EP0338188B1 - Matériau stratifié en bande enduit à surface grainée fine et son procédé de fabrication - Google Patents

Matériau stratifié en bande enduit à surface grainée fine et son procédé de fabrication Download PDF

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Publication number
EP0338188B1
EP0338188B1 EP19890100625 EP89100625A EP0338188B1 EP 0338188 B1 EP0338188 B1 EP 0338188B1 EP 19890100625 EP19890100625 EP 19890100625 EP 89100625 A EP89100625 A EP 89100625A EP 0338188 B1 EP0338188 B1 EP 0338188B1
Authority
EP
European Patent Office
Prior art keywords
layer
interlayer
laminate material
adhesive
pvc
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
EP19890100625
Other languages
German (de)
English (en)
Other versions
EP0338188A2 (fr
EP0338188A3 (fr
Inventor
Hanns-Jürgen Dr. Wald
Wilfried Getrost
Sigrid Lang
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.)
Carl Freudenberg KG
Original Assignee
Carl Freudenberg KG
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 Carl Freudenberg KG filed Critical Carl Freudenberg KG
Priority to AT89100625T priority Critical patent/ATE87340T1/de
Publication of EP0338188A2 publication Critical patent/EP0338188A2/fr
Publication of EP0338188A3 publication Critical patent/EP0338188A3/fr
Application granted granted Critical
Publication of EP0338188B1 publication Critical patent/EP0338188B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/18—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with two layers of different macromolecular materials
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0013—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using multilayer webs
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
    • D06N3/0095—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by inversion technique; by transfer processes
    • 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
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/904—Artificial leather
    • 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.]
    • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
    • Y10T428/24438—Artificial wood or leather grain surface
    • 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.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • 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.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y10T428/2495—Thickness [relative or absolute]
    • Y10T428/24967—Absolute thicknesses specified
    • 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
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/30—Woven fabric [i.e., woven strand or strip material]
    • Y10T442/3707—Woven fabric including a nonwoven fabric layer other than paper
    • Y10T442/378—Coated, impregnated, or autogenously bonded
    • Y10T442/3813—Coating or impregnation contains synthetic polymeric material
    • 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
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/40—Knit fabric [i.e., knit strand or strip material]
    • Y10T442/494—Including a nonwoven fabric layer other than paper

Definitions

  • the invention relates to a web-shaped coated composite material according to the features of the first claim and a method for its production.
  • Such composite materials are required as synthetic leather for the production of shoes with a fine-grain surface and, at the same time, open-edged processing.
  • DE-GM 87 02 810 describes a synthetic leather piece in which the nonwoven unrest is to be eliminated in that a knitted fabric is woven into the nonwoven.
  • the disadvantage of this solution is that the knitted fabric or fabric is damaged by the needling and must be covered with a thin nonwoven layer on at least one side for secure anchoring.
  • GB-A-12 63 512 describes a process for producing leather-like material and such a material, the purpose of which is to achieve very good physical and aesthetic properties and good permeability to water vapor, so that the material can be used as upper leather and for slippers allowed.
  • a method is used in which two separate, composite structures are prepared, the first composite structure being obtained by the following stages: Applying a expandable urethane mixture to a (preferably silicone paper) support which has previously been coated with a film of thermoplastic urethane resin, expanding and crosslinking the foam.
  • the second composite structure is created by impregnating a nonwoven with rubber latex, attaching it via a polyurethane binder layer solution to a knitted or knitted textile made of polyamide fibers, vulcanizing the rubber and crosslinking the binder.
  • Both multilayer fabrics are connected to one another in such a way that the knitted or knitted layer is in contact with the polyurethane foam layer, after which the polyurethane foam is completely crosslinked in the oven. Then the silicone paper is peeled off.
  • the process therefore requires the separate, multi-stage production of two laminates which are present separately from one another and which are only joined together in a later process step.
  • US-A-25 33 976 discloses a synthetic leather for shoes, in which special stretch and elastic properties are important.
  • Two soft, flexible fiber sheets as inner layers are held together by a rubber layer.
  • a plastic layer serves as the outer layer.
  • the inner fibrous sheet may be woven or fine knitted from rayon or other synthetic filaments to ensure a soft surface.
  • the outer fabric is a knitted fabric and of a somewhat coarser structure; it is preferably made of cotton fibers in the interest of better binding to the plastic outer skin.
  • US-A-37 78 325 is concerned with a process for the production of a synthetic leather, whereby good water vapor permeability, abrasion resistance, kink resistance, dimensional stability, surface softness, homogeneity and delamination resistance are to be achieved.
  • an organic polyurethane solution as an adhesive to a nonwoven fabric, to place a fabric on the adhesive, to apply an organic polyurethane cover solution thereon, to soak the four-layer laminate with a coagulant and thus to coagulate the adhesive and cover solution.
  • FR-A-20 63 075 relates to a particularly simple process for the production of synthetic leather, in which two completely prefabricated, composite flat structures are produced, one of which is applied to a separable carrier web, both structures using a polyurethane adhesive first be connected together after separate completion.
  • a knitted fabric consisting only of polyamide fibers
  • a knitted fabric is used as an intermediate layer, some of which contains natural fibers.
  • the present invention therefore has the task of specifying a generic composite material which has a fine-grained surface, the support structure not penetrating to the cover layer.
  • the firmness and appearance of the cut edges should be the same as that of natural leather.
  • the knitted intermediate layer should have a surface that is as smooth as possible on both sides, so that, on the one hand, no structure is formed on the surface during shoe manufacture and, on the other hand, not too much adhesive is required in the manufacturing process, when bonding to the backing layer, so that the end product is flexible, soft and round remains.
  • the knitted intermediate layer must have an elongation at break of at least 8% after being embedded in both adhesive lines.
  • a 100 g / m2 polyester jersey knitted fabric proved to be particularly suitable, also because of its smooth surface structure, as an intermediate layer.
  • the backing layer is preferably an impregnated needle fleece because of the required cut edge strength.
  • the desired final thickness of the composite material can be set with beam thicknesses between 0.2 and 3.5 mm. If the carrier material is a fabric, the cut edge strength must be ensured by impregnation.
  • the visible surface of the composite material consists of 1 to 2 g / m2 heavy PVC, polyurethane or acrylate lacquer. Underneath there is a soft PVC layer with 45 to 65% by weight plasticizer content or a polyurethane layer.
  • Soft PVC with a plasticizer content of 45 to 65% by weight was found as a particularly suitable adhesive screed.
  • first the intermediate layer is applied to the cover layer and then the carrier layer to the intermediate layer.
  • the adhesive must be done with adhesive lines, hot melt adhesive or adhesive films with very soft consistency.
  • a solvent-containing topcoat consisting of e.g. PVC is applied to the release paper with fine embossing and the solvent is removed in a convection oven.
  • This top coat is coated with soft top coat paste and dried in a convection oven.
  • the intermediate and carrier layers are applied in succession, in each case by means of a soft adhesive paste, hot-melt adhesive or adhesive film, which, if necessary, is dried in a forced-air oven after each application process. Only then and after the entire composite has cooled down is the release paper removed. This procedure protects the fine-grain embossed surface during the gluing process.
  • smooth release paper is used.
  • the fine-grained surface is created using an embossing calender with a fine-grain embossing roller.
  • the lamination of the backing layer can also be done in a separate operation, but before the calendar is embossed. After embossing, the goods are printed and varnished if desired.
  • 300 g / m2 of a soft PVC paste with 50% by weight plasticizer content are applied to it and gelled in a second convection oven at 190.degree.
  • 100 g / m2 of soft PVC adhesive screed (plasticizer content: 55% by weight) is used to laminate a polyester jersey knitted fabric of 100 g / m2 to the gelled PVC top layer and the adhesive screed is gelled in a third convection oven at 190 ° C .
  • the lamination of the carrier layer, a 0.8 mm thick, 200 g / m2 polyester needle fleece, is then carried out with 300 g / m2 of the same adhesive layer as above on the knitted fabric.
  • the entire composite with the release paper is heated in the fourth convection oven at 190 degrees C. After cooling, the entire composite is separated from the release paper as a 1.6 mm thick, fine-grained and cut-edge-resistant sports shoe upper material.
  • Example 2 The procedure is as in Example 1, but a 300 g / m2, 1.1 mm thick, impregnated needle punch is used as the carrier material.
  • the end product has a thickness of 1.8 mm and can be used as a shoe upper.
  • the advantages of the present invention thus lie in the possibility of producing fine-grained shoe upper materials which can also be processed with open edges. Compared to real leather and fine-grain non-woven fabrics, the product according to the invention and its manufacturing process are characterized by up to 50% lower manufacturing costs.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Laminated Bodies (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
  • Paper (AREA)
  • Manufacturing Of Multi-Layer Textile Fabrics (AREA)
  • Absorbent Articles And Supports Therefor (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatment Of Fiber Materials (AREA)
  • Cephalosporin Compounds (AREA)

Claims (7)

  1. Matière composite revêtue sous forme de bande, ayant un aspect analogue au cuir et une surface finement grainée, et une épaisseur de 0,7 à 5,0 mm, se composant d'un revêtement de chlorure de polyvinyle mou, de polyuréthanne, de NBR, de SBR ou d'acrylate d'une épaisseur de 0,03 à 0,4 mm, d'une couche d'enduit adhésif et d'une couche porteuse formée d'une nappe ou d'un tissu imprégné d'une dispersion d'acrylate, d'une épaisseur de 0,2 à 3,5 mm et d'un poids surfacique de 30 à 500 g/m², une couche intermédiaire textile lisse, peu texturée, étant disposée entre la couche porteuse et le revêtement et étant entourée des deux côtés par une couche de polymère molle, reliant la couche porteuse avec cette couche intermédiaire, et la matière composite ayant dans l'état stratifié un allongement à la rupture d'au moins 8 % et comportant également, après déformation, une surface exempte de structures de nappe, caractérisée en ce que la couche intermédiaire est un tricot-jersey en polyester d'un poids surfacique de 100 g/m².
  2. Matière composite selon la revendication 1, caractérisée en ce que le revêtement comporte une couche de laque formée d'une laque de PVC, PUR ou d'acrylate d'un poids surfacique de 1 à 2 g/m², qui est située sur une couche de chlorure de polyvinyle mou ayant une teneur en émollient de 45 à 65 % en poids ou bien sur une couche de polyuréthanne.
  3. Matière composite selon la revendication 2, caractérisée en ce que la couche intermédiaire comporte sur les deux côtés un enduit adhésif de chlorure de polyvinyle mou ayant une teneur en émollient de 45 à 65 % en poids.
  4. Matière composite selon une des revendications 1 à 3, caractérisée en ce que la couche porteuse est une nappe aiguilletée de polyester imprégnée.
  5. Procédé de fabrication d'une matière composite revêtue sous forme de bande ayant les particularités définies dans la revendication 1, caractérisé par la séquence des étapes opératoires suivantes :
    a) dépôt de la couche supérieure sur un papier détachable et ensuite séchage dans un four à circulation d'air ;
    b) mise en place de la couche intermédiaire sur la couche de revêtement au moyen d'une couche de polymère adhésive et molle et ensuite séchage dans un four à circulation d'air ;
    c) mise en place de la couche porteuse sur la couche intermédiaire au moyen d'une couche adhésive de polymère et le cas échéant ensuite séchage dans un four à circulation d'air ;
    d) refroidissement de la structure stratifiée et ensuite enlèvement du papier détachable.
  6. Procédé selon la revendication 5, caractérisé en ce qu'avant le dépôt de la pâte molle d'enduit de recouvrement, on dépose une couche de laque contenant un liant sur un papier détachable ayant un grainage fin et ensuite le liant est enlevé dans un four à circulation d'air.
  7. Procédé selon la revendication 5, caractérisé en ce qu'on utilise un papier détachable lisse et à la suite de la fabrication de la matière composite, on produit sur la couche de recouvrement le grainage par empreinte au moyen d'une calandreuse de grainage, la couche de recouvrement étant ensuite le cas échéant imprimée et laquée.
EP19890100625 1988-04-19 1989-01-14 Matériau stratifié en bande enduit à surface grainée fine et son procédé de fabrication Expired - Lifetime EP0338188B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT89100625T ATE87340T1 (de) 1988-04-19 1989-01-14 Bahnfoermiges beschichtetes verbundmaterial mit feinnarbiger oberflaeche und verfahren zu seiner herstellung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3812948A DE3812948C1 (fr) 1988-04-19 1988-04-19
DE3812948 1988-04-19

Publications (3)

Publication Number Publication Date
EP0338188A2 EP0338188A2 (fr) 1989-10-25
EP0338188A3 EP0338188A3 (fr) 1991-08-14
EP0338188B1 true EP0338188B1 (fr) 1993-03-24

Family

ID=6352279

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19890100625 Expired - Lifetime EP0338188B1 (fr) 1988-04-19 1989-01-14 Matériau stratifié en bande enduit à surface grainée fine et son procédé de fabrication

Country Status (10)

Country Link
US (1) US4892777A (fr)
EP (1) EP0338188B1 (fr)
JP (1) JPH0651952B2 (fr)
KR (1) KR920001021B1 (fr)
AT (1) ATE87340T1 (fr)
BR (1) BR8901822A (fr)
CA (1) CA1302216C (fr)
DE (2) DE3812948C1 (fr)
ES (1) ES2039706T3 (fr)
PT (1) PT90317B (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4003763A1 (de) * 1990-02-08 1991-08-14 Ruiter Ernest De Wasserdampfdurchlaessige, wasserdichte schutzhandschuhe
CN1056660C (zh) * 1997-09-19 2000-09-20 长沙安塑塑料制品厂 针织布基湿式聚氨酯皮革加工方法
US20030162454A1 (en) * 1998-12-30 2003-08-28 Kuo-Ho Kuo Structure of synthetic leather
US7431975B2 (en) * 2002-11-29 2008-10-07 Dzs, L.L.C. Textured composite material
US20050010701A1 (en) * 2003-06-30 2005-01-13 Intel Corporation Frequency translation techniques
US7622408B2 (en) * 2003-07-01 2009-11-24 Dzs, Llc Fabric-faced composites and methods for making same
US20050118394A1 (en) * 2003-11-25 2005-06-02 Kuraray Co., Ltd. Artificial leather sheet substrate and production method thereof
IT1403385B1 (it) * 2010-12-24 2013-10-17 Polifloor S R L Suporto rivestito tipo finta pelle.

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2533976A (en) * 1945-03-01 1950-12-12 Us Rubber Co Leather-like material
ES376679A1 (es) * 1968-08-03 1971-07-01 Pirelli Un procedimiento para la fabricacion de un material susti- tuto del cuero.
NL7011714A (fr) * 1968-08-03 1971-04-01
BE754909A (fr) * 1969-08-14 1971-01-18 Kanegafuchi Spinning Co Ltd Cuir artificiel et procede et appareil pour sa fabrication
US4764412A (en) * 1985-04-04 1988-08-16 Pioneer-Leimel Fabrics, Inc. Highly plasticized laminated vinyl fabric
DE3636349A1 (de) * 1986-10-25 1988-04-28 Huels Chemische Werke Ag Bauteile auf basis von polyphenylenethern und kautschuken sowie verfahren zu ihrer herstellung
DE8702810U1 (fr) * 1987-02-24 1987-06-11 J.H. Benecke Gmbh, 3000 Hannover, De

Also Published As

Publication number Publication date
KR920001021B1 (ko) 1992-02-01
JPH0651952B2 (ja) 1994-07-06
EP0338188A2 (fr) 1989-10-25
ES2039706T3 (es) 1993-10-01
DE3812948C1 (fr) 1989-06-22
JPH01306685A (ja) 1989-12-11
PT90317A (pt) 1989-11-10
ATE87340T1 (de) 1993-04-15
KR890016249A (ko) 1989-11-28
EP0338188A3 (fr) 1991-08-14
BR8901822A (pt) 1989-11-28
DE58903855D1 (de) 1993-04-29
CA1302216C (fr) 1992-06-02
PT90317B (pt) 1994-03-31
US4892777A (en) 1990-01-09

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