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    • 专利摘要:
    The present invention relates to a silane-modified, one-component water-, solvent- and phthalate-free parquet adhesive and its use for the highly dimensionally stable bonding of parquet, wood flooring and wood-based panels with substrates in interior work.
    公开号:AT13606U1
    申请号:TGM9007/2011U
    申请日:2011-08-19
    公开日:2014-04-15
    发明作者:Frank Gahlmann
    申请人:Stauf Klebstoffwerk Gmbh；
    IPC主号:
    专利说明:

    Austrian Patent Office AT 13 606 Ul 2014-04-15
    Description: The present invention relates to a silane-modified, one-component water-, solvent- and phthalate-free parquet adhesive and its use for the highly dimensionally stable bonding of parquet, wooden floor coverings and wood-based panels with substrates for interior work.
    Conventional one and two-component parquet adhesive systems contain either solvents, water, hazardous substances such. Isocyanates or they do not reach the mechanical characteristics required for highly dimensionally stable parquet bonding, in particular with regard to tensile shear strength and elastic modulus. The parquet adhesive of the invention overcomes this problem by its specific, described in claim 1 composition based on at least one silane-terminated moisture-reactive polyalkylene oxide oligomer with at least three mineral components and suitable desiccant and adhesion promoter. Advantageously, additionally at least one curing catalyst, UV light absorber, antioxidant, plasticizer (phthalate-free), liquid extender and rheological additive are included. The terminal silane groups of the at least one polyakylene oxide oligomer are connected via urethane and / or urea groups with the oligomeric backbone. Desiccants and adhesion promoters contain moisture-reactive silane groups, preferably trimethoxysilane groups. The at least three mineral components are within each other and in relation to the ready-to-use product in defined mixing ratios and are characterized in terms of type, surface texture and particle size.
    The present invention relates to a silane-modified, one-component water, solvent and phthalate-free parquet adhesive and its use for highly dimensionally stable bonding of parquet, wood flooring and wood-based panels with substrates in interior design.
    When bonding wooden floor elements, in particular parquet, it has to be taken into consideration that wood is a working one. Material is. The wood flooring expands when absorbed by moisture and contracts when dried. The wood moisture can be e.g. by absorbing water from the substrate during the drying process of a fresh concrete or screed substrate or by varying the humidity levels over the course of the season. Additional influence is provided by the nature and intensity of the use of space, such as Duration and intensity of room heating, air conditioning or amount and frequency of water and / or snow inputs via e.g. Clothes or shoes. Another influence on the wood dimension is the ambient temperature, which depends mainly on the seasonal changes and the space heating or air conditioning.
    The expansions and shrinkages of the wood flooring occurring under these influences lead to shear forces, which must withstand the parquet adhesive and the bond and must reduce the parquet adhesive to a defined extent by deformation. Otherwise, there would be a risk of buckling, warping, cracks and fissures in the wood or the destruction of the substrate with the resulting damage patterns and problems in terms of safety, hygiene and appearance.
    In order to minimize this structural-physical problem, a minimum tensile shear strength of 3.5 N / mm 2 (type of storage A) is required in the DIN EN standard 14293: 2006-10 applicable to parquet adhesives.
    In addition to the tensile shear strength of the modulus of elasticity is a significant indicator of dimensional accuracy of the parquet bonding. As the modulus of elasticity increases, the elasticity of the cured adhesive decreases. This results in higher restoring forces of the adhesive matrix and causes the lining wood remains better fixed to the splice and a lower risk of buckling, warping, cracking and jointing formed.
    For bonding wood covering elements, in particular parquet, are usually 1/17 Austrian Patent Office AT13606U1 2014-04-15
    Adhesives, which can be divided into the following classes: dispersion adhesives, solvent adhesives, powder adhesives, methylene diisocyanate (MDI) based two-component polyurethane adhesives, MDI-based one-component polyurethane adhesives, toluene diisocyanate (TDI) based polyurethane adhesives and silane-modified polymer adhesives (SMP). adhesives).
    Since the fifties, dispersion adhesives based on vinyl acetate homopolymer dispersions are used for parquet bonding. They bind by evaporation of the water, whereby the adhesion is based solely on physical interactions of the molecules (dipole-dipole, van der Waals interactions). A disadvantage of these parquet adhesives used to date is the high water content, which can lead to significant swelling of the wood and consequently to large dimensional changes of the parquet and other wood flooring. Another disadvantage is the short time that remains for laying the wood flooring elements after the application of the adhesive on the ground (open time). The high glass transition temperature of the vinyl acetate homopolymers also requires the use of coalescing agents in order to achieve a filming of the dispersion at the processing temperature (room temperature). Coalescents are volatile organic compounds (VOCs) that are released into the indoor air even after a long period of time, even after parquet bonding, and can therefore pose environmental and health risks.
    A further development of the dispersion parquet adhesives based on vinyl acetate homopolymer dispersions are the parquet adhesives based on vinyl acetate-ethylene copolymer dispersions. For these similarly formulated adhesives, the lower glass transition temperature of the copolymer dispersions does not require coalescing agents. In addition, special dispersions based on styrene-acrylic acid ester copolymers are also used today. These adhesives can also be formulated without coalescents due to the low glass transition temperature of the dispersions. The disadvantage, however, remain the wood-swelling properties and the low open times of only 10 to 20 minutes.
    At the end of the sixties, solvent-resin parquet adhesives were introduced. These adhesives are based on solutions of vinyl acetate homopolymers in a solvent mixture which may contain methanol, ethanol, methyl acetate, ethyl acetate and acetone. They bind very quickly by evaporation of the solvent. The advantage of these parquet adhesives, which are still used today, is about 50 to 70% reduced wood-swelling properties compared to dispersion parquet adhesives. A disadvantage, however, is the high content of solvents, the emission of which means a burden for the processor and the environment, and consequently the use in interiors is limited. The products are usually characterized as highly flammable and harmful or irritating. In addition, the open times of this parquet adhesive class are particularly short (5 to 10 minutes) and thus detrimental to the processing process.
    A with respect to the solvent emissions advantageous development of these parquet adhesives is disclosed in a patent Stauf adhesive GmbH (US 7,420,009 B2: LOW EMISSION ADHESIVE COMPOSITION BASED A SOLVENT).
    Another development of the dispersion parquet adhesives are powdered adhesive formulations. These are based on re-emulsifiable dispersion powders - usually vinyl acetate-ethylene copolymers. They contain a mineral component, which may contain calcium sulfate hemihydrate, Portland cement or aluminate cement. These adhesives are 2-component systems consisting of powder and another component. The second component which is mixed with the powder component is water or a polymer dispersion. The advantage of this parquet adhesive class is the chemical water binding of the mineral component. The unfavorable wood swelling of the dispersion adhesives thereby reduces to about the level of the solvent-resin parquet adhesives. A disadvantage is the limited pot life between the mixing of the components and the processing end, in which the chemical reaction takes place, which increasingly causes an increase in viscosity. The insertion time (open time) between the application of the adhesive and the Austrian Patent Office AT13 606U1 2014-04-15
    Inserting the wooden floor element is just as short as with the dispersion parquet adhesives. Also disadvantageous are the inherent inherent in all two-component systems difficulties that are in the additional mixing effort, in the risk of non-homogeneous mixing and in an inadequate setting of the mixing ratio by the user.
    In the nineties reaction adhesives were introduced polyurethane-based for bonding parquet. Initially, they were two-component systems consisting of a resin component and an isocyanate hardener. The binder in the resin component is a hydroxy-functional polyol; the formulated resin component additionally contains water scavengers, mineral fillers, catalysts and additives. The isocyanate hardener component usually consists of technical, oligomeric methylene diphenyl diisocyanate (MDI, often referred to as polymer MDI). An advantage of these adhesives is compared to powder parquet adhesives again reduced and thus no longer relevant for practice wood-swelling effect and the longer open times of about 30 to 60 minutes. The very high strength of the bond with moduli of elasticity in the order of 40 to 100 N / mm2 and tensile shear strengths of 5 to 9 N / mm2 stands for excellent dimensional stability, which, however, comes with the disadvantage of a relatively high stress of the substrate. The shearing forces that occur can lead to fractures and cracking, especially in the case of substrates subject to weak points. Another disadvantage is the risk to health and the environment, which is based on the isocyanate content, and which may arise, inter alia. in the hazardous substance labeling according to the international GHS system or the German Hazardous Substances Ordinance. Thereafter, these adhesives are classified as harmful, irritating and sensitizing. Another disadvantage is the inherent problems of all two-component systems, as already described in the powder adhesives.
    Shortly after the two-component polyurethane adhesives reactive einkompo-nentige polyurethane parquet adhesives were developed. These adhesives are based on isocyanate-group-containing moisture-reactive prepolymers or oligomers based on methylene diphenyl diisocyanate (MDI), which often still contain oligomeric and monomeric MDI. Other components of these adhesives are mineral fillers, catalysts and additives. In comparison to the two-component polyurethane adhesives, the further extended open times (45 to 120 minutes), which together with the one-component facilitate the handling and processing of the adhesive, are advantageous. The wood-swelling effect corresponds to that of the two-component polyurethane adhesives and is accordingly unproblematic. Also advantageous are the mechanical properties. The bond strengths achieved on the one hand cause a high degree of dimensional stability, on the other hand a background stress which is lower than that of the two-component polyurethane systems. However, a disadvantage of the one-component polyurethane adhesives is still the risk to health and the environment, which corresponds to that of the two-component polyurethane parquet adhesives and based on a residual content of monomeric and oligomeric MDI in the prepolymers or oligomers ren.
    End of the nineties, one-component reaction adhesives based on toluene diisocyanate oligomers (TDI adhesives) were introduced for bonding wood flooring.
    The advantage of these adhesives compared to the established MDl-based polyurethane adhesives is that they are not classified as harmful, irritating or sensitizing and are not subject to labeling under the current international GHS labeling system and the German Hazardous Substances Regulation. This property is due to their extremely low residual content of monomeric TDI. In terms of open time and wood-swelling properties, they are similar to MDI-based polyurethane adhesives. A disadvantage in comparison to these, however, is the significantly higher elasticity and lower strength and dimensional stability of the bond produced. The usual in MDl-based polyurethane, dispersion, powder and solvent adhesives moduli are below in the range of an order of magnitude. Thus, TDI-based polyurethane adhesives are particularly suitable for parquet bonding on unstable substrates, which require only a minimum of stress from shear and abrasion. The Austrian Patent Office AT 13 606 Ul 2014-04-15
    Traction forces tolerate.
    The latest development are parquet adhesives based on silane-modified oligomeric compounds, so-called SMP adhesives (sometimes referred to as hybrid adhesives). These adhesives are characterized by oligomeric organic compounds (often referred to as prepolymers), the moisture-reactive silane groups, usually dimethoxymethyl-silane or Trimethoxysilangruppen wear. After contact with moisture from the ground, the plank wood or the air, the moisture-reactive silane groups crosslink by hydrolysis and subsequent condensation to form a three-dimensional siloxane network, the adhesive matrix.
    Further constituents of these adhesives are typically liquid extenders, plasticizers, mineral fillers, water scavengers, adhesion promoters, catalysts and other additives.
    For the bonding of parquet silane-modified adhesives usually have the following advantages: - One-component - free of water and solvents - sufficiently long open times - no practice-relevant wood-swelling effect [0025 ] - no classification as harmful to health or to the environment and thus free of labeling according to the German Ordinance on Hazardous Substances and the international GHS labeling system The pseudoplastic rheology of SMP parquet adhesives is furthermore advantageous. In practice, this means that the adhesives do not run and can be applied well with a toothed spatula. Drawn adhesive beads remain dimensionally stable and thus provide an important prerequisite to be able to bridge smaller cavities between wood flooring and substrate.
    A disadvantage of the SMP parquet adhesives - similar to the label-free TDI-based polyurethane adhesives - the high elasticity and low strength of the polymer matrix formed after curing. The mechanical properties are better than those of the label-free TDI-based polyurethane adhesives. However, they are still insufficient for a highly dimensionally stable bond. Typically, the tensile shear strengths are in the range of 1.0 to 2.0 N / mm 2 and the moduli of elasticity in the range of 1.0 to 3.0 N / mm 2. They are thus well below the levels achieved by conventional parquet adhesives from the group of polyurethane, dispersion, powder and solvent adhesives. While the latter usually comply with the requirements of DIN EN 14293 regarding minimum tensile shear strength, this is not the case with SMP parquet adhesives. According to the current state of the art, a tensile shear strength of 4.0 N / mm 2 (test conditions DIN EN 14293: 2006-10, storage type A) and a modulus of elasticity of 7.5 N / mm 2 (test conditions DIN EN ISO 527-1: 1996-04 and DIN EN ISO 527-3: 2003-07) of no silane-modified parquet adhesive - a circumstance that hitherto precludes greater acceptance and use of these parquet adhesives.
    Starting from this prior art, it is an object of the present invention to provide a parquet adhesive available, which has all or more of the following advantages: It should be easy to use, ensure a sufficiently long open time, no relevant wood-swelling effect have good health and environmental properties, be free of water, solvents and phthalates, have good adhesion properties to the usual interior surfaces, produce a high bond strength and ensure a high dimensional stability of the bonded wood surface. Advantageously, the provided parquet adhesive should have a tensile shear strength of at least 4.0 N / mm 2 (test conditions DIN EN 14293: 2006-10, storage type A) and a modulus of elasticity of at least 4/17 Austrian Patent Office AT 13 606 Ul 2014-04-15 7 , 5 N / mm2 (test conditions DIN EN ISO 527-1: 1996-04 and DIN EN ISO 527-3: 2003-07). Another object of the invention is to provide the use of the parquet adhesive according to the invention for the bonding of parquet, wood flooring and wood-based panels with customary in interior surfaces under the stated objectives for the parquet adhesive.
    This object is achieved by the one-component, silane-modified, water-solvent and phthalate-free parquet adhesive according to claim 1, and its use according to claim 10. Advantageous developments of the parquet adhesive according to the invention and the use of the invention are given in the respective dependent claims.
    The parquet adhesive according to the invention is a silane-modified parquet adhesive with significantly improved mechanical properties. He has the processing and application advantages of the state of the art SMP parquet adhesives, without having their disadvantageous low strengths and the associated Maßhaltigkeitsprobleme. The advantageous mechanical properties of the parquet adhesive according to the invention, in particular with regard to tensile shear strength and elastic modulus, are essentially attributable to the selection of a suitable base polymer in combination with a specially composed composition of at least three mineral components of defined type, surface quality and particle size. In addition, the selection of a suitable drying agent and adhesion promoter is responsible for the advantageous adhesive properties.
    According to the invention, the one-component, silane-modified, water-solvent and phthalate-free parquet adhesive which is suitable for highly dimensionally stable bonding of parquet, wooden floor coverings and wood-based panels with surfaces customary in interior construction contains the following substances or consists of them: [0033] a) 10 to 30% by mass of a moisture-reactive silane-terminated polyalkylene oxide binder having an average molecular weight of 6,000 to 20,000 g / mol, wherein the silane functions via urethane and / or urea groups are connected to the oligomeric skeleton, b) 30 to 60 % By mass of a surface-hydrophobized chalk powder having an average particle diameter of 0.8 to 4.0 μm, c) 2 to 10% by mass of a surface-hydrophobized chalk powder having an average particle diameter of 0.2 to 0.7 μm, [0036] d) 3 to 15% by mass of a surface hydrophobized wollastonite with a medium a needle length of 15 to 60 pm and an average aspect ratio of 3: 1 to 12: 1, e) 0.2 to 3% by mass of a moisture-reactive silane-modified drying agent, f) 0.3 to 4% by mass of a moisture-reactive silane-modified adhesion promoter, wherein the percentages refer to the mass of the ready-to-use parquet adhesive and the sum of the components a) to f) is 45.5% to 100%.
    In particular, the parquet adhesive may have the following proportions of constituents: a) 16 to 26% by mass of a moisture-reactive silane-terminated polyalkylene oxide binder having an average molecular weight of 7,000 to 13,000 g / mol, the terminal silane functions via urethane and / or or urea groups are bonded to the oligomeric skeleton, b) 44 to 54% by mass of a surface-hydrophobized chalk powder having a mean particle diameter of 0.8 to 1.8 μm, 5/17 Austrian Patent Office AT13 606U1 2014-04-15 [0042] c) 3 to 6 mass% of a surface hydrophobized chalk powder having an average particle diameter of 0.3 to 0.6 μm, d) 5 to 10 mass% of a surface hydrophobized wollastonite having an average needle length of 25 to 45 μm and an average aspect ratio of 5 : 1 to 10: 1, e) 0.5 to 1.5 mass% of a moisture-reactive silane-modified T rockenmit means, f) 1 to 3 percent by mass of a moisture-reactive silane-modified adhesion promoter, wherein the percentages refer to the mass of the ready-to-use parquet adhesive and the sum of the components a) to f) is 69.5% to 100%.
    According to a preferred embodiment, the mass ratio of component b) to component c) is 6: 1 to 16: 1 and the mass ratio of component c) to component d) 1: 1 to 1: 2. It is particularly advantageous if the mass ratio of component b) to component c) is 9: 1 to 15: 1 and the mass ratio of component c) to component d) is 1: 1.5 to 1: 2.
    As a base polymer and binder of parquet adhesive according to the invention contains 10 to 30 mass%, preferably 16 to 26 mass%, most preferably 21.5 mass% of a moisture-reactive silane-terminated polyalkylene whose silane functions are connected via urethane and / or urea groups with the oligomeric backbone. Preferably, the oligomeric backbone is a polypropylene oxide and the silane functions are trimethoxysilane groups. The average molecular weight of the oligomer is between 6,000 and 20,000 g / mol, preferably between 7,000 and 13,000 g / mol, most preferably at 10,000 g / mol.
    At least two mineral components are chalk powder having an average particle size in each case from 0.8 to 4.0 μm, preferably 0.8 to 1.8 μm, very particularly preferably 1.0 μm and from 0.2 to 0.7 pm, preferably 0.3 to 0.6 pm, very particularly preferably 0.4 pm.
    The chalk powder having the larger particle size is 30 to 60% by mass, preferably 44 to 54% by mass, most preferably 49.1% by mass in the parquet adhesive of the present invention, while the smaller particle size is 2 to 10% by mass, preferably 3 to 6 Mass percent, most preferably 4 percent by mass is included.
    A substitution of the chalks by precipitated calcium carbonate powder is not possible because they have smaller than the particle sizes required according to the invention. Likewise, the substitution of the chalks with other calcium carbonate rocks, such as limestone, does not lead to the advantages according to the invention. The surfaces of the chalk particles are hydrophobic.
    At least one further mineral component is the fibrous structured silicate wollastonite, which is 3 to 15 percent by mass, preferably 5 to 10 percent by mass, most preferably 7 percent by mass and has an average needle length of 15 to 60 pm, preferably 25 to 45 pm , most preferably 39 pm and an average aspect ratio of 3: 1 to 12: 1, preferably 5: 1 to 10: 1, most preferably 7: 1. The surfaces of wollastonite are hydrophobic.
    The hydrophobization of the chalk and silicate particles is carried out either by treatment with one or more fatty acids and / or their salt (s), preferably by treatment with stearic acid and / or stearate or by silanization, preferably by reaction with a reactive silane. most preferably by reaction with aminosilane.
    As a water scavenger the parquet adhesive according to the invention contains 0.2 to 3 mass%, preferably 0.5 to 1.5 mass%, most preferably 0.8 mass% of a moisture-reactive silane-modified drying agent. Trimethoxysilane-terminated 6/17 Austrian Patent Office AT 13 606 Ul 2014-04-15
    Alkenes are preferably used, vinyl trimethoxysilane is very particularly preferred.
    To improve the adhesion properties of parquet adhesive according to the invention contains 0.3 to 4 mass%, preferably 1 to 3 mass%, most preferably 1.9 mass% of a moisture-reactive silane-modified adhesion promoter. Tri-methoxysilane-terminated aminoalkyl compounds are preferably used, very particular preference is given to 3-aminopropyltrimethoxysilane.
    To accelerate the curing process, the parquet adhesive according to the invention may advantageously contain up to 0.1 mass%, preferably 0.005 to 0.05 mass%, most preferably 0.025 mass% of a curing catalyst. Organo-transition metal compounds are preferred curing catalysts, most preferably dibutyltin diacetylacetonate.
    To improve the durability of parquet adhesive according to the invention may advantageously additionally antioxidant and / or UV light absorber (photostabilizers) of up to 3 percent by mass, preferably 0.1 to 1 mass percent, most preferably 0.2 percent by mass.
    The antioxidants used are preferably sterically hindered phenols, preferably 3,5-bis (1,1-dimethylethyl) -4-hydroxybenzylpropanoic acid C7-C9 isoalkyl esters.
    Sterically hindered amines are preferably used as UV light absorbers, preferably bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate or methyl-1,2,2,6,6-pentamethyl -4-piperidyl; very particular preference is given to a mixture of these sebacates.
    To set a processing-friendly viscosity of parquet adhesive according to the invention may advantageously plasticizer and / or liquid extender of up to 20 percent by mass, preferably 7 to 15 mass percent, most preferably 10.8 mass percent included.
    As plasticizers it is possible to use aromatic alkylsulfonic acid esters, aliphatic cyclic carboxylic acid esters or aliphatic cyclic dicarboxylic esters, preferably 1,2-cyclohexanedioic acid diisononyl esters.
    As a liquid extender, polyether polyols, preferably polypropylene oxide having a molecular weight of 300 to 3000 g / mol, preferably 700 to 1300 g / mol; most preferably used at 1,000 g / mol.
    On the use of otherwise commonly used phthalates is completely omitted due to the suspected toxic effects on reproduction. The composition of the parquet adhesive according to the invention has the effect that this does not have a disadvantageous effect but that the advantageous properties of silane-modified parquet adhesives remain. In addition, the mechanical properties are significantly improved and a high dimensional accuracy of the parquet bonding is guaranteed.
    As an additional binder and reactive diluent, the parquet adhesive according to the invention may contain up to 10% by mass, preferably 2 to 6% by mass, most preferably 4% by mass of a moisture-reactive silane-terminated polyalkylene oxide whose silane functions are linked to the oligomeric backbone via alkyl groups. Preferably, the oligomeric backbone is a polypropylene oxide and the silane functions are dimethoxymethylsilane groups. The average molecular weight of the oligomer is between 300 and 3000 g / mol, preferably between 700 and 1300 g / mol, very particularly preferably at 1000 g / mol.
    As a rheological additive, the parquet adhesive according to the invention may additionally contain up to 3% by mass, preferably 0.3 to 1.3% by mass, very particularly preferably 0.675% by mass of a wax, preferably a polyamide wax.
    The individual constituents of the adhesive composition according to the invention may in each case be present as pure substances or, if applicable to the respective constituent AT13 606U1 2014-04-15
    Criteria such as total proportion, mass ratio, molecular weight, structure, chemistry, particle size, needle length, aspect ratio and / or surface finish remain met, as a mixture of similar substances.
    To improve or adjust the appearance, rheology and / or stability of the parquet adhesive of the invention may contain other additives such as pigments, dyes, organic / inorganic fillers, resins, waxes or preservatives.
    The parquet adhesive according to the invention has a number of processing and application-technical advantages, which does not combine in this combination any other parquet adhesive: Single-component · free of water, solvents and phthalates. · Sufficiently long open time no practice-relevant wood-swelling effect no classification as hazardous to health and without labeling according to current GHS labeling system and German Hazardous Substance Regulation high adhesion strength, to be read in particular at the tensile shear strength high Dimensional accuracy of the glued plank wood, to be read in particular on the modulus of elasticity · pronounced pseudoplastic rheology with suitable processing viscosity easy application by means of toothed spatula and structurally resistant adhesive beads good adhesion properties to damp and dry in the interior finishing übli chen
    Substrates Simple and Safe Handling and Processing The parquet adhesive according to the invention is one-component and free of water, solvents and phthalates.
    The open time is in the range of 50 to 70 minutes (DIN EN 14293: 2006-10), which ensures a comparatively long processing time.
    Due to its freedom from water and solvents, there is no practice-relevant wood-swelling effect of the adhesive.
    The absence of solvents and the complete abandonment of the addition of phthalates, isocyanates and other potentially harmful substances requires the health and environmental compatibility of the parquet adhesive according to the invention. This can be deduced from the fact that the adhesive does not require labeling in accordance with the current German Hazardous Substances Ordinance and the international GHS Hazardous Substance Labeling System.
    The parquet adhesive of the invention has a tensile shear strength of > 4.0 N / mm 2 (DIN EN 14293: 2006-10, storage type A) and a modulus of elasticity of > 7.5 N / mm2 (DIN EN ISO 527-1: 1996-04 and DIN EN ISO 527-3: 2003-07). Strength values of this magnitude are unprecedented with silane-modified parquet adhesives. They guarantee a high dimensional accuracy of the bonded wood flooring even under mechanical and / or climatic stress. The substrate is also not mechanically stressed as much as is the case with two-component polyurethane adhesives.
    The pronounced pseudoplastic rheology and a viscosity between 80,000 and 140,000 mPa * s (test conditions according to DIN EN ISO 2555: 2000-01, 20 revolutions per minute) together with the one-component guarantee easy handling and processing of the adhesive according to the invention. The adhesive can be easily applied with a toothed spatula and allows for more stable adhesive beads up to a height of 10 mm and 8/17 Austrian Patent Office AT 13 606 Ul 2014-04-15.
    The parquet adhesive according to the invention has excellent adhesion properties on interior surfaces usual substrates, such as concrete, cement, cement screed, Zementfließestrich, cement mortar, cement bonded wood fiber, ceramic, natural stone, calcium sulfate screed, calcium sulfate flow, magnesite screed, wood, wood material, plywood, cork, gypsum, gypsum fiber , Plasterboard, hardboard, mineral putty, textile fibrous material or a combination of these substrates. The adhesion is also limited to substrates containing up to 8% by mass of water, e.g. damp concrete or cement screed, not impaired.
    Commercially available parquet, wood flooring and / or wood-based panels, which consist entirely or partially of European hardwood and / or softwood, non-European wood or a combination of these types of wood, are securely and highly dimensionally adhered to the substrate.
    The advantageous properties of the parquet adhesive according to the invention guarantee a simple and safe handling and processing of the adhesive.
    In Table 1, an embodiment of the parquet adhesive according to the invention is given with a particularly preferred composition.
    In Table 5 and 6, the compositions of the commercial parquet adhesives SMP-920 and SMP-930 (Stauf adhesive GmbH) are summarized. They serve in subsequent investigations as a reference to the adhesive according to the invention.
    In their composition, the two commercial parquet adhesives differ from the parquet adhesive according to the invention essentially by a different composition of base polymer and mineral components and their phthalate content. For example, the surface-hydrophobized fibrous-structured silicate wollastonite-an indispensable mineral constituent of the adhesive according to the invention-is not contained in the commercial adhesives. On the other hand, both commercially available adhesives contain limestone powder and in some cases also precipitated calcium carbonates and silica, which does not occur in the parquet adhesive according to the invention. Also, the mean particle diameters and their distribution profiles differ between inventive adhesive and the commercial formulations. Thus, e.g. Particle sizes of powdery mineral components of > 4 pm not included in the parquet adhesive according to the invention. Another difference lies in the phthalate content, which is 11% by mass (bis (2-propylheptyl phthalate) in the case of SMP-930 and 20% by mass (diisononyl phthalate) of the ready-to-use adhesive mixture in the parquet adhesive according to the invention, on the other hand, in the context of a reprotoxic Effect of phthalates, SMP-930 is considered to be of higher value compared to SMP-920.
    The tensile shear strength of the parquet adhesive according to the invention (composition according to Table 1) was determined according to DIN EN 14293: 2006-10 (storage type A) and compared with the commercially available silane-modified parquet adhesives (SMP-920 and SMP-930, Stauf adhesive GmbH).
    Compared to the commercially available silane-modified parquet adhesives SMP-920 and SMP-930 (Stauf adhesive GmbH), the tensile shear strengths summarized in Table 2 were obtained.
    The results show that the parquet adhesive according to the invention in comparison to SMP-930 has a 124% higher tensile shear strength and in comparison to SMP-920 even a 146% higher tensile shear strength. The minimum tensile shear strength of 3.5 N / mm 2 required according to DIN EN 14293: 2006-10 and the tensile shear strength of at least 4.0 N / mm 2 (bearing type A) claimed in accordance with the invention are achieved or significantly exceeded.
    The modulus of elasticity of the parquet adhesive according to the invention (composition according to Table 1) was determined in accordance with DIN EN ISO 527-1: 1996-04 and DIN EN ISO 527-3: 2003-07 9/17 Austrian Patent Office AT 13 606 Ul 2014-04- 15 determined. In comparison with the commercially available silane-modified parquet adhesives SMP-920 and SMP-930, the moduli of elasticity summarized in Table 3 resulted.
    The results show that the parquet adhesive according to the invention in comparison to SMP-930 has a 367% higher modulus of elasticity and compared to SMP-920 even 462% higher elastic modulus. The modulus of elasticity of at least 7.5 N / mm 2 claimed according to the invention is not only achieved but significantly exceeded.
    With the inventive parquet adhesive described in Table 1, the dimensional stability of the bonded parquet was determined (experimental design according to the single figure) and with the commercially available silane-modified parquet adhesives (SMP-920 and SMP-930, Stauf adhesive GmbH) with phthalate content of 20 (SMP -920) and 11 mass% (SMP-930).
    For this purpose, 120 cm x 50 cm x 5 cm concrete slabs (strength class C 20/25 according to DIN EN 206-1: 2001-07) were stored to constant weight under normal conditions, 23 ° C and 50% relative humidity to constant weight. The adhesive to be tested was uniformly applied to the concrete slabs in a defined layer thickness of 0.85 mm. Immediately after the application of adhesive, twenty square-cut and planed red beech sticks measuring 25 cm × 5 cm × 1 cm long were inserted without seams on the longitudinal side and pressed lightly under normal climatic conditions. Only red beech sticks with half-rift incision were used, i. the orientation of the annual rings on the 1cm x 5cm head was 45 °. The bond was then allowed to cure for 28 days under normal conditions (23 ° C / 50% relative humidity) in a climatic chamber and stored. The initial length of the measuring section was measured perpendicular to the width of the adjacent bars (initial length LA, with 20 bars approx. 1 m). Subsequently, the climate was changed to 10Ό and 85% relative humidity. Under these climatic conditions, the wood moisture increases, the red beech rods try to expand and, as a result of the broad growth of the rods, the measuring section lengthens. The extent of this horizontal expansion depends on the mechanical properties of the adhesive. After 20 days, the length value of the measuring section (LB) was read again. The results are summarized in Table 4.
    From the results it can be seen that the parquet adhesive according to the invention, in contrast to the commercially available silane-modified parquet adhesives SMP-920 and SMP-930 allows a significantly lower wood expansion. Compared to SMP-930, the horizontal wood extent is reduced by 55.6% and 60.1% compared to the slightly more elastic SMP-920. This directly confirms the high dimensional stability of the covering wood glued with the parquet adhesive according to the invention.
    The open time of the adhesive according to the invention (composition according to Table 1) was determined according to DIN EN 14293: 2006-10. It was 60 minutes, i. Within this period after applying the adhesive, wooden floor coverings can still be pressed into the adhesive layer and glued to the substrate. The removal of already laid coverings and their realignment is within this period readily feasible.
    With the inventive parquet adhesive described in Table 1, the viscosity was determined according to DIN EN ISO 2555: 2000-01 (20 rev / min). At 20 rpm, a viscosity of 109,700 ± 6,800 mPa * s (n = 5) was measured. The viscosity is therefore in the range of 80,000 to 140,000 mPa * s, which guarantees easy spreadability and dimensionally stable adhesive beads up to a height of more than 10 mm. In combination with the one-component and the open time, this means easy handling and processing of the parquet adhesive according to the invention. 10/17 AT 13 606 Ul 2014-04-15 Austrian
    Patent Office
    Raw material Chemistry Function Manufacturer Percentage [%] Geniosil STP-E 15 Trimethoxysilane-terminated polyurethane oligomer, MW: approx. 10,000 g / mol binder, base polymer Wacker Chemie 21,5 Omyalite 95 T chalk powder, surface-hydrophobic with stearic acid, medium Particle diameter: 1.0 μm Mineral component Omya 49.1 Omyabond 302 Cretaceous powder surface-hydrophobicized with stearic acid, average particle diameter: 0.4 μm Mineral component Omya 4 Tremin 939 100 AST Wollastonite, surface silanized, mean needle length 39 μm, average aspect ratio 7: 1 Mineral component Quartz works 7 Geniosil XL 10 Vinyltrimethoxysilane Desiccant Wacker Chemie 0.8 Geniosil GF 96 3-aminopropyltrimethoxysilane Bonding agent Wacker Chemie 1,9 Metatin K 740 Dibutyltin diacetylacetonate Catalyst Acima 0,025 Tinuvin 765 Mixture of bis (1,2,2,6,6 pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate UV light absorber Ciba 0.05 Irganox 1135 3,5-bis (1,1-dimethylethyl) -4-hydroxybenzylpropanoic acid C7-C9 isoalkyl ester Antioxidant Ciba 0.15 Hexamoll DINCH 1,2-cyclohexanedicarboxylic acid diisononyl ester Plasticizer BASF 5 Desmophen 1110 BD Polypropylene oxide, MW : about 1,000 g / mol of liquid extender Bayer Material Science 5,8 SAT 010 dimethoxymethylsilane-terminated polypropylene oxide oligomer, MW: about 1,000 g / mol binder, reactive diluent Kaneka 4 Disparlon 6100 polyamide wax rheological additive Kusumoto 0.675 [00101] Table 1 Exemplary, particularly preferred composition of the parquet adhesive according to the invention (percentages by weight).
    Adhesive Tensile shear strength ± SD Inventive adhesive (composition shown in Table 1) 4.31 ± 0.27 N / mm 2 (n = 8) SMP-930 1.92 ± 0.17 N / mm 2 (n = 7) SMP-920 1 , 75 ± 0.20 N / mm 2 (n = 6) Table 2: Results of the tensile shear strength test according to DIN EN 14293: 2006-10 (Type A storage) of parquet adhesive according to the invention, SMP-930 and SMP-920. Measured values ± standard deviation (SD) and number of the respective measurements (s). 11/17 AT 13 606 Ul 2014-04-15 Austrian
    Patent Office
    Adhesive Modulus of elasticity ± SD Inventive Adhesive (composition shown in Table 1) 8.54 ± 0.46 N / mm 2 (n = 8) SMP-930 1.83 ± 0.26 N / mm 2 (n = 7) SMP-920 1 , 52 ± 0.18 N / mm 2 (n = 7) Table 3: Results of the elastic modulus test according to DIN EN ISO 527-1: 1996-04 and DIN EN ISO 527-3: 2003-07 on parquet adhesive according to the invention, SMP -930 and SMP-920. Measured values ± standard deviation (SD) and number of the respective measurements (s).
    Adhesive No. of Measurement La [mm] Lb [mm] Change La - Lb [% 1 According to Table 1 1 1018.2 1021.7 0.3437 μ 2 1017.6 1020.4 0.2752 μ 3 1020.3 1023.6 0.3234 μ 4 1019.7 1022.5 0.2746 H 5 1016.1 1019.3 0.3149 H 6 1018.8 1021.1 0.2258 H 7 1016.6 1019.8 0.3148 H 8 1017.4 1019.7 0.2261 Mean 1018.1 1021.0 0.2873 Standard Deviation 1.46 1.51 0.0445 SMP-930 1 1017.1 1024.7 0.7472 M 2 1019.8 1026 , 4 0.6472 M 3 1020.3 1025.9 0.5489 H 4 1016.3 1022.5 0.6101 M 5 1017.6 1026.7 0.8943 M 6 1018.5 1024.5 0.5891 M 7 1020.3 1025.3 0.4901 mean 1018.6 1025.1 0.6446 standard deviation 1.62 1.43 0.1335 SMP-920 1 1020.8 1027.9 0.6955 M 2 1020.1 1028, 4 0.8136 II 3 1018.1 1025.9 0.7661 ((4 1017.9 1025.5 0.7466 II 5 1020.1 1026.7 0.6470 II 6 1017.4 1025.5 0.7961 II 7 1019.4 1025.3 0.5788 mean value 1019.1 1026.5 0.7206 standard deviation 1.31 1.25 0.0849 [00104] Table 4: Results of the dimensional measurement of inventive P arkettklebstoff (composition according to Table 1), SMP-920 and SMP-930 (Stauf adhesive GmbH). 12/17 AT13 606U1 2014-04-15 Austrian
    Patent Office
    Raw material Chemistry Function Manufacturer Percent [%] S 203 H Dimethoxymethylsilane-terminated polypropylene oxide oligomer; MW: about 12,000 g / mol binder, base polymer Kaneka 11 S 303 H dimethoxymethylsilane-terminated polypropylene oxide oligomer; MW: approx. 18,000 g / mol binder, base polymer Kaneka 6 Silquest A-171 vinyltrimethoxysilane desiccant mimic 0,7 Silquest A-1637 4-amino-3,3-dimethylbutyltrimethoxysilane adhesion promoter motto 0.7 TIB KAT 223 dioctyltin bis (2,4-pentanedionate) Catalyst TIB Chemicals 0.34 Irganox 1726 4,6-Bis (dodecylthiomethyl) -o-cresol Antioxidant Ciba 0.1 DINP Diisononyl phthalate Plasticizer BASF 20 Crayvallac SLX Polyamide wax Rheological additive Cray Valley 0.4 Omya BLP 3 Limestone powder, surface-hydrophobed with stearic acid, average particle diameter: 5.7 μm Mineral component Omya 19.5 Calcilite 6 HS Limestone powder, surface-hydrophobic with stearic acid, average particle diameter: 7 μm Mineral component Alpha-Calcite 8.66 MS 70 F Limestone powder, average particle diameter: 4.5 pm Mineral component Beautiful and Hippelein 15 Calcifin 20 H Limestone powder, surface-hydrophobic with stearic acid, average particle diameter diameter: 4.4 μm Mineral component alpha-calcite 16 HDKH 18 Highly dispersed silicic acid, surface silanized Mineral component Wacker 1.6 [00105] Table 5: Composition of the commercially available parquet adhesive SMP-920 (Stauf Klebstoffwerk GmbH; Shares in mass percent). 13/17 Austrian Patent Office AT13 606U1 2014-04-15
    Raw material Chemistry Function Manufacturer Percent [%] S 203 H Dimethoxymethylsilane-terminated polypropylene oxide oligomer; MW: about 12,000 g / mol of binder, base polymer Kaneka 3 S 303 H dimethoxymethylsilane-terminated polypropylene oxide oligomer; MW: approx. 18,000 g / mol binder, base polymer Kaneka 16 Dynasylan VTMO vinyltrimethoxysilane dry agent Degussa 0.8 KBM 603 N-2- (aminoethyl) -3-aminopropyltrimethoxysilane adhesion promoter Shin-Etsu 0.8 Neostann U 220 H dibutyltin diacetylacetonate catalyst Nitto Kasei 0.32 Irganox 1726 4,6-Bis (dodecylthiomethyl) -o-cresol Antioxidant Ciba 0.1 Paiatinol 10-P Bis (2-propylheptylphthalate) Plasticizer BASF 11 Mesamoll Phenolalkylsulfonic acid ester Plasticizer Bayer 4 Thixatrol MAX Polyamide wax Rheological additive elementis 0 , 5 Omyacarb 10 BG Limestone Powder, average particle diameter: 7 pm Mineral component Omya 19.5 Calcifin 20 H Limestone powder, surface-hydrophobic with stearic acid, average particle diameter: 4.4 pm Mineral component Alpha Calcite 41.58 Socal 312 Precipitated calcium carbonate, coated, average particle diameter: 0.07 pm Mineral component Solvay 2.4 Table 6: Composition of the commercial parquet Influent SMP-930 (Stauf Klebstoffwerk GmbH; Shares in mass percent). 14/17
    权利要求:
    Claims (10)
    [1]
    Austrian Patent Office AT 13 606 Ul 2014-04-15 Claims 1. Water-based, solvent-free and phthalate-free one-component parquet adhesive based on silane-terminated polyalkylene oxide oligomers, characterized in that it contains or consists of the following substances: a) 10 bis 30 mass percent of a moisture-reactive silane-terminated polyalkylene oxide binder having an average molecular weight of 6,000 to 20,000 g / mol, wherein the silane functions are connected via urethane and / or urea groups with the oligomeric skeleton, b) 30 to 60 mass percent of a surface hydrophobicized chalk powder with a c) 2 to 10% by mass of a surface-hydrophobized chalk powder having an average particle diameter of 0.2 to 0.7 gm, d) 3 to 15% by mass of a surface-hydrophobized wollastonite having an average needle length of 15 to 60 pm and a mean aspect ratio of n 3: 1 to 12: 1, e) 0.2 to 3% by mass of a moisture-reactive silane-modified desiccant, and f) 0.3 to 4% by mass of a moisture-reactive silane-modified adhesion promoter, the percentages being based on the mass of the ready-to-use parquet adhesive and the sum the constituents a) to f) is 45.5% to 100%.
    [2]
    2. water, solvent and phthalate-free one-component parquet adhesive according to claim 1, characterized in that it contains or consists of the following substances: a) 16 to 26 mass% of a moisture-reactive silane-terminated polyalkylene oxide binder having an average molecular weight of 7,000 to 13,000 g / mol, wherein the terminal silane functions via urethane and / or urea groups are connected to the oligomeric skeleton, b) 44 to 54% by mass of a surface-hydrophobized chalk powder having an average particle diameter of 0.8 to 1.8 pm, c) 3 bis 6% by mass of a surface hydrophobized chalk powder having an average particle diameter of 0.3 to 0.6 μm, d) 5 to 10% by weight of a surface-hydrophobized wollastonite having an average needle length of 25 to 45 μm and an average aspect ratio of 5: 1 to 10: 1, e) 0.5 to 1.5% by mass of a moisture-reactive silane-modified Tro and f) 1 to 3% by mass of a moisture-reactive silane-modified adhesion promoter, the percentages being based on the mass of the ready-to-use parquet adhesive and the sum of constituents a) to f) being 69.5% to 100%.
    [3]
    3. water, solvent and phthalate-free one-component parquet adhesive according to one of the preceding claims, characterized in that the mass ratio of component b) to component c) 9: 1 to 15: 1 and the mass ratio of component c) to component d) is 1: 1.5 to 1: 2.
    [4]
    4. Water-, solvent- and phthalate-free one-component parquet adhesive according to one of the preceding claims, characterized in that the terminal silane groups of the silane-terminated polyalkylene oxide binder according to a) are trimethoxysilane groups, the polymeric backbone is polypropylene oxide and the average molecular weight is 10,000 g / mol is.
    [5]
    5. Water-, solvent- and phthalate-free one-component parquet adhesive according to one of the preceding claims, characterized in that the chalk powder according to b) has an average particle diameter of 1.0 pm and the chalk powder according to c) an average particle diameter of 0.4 pm owns. 15/17 Austrian Patent Office AT13 606U1 2014-04-15
    [6]
    6. Water-, solvent- and phthalate-free one-component parquet adhesive according to one of the preceding claims, characterized in that the wollastonite according to d) has an average needle length of 39 pm and an average aspect ratio of 7: 1.
    [7]
    7. water, solvent and phthalate-free one-component parquet adhesive according to one of the preceding claims, characterized in that the viscosity of the ready-to-use adhesive, measured according to DIN EN ISO 2555: 2000-01 (20 rev / min), 109,700 ± 6,800 mPa »s is.
    [8]
    8. water, solvent and phthalate-free one-component parquet adhesive according to one of the preceding claims, characterized in that the tensile shear strength, measured according to DIN EN 14293: 2006-10 (Storage Type A), 4.31 ± 0.27 N / mm2 and the modulus of elasticity, measured according to DIN EN ISO 527-1: 1996-04 and DIN EN ISO 527-3: 2003-07, is 8.54 ± 0.46 N / mm2.
    [9]
    9. Use of the water, solvent and phthalate-free one-component parquet adhesive based on silane-terminated polyalkylene oxide oligomers according to one of the preceding claims for bonding parquet, wood flooring and / or wood-based panels with a substrate.
    [10]
    10. Use of the water, solvent and phthalate-free one-component parquet adhesive according to the preceding claim, characterized in that the substrate is dry or moist and concrete, cement, cement screed, cementitious mortar, cement mortar cement-bonded wood fiber, ceramics, natural stone, calcium sulfate screed, Calcium sulphate flow, Magnesitestrich, wood, wood material, plywood, cork, gypsum, gypsum fiber, plasterboard, hardboard, mineral filler, textile fibrous material or a combination of these substrates and the bonded parquet, wood flooring and / or the wood material panels wholly or partly from European Hardwood and / or softwood species, non-European wood species or a combination of these types of wood. For this 1 sheet drawings 16/17
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    法律状态:
    2017-04-15| MM01| Lapse because of not paying annual fees|Effective date: 20160831 |
    优先权:
    申请号 | 申请日 | 专利标题
    DE102010034997A|DE102010034997A1|2010-08-20|2010-08-20|Water-, solvent- and phthalate-free silane-modified one-component parquet adhesive and its use for the highly dimensional bonding of parquet, wooden floor coverings and wood-based panels in interior work|
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