EP2102262A1 - Composition adhésive monocomposante à base de polyuréthanne non moussante - Google Patents

Composition adhésive monocomposante à base de polyuréthanne non moussante

Info

Publication number
EP2102262A1
EP2102262A1 EP07822750A EP07822750A EP2102262A1 EP 2102262 A1 EP2102262 A1 EP 2102262A1 EP 07822750 A EP07822750 A EP 07822750A EP 07822750 A EP07822750 A EP 07822750A EP 2102262 A1 EP2102262 A1 EP 2102262A1
Authority
EP
European Patent Office
Prior art keywords
adhesive
composition according
composition
polyamide fibers
fibers
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Withdrawn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
EP07822750A
Other languages
German (de)
English (en)
Inventor
Bernhard Grünewälder
Thomas Bachon
Birgit Ness
Kerstin Schröder
Thomas Empt
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP2102262A1 publication Critical patent/EP2102262A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
    • C08L2666/20—Macromolecular compounds having nitrogen in the main chain according to C08L75/00 - C08L79/00; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/54—Inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention is a 1-component polyurethane adhesive composition based on at least one NCO-terminated polyurethane prepolymer containing polyamide fibers and at least 10 wt .-% of fillers.
  • One-component, reactive polyurethane systems in liquid, thixotropic or pasty form are known from the prior art.
  • the main field of application of such adhesive systems is in the field of constructive bonding, which is about to achieve connections with the highest possible strength and a high degree of heat and water resistance, such as in bonding of wood in the outdoor area.
  • one-component polyurethane adhesives are being used more and more often because they have considerable advantages in terms of heat and water resistance compared to polyvinyl acetate dispersions.
  • the object of the present invention was therefore to provide a one-component polyurethane adhesive system with which it is possible to achieve mechanically stable and permanent bonds without the use of mechanical clamping tools for fixing the freshly bonded substrates.
  • one-component polyurethane adhesive systems which already contain at least about 10 wt .-% of fillers, can be modified by the addition of polyamide fibers such that they virtually no longer foam during curing.
  • the adhesive is introduced bubble-free into the holes of the test specimen described above using a caulking gun and immediately removed flat with a spatula. The thus prepared specimens then remain for 24 h under the same climatic conditions.
  • the height of the adhesive leaked out of the hole is determined with a thickness gauge.
  • the arithmetic mean of 6 readings is given as a percentage of the hole depth.
  • the information is given in%.
  • the beechwood bar In order to achieve the highest possible reproducibility, the beechwood bar must be conditioned for at least 7 days in the standard climate before the test, since the wood moisture greatly influences the measurement result.
  • the adhesive to be tested should also be stored at a temperature of 23 ° C.
  • the almost non-foaming adhesive compositions during curing are understood as meaning the compositions which exhibit a foaming behavior of less than 45% according to the method described above, preferably less than 35%, particularly preferably less than 30%.
  • the foaming of the adhesive due to the released and released carbon dioxide during curing is the main reason that the freshly bonded substrates must be fixed until the final curing of the adhesive by means of clamping tools or the like. Since the use of polyamide fibers in such adhesive systems foaming of the adhesive during curing are almost completely suppressed can, is the use of the above-mentioned clamping tools for fixing the parts superfluous.
  • the present invention therefore provides a 1-component polyurethane adhesive composition based on at least one NCO-terminated polyurethane prepolymer containing polyamide fibers and at least 10% by weight of fillers.
  • an NCO-terminated polyurethane prepolymer is understood as meaning a compound which is prepared from at least one polyol compound and at least one polyisocyanate and which after the reaction has a content of unreacted NCO groups in the range from 8 to 22 wt .-% based on the prepolymer, preferably 12 to 15 wt .-% based on the prepolymer.
  • the NCO content is in this case generally adjusted by the excess of NCO groups of the polyisocyanate component with respect to the OH groups of the polyol compound. How such prepolymers are prepared is known to the person skilled in the art.
  • the polyol component for preparing the PU prepolymer should contain at least one polyol.
  • Suitable polyols may be: polyester polyols - z.
  • the polyols should have a molecular weight of from 1,000 to 12,000, preferably from 2,000 to 8,000 and especially from 3,000 to 6,000 g / mol.
  • the polyisocyanate component for the preparation of the PU prepolymer should contain at least one polyisocyanate. It may be aliphatic as well as cycloaliphatic and in particular aromatic. Preferred isocyanates are: MDI, polymeric MDI, IPDI, TDI and TMXDI.
  • the viscosity of the PU prepolymer should be at 23 0 C in the range of 500 to 25,000, preferably in the range from 2000 to 10,000 and particularly in the range from 3000 to 7000 mPas, measured with a Brookfield (spindle 6/20 rpm).
  • the composition according to the invention also contains at least 10% by weight of fillers.
  • Fillers Their purpose is u.a. to increase the volume and / or the weight or the density, as well as to influence the rheology of the adhesive system. But they can also improve the technical usability, e.g. reduce shrinkage or affect hardness, firmness and elasticity. But they can also serve as a colorant.
  • These fillers include above all carbonates, in particular calcium carbonate, but also silicates, in particular sand, talc, clay and mica, and sulfates, in particular calcium and barium sulfate, and aluminum hydroxide, glass and carbon blacks.
  • silicates in particular sand, talc, clay and mica
  • sulfates in particular calcium and barium sulfate
  • aluminum hydroxide glass and carbon blacks.
  • the minimum filler content of about 10% by weight claimed in the invention is primarily required to adjust the density or viscosity of the polyurethane prepolymer such that it does not cause segregation between the fibers and the prepolymer component after blending with the polyamide fibers comes.
  • filler levels below about 10% by weight the effect of foam suppression by the polyamide fibers of the invention decreases. A possible This can be explained by the fact that the resulting density differences between the fibers and the remaining composition lead to segregation, which worsens the foam suppression of the polyamide fibers.
  • the polyamide fibers used according to the invention may consist, for example, of nylon or perlon, but also of compact polyamides, such as e.g. Akulon or from aromatic polyamides, such. Aramid.
  • Particularly suitable for the purposes of the present invention are fibers of polyamide 6.6 having a fiber length of 1.0 mm and a linear density of 3.3 dtex.
  • the content of polyurethane prepolymer in the composition according to the invention is between 30 and 80% by weight, based on the total composition, preferably between 40 and 60% by weight. This is particularly advantageous because these amounts of polyurethane prepolymer on the one hand good final strengths are achieved and on the other hand, the cost of such an adhesive can be kept moderate.
  • the polyurethane prepolymer has a viscosity of between 500 and 25,000 mPas, preferably 2,000 to 10,000 mPas, in particular 3,000 to 7,000 mPas, measured at 23 ° C. according to Brookfield (spindle 6/20 rpm). Most preferably, the viscosity of the polyurethane prepolymer is about 4,000 mPas.
  • viscosities in this range prevent after the adhesive application run down or dripping of the adhesive and fix the Fügemaschine directly, but on the other hand, an applicability by pressing out of a cartridge or tube allows.
  • viscosities in the abovementioned ranges prevent segregation in density differences between the polyurethane prepolymer and the polyamide fibers likewise used in the adhesive system according to the invention, which does not result in the storage stability of an adhesive as a tube or cartridge product, which does not stir before use would allow to significantly reduce.
  • the NCO content of the polyurethane prepolymer is between 8 and 22% by weight, in particular between 12 and 15% by weight, based on the polyurethane prepolymer.
  • adhesive systems with a polyurethane prepolymer of the stated NCO contents exhibit a sufficient setting speed with simultaneously good final strength.
  • the use of the polyamide fibers according to the invention during the curing of the adhesive virtually eliminates gas bubble formation within the adhesive layer.
  • the content of fillers in the composition according to the invention is between 20 and 65% by weight, preferably between 35 and 55% by weight, based on the 1-component polyurethane adhesive composition. This is particularly advantageous, as the workability and final strength of the adhesive system is particularly good through the use of fillers in these amounts.
  • the use of fillers can reduce the volume shrinkage during curing of the adhesive.
  • the content of polyurethane prepolymer can be determined by the use of fillers in these amounts reduce, whereby the entire adhesive composition can be produced cheaper.
  • the polyol component for preparing the polyurethane prepolymer contains at least one polyol selected from the group consisting of polyester polyol and polyether polyol, wherein the average molecular weight of the polyols is in the range of 1,000 to 12,000 g / mol, preferably 2,000 to 8,000 g / mol, in particular 3,000 to 6,000 g / mol. This is particularly advantageous since high molecular weight polyols result in a viscosity reduction of the polyurethane prepolymer.
  • Polypropylene glycols are better suited for preparing the polyurethane prepolymers for the compositions of the invention than polyethylene glycols, since polyethylene glycols, due to their waxy consistency, are less compatible with the other components and the storage stability is reduced.
  • Polyols which can be used according to the invention are, in particular, diols and triols, the triols being particularly preferred, since polyurethane prepolymers prepared therewith lead to a higher strength of the bond when the adhesive compositions according to the invention cure.
  • the 1-component polyurethane adhesive composition contains at least 0.5% by weight of polyamide fibers based on the total composition. This is particularly advantageous since such a content of polyamide fibers greatly reduces foaming without at the same time changing too much the rheological properties of the adhesive composition. A conversion of existing formulations without polyamide fibers is thus without much adaptation of the other components, in particular with respect to thickener or th ixotropierstoff possible.
  • the 1-component polyurethane adhesive composition contains up to 10 wt .-%, preferably up to 6 wt .-%, most preferably, in particular between 1, 5 and 4 wt .-% of polyamide fiber.
  • This is particularly advantageous, since such a proportion of polyamide fibers in the composition according to the invention almost completely prevents the formation of carbon dioxide bubbles during the curing of the adhesive and thus the foaming during bonding and, on the other hand, does not change the rheological properties of the adhesive composition, in particular the viscosity the glue can not be pushed out of a cartridge or a tube.
  • the use of the polyamide fibers on the one hand can be used to adjust the desired processing consistency of the 1-component polyurethane adhesive while at the same time preventing foaming during the curing of the adhesive during the bonding of components.
  • the polyamide fibers have a length of 0.1 to 7 mm, in particular 0.5 to 2 mm and a diameter of 10 to 100 .mu.m, in particular 15 to 35 .mu.m. This is particularly advantageous since polyamide fibers of these dimensions are particularly effective at preventing the formation of carbon dioxide bubbles in the adhesive and thus foaming during curing.
  • the polyamide fibers have a titer of 1 to 100 dtex, in particular 2 to 20 dtex.
  • polyamide fibers with such a titre almost completely prevent the formation of carbon dioxide bubbles during the curing of the adhesive systems according to the invention.
  • Polyamide fibers with such a titre can be used in comparatively small amounts, which on the one hand are sufficient to almost completely prevent carbon dioxide bubble formation on curing of the adhesive and, on the other hand, do not lead to such a great increase in the viscosity of the adhesive Adhesive system lead that this can no longer be applied from a tube or a cartridge.
  • the polyamide fibers are selected from nylon, perlon, Akulon and aramid fibers. Most preferred are polyamide fibers of nylon 6.6. This is particularly advantageous because polyamide fibers of these materials are particularly well suited to almost completely suppress the formation of carbon dioxide bubbles and thus foaming of the adhesive during curing. This can be clearly seen in the two figures (1) and (2). In both cases, a bonding of two wood specimens made of beech was performed with a 1 K polyurethane adhesive; in Figure (1) with an adhesive composition according to the invention and in Figure (2) with a commercially available 1-component polyurethane adhesive, ie without polyamide fibers. The adhesive application is about 175 g / m 2 .
  • the parts were joined by brushing with the two adhesives by hand on a horizontal surface and allowed to harden without staples, clamps, etc.
  • the adhesive joint was ground after curing for better optical evaluation.
  • Clearly visible is the foamed adhesive joint in the bonding in Figure 2, which is caused by the foaming by escaping carbon dioxide.
  • the adhesive joint with the adhesive according to the invention remains free of bubbles and much narrower and less visible.
  • this contains 0 to 10 wt .-% of excipients based on the total composition, which are selected from the group comprising thickeners, thixotropic agents, catalysts, defoamers, wetting agents, stabilizers, dyes, light fillers, optical brighteners, solvents and UV protectants.
  • Suitable thickeners are, for example, urea derivatives such as, for example, the products of Byk.
  • Thixotropic agents cause a plastic flow behavior. That is, up to stress values that are smaller than the yield point, the PU adhesive behaves like a solid body and as such, for example, is elastically deformable.
  • the PU adhesive flows only when the shear stress exceeds a certain value (yield point). Then the shear rate increases with the shear stress reduced by the yield point. However, the shear rate-dependent change in viscosity should be as independent of the shear time as possible, so that the viscosity returns to its original value with virtually no rest time when the shear stress is removed.
  • a suitable thixotropic agent in this sense is the highly disperse silica, with an addition of about 2 to 8, especially 3 to 7 and in particular 4 to 6 wt .-%, based on the prepolymer.
  • highly dispersed silicic acid is meant in particular a fumed silica which has been prepared by flame hydrolysis.
  • the fumed silica should be predominantly hydrophobic. This is the case when it is wetted only by a mixture of methanol and water, the methanol content is more than 50 vol .-%.
  • catalysts are especially tert. Amines or organometallic compounds, e.g. Iron, titanium or tin compounds.
  • Suitable defoamers are especially silicone oils such as z. Perenol 3270 company
  • wetting agents are primarily fatty chemical ester compounds such as e.g. Sovermol
  • Stabilizers are especially acid chlorides, e.g. Benzoyl chloride.
  • Dyes are mainly iron oxides or organic pigments.
  • Lightweight fillers are, above all, expanded organic polymers, such as, for example, products from EKA Chemicals or foamed glass, for example glass bubbles from 3M.
  • the 1-component polyurethane adhesive according to the invention is predominantly solvent-free. However, it may contain up to 5 wt .-%, preferably up to 2.5 wt .-%, in particular up to 1 wt .-% based on the total composition of solvent, for example, the theological behavior or the open or the processing time to influence.
  • adhesive compositions according to the invention also with solvent contents of up to 20 wt .-%. These still show the effects according to the invention of non-foaming during curing, but are not preferred for the above-mentioned environmental and health reasons.
  • the solvent used is an inert substance which is liquid at room temperature and boils at 200 ° C. under atmospheric pressure. Typical solvents are ethers, esters, ketones and aliphatic, cycloaliphatic or aromatic hydrocarbons.
  • the 1-component polyurethane adhesive is predominantly plasticizer-free. At most up to 5 wt .-% based on the total composition may be included.
  • Suitable plasticizers are, for example, esters such as adipic acid esters, phthalates, pure or mixed ethers or end-capped polyethylene glycols.
  • the 1-component polyurethane adhesive according to the invention is furthermore predominantly free of water. At most up to 1 wt .-% based on the total composition may be included.
  • UV protectants which can be used in the adhesive composition according to the invention are, for example, the so-called D Hindered Amine Light Stabilizers (HW).
  • HW D Hindered Amine Light Stabilizers
  • the one-component polyurethane adhesive foams almost completely during the bonding of substrates during curing. This is particularly advantageous because after the joining together and pressing of the substrates to be bonded to each other, a permanent pressing with the help of brackets or similar tools until the adhesive is completely cured is not required to achieve a firm and permanent bonding of the parts to be joined.
  • a further subject matter of the present invention is a process for preparing a 1-component polyurethane adhesive composition
  • a 1-component polyurethane adhesive composition comprising at least one NCO-terminated polyurethane prepolymer prepared from at least one polyol compound and at least one polyisocyanate with polyamide fibers and at least 10% by weight. based on fillers based on the total composition.
  • Another object of the present invention is the use of polyamide fibers in a 1-component polyurethane adhesive composition containing at least 10% by weight of fillers to reduce foaming upon curing. This is particularly advantageous because the nearly completely suppressed foaming or carbon dioxide bubble development during curing of the adhesive, the freshly bonded parts remain due to the cohesion of the uncured adhesive in position, without requiring fixing by means of brackets or similar clamping tools is.
  • Another object of the present invention is an adhesive method for virtually bubble-free bonding of substrates with a 1-component polyurethane adhesive composition in which a first adhesive surface coated with the adhesive composition, the second to adhering surface is pressed and then allowed to cure without the use of clamps or pressing.
  • the bond produced by two beechwood test specimens without the aid of pressing pressure has a tensile shear strength of at least 2.0 N / mm 2 , preferably more than 2.5 N / mm 2 , in particular more than 3 , 0 N / mm 2 , most preferably more than 3.5 N / mm 2
  • the adhesive is applied by means of a caulking gun to the broad side of the test specimen halfway along the length, and a second test specimen is placed 4 cm by hand, overlapping it on the adhesive test piece and joined until the adhesive visibly emerges from the joints.
  • the bonding takes place without clamping tools, ie without pressing pressure. This results in an adhesive surface of 50mm x 40mm and the Automatprüfenia has a total length of 120 mm.
  • test specimens After a curing time of 24 hours under standard conditions (23 ° C./50% relative humidity), the test specimens are torn in the tensile test using a testing machine (Instron, model 4302) (feed rate 50 mm / min.) And the maximum value determined. An average of 5 measurement results is determined.
  • Another object of the present invention is the use of the adhesive composition of the invention for bonding materials such as wood, wood-based materials, mineral substrates, metals, paper, cardboard, leather, textiles, non-woven fabrics, natural fibers, synthetic fibers or plastics. Test methods:
  • NCO content According to EN 1242 of 01/2006, in% by weight
  • the adhesive is introduced bubble-free into the holes of the test specimen described above using a caulking gun and immediately removed flat with a spatula.
  • the thus prepared test specimens then remain in the same climatic conditions for 24 h.
  • the height of the adhesive leaked out of the hole is determined with a thickness gauge.
  • the arithmetic mean of 6 readings is given as a percentage of the hole depth.
  • the information is given in%.
  • the beech wood bar In order to achieve the highest possible reproducibility, the beech wood bar must be left in the standard climate for at least 7 days before the test be conditioned, since the wood moisture greatly affects the measurement result.
  • the adhesive to be tested should also be stored at a temperature of 23 ° C.
  • the plate is fixed with the long broad side vertical in the Lot, pointing with the rough side to the front.
  • the test piece is thus 7 cm horizontally at an angle of 90 0 C to the plate free out.
  • test specimen After 24 h under the same climatic conditions, it is then checked whether the test specimen has come loose or is still in the same position in which it was positioned. Two measurement results are possible:
  • the screen printing plate (plate and test specimen) must be conditioned for at least 7 days in the standard atmosphere before the test, since the wood moisture greatly influences the measurement result.
  • the adhesive to be tested should also be stored at a temperature of 23 ° C. The test allows an almost practical statement as to whether an adhesive is suitable for assembly, firstly because the test specimen used in relation to its size brings a high weight, secondly, the dimensions of the specimen creates a large load lever and third, the surface on the test specimen being positioned is not flat but is rough.
  • the adhesive is applied by means of a caulking gun to the broad side of the test specimen halfway along the length, and a second test specimen is placed 4 cm by hand, overlapping it on the adhesive test piece and joined until the adhesive visibly emerges from the joints.
  • the bonding takes place without clamping tools, ie without pressing pressure. This results in an adhesive surface of 50mm x 40mm and the Automatprüfenia has a total length of 120 mm.
  • test specimens are torn in a tensile test using a testing machine (feed rate 50 mm / min.) And the maximum value is determined. An average of 5 measurement results is determined.
  • the beech timbers In order to achieve the highest possible reproducibility, the beech timbers must be conditioned for at least 7 days under standard conditions before the test, since the wood moisture strongly influences the measurement result.
  • the adhesive to be tested should also be stored at a temperature of 23 ° C.
  • test specimens are produced analogously to the test Tensile shear strength 1
  • test pieces After 24 hours curing under standard conditions, the test pieces for 3 to hours under tap water having a temperature of 23 ° C + - stored 1 0 C and subsequently torn apart (50 mm / min feed rate.) In the wet state in a tensile test using a testing machine and the maximum value certainly. An average of 5 measurement results is determined.
  • the beech timbers In order to achieve the highest possible reproducibility, the beech timbers must be conditioned for at least 7 days under standard conditions before the test, since the wood moisture strongly influences the measurement result.
  • the adhesive to be tested should also be stored at a temperature of 23 ° C.
  • test specimens are produced analogously to the test Tensile shear strength 1
  • test specimens 1 are h at 80 0 C + - stored for 1 ° C in a circulating air drying cabinet and torn (50 mm / min feed rate.) After removal hot within 10 seconds with the aid of a testing machine and the maximum value determined. An average of 5 measurement results is determined.
  • the beech timbers must be conditioned for at least 7 days under standard conditions before the test, since the wood moisture strongly influences the measurement result.
  • the adhesive to be tested should also be stored at a temperature of 23 ° C.
  • thermosetting wood adhesives for non-structural applications. Testing with a thin glue line.
  • Tested stress group C4, data in N / mm 2
  • the mixture is heated to 70 0 C. This is followed by the addition of 0.23 g of DBTL catalyst (dibutyldizine laurate, Brenntag). Due to the enthalpy of reaction, the reactor temperature automatically rises to over 95 ° C within two minutes. This temperature should not be exceeded, if necessary cool. At a post-stirring temperature of 80-85 0 C, the resulting prepolymer is stirred until the theoretical NCO content of 12.9% + - 0.3% is reached. This is followed by cooling to ⁇ 40 ° C under N 2 .
  • DBTL catalyst dibutyldizine laurate
  • the freshly prepared prepolymer is placed at a temperature between 30 0 C and 40 0 C in a Planetendissolver and incorporated 510 g of barium sulfate (EWO powder, Fa. Sachtleben) homogeneously. This is followed by a mixing for 30 min. under N2. Subsequently, 20 g of polyamide nylon 6.6 fiber (STW Schenkelzell) are incorporated homogeneously and another 45 min. at a temperature between 40 ° C and 50 0 C under vacuum ⁇ 30 mbar. The product thus obtained is then subsequently filled under protective gas into a PE cartridge without bubbles. After a maturing time of approx. 24 hours at approx. 23 ° C, the product has almost reached its final properties. A slight increase in the yield point is usually observed within a few days.
  • barium sulfate EWO powder, Fa. Sachtleben
  • Example 1 Adhesive properties, according to the invention
  • Example 2 Not according to the invention, comparative example
  • Example 1 Prepolymer as Example 1 and adhesive preparation as Example 1. but with 10 g nylon 6.6 nylon fiber and 520 g barium sulfate.
  • Example 1 Prepolymer as Example 1 and adhesive preparation as Example 1. but with 30 g nylon 6.6 nylon fiber and 500 g barium sulfate.
  • Example 5 Not according to the invention, comparative example with polyester fiber
  • Example 6 Not according to the invention, comparative example with polypropylene fiber
  • Example 7 Not according to the invention, comparative example with glass fiber
  • Example 8 Not according to the invention, comparative example with cotton fiber
  • 109.0 g of lupranate MIS (MDI mixture of 50% 4.4 and 50% 2,4, MDI Fa. BASF, NCO 33%) is placed in a stirrer glass reactor at 50 0 C under N2 and 109.0 g Desmodur M 44 (4.4 MDI Fa. Bayer, NCO 33%) was added and melted homogeneous. 251.7 g of dehydrated Accliam Polyol 6300 DWassergehalt ⁇ 400 ppm - (Trifunctional Polypropylenetherpolyol Fa. Bayer, OHZ 28) are then added to the approach. After a stirring time of 5 min. the mixture is heated to 70 0 C.
  • prepolymer 2 This gives a slightly yellowish turbid prepolymer (referred to below as prepolymer 2) having a viscosity of 1950 mPas and a practical NCO content of 14.1%.
  • the preparation of the adhesive (incorporation of fillers and / or fibers) was carried out as described in Example 1 in an evacuable dissolver, wherein first always the addition of the barium sulfate was carried out and after appropriate stirring and evacuation time, the polyamide substrate was incorporated.
  • the preparation of the adhesive without barium sulfate was carried out analogously. The received so Depending on their consistency, products were filled in cartridges or in a steam-tight container under N 2 .
  • Example 9 Not according to the invention, comparative example
  • Example 10 Not according to the invention, comparative example
  • Prepolymer 2 Preparation as described above, then admixed with 117.5 g of barium sulfate.
  • Example 11 Not according to the invention, comparative example
  • Prepolymer 2 Preparation as described above, then admixed with 9.6 g of polyamide fiber.
  • Example 15 Not according to the invention, Comparative Example Prepolymer 2 Preparation as described above, then admixed with 452.9 g of barium sulfate and 26.6 g of Disparlon 6500 (Synthetic polyamide wax from Kusumoto Chemicals Ltd.).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

La présente invention concerne une composition adhésive monocomposante de polyuréthanne à base d'au moins un prépolymère de polyuréthanne à terminaison NCO, comprenant des fibres de polyamide et au moins 10 % en poids de charges.
EP07822750A 2006-12-21 2007-11-20 Composition adhésive monocomposante à base de polyuréthanne non moussante Withdrawn EP2102262A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102006061787A DE102006061787A1 (de) 2006-12-21 2006-12-21 Nichtschäumende 1-Komponenten-Polyurethan-Klebstoffzusammensetzung
PCT/EP2007/062577 WO2008077689A1 (fr) 2006-12-21 2007-11-20 Composition adhésive monocomposante à base de polyuréthanne non moussante

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CN103360599B (zh) * 2013-08-15 2016-08-10 金发科技股份有限公司 一种半芳香族和脂肪族聚酰胺嵌段共聚物及其制备方法

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US5714563A (en) * 1996-01-16 1998-02-03 Depompei; Michael Frederick One-part, low viscosity, moisture curable composition
DE69908524T2 (de) * 1998-09-25 2004-05-06 Bando Chemical Industries Ltd., Kobe Treibriemen
DE19935452A1 (de) * 1999-07-28 2001-03-08 Basf Ag Faserhaltige Klebstoffzusammensetzung
DE10002236A1 (de) * 2000-01-20 2001-07-26 Frederik Piestert Rohrgewindeabdichtmittel
EP1199319B1 (fr) * 2000-10-20 2005-05-11 Basf Aktiengesellschaft Composition d'adhésif contenant des fibres
DE102005001565A1 (de) * 2005-01-13 2006-07-27 Bayer Materialscience Ag Holzklebstoffe

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US20100065211A1 (en) 2010-03-18
WO2008077689A1 (fr) 2008-07-03
DE102006061787A1 (de) 2008-06-26

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