EP0633964B1 - Antistatische folie - Google Patents

Antistatische folie Download PDF

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Publication number
EP0633964B1
EP0633964B1 EP93907902A EP93907902A EP0633964B1 EP 0633964 B1 EP0633964 B1 EP 0633964B1 EP 93907902 A EP93907902 A EP 93907902A EP 93907902 A EP93907902 A EP 93907902A EP 0633964 B1 EP0633964 B1 EP 0633964B1
Authority
EP
European Patent Office
Prior art keywords
sheet
conductive
layer
pigments
sheet according
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
EP93907902A
Other languages
English (en)
French (fr)
Other versions
EP0633964A1 (de
Inventor
Claude Perrin
Christophe Simon
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.)
ArjoWiggins SAS
Original Assignee
ArjoWiggins SAS
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 ArjoWiggins SAS filed Critical ArjoWiggins SAS
Publication of EP0633964A1 publication Critical patent/EP0633964A1/de
Application granted granted Critical
Publication of EP0633964B1 publication Critical patent/EP0633964B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/38—Coatings with pigments characterised by the pigments
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24851—Intermediate layer is discontinuous or differential
    • Y10T428/24868—Translucent outer layer
    • Y10T428/24884—Translucent layer comprises natural oil, wax, resin, gum, glue, gelatin
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24893—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material
    • Y10T428/24901—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material including coloring matter
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31971—Of carbohydrate
    • Y10T428/31993—Of paper

Definitions

  • the invention relates to a sheet of paper having properties. antistatic.
  • Such a sheet can be used in various fields. It can be used to make items for which it it is necessary to dissipate the electrostatic charges produced when in use or for items which have as primary or secondary function of dissipating charges forming electrostatic and can be dangerous in a given environment.
  • Flexible abrasives consist of a support sheet on which abrasive grains are bonded with an adhesive for which it is necessary to dissipate the electrostatic charges created during their use.
  • the abrasive is not treated to dissipate the charges, the dust formed during the abrasion of an object is deposited and fouls the abrasive grains; it then reduces the abrasion yield.
  • workers can suffer electric shocks which make them react with uncontrolled gestures putting them in danger during their work.
  • abrasives In the field of abrasives we treat with a conductive product the support or the layer of adhesive or the surface of the grains abrasive.
  • conductive products salts have been used quaternary ammonium, carbon black, powders or fibers metals, metal alloys, metal salts, conductive doped polymers or rendered mineral pigments conductors by coating them with an electrically conductive layer metal oxide.
  • the abrasive is made conductive by incorporating carbon black into the adhesive used to bond abrasive grains.
  • the abrasive is made conductive by to a layer of a conductive compound which can be a metal, a metallic alloy, metallic pigment, salt or complex metallic, this layer being placed between two layers insulating.
  • the conductive product can be put on the back of the support, on the face of the support (below the adhesive), mixed with the adhesive or on the grains.
  • an abrasive is made conductive by having a conductive layer on top of the abrasive grains, the conductive product being in particular graphite.
  • the abrasive is made conductive by treating the surface of the layer containing the abrasive grains with a solution containing a quaternary ammonium salt.
  • the abrasive is made conductive by treating the surface of the layer containing the abrasive grains by a doped conjugated polymer such as for example polythiophene, polyaniline, polypyrrole.
  • the paper sheets constituting them are treated with a conductive product.
  • the so-called high pressure laminates are produced from a core consisting of a stack of sheets, generally kraft paper, impregnated with a thermosetting resin, in particular a phenolic resin. Once the sheets of kraft paper impregnated with resin, they are dried, cut, then stacked on top of each other; the number of stacked sheets depends on the applications, it generally varies between three and nine.
  • a decorative sheet which can be plain, with printed patterns or even presented an iridescent or metallic appearance and being impregnated with a thermosetting resin which does not blacken with heat (for example a resin melamine-formaldehyde).
  • a protective covering sheet called “overlay”, also impregnated with a resin, devoid of pattern and transparent in the final laminate, is placed above the decorative sheet.
  • the pile of the various types of impregnated sheets is placed in a press provided with a sheet conferring the surface appearance; the assembly is laminated under pressure and hot; an extremely hard unitary structure is obtained which has a decorative effect.
  • low pressure laminates are produced in a similar manner to that of high pressure laminates, but the lamination of the decorative sheet directly on a particle board or any other basic support.
  • the finished sheet which also belongs to the category of decorative papers.
  • This sheet of paper that is pre or post impregnated (usually of a mixture of latex and melamine-formaldehyde resin) is intended to be glued on a particle board or any other support.
  • a laminate is made conductive by the fact that part of the leaves constituting the core is conductive by incorporating a material into each sheet electrically conductive such as carbon black, metal or metallic salts or conductive fibers.
  • fibers conductive in a paper are carbon fibers, metallic fibers or fibers covered with a metal.
  • an anti-static agent for plastics, a conductive pigment obtained by deposition tin or indium on a non-conductive mineral base pigment followed by heating in an oxygen atmosphere to form their oxide.
  • the metal oxide is therefore not doped.
  • pigments As basic pigments which can be used, many pigments are cited without specifying any advantage linked to a particular pigment or to a geometric form of a family of pigments.
  • US-A-5071676 describes a conductive pigment usable for imparting antistatic properties to paper and cardboard.
  • This pigment consists of a non-substrate conductor covered with an electroconductive oxide layer antimony-doped tin, itself covered with a layer giving the pigment an isoelectric point between 5 and 9 in order to facilitate its dispersion.
  • the substrate can be any, it is not critical to the invention.
  • Application EP-A-415478 describes a colored and conductive pigment usable in laminated papers.
  • This pigment consists of a base pigment of rutile titanium dioxide and mixed phase coated with a layer of tin oxide doped with antimony.
  • Rutile has a spherical geometric shape, so this pigment is spherical.
  • a disadvantage of certain products such as doped polymers is their high price.
  • a disadvantage of certain products such as quaternary ammonium salts is that it gives the articles a conductivity too low to have a good flow of electrostatic charges.
  • Another disadvantage of conductive salts is that the level of conductivity of the products containing them varies with relative humidity.
  • a disadvantage of certain conductive products such as aluminum is the sensitivity to water; in the presence of water a dangerous release of hydrogen takes place. They cannot therefore be easily used in an aqueous medium.
  • Drawbacks linked to the use of conductive fibers are, on the one hand, the mottled aesthetic appearance given to paper, in particular with carbon fibers, and, on the other hand, the reduction in the physical characteristics of the paper sheet.
  • Certain inorganic conductive pigments made conductive by a layer of metal oxide can give a conductivity which is too low to ensure good dissipation of electrostatic charges, especially once used in a paper application.
  • the object of the invention is to provide a sheet of paper which has a sufficient level of electrical conductivity giving it antistatic properties.
  • Those skilled in the art know from experience that, for an article to effectively dissipate electrostatic charges, it is preferable that its surface resistivity is not greater than about 10 7 ohms, measurement made according to standard ASTM 257-66.
  • a second aim is to provide a sheet having antistatic properties which can be produced entirely in an aqueous medium.
  • a third object is to provide a sheet having antistatic properties which do not vary with the relative humidity.
  • a fourth aim is to provide a sheet having antistatic properties which has a neutral aesthetic appearance, that is to say that the product which will make the sheet conductive must not or only slightly modify the appearance of the sheet.
  • Another object is to provide a sheet having antistatic properties whose mechanical characteristics are good.
  • Another object is to provide a sheet having antistatic properties which has a low cost price.
  • the Applicant has found that the objects of the invention are achieved by making a sheet with pigments conductors having a basic structure of the lamellar type and provided with an electroconductive layer of doped metal oxide.
  • the mineral pigments covered with doped metal oxides are known for their electroconductive properties, however the Applicant has found that, for pigments having an electroconductive layer based on the same oxide and for the same dopant, therefore having a priori comparable intrinsic conductivity levels, the sheets of paper containing these pigments have very different final conductivities depending on the basic structure (geometric shape) of the support pigment of the layer.
  • the doped metal oxide chosen being tin oxide doped with antimony, this doped oxide is deposited on support pigments of different geometric shapes.
  • the conductive pigments were coated in an aqueous medium under the same conditions using the same binder (polyvinyl alcohol PVA) and in the same 1: 1 ratio, on the surface of a sheet of paper.
  • the surface resistivity of the sheets was measured according to standard ASTM 257-66 for a relative humidity of 50% (the conductivity of the sheets can be obtained by taking the inverse of the resistivity). From this study it seems that the basic structure of the pigment has an influence on the final conductivity of the sheet.
  • the level of resistivity desirable for good dissipation of electrostatic charges (less than 10 7 ohms) is only achieved with pigments having a basic structure of the lamellar type (therefore of flat geometric shape); the resistivity is indeed of the order of 10 5 ohms.
  • the invention therefore provides a sheet of paper having antistatic properties characterized by the fact that it contains conductive pigments having a basic structure of lamellar type and provided with at least one electrically conductive layer doped metal oxide.
  • the doped metal oxide is a tin oxide spiked with antimony.
  • the pigments having a lamellar type structure can be chosen for example from micas, talc, kaolin, bentonites, montmorillionites or glass particles.
  • the conductive pigment is a mica coated with a layer of tin oxide doped with antimony.
  • the mica pigments covered with a layer of tin oxide doped with antimony have good light transparency, they do not modify the aesthetic appearance of the paper which contains them.
  • the pigment conductor is a mica coated with a layer of titanium oxide, optionally with a layer of silica, and coated with a layer of tin oxide doped with antimony.
  • These pigments have some iridescence but they have little effect on appearance aesthetics of the paper containing them. It may be interesting to use them in areas where the decorative effect of iridescence is sought after, for example in the field of laminates.
  • the conductive pigments can be incorporated en masse during the manufacture of the sheet on the paper machine or be deposited on the surface of the sheet by impregnation in a size press or by any coating means or even by printing.
  • the conductive pigments are provided in an aqueous medium.
  • the sheet is characterized in that it carries, on at least one face, a layer containing at least the said conductive pigments and at least one binder.
  • the binder is a binder usually used in stationery such as water-soluble binders, latexes. It may be advantageous to use a water-soluble binder, such as, for example, polyvinyl alcohols or starches, to obtain an easily repulpable sheet.
  • the layer may optionally contain other adjuvants commonly used in stationery such as viscosity regulating agents, for example carboxymethylcellulose, defoamers, etc.
  • the quantity of conductive pigments deposited on the surface of the sheet is between 1 and 10 g / m 2 , by dry weight.
  • the treated sheet is based on cellulose fibers, it can contain other organic fibers (polyethylene fibers, polypropylene, polyester ...) or mineral fibers such as glass fibers. It can also contain other additives used in stationery as fillers, bonding agents, binders, wet strength agents, retention, anti-foaming agents, regulating agents viscosity, pH regulating agents etc ....
  • the invention also provides a flexible abrasive product having antistatic properties which is characterized by the fact that it is supported by said sheet with antistatic properties.
  • the abrasive can obviously be in the form of a sheet, but also in other forms such as, for example, continuous tape, disc, etc.
  • the sheet used contains the conductive pigments on the surface.
  • the conductive pigments can be on the back of the abrasive or on the face carrying the grains, below the adhesive. Since it is known to use a conductive product in the adhesive or on the grains, one can envisage such a use of conductive pigments.
  • the invention also relates to a decorative sheet obtained from said sheet with antistatic properties.
  • the invention also relates to a laminate having antistatic properties which is characterized in that it comprises at least one sheet like the said sheet with antistatic properties.
  • Said sheet can be used as a component of the core of the laminate or as a decorative sheet or possibly as an overlay. Said sheet can also be a finished sheet.
  • the pigment-binder ratio is 5: 1.
  • Samples are produced with different layer weights of conductive pigments (expressed in dry weight in the table below). The surface resistivity of each sample is measured according to standard ASTM 257-66 and this at relative humidity levels (denoted RH) of 50 and 20%. The results in the table below show that the resistivity of the sheet does not vary with the relative humidity.
  • Samples are produced as in Example 1, but a conductive pigment is used, a mica covered with a layer of titanium oxide then with a layer of silica and finally coated with a layer of tin oxide doped with antimony, the tin / antimony ratio being 85:15.
  • This pigment is marketed by MERCK. According to the results in the table below, it can be seen that the relative humidity has no influence on the level of conductivity of the sheets obtained according to the invention. The leaves have a slight iridescence which has little effect on their aesthetic appearance.

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Laminated Bodies (AREA)
  • Paper (AREA)
  • Polarising Elements (AREA)
  • Elimination Of Static Electricity (AREA)

Claims (10)

  1. Papierfolie mit antistatischen Eigenschaften, die leitende Pigmente aufweist, die mit einer elektrisch leitenden Schicht aus dotiertem Metalloxid versehen sind, dadurch gekennzeichnet, daß die leitenden Pigmente einen lamellenartigen Grundaufbau aufweisen.
  2. Folie nach Anspruch 1, dadurch gekennzeichnet, daß die einen Lamellenaufbau aufweisenden Pigmente unter Micas, Talk, Kaolin, Bentoniten, Montmorilloniten oder Glaspartikeln ausgewählt werden.
  3. Folie nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das dotierte Metalloxid der elektrisch leitenden Schicht ein mit Antimon dotiertes Zinnoxid ist.
  4. Folie nach den Ansprüchen 2 bis 3, dadurch gekennzeichnet, daß das leitende Pigment eine Mica ist, die mit einer Schicht aus mit Antimon dotiertem Zinnoxid versehen ist.
  5. Folie nach den Ansprüchen 2 bis 4, dadurch gekennzeichnet, daß das leitende Pigment eine Mica ist, die mit einer Titanoxidschicht, gegebenenfalls mit einer Siliciumoxidschicht überzogen, und mit einer Schichte aus mit Antimon dotierten Zinnoxidschicht versehen ist.
  6. Folie nach den Ansprüchen 1 bis 5, dadurch gekennzeichnet, daß sie auf mindestens einer Seite eine Schicht trägt, die mindestens die leitenden Pigmente und mindestens ein Bindemittel enthält.
  7. Folie nach Anspruch 6, dadurch gekennzeichnet, daß die Menge der auf der Folie abgesetzten leitenden Pigmente zwischen 1 und 10 g/m2 Trockengewicht beträgt.
  8. Elastisches Schleifmittel mit antistatischen Eigenschaften, dadurch gekennzeichnet, daß es als Träger die Folie nach den Ansprüchen 1 bis 7 aufweist.
  9. Dekorationsfolie, dadurch gekennzeichnet, daß sie ausgehend von einer Folie nach den Ansprüchen 1 bis 7 erhalten wird.
  10. Schichtmaterial mit antistatischen Eigenschaften, dadurch gekennzeichnet, daß es mindestens eine Folie nach den Ansprüchen 1 bis 7 oder 9 aufweist.
EP93907902A 1992-04-07 1993-03-29 Antistatische folie Expired - Lifetime EP0633964B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9204230 1992-04-07
FR9204230A FR2689531B1 (fr) 1992-04-07 1992-04-07 Feuille antistatique.
PCT/FR1993/000310 WO1993020280A1 (fr) 1992-04-07 1993-03-29 Feuille antistatique

Publications (2)

Publication Number Publication Date
EP0633964A1 EP0633964A1 (de) 1995-01-18
EP0633964B1 true EP0633964B1 (de) 1998-01-14

Family

ID=9428579

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93907902A Expired - Lifetime EP0633964B1 (de) 1992-04-07 1993-03-29 Antistatische folie

Country Status (13)

Country Link
US (1) US5677039A (de)
EP (1) EP0633964B1 (de)
AT (1) ATE162250T1 (de)
AU (1) AU661902B2 (de)
BR (1) BR9306198A (de)
DE (1) DE69316346T2 (de)
DK (1) DK0633964T3 (de)
ES (1) ES2111742T3 (de)
FI (1) FI114651B (de)
FR (1) FR2689531B1 (de)
MX (1) MX9302060A (de)
NO (1) NO302248B1 (de)
WO (1) WO1993020280A1 (de)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19511012A1 (de) * 1994-04-06 1995-10-12 Merck Patent Gmbh Oberflächenmodifiziertes, leitfähiges Pigment
EP1053099B1 (de) * 1998-02-02 2002-08-14 International Paper Company Feuchtigkeitsabhängiger statische elektrizität zerstreuender schichtstoff
US6114079A (en) * 1998-04-01 2000-09-05 Eastman Kodak Company Electrically-conductive layer for imaging element containing composite metal-containing particles
WO2004003293A1 (en) * 2002-06-27 2004-01-08 Upm-Kymmene Oyj Printed substrate and printing method
KR20050065573A (ko) * 2002-10-03 2005-06-29 메츠 코퍼레이숀 정전하 방출 경질 라미네이트 구조
DE202004002832U1 (de) * 2004-02-20 2005-06-30 Kronospan Technical Company Ltd., Engomi Kohlenstoffhaltiges Papier nebst Paneel
US20090176074A1 (en) * 2006-05-05 2009-07-09 Meadwestvaco Corporation Conductive/absorbtive sheet materials with enhanced properties
DE102008009716B4 (de) * 2008-02-19 2013-08-29 Nanogate Ag Verfahren zur Herstellung einer Elektretbeschichtung und die Verwendung der damit hergestellten Beschichtung
LT2284019T (lt) * 2009-06-22 2016-09-12 Polska Wytwornia Papierow Wartosciowych S.A. Apsauginis popierius lazeriniam graviravimui, saugus dokumentas ir apsaugos gavimo būdas
JP5389568B2 (ja) * 2009-08-19 2014-01-15 富士フイルム株式会社 透明導電性フィルム
PL2537597T3 (pl) 2011-06-21 2017-02-28 Flooring Technologies Ltd. Płyta drewnopochodna oraz sposób jej wytwarzania
WO2013018111A1 (en) 2011-08-02 2013-02-07 C.I.M. CALCI IDRATE MARCELLINA SpA Self-cleaning, anti-smog, anti-mould photocatalytic powdered water based paint
US9881727B2 (en) 2014-10-10 2018-01-30 The Diller Corporation Decorative multi-layer surfacing materials having embedded conductive materials, solid surfaces made therewith, methods for making such surfacing materials and uses therefor

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5834861A (ja) * 1981-08-27 1983-03-01 Ricoh Co Ltd 導電性顔料の製造法
JPS6050813A (ja) * 1983-08-31 1985-03-20 触媒化成工業株式会社 プラスチック又は塗料配合用透光性導電性粉末素材
US5071676A (en) * 1989-08-03 1991-12-10 E. I. Du Pont De Nemours And Company Electroconductive particles and method for adjusting the isoelectric point thereof
DE3929057A1 (de) * 1989-09-01 1991-03-07 Metallgesellschaft Ag Elektrisch leitfaehiges rutilmischphasen-pigment, verfahren zu seiner herstellung sowie dessen verwendung

Also Published As

Publication number Publication date
NO302248B1 (no) 1998-02-09
FR2689531A1 (fr) 1993-10-08
US5677039A (en) 1997-10-14
FI944645L (fi) 1994-10-05
MX9302060A (es) 1994-07-29
NO943756L (no) 1994-12-01
FI114651B (fi) 2004-11-30
AU3892993A (en) 1993-11-08
DE69316346D1 (de) 1998-02-19
WO1993020280A1 (fr) 1993-10-14
DK0633964T3 (da) 1998-09-14
NO943756D0 (no) 1994-10-06
BR9306198A (pt) 1998-06-23
FI944645A0 (fi) 1994-10-05
EP0633964A1 (de) 1995-01-18
ES2111742T3 (es) 1998-03-16
ATE162250T1 (de) 1998-01-15
FR2689531B1 (fr) 1994-12-23
DE69316346T2 (de) 1998-05-14
AU661902B2 (en) 1995-08-10

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