EP2408615A1 - Éléments adhérents comportant une couche d'adhésif - Google Patents

Éléments adhérents comportant une couche d'adhésif

Info

Publication number
EP2408615A1
EP2408615A1 EP10710307A EP10710307A EP2408615A1 EP 2408615 A1 EP2408615 A1 EP 2408615A1 EP 10710307 A EP10710307 A EP 10710307A EP 10710307 A EP10710307 A EP 10710307A EP 2408615 A1 EP2408615 A1 EP 2408615A1
Authority
EP
European Patent Office
Prior art keywords
layer
foam
composite element
cover layer
element 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.)
Withdrawn
Application number
EP10710307A
Other languages
German (de)
English (en)
Inventor
Jörn KÜSTER
Klaus Becker-Weimann
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.)
Kleiberit SE and Co KG
Original Assignee
Klebchemie MG Becker GmbH and Co 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 Klebchemie MG Becker GmbH and Co KG filed Critical Klebchemie MG Becker GmbH and Co KG
Publication of EP2408615A1 publication Critical patent/EP2408615A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

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    • B32B7/04Interconnection of layers
    • B32B7/12Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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    • B32B11/00Layered products comprising a layer of bituminous or tarry substances
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    • B32B11/046Layered products comprising a layer of bituminous or tarry substances comprising such bituminous or tarry substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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    • B32B11/04Layered products comprising a layer of bituminous or tarry substances comprising such bituminous or tarry substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B11/048Layered products comprising a layer of bituminous or tarry substances comprising such bituminous or tarry substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
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Definitions

  • the present invention relates to composite elements and their preparation.
  • Composite elements e.g., sandwich panels
  • a core of foamed material e.g., PIR, PUR, phenolic resin
  • the foamed materials can usually form some adhesion to the cover layers during the foaming and curing process, this is for later use of the composite materials - e.g. as components - not always sufficient. Therefore, the cover layers are provided in part before the application of the foamed material with a primer.
  • the materials used for the core are foamed in situ by applying a 2K reactive mixture to a topcoat. Due to the chemical reaction of the two components of the reactive mixture, this foams up and begins to cure within a few minutes.
  • Adhesion promoters are generally 2K systems which are also used at room temperature. These are advantageously adjusted so that they are not cured when contacted with the intumescent material and can thus enter into a chemical compound with this.
  • EP-A 1 516 720 describes composite elements with a foam layer in which a two-component polyurethane adhesive is used as adhesion-promoting layer.
  • a primer layer for adhesion promotion between a polyisocyanurate or polyurethane foam and a metal top plate is also described in WO-A 99/00559.
  • An object of the present invention is thus to provide such composite elements with adhesion promoters.
  • a composite element having a first and a second cover layer, wherein between the first and second cover layer is a foam layer and the interface between the foam layer and at least one cover layer has a primer layer, wherein the primer layer is a hot-liquid, solid at room temperature hot melt adhesive contains.
  • a (one-component) hot-liquid, solid at room temperature hot melt adhesive in contrast to the known from the prior art two-component systems has advantageous properties without the adhesion promoter properties are adversely affected. For example, no reactivation of the primer or primer system is required. Furthermore, no errors in the mixing ratio, such as in 2-component systems occur. Complete hardening of the bonding agent layer is always ensured (cooling), regardless of the process conditions of the 2K mixing and dosing system when using a hotmelt adhesive. The same applies to the chemical post-crosslinking in reactive hot melt adhesives, which is ensured either by diffusion of atmospheric moisture in the interface surface layer / primer (adhesion promoter) or by reaction with the reactive constituents of the applied foam mixtures.
  • the reaction begins immediately with the merging of the two components.
  • the 2K system reacts chemically within a few minutes, especially if it is a 2K PU system as a bonding agent.
  • a hot-liquid, solid at room temperature hot melt adhesive needed after
  • the physical strength structure (cooling) is not necessarily a further chemical reaction to build strength, but it can advantageously chemically ausureagieren to achieve a higher heat resistance, but this is done over a longer period.
  • Typical polyurethane-based or polyolefin-based hot melt adhesives require several days for this. This longer process window has a positive effect on the production process in such a way that the production of a composite element can even be carried out at least partially discontinuously.
  • the time window in which chemical reactions with the foam layer are possible substantially longer.
  • the (reactive) hot melt adhesive systems are solid for a short time after application, but still have a long time reactivity to the foam layer (see above).
  • the provided with primer coatings are thus much easier to handle (no bleeding, dripping down of the primer).
  • hot melt adhesives do not require harmful aerosols and are therefore to be preferred in terms of occupational safety and health protection.
  • Hot-liquid, solid at room temperature hot melt adhesives are known in the art as such. They are often called “hot melts” or “hotmelts”. As the name suggests, such substances serve as adhesives and are suitable and known for example in the packaging industry for bonding paper or in the furniture and wood industry, for example as a laminate and bookbinding. Reactive hotmelts are sold, for example, as PUR-SK series by the company Klebchemie M.G. Becker GmbH & Co. KG, Weingarten (Germany).
  • Such hot melts are often based on polyamides, polyethylenes, amorphous poly- ⁇ -olefins, ethylene-vinyl acetate copolymers, polyesters, polyurethane, polyolefins or copolyamide elastomers.
  • an adhesion action of the adhesion promoter layer is not exclusive physical hardening (cooling). Rather, it is preferred if the hot melt adhesive additionally hardens by chemical reaction.
  • the adhesion promoter layer may also contain further adhesion-promoting agents (acrylates, silanes, etc.). Preferably, however, the adhesion promoter layer consists exclusively of the hotmelt adhesive. If the second cover layer also has an adhesion promoter layer, this may be the same as or different from that for the first cover layer. Preferably, however, at
  • Adhesion promotion for both outer layers used the same adhesive layer material. This is especially true in the event that the material of the first and second
  • a particularly preferred adhesion promoter layer in the context of the present invention comprises a polymer or consists of a polymer based on a moisture-crosslinking polyurethane.
  • the term "contains” should also include the case that the primer layer consists solely of the hot melt adhesive.
  • the term "hot-liquid” means that the material is applied in a liquid state at least to the first cover layer.
  • the material should be solid at room temperature.
  • the strength at room temperature is achieved on the one hand by cooling and can also be further promoted by chemical reaction with the environment in addition.
  • cooling with the reaction of isocyanate groups present in the polymer with ambient humidity can contribute to further crosslinking of the polymer and thus to solidification.
  • radiation curing - such as UV curing - can be carried out for corresponding systems.
  • the polymers used in the present invention typically have a melting point in the range of 50 to 200 0 C.
  • Suitable foam layers are known in the art. These can already be applied as such or generated in situ on a cover layer.
  • PIR polyisocyanurates
  • PU polyurethanes
  • phenolic resins to call.
  • PIRs are used, as described, for example, in EP-A 1 516 720.
  • the foam layer is a generally known polyisocyanurate foam which is preferably used as a heat-insulating layer in the
  • the polyisocyanurate foam forming the foam layer can be obtained, for example, by reacting components a) polyisocyanates with b) compounds which are reactive towards isocyanates, in the presence of c)
  • reaction ratio is chosen so that in the reaction mixture, the ratio of the number of isocyanate groups to the number of isocyanate-reactive groups 1.8 to 8: 1, preferably 1.9 to 4: 1.
  • the isocyanurate catalyst c) used are generally the isocyanurate group-forming catalysts known from the prior art, preferably alkali metal salts, such as potassium octoate and / or potassium acetate, alone or in combination with tertiary amines.
  • alkali metal salts such as potassium octoate and / or potassium acetate
  • the Isocyanurat Guess preferably takes place at temperatures above 60 0 C.
  • blowing agent (d) As propellant (d) generally so-called physical blowing agents and optionally water are used. Physical blowing agents are understood as meaning compounds which are dissolved or emulsified in the starting materials of the polyurethane preparation and evaporate under the conditions of polyurethane formation. These are, for example, hydrocarbons, halogenated hydrocarbons, and other compounds, such as perfluorinated alkanes, such as perfluorohexane, chlorofluorocarbons, and ethers, esters, ketones and / or acetals. In addition, it is possible to dissolve inert gases, such as nitrogen, carbon dioxide or noble gases under pressure in the polyurethane building components.
  • inert gases such as nitrogen, carbon dioxide or noble gases under pressure in the polyurethane building components.
  • the blowing agent (d) is generally used in an amount such that the resulting polyisocyanurate foams have a density of from 20 to 300 g / l, preferably from 30 to 100 g / l, particularly preferably from 35 to 80 g / l.
  • the PIR foam is a
  • Rigid foam i. the foam has a compressive stress at 10% compression or compressive strength according to DIN 53 421 / DIN EN ISO 604 greater than or equal to 100 kPa.
  • the rigid foam generally has a DIN ISO 4590 on a Closed cell size of greater 85%, preferably greater than 90%.
  • the PIR foam preferably has an average cell diameter of from 10 to 600 ⁇ m, preferably from 50 to 400 ⁇ m, measured according to ASTM 3576-77.
  • the adhesion promoter layer has an average layer thickness in the range from 1 to 500 ⁇ m; More preferably in the range of 20 to 250 microns; More preferably in the range of 20 to 120 microns and more preferably in a range of 20 to less than 50 microns, such as 45 microns or 40 microns.
  • the term "average layer thickness" in the context of the present invention means that the thickness of the layer can vary and it is sufficient for the purposes of the present invention if the layer thickness averaged over the entire area lies within the stated range. However, it is preferred that no full area application takes place, so that partial areas occur at which the layer is interrupted. Nevertheless, preferably on average, the strength ranges given above should be fulfilled.
  • first and second cover layers are basically all commonly used, flexible and rigid cover layers, such as metals such as aluminum, steel, in particular pre-primed steel sheets (coil coating sheets), bitumen, paper, mineral nonwovens, nonwoven fabrics containing organic fibers, plastic (eg Polystyrene, PVC, GRP, ABS), plastic films (eg PE film), wood panels, stone, ceramics or mixtures or laminates thereof, can be used.
  • metals such as aluminum, steel, in particular pre-primed steel sheets (coil coating sheets), bitumen, paper, mineral nonwovens, nonwoven fabrics containing organic fibers, plastic (eg Polystyrene, PVC, GRP, ABS), plastic films (eg PE film), wood panels, stone, ceramics or mixtures or laminates thereof, can be used.
  • plastic eg Polystyrene, PVC, GRP, ABS
  • plastic films eg PE film
  • wood panels eg stone, ceramics or mixtures or laminates thereof
  • First and second cover layers may be the
  • Another object of the present invention is a method for producing a composite element according to the invention comprising the steps
  • the adhesion promoter layer is physically solidified on its surface before step (c) and, in particular, that the material is no longer able to flow due to the cooling process, but the crystallization process necessary for the final physical strength build-up has not yet been completed. This has the advantage that a problem-free application of the components for the foam layer is possible.
  • the adhesion promoter layer cures completely chemically after step (d), ie after completion of the composite element. This allows a longer process window for the production of the composite element according to the invention.
  • An advantage of the hot-liquid room temperature solid hot melt adhesive for the present invention is that it is applied in a liquid state. As a result, a simplification in handling when applying the adhesive layer compared to 2K systems is possible. This also avoids overspray, which is often associated with 2K systems with aerosol formation and represents a significant occupational hygiene disadvantage.
  • the primer layer for the present invention may preferably be applied in a simple manner by means of a roller, a doctor blade, a slot die, curtain coating or by spraying (in thread form). Such a step can be easily incorporated into the existing composite element manufacturing facility. A special handling of the cover layers to be coated is not required in principle.
  • the material for the primer layer is first applied to a transfer agent, which in turn applies the layer or material formed on the top surface.
  • the transfer means may be one or more rolls or one or more strips or combinations thereof.
  • the order for the transfer means i. the application of the hot-liquid material
  • the order for the transfer means is separated in time from the generation of the primer layer, if necessary, for example, to allow a cooling or certain tempering.
  • the material for the primer layer is applied in a hot liquid state.
  • the temperature of the material during application is preferably in the range from 80 ° C. to 190 ° C. It is further preferred that the temperature is in the range from 100 ° C. to 130 ° C.
  • the temperature may also assume higher values, for example up to 220 ° 0 C, wherein preferably the application to the cover layer, however, takes place in the above-mentioned temperature range.
  • non-reactive hot melt adhesives may require higher application temperatures of up to 280 ° C because of their chemical and physical properties.
  • steps (b) and (c) take place in discontinuous mode of operation in the method according to the invention for producing a composite element.
  • it can be done both a continuous and a discontinuous driving.
  • continuous driving is preferred.
  • the discontinuous driving style It is possible to design the production of cover layers provided with a primer layer as an endless belt analogous to existing coil coating processes or else the temporal and / or spatial separation of the application of the adhesion promoter layer from the application of the foam or its components also a high flexibility with regard to the selected blowing agent for the foam (n-, i-, cyclo-pentane, 365mfc, 245fa, 134a, formic acid, water).
  • the selected blowing agent for the foam n-, i-, cyclo-pentane, 365mfc, 245fa, 134a, formic acid, water.
  • step (d) of the method according to the invention the foam layer is brought into contact with the second cover layer.
  • This can be done, in particular, by bringing the second cover layer into contact by foaming the foam layer.
  • the second cover layer can also be supplied by application to the foam layer or bringing into contact takes place both by applying the second cover layer and by foaming the foam layer.
  • first and second cover layers wherein at least one of the two cover layers has a primer layer containing a hot-liquid, solid at room temperature hot melt adhesive, so that a gap between the first and second cover layer occurs, and in this space the Foam layer-forming components introduces and can foam.
  • a further subject of the present invention is therefore a method for producing a composite element according to the invention comprising the steps
  • This method is particularly suitable for a discontinuous driving style.
  • Preferred embodiments correspond to those for the above-mentioned likewise inventive method.
  • the bonding agent layer is physically solidified on its surface prior to introduction of the components of the foam layer. It is likewise advantageous if the bonding agent layer hardens completely chemically after step (b). Also applies to the application of the primer layer, the above.
  • the composite element according to the invention can be used, for example, as a thermal insulation element, i. used as a composite element for thermal insulation, as proposed in EP-A 1 516 720. Accordingly, a thermal conductivity of the composite element is preferred which is less than 35 mW / mK, more preferably less than 25 mW / mK, measured according to DIN 52612 Part 1.
  • the layers of the composite element according to the invention have the following average layer thicknesses.
  • the cover layers independently have an average layer thickness of 200 ⁇ m to 5 mm, preferably 300 ⁇ m to 2 mm, particularly preferably 400 ⁇ m to 1 mm.
  • the foam layer preferably has an average layer thickness of from 2 cm to 25 cm, preferably from 2.5 cm to 20 cm, particularly preferably from 3 cm to 15 cm.
  • KLEIBERIT PUR SK 703.5 Application of the KLEIBERIT PUR SK 703.5 to steel sheet prior to introducing the PUR or PIR foam improves the adhesion of the foam to the steel sheet.
  • the manual lifting test leads to a partial adhesion loss of the foam to the steel sheet without prior application of the KLEIBERIT PUR SK 703.5.
  • Test specimens with spray-on KLEIBERIT PUR SK 703.5 show a full-surface material breakage of the foam. To lift the foam higher forces are required compared to non-pretreated steel sheets.
  • KLEIBERIT PUR SK 703.5 Application of the KLEIBERIT PUR SK 703.5 to steel sheet before introducing the PUR or PIR foam improves the adhesion of the foam to the steel sheet.
  • the manual lifting test leads to a partial adhesion loss of the foam to the steel sheet without prior application of the KLEIBERIT PUR SK 703.5.
  • Test specimens with spray-on KLEIBERIT PUR SK 703.5 show a full-surface material breakage of the foam. To lift the foam higher forces are required compared to non-pretreated steel sheets.
  • the two examples demonstrate that a primer PURSK the adhesion between steel and foam in the two very critical cases of an n-pentane-driven PIR foam Example 1 and a pure water-driven PIR foam with high index Example 2 so far improved that instead a loss of adhesion steel foam a material break in the foam is observed. That is, the adhesion exceeds the cohesion of the foam.

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  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne un élément adhérent comprenant une première et une seconde couche de protection et comportant, entre ces deux couches de protection, une couche de mousse, l'interface entre la couche de mousse et l'une au moins des couches de protection comportant quant à elle une couche d'adhésif. En l'occurrence, l'élément adhérent de l'invention est caractérisé en ce que la couche d'adhésif contient une colle fondue qui est liquide à chaud et qui prend à température ambiante. L'invention concerne également un procédé de fabrication d'un tel produit.
EP10710307A 2009-03-20 2010-03-22 Éléments adhérents comportant une couche d'adhésif Withdrawn EP2408615A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102009013712A DE102009013712A1 (de) 2009-03-20 2009-03-20 Verbundelemente mit Haftvermittlerschicht
PCT/EP2010/053695 WO2010106189A1 (fr) 2009-03-20 2010-03-22 Éléments adhérents comportant une couche d'adhésif

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EP2408615A1 true EP2408615A1 (fr) 2012-01-25

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WO (1) WO2010106189A1 (fr)

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DE102012017529A1 (de) * 2012-09-04 2014-03-06 Gottlieb Binder Gmbh & Co. Kg Abdecksystem für Isolationseinrichtungen an Bau- und Tragwerken
DE102015117201A1 (de) * 2015-10-08 2017-04-13 Bwg Bergwerk- Und Walzwerk-Maschinenbau Gmbh Verfahren und Anlage zum kontinuierlichen Herstellen von Verbundbändern oder -blechen
DE102018005393A1 (de) * 2018-07-09 2020-01-09 Fahrzeugwerk Bernard Krone GmbH & Co. KG Verfahren zur Herstellung von Sandwich-Paneelen für insbesondere Nutzfahrzeugaufbauten von Kühlfahrzeugen
US11794450B2 (en) 2020-12-18 2023-10-24 Altria Client Services Llc Polymer-laminated metal lid

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DE4101806A1 (de) * 1991-01-23 1992-07-30 Basf Ag Schockabsorbierende propylenpolymer-verbundformteile
DE4109397A1 (de) 1991-03-22 1992-09-24 Agrodur Grosalski & Co Verfahren zur herstellung eines metall-kunststoffverbundes
DE4419449A1 (de) * 1994-06-03 1995-12-07 Henkel Kgaa Schnell abbindender Polyurethan-Schmelzklebstoff
US6096416A (en) 1997-06-26 2000-08-01 Altenberg; Milton J. Metal sandwich panels
FR2772778B1 (fr) * 1997-12-19 2002-03-29 Ato Findley Sa Adhesif polyurethane reticulable par l'humidite, procede de collage d'un textile et d'un materiau cellulaire au moyen dudit adhesif et assemblage colle ainsi obtenu
TW200305587A (en) * 2002-03-19 2003-11-01 Rohm & Haas Urethane polymer compositions
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JP4381941B2 (ja) * 2004-09-17 2009-12-09 王子インターパック株式会社 自動車内装天井材用の積層部材
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EP2060378A1 (fr) * 2007-11-14 2009-05-20 Alcan Technology & Management Ltd. Procédé de fabrication d'un matériau composite

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WO2010106189A1 (fr) 2010-09-23

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