition metal complexes e.g. cobalt compound, iron compound, copper compound, lead compound, TiO 2
  • a suitable proportion of pigments (by weight) is from 0.5 - 5%.
  • a material according to the invention is provided by pre-mixing in a closed chamber the powdered pigment with the thermoplastic polymer granules.
  • the pre-mixed material is then melt compounded in a twin screw extruder and extruded as pellets for subsequent injection moulding applications.
  • the pellets are heated and injected into moulds, in a conventional manner.
  • the description makes particular reference to keymats for portable devices.
  • the material has many other uses.
  • the laser beam directed at the material has a bandwidth in the region of the absorption band of the pigment.
  • the lasers used produce a photo-chemical reaction in the material and may be an infrared laser (in which a harmonic in the UV band may be used) or a laser the output of which is in the UV band.
  • an infrared laser in which a harmonic in the UV band may be used
  • a laser the output of which is in the UV band when a white or light-coloured substrate is used, use is made of a pigment which becomes dark after undergoing a photo-chemical reaction so that the laser-induced marks are dark against the substrate.
  • the preferred pulse duration is 1-10 ns. This short pulse duration leads to high peak power, which induces photo-chemical reactions. This short pulse duration also reduces the thermal/heat transfer to surrounding materials and thus leads to minimal thermal effect.
  • the colour change is primarily due to photo-chemical reactions with no or minimal material removal.
  • KratonTM-based thermoplastic elastomer has been selected and tested as a potential keymat material to replace silicon rubber.
  • KratonTM is the trade name for a series of thermoplastic elastomer materials manufactured by Shell Chemicals.
  • Pigment The pigment selected is a surface-treated, ultrafine rutile titanium dioxide. It is organically coated to achieve fast and complete dispersion into various plastics. The major properties are listed in the table below:
  • Pigment loading was 1.5% by weight.
  • Laser pulse duration lifetime of a laser pulse.
  • Laser peak power maximum power of a laser pulse.
  • Focal spot size the smallest laser beam diameter after a focusing lens Depth of focus: the distance where the focal spot size is constant Pulse repetition rate: number of laser pulses emitted per second.
  • the TPE material is economically recyclable. Keymats made by recycled TPEs have shown the same laser marking contrast as the original keymats.
  • the majority of the material properties of the selected TPE are comparable to those of silicon rubber except the keymat wearability. It is recommended that an overcoat is applied to enhance the wearability of the material, as is the case with conventional silicon rubber keymats.
  • An inorganic pigment, rutile Ti0 2 has been chosen and tested for enhancing the laser marking contrast.
  • the optimised loading is 1.5% in weight percentage, which gives good marking contrast and adequate translucency.
  • a pulsed 3 rd harmonic YAG laser with a wavelength of 355 nm, together with a beam scanning unit has been developed to produce texts and graphics on the keymats.
  • the laser marks are durable and not affected by solar radiation, temperature and humidity when subjected to cycle tests.
  • the Cpk values for all the relevant parameters of the laser marks are good (higher than 1.35-2.63), which indicate that the laser marking process is reliable and produces consistent results.
  • the process yield by visual inspection is 100%.
  • the new material and process are more productive and more economical compared with existing silicon rubber techniques.
  • the low keymat material cost and low operating cost will lead to significant cost reduction. Recycling of the TPE materials will further reduce the material cost.
  • Quantitative analysis of the laser marks is a great improvement over the conventional subjective visual inspection technique.
  • a second harmonic YAG laser has also been found to result in a photo- chemical reaction although the results are not as satisfactory as using a higher frequency laser.

Landscapes

  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)

Abstract

L'invention concerne une matière pouvant être marquée au laser, comprenant un élastomère thermoplastique et un additif pigmentaire. L'additif pigmentaire possède une bande d'absorption dans une bande de rayonnement e.m., provoquant une réaction photo-chimique lorsque la matière est soumise à un rayonnement e.m. dans la bande d'absorption. L'invention concerne également un procédé de marquage de ladite matière, consistant à soumettre la matière à un faisceau laser dont la longueur d'onde de rayonnement dans la bande d'absorption provoque une réaction photo-chimique du pigment.
PCT/EP2000/007304 1999-07-30 2000-07-31 Matiere pouvant etre marquee au laser WO2001009230A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU74075/00A AU7407500A (en) 1999-07-30 2000-07-31 Laser markable material

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9918044A GB2352824A (en) 1999-07-30 1999-07-30 Laser markable material comprising TiO2 pigmented thermoplstic elastomer
GB9918044.0 1999-07-30

Publications (1)

Publication Number Publication Date
WO2001009230A1 true WO2001009230A1 (fr) 2001-02-08

Family

ID=10858326

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2000/007304 WO2001009230A1 (fr) 1999-07-30 2000-07-31 Matiere pouvant etre marquee au laser

Country Status (3)

Country Link
AU (1) AU7407500A (fr)
GB (1) GB2352824A (fr)
WO (1) WO2001009230A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004089638A1 (fr) * 2003-04-07 2004-10-21 Bundesdruckerei Gmbh Procede permettant de produire une information, corps support dans lequel l'information est produite et utilisation d'un corps support de ce type
WO2005102724A1 (fr) * 2004-03-23 2005-11-03 3M Innovative Properties Company Manchon marqueur retractable a froid
WO2011103200A2 (fr) * 2010-02-22 2011-08-25 Polyone Corporation Composé élastomère thermoplastique marquable au laser uv
US9168696B2 (en) 2012-06-04 2015-10-27 Sabic Global Technologies B.V. Marked thermoplastic compositions, methods of making and articles comprising the same, and uses thereof
US9209443B2 (en) 2013-01-10 2015-12-08 Sabic Global Technologies B.V. Laser-perforated porous solid-state films and applications thereof
US9662833B2 (en) 2012-06-04 2017-05-30 Sabic Global Technologies B.V. Marked thermoplastic compositions, methods of making and articles comprising the same, and uses thereof
US10687588B2 (en) 2014-10-22 2020-06-23 3M Innovative Properties Company Printed components and methods for making the same
CN115386239A (zh) * 2022-09-14 2022-11-25 上海微巨高分子材料有限公司 一种用于激光打标的tpe材料

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1839554B1 (fr) * 2005-01-21 2013-12-25 Olympus Corporation Endoscope, appareil medical pour l'endoscope et procede d'application de marquage de cellui-ci
EP2135232A1 (fr) * 2007-03-08 2009-12-23 Forbo Siegling Gmbh Procédé pour apposer un marquage sur une bande transporteuse
GB201222955D0 (en) 2012-12-19 2013-01-30 Innovia Films Ltd Film

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6172049A (ja) * 1984-09-17 1986-04-14 Nippon Erasutomaa Kk 熱可塑性弾性体組成物
EP0400305A2 (fr) * 1989-05-27 1990-12-05 Hüls Aktiengesellschaft Matériaux polymères d'inscription par laser
EP0447032A2 (fr) * 1990-03-15 1991-09-18 British Aerospace Public Limited Company Composition de pigment blanc marquable par laser
EP0550032A2 (fr) * 1991-12-31 1993-07-07 Hoechst Aktiengesellschaft Compositions à mouler en matières synthétiques, marquables au laser; procédé pour les préparer et leur utilisation
JPH1120316A (ja) * 1997-06-27 1999-01-26 Nok Corp ゴム製品のマーキング方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5059265A (fr) * 1973-09-27 1975-05-22
US4595647A (en) * 1985-02-01 1986-06-17 Motorola, Inc. Method for encapsulating and marking electronic devices
AU597240B2 (en) * 1985-02-05 1990-05-31 Ciba-Geigy Ag Laser marking of pigmented systems
WO1990006966A1 (fr) * 1988-12-22 1990-06-28 The Dow Chemical Company Agents de photodegradation et de thermocollage pour materiaux de matrices polymeres
CH677756A5 (fr) * 1989-01-26 1991-06-28 Ciba Geigy Ag
GB2234601A (en) * 1989-06-23 1991-02-06 Cookson Group Plc Imaging method
JPH1036605A (ja) * 1996-07-19 1998-02-10 Asahi Chem Ind Co Ltd レーザ印刷用ゴム強化ポリスチレン樹脂組成物及びレーザ印刷された成形体

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6172049A (ja) * 1984-09-17 1986-04-14 Nippon Erasutomaa Kk 熱可塑性弾性体組成物
EP0400305A2 (fr) * 1989-05-27 1990-12-05 Hüls Aktiengesellschaft Matériaux polymères d'inscription par laser
EP0447032A2 (fr) * 1990-03-15 1991-09-18 British Aerospace Public Limited Company Composition de pigment blanc marquable par laser
EP0550032A2 (fr) * 1991-12-31 1993-07-07 Hoechst Aktiengesellschaft Compositions à mouler en matières synthétiques, marquables au laser; procédé pour les préparer et leur utilisation
JPH1120316A (ja) * 1997-06-27 1999-01-26 Nok Corp ゴム製品のマーキング方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 198621, Derwent World Patents Index; Class A18, AN 1986-134845, XP002152620 *
DATABASE WPI Section Ch Week 199914, Derwent World Patents Index; Class A35, AN 1999-162374, XP002152621 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004089638A1 (fr) * 2003-04-07 2004-10-21 Bundesdruckerei Gmbh Procede permettant de produire une information, corps support dans lequel l'information est produite et utilisation d'un corps support de ce type
WO2005102724A1 (fr) * 2004-03-23 2005-11-03 3M Innovative Properties Company Manchon marqueur retractable a froid
WO2011103200A2 (fr) * 2010-02-22 2011-08-25 Polyone Corporation Composé élastomère thermoplastique marquable au laser uv
WO2011103200A3 (fr) * 2010-02-22 2011-12-29 Polyone Corporation Composé élastomère thermoplastique marquable au laser uv
US9168696B2 (en) 2012-06-04 2015-10-27 Sabic Global Technologies B.V. Marked thermoplastic compositions, methods of making and articles comprising the same, and uses thereof
US9662833B2 (en) 2012-06-04 2017-05-30 Sabic Global Technologies B.V. Marked thermoplastic compositions, methods of making and articles comprising the same, and uses thereof
US10639851B2 (en) 2012-06-04 2020-05-05 Sabic Global Technologies Ip B.V. Marked thermoplastic compositions, methods of making and articles comprising the same, and uses thereof
US9209443B2 (en) 2013-01-10 2015-12-08 Sabic Global Technologies B.V. Laser-perforated porous solid-state films and applications thereof
US10687588B2 (en) 2014-10-22 2020-06-23 3M Innovative Properties Company Printed components and methods for making the same
CN115386239A (zh) * 2022-09-14 2022-11-25 上海微巨高分子材料有限公司 一种用于激光打标的tpe材料

Also Published As

Publication number Publication date
AU7407500A (en) 2001-02-19
GB9918044D0 (en) 1999-10-06
GB2352824A (en) 2001-02-07

Similar Documents

Publication Publication Date Title
JP3782096B2 (ja) レーザー光透過性樹脂組成物、及びそれを用いたレーザー溶着方法
CN109963702B (zh) 用于激光可标记及激光可焊接的聚合物材料的添加剂
KR100349019B1 (ko) 착색된플라스틱성형조성물및이의용도
WO2001009230A1 (fr) Matiere pouvant etre marquee au laser
JP4734303B2 (ja) 樹脂とレーザー光線透過性着色剤とを含み、０．５〜１．２の透過率比（ｔレーザー透過用黒色樹脂／ｔ自然樹脂）を有するレーザー溶着用樹脂組成物
JPS6111771B2 (fr)
JPH08187951A (ja) 熱可塑性樹脂組成物のレーザーマーキング用の銅塩
WO2000078554A1 (fr) Compositions et procede de marquage au laser
KR102454337B1 (ko) 레이저-마킹성 및 레이저-용접성 중합체 물질
NL9202096A (nl) Polymeersamenstelling, bevattende een polymeer en tenminste een stralingsgevoelig bestanddeel.
JP6502932B2 (ja) マイクロスフェア
TW201609556A (zh) 微球體
KR101355365B1 (ko) 레이저 마킹가능한 어두운 색상의 중합체 조성물
US20180223115A1 (en) Laser-markable polymers and coatings
JP2008012869A (ja) レーザマーキング方法
Layher et al. Laser Beam Polishing of Polymers: Selection of polymers suitable for laser‐based post processing of FLM‐printed parts
Clemente et al. UV‐laser marking of a TiO2‐containing ABS material
JP2006305926A (ja) レーザーマーキング用樹脂組成物及びレーザーマーキング方法
JP2005290372A (ja) レーザー光透過性組成物及びレーザー溶着方法
JP3413329B2 (ja) レーザーマーキング方法およびレーザーマーキングされた成形品
JP6842104B2 (ja) レーザーマーキングされた樹脂製成形体およびその製造方法
JP2001089632A (ja) レーザーマーキング用ポリアセタール樹脂組成物およびレーザーマーキングされた成形品
JPH10305661A (ja) レーザマーキング方法及びレーザマーキング用樹脂組成物
US20170101523A1 (en) Laser-markable and laser-weldable polymeric materials
JP2002188016A (ja) レーザマーキング用樹脂組成物

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CR CU CZ DE DK DM DZ EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP