EP2424726A1 - Verwendung eines verbundwerkstoffes auf basis eines einkomponenten-polyurethanklebstoffes - Google Patents

Verwendung eines verbundwerkstoffes auf basis eines einkomponenten-polyurethanklebstoffes

Info

Publication number
EP2424726A1
EP2424726A1 EP10715826A EP10715826A EP2424726A1 EP 2424726 A1 EP2424726 A1 EP 2424726A1 EP 10715826 A EP10715826 A EP 10715826A EP 10715826 A EP10715826 A EP 10715826A EP 2424726 A1 EP2424726 A1 EP 2424726A1
Authority
EP
European Patent Office
Prior art keywords
wood
composite material
adhesive
prepolymer
materials
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Withdrawn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
EP10715826A
Other languages
German (de)
English (en)
French (fr)
Inventor
Manfred Genz
Hans Ulrich Schmidt
Timo Prozeske
Stefan Meyer
Harald RÖDEL
Norbert Strubel
Johann GÖRTZ
Frank LÖWER
Karl-Heinz Koch
Hasan Kuscu
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Priority to EP10715826A priority Critical patent/EP2424726A1/de
Publication of EP2424726A1 publication Critical patent/EP2424726A1/de
Withdrawn legal-status Critical Current

Links

Classifications

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    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27D—WORKING VENEER OR PLYWOOD
    • B27D1/00—Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring
    • B27D1/04—Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring to produce plywood or articles made therefrom; Plywood sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B21/00—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
    • B32B21/04—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B21/042—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material of wood
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B21/04—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B21/08—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B21/00—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
    • B32B21/10—Next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B21/00—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
    • B32B21/14—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood board or veneer
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin 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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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
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    • B32B3/04—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions characterised by at least one layer folded at the edge, e.g. over another layer ; characterised by at least one layer enveloping or enclosing a material
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    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
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    • 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
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    • 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
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    • Y10T428/31591—Next to cellulosic

Definitions

  • the invention relates to the use of a composite material comprising two or more superimposed layers of a wood-like material.
  • the layers of the composite material may be lignoszellulosische layers, in particular cork, wood, grass or straw.
  • LP Futo (Electron microscopic direct imaging of glue joints and surface coatings of wood-based materials ", ETH Zurich, in: Wood as a raw material 31 (1973) pp 52-61), for example, has demonstrated the incorporation of phenol-formaldehyde resins in it bonded beech wood veneers
  • wood-based laminates made with phenol-formaldehyde adhesives may in part have a relatively high density, from 0.75 to 1.0 kg / l, or even> 1 kg / l, but particularly disadvantageous is the insufficient static and in particular their insufficient dynamic Efficiency.
  • the solution is to use a composite material comprising two or more layers of a wood arranged one above another, the layers being interconnected with a one-component polyurethane adhesive containing a prepolymer having free NCO groups, and wherein the wood has a structure having a volume fraction of Libriformmaschinen of 50% to 70%, as a construction element in construction, civil, marine, vehicle, aircraft, energy equipment, mining or furniture.
  • Libriform fibers are elongated, more or less thick-walled, narrow-lumen, tipped, and closed tubular cells carrying air or water.
  • Table 1 Percentage of libriform fibers or tracheids (in the case of softwoods) in volume percentages for different types of wood
  • woods with a high proportion by volume of libriform fibers namely a volume fraction between 50 and 70% of libriform fibers.
  • These libriform fibers are at least predominantly closed chambers, and these remain even after bonding with a one-component polyurethane adhesive, without being penetrated or filled by the adhesive, so that in the finished composite material as an integrated air pump integrated air damper act. It is believed that the above relationships are responsible for obtaining a composite material with significantly improved static and dynamic properties.
  • the wood with closed chambers is birch wood.
  • woods are aspen, eucalyptus, rubber tree, silk tree, cotton tree, acacia or poplar or hornbeam.
  • the composite material according to the invention preferably has 5 to 31 layers arranged one above the other.
  • the wood is preferably used as a veneer, that is, as peeled from the trunk, generally between 0.5 and 2 mm thin layers of wood.
  • one or more of the one or more layers of a wood one or more plastic layers, in particular one or more polyurethane and / or polyurea layers, in particular as a cover layer (s) may be additionally provided.
  • These additional plastic layers may in particular contain further, organic and / or inorganic fillers, for example organic clays, quartz sand, corundum, glass or other minerals or else fibers or fiber mats of all kinds.
  • organic and / or inorganic fillers for example organic clays, quartz sand, corundum, glass or other minerals or else fibers or fiber mats of all kinds.
  • one or more layers formed from a glass fiber fleece, a natural fiber fleece, a glass fiber mat or a natural fiber mat can be provided in the composite material according to the invention.
  • the two or more layers of a wood having a volume fraction of libriform fibers of 50 to 70% closed chambers, in particular birch with a one-component polyurethane adhesive containing a prepolymer are combined with free NCO groups.
  • the one-component polyurethane adhesive preferably contains the prepolymer with free NCO groups in an amount of up to 99% by weight, the prepolymer being obtainable from at least one component A which has an isocyanate-reactive compound and at least one isocyanate having component B,
  • the at least one fiber has a diameter in the range of 5 to 100 microns and a length in the range of 0.02 to 6 mm.
  • a one-component polyurethane adhesive is used without the addition of a filler containing a fiber.
  • the one-component polyurethane adhesive contains the prepolymer in a proportion of up to 99.999% by weight, the prepolymer being obtainable from at least one isocyanate-reactive compound component A and at least one isocyanate-containing component B, and the one-component polyurethane adhesive
  • At least one activator selected from one or more of the following substances: 4-methylmorpholine, 4-ethylmorpholine, 4-cyclohexylmorpholine, 2,2'-dimorpholinodiethyl ether or dimorpholinopolyethylene glycol
  • the prepolymer has the following characteristics: i) an NCO content of 5 to 30 wt .-%, based on the prepolymer ii) a viscosity at 25 ° C in the range of 300 to 15,000 mPas, and
  • the component A has the following characteristics: i) the component A contains at least one diol, ii) the OH number of the component A is in the range from 10 to 500 KOH / g, and wherein the one-component polyurethane adhesive contains a filler and has a viscosity at 25 ° C in the range of 300 to 15,000 mPas.
  • the components A and B are preferably used in such a ratio that the above-described properties of the prepolymer, in particular the NCO content and the viscosity are achieved.
  • auxiliaries and additives or catalysts can be used to prepare the prepolymer.
  • isocyanate-reactive compounds namely component A
  • polyols selected from the group of polyetherols and polyesterols, Polythioetherpolyole, hydroxyl-containing polyacetals and hydroxyl-containing aliphatic polycarbonates, Polycarbon- bonatdiole and Polycaprolactondiole or mixtures of at least two of said polyols.
  • the hydroxyl number of the polyhydroxyl compounds is usually 20 to 850 mg KOH / g and preferably 25 to 500 mg KOH / g.
  • chain extenders and / or crosslinking agents As isocyanate-reactive compounds it is also possible to use diols and / or triols having molecular weights of from 60 to ⁇ 400 as chain extenders and / or crosslinking agents in the process according to the invention.
  • chain extenders and / or crosslinkers preferably have a molecular weight of 60 to 300 g / mol. Suitable examples include aliphatic, cycloaliphatic and / or araliphatic diols having 2 to 14, preferably 4 to 10 carbon atoms, for.
  • Highly functional polyols in particular polyetherols based on highly functional alcohols, sugar alcohols and / or saccharides as starter molecules, can generally also be used as polyol components.
  • 2- and / or 3-functional polyether or polyesterols based on glycerol and / or trimethylolpropane and / or glycols are used as starter molecules or alcohols to be esterified.
  • the preparation of the polyetherols is carried out according to a known technology.
  • Suitable alkylene oxides for the preparation of the polyols are, for example, tetrahydrofuran, ethylene oxide, 1, 3-propylene oxide, 1, 2 or 2,3-butylene oxide, styrene oxide, preferably ethylene oxide and 1, 2-propylene oxide.
  • the alkylene oxides can be used individually, alternately in succession or as mixtures. Particular preference is given in the prepolymer in the adhesive composition of the invention as Polyethe- role used those which were alkoxylated to complete the alkoxylation with ethylene oxide and thus have primary hydroxyl groups.
  • Suitable starter molecules are, for example: water, glycols, such as ethylene glycol, propylene glycol, 1,4-butanediol and 1,6-hexanediol, amines, such as ethylenediamine, hexamethylenediamine, and 4,4'-diaminodiphenylmethane and amino alcohols, such as ethane nolamin or triethanolamine.
  • glycols such as ethylene glycol, propylene glycol, 1,4-butanediol and 1,6-hexanediol
  • amines such as ethylenediamine, hexamethylenediamine
  • 4,4'-diaminodiphenylmethane and amino alcohols such as ethane nolamin or triethanolamine.
  • the polyetherols have a functionality of preferably 2 to 6 and in particular 2 to 3 and molecular weights of 400 to 10,000, preferably 1,000 to 7,000.
  • the polyetherols can be used alone or in mixtures.
  • Polycarbonate diols are also suitable.
  • polycarbonate diols such come with aromatic dihydroxy compounds, for. B. based on 4,4'-dihydroxydiphenyl-2,2-propane or those based on aliphatic dihydroxy compounds, eg. B. 1, 6-hexanediol, in question.
  • the molecular weights range from 500 to 4,000, preferably from 1,000 to 2,000.
  • Suitable polyesterols as the polyol component may be, for example, from organic dicarboxylic acids having 2 to 12 carbon atoms, preferably aliphatic dicarboxylic acids having 4 to 6 carbon atoms, and polyhydric alcohols, preferably diols, having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms or by polymerization of lactones with 3 to 20 carbon atoms are produced.
  • organic dicarboxylic acids for example, glutaric acid, pimelic acid, suberic acid, sebacic acid, dodecanoic acid and preferably adipic acid, succinic acid and phthalic acid can be used.
  • the dicarboxylic acids can be used individually or as mixtures.
  • polyesterols it may be advantageous, instead of the dicarboxylic acids, to use the corresponding acid derivatives, such as carboxylic acids. to use anhydrides or carboxylic acid chlorides.
  • Suitable aromatic dicarboxylic acids are terephthalic acid, isophthalic acid or mixtures thereof with other dicarboxylic acids, eg. For example, diphenic acid, sebacic acid, succinic acid and adipic acid.
  • suitable glycols are diethylene glycol, 1, 5-pentanediol, 1, 10-decanediol and 2,2,4-Trimenthylpentandiol-1, 5.
  • Preferably used are 1, 2-ethanediol, 1, 4-butanediol, 1, 6-hexanediol and 2,2-dimethylpropanediol-1, 3; 1, 4-dimethylolcyclohexane; 1, 4-Diethanolcyclohexane, ethoxylated / propoxylated products of 2,2-bis (4-hydroxy-phenylene) -propane (bisphenol A).
  • the polyols can be used alone or as a mixture in various proportions.
  • lactones for the preparation of polyesterols are z. B.
  • polyesterols preferably have a functionality of 2 to 4, in particular 2 to 3, and a molecular weight of 1,200 to 3,000, preferably 1,500 to 3,000 and in particular 1,500 to 2,500.
  • polyol mixtures For the prepolymer in particular polyol mixtures have proven.
  • Such polyol mixtures preferably have at least one diol, preferably polypropylene glycol, and at least one triol, preferably polyether triol.
  • Particularly suitable diols have an average molecular weight in the range from 500 to 3,000, preferably 700 to 1,500 and particularly preferably 800 to 1,500 and moreover preferably 800 to 1,200.
  • triol those having an average molecular weight of from 1,000 to 8,000, preferably from 2,000 to 6,000 and more preferably from 3,000 to 5,000 have proven useful.
  • the polyol mixture has an OH number in the range from 30 to 140, preferably 50 to 90 and particularly preferably 60 to 80 mg KOH / g.
  • the abovementioned diols and triols can be used not only as a polyol mixture but also individually for the preparation of the prepolymer.
  • a polyetherpolyol which preferably has primary hydroxyl groups, with an OH number in the range of 10 to 200, preferably 20 to 150 and particularly preferably 25 to 100 mg KOH / g has proven.
  • chain extenders, crosslinking agents or mixtures thereof are used to prepare the prepolymers, these are expediently used in an amount of from 0 to 20% by weight, preferably from 0.5 to 5% by weight, based on the weight of the total used Isocyanate-reactive compounds are used.
  • Suitable isocyanates or polyisocyanates of component B are the aliphatic, cycloaliphatic, araliphatic and / or aromatic isocyanates known per se, preferably diisocyanates, which may, if appropriate, have been biuretized and / or isocyanurated by generally known processes.
  • alkylene diisocyanates having 4 to 12 carbon atoms in the alkylene radical such as 1,12-dodecane diisocyanate, 2-ethyltetramethylene diisocyanate-1,4-2-methylpentamethylene diisocyanate-1, 5, tetramethylene diisocyanate-1,4, lysine ester diisocyanate (LDI), Hexamethylene diisocyanate-1, 6 (HDI), cyclohexane-1, 3- and / or -1, 4-diisocyanate, 2,4- and 2,6-hexahydro-toluene diisocyanate and the corresponding isomer mixtures, 4,4'-, 2, 2'- and 2,4'-dicyclohexylmethane diisocyanate and the corresponding isomer mixtures, 1-isocyanato-S ⁇ - trimethyl- ⁇ -isocyanotomethylcyclohexane (IPDI),
  • IPDI 1-is
  • MDI such as polymeric MDI or preferably monomeric MDI, especially 4,4'-MDI, or mixtures of 2,4'-MDI and 4,4'-MDI.
  • a polymer MDI having an average functionality in the range of 1 to 5, preferably 1, 5 to 4 and particularly preferably 2 to 3.5 and a viscosity in the range of 100 to 400 has proven particularly suitable for the prepolymer , preferably 150 to 300 and particularly preferably 160 to 260 mPas to use.
  • catalysts it is possible to use generally known compounds which greatly accelerate the reaction of isocyanates with the compounds reactive toward isocyanates, preferably a total catalyst content of from 0.01 to 8% by weight, in particular from 0.1 to 5% by weight on the weight of the total isocyanate-reactive compounds used.
  • the following compounds can be used: triethylamine, tributylamine, dimethylbenzylamine, dicyclohexylmethylamine, dimethylcyclohexylamine, N, N, N ', N'-tetramethyl-diamino-diethyl ether, bis (dimethylaminopropyl) -urea, N-methyl or N Ethylmorpholine, N, N'-dimorpholinodiethyl ether (DMDEE), N-cyclohexylmorpholine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylbutanediamine, N, N, N ', N' Tetramethylhexanediamine-1, 6, pentamethyldiethylenetriamine, dimethylpiperazine, N-dimethylaminoethylpiperidine, 1, 2-dimethylimidazole, N-hydroxypropylimidazole
  • iron (II) chloride zinc chloride
  • trimerization catalysts such as alkali metal or alkaline earth metal acetate, preferably potassium acetate, may be mentioned.
  • the above catalysts can also be used as an activator for the morpholine derivatives used as activators.
  • catalysts are incorporated in the prepolymer as such in its manufacture and activators with the prepolymer as an additional component of the adhesive composition of the invention in this.
  • auxiliaries and / or additives may also be added to the reaction mixture for the preparation of the prepolymers.
  • examples which may be mentioned are surface-active substances, stabilizers, cell regulators, dyes, pigments, flame retardants, hydrolysis protectants, insecticides, fungistatic and bacteriostatic substances.
  • the surface-active substances and stabilizers counteract a "skin formation" of the air-facing surface of the adhesive composition, and the surface-active substances and stabilizers also improve the running of the adhesive composition and the creeping ability of the adhesive composition and the degassing thereof.
  • emulsifiers such as the sodium salts of castor oil sulfates or fatty acids, and salts of fatty acids with amines, for example diethylamine, stearic diethanolamine, diethanolamine, diethanolamine, Salts of sulfonic acids, for example alkali metal or ammonium salts of dodecylbenzene- or dinaphthylmethanedisulfonic acid and ricinoleic acid, stabilizers, such as siloxane-oxalkylene copolymers and other organopolysiloxanes, ethoxylated alkylphenols, oxet hylated fatty alcohols, paraffin oils, castor oil or ricinoleic acid esters, Turkish red oil and peanut oil, and cell regulators, such as paraffins, fatty alcohols and dimethylpolysiloxanes.
  • amines for example diethylamine, stearic diethanolamine, diethanolamine
  • the above-described oligomeric acrylates having polyoxyalkylene and fluoroalkane radicals are also suitable as side groups. If foam formation is to be reduced or avoided, trialkyl phosphates are preferred as defoamers.
  • alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, 2-pentyl, Pentyl, preferably ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl.
  • the surface-active substances are usually used in amounts of from 0.01 to 5% by weight, based on 100% by weight, of the total isocyanate-reactive compounds used.
  • Suitable flame retardants are, for example, tricresyl phosphate, tris (2-chloroethyl) phosphate, tris (2-chloropropyl) phosphate, tris (1,3-dichloropropyl) phosphate, tris (2,3-dibromopropyl) phosphate, tetrakis.
  • inorganic or organic flame retardants such as red phosphorus, alumina hydrate, antimony trioxide, arsenic oxide, ammonium polyphosphate and calcium sulfate, expandable graphite or cyanuric acid derivatives, such as.
  • melamine or mixtures of at least two flame retardants, such as.
  • ammonium polyphosphates and melamine and optionally corn starch or ammonium polyphosphate, melamine and expandable graphite and / or optionally aromatic polyester to increase the flame resistance of the prepolymer or the adhesive composition can be used.
  • a one-component polyurethane adhesive is used which has a filler containing at least one fiber.
  • the one-component polyurethane adhesive preferably has at least one of the following main features (i) to (iii):
  • the prepolymer has at least one of the following sub-features (a) and (b):
  • Component A has at least one of the following sub-features (c) and (d):
  • the component A contains at least one diol or polyol, preferably a diol or triol and more preferably a diol and triol,
  • the OH number of component A is in the range of 10 to 500 mg KOH / g,
  • the filler has at least one of the following sub-features (e) or (f):
  • the fiber consists of at least one fiber polymer
  • the filler is in addition to the fiber of at least one non-fibrous packing.
  • the viscosity at 25 ° C of the prepolymer is preferably in a range between 300 and 15,000, preferably 500 and 10,000 mPas, if the adhesive composition is to be pumpable. If, on the other hand, it is intended to use the adhesive composition as a pasty, coatable composition, the viscosity at 25 ° C. of the prepolymer is preferably in the range> 15,000 to 150,000 and particularly preferably in the range from 20,000 to 100,000 mPas.
  • the adhesive composition is low in solvent. This is the case when the amount of solvent contained in the adhesive composition is ⁇ 10, preferably ⁇ 5, and more preferably ⁇ 2 wt .-%.
  • solvents are organic and inorganic liquids which are suitable as carriers of the other constituents of the adhesive composition and do not cure with at least some of the other constituents.
  • the adhesive composition is solvent-free.
  • both the aforementioned main feature of the prepolymer (i) and the main feature (ii) of the component A are realized.
  • the main feature (ii) of the component A and the main feature of the filler (iii) are fulfilled.
  • Preferred embodiments of the adhesive composition are those in which both the sub-features (a) and (b) or (c) and (d) or (e) and (f) are fulfilled in the prepolymer, component A and the filler.
  • all the main features (i) to (iii) as well as all sub-features (a) to (f) are satisfied.
  • the fiber polymer is at least one polyamide
  • the filler is composed of at least one inorganic material.
  • the fiber polymers of the adhesive composition be formed predominantly of organic or inorganic materials.
  • Suitable organic materials for fiber polymers are, in particular, polycondensates and polyaddition polymers, which are preferably not polyurethane, with polycondensates being preferred.
  • polycondensates polycarbonates, polyesters, polyamides, polyimides, melamine-formaldehyde resin are particularly suitable.
  • Polyaddition polymers are in particular polyacrylates, polymethacrylates, polystyrenes, polyacrylonitriles, polyethylene, polypropylene, polyvinyl alcohol and the copolymers of at least two monomers of the abovementioned unipolymers and their blends of at least two thereof.
  • a polyamide is used as the fiber polymer.
  • all commercially available polyamides known to the person skilled in the art are suitable.
  • polyamides such as nylon, in particular nylon-6,6 or nylon-6 and polyaramides have proven particularly suitable.
  • the fibers may be based on natural organic fiber polymers such as cellulose, cotton, jute, viscose and sisal.
  • the fibers can also be formed from inorganic materials.
  • the inorganic fiber polymers carbon, glass and mineral wool fibers are preferable.
  • the fibers are obtained from different materials, for example by spinning.
  • the fibers used preferably have a diameter in the range of 5 to 100, preferably 10 to 60 and particularly preferably 10 to 30 .mu.m and a length in the range of 0.02 to 6, preferably 0.05 to 4 and particularly preferably 0.1 to 2 mm.
  • the adhesive composition has a non-fibrous packing consisting of at least one inorganic material.
  • inorganic materials Basically, all known to the expert and in particular the commercially available inorganic materials for the adhesive according to the invention are suitable, which are present as a solid.
  • the inorganic materials must be present as a solid in the temperature range in which the adhesive composition according to the invention is processed and the bonded article is used later. This temperature range preferably starts at -50 and reaches +160 0 C.
  • Particularly suitable inorganic materials have proven to be the oxygen compounds of silicon or aluminum, or magnesium, or at least two thereof, which may also contain other elements.
  • Particularly suitable are silicates and aluminum oxides, for example alumina, such as China clay, and quartz compounds or silica.
  • the non-fibrous filling bodies are preferably particulate. 80% of the particulate fillers have a particle size in the range from 0.01 to 50, preferably 0.1 to 10 and particularly preferably 0.2 to 8 ⁇ m.
  • the filler used according to the invention may comprise fibers or additionally fillers. If the filler has both fibers and filler, it is preferred that at least as much filler as fibers, preferably filler in excess, are found in the filler.
  • fillers are included in the adhesive composition to improve their physical properties for the various uses.
  • the adhesive composition must form a compact as possible, bubble-free adhesive layer after curing and the joints between the substrates must be filled as completely as possible.
  • the adhesive composition must form a compact as possible, bubble-free adhesive layer after curing and the joints between the substrates must be filled as completely as possible.
  • Adhesive composition penetrate into a part of the substrate surface. However, after curing of the adhesive composition to the adhesive, it is not allowed to cause voids through this infiltration or shrinkage, which could degrade the cohesion. Especially in thicker joints, in the range of greater than 0.1 to 1 mm, preferably 0.2 to 1 mm, these requirements can be met particularly well by the incorporation of fillers in the composition described above in the adhesive composition.
  • the fillers contained in the adhesive compositions it has proven particularly useful to have a water content of less than 5, preferably less than 1, and particularly preferably less than 0.1,% by weight, based on the filler. This is particularly advantageous with regard to the preparation of the adhesive composition according to the invention.
  • the activator of the adhesive composition consists of at least one morpholine derivative.
  • Particularly suitable morpholine derivatives are 4-methylmorpholine, 4-ethylmorpholine, 4-cyclohexylmorpholine, 2,2'-dimorpholinodiethyl ether or dimorpholino-polyethylene glycol, or at least two thereof.
  • further activating compounds can be used, as described, for example, as polyurethane catalysts in Becker / Braun, Kunststoffhandbuch 7 (1993), the proportion of morpholine derivatives preferably predominating.
  • thixotropic adjuvants have proved themselves.
  • Particularly preferred thixotropic auxiliaries are bentonites, kaolins, alginic acid and silicic acid, with silicic acid being particularly preferred.
  • thixotropic auxiliaries are preferably soluble thixotropic auxiliaries which can be obtained, for example, via the reaction of an isocyanate in the presence of amines, as described in the publications EP 300 388 A1, DD 156 480, DD 211 689, DD 211 930 and DD 211 931.
  • Thixotropic auxiliaries are very finely divided substances which already thicken liquids when they are added in small amounts to the liquid, for example up to a maximum of 10% by weight, based on the liquid.
  • these small particles have on their surface silane groups which interact with the liquid with which they are dispersed to form hydrogen bonds and thus lead to a thickening of this liquid.
  • Typical of thixotropic auxiliaries is that, for the same amount, the thickening effect increases with decreasing particle size with correspondingly thorough dispersion by vigorous mixing.
  • the thixotropic aids have the advantage that they do not sediment in the dispersed liquid.
  • the thixotropic adjuvants prevent or delay the sedimentation of fillers.
  • thixotropic aids are in fine powder form montmorillonite, Mg / Al silicate, Al / Na silicate, bentonites, hectorite, Na / Mg silicate, fumed silicas, hydrated silicas, hornblende chrysotile, chrysotile asbestos, chrysotile Silica and precipitated MgO are preferred, pyrogenic silicas, for example obtainable as Aerosil from Degussa-Hüls AG, and Mg silicates, available as Bentones from Kronos Titan GmbH Leverkusen, being preferred, and Aerosil being particularly preferred.
  • the invention relates to the use of a composite material comprising two or more superimposed layers of a wood, wherein the layers are interconnected with a one-component polyurethane adhesive containing a prepolymer having free NCO groups, and wherein the wood is a closed structure Has chambers, as a construction element in construction, civil engineering, ship, vehicle, aircraft, energy equipment, mining or furniture.
  • the composite used according to the invention is also characterized in particular by an elastic reversible energy absorption, it acts as an energy-dissipating agent. This results in a variety of possible applications, especially in areas where increased energy absorption is required, for example for bullet-proof elements, or in explosive environments, for example in mining or in chemical plants.
  • the composite material may preferably be used as a load-bearing element, in particular as a floor, intermediate floor, wall or roof element.
  • the composite material can continue to be used as a support and / or shuttering element.
  • Particularly preferred is the use of a composite material described above as a container or trailer floor.
  • the composite material according to the invention is also particularly suitable for reinforcing wind rotor blades or other components of energy plants.
  • Particularly preferred is the use in building construction and civil engineering, for boarding concrete and other constructions, where good load-bearing capacities and in particular good separation effects to other building materials, especially plastics or concrete, are important.
  • the invention also relates to a container or trailer floor, formed from a composite material described above.
  • a container or trailer floor formed from a composite material described above, being used as wood birch wood.
  • Adhesive is achieved to the matrix of the layers of the wood on the free NCO groups of the prepolymer by these with the free OH groups from the wood, in particular from the starch or cellulose, or Lingnin and components of siliceous derivatives, in particular in outer layers, as well as react with the residual moisture from the wood.
  • Light microscopic images allow the conclusion that the one-component adhesive surprisingly does not penetrate into the wood fibers or vessels, so that they remain intact.
  • the wood has a structure with largely closed chambers, which also remain in the bonded composite, and are not penetrated or filled by the adhesive.
  • Container or trailer floors must meet specific specification requirements: The usual dimensions are 2.40 mx 1, 16 mx 28 mm (length x width x thickness). However, your application is not limited to these dimensions. In particular, the use of the composite material described herein is not limited to these dimensions or density ranges. The density should be 0.8 ⁇ 0.1 kg / l.
  • HCL International Container Lessors
  • Technical Bulletin 001 September 1, 2002
  • "Short Span Test" 250 mm "Span Shear Test” for Static Flexural Strength in Three-Point Bending Test normalizes a force to for damage of at least 6900 N.
  • the experimental procedure and the dimensions of the test specimen are described in detail in the HCL TB 001. Here, not only a failure by breakage, but in particular a delamination between the layers is considered damage, which occurs especially in case of insufficient bonding.
  • the tests are carried out in standard climate (23 ° C and 55% relative humidity).
  • Coating materials also commonly called “plywood” made of apitong wood with phenol formaldehyde as adhesive have a density of approx. 0.8 kg / l and a load limit of approx. 7000 to 7300 N im static three-point bending test at 23 ° C / 55% relative humidity.
  • the birch composite material according to the invention and the one-component PUR adhesive has a maximum force for failure of 12801 N in the certification test for container floors according to HCL TB 001 and is thus almost twice as high as the corresponding standard demands.
  • the maximum failure force for birch composite and 1K-PUR adhesive for 12801N use according to the present invention far exceeds the levels for bamboo and plywood bonded to phenol-formaldehyde (6282N and 6558 respectively), which do not meet the requirements of TB 001 fulfill.
  • the measured test data further determined the maximum bending stress (in MPa) resulting from the prescribed sample geometry (according to HCL TB 001) and the value measured in the test maximum force at failure results, determined.
  • This is for the no longer available tropical hardwoods Apitong 71, 6 MPa and for the phenol-formaldehyde glued replacement materials Plywood 66.5 MPa and for bamboo 64.8 MPa.
  • the composite material based on birch and 1-K PU R adhesive has a maximum bending stress of 1 12.3 MPa, which is thus also almost twice as large as that of Comparative materials.
  • the bending stress is described in Dubbel, Taschenbuch für Maschinenbau.
  • the modulus of elasticity is generally known to the person skilled in the art as a material characteristic parameter.
  • the flexural modulus of elasticity shown in the measurements made here is for the tropical rainforest timbers Apitong 6562 MPa, for plywood 5323 MPa and for bamboo 5974 MPa.
  • the bending modulus of elasticity of the composite material, birch with 1 -K-PUR 7267 MPa is thus at the level of apitong and significantly higher than that of the comparison materials based on substitute woods with phenol formaldehyde, resulting in the significantly higher strength of the invention Material makes noticeable.
  • Table 3 shows the corresponding measurements according to HCL TB 001 at 80 ° C., although such measurements are not required or described in the specification.
  • the maximum force of the composite material according to the invention based on birch and the 1-component PUR adhesive at failure with 9973 N at 80 0 C is almost twice as high as that of the comparative materials and its maximum bending stress is 86.6 MPa 30% above that of Apitong and 80% over that of bamboo with phenolformaldehyde.
  • the composite material selected for the use according to the invention also has excellent dynamic properties.
  • a measurement method was developed in order to determine the dynamic load limit. So-called Wöhler curves were recorded in the dynamic step test. Wöhler curves are described, for example, in: Dubbel, Taschenbuch für Maschinenbau.
  • the number of cycles without damage thus provides information about the expected dynamic performance level or about the fatigue behavior of the respective material during its use as a container floor.
  • the higher the number of cycles passed without damage and the higher the maximum bending stress introduced the higher the dynamic performance level of the material and thus also the real life of the respective container floors.
  • the maximum bending stresses in the event of failure from HCL TB 001 serve to determine the maximum bending stresses that are used in each case. Since this is the maximum bending stress in the event of failure, ie the bending stress at which the respective material fails under a single load, correspondingly lower bending stresses are selected for the Wöhler curves.
  • the sample is loaded 5000 times at a frequency of 10 Hz. If the sample passes this test, the maximum bending stress is increased to 40 MPa and the same sample again cycles through 5000 cycles at 10 Hz. If this test is also passed without damage, the maximum bending stress is increased successively and in steps by a further 20 MPa until failure occurs.
  • Wöhler curves are used in this shortened and compared to the normal Wöhler test harder dynamic step test for comparison materials as well as for the Birch composite performed with 1 K-PUR adhesive and are shown in Table 4. The tests in Table 4 were carried out in standard climate, 23 ° C and 55% relative humidity.
  • Table 4 Dynamic step test at 23 ° C / 55% relative humidity.
  • the significantly higher dynamic performance level of the composite material based on birch with the one-component PUR adhesive is clearly expressed in the significantly higher max. Bending stress of 100 MPa and cycled number of cycles of 20800. Compared to the birch composite material, the bamboo / plywood comparison materials with phenolformaldehyde are already destroyed at 60 MPa or even at 40 MPa and accumulated 10400 cycles.
  • the dynamic performance level of the composite material based on birch and 1 K PUR adhesive thus exceeds that of the comparison materials by a factor of 2.5 or 1.66 in the max. Bending stress as dynamic load capacity with additionally clearly higher cumulated load cycles.
  • the clearly superior dynamic performance of the composite material based on birch and the 1-component PUR adhesive shows: While the comparison materials made of plywood or bamboo at 80 0 C just 40 MPa max. To achieve bending stress and 7100 or 8700 cycles, the birch composite material and the 1-component PUR adhesive with 80 MPa bending stress clearly go through more than 20,000 cycles. It should be noted that the 80 MPa max. Bending stress, which the composite material easily applies here as a continuous load in the dynamic step test at 80 ° C., all other comparative materials are not even at 23 ° C. as max. Apply bending stress under failure under a single load (see Table 3).
  • FIG. 1 shows the results of drop tests with a composite material for use according to the invention
  • FIG. 2 shows a photomicrograph for a composite material for use according to the invention
  • FIG. 3 shows a light-microscopic task of the same composite material as in FIG.
  • FIG. 4 is a light micrograph of Apitong for comparison, as wood with an open cell structure, that is, a wood that has no volume fraction of Libriformmaschinen in the range of 50 to 70%.
  • FIG. 1 shows diagrams of drop test experiments with a hemisphere with a diameter of 100 mm and a weight of 99 kg, with a drop height of 0.624 m. Thus, the registered energy was 609 J.
  • the abscissa represents the strain or residual set amount V in mm and the ordinate the force F in kN.
  • the values for the composite birch combined with a one-component polyurethane adhesive are represented by circles, the values for a comparative material of bamboo with phenol-formaldehyde adhesive by triangles and the values for a comparison material from plywood with phenol-formaldehyde adhesive by diamonds.
  • the plywood composite panel with PF adhesive (shown by diamonds) was completely destroyed in the experiment, which corresponds to an irreversible energy intake.
  • the plate showed a permanent deformation or a set amount of 12-13 mm, corresponding to 50%, based on the original plate thickness.
  • the bamboo composite plate with phenol-formaldehyde adhesive (represented by triangles) was destroyed in the experiment, which corresponds to an irreversible energy intake. It showed a permanent deformation, or a set amount of 6 to 7 mm, corresponding to about 30% of the original plate thickness.
  • the resistance of the plate to the energy introduced in this experiment is expressed in the measured force as the response of the material.
  • This reaction force or the resistance to destruction is at the plywood plate with PF adhesive at about 25 kN, in the reference material bamboo with phenol formaldehyde at about 30 kN to max. 35 kN.
  • the sheet of birch -1 -K-PUR glue (represented by circles) remained perfectly intact and did not have any permanent setting.
  • the entire energy intake is reversible and is thereby elastically dissipated, without causing damage to the test plate.
  • the max. Response force of approx. 50 kN is twice as high as that of plywood phenolformaldehyde or up to 66% higher than that of the comparative material bamboo phenolformaldehyde.
  • Figure 2 shows a light micrograph of a composite material of birch wood and a 1-K PUR adhesive. The image shows the orthogonal layer structure and that the libriform fibers are not penetrated by adhesive.
  • FIG. 3 further illustrates the composite material shown in FIG. 2 by selecting a higher resolution.
  • the photograph shows that in two successive orthogonal layers of birch wood, the libriform fibers are clearly preserved and are not penetrated by the adhesive.
  • FIG. 4 shows a photomicrograph of apitong and illustrates, by way of example, the open-cell structure of this wood.

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  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Forests & Forestry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
EP10715826A 2009-04-30 2010-04-26 Verwendung eines verbundwerkstoffes auf basis eines einkomponenten-polyurethanklebstoffes Withdrawn EP2424726A1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP10715826A EP2424726A1 (de) 2009-04-30 2010-04-26 Verwendung eines verbundwerkstoffes auf basis eines einkomponenten-polyurethanklebstoffes

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP09159168 2009-04-30
PCT/EP2010/055503 WO2010125012A1 (de) 2009-04-30 2010-04-26 Verwendung eines verbundwerkstoffes auf basis eines einkomponenten-polyurethanklebstoffes
EP10715826A EP2424726A1 (de) 2009-04-30 2010-04-26 Verwendung eines verbundwerkstoffes auf basis eines einkomponenten-polyurethanklebstoffes

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EP2424726A1 true EP2424726A1 (de) 2012-03-07

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JP (1) JP2012525280A (zh)
KR (1) KR20120023047A (zh)
CN (1) CN102458829B (zh)
CA (1) CA2760402A1 (zh)
RU (1) RU2011148457A (zh)
WO (1) WO2010125012A1 (zh)

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DE102011004723A1 (de) * 2011-02-25 2012-08-30 Bayer Materialscience Aktiengesellschaft Verwendung von Schichtaufbauten in Windkraftanlagen
US9126386B2 (en) 2011-03-04 2015-09-08 Basf Se Composite elements
PL2952344T3 (pl) * 2014-06-06 2020-09-07 Upm Plywood Oy Ognioodporna płyta ze sklejki jako materiał na podłogi oraz sposób jej wytwarzania
WO2016001734A1 (en) * 2014-07-02 2016-01-07 Mosca Thomas Wood based, panel-shaped product for the fabrication of different objects and structural elements
US10195821B1 (en) * 2015-07-22 2019-02-05 Bamcore LLC Bamboo laminated construction panel and method of manufacture
EP3325266B1 (en) * 2015-07-23 2019-09-11 Basf Se Plywood article
EP3335847B1 (en) 2016-12-16 2020-09-30 Mayfair Vermögensverwaltungs SE Floor panel for a shipping container
CN112918041B (zh) * 2021-03-11 2022-05-17 湖南省杨林木业有限公司 一种高抗压高弯曲性能环保木胶板及其制备方法

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DD211930A3 (de) 1982-11-08 1984-07-25 Schwarzheide Synthesewerk Veb Verfahren zur herstellung thixotroper diisocyanate
DD211931A3 (de) 1982-11-08 1984-07-25 Schwarzheide Synthesewerk Veb Verfahren zur herstellung thixotroper urethanhaltiger isocyanate
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US8557389B2 (en) 2013-10-15
US20120070671A1 (en) 2012-03-22
CA2760402A1 (en) 2010-11-04
KR20120023047A (ko) 2012-03-12
WO2010125012A1 (de) 2010-11-04
JP2012525280A (ja) 2012-10-22
CN102458829B (zh) 2016-03-23
RU2011148457A (ru) 2013-06-10
CN102458829A (zh) 2012-05-16

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