EP0392983B1 - Verfahren zum Herstellen eines geformten Bauelements - Google Patents

Verfahren zum Herstellen eines geformten Bauelements Download PDF

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Publication number
EP0392983B1
EP0392983B1 EP90810292A EP90810292A EP0392983B1 EP 0392983 B1 EP0392983 B1 EP 0392983B1 EP 90810292 A EP90810292 A EP 90810292A EP 90810292 A EP90810292 A EP 90810292A EP 0392983 B1 EP0392983 B1 EP 0392983B1
Authority
EP
European Patent Office
Prior art keywords
synthetic resin
resin binder
fleece
female mould
tower
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
EP90810292A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0392983A1 (de
Inventor
Eusebio C/O Soc. Az. Italiana Keller Lucca
Paul Henri Gillard
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.)
Matec Holding AG
Original Assignee
Matec Holding AG
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 Matec Holding AG filed Critical Matec Holding AG
Priority to AT90810292T priority Critical patent/ATE101665T1/de
Publication of EP0392983A1 publication Critical patent/EP0392983A1/de
Application granted granted Critical
Publication of EP0392983B1 publication Critical patent/EP0392983B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/64—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4266—Natural fibres not provided for in group D04H1/425
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/60—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in dry state, e.g. thermo-activatable agents in solid or molten state, and heat being applied subsequently
    • 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
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S83/00—Cutting
    • Y10S83/913—Filament to staple fiber cutting
    • 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
    • Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
    • Y10T156/10—Methods of surface bonding and/or assembly therefor
    • Y10T156/1052—Methods of surface bonding and/or assembly therefor with cutting, punching, tearing or severing
    • Y10T156/1062—Prior to assembly

Definitions

  • the present invention relates to a method for producing a shaped component from synthetic resin-bonded fiber material, a fine-grained or free-flowing synthetic resin binder being sprinkled or sprayed onto a nonwoven made of pure or predominantly natural fibers and the nonwoven fabric mixed with the synthetic resin binder being divided, after which the parts are combined in one
  • the tower is deposited on a perforated die belonging to a molding press and precompressed on the die by means of an air stream drawn through the perforations and to form dimensionally stable shaped components of the synthetic resin binder after the attachment and pressing on of a likewise perforated die by means of one through the perforations in the die and the Die-guided hot air flow is cured, and a device for performing this method.
  • a method of the type described is known, for example, from FR patent specification 76-20950 (publication No. 2,357,675). This method enables the production of components which have good cushioning properties, sound absorption and heat insulation and are therefore preferably used for the interior lining of vehicle cabins. The method also makes it possible to produce components with a predetermined outline and in this way to avoid material losses caused by cutting, which experience has shown to average about 30% in the case of the use mentioned.
  • a disadvantage of this known method is seen in the fact that the sound absorption, which is particularly important for the use described for the interior lining of vehicle cabins, cannot be optimized in practice. It is possible that the fleece parts or fibers and a fine-grained synthetic resin binder separate when deposited in the tower, so that the deposited non-woven parts or fibers contain different amounts of synthetic resin binders in some areas, which results in areas with different bonding between the non-woven parts and fibers and when the synthetic resin binder hardens resulting in different areas of elasticity and dependent sound absorption. If, in the known methods, a deposit that is practically constant in thickness over its entire surface is used to produce relief-shaped components with different thicknesses in some areas, then the deposit has to be compressed to different extents in some areas. This different degree of compression creates areas with different material density, which in turn leads to areas with different modulus of elasticity and therefore also different sound absorption.
  • FR patent application 2'439'082 describes a device with which nonwoven fabrics can be produced from cellulose fibers using thermoplastic and thermosetting binders.
  • the cellulose fibers e.g. waste paper fibers
  • the cellulose fleece produced in this way is then passed through an oven in which the thermoplastic fiber is melted.
  • the further processing and in particular solidification of the thermosetting binder is carried out in a conventional manner during the pressing process.
  • This device is also not suitable for the production of shaped components which, even in the case of locally strongly fluctuating shapes (curvature, thickness, etc.), continue to have all the desired physical properties (density, strength, etc.).
  • the present invention was therefore based on the object to provide a method for producing a shaped component in which a separation of fiber parts or fibers and synthetic resin binders is practically not possible and which also enables a relief-shaped component with regions of different thickness, but practically in to produce all areas of uniform material density.
  • this object is achieved with a method of Solved type mentioned above, which is characterized in that the synthetic resin binder after sprinkling or spraying and before cutting the nonwoven fabric is pre-hardened and the nonwoven fabric bonded with the pre-hardened synthetic resin binder is divided into fiber bundles or flakes before insertion into the tower.
  • the method according to the invention enables large-area deposition of fiber material with a practically uniform thickness and the same distribution of the synthetic resin binder.
  • the flakes of the divided nonwoven are deposited to form a deposit with regions of different thickness.
  • This preferred embodiment of the method makes it possible to use a suitably designed die and / or patrix to produce relief-shaped components with different thicknesses and practically the same material density in all areas. Because in the case of a component made of synthetic resin-bonded fiber material, the material density influences the flow resistance for air and the coefficient of elasticity, on which in turn the sound absorption or sound insulation depends, this embodiment of the method also enables components with different thicknesses in different areas and practically the same optimized sound absorption in all areas and insulation.
  • a preferred device for carrying out the inventive The process contains a fiber magazine and a loading device which loads the fibers for forming a nonwoven onto a conveyor belt, a scattering or spraying device which sprinkles or sprays a suitably prepared synthetic resin binder onto the nonwoven, a transport device which transports the nonwoven with the synthetic resin binder to a rice drum leads, the output of which is connected to the inlet opening of a tower for depositing the parts of the torn nonwoven fabric, and with a die, which is arranged for depositing the parts below or at the lower end of the tower, and with one for placement on the part occupied
  • FIGS. 1 and 2 A device suitable for carrying out the method according to the invention is shown schematically in FIGS. 1 and 2.
  • This device contains a magazine 10 for the fibers to be processed.
  • the magazine is assigned a loading device 11, which contains a plurality of conveyor belts, and an impeller, which deposits the fibers fed through a shaft onto the feed belt 12 of a card 13.
  • an allocation device 14 is provided with a storage container for fine-grained, thermosetting material suitable as a synthetic resin binder and with a screw conveyor for the metered feeding of this material into the area of a carding machine inlet.
  • the card 13 is enclosed in a housing 16 and a first blower 17 is provided, which draws air from the area of the card spout and is connected via a pipe to a cyclone 18, the outlet of which leads to the card inlet.
  • a further conveyor belt 19 is arranged in the card outlet, which transports the fiber fleece removed from the card and interspersed with the fine-grained, thermosetting material to a continuous furnace 21.
  • the conveyor belt runs past a supply roll 20, which carries a roll of a non-woven textile composite (non-woven), which is used to cover the conveyor belt as it passes.
  • a magazine 22 with deflecting rollers which can be displaced in the vertical direction is set up adjacent to the exit of the continuous furnace.
  • a friction lock 23 arranged between which the nonwoven fabric is gripped and passed on to the inlet of a shredder 24.
  • the shredder is arranged above a trickle tower 26, under the lower end of which a support 28 suitable for placing a die 27 is fastened.
  • the upper side of the carrier provided for placing the die has holes which lead into a cavity which is connected to a second blower 29 via a pipeline.
  • the fiber magazine 10 is filled with textile fibers and preferably with rice wool, which was obtained by shredding textile waste from spinning mills, weaving mills, knitting mills, tailoring shops and from households.
  • the fibers are scattered by the loading device 11 from the magazine via the impeller and the sink shaft onto the feed belt 12 and from there to the card 13.
  • the blower 17 sucks air into the suction area from the area surrounding the card and with it also the part of the fine-grained material that was not embedded in the nonwoven fabric or during the rotation of the card or during the transfer of the nonwoven from the card onto the transport path from the Fleece falls out.
  • the fan transports the sucked air and the fine-grained material to the cyclone 18, where the material is separated from the air and returned to the outlet of the metering device for new use.
  • Fleece with the embedded material is heated to a medium temperature at which the thermosetting material softens and the fibers of the fleece stick to one another and to the textile composite without polymerizing or hardening.
  • the fleece with the bonded fibers is then drawn into the magazine 22, where it cools down and the fine-grained material previously softened in the oven is solidified again and at the same time differences in the pulling speed of the fleece are compensated for.
  • the fleece together with the textile composite is reopened, for which purpose the shredder is set in such a way that it does not produce individual fibers, but rather fiber bundles or flakes consisting of a few fibers that are glued together.
  • the fiber bundles fall into the tower 26, where they sink under the effect of their own weight and the weak air flow generated by the fan 29, in order to form a homogeneous deposit on the die 27, which is caused by the air sucked through the holes in the matrix is slightly compressed.
  • the die is lifted off the support structure or swung out to the side.
  • a preforming tool 31 is preferably used, which presses the fiber bundles deposited on the projecting inner edge laterally against the edge and pre-compresses them, so that the deposit when fitting the male 32 can no longer be pushed down.
  • a patrix is then placed on the die, which compresses the deposit to the desired final thickness and shape.
  • the female, male and the enclosed fiber deposit are then heated in a heatable press (not shown) under suitable pressure and temperature until the plastic material is polymerized to a thermoset.
  • a tower 40 which has a plurality of guide surfaces (41, 42; 43, 44, 45) distributed at different heights and over the circumference, as is shown schematically in FIG. 3. These guide surfaces make it possible to steer the fiber bundles sinking in the tower in certain directions and in this way to produce deposits with regions of different thickness. It goes without saying that the guide surfaces for the production of simple components in large quantities are simply permanently installed and are preferably arranged movably for the production of components with a very strong relief-like shape in order to enable the direction of the surfaces to be readjusted and thus the correction of manufacturing parameters .
  • the fiber bundles do not sink freely onto the die in the entire cross section of the tower, but are introduced into a flexible tube 50 with a relatively narrow cross section, as is shown schematically in FIG. 4.
  • the outlet opening 51 of the tube is connected in motion to a guide device 52 which moves the outlet opening at different speeds over the surface of the die intended for the deposition of fiber bundles.
  • the guide device can be controlled by a mechanical control device 53, which is equipped, for example, with cam disks, or also by an electronic-numerical working device.
  • a die with bores of different diameters can simply be used. Through these holes, different amounts of air corresponding to the diameter are then sucked in, which results in the deposition of different amounts of fiber bundles.
  • Textile fibers obtained from textile waste, to which no or no more than 50% synthetic fibers are added, are preferably used in the shredder to manufacture components for the interior lining of automobiles.
  • Proven fine-grained materials that can be used for thermosetting hardening are, for example, phenolic resins.
  • the weight ratio of fiber material to fine-grained material is approximately 2: 1.
  • the thickness of a middle deposit on the die is, for example, between 50-100 mm before the patrix is placed, which deposit after the pressing and curing of the synthetic resin binder gives components with thicknesses between 5 to 50 mm and an elastic modulus between 1 to 10 N / cm2.
  • thermosetting the plastic binder depend on the thickness of the deposit and the type of synthetic resin binder used. Their correct selection lies in the area of professional skill, which is why this is not further here are explained.
  • the new method and the device used to carry it out enable a previously unattainable uniformity of the mixture of fiber material and plastic adhesive.
  • the use of a fine-grained and prepolymerized binder has the advantage over a liquid binder that neither the adhesive nor fibers or fiber bundles "wetted" by the adhesive get caught on the inner walls or edges of any device of the device and in particular the holes in the die with their relatively small diameter clog. It has already been mentioned that the prepolymerization of the powdered synthetic resin binder can prevent losses of binder, in particular in the tower and during thermosetting in a hot air stream.
  • the conveyor belt 19, which guides the nonwoven from the card to the continuous furnace 21, is covered with a thin, non-woven, textile composite (non-woven).
  • This composite material is introduced into the continuous furnace with the nonwoven on top and glued to the nonwoven.
  • the composite is then opened together with the fleece lying on top in the shredder so that parts of the composite are also deposited on the die with the fiber bundles and ultimately form part of the component to be produced.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonwoven Fabrics (AREA)
  • Reinforced Plastic Materials (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)
  • Moulding By Coating Moulds (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Compositions Of Oxide Ceramics (AREA)
EP90810292A 1989-04-14 1990-04-11 Verfahren zum Herstellen eines geformten Bauelements Expired - Lifetime EP0392983B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT90810292T ATE101665T1 (de) 1989-04-14 1990-04-11 Verfahren zum herstellen eines geformten bauelements.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH1425/89A CH681990A5 (en, 2012) 1989-04-14 1989-04-14
CH1425/89 1989-04-14

Publications (2)

Publication Number Publication Date
EP0392983A1 EP0392983A1 (de) 1990-10-17
EP0392983B1 true EP0392983B1 (de) 1994-02-16

Family

ID=4210163

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90810292A Expired - Lifetime EP0392983B1 (de) 1989-04-14 1990-04-11 Verfahren zum Herstellen eines geformten Bauelements

Country Status (7)

Country Link
US (1) US5160406A (en, 2012)
EP (1) EP0392983B1 (en, 2012)
JP (1) JPH0347712A (en, 2012)
AT (1) ATE101665T1 (en, 2012)
CH (1) CH681990A5 (en, 2012)
DE (1) DE59004576D1 (en, 2012)
ES (1) ES2049453T3 (en, 2012)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT398438B (de) * 1992-07-17 1994-12-27 Kuehnsdorfer Gmbh Verfahren zur strömungsdynamischen herstellung von verformbaren fasermatten hoher reissfestigkeit sowie vorrichtung zu deren herstellung
JPH0667010U (ja) * 1993-03-10 1994-09-20 日本特殊塗料株式会社 レジン回収装置
DE602004031659D1 (de) 2003-10-23 2011-04-14 Delta Tooling Co Ltd Htung zum nachweis von müdigkeit und computerprogramm
CN102776717B (zh) * 2012-07-11 2014-05-14 常熟市飞龙无纺机械有限公司 空气填充法汽车内饰件预成型机
CN102776718B (zh) * 2012-07-11 2014-05-07 常熟市飞龙无纺机械有限公司 汽车内饰件预成型机
CN102776719B (zh) * 2012-07-11 2014-04-16 常熟市飞龙无纺机械有限公司 空气填充法汽车内饰件预成型机的预成型箱结构

Family Cites Families (18)

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US2745491A (en) * 1952-05-16 1956-05-15 Owens Corning Fiberglass Corp Apparatus for the preparation of glass fiber reinforced molding compositions
US2890146A (en) * 1955-09-21 1959-06-09 Queen City Tulatex Corp Method of producing preformed combination upholstery and insulator padding
BE617864A (en, 2012) * 1961-05-29
FR1399062A (fr) * 1964-06-11 1965-05-14 Feutres non tissés avec charges minérales incorporées et leur procédé de fabrication
US4153488A (en) * 1970-06-16 1979-05-08 Conwed Corporation Manufacture of fibrous web structures
US3873290A (en) * 1973-06-08 1975-03-25 Owens Corning Fiberglass Corp Method of producing discontinuous lengths of dispersed filament strand
US4043779A (en) * 1976-03-08 1977-08-23 Ppg Industries, Inc. Apparatus for chopping coated glass fibers
FR2357675A1 (fr) * 1976-07-08 1978-02-03 Matec Holding Perfectionnements apportes aux procedes et installations pour fabriquer des produits non tisses et aux produits obtenus
US4097965A (en) * 1976-08-17 1978-07-04 Scott Paper Company Apparatus and method for forming fibrous structures comprising predominantly short fibers
GB1602701A (en) * 1977-11-16 1981-11-18 Pianfei Ipa Spa Manufacture of bonded fibrous webs
DE2845112C3 (de) * 1978-10-17 1981-11-05 Casimir Kast Gmbh & Co Kg, 7562 Gernsbach Verfahren und Anlage zur Herstellung von Matten aus zellulosehaltigen Fasern und Verfahren zur Herstellung von Formteilen aus diesen
FR2537495A3 (fr) * 1982-12-08 1984-06-15 Isoring Srl Moule destine a la realisation des parties coudees des elements isolants tubulaires
US4650538A (en) * 1982-12-29 1987-03-17 Usm Corporation Linear deposition apparatus
US4483727A (en) * 1983-02-07 1984-11-20 Celanese Corporation High modulus polyethylene fiber bundles as reinforcement for brittle matrices
JPS59158242A (ja) * 1983-02-28 1984-09-07 Nippon Sekisoo Kogyo Kk 有機物質成形品の成形方法
US4761258A (en) * 1985-12-10 1988-08-02 Kimberly-Clark Corporation Controlled formation of light and heavy fluff zones
EP0292581B1 (de) * 1987-05-23 1990-11-14 Carl Schenck Ag Verfahren zum Streuen eines Spänevlieses
JPH03501142A (ja) * 1987-11-25 1991-03-14 レーン，マックスウェル，ビクター 結合されたファイバー製断熱バット

Also Published As

Publication number Publication date
ATE101665T1 (de) 1994-03-15
JPH0347712A (ja) 1991-02-28
US5160406A (en) 1992-11-03
EP0392983A1 (de) 1990-10-17
DE59004576D1 (de) 1994-03-24
ES2049453T3 (es) 1994-04-16
CH681990A5 (en, 2012) 1993-06-30

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