EP0914251A2 - Materiau de renforcement, procede de production correspondant et utilisation dudit materiau - Google Patents

Materiau de renforcement, procede de production correspondant et utilisation dudit materiau

Info

Publication number
EP0914251A2
EP0914251A2 EP97940026A EP97940026A EP0914251A2 EP 0914251 A2 EP0914251 A2 EP 0914251A2 EP 97940026 A EP97940026 A EP 97940026A EP 97940026 A EP97940026 A EP 97940026A EP 0914251 A2 EP0914251 A2 EP 0914251A2
Authority
EP
European Patent Office
Prior art keywords
reinforcing material
carrier
diisocyanate
layer
polyurea
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.)
Withdrawn
Application number
EP97940026A
Other languages
German (de)
English (en)
Inventor
Georg Adolphs
Núria MOR
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.)
Emfisint Automotive Sa
Original Assignee
Emfisint Automotive Sa
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 Emfisint Automotive Sa filed Critical Emfisint Automotive Sa
Publication of EP0914251A2 publication Critical patent/EP0914251A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • B32B29/08—Corrugated paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/08—Impregnating
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
    • D21H17/57—Polyureas; Polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/08—Reinforcements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2317/00—Animal or vegetable based
    • B32B2317/12—Paper, e.g. cardboard
    • B32B2317/127—Corrugated cardboard
    • 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
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/30—Multi-ply
    • D21H27/40—Multi-ply at least one of the sheets being non-planar, e.g. crêped

Definitions

  • the present invention relates to a reinforcing material comprising a cardboard-based carrier and a polyurea. More specifically, the invention relates to a reinforcing material in which the cardboard-based carrier is penetrated by the polyurea and which i.a. as reinforcement of molded parts made of sheet metal,
  • Textiles or plastics such as a roof of a motor vehicle, can be used.
  • the present invention further relates to a method for producing the reinforcing material.
  • Reinforcing materials consisting of a carrier and additional substances which improve the mechanical strength of the carrier are known and are used for a wide variety of purposes.
  • resin-coated paper and cardboard boxes are known, and a wide variety of synthetic resins are used, such as Polyurethanes, phenolic resins and the like.
  • Paper or cardboard as a carrier material has great advantages because of its relatively low price and because it is available as a practically unlimited raw material.
  • such paper or cardboard-based surface-coated materials include the disadvantage that they are not resistant to moisture and wet.
  • To the materials in addition to strength and mechanical stability also resistance to
  • the paper or cardboard carriers are usually impregnated with a synthetic resin, although many synthetic resins, such as polyurethanes, cannot be used, since their relatively high viscosity means that they do not penetrate into the paper or the cardboard without the use of a solvent. can penetrate.
  • synthetic resins such as polyurethanes
  • the paper or cardboard is impregnated with a solution of a polyurethane in an organic solvent, it is difficult, if not impossible, to remove the solvent without residue before the intended use of the reinforced paper or cardboard remove. This causes health problems, especially when using the reinforced paper or cardboard in closed or insufficiently ventilated rooms.
  • paper or cardboard-based supports impregnated with phenol-formaldehyde resins are unsuitable for indoor use because of the health hazard of formaldehyde.
  • the present invention is therefore based on the object of providing a reinforcing material with a carrier based on cardboard which retains the advantages of the known materials of the generic type but no longer has their disadvantages.
  • the invention has for its object to provide a reinforcing material of the type mentioned, which is inexpensive to manufacture, even has a high mechanical strength, a material reinforced with it, such as e.g. a sheet metal or sheet metal part, also gives excellent mechanical strength, is resistant to moisture and moisture, is harmless to health and is excellent with the materials to be reinforced, e.g. can be connected by gluing.
  • Reinforcing materials are reinforced to provide.
  • the invention is essentially based on the knowledge that a reinforcing material with a paper or cardboard base, which has the desired properties, can be produced by impregnating a paper or cardboard base with a diisocyanate, which by existing in the carrier or possibly added to the carrier
  • the reinforcing material according to the invention is suitable due to its excellent bondability for reinforcing molded parts made of sheet metal, textiles or plastics or composite materials made of these materials and can be used in particular as an internal reinforcement in the roof area of motor vehicles, in particular passenger vehicles.
  • the reinforcement ribs are usually glued to the roof panel, but this means that reinforcement can only be achieved to a certain degree, since the number of reinforcement ribs is restricted to a relatively small number for reasons of cost and weight.
  • the reinforcement material it is possible, with the shape of the reinforcement material and the material to be reinforced, e.g. of the motor vehicle roof to glue them together over the entire surface, whereby a substantial improvement in the dimensional stability of the motor vehicle roof can be achieved.
  • Fig. 1 shows a cross section of a reinforcing material with two corrugated
  • FIG. 2 shows a concentration profile of the polyurea over the cross section of the reinforcing material according to the invention according to FIG. 1;
  • FIG. 3 shows a cross section of a reinforcing material according to the invention with three corrugated layers;
  • FIG. 4 shows a concentration profile of the polyurea over the cross section of the reinforcing material according to the invention according to FIG. 3;
  • FIG. 5 shows a cross section of a molded part reinforced with a reinforcing material according to the invention, for example a sheet metal from the area of a motor vehicle roof;
  • FIG. 6 shows a cross section of a decorative material reinforced with a reinforcing material according to the invention.
  • any e.g. Paper defined in DIN 6730 may be used, preferably a cardboard or a cardboard with a weight of 1 50 g or more.
  • the material for the carrier is also referred to as cardboard for the sake of simplicity. It is essential to the invention that the carrier material can be impregnated with the diisocyanate.
  • the cardboard-based carrier is preferably constructed in multiple layers.
  • a layer of corrugated cardboard a so-called corrugated layer of e.g. Wrapping paper, either on one or both sides, with a flat cardboard, a so-called cover card (e.g. test or kraft liner), as with the known corrugated cardboard, glued.
  • cover card e.g. test or kraft liner
  • Layers of a honeycomb-structured intermediate layer can be used, which can be covered with a cover cardboard on one or on both open sides of the honeycomb structure.
  • the carrier is constructed in such a way that at least two corrugated or honeycomb-shaped layers are present, these layers being by means of a cover layer (e.g. intermediate layer or
  • Such a carrier material can be built up only from corrugated or honeycomb-shaped layers, or can have both types of layers. Furthermore, more than two corrugated or honeycomb layers with a corresponding number of
  • intermediate layers and the two outer cover boxes are present.
  • the distances between the intermediate or cover cartons can be constant or to be different.
  • the corrugated or honeycomb-shaped layers serve as spacers between the flat intermediate or cover layers (cover boxes), which on the one hand achieves a weight-saving construction and on the other hand forms a sandwich structure which is relatively solid per se, ie without resin impregnation.
  • FIG. 1 A reinforcing material according to the invention with two corrugated layers (corrugated layers) is shown in FIG. 1, the reference numerals 1 an upper layer (for example test or kraft liner), 2 a first corrugated layer (for example corrugated or Schrenz paper), 3 an intermediate layer (eg Schrenzpapier), 4 a second corrugated layer
  • the corrugated layers 2 and 4 have a different thickness.
  • the reinforcing materials according to the invention have a total thickness of approximately 4 mm to approximately 30 mm, preferably approximately 6 mm to approximately 12 mm.
  • Cartons of about 40 g / m 2 to about 500 g / m 2 are used as cover or intermediate layers, and the corrugated or honeycomb-shaped layers have a thickness of usually about 8 mm to about 28 mm, preferably 8 mm to 14 mm .
  • the distances between the intermediate or cover layers can be constant or different from one another.
  • the strength of this sandwich structure and above all the moisture resistance is significantly improved by the resin impregnation.
  • the cardboard is impregnated in such a way that the cardboard is permeated with the diisocyanate over essentially its entire cross section.
  • the impregnation is preferably carried out in such a way that an increased resin content is achieved in the outer cover layers, i.e. that there is an integral concentration profile of the polyurea over the cross section of the carrier, with decreasing concentration from the outer top surfaces of the carrier to it Middle.
  • an integral concentration profile is illustrated in FIG. 2.
  • the total thickness of the reinforcing material is approximately 1 2 mm and the resin mass fraction in the carton is given in% by weight, based on the total weight of carton and polyurea.
  • FIG. 3 shows a reinforcing agent according to the invention with three corrugated layers.
  • the reference numerals 1 and 5 each mean outer layers (test or kraft liner), 2 and 4 each corrugated layers (made of e.g. weft paper) and 3 intermediate layers (e.g. made of wreath paper). With a reinforcement material constructed in this way, a concentration profile of the impregnated resin as shown in FIG. 4 can result.
  • the resin mass fraction in the reinforcing materials according to the invention is in the range from approximately 4% by weight to approximately 30% by weight, preferably approximately 5% by weight to approximately 15% by weight.
  • the resin mass fraction is less than about 4% by weight, sufficient strength improvement and moisture resistance are not achieved, and above about 30% by weight the strength and moisture resistance can no longer be improved, but there are unnecessary material costs and the reinforcing material becomes too heavy overall.
  • the reinforcement material according to the invention is also excellent with other materials, for example a bodywork sheet, glued.
  • the reinforcing material according to the invention is also distinguished by excellent dimensional stability in a wide temperature range.
  • a reinforcing material according to the invention bonded to a body panel shows only very little thermal dilatation in the event of temperature changes, in contrast to more recent developments of reinforcing materials based on thermoplastic, which tend to deform the composite material due to the thermal dilatation and moreover soften at temperatures above approximately 100 ° C. .
  • the reinforcing material according to the invention has acoustic damping properties and acts as additional cushioning in the event of an impact, which is important with regard to the accident protection of the occupants of a motor vehicle when used as reinforcement in the roof area.
  • Fig. 5 is the use of the reinforcing material according to the invention as reinforcement of a sheet or other part of a motor vehicle, e.g. one
  • Roof body sheet metal illustrated.
  • the reference numerals mean: 10 a cross section of the entire construction, 1 1 the material to be reinforced (for example a body panel), 1 2 an adhesive layer, 13 the reinforcing material according to the invention, 14 an optionally introduced foam layer of, for example, polyurethane or an air space between the Headliner and the reinforcement material and 1 5 a decorative layer or a headliner (headliner).
  • a construction can be, for example, a motor vehicle roof with an interior lining (headlining).
  • the reinforcing material according to the invention is used to reinforce a molded part, e.g. of a roof body sheet is used, its shape is adapted to the sheet in the manufacture in order to achieve a full-surface gluing and thus an optimal reinforcement.
  • the reinforcing material can also keep a flat shape.
  • the reference numerals 21 mean a decorative material, e.g. a textile decorative material, 22 an optional adhesive layer and 23 a reinforcing material according to the invention.
  • the reference numeral 24 (dash-dotted line) is intended to indicate that the construction can be constructed symmetrically (i.e. with further layers 22 and 21 on the other side of the reinforcing material 23) or that the layers shown in Fig. 6 can be connected to other materials.
  • the reinforcing material according to the invention can be used in the motor vehicle in the areas of door linings, trunk flooring, parcel shelf, etc. as reinforcement.
  • the polyurea is formed in the carrier material by reacting the diisocyanate previously introduced by impregnation with water.
  • This polymerization or polycondensation reaction proceeds with elimination of carbon dioxide via diamines formed as intermediates, which react rapidly with excess diisocyanate to give polyurea.
  • the moisture content in the carton to be impregnated should therefore be at least 3% by weight and preferably slightly above the stoichiometric reaction equilibrium of the diisocyanate used and should be adjusted accordingly by drying or adding water.
  • Cardboard can also be sprayed specifically with water or possibly with dilute acid to accelerate the reaction before the molding process (eg deep drawing) become.
  • Any diisocyanate can be used to produce the reinforcing materials according to the invention, provided that it can be brought into a viscosity in monomeric or oligomeric form without the addition of solvent and without the use of too high a temperature at which a premature reaction would occur, which makes it possible to impregnate the cardboard .
  • the viscosity when impregnating the carton should not be higher than about 250 mPa-s, preferably not higher than about 150 mPa-s, measured according to DIN 5301 8, at a temperature of 25 ° C.
  • 4,4'-Methyle ⁇ d ⁇ phenyl isocyanate
  • 2,4'-MDI and 2,2'-MDI are preferred.
  • an oligomer of one of the diisocyanates mentioned can also be used alone or in a mixture with other monomers or oomers of the isomeric compounds.
  • Usual, i.e. commercially available MDI monomer or polymer consists of a mixture of the different isomers, for example 2,2'-MDI (less than 1%), 2,4'-MDI (between 2% and 5% ), the rest is 4,4'-MDI.
  • Polymeric or oligomeric MDI usually consists of about 40% dnsocyanates, about 20 - 25% trnsocyanates, the rest consists of polymer chains with more than three isocyanate building blocks Functionality, which is usually 2.0 to about 3.1.
  • the reinforcing material according to the invention can also be provided with further layers.
  • a moisture barrier layer between the sheet and the reinforcing material, which layer can consist, for example, of a polyurethane, polypropylene or polyethylene film.
  • Resin impregnation of the reinforcing materials according to the invention can, however, also dispense with the moisture barrier layer.
  • a decorative layer composed of different flat structures known per se, such as, for example, a printed nonwoven or a textile fabric or knitted fabric, can be applied as the inside finish.
  • a so-called headliner headliner
  • an air layer the so-called head space
  • the decorative layer can be applied to the headliner.
  • the individual layers of the aforementioned construction are preferably connected to one another as well as to the body panel by gluing.
  • Any of the adhesives known in the art can be used as the adhesive, preferably polyamide-based hot melt adhesive.
  • the reinforcing materials according to the invention can be produced in the following way:
  • a single or multi-layer cardboard-based carrier as described above is cut to the desired shape and size.
  • the carrier is then impregnated with the diisocyanate or the mixture of diisocyanates.
  • the impregnation is carried out by spraying, printing or pouring the diisocyanate onto the support. Both are preferably impregnated Sides of the carrier in order to achieve an even distribution of resin in the carrier material.
  • the parameters, such as temperature and viscosity of the diisocyanate, pressure and amount of the diisocyanate when applied to the carrier, moisture content of the carrier carton and the like are set in dependence on the materials used in such a way that, as far as possible, one as shown in FIG. 2 or 3 , integral concentration profile of the resin is achieved over the entire cross section of the carrier, it being important to ensure that the carrier carton is impregnated with the diisocyanate over substantially the entire cross section.
  • the support is heated to a temperature at which the polymerization reaction is carried out in a sufficiently short time.
  • the temperature is usually in the range from 120 ° C. to 90 ° C. At this temperature, the polymerization is almost completely completed in a period of at least 40 seconds to about 3 minutes, the residual curing at a lower temperature, e.g. by storage at room temperature.
  • the reaction can be accelerated by adding a catalyst.
  • the base material and the polyurea that forms are deformable and can therefore be molded in a suitable heated molding tool, e.g. by pressing,
  • the impregnated cardboard can be thermoformed on one or both sides with a textile decorative material.
  • the textile decorative material can be a woven fabric, foam-laminated fabric, nonwoven fabric (needle felt), foam-laminated nonwoven fabric or also an embossed or embossed and foam-laminated film made of polyurethane, polypropylene, polyvinyl chloride, EPDM and the like, which can be printed with a decor.
  • the mold half facing the decorative material is heated to a lower temperature (depending on the decorative material, e.g. to about 80 ° C - 90 ° C), the mold half facing away from the decorative material is heated to approximately
  • the reinforcing material is removed from the mold, cooled, and then, if desired, provided with further layers before it is used for further determination, for example an adhesive bond with an identical body panel.
  • the reinforcing material according to the invention has excellent properties with regard to dimensional stability, moisture resistance, temperature resistance, harmlessness to health and the like and is therefore outstandingly suitable as a reinforcement of molded parts made of sheet metal, textiles or plastics and composite materials made from these materials.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Laminated Bodies (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

L'invention concerne un matériau de renforcement composé d'un support à base de carton et d'un polycarbamide. Le support à base de carton est imprégné de polycarbamide sur sensiblement toute sa coupe transversale. Ce matériau de renforcement (13) est particulièrement adapté pour être collé (12) aux pièces façonnées en tôle (11), textile (15), matières plastiques ou encore composites de ces matériaux. L'invention concerne également un procédé de production correspondant.
EP97940026A 1996-07-26 1997-07-24 Materiau de renforcement, procede de production correspondant et utilisation dudit materiau Withdrawn EP0914251A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19630408 1996-07-26
DE19630408A DE19630408A1 (de) 1996-07-26 1996-07-26 Verstärkungsmaterial, Verfahren zu seiner Herstellung und Verwendung davon
PCT/EP1997/004039 WO1998004413A2 (fr) 1996-07-26 1997-07-24 Materiau de renforcement, procede de production correspondant et utilisation dudit materiau

Publications (1)

Publication Number Publication Date
EP0914251A2 true EP0914251A2 (fr) 1999-05-12

Family

ID=7801066

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97940026A Withdrawn EP0914251A2 (fr) 1996-07-26 1997-07-24 Materiau de renforcement, procede de production correspondant et utilisation dudit materiau

Country Status (4)

Country Link
EP (1) EP0914251A2 (fr)
JP (1) JP2000515823A (fr)
DE (1) DE19630408A1 (fr)
WO (1) WO1998004413A2 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7798549B2 (en) * 2008-10-30 2010-09-21 Honda Motor Co., Ltd. Trunk liner method and apparatus
PL2186940T3 (pl) 2008-11-14 2013-05-31 Ruehl Puromer Gmbh Sposób ciągłej produkcji impregnowanych papierowych plastrów miodu
ES2728777T3 (es) 2014-12-22 2019-10-28 Magna Steyr Fahrzeugtechnik Ag & Co Kg Componente de sándwich

Family Cites Families (9)

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Publication number Priority date Publication date Assignee Title
US3785911A (en) * 1971-06-29 1974-01-15 Exxon Research Engineering Co Metallic appearing laminate
JPS63251486A (ja) * 1987-04-07 1988-10-18 Nippon Koonsutaac Kk 段ボ−ル用接着剤
JPH0623355B2 (ja) * 1988-08-01 1994-03-30 松谷化学工業株式会社 段ボール用接着剤組成物
AU2557592A (en) * 1991-08-30 1993-04-05 Weyerhaeuser Company Polyurea-cellulose composites and methods for their manufacture
CA2120524A1 (fr) * 1991-10-02 1993-04-15 George T. Tiedeman Materiaux a base de polyuree-resine renforcee de fibres
DE4223604A1 (de) * 1992-07-17 1994-01-20 Mueller Schulte Detlef Dr Verfahren zur Nassverfestigung von Cellulose, Papier, Papierderivaten sowie Formteilen oder Preßmassen derselben
US5459222A (en) * 1993-06-04 1995-10-17 Ciba-Geigy Corporation UV-absorbing polyurethanes and polyesters
US6187892B1 (en) * 1995-06-07 2001-02-13 Bayer Corporation Method of making a coated substrate with polyurethane/urea contact adhesive formulations and the coated substrate by this method
DE19548030A1 (de) * 1995-12-21 1997-06-26 Bayer Ag Verwendung wässriger Dispersionen nachvernetzbarer Beschichtungsmittel zur Textil- und Lederbeschichtung

Non-Patent Citations (1)

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Title
See references of WO9804413A2 *

Also Published As

Publication number Publication date
WO1998004413A3 (fr) 1998-03-12
WO1998004413A2 (fr) 1998-02-05
JP2000515823A (ja) 2000-11-28
DE19630408A1 (de) 1998-01-29

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