WO2001043146A1 - Non-silicone conductive paste for the electrical industry, and its use - Google Patents

Non-silicone conductive paste for the electrical industry, and its use Download PDF

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Publication number
WO2001043146A1
WO2001043146A1 PCT/EP2000/011371 EP0011371W WO0143146A1 WO 2001043146 A1 WO2001043146 A1 WO 2001043146A1 EP 0011371 W EP0011371 W EP 0011371W WO 0143146 A1 WO0143146 A1 WO 0143146A1
Authority
WO
WIPO (PCT)
Prior art keywords
admixture
elastomer
powder
particles
conductive particles
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.)
Ceased
Application number
PCT/EP2000/011371
Other languages
English (en)
French (fr)
Inventor
Mohamed Ait El Cadi
Jean-Alec Ducros
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.)
Laird Technologies Inc
Original Assignee
Instrument Specialties Co Inc
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 Instrument Specialties Co Inc filed Critical Instrument Specialties Co Inc
Priority to DE60010515T priority Critical patent/DE60010515T2/de
Priority to AU21594/01A priority patent/AU2159401A/en
Priority to EP00985043A priority patent/EP1240648B8/en
Priority to CA002394050A priority patent/CA2394050A1/en
Priority to JP2001543744A priority patent/JP4436993B2/ja
Priority to AT00985043T priority patent/ATE266241T1/de
Publication of WO2001043146A1 publication Critical patent/WO2001043146A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01RELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R13/00Details of coupling devices of the kinds covered by groups H01R12/70 or H01R24/00 - H01R33/00
    • H01R13/02Contact members
    • H01R13/22Contacts for co-operating by abutting
    • H01R13/24Contacts for co-operating by abutting resilient; resiliently-mounted
    • H01R13/2407Contacts for co-operating by abutting resilient; resiliently-mounted characterized by the resilient means
    • H01R13/2414Contacts for co-operating by abutting resilient; resiliently-mounted characterized by the resilient means conductive elastomers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20Conductive material dispersed in non-conductive organic material
    • H01B1/22Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/08Metals
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20Conductive material dispersed in non-conductive organic material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20Conductive material dispersed in non-conductive organic material
    • H01B1/24Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01RELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R13/00Details of coupling devices of the kinds covered by groups H01R12/70 or H01R24/00 - H01R33/00
    • H01R13/648Protective earth or shield arrangements on coupling devices, e.g. anti-static shielding  
    • H01R13/658High frequency shielding arrangements, e.g. against EMI [Electro-Magnetic Interference] or EMP [Electro-Magnetic Pulse]
    • H01R13/6598Shield material
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/08Metals
    • C08K2003/0806Silver
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/08Metals
    • C08K2003/0831Gold
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/08Metals
    • C08K2003/0862Nickel
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits
    • H05K1/02Details
    • H05K1/09Use of materials for the conductive, e.g. metallic pattern
    • H05K1/092Dispersed materials, e.g. conductive pastes or inks
    • H05K1/095Dispersed materials, e.g. conductive pastes or inks for polymer thick films, i.e. having a permanent organic polymeric binder
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S277/00Seal for a joint or juncture
    • Y10S277/92Seal including electromagnetic shielding feature
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12014All metal or with adjacent metals having metal particles
    • Y10T428/12028Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y10T428/12063Nonparticulate metal component
    • Y10T428/12104Particles discontinuous
    • Y10T428/12111Separated by nonmetal matrix or binder [e.g., welding electrode, etc.]
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/24Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24008Structurally defined web or sheet [e.g., overall dimension, etc.] including fastener for attaching to external surface
    • Y10T428/24017Hook or barb
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/25Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/25Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/254Polymeric or resinous material
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/25Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/256Heavy metal or aluminum or compound thereof
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/25Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/256Heavy metal or aluminum or compound thereof
    • Y10T428/257Iron oxide or aluminum oxide
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/25Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/259Silicic material

Definitions

  • the invention relates to a conductive paste for the electrical industry and also to its use.
  • the material has particular importance m connection with the sealing of electro agnetically shielded housings m electronic devices which emit electromagnetic radiation or can be disturbed by electromagnetic radiation penetrating from outside.
  • the housings are produced from an electrically conducting material, or from a material coated so as to be electrically conducting, m order to provide EMI
  • DE 43 19 965 C2 discloses the use of a material of this type for the production of the housings described at the outset.
  • the starting material is extruded as a strand of paste directly m the region of the ici.-.t onto one of the parts of the housing, and polymerizes there to form the gasket. This process is also known to the skilled worker as the formed-in-place-gasket process.
  • thermally conductive particles in order to form what are known as thermal pads. These have the task of dissipating, for example, heat from an electronic component and of passing the same to a cooling element.
  • One of the most important examples of the application is a microprocessor unit in which the heat generated by the processor is to be passed to a cooling carrier exposed to a fan.
  • the silicone has the property of emitting gaseous materials with short molecular chains. These constituents condense on (adjacent) metal parts or cold sections of surfaces.
  • the silicone oil deposit insulates the surface (mostly undesirably) .
  • a deposit of this type considerably impairs, or destroys, the function of contact relays- Even if the contact is closed mechanically, the deposited silicone oil film can completely prevent electrical contact.
  • ⁇ licone-containin ⁇ materials they have therefore been largely eliminated by the telephone industry.
  • the object of the present invention is therefore to provide a material of the type mentioned at the outset in which the problems described have been eliminated.
  • the material provided should be capable of unrestricted application while retaining the good properties of silicone-based materials as mentioned at the outset.
  • the invention is based on the concept of using, instead of silicone, an elastomer of the polyoxypolyolefin type or a member of the polyolefin family, as in the formula:
  • R is alkyl, preferably methyl or ethyl
  • R' is alkyl, preferably methyl or ethyl
  • POP is a polyoxyolefin, preferably polyoxypropylene .
  • This material has excellent mechanical properties and is particularly suitable for the formed-in-place-gasket process to make sealing elements or damping elements for housings of electronic or telecommunications devices.
  • the sealing or damping elements produced in this way are soft, flexible and nontacky, but they adhere particularly well to the substrate used. They may be applied either manually or by way of computer-controlled equipment or robots.
  • the excellent properties of the material also mean that it can be processed by further processes known per se, such as (mold) casting, spraying, dispensing or printing.
  • the material has good environmental compatibility, since it is free from halogens and nontoxic. In addition, no hazardous gases of any type are produced in the event of a fire.
  • the novel material is a paste, it is firstly easy to process and can be shaped as desired by the processing methods described above. Secondly, its viscosity is such that, specifically if the formed-in- place-gasket process is used, the dimensional stability of the strand produced is sufficient for it to retain its profile without the use of any additional pressures. The polymerization can therefore take place under ambient conditions.
  • the admixtures of conductive particles represent a filling material which permits the desired property tc be achieved m the product by varying the amount, s te and makeup of the particles.
  • One of the most important applications relates to the production of gaskets on housings, or on sections of housings, printed circuit boards or the like, m order to achieve shielding with respect to high-frequency electromagnetic waves.
  • Examples of admixtures used for this are nickel powder, silver powder or gold powder or appropriate dusts.
  • powders or dusts made from other materials such as those based on aluminum, copper, nickel, iron or steel, as long as these are suitably covered or coated. Materials which can be used for the covering or coating are again nickel, silver or gold.
  • nonconducting particles such as those based on glass, mica or plastic, as long as these are coated or covered as described above and the electrical conductivity of the particles which is required for an application of this type is achieved.
  • Suitable admixtures are that of particles based on graphite, in particular nickel- graphite or ferrite, which are extremely effective in absorbing the electromagnetic waves. These are therefore used in elements which both damp or seal and have an electromagnetic action.
  • a final group of admixtures is used to improve thermal conductivity.
  • the materials used for this for example aluminum oxide (A1 2 0 3 ) , boron oxide or magnesium, have particularly high thermal conductivity. These, like the materials described above, are in the form of particles or filling materials when admixed with the base elastomer.
  • the structure of the conductive paste is usually that of what is known as a single-component material, which cures under ambient conditions at room temperature.
  • the curing time may, if desired, be shortened by exposure to heat, in order to optimize the production process for mass production.
  • the conductive paste may moreover also be thought of in a manner known per se as a two- component material .
  • the conductive paste be used for the production of a flexible gasket for an electromagnetically shielded housing.
  • a paste of the material is applied directly to a part of a housing in the region in which the housing has a joint to be sealed.
  • computer-controlled handling equipment is used to move the nozzle across the part of the housing. The velocity of relative movement of nozzle and housing part is determined by the viscosity of the paste, by the amount and velocity of the material discharging from the die, by the cross- sectional area of the die passage, by the desired cross section of the gasket to be produced and by the makeup of the material.
  • the strand of material dispensed in this way polymerizes under ambient conditions at room temperature. This procedure takes a relatively long time, but can be accelerated by controlled exposure to heat.
  • the starting material used is polyoxypolyolefin with an admixture of a powder made from electrically conducting particles.
  • the material is a single-component material and cures under ambient conditions at normal room temperature.
  • contact pads which may per se have any desired shape, for example may be an area or a dot.
  • a comparable method is used to produce a heat- conducting contact element, and here the paste comprises an admixture of particles with high thermal conductivity.
  • the resultant element has a high level of thermal conductivity and prevents build-up of heat on the surface used.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Conductive Materials (AREA)
  • Paints Or Removers (AREA)
PCT/EP2000/011371 1999-12-09 2000-11-16 Non-silicone conductive paste for the electrical industry, and its use Ceased WO2001043146A1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
DE60010515T DE60010515T2 (de) 1999-12-09 2000-11-16 Leitfähige, nichtsilikonische paste für die elektrische industrie und ihre verwendung
AU21594/01A AU2159401A (en) 1999-12-09 2000-11-16 Non-silicone conductive paste for the electrical industry, and its use
EP00985043A EP1240648B8 (en) 1999-12-09 2000-11-16 Non-silicone conductive paste for the electrical industry, and its use
CA002394050A CA2394050A1 (en) 1999-12-09 2000-11-16 Non-silicone conductive paste for the electrical industry, and its use
JP2001543744A JP4436993B2 (ja) 1999-12-09 2000-11-16 電気工業用の非シリコーン伝導性ペースト及びその使用方法
AT00985043T ATE266241T1 (de) 1999-12-09 2000-11-16 Leitfähige, nichtsilikonische paste für die elektrische industrie und ihre verwendung

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19959262A DE19959262A1 (de) 1999-12-09 1999-12-09 Leitfähiges pastöses Material und dessen Verwendung
DE19959262.4 1999-12-09

Publications (1)

Publication Number Publication Date
WO2001043146A1 true WO2001043146A1 (en) 2001-06-14

Family

ID=7931917

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2000/011371 Ceased WO2001043146A1 (en) 1999-12-09 2000-11-16 Non-silicone conductive paste for the electrical industry, and its use

Country Status (10)

Country Link
US (4) US6518496B1 (enExample)
EP (1) EP1240648B8 (enExample)
JP (1) JP4436993B2 (enExample)
KR (1) KR100743732B1 (enExample)
AT (1) ATE266241T1 (enExample)
AU (1) AU2159401A (enExample)
CA (1) CA2394050A1 (enExample)
DE (2) DE19959262A1 (enExample)
ES (1) ES2220577T3 (enExample)
WO (1) WO2001043146A1 (enExample)

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CN100375276C (zh) * 2002-06-06 2008-03-12 富士高分子工业株式会社 导热片材及其制造方法
US7695817B2 (en) 2003-11-05 2010-04-13 Dow Corning Corporation Thermally conductive grease and methods and devices in which said grease is used
US8618211B2 (en) 2009-03-16 2013-12-31 Dow Corning Corporation Thermally conductive grease and methods and devices in which said grease is used

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JP2005187793A (ja) * 2003-12-24 2005-07-14 Rohm & Haas Electronic Materials Llc 改良された接着剤
US20090169724A1 (en) * 2007-12-27 2009-07-02 Toshiaki Ogiwara Conductive paste for use in membrane touch switch applications
FR2939441B1 (fr) 2008-12-08 2010-12-24 Solvay Procede de preparation d'un materiau polymere transparent comprenant des nanoparticules minerales ayant un facteur de forme strictement superieur a 1,0
US7816785B2 (en) * 2009-01-22 2010-10-19 International Business Machines Corporation Low compressive force, non-silicone, high thermal conducting formulation for thermal interface material and package
US8673049B2 (en) * 2010-08-27 2014-03-18 Dowa Electronics Materials Co., Ltd. Low-temperature sintered silver nanoparticle composition and electronic articles formed using the same
KR101048083B1 (ko) * 2010-10-14 2011-07-11 주식회사 이노칩테크놀로지 전자파 차폐 가스켓
US9999158B2 (en) 2013-01-03 2018-06-12 Henkel IP & Holding GmbH Thermally conductive EMI suppression compositions
CN105980512A (zh) 2014-02-13 2016-09-28 霍尼韦尔国际公司 可压缩热界面材料
WO2017152353A1 (en) 2016-03-08 2017-09-14 Honeywell International Inc. Phase change material
US11041103B2 (en) 2017-09-08 2021-06-22 Honeywell International Inc. Silicone-free thermal gel
US11072706B2 (en) 2018-02-15 2021-07-27 Honeywell International Inc. Gel-type thermal interface material
US11373921B2 (en) 2019-04-23 2022-06-28 Honeywell International Inc. Gel-type thermal interface material with low pre-curing viscosity and elastic properties post-curing

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AU2159401A (en) 2001-06-18
DE60010515T2 (de) 2005-05-12
EP1240648B1 (en) 2004-05-06
CA2394050A1 (en) 2001-06-14
US6563044B2 (en) 2003-05-13
US20020068145A1 (en) 2002-06-06
DE60010515D1 (de) 2004-06-09
EP1240648A1 (en) 2002-09-18
KR100743732B1 (ko) 2007-07-27
US20020051862A1 (en) 2002-05-02
US6518496B1 (en) 2003-02-11
DE19959262A1 (de) 2001-06-21
KR20030076920A (ko) 2003-09-29
US6921780B2 (en) 2005-07-26
EP1240648B8 (en) 2005-01-19
JP2003516610A (ja) 2003-05-13
US20020039662A1 (en) 2002-04-04
JP4436993B2 (ja) 2010-03-24
ES2220577T3 (es) 2004-12-16
ATE266241T1 (de) 2004-05-15
US6780927B2 (en) 2004-08-24

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