EP1225599B1 - Herstellungsverfahren für ein PCT-Polymer Produkt - Google Patents

Herstellungsverfahren für ein PCT-Polymer Produkt Download PDF

Info

Publication number
EP1225599B1
EP1225599B1 EP01101331A EP01101331A EP1225599B1 EP 1225599 B1 EP1225599 B1 EP 1225599B1 EP 01101331 A EP01101331 A EP 01101331A EP 01101331 A EP01101331 A EP 01101331A EP 1225599 B1 EP1225599 B1 EP 1225599B1
Authority
EP
European Patent Office
Prior art keywords
ptc
polymer material
vol
amount
filler material
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
EP01101331A
Other languages
English (en)
French (fr)
Other versions
EP1225599A1 (de
Inventor
Joachim Glatz-Reichenbach
Ralf Strümpler
Ruzica Loitzl-Jelenic
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.)
ABB Research Ltd Switzerland
ABB Research Ltd Sweden
Original Assignee
ABB Research Ltd Switzerland
ABB Research Ltd Sweden
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 ABB Research Ltd Switzerland, ABB Research Ltd Sweden filed Critical ABB Research Ltd Switzerland
Priority to AT01101331T priority Critical patent/ATE253768T1/de
Priority to DE60101141T priority patent/DE60101141T2/de
Priority to EP01101331A priority patent/EP1225599B1/de
Publication of EP1225599A1 publication Critical patent/EP1225599A1/de
Application granted granted Critical
Publication of EP1225599B1 publication Critical patent/EP1225599B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/02—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient
    • H01C7/027—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient consisting of conducting or semi-conducting material dispersed in a non-conductive organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
    • H01C17/065—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thick film techniques, e.g. serigraphy
    • H01C17/06506—Precursor compositions therefor, e.g. pastes, inks, glass frits
    • H01C17/06573—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the permanent binder
    • H01C17/06586—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the permanent binder composed of organic material

Definitions

  • the present invention relates to a production process for a product made of a polymer having an electric resistivity with a positive temperature coefficient (PTC resistivity; in the following: PTC-polymer product), namely, it relates to a forming process in which heat and pressure are applied to PTC-polymer material to deform said material in order to arrive at a desired product form.
  • PTC resistivity positive temperature coefficient
  • polymers In order to be deformable, polymers generally must be heated to decrease their viscosity and to avoid breaks and cracks. Especially for mass-produced parts, the time required for the forming process is an essential parameter. Further, the pressures to be applied during forming shall not be too high in order to avoid excessive technical equipment. Consequently, in conventional polymer forming processes the polymer material temperature is much higher than the so called melting temperature of this material.
  • the above at first, relates to pure polymer materials.
  • PTC-polymer materials to which the invention relates there are solid filler materials included in a polymer matrix, e.g. carbon powder or metal powder. It goes without saying that the inclusion of substantive amounts of filler materials drastically increases the viscosity of the polymer material so that the pressure or the temperature of the forming process have to be increased even more.
  • the technical problem underlying the present invention is to provide a production process for forming a PTC-polymer product with improved and stabilised quality.
  • the present invention relates to a method of producing a form product from PTC-polymer material consisting of a conducting filler material and optionally further filler material in a matrix of polymer material, wherein said product is formed by a forming method which deforms said PTC-polymer material by means of heat and pressure, characterised in that said PTC-polymer material is heated during said forming process on an absolute temperature of at most 1,1 x the absolute melting temperature of said matrix polymer material, as well as to a method of producing elements from PTC-polymer material, wherein semi-finished products are produced from said PTC-polymer material with a method as defined above and wherein said semi-finished product is divided in order to produce said elements.
  • the idea underlying the invention is to use a relatively low temperature in deforming the PTC-polymer material.
  • the inventors have found that higher temperatures decrease the quality of the PTC-products, namely the stability of their tripping behaviour.
  • the resistance values in the cold, normal conducting state are stabilised over an increased number of repetitive tripping actions, when reduced temperatures according to the invention are used during forming.
  • a general formulation for the upper limits of the maximum temperatures of the forming process is used which relates to the so called melting temperature of the polymer of the matrix. According to the invention, this melting temperature shall not be exceeded by more than 10 % with regard to the absolute temperatures. It has to be noted, that this criterion uses the absolute temperature for the process temperature and the melting temperature, namely the Kelvin temperature scale.
  • T S melting temperature
  • the forming process used with the above described temperature limit can be a pressing process, an injection-moulding process or an extrusion process. Of these process types, however, extrusion and pressing are preferred. Especially, it is preferred to use such a process to produce semi-finished products that shall be divided into smaller elements later on. These elements can be used as PTC-elements, e.g. for resistor elements for short-circuit interruption or current limitation. Producing semi-finished products and dividing them afterwards into a multiplicity of PTC elements compensates for the increased time consumption in the forming process, that follows from the relatively low temperature used, if excessive pressures, which can also lead to material problems, are avoided.
  • Subdividing the comparatively large semi-finished product can be a process step that runs very fast without being of large relevance for the material quality, especially if dividing techniques are used that avoid excessive melting of the polymer.
  • One simple and preferred embodiment refers to a plate-like semi-finished product.
  • Such plates can be pressed from PTC-polymer material without any problems even with very low temperatures (which, however, preferably are above T S ).
  • injection-moulding or extrusion is possible, however, these techniques require higher pressures in comparison to pressing.
  • Preferred pressures are not higher than 300 bar, more preferably not higher than 200 bar and further preferably not higher than 120 bar.
  • polystyrene resin e.g. polystyrene resin
  • PES polystyrene resin
  • PEEK polystyrene resin
  • the most preferred material is high-density PE (HDPE).
  • PTC-polymer materials generally include a conductive filler material.
  • Preferred quantitative ranges for the inclusion of the highly conductive first filler material inherent to PTC-polymer materials are 20-60 vol.-%, more preferably 30-55 vol.-% and even more preferably 35-50 vol.-% (with respect to the total volume of the PTC-polymer material).
  • a preferred choice for this (first) conductive filler material is TiB 2 .
  • the PTC-polymer material may include a second filler material having varistor characteristics.
  • This second filler material preferably is SiC.
  • the preferred quantity ranges are 10-30 vol.-%, preferably 12-28 vol.-% and more preferably 14-26 vol.-% of that second filler material.
  • the invention should also hold without second (SiC) filler, e.g. 50% HDPE and 50% TiB 2 .
  • filler materials are included in powder form dispersed in the polymer matrix. Further the average particle size of the second filler material should be larger than the one of the first filler material, namely by a factor of 2 - 5. Preferred ranges for the particle sizes are 10 ⁇ m to 50 ⁇ m for the first filler material and 20 ⁇ m to 250 ⁇ m for the second filler material.
  • thermoplastic polymer matrix is preferably comprised in an amount of 30 - 55 vol.-% and more preferably of 37 - 50 vol.-%.
  • the above specified PTC-polymer material at a predetermined voltage, shows a notably large zone of high resistance ("hot zone").
  • a typical example for a PTC-polymer material according to the invention thus is comprised of 40 vol.-% HDPE, 40 vol.-% TiB 2 , and 20 vol.-% SiC.
  • the particle sizes defined above are - besides the materials themselves, especially the polymer material - of relevance for the viscosities of the complete mixture.
  • Such viscosities can be defined by a melt flow index, which can be measured according to the German Industrial Standard (DIN) with a standard orifice at a standard temperature of 190°C and a standard load of 21,6 kg by the amount of material running through the orifice in ten minutes.
  • DIN German Industrial Standard
  • Preferred values for this invention are melt flow indices of at least 1 g/10 min., preferably at least 1,5 g/10 min., and most preferably at least 2 g/10 min.
  • Fig. 1 illustrates a typical structure of a PTC-polymer element according to the invention
  • Fig. 2 and fig. 3 are diagrams illustrating the improvement of the tripping characteristics achieved by the invention.
  • the production process starts with compounding the appropriate amounts of a polymer powder or granulate, in this case HDPE, and filler material by standard compounding with a BUSS MDK/E46-11D (screw compounder). For about 2 ⁇ 10 4 samples as referred to in Fig. 1 about 100 kg compound must be produced .
  • the compound material is then pressed in a standard pressing device (PINETTE EMIDECAU INDUSTRIE, max. load of 15 tons) at a temperature of 140-145°C, i.e. 413-418 K, to form a rectangular plate with side lengths of 16 cms, 4 cms and a thickness of e.g. 0.2 cms. Also much larger plates can be pressed for purposes of mass-production.
  • PINETTE EMIDECAU INDUSTRIE max. load of 15 tons
  • Table 1 lists several melting temperatures of typical polymers to be used, and further typical forming temperatures according to the invention. Melting temperatures are abbreviated T S and given in °C, maximum forming temperatures are abbreviated with T P and also given in °C. The last column gives the temperature difference ⁇ T therebetween divided by the melting temperature T S (as given in K) in %.. Polymer T S (°C) T P (°C) ⁇ T / T S (%) PE 134 140-145 1,47-2,7 PP 175 192 3,8 ETFE 265 284 3,5 Aurum 388 410 3,3 PPS 288 303 2,7 PEEK 335 360 4,1 Incidentally, Aurum is the name of a polyimide.
  • melt-injection of pure PE are between 200 and 280 °C, i.e. at ⁇ T/T S values of 16 - 36 %.
  • the usual forming temperatures are much higher than the ones given in table 1. It is to be noted, however, that the conventional temperatures relate to pure polymer without filler material. Because the substantial amounts of the filler materials drastically increase the viscosity, usually much higher temperatures would have been chosen for PTC-polymer materials including filler.
  • the pressure used is still not very high, e.g. 110 bar in the case of HDPE as filled with 50 vol.-% of metal powders. Pressure values for other materials are in the same range.
  • the plates so formed can now be stored without any quality problems for longer periods. They can be used for cutting special and also very complicated device geometries.
  • high-pressure water jet cutting is used.
  • a typical geometry to be cut is shown in fig. 1.
  • the direction of pressure during the pressing process is perpendicular to the plane of the figure.
  • the plates are produced by pressed in the thickness of the device shown in fig. 1
  • only the borderlines to be seen in fig. 1 must be cut in order to subdivide the pressed plate into single devices and in order to arrive at the desired geometry.
  • the current direction is in the plane of the drawing and horizontal.
  • the preferred geometry shows pronounced webs 1 wherein the opening angles 2 of the material at each side of each web are 60°.
  • a typical web-length can be around 2 cm.
  • Several webs are mutually parallel, also in an electrical sense.
  • the aperture angle of the constriction at the border of the web in a longitudinal section plane containing the main current direction should be at least 100°, preferably at least 110° in the sum of both sides (i.e. it is 120° in fig. 1).
  • the pressing method according to the invention has various advantages for the above sketched geometry because such long webs are quite difficult to produce with injection molding. It is very important to arrive at an optimal material quality, especially within the webs, so that the temperature reduction according to the invention results in a much improved performance of the devices produced.
  • Fig. 2 and 3 show the improvement in the electrical characteristics achieved by the invention.
  • fig. 2 a comparison between injection moulded parts (triangular symbols) and parts according to the invention (square symbols) is shown.
  • the material composition has been 45 vol.-% HDPE / 35 vol.-% TiB 2 20 vol.-% SiC with a geometry according to fig. 1 and a web-length of 1,8 cm.
  • the resistor elements according to the invention have a higher cold resistance, i.e. resistance at a normal conducting state, the cold resistance is much stabilised in comparison to the injection moulding example. This applies to the cold resistance after the first tripping and to each following cold resistance value after a further tripping up to the value after a tenth tripping. Thus, this resistor element can very well be described by a constant resistance value at least between the first and the ninth tripping.
  • the injection moulded resistor element has been destroyed after the fourth tripping compared to ten tripping actions in the example according to the invention.
  • the tests were short-circuit tests at 690V (root mean square) system voltage and a prospective short-circuit current of 12kA (root mean square) at 50 Hz.
  • Fig. 3 shows another example for the electrical characteristics of resistor elements according to the invention.
  • the square symbols refer to pressed and cut elements according to the invention whereas the triangular and circular symbols refer to injection-moulded and press-injected samples.
  • Press-injection is a technique quasi between injection-moulding and pressing. It is a quasi-static pressing of molten composite material into a mould to form an end product.
  • the parameters are close to the limits defined by the melt flow of the material, e.g. the polymer material is at a lower temperature compared to injection moulding.
  • the press-injected elements are a part of the invention in that the temperature limit is fulfilled.
  • fig. 3 shows that the pressed and cut elements are still better.
  • Table 2 shows the parameters relevant for the examples of figure 2 and 3.
  • the mould temperature and material temperature are identical in the case of press-injection and the case of pressing and are both below 1.1 T S .
  • the temperature of 146°C in the case of pressing is even below 1.03 T S .
  • the material temperature of the injection-moulded elements has been at 260°C, i.e. at approximately 1.31 T S .
  • the pressure in the pressing process has been as low as 110 bar but has been much higher in both other cases.
  • the geometry was the one of fig. 1 with a web-length of 2 cm.
  • the material composition was 40 vol.-% HDPE / 40 vol.-% TiB 2 / 20 vol.-% SiC.
  • the electrical data of the tests in fig. 3 were the same as given above.
  • the pressed and cut resistor element according to the invention shows a larger member of possible tripping actions and a more stable behaviour between the first and the ninth tripping.
  • the differences between the cold resistance before the first tripping and the cold resistance after the first tripping can, if necessary, be avoided by including one tripping action in the manufacture process.

Claims (19)

  1. Verfahren zum Herstellen eines Formprodukts aus einem PTC-Polymermaterial, das aus einem leitenden Füllmaterial und wahlweise weiterem Füllmaterial in einer Matrix aus Polymermaterial besteht,
    wobei das Produkt durch ein Formungsverfahren ausgebildet wird, das das PTC-Polymermaterial mit Hilfe von Wärme und Druck verformt,
    dadurch gekennzeichnet, daß das PTC-Polymermaterial während des Formungsprozesses auf eine Absoluttemperatur von höchstens 1,1 x TS erwärmt wird, wobei TS die absolute Schmelztemperatur des Matrixpolymermaterials ist.
  2. Verfahren nach Anspruch 1, wobei der Formungsprozeß ein Pressen, ein Spritzguß, ein Extrusionsprozeß oder ein Infiltrationsprozeß ist.
  3. Verfahren nach Anspruch 2, wobei der Formungsprozeß ein Preßprozeß oder ein Extrusionsprozeß ist.
  4. Verfahren nach einem der vorhergehenden Ansprüche, wobei das Matrixpolymermaterial PE, PP, ETFE, Polyimid, PPS oder PEEK umfaßt.
  5. Verfahren nach Anspruch 4, wobei das Matrixpolymermaterial hauptsächlich aus HDPE besteht.
  6. Verfahren nach den Ansprüchen 3 und 5, wobei der Preßprozeß mit einem Druck in dem PTC-Polymermaterial von höchstens 300 Bar, bevorzugt 200 Bar und weiter bevorzugt 120 Bar erfolgt.
  7. Verfahren nach einem der vorhergehenden Ansprüche, wobei die Temperatur höchstens 1,075 x TS und weiter bevorzugt höchstens 1,05 x TS beträgt.
  8. Verfahren nach einem der vorhergehenden Ansprüche, wobei das PTC-Polymermaterial ein erstes leitendes Füllmaterial in einer Menge von 20 - 60 Vol.-%, bevorzugt in einer Menge von 30 - 55 Vol.-% und ganz besonders bevorzugt in einer Menge von 35 - 50 Vol.-% umfaßt.
  9. Verfahren nach einem der vorhergehenden Ansprüche, wobei das PTC-Polymermaterial ein erstes leitendes Füllmaterial umfaßt, nämlich TiB2.
  10. Verfahren nach einem der vorhergehenden Ansprüche, wobei das PTC-Polymermaterial ein zweites Füllmaterial mit einer Varistorcharakteristik umfaßt.
  11. Verfahren nach Anspruch 10, wobei das zweite Füllmaterial dotiertes SiC ist.
  12. Verfahren nach Anspruch 10 oder 11, wobei das zweite Füllmaterial in einer Menge von 10 - 30 Vol.-%, bevorzugt in einer Menge von 14 - 26 Vol.-% enthalten ist.
  13. Verfahren nach einem der vorhergehenden Ansprüche, wobei das Matrixpolymermaterial in einer Menge von 30 - 55 Vol.-%, bevorzugt in einer Menge von 37 - 50 Vol.-% enthalten ist.
  14. Verfahren zum Herstellen von PTC-Elementen aus PTC-Polymermaterial, wobei Halbfertigprodukte mit einem Verfahren nach einem der vorhergehenden Ansprüche aus dem PTC-Polymermaterial hergestellt werden und wobei das Halbfertigprodukt unterteilt wird, um die PTC-Elemente zu erzeugen.
  15. Verfahren nach Anspruch 14, wobei das Unterteilen durch Schneiden (einschließlich Sägen) erfolgt.
  16. Verfahren nach Anspruch 15, wobei das Schneiden durch einen Hochdruckwasserstrahl oder mit Hilfe eines Lasers erfolgt.
  17. Verfahren nach einem der Ansprüche 14 bis 16, wobei das Halbfertigprodukt im wesentlichen eine Platte aus PTC-Polymermaterial ist.
  18. Verfahren nach einem der Ansprüche 14 bis 17, wobei aus den PTC-Elementen Widerstandselemente für die Kurzschlußunterbrechung oder die Strombegrenzung hergestellt werden.
  19. Verfahren nach Anspruch 18, wobei die Widerstandselemente vor Inbetriebsetzung einer vorläufigen Auslöseaktion unterzogen werden.
EP01101331A 2001-01-22 2001-01-22 Herstellungsverfahren für ein PCT-Polymer Produkt Expired - Lifetime EP1225599B1 (de)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AT01101331T ATE253768T1 (de) 2001-01-22 2001-01-22 Herstellungsverfahren für ein pct-polymer produkt
DE60101141T DE60101141T2 (de) 2001-01-22 2001-01-22 Herstellungsverfahren für ein PCT-Polymer Produkt
EP01101331A EP1225599B1 (de) 2001-01-22 2001-01-22 Herstellungsverfahren für ein PCT-Polymer Produkt

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP01101331A EP1225599B1 (de) 2001-01-22 2001-01-22 Herstellungsverfahren für ein PCT-Polymer Produkt

Publications (2)

Publication Number Publication Date
EP1225599A1 EP1225599A1 (de) 2002-07-24
EP1225599B1 true EP1225599B1 (de) 2003-11-05

Family

ID=8176264

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01101331A Expired - Lifetime EP1225599B1 (de) 2001-01-22 2001-01-22 Herstellungsverfahren für ein PCT-Polymer Produkt

Country Status (3)

Country Link
EP (1) EP1225599B1 (de)
AT (1) ATE253768T1 (de)
DE (1) DE60101141T2 (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012001465A1 (en) * 2010-06-29 2012-01-05 Indian Institute Of Technology Kanpur Flexible temperature sensor and sensor array

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69633718T2 (de) * 1995-03-22 2006-02-02 Tyco Electronics Corp. Leitfähige polymerzusammensetzung und vorrichtung
TW309619B (de) * 1995-08-15 1997-07-01 Mourns Multifuse Hong Kong Ltd
DE69736662T2 (de) * 1996-09-18 2007-09-13 Kabushiki Kaisha Toyota Chuo Kenkyusho Grossbereichthermistormaterial und dessen herstellungsverfahren

Also Published As

Publication number Publication date
DE60101141D1 (de) 2003-12-11
EP1225599A1 (de) 2002-07-24
ATE253768T1 (de) 2003-11-15
DE60101141T2 (de) 2005-06-16

Similar Documents

Publication Publication Date Title
CN103797548B (zh) 高分子基导电复合材料及ptc元件
US3914363A (en) Method of forming self-limiting conductive extrudates
EP2592628B1 (de) Leitender verbundstoff mit positivem temperaturkoeffizient des widerstands und überspannungsschutzelement
CA1142342A (en) Low resistivity ptc compositions
US5378407A (en) Conductive polymer composition
CN100343925C (zh) 含有低分子量聚乙烯加工助剂的ptc导电组合物
JP2004531873A (ja) Ｎ−Ｎ−ｍ−フェニレンジマレイミドを含む導電性の高分子組成物および素子
CA2289824A1 (en) Conductive polymer materials for high voltage ptc devices
EP1225599B1 (de) Herstellungsverfahren für ein PCT-Polymer Produkt
DE3135716A1 (de) Verfahren zur verwertung von alu-pvc-abfallfolien, insbesondere der pharmaindustrie
US5814264A (en) Continuous manufacturing methods for positive temperature coefficient materials
US6373372B1 (en) Current limiting device with conductive composite material and method of manufacturing the conductive composite material and the current limiting device
US6197220B1 (en) Conductive polymer compositions containing fibrillated fibers and devices
US6396384B1 (en) Conductive polymer compositions containing perhydrotriphenylene
WO1999030329A1 (en) Conductive polymer compositions, electrical devices and methods of making
US20180061535A1 (en) A varistor and production method thereof
US9034210B2 (en) Feedstock and method for preparing the feedstock
JP2001085203A (ja) Ｐｔｃ組成物
KR100378927B1 (ko) 과전류 차단용 피티씨 폴리머 퓨즈 제조 방법
KR101947518B1 (ko) 셀프 스위치 기능을 부가한 고온용 ptc 페이스트 조성물 제조방법
JPH0433958A (ja) 封止用樹脂組成物
KR100436580B1 (ko) 우수한 저항복구 특성의 조성을 갖는 ｐｔｃ 디바이스제조방법
KR100381918B1 (ko) 과전류 차단용 피티씨 폴리머 퓨즈 제조 방법
KR100381919B1 (ko) 과전류 차단용 피티씨 폴리머 퓨즈 제조 방법
US20210354332A1 (en) Compositions for bipolar plates and methods for manufacturing said compositions

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): 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

Free format text: AL;LT;LV;MK;RO;SI

17P Request for examination filed

Effective date: 20021220

AKX Designation fees paid

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

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

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: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20031105

Ref country code: CH

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: 20031105

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: 20031105

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: 20031105

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: 20031105

Ref country code: LI

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: 20031105

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: 20031105

Ref country code: AT

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: 20031105

Ref country code: BE

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: 20031105

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 60101141

Country of ref document: DE

Date of ref document: 20031211

Kind code of ref document: P

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

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

Ref country code: IE

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

Effective date: 20040122

Ref country code: LU

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

Effective date: 20040122

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: 20040131

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

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: 20040205

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: 20040205

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: 20040205

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: 20040216

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: CH

Ref legal event code: PL

ET Fr: translation filed
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

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

26N No opposition filed

Effective date: 20040806

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: 20040405

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

Ref country code: FR

Payment date: 20100223

Year of fee payment: 10

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

Ref country code: DE

Payment date: 20100121

Year of fee payment: 10

Ref country code: GB

Payment date: 20100121

Year of fee payment: 10

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

Effective date: 20110122

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20110930

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

Ref country code: FR

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

Effective date: 20110131

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: 20110122

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 60101141

Country of ref document: DE

Effective date: 20110802

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110802