Curable Compositions for Alkaline Substrates

Abstract

The present invention relates to the use of a curable composition containing at least one polyether with blocked hydroxyl groups as a plasticizer on at least one alkaline substrate. The curable composition is storage stable, easy to handle, highly elastic after curing, and does not tend to separate or migrate. The composition allows for elastic bonding, sealing, or coating of alkaline substrates, particularly fresh or green concrete or cement mortar, without the generation of objectionable odors caused by saponification (hydrolysis) of the plasticizer.

Description

[Technical field]

[0001] The present invention relates to curable compositions based on polyurethanes or SMPs, which are particularly suitable for use as adhesives, sealants or coatings, especially in alkaline substrates such as fresh (green) concrete or cement mortar. [Background technology]

[0002] Curable compositions based on polyurethanes or silane-modified polymers (SMPs) are often used as adhesives, sealants or coatings in the construction sector. Typical substrates for the application of such products are derived from building materials bound to cement, lime or silicates, such as concrete or cement mortar. When these building materials have just been processed and thus the substrates in the form of foundations, walls, screeds, undercoats, etc. are still in a fresh state, the hydroxides present in them have not yet been carbonated, so that they have a significantly alkaline surface with a pH value of 10 or more. Fresh concrete is also called "early age", or "green", or "wet". To protect the curable composition from contact with alkaline surfaces, it can be fully aged before the application of the composition or can be pretreated, for example by neutralization with fluorides, such as fluorosilicates, or by sealing with a primer, for example by an epoxy resin coating. However, in practice, in order to save time and costs, this is often not done. In the boundary layer, hydrolysis reactions of the components of the curable composition can take place under alkaline conditions, which can cause the release of bothersome odors. Among the reactive compounds, mention may be made in particular of the plasticizers present in most compositions of this type, which are typically fatty alcohol dicarboxylates such as diisodecyl phthalate (DIDP), diisononyl cyclohexane-1,2-dicarboxylate (DINCH) or di(2-ethylhexyl)adipate (DOA). Their hydrolysis releases fatty alcohols, which have a very unpleasant odor and migrate into the pore structure of the substrate, from where they evaporate or are washed away into the environment, causing a moldy odor over a long period of time. Such long-lasting odor annoyance is observed in particular when gluing parquet to fresh cement screeds by means of elastic polyurethane or SMP adhesives. Summary of the Invention [Problem to be solved by the invention]

[0003] It is therefore an object of the present invention to provide a curable composition for use in alkaline substrates that is suitable as an adhesive, sealant or coating in the construction field and that overcomes the drawbacks of the prior art. [Means for solving the problem]

[0004] This object is achieved by a curable composition according to claim 1. The curable composition comprises at least one polyether with blocked hydroxyl groups as plasticizer. The latter can be prepared from readily available commercial products in a simple manner, has good compatibility in the composition, has a high elasticizing action, and releases the odorless parent compound, the hydroxy-functional polyether, in the event of a hydrolysis reaction on an alkaline substrate, without other problematic effects. The polyether with blocked hydroxyl groups promotes good storage stability and processability of the curable composition and has no tendency to migrate or separate. That is, it does not result in the formation of sticky surfaces or stains on the substrate. The curable composition is storage stable, easy to handle, has a high elasticity after curing, and does not show any tendency to separate or migrate. This allows elastic bonding, sealing or coating, especially of alkaline substrates such as fresh or green concrete or cement mortar, without the generation of bothersome odors caused by the hydrolysis of the plasticizer.

[0005] Thus, by using the present invention, substrates having highly alkaline surfaces can also be reliably and permanently bonded or sealed or coated, where the resulting adhesive bond does not cause troublesome odor emissions and is highly resistant to migration effects.

[0006] Further aspects of the invention are the subject matter of the further independent claims. Particularly preferred embodiments of the invention are the subject matter of the dependent claims. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] The present invention provides the use of a curable composition comprising at least one polyether with blocked hydroxyl groups as a plasticizer on at least one alkaline substrate having a pH of at least 10 when wetted with water.

[0008] "Hardenable composition" refers to a composition that includes a polymerizable polymer, which is capable of being hardened or acquiring increased mechanical strength through a crosslinking reaction of its reactive groups.

[0009] "Polyether" refers to a group of molecules or oligomeric and / or polymeric molecules composed primarily of alkyleneoxy repeating units.

[0010] A "blocked hydroxyl group" refers to a hydroxyl group that has been converted, through a chemical reaction, into a group that is non-reactive toward isocyanate groups.

[0011] "Plasticizer" refers to a non-volatile substance that is not chemically incorporated into a polymer during curing and that exerts a plasticizing effect on the cured polymer.

[0012] A "silane group" refers to a silyl group bonded to an organic group and having one to three, especially two or three, hydrolyzable alkoxy groups on the silicon atom.

[0013] "Silane" refers to both organoalkoxysilanes and tetraalkoxysilanes, which have one to three organic substituents on each silane group. Silanes which have one or more hydroxyl, isocyanato, amino, or mercapto groups in addition to the silane group on the organic radical are referred to as "hydroxysilanes," "isocyanatosilanes," "aminosilanes," and "mercaptosilanes," respectively.

[0014] Substance names beginning with "poly", such as polyamine, polyol, or polyisocyanate, refer in a formal sense to substances that contain two or more functional groups appearing in the name per molecule.

[0015] "Molecular weight" refers to the molar mass (g / mol) of a molecule or molecular residue. "Average molecular weight" refers to the number average molecular weight (M n ), which is typically determined by gel permeation chromatography (GPC) against polystyrene as a standard.

[0016] A curable composition that is termed "storage stable" or "storable" is one that can be stored in a suitable container at room temperature for an extended period of time, typically at least 3 to 6 months or more, without its application or properties of use being altered to the extent relevant to its use by such storage.

[0017] "Room temperature" refers to a temperature of 23°C.

[0018] More specifically, the pH of the water-wet alkaline substrate is determined using pH paper.

[0019] The alkaline substrate is preferably a substrate based on cement, lime (calcium hydroxide) and / or silicates (water glass) that is fresh and still only incompletely carbonated.

[0020] More preferably, the alkaline substrate is fresh concrete, fresh cement mortar, fresh lime mortar or fresh lime or silicate paint.

[0021] Concrete is said to be "fresh" as long as it has an alkaline reaction with a pH of 10 or greater. The period during which concrete remains fresh depends on its setting time and the ambient temperature. The period typically varies between 1 and 10 days. Fresh concrete is also called "early age", or "green", or "wet".

[0022] The curable composition comprises at least one polyether having blocked hydroxyl groups as a plasticizer.

[0023] Polyethers having blocked hydroxyl groups are essentially free of unblocked hydroxyl groups, where "essentially free" means that 95%, preferably 99%, in particular 99.9%, and most preferably 100% of the hydroxyl groups present are blocked.

[0024] The polyether with blocked hydroxyl groups is present in the curable composition as a plasticizer. It therefore preferably does not contain reactive groups that are involved in crosslinking reactions with moisture or with components present in the composition. It in particular does not contain isocyanate and silane groups.

[0025] Polyethers with blocked hydroxyl groups are especially liquid at room temperature.

[0026] The polyether having blocked hydroxyl groups preferably has a viscosity in the range of 30 to 5000 mPa·s, more preferably 40 to 2000 mPa·s, particularly preferably 50 to 1000 mPas, and especially 50 to 500 mPas at 20° C. In this specification, the viscosity is measured at a cone diameter of 25 mm, a cone angle of 1°, a cone tip-plate distance of 0.05 mm, and a shear rate of 10 s -1 The viscosity is determined using a cone and plate viscometer. Such polyethers are easy to handle and allow for compositions with high elasticity.

[0027] The blocked hydroxyl groups are preferably selected from the group consisting of acetal, ester, acetoester, carbonate and urethane groups.

[0028] These acetal groups, ester groups, acetoester groups, carbonate groups and urethane groups preferably have 1 to 15 carbon atoms.

[0029] Particular preference is given to ester or urethane groups. Hydroxyl groups can be converted into these groups in a particularly simple manner.

[0030] Particular preference is given to ester groups, in particular ester groups having 1 to 8 carbon atoms.

[0031] The most preferred is the acetate group. Polyethers with blocked hydroxyl groups in the form of acetate groups have low viscosity, can be obtained in a very simple manner, and are particularly inexpensive. When they are hydrolyzed on an alkaline medium, odorless hydroxy-functional polyethers and acetates are released, the latter being non-volatile in alkaline medium and having no significant odor.

[0032] Also preferred are urethane groups, especially phenylurethane groups or p-toluenesulfonylurethane groups.Polyethers containing such blocked hydroxyl groups have manageable viscosities and can be prepared in a particularly simple manner.

[0033] Preferred acetal groups are the 1-(isobutoxy)ethoxy, or tetrahydropyran-2-oxy, or tetrahydrofuran-2-oxy groups, in particular the 1-(isobutoxy)ethoxy group.

[0034] A preferred acetoester group is an acetoacetate group.

[0035] A preferred carbonate group is a methyl carbonate group.

[0036] They have low viscosity and are obtained from inexpensive raw materials.

[0037] The repeat units present in the polyethers having blocked hydroxyl groups are preferably 1,2-ethyleneoxy, 1,2-propyleneoxy, 1,3-propyleneoxy, 1,2-butyleneoxy or 1,4-butyleneoxy groups, in particular 1,2-propyleneoxy groups.

[0038] Preferably, 70% to 100% by weight, particularly 80% to 100% by weight of the repeating units are made up of 1,2-propyleneoxy groups, and 0% to 30% by weight, particularly 0% to 20% by weight of the repeating units are made up of 1,2-ethyleneoxy groups.

[0039] More preferably, the repeat units consist entirely of 1,2-propyleneoxy groups.

[0040] Such polyethers are readily available and are hydrophobic, making them particularly suitable as components of curable compositions having low water absorption and good stability.

[0041] The polyethers having blocked hydroxyl groups preferably have an average molecular weight M in the range of 600 to 10000 g / mol, more preferably 700 to 5000 g / mol, in particular 800 to 2500 g / mol, determined by gel permeation chromatography (GPC) against polystyrene as standard using tetrahydrofuran as the mobile phase, a refractive index detector and an evaluation from 200 g / mol. n has.

[0042] Such polyethers with blocked hydroxyl groups have a viscosity such that they are easy to handle and do not cause migration effects, emissions, or odors in the curable composition.

[0043] The polyether having blocked hydroxyl groups is preferably polyoxypropylene monools starting from alcohols, in particular starting from n-butanol, having an OH number in the range from 25 to 90 mg KOH / g, preferably from 50 to 80 mg KOH / g; polyoxypropylene diols having an OH number in the range from 12 to 155 mg KOH / g, preferably from 22 to 125 mg KOH / g and in particular from 45 to 125 mg KOH / g, - polyoxypropylene triols, optionally ethylene oxide terminated, starting from trimethylolpropane or in particular from glycerol and having an average OH functionality ranging from 2.2 to 3 and an OH number ranging from 22 to 230 mg KOH / g, preferably from 56 to 165 mg KOH / g, and - polyoxypropylene polyols having an average OH functionality ranging from 3 to 6, starting from sugar alcohols, in particular threitol, erythritol, xylitol, mannitol or sorbitol as the starting molecule (initiator molecule); The polyether is derived from at least one hydroxy-functional polyether selected from the group consisting of: Such polyethers having blocked hydroxyl groups are commercially available as Sanflex® SPX-80 (from Sanyo Chem. Ind.).

[0044] Among these, preference is given to polyoxypropylene mono- or diols which start from alcohols, in particular from n-butanol.

[0045] Particular preference is given to polyoxypropylene diols, as these are particularly inexpensive.

[0046] The preferred polyethers having blocked hydroxyl groups can be prepared in a simple manner from readily available commercial products, are low viscosities, and allow for curable compositions with good storage stability, ease of handling and high selectivity and elasticity in the cured state, without any tendency for migration, emissions or odors.

[0047] Polyethers having blocked hydroxyl groups are obtainable in particular by reacting at least one hydroxy-functional polyether with at least one suitable blocking agent for hydroxyl groups.

[0048] For the reaction, blocking agent is used in at least stoichiometric amount relative to hydroxyl group, so that hydroxyl group is essentially completely blocked, and thus the resulting polyether is essentially free of hydroxyl group. For blocking, a method customary for each reactive group is used, and optionally a catalyst or a solvent is additionally used. If blocking reaction forms elimination products, these are removed from the reaction mixture by suitable methods, in particular by distillation.

[0049] Suitable blocking agents are nucleophilic compounds that undergo addition or substitution reactions with hydroxyl groups.

[0050] Particularly suitable are vinyl ethers, carboxylic acids, carbonyl chlorides, carboxylic esters or anhydrides, diketenes, 2,2,5-trimethyl-4H-1,3-dioxin-4-one, alkyl acetoacetates, dialkyl carbonates, monoisocyanates, (meth)acrylamides, methylene malonates or cyanoacrylates.

[0051] Preference is given in particular to vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, isopropenyl methyl ether, isopropenyl ethyl ether, 2,3-dihydrofuran or 3,4-dihydro-2H-pyran, more preferably isobutyl vinyl ether, 2,3-dihydrofuran or 3,4-dihydro-2H-pyran, with the formation of blocked hydroxyl groups in the form of acetal groups. The reaction is preferably carried out in the presence of an acid as catalyst, in particular hydrochloric acid, sulfuric acid, phosphoric acid or sulfonic acid, which may optionally be in the form of an acidic ion exchange resin.

[0052] Preference is given to carboxylic acids, carbonyl chlorides, carboxylic esters or carboxylic anhydrides with the formation of a blocked hydroxyl group in the form of an ester group. Among these, preference is given to carboxylic anhydrides or carboxylic esters, in particular acetic anhydride.

[0053] In the case of acetic anhydride as the blocking agent, the reaction releases acetic acid and forms a blocked hydroxyl group in the form of an acetate group.

[0054] In the case of isopropenyl acetate as blocking agent, the reaction releases acetone and likewise forms a blocked hydroxyl group in the form of an acetate group.

[0055] Furthermore, preference is given to diketenes with the formation of blocked hydroxyl groups in the form of acetoester groups, sterically hindered alkyl acetoacetates such as 2,2,5-trimethyl-4H-1,3-dioxin-4-one or especially tert-butyl acetoacetate.

[0056] Preference is further given to dialkyl carbonates, especially dimethyl carbonate, with the formation of blocked hydroxyl groups in the form of carbonate groups, especially methyl carbonate groups.

[0057] Further preference is given to monoisocyanates with the formation of blocked hydroxyl groups in the form of urethane groups. Preference is given to phenylisocyanate or p-toluenesulfonyl isocyanate.

[0058] Suitable hydroxy-functionalized polyethers are in particular those having an average OH functionality in the range from 1 to 6 and an average molecular weight in the range from 500 to 10 000 g / mol, more preferably from 600 to 5000 g / mol and in particular from 700 to 2500 g / mol.

[0059] Preference is given to polyoxypropylene monools having an OH value in the range of 25 to 90 mg KOH / g, preferably 50 to 80 mg KOH / g, in particular polyoxypropylene monools starting from alcohols, in particular those starting from methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, tert-butanol, pentanol, hexanol, 2-ethylhexanol, lauryl alcohol, myristyl alcohol, palmityl alcohol, allyl alcohol, cyclohexanol, benzyl alcohol or phenol. Among these, preference is given to polyoxypropylene monools starting from alkyl alcohols, in particular those starting from methanol, ethanol or n-butanol. Particular preference is given to polyoxypropylene monools starting from n-butanol, having an average molecular weight in the range of 650 to 2000 g / mol, in particular 700 to 1500 g / mol. Polyoxypropylene monols starting from n-butanol are commercially available, for example, as Synalox® 100-20B, Synalox® 100-40B, or Synalox® 100-85B (all from DowDuPont Inc.).

[0060] Further preference is given to polyoxypropylene diols having an OH number in the range from 12 to 155 mg KOH / g, preferably from 22 to 125 mg KOH / g and in particular from 45 to 125 mg KOH / g.

[0061] Preference is further given to polyoxypropylene triols, optionally terminated with ethylene oxide, starting from trimethylolpropane or, in particular, from glycerol, having an average OH functionality in the range from 2.2 to 3 and an OH number in the range from 22 to 230 mg KOH / g, preferably from 56 to 165 mg KOH / g.

[0062] Preference is further given to polyoxypropylene polyols starting from sugar alcohols, in particular those starting from threitol, erythritol, xylitol, mannitol or sorbitol as starting molecules (initiator molecules), having an average OH functionality of at least 3, in particular in the range from at least 3 to 6.

[0063] The curable composition preferably comprises at least one curable polymer having a fraction of polyether structural units, in particular polyoxypropylene structural units. Polyethers having blocked hydroxyl groups are particularly compatible in such curable compositions and show little tendency to separate or migrate.

[0064] The curable composition preferably comprises at least one polymer containing isocyanate and / or silane groups.

[0065] The polymers containing isocyanate and / or silane groups preferably have an average molecular weight in the range from 1000 to 30 000 g / mol, in particular from 2000 to 20 000 g / mol.

[0066] It is preferably a liquid at room temperature.

[0067] In a preferred embodiment, the composition contains at least one polymer containing isocyanate groups. Such compositions are also called "polyurethane compositions."

[0068] Suitable polymers containing isocyanate groups are obtained in particular from the reaction of at least one polyol with at least one diisocyanate in a more than stoichiometric amount, the reaction being preferably carried out at temperatures ranging from 20 to 160° C., in particular from 40 to 140° C., with the exclusion of moisture, optionally in the presence of a suitable catalyst.

[0069] The NCO / OH ratio is preferably in the range from 1.3 / 1 to 10 / 1. The monomeric diisocyanates remaining in the reaction mixture after reaction of the OH groups can be removed, in particular by distillation.

[0070] When the excess monomeric diisocyanate is removed by distillation, the NCO / OH ratio during the reaction is preferably in the range of 4 / 1 to 7 / 1, and the resulting isocyanate group-containing polymer contains, after distillation, preferably 0.5% by weight or less, more preferably 0.3% by weight or less of monomeric diisocyanate. The monomeric diisocyanate is removed by short-path distillation, especially under reduced pressure.

[0071] If excess monomeric diisocyanate is not removed from the polymer, the NCO / OH ratio in the reaction is preferably in the range of 1.3 / 1 to 2.5 / 1.

[0072] The obtained polymer preferably has an isocyanate group content in the range of 0.5 to 10% by weight, particularly 1 to 5% by weight, more preferably 1 to 3% by weight, and an average molecular weight in the range of 1500 to 20000 g / mol, particularly 2000 to 15000 g / mol.

[0073] The polymer is optionally prepared with the additional use of a plasticizer or solvent, in which case the plasticizer or solvent used does not contain groups reactive towards isocyanates.

[0074] Aliphatic, cycloaliphatic or aromatic diisocyanates, in particular hexamethylene 1,6-diisocyanate (HDI), 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate or IPDI), perhydro(diphenylmethane 2,4'- and / or 4,4'-diisocyanate) (H 12Preference is given to diphenylmethane 4,4'-diisocyanate (MDI) with or without fractions of diphenylmethane 2,4'- and / or 2,2'-diisocyanate or tolylene 2,4-diisocyanate or mixtures thereof with tolylene 2,6-diisocyanate (TDI).

[0075] Particular preference is given to HDI, IPDI, MDI or TDI or mixtures thereof.

[0076] Suitable polyols are commercially available polyols or mixtures thereof, in particular: - the polymerization products of polyether polyols, in particular polyoxyalkylene diols and / or polyoxyalkylene triols, in particular ethylene oxide, or 1,2-propylene oxide, or 1,2- or 2,3-butylene oxide, or oxetane, or tetrahydrofuran or mixtures thereof, which are reacted with starter molecules (initiator molecules) having two or three active hydrogen atoms, in particular water, ammonia or compounds having several OH or NH groups, such as, for example, ethane-1,2-diol, propane-1,2- or -1,3-diol, neopentyl glycol, diethylene The polymerization can be carried out using starter molecules (initiator molecules) such as ethylene glycol, triethylene glycol, the isomeric dipropylene glycols or tripropylene glycols, the isomeric butanediols, pentanediols, hexanediols, heptanediols, octanediols, nonanediols, decanediols, undecanediols, cyclohexane-1,3- or -1,4-dimethanol, bisphenol A, hydrogenated bisphenol A, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, glycerol or aniline or mixtures of the aforementioned compounds. Also suitable are polyether polyols in which polymer particles are dispersed, in particular those containing styrene / acrylonitrile (SAN) particles or polyurea or polyhydrazodicarbonamide (PHD) particles.

[0077] Preferred polyether polyols are polyoxypropylene diols or triols or so-called ethylene oxide-terminated (EO-capped or EO-terminated) polyoxypropylene diols or triols, the latter being mixed polyoxyethylene / polyoxypropylene polyols, which are obtained in particular by further alkoxylation of polyoxypropylene diols or triols with ethylene oxide, as a result of a polypropoxylation reaction, resulting in primary hydroxyl groups.

[0078] Preferred polyether polyols have unsaturation levels of less than 0.02 meq / g, especially less than 0.01 meq / g. - polyester polyols, also called oligoesterols, which are prepared by known processes, in particular by polycondensation of hydroxycarboxylic acids or lactones or of aliphatic and / or aromatic polycarboxylic acids with di- or polyhydric alcohols. Preference is given in particular to polyesterdiols from the reaction of dihydric alcohols, such as 1,2-ethanediol, diethylene glycol, 1,2-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, glycerol, 1,1,1-trimethylolpropane or mixtures of the aforementioned alcohols, with organic dicarboxylic acids or their anhydrides or esters, such as, in particular, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, cyclohexane-1,2-dicarboxylic acid, cyclohexane-1,3-dicarboxylic acid or cyclohexane-1,4-dicarboxylic acid or mixtures of the aforementioned acids, or polyesterpolyols formed from lactones, such as, in particular, ε-caprolactone. Particular preference is given to polyester polyols formed from adipic acid or sebacic acid or dodecanedicarboxylic acid and hexanediol or neopentyl glycol. Polycarbonate polyols, obtainable, for example, by reaction of the alcohols mentioned above used to form the polyester polyols with dialkyl carbonates, diaryl carbonates or phosgene. - block copolymers having at least two OH groups and having at least two different blocks with polyether, polyester and / or polycarbonate structures of the type mentioned above, in particular polyether polyester polyols. - Polyacrylate or polymethacrylate polyols. - polyhydroxy-functional fats and oils, such as natural fats and oils, in particular castor oil; or polyols obtained by chemical modification of natural fats and oils (called oleochemical polyols), for example epoxy polyesters or epoxy polyethers obtained by epoxidation of unsaturated oils followed by ring opening with carboxylic acids or alcohols or polyols obtained by hydroformylation and hydrogenation of unsaturated oils; or polyols obtained from natural fats and oils by decomposition processes, such as alcoholysis or ozonolysis followed by chemical coupling, for example by transesterification or dimerization, of the decomposition products thus obtained or their derivatives. Suitable decomposition products of natural fats and oils are in particular fatty acids and fatty alcohols as well as fatty acid esters, in particular methyl esters (FAMEs), which can be derivatized, for example, by hydroformylation and hydrogenation, to hydroxy fatty acid esters. - polyhydrocarbon polyols, also called oligohydrocarbonols, such as in particular polyhydroxy-functional polyolefins, polyisobutylenes, polyisoprenes; polyhydroxy-functional ethylene / propylene, ethylene / butylene or ethylene / propylene / diene copolymers, such as those produced, for example, by Kraton Polymers; polyhydroxy-functional polymers of dienes, in particular 1,3-butadiene, which may also be prepared in particular by anionic polymerization; polyhydroxy-functional copolymers of dienes, such as 1,3-butadiene or mixtures of dienes, with vinyl monomers, such as styrene, acrylonitrile, vinyl chloride, vinyl acetate, vinyl alcohol, isobutylene or isoprene, in particular polyhydroxy-functional acrylonitrile / butadiene copolymers, which may be prepared in particular from epoxides or amino alcohols and carboxyl-terminated acrylonitrile / butadiene copolymers (commercially available, for example, under the name Hypro® CTBN or CTBNX or ETBN from Emerald Performance Materials); or hydrogenated polyhydroxy-functional polymers or copolymers of dienes.

[0079] Mixtures of polyols are also particularly suitable.

[0080] Preference is given to polyether polyols, polyester polyols, polycarbonate polyols, poly(meth)acrylate polyols or polybutadiene polyols.

[0081] Particular preference is given to polyether polyols, polyester polyols, especially aliphatic polyester polyols, or polycarbonate polyols, especially aliphatic polycarbonate polyols.

[0082] Particularly preferred are the polyether polyols, especially the polyoxyalkylene polyols.

[0083] Most preferred are polyoxypropylene di- or triols or ethylene oxide terminated polyoxypropylene di- or triols.

[0084] Preference is given to polyols whose average molecular weight ranges from 400 to 20 000 g / mol, preferably from 1 000 to 15 000 g / mol.

[0085] Preference is given to polyols having an average OH functionality in the range from 1.6 to 3.

[0086] Preference is given to polyols which are liquid at room temperature.

[0087] In the preparation of polymers containing isocyanate groups, difunctional or polyfunctional alcohol fractions are used, in particular ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, 2-methylolpropane-1,3-diol, butane-1,2-diol, butane-1,3-diol, butane-1,4-diol, pentane-1,3-diol, pentane-1,5-diol, 3-methylpentane-1,5-diol, neopentyl glycol, dibromoneopentyl glycol, hexane-1,2-diol, hexane-1,6-diol, heptane-1,7-diol, octane-1,2-diol, octane-1,8-diol, 2-ethylhexane-1 It is also possible to use, in addition, 1,3-diols, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, cyclohexane-1,3- or -1,4-dimethanol, ethoxylated bisphenol A, propoxylated bisphenol A, cyclohexanediol, hydrogenated bisphenol A, dimeric fatty acid alcohols, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, glycerol, pentaerythritol, sugar alcohols (such as in particular xylitol, sorbitol or mannitol) or sugars (such as in particular sucrose) or alkoxylated derivatives of the alcohols mentioned or mixtures of the alcohols mentioned.

[0088] The polymer containing isocyanate groups preferably has an average molecular weight in the range of 1500 to 20000 g / mol, in particular 2000 to 15000 g / mol.

[0089] In addition to the polymer containing isocyanate groups, the composition may contain at least one oligomeric isocyanate or a form of MDI that is liquid at room temperature.

[0090] Suitable oligomeric isocyanates are in particular HDI biurets such as Desmodur® N100 or N3200 (from Covestro AG), Tolonate® HDB or HDB-LV (from Vencorex Holding SAS) or Duranate® 24A-100 (from Asahi Kasei); HDI isocyanurates such as Desmodur® N3300, N3600 or N3790 BA (all from Covestro AG), Tolonate® HDT, HDT-LV or HDT-LV2 (from Vencorex Holding SAS), Duranate® TPA-100 or THA-100 (from Asahi Kasei Corporation) or Coronate® HX (from Tosoh Corporation); HDI uretdiones, such as Desmodur® XP 2410 (from Covestro AG); HDI iminooxadiazinediones, such as Desmodur® VP LS 2102 (from Covestro AG); IPDI isocyanurates, for example in solution, such as Desmodur® Z4470 (from Covestro AG) or in solid form, such as Vestanat® T1890 / 100 (from Evonik Industries AG); TDI oligomers, such as Desmodur® IL (from Covestro AG); or mixed isocyanurates based on TDI / HDI, such as Desmodur® HL (from Covestro AG).

[0091] The forms of MDI that are liquid at room temperature are either 4,4'-MDI liquefied by partial chemical modification (in particular by carbodiimidization, or uretonimine formation, or adduct formation with polyols) or it is a mixture of 4,4'-MDI with other MDI isomers (2,4'-MDI and / or 2,2'-MDI), obtained selectively by blending or obtained by the manufacturing process, and / or MDI oligomers and / or MDI analogues (polymeric MDI or PMDI).

[0092] In a preferred embodiment of the present invention, the curable composition comprises at least one latent curing agent in addition to at least one polymer containing isocyanate groups. Such polyurethane compositions are particularly resistant to blistering during curing.

[0093] Preferred latent hardeners are ketimines, aldimines or oxazolidines, especially oxazolidines or aldimines, most preferably aldimines.

[0094] formula [ka] Preference is given to aldimines of the formula: in which y is 2 or 3, A is an organic group having 2 to 23 carbon atoms and B is an organic group having 6 to 30 carbon atoms.

[0095] A is preferably an alkylene group, optionally having a cyclic moiety, or a divalent or trivalent polyoxyalkylene group having 5 to 15 carbon atoms, in particular 1,6-hexylene, (1,5,5-trimethylcyclohexan-1-yl)methane-1,3 having an average molecular weight in the range of 170 to 300 g / mol, or α,ω-polyoxypropylene, or tris(ω-polyoxypropylene) starting from trimethylolpropane having an average molecular weight in the range of 330 to 500 g / mol.

[0096] B is preferably an organic group having 7 to 22 carbon atoms, in particular 2,2-dimethyl-3-acetoxypropylidene, 2,2-dimethyl-3-lauroyloxypropylidene, 2,2-dimethyl-3-(N-morpholino)propylidene, benzylidene or alkyl-substituted benzylidene, in particular 4-decylbenzylidene, 4-undecylbenzylidene, 4-dodecylbenzylidene, 4-tridecylbenzylidene or 4-tetradecylbenzylidene, in which the 4-alkyl group is predominantly branched.

[0097] More preferably, B is a group having at least 15 carbon atoms, especially 2,2-dimethyl-3-lauroyloxypropylidene or an alkyl-substituted benzylidene. Such aldimines are odorless.

[0098] formula [ka] Aldimines of the formula A-(NH2) can be obtained by, in particular, reacting with aldehydes of the formula A-(NH2) with the elimination of water of condensation. y with an aldehyde of formula O=B.

[0099] Preferred amines A-(NH2) y are aliphatic or alicyclic primary diamines or triamines, in particular hexamethylene-1,6-diamine, isophorone diamine, α,ω-polyoxypropylene diamines having an average molecular weight in the range of 200 to 350 g / mol, in particular Jeffamine® D-230 (from Huntsman Corp.) or tris(ω-polyoxypropylene amines) starting from trimethylolpropane, in particular Jeffamine® T-403 (from Huntsman Corp.).

[0100] Preferred aldehydes O=B are aldol esters of carboxylic acids, in particular 2,2-dimethyl-3-acetoxypropanal, 2,2-dimethyl-3-lauroyloxypropanal, 2,2-dimethyl-3-(N-morpholino)propanal, benzaldehyde or benzaldehydes substituted by alkyl groups, in particular 4-decylbenzaldehyde, 4-undecylbenzaldehyde, 4-dodecylbenzaldehyde, 4-tridecylbenzaldehyde or 4-tetradecylbenzaldehyde, in which the 4-alkyl group is predominantly branched, and mixtures of these benzaldehydes substituted by alkyl groups.

[0101] Upon exposure to moisture, the latent hardener releases amino groups and possibly hydroxyl groups, which react with isocyanates and act as crosslinkers, thereby releasing aldehydes or ketones.

[0102] In the case of the preferred aldehydes of formula O=B, where B is a long-chain group, in particular a group having 15 or more carbon atoms, it does not cause odor problems, remains in the composition after curing, has excellent compatibility and functions as an additional plasticizer.

[0103] Compared to the direct reaction of water with isocyanates, crosslinking with latent hardeners has the advantage that no CO2 is released and the tendency for blisters to form during curing is significantly reduced.

[0104] In an additional preferred embodiment, the curable composition contains at least one organic polymer containing silane groups. Such polymers are also called "silane-modified polymers" (SMPs), and therefore such compositions are also called SMP compositions.

[0105] The organic polymer containing silane groups preferably has the formula [ka] wherein: R ais a linear or branched monovalent hydrocarbyl group having 1 to 5 carbon atoms, in particular methyl or ethyl; R b is a linear or branched monovalent hydrocarbyl group having 1 to 8 carbon atoms, in particular methyl; x has a value of 0 or 1 or 2, preferably 0 or 1, in particular 0.

[0106] Methoxysilane groups have the advantage here that they are particularly reactive, while ethoxysilane groups have the advantage that they are toxicologically advantageous and especially storage stable.

[0107] Particular preference is given to trimethoxysilane, dimethoxymethylsilane or triethoxysilane groups.

[0108] Most preferred are trimethoxysilane or triethoxysilane groups.

[0109] Preferred organic polymers containing silane groups are polyolefins, or polyesters, or polyamides, or poly(meth)acrylates, or polyethers, or mixed forms of these polymers. The silane groups can be in pendant or terminal positions of the chain and are attached to the organic polymer via a carbon atom.

[0110] More preferably, the organic polymer containing silane groups is a polyether containing silane groups.

[0111] "Polyethers containing silane groups" refers to organic polymers containing at least one silane group, the polymer chains having predominantly polyether units, in particular 1,2-oxypropylene units. As well as polyether units, it is especially possible for urethane, urea, thiourethane, ester or amide groups to be present.

[0112] The polyethers containing silane groups preferably contain at least 50% by weight, in particular at least 70% by weight, more preferably at least 80% by weight, of 1,2-oxypropylene units.

[0113] Processes for preparing suitable polyethers containing silane groups are known to those skilled in the art.

[0114] In a preferred process, polyethers containing silane groups are obtained from the reaction of polyethers containing allyl groups with hydrosilanes, optionally followed by chain extension, for example using diisocyanates.

[0115] In a more preferred process, polyethers containing silane groups are obtained from the copolymerization of alkylene oxides with epoxysilanes, optionally with chain extension, for example using diisocyanates.

[0116] In a more preferred process, polyethers containing silane groups are obtained from the reaction of polyether polyols with isocyanatosilanes, optionally with chain extension using diisocyanates.

[0117] In a further preferred process, the polyether containing silane groups is obtained by reacting the polyether containing isocyanate groups with aminosilane, hydroxysilane or mercaptosilane.The polyether containing silane groups from this process is particularly preferred.This process allows the use of a large number of inexpensive starting materials that are readily available on the market, which provide various polymer properties, especially high extensibility, high strength, low modulus, low glass transition temperature or high weatherability.

[0118] More preferably, the polyether containing silane groups results from the reaction of a polyether containing isocyanate groups with an aminosilane, and / or a hydroxysilane, and / or a mercaptosilane.

[0119] Suitable polyethers containing isocyanate groups are obtainable in particular from the reaction of polyether polyols, in particular polyoxyalkylene diols or triols, preferably polyoxypropylene diols or triols, with more than stoichiometric amounts of diisocyanates.

[0120] The reaction between the diisocyanate and the polyether polyol is preferably carried out at a temperature between 50°C and 160°C, optionally in the presence of a suitable catalyst, with the exclusion of moisture, and the diisocyanate is added so that the isocyanate groups are present in a stoichiometric excess relative to the hydroxyl groups of the polyol. In particular, the excess diisocyanate is selected so as to leave, after reaction of all the hydroxyl groups, a content of free isocyanate groups of 0.1% to 5% by weight, preferably 0.2% to 4% by weight, more preferably 0.3% to 3% by weight, based on the total polymer.

[0121] Preferred diisocyanates are those already mentioned above. Particular preference is given to IPDI or TDI. Most preferred is IPDI. This gives silane group-containing polyethers with particularly good light resistance.

[0122] Particularly suitable as polyether polyols are polyoxypropylene diols having a degree of unsaturation of less than 0.02 meq / g, in particular less than 0.01 meq / g, and an average molecular weight in the range from 400 to 25 000 g / mol, in particular from 1 000 to 20 000 g / mol.

[0123] In addition to the polyether polyols, it is also possible to use certain proportions of other polyols, in particular polyacrylate polyols and low molecular weight diols or triols.

[0124] Aminosilanes suitable for reaction with polyethers containing isocyanate groups are primary and especially secondary aminosilanes. Preference is given to 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, 4-aminobutyltrimethoxysilane, 4-amino-3-methylbutyltrimethoxysilane, 4-amino-3,3-dimethylbutyltrimethoxysilane, N-butyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, adducts formed from primary aminosilanes (such as 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane or N-(2-aminoethyl)-3-aminopropyltrimethoxysilane) with Michael acceptors (such as acrylonitrile, (meth)acrylic esters, (meth)acrylamides, maleic or fumaric acid diesters, citraconic acid diesters or itaconic acid diesters), especially dimethyl or diethyl N-(3-trimethoxysilylpropyl)aminosuccinate. Also suitable are analogs of the listed aminosilanes which have ethoxy groups in place of the methoxy groups on the silicon.

[0125] Hydroxysilanes suitable for reaction with polyethers containing isocyanate groups are obtained in particular from the addition of aminosilanes to lactones or cyclic carbonates or lactides.

[0126] Preferred hydroxysilanes thus obtained are N-(3-triethoxysilylpropyl)-2-hydroxypropanamide, N-(3-trimethoxysilylpropyl)-2-hydroxypropanamide, N-(3-triethoxysilylpropyl)-4-hydroxypentanamide, N-(3-triethoxysilylpropyl)-4-hydroxyoctanamide, N-(3-triethoxysilylpropyl)-5-hydroxydecanamide or N-(3-triethoxysilylpropyl)-2-hydroxypropylcarbamate.

[0127] Further suitable hydroxysilanes are obtained from the addition of aminosilanes to epoxides or amines to epoxysilanes.

[0128] Preferred hydroxysilanes thus obtained are 2-morpholino-4(5)-(2-trimethoxysilylethyl)cyclohexan-1-ol, 2-morpholino-4(5)-(2-triethoxysilylethyl)cyclohexan-1-ol or 1-morpholino-3-(3-(triethoxysilyl)propoxy)propan-2-ol.

[0129] Suitable mercaptosilanes for reaction with polyethers containing isocyanate groups are in particular 3-mercaptopropyltrimethoxysilane or 3-mercaptopropyltriethoxysilane.

[0130] Further suitable polyethers containing silane groups are commercially available products, in particular: MS Polymer™ (from Kaneka Corporation; in particular the S203H, S303H, S227, S810, MA903 and S943 products); MS Polymer™ or Silyl™ (from Kaneka Corporation; in particular the SAT010, SAT030, SAT200, SAX350, SAX400, SAX725, MAX450, MAX951 products); Excestar™ (from Asahi Glass Co., Ltd.; in particular the S2410, S2420, S3430, S3630 products); SPUR+* (from Momentive Performance Materials Inc.; in particular the 1010LM, 1015LM, 1050MM products); Vorasil™ (from DowDuPont Inc.; in particular the 602 and 604 products); Desmoseal™ (from Covestro AG; in particular the S XP 2458, S XP 2636, S XP 2749, S XP 2774 and S XP 2821 products), TEGOPAC® (from Evonik Industries AG; in particular the Seal 100, Bond 150, Bond 250 products), Polymer ST (from Hanse Chemie AG / Evonik Industries AG; in particular the 47, 48, 61, 61LV, 77, 80, 81 products); Geniosil® STP (from Wacker Chemie AG; in particular the E10, E15, E30, E35 products).

[0131] More preferably, the polyether containing silane groups results from the reaction of at least one polyether containing isocyanate groups with at least one aminosilane, and / or hydroxysilane, and / or mercaptosilane.

[0132] Preferably, the aminosilanes and / or hydroxysilanes and / or mercaptosilanes here are selected from the group consisting of dimethyl N-(3-trimethoxysilylpropyl)aminosuccinate, diethyl N-(3-trimethoxysilylpropyl)aminosuccinate, dimethyl N-(3-triethoxysilylpropyl)aminosuccinate, diethyl N-(3-triethoxysilylpropyl)aminosuccinate, N-(3-trimethoxysilylpropyl)-2-hydroxypropanamide, N-(3-triethoxysilylpropyl)-2-hydroxypropanamide, 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane.

[0133] Preferred embodiments of organic polymers containing silane groups allow compositions with good storage stability, rapid curing and particularly good mechanical properties, especially high elasticity and extensibility combined with good strength and high thermal stability.

[0134] The curable composition preferably further comprises one or more further components, especially selected from the group consisting of fillers, adhesion promoters, drying agents, thickeners and catalysts.

[0135] Suitable fillers are in particular ground or precipitated calcium carbonate, barite, quartz flour, quartz sand, dolomite, wollastonite, calcined kaolin, layered silicates such as mica or talc, zeolites, aluminium hydroxide, magnesium hydroxide, silica (including finely divided silica from pyrolysis processes), cement, gypsum, fly ash, industrially produced carbon black, graphite, metal powders such as aluminium, copper, iron, silver or steel, PVC powder or hollow beads, which can optionally be coated with fatty acids (especially stearic acid esters).

[0136] Preference is given to calcium carbonate, calcined kaolin or industrially produced carbon black, which may optionally be coated with fatty acids (especially stearic acid esters).

[0137] In a preferred embodiment, the composition comprises at least one filler based on calcium carbonate, which is particularly advantageous in the case of polyethers having hydroxyl groups blocked in the form of ester groups, such as acetate groups, since the acids released therefrom by hydrolysis, such as acetic acid, are bound by the calcium carbonate and do not result in the emission of odorous substances.

[0138] The composition preferably contains from 5% to 50% by weight, in particular from 10% to 40% by weight, of a filler based on calcium carbonate.

[0139] Suitable adhesion promoters are in particular aminosilanes, such as in particular 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyldimethoxymethylsilane, N-(2-aminoethyl)-N'-[3-(trimethoxysilyl)propyl]ethylenediamine or analogues thereof which have ethoxy instead of the methoxy group, as well as N-phenyl-, N-cyclohexyl- or are N-alkylaminosilanes, mercaptosilanes, epoxysilanes, (meth)acryloylsilanes, anhydridosilanes, carbamatosilanes, alkylsilanes or iminosilanes, oligomeric forms of these silanes, adducts formed from primary aminosilanes with epoxysilanes or (meth)acryloylsilanes or anhydridosilanes, amino-functional alkylsilsesquioxanes, in particular amino-functional methylsilsesquioxanes or amino-functional propylsilsesquioxanes or titanates.

[0140] Particularly suitable as adhesion promoters for compositions containing isocyanate groups are in particular epoxysilanes, such as 3-glycidoxypropyltrimethoxysilane or 3-glycidoxypropyltriethoxysilane, (meth)acryloylsilanes, anhydridosilanes, carbamatosilanes, alkylsilanes or iminosilanes or oligomeric forms of these silanes.

[0141] Suitable desiccants for compositions comprising polymers containing silane groups are especially tetraethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane or organoalkoxysilanes having a functional group in the alpha position to the silane group, in particular N-(methyldimethoxysilylmethyl)-O-methylcarbamate, (methacryloyloxymethyl)silane, methoxymethylsilane, orthoformates, calcium oxide or molecular sieve powder.

[0142] Suitable drying agents for compositions containing isocyanate groups are especially molecular sieve powders, calcium oxide, highly reactive isocyanates such as p-tosylisocyanate, monomeric diisocyanates or orthoformates.

[0143] Suitable thickeners are especially urea, sheet silicates such as bentonite, derivatives of castor oil, hydrogenated castor oil, polyamides, polyurethanes or fumed silica.

[0144] A preferred thickener is a paste that is spreadable at room temperature and contains 10% to 25% by weight of a urea compound and 75% to 90% by weight of the above-mentioned blocked hydroxyl polyether. Such a paste is produced in particular by reacting a diisocyanate, in particular diphenylmethane 4,4'-diisocyanate, with a monoamine, in particular n-butylamine, in the blocked hydroxyl polyether.

[0145] Suitable catalysts are catalysts for the crosslinking of silane groups, in particular metal catalysts such as compounds of tin, titanium, zirconium, aluminum or zinc and / or nitrogen compounds, in particular diorganotin(IV) compounds such as dibutyltin(IV) diacetate, dibutyltin(IV) dilaurate, dibutyltin(IV) dineodecanoate, dibutyltin(IV) bis(acetylacetonate) or dioctyltin(IV) dilaurate; titanium(IV) or zirconium(IV) or aluminum(III) or zinc(II) complexes, in particular with alkoxy, carboxylate, 1,3-diketonate, 1,3-ketoesterate or 1,3-ketoamidate ligands, in particular organotitanates. and in particular 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 6-dibutylamino-1,8-diazabicyclo[5.4.0]undec-7-ene, 6-dibutylamino-1,8-diazabicyclo[5.4.0]undec-7-ene, N,N'-di-n-hexylacetamidine (DHA), 2-methyl-1,4,5,6-tetrahydropyrimidine, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 2, Amines, amidines such as 5,5-trimethyl-1,4,5,6-tetrahydropyrimidine, N-(3-trimethoxysilylpropyl)-4,5-dihydroimidazole, N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole, 1-(3-dimethylaminopropyl)-2-methyl-1,4,5,6-tetrahydropyrimidine, 1-(3-aminopropyl)-2-methyl-1,4,5,6-tetrahydropyrimidine or reaction products thereof; or in particular 1-butylguanidine, 1,1-dimethylguanidine, nidin, 1,3-dimethylguanidine, 1,1,3,3-tetramethylguanidine (TMG), 2-(3-(trimethoxysilyl)propyl)-1,1,3,3-tetramethylguanidine, 2-(3-(methyldimethoxysilyl)propyl)-1,1,3,3-tetramethylguanidine, 2-(3-(triethoxysilyl)propyl)-1,1,3,3-tetramethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 7-methyl-1,5,7-triazabicyclo[4.4.Preference is given to 0]dec-5-ene, 7-cyclohexyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-phenylguanidine, 1-(o-tolyl)guanidine (OTG), 1,3-diphenylguanidine, 1,3-di(o-tolyl)guanidine, 2-guanidinobenzimidazole or guanidines from the reaction of monoamines, polyamines or aminosilanes with carbodiimides, in particular dicyclohexylcarbodiimide or diisopropylcarbodiimide; as well as biguanides or imidazoles.

[0146] Organotitanates, particularly bis(ethylacetoacetato)diisobutoxytitanium(IV) (available, for example, from Dorf Ketal as Tysor® IBAY), bis(ethylacetoacetato)diisopropoxytitanium(IV) (available, for example, from Dorf Ketal as Tysor® IBAY), Preference is given to titanium dioxide (commercially available as Tyzor® DC from Ketal), bis(acetylacetonato)diisopropoxytitanium(IV), bis(acetylacetonato)diisobutoxytitanium(IV), tris(oxyethyl)amineisopropoxytitanium(IV), bis[tris(oxyethyl)amine]diisopropoxytitanium(IV), bis(2-ethylhexane-1,3-dioxy)titanium(IV), tris[2-((2-aminoethyl)amino)ethoxy]ethoxytitanium(IV), bis(neopentyl(diallyl)oxy)diethoxytitanium(IV), tetra(isopropoxy)titanate, tetra(n-butoxy)titanate, tetra(2-ethylhexyloxy)titanate or polybutyltitanate, in particular bis(ethylacetoacetato)diisobutoxytitanium(IV) or bis(ethylacetoacetato)diisopropoxytitanium(IV).

[0147] Preference is further given to amidines or guanidines, in particular DBU, 1-(3-dimethylaminopropyl)-2-methyl-1,4,5,6-tetrahydropyrimidine, 1-(3-aminopropyl)-2-methyl-1,4,5,6-tetrahydropyrimidine or reaction products thereof or guanidines from the reaction of monoamines, polyamines or aminosilanes with dicyclohexylcarbodiimide or diisopropylcarbodiimide.

[0148] Further preference is given to combinations of these catalysts, in particular the combination of at least one organotitanate with at least one amidine or guanidine.

[0149] Suitable catalysts are also catalysts for accelerating the reaction of isocyanate groups, in particular organotin(IV) compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dibutyltin diacetylacetonate, dimethyltin dilaurate, dioctyltin diacetate, dioctyltin dilaurate or dioctyltin diacetylacetonate; complexes of bismuth(III) or zirconium(IV), in particular with ligands selected from alkoxides, carboxylates, 1,3-diketonates, oxinates, 1,3-ketoesterates and 1,3-ketoamidates; or compounds containing tertiary amino groups, in particular 2,2'-dimorpholinodiethyl ether (DMDEE).

[0150] Suitable catalysts are also catalysts for the hydrolysis of the latent hardeners, in particular carboxylic acids such as 2-ethylhexanoic acid, lauric acid, stearic acid, neodecanoic acid, benzoic acid, salicylic acid or 2-nitrobenzoic acid, organic carboxylic acid anhydrides, silyl esters of carboxylic acids, organic sulfonic acids, sulfonic acid esters, other organic or inorganic acids or mixtures of the abovementioned acids or esters. Preference is given to aromatic carboxylic acids such as benzoic acid, 2-nitrobenzoic acid or, in particular, salicylic acid.

[0151] The curable composition may contain further additives, in particular: - inorganic or organic pigments, in particular titanium dioxide, chromium oxide or iron oxide; - additional plasticizers; - fibres, in particular glass, carbon, metal, ceramic, polymer (such as polyamide or polyethylene) or natural fibres (such as wool, cellulose, hemp or sisal); - nanofillers such as graphene or carbon nanotubes; - dye; - additional catalysts which accelerate the reaction of the isocyanate and / or silane groups, in particular salts, soaps or complexes of tin(II), iron, aluminium, molybdenum, dioxomolybdenum or potassium, in particular aluminium lactate, aluminium oleate or potassium acetate; compounds containing tertiary amino groups, in particular N-ethyldiisopropylamine, N,N,N',N'-tetramethylalkylenediamines, pentamethylalkylenetriamines and their higher analogues, bis(N,N-diethylaminoethyl)adipate, trimethylaminoethylamine ... aromatic nitrogen compounds such as 4-dimethylaminopyridine, N-methylimidazole, N-vinylimidazole or 1,2-dimethylimidazole; organic ammonium compounds such as benzyltrimethylammonium hydroxide or alkoxylated tertiary amines; and so-called "delayed action" catalysts, which are modifications of known metal or amine catalysts; solvents, in particular acetone, methyl acetate, tert-butyl acetate, 1-methoxy-2-propyl acetate, ethyl 3-ethoxypropionate, diisopropyl ether, diethylene glycol diethyl ether, ethylene glycol diethyl ether, ethylene glycol monobutyl ether, ethylene glycol mono-2-ethylhexyl ether, acetals (such as propylal, butyral, 2-ethylhexylal, dioxolane, glycerol formal or 2,5,7,10-tetraoxaundecane (TOU)), toluene, xylene, heptane, octane, naphtha, white spirit, petroleum ether or gasoline, in particular SolvessoTM grades (from ExxonMobil Chemical Co.) and propylene carbonate, dimethyl carbonate, butyrolactone, N-methylpyrrolidone, N-ethylpyrrolidone, p-chlorobenzotrifluoride or benzotrifluoride; - natural resins, oils and fats, such as rosin, shellac, linseed oil, castor oil or soybean oil; - non-reactive polymers, in particular homopolymers or copolymers of unsaturated monomers, in particular those selected from the group comprising ethylene, propylene, butylene, isobutylene, isoprene, vinyl acetate or alkyl (meth)acrylates, in particular polyethylene (PE), polypropylene (PP), polyisobutylene, ethylene / vinyl acetate copolymers (EVA) or atactic poly-α-olefins (APAO); - flame-retardant substances, in particular the aforementioned aluminium hydroxide or magnesium hydroxide fillers and in particular organic phosphates, such as in particular triethyl phosphate, tricresyl phosphate, triphenyl phosphate, diphenyl cresyl phosphate, isodecyl diphenyl phosphate, tris(1,3-dichloro-2-propyl) phosphate, tris(2-chloroethyl) phosphate, tris(2-ethylhexyl) phosphate, tris(chloroisopropyl) phosphate, tris(chloropropyl) phosphate, isopropylated triphenyl phosphate, mono-, bis- or tris(isopropylphenyl) phosphates of various degrees of isopropylation, resorcinol bis(diphenyl phosphate), bisphenol A bis(diphenyl phosphate) or ammonium polyphosphate; additives, in particular wetting agents, levelling agents, defoamers, degassing agents, stabilisers against oxidation, heat, light or UV light or biocides; or Further substances commonly used in curable compositions.

[0152] It may be desirable to chemically or physically dry certain materials before incorporating them into the composition.

[0153] The curable composition is preferably substantially free of aliphatic alcohol ester-containing plasticizers, in particular substantially free of phthalates, preferably containing less than 2% by weight, more preferably less than 1% by weight, in particular less than 0.5% by weight of phthalates.

[0154] The curable composition preferably contains 10% to 40% by weight of a polyether having blocked hydroxyl groups.

[0155] Preferred curable compositions are - 10% to 50% by weight of polymers containing isocyanate and / or silane groups, - 20% to 60% by weight of a filler, and - 10% to 40% by weight of polyethers with blocked hydroxyl groups Includes.

[0156] The curable composition is in particular prepared with the exclusion of moisture and stored at ambient temperature in a moisture-proof container, suitable moisture-proof containers being in particular made of optionally coated metal and / or plastic, in particular drums, transport boxes, pails, buckets, canisters, tins, bags, tubular bags, cartridges or tubes.

[0157] The curable composition may be in the form of a one-part (single-component) composition or it may be a multi-part (multi-component), in particular a two-part (two-component), composition.

[0158] A composition that is termed a "one-part" composition is one in which all components of the composition are in the same container and are themselves storage stable and moisture curable.

[0159] Compositions that are referred to as "two-part" compositions are those in which the components of the composition are two distinct components that are stored in separate containers and are not mixed with each other until just before or during application of the composition.

[0160] The curable composition is preferably a one-part moisture-curable composition, which, when properly packaged and stored, is shelf stable, typically for several months up to a year or more.

[0161] In the use of the present invention, the curable composition is applied to at least one alkaline substrate.The substrate may be pretreated before application, in particular by cleaning method or application of activator or primer, in which case the applied activator or primer typically does not completely seal the surface of the substrate, so that it still gives alkaline reaction at least in part.

[0162] Once the composition is applied, the curing process begins, which results in a cured composition.

[0163] In the case of a one-part moisture-curable composition, it is applied as is and then begins to cure under the influence of moisture or water. To accelerate the cure, accelerator components that contain or release water and / or catalysts can be mixed into the composition at the time of application, or the composition can be contacted with such accelerator components after its application.

[0164] In the case of a two-part composition, the two components are mixed and then applied, and hardening begins by an internal reaction, and hardening can be completed by the action of external moisture. The two components can be mixed continuously or in batches using dynamic or static mixers.

[0165] In the course of curing, the isocyanate groups present react with each other under the influence of moisture and / or with any additional reactive groups present in the composition, in particular hydroxyl or amino groups. Furthermore, the isocyanate groups present react with the hydrolysis reactive groups of any latent curing agent present. The silane groups present react with each other under the influence of moisture in the course of curing. They can be hydrolyzed on contact with moisture to give silanol groups (Si-OH groups). The silane groups present can condense with the silanol groups present to give siloxane groups (Si-O-Si groups).

[0166] The moisture required for the curing of moisture-curable compositions preferably enters the composition by diffusion from the air (air humidity). In the process, a solid layer (skin) of the cured composition is formed on the surface of the composition in contact with the air. As the curing continues in the direction of diffusion from the outside to the inside, the skin becomes thicker and thicker, eventually surrounding the entire applied composition. Moisture can also enter the composition additionally or completely from one or more substrates to which the composition is applied, and / or may come from accelerator components that are mixed into the composition during application or that come into contact with it after application, for example by painting or spraying.

[0167] The curable composition is preferably applied at ambient temperature, especially in the range of about -10 to 50°C, preferably in the range of -5 to 45°C, especially 0 to 40°C.

[0168] The composition is preferably similarly cured at ambient temperature.

[0169] The curable composition can be formulated to have a high yield point and a paste-like consistency, in particular for use as an adhesive or sealant. Such compositions can be applied under pressure by a spatula or a suitable device, for example by a cartridge gun, or a drum pump, or by an application robot, and the composition is especially released in the form of a bead with an essentially circular or triangular cross-sectional area. The thickness of the layer of the applied composition is especially in the range of 0.5 to 50 mm, preferably 1 to 30 mm.

[0170] The curable composition can also be formulated to be flowable and "self-leveling" or only slightly thixotropic, especially for use as a sealing compound or coating. Such a composition can be applied by pouring it or with a spatula. It can then be distributed over the area in the form of a coating, for example with a roller, doctor blade, trowel or rubber squeegee, to obtain the desired layer thickness. In one operation, a layer thickness in the range of 0.5 to 5 mm, especially 1 to 3 mm, is typically applied.

[0171] The curable compositions are storage stable, easy to handle, highly elastic after curing, and do not tend to separate or migrate, which allows for elastic bonding, sealing or coating, especially of alkaline substrates such as fresh or green concrete or cement mortar, without the generation of troublesome odors caused by the hydrolysis of plasticizers.

[0172] The present invention relates to a method of bonding, or sealing, or coating, comprising the steps of: (i) providing a curable composition as described above; (ii) providing at least one alkaline substrate as described above; (iii) contacting the hardenable composition with an alkaline substrate; (iv) curing the composition The present invention further provides a method comprising:

[0173] In the case of a two-part or multi-part composition, the components are mixed prior to step (iii).

[0174] Step (iii) may be carried out by applying the curable composition to an alkaline substrate.

[0175] Additionally, step (iii) can be carried out by applying the curable composition to any substrate and then contacting the applied composition with an alkaline substrate.

[0176] The composition can be applied between two or more substrates, or can be applied to a first substrate and then contacted with another substrate, where at least one of the substrates contacted by the applied composition is an alkaline substrate as described above.

[0177] Additional substrates that may be contacted with the composition include, inter alia: - glass, glass ceramics, concrete, mortar, cement screed, fibre cement, in particular fibre cement boards, bricks, tiles, gypsum, in particular gypsum boards or anhydrous screeds or natural stone such as granite or marble; - Repair or levelling compounds based on PCC (polymer modified cement mortar) or ECC (epoxy resin modified cement mortar); - Metals or alloys such as aluminium, copper, iron, steel, non-ferrous metals, including metals or alloys with a surface finish such as galvanised or chrome-plated metals; - Asphalt or bitumen; - leather, textiles, paper, wood, wood bonded with resins (such as phenolic, melamine or epoxy resins), further materials called resin / textile composites or polymer composites; - plastics such as rigid and flexible PVC, polycarbonate, polystyrene, polyester, polyamide, PMMA, ABS, SAN, epoxy resins, phenolic resins, PUR, POM, TPO, PE, PP, EPM or EPDM, in each case untreated or surface-treated, for example by plasma, corona or flame; - Fiber reinforced plastics such as Carbon Fiber Reinforced Plastics (CFP), Glass Fiber Reinforced Plastics (GFP) and Sheet Moulding Compounds (SMC); - Thermal insulation foams, in particular those made of EPS, XPS, PUR, PIR, rock wool, glass wool or foam glass; - Coated or painted substrates, in particular painted tiles, coated concrete, powder-coated metals or alloys or painted metal sheets It is.

[0178] If necessary, the substrate can be pretreated before application, especially by physical and / or chemical cleaning methods or by application of an activator or primer.

[0179] It is possible to bond and / or seal the same or different substrates.

[0180] Application between multiple substrates is typical, especially for sealants for bonding, while application to a first substrate and subsequent contact with a second substrate is typical for adhesives. Such adhesives may also have a sealing function.

[0181] Although a coating is typically applied to only one substrate, it is contemplated that the coating may contact another substrate, for example at an edge region.

[0182] The curable composition is preferably an adhesive, or a sealant, or a coating, depending on its application.

[0183] The cured adhesive, sealant, or coating is preferably elastic.

[0184] As an adhesive, the composition is particularly suitable for bonding and sealing applications in the construction industry on alkaline substrates, in particular for bonding parquet to fresh cement screeds or for bonding components to fresh concrete.

[0185] As a sealant, the composition is particularly suitable for sealing alkaline based joints, seams or cavities in structures, especially expansion or bond joints between components.

[0186] The compositions are particularly suitable as coatings, for the protection of alkaline substrates, in particular floors or walls, in particular as coatings for balconies, terraces, open spaces, bridges, car parks, or for sealing roofs, in particular flat roofs or slightly sloping roof areas, or roof gardens, or in the interior decoration of buildings for waterproofing, for example in plumbing units, or kitchen floor tiles, or ceramic plates, or as flooring in kitchens, industrial buildings or production spaces, or as sealings for collection tanks, channels, shafts, silos, tanks or wastewater treatment plants.

[0187] By a method of bonding, or sealing, or coating, an article is obtained.

[0188] Thus, the present invention further provides an article bonded or sealed or coated with the composition described above.

[0189] This article may in particular be an architectural structure above or below ground or part thereof, in particular a bridge, a roof, a staircase, a floor or a facade or an attachable component thereof.

[0190] More preferably, the article is a parquet floor glued to a concrete or cement mortar screed that is fresh and therefore glued to an alkaline screed. The use of an adhesive that does not release strongly odorous cleavage products in an alkaline medium is particularly important here, since the adhesive is applied indoors over a relatively large area, i.e. the odor emission that occurs is particularly strong, persistent and troublesome.

[0191] The adhesive bond is obtained by means of gluing, or sealing, or coating methods.

[0192] The present invention therefore further provides an adhesive bond comprising a cured composition as described above and at least one substrate adhering to the composition, the surface of the at least one substrate being alkaline at the time of contact with the composition as described above.

[0193] The cured composition preferably comprises - 10% to 50% by weight of a cured polymer, - 20% to 60% by weight of a filler, and - 10% to 40% by weight of polyethers with blocked hydroxyl groups Includes.

[0194] The cured compositions in the adhesive bonds according to the invention preferably have a layer thickness in the range of 0.5 to 50 mm, preferably 1 to 30 mm.

[0195] An adhesive bond is the portion of an article that is bonded, sealed or coated with the composition.

[0196] The use of the present invention allows for elastic bonding, sealing or coating, especially of alkaline substrates such as fresh or green concrete or cement mortar, without the generation of troublesome odors caused by hydrolysis of the plasticizer, as typically occurs with common plasticizers such as DIDP or DINCH. EXAMPLES

[0197] In the following, examples are presented that are intended to clarify the invention as described. It will be understood that the invention is not limited to these described examples.

[0198] "Standard Climatic Conditions" ("SCC") refers to a temperature of 23±1°C and a relative humidity of air of 50±5%.

[0199] Unless otherwise stated, chemicals used were from Sigma-Aldrich Chemie GmbH.

[0200] Preparation of polyethers with blocked hydroxyl groups: Viscosity was measured using a thermostated Rheotec RC30 cone-plate viscometer (cone diameter 25 mm, cone angle 1°, cone tip-plate distance 0.05 mm, shear rate 10 s -1 ) was measured.

[0201] Infrared spectra (FT-IR) were measured as undiluted films on a Thermo Scientific Nicolet iS5 FT-IR instrument equipped with a horizontal ATR measurement unit with a diamond crystal. Absorption bands are expressed in wavenumbers (cm -1 ) has been reported.

[0202] 1 H NMR spectra were recorded on a Bruker Ascend 400 type spectrometer at 400.14 MHz. Chemical shifts δ are reported in ppm relative to tetramethylsilane (TMS). True and spurious coupling patterns could not be distinguished.

[0203] Polyether-1: Acetylated PPG monool with an average molecular weight of about 800 g / mol, starting from n-butanol 120.00 g of n-butanol-based polyoxypropylene monol (Synalox® 100-20B, average molecular weight approximately 750 g / mol; from DowDuPont Inc.) and 18.74 g of acetic anhydride were initially placed in a round-bottom flask equipped with a distillation attachment under nitrogen atmosphere. The reaction mixture was then stirred under a gentle stream of nitrogen at 130° C. while acetic acid was collected as a distillate. Volatile components were subsequently removed from the reaction mixture at 80° C. and a reduced pressure of 10 mbar. A clear, colorless liquid with a viscosity of 75 mPa·s at 20° C. was obtained.

[0204] FT-IR:2970,2931,2867,1738,1454,1372,1345,1296,1241,1098,1014,959,925,866,827.

[0205] 1 H NMR(CDCl3):5.02(hept.,1H,CH2(CH3)CH-OAc),3.75-3.34(2xm,about 39H,OCH2CH(CH3)O),3.33-3.28(m,2H,CH3CH2CH2CH2O),2.04(s,3H,O(CO)CH3),1.55(qui nt.,2H,CH3CH2CH2CH2O),1.36(sext.,2H,CH3CH2CH2CH2O),1.22(d,3H,CH2(CH3)CH-OAc),1.17-1.10(m,about 36H,OCH2CH(CH3)O),0.91(t,3H,CH3CH2CH2CH2O).

[0206] Polyether-2: Diacetylated PPG diol with an average molecular weight of approximately 1100 g / mol 80.00 g of polyoxypropylene diol (Voranol® P1010, OH value 110 mg KOH / g; from DowDuPont Inc.) and 18.74 g of acetic anhydride were converted as described for polyether-1. A clear, colorless liquid with a viscosity of 145 mPa·s at 20° C. was obtained.

[0207] Polyether-3: Diacetylated PPG diol with an average molecular weight of approximately 2100 g / mol 160.00 g of polyoxypropylene diol (Voranol® P2000L, OH value 56 mg KOH / g; from DowDuPont Inc.) and 18.74 g of acetic anhydride were converted as described for polyether-1. A clear, colorless liquid with a viscosity of 400 mPa·s at 20° C. was obtained.

[0208] Preparation of further starting materials: Polymer P1: 3080 g of polyoxypropylene diol (Acclaim® 4200 from Covestro AG; OH value 28.5 mg KOH / g), 1540 g of polyoxypropylene polyoxyethylene triol (Caradol® MD34-02 from Shell Chemicals Co.; OH value 35.0 mg KOH / g) and 385 g of tolylene diisocyanate (Desmodur® T80P from Covestro AG) were reacted in a known manner at 80° C. to give an NCO-terminated polyurethane polymer which was liquid at room temperature and had a content of free isocyanate groups of 1.50% by weight.

[0209] Aldimine-1: N,N'-bis(2,2-dimethyl-3-lauroyloxypropylidene)-3-aminomethyl-3,5,5-trimethylcyclohexylamine 598g (2.1mol) of 2,2-dimethyl-3-lauroyloxypropanal is first placed in a round-bottom flask under nitrogen atmosphere.Then, 170.3g (1mol) of 3-aminomethyl-3,5,5-trimethylcyclohexylamine (Vestamin® IPD, from Evonik Industries AG) is added with good stirring, and then volatile components are removed under reduced pressure at 80°C and 10mbar.732g of colorless liquid is obtained with an amine content of 2.73mmol N / g, which corresponds to a calculated aldimine equivalent of 367g / mol.

[0210] Thixotropic agent T-1: A vacuum mixer was initially charged with 300 g of polyether-1 and 48 g of methylenediphenyl 4,4'-diisocyanate (Desmodur® 44MCL from Covestro AG), which was then slightly heated and 27 g of n-butylamine was slowly added dropwise with vigorous stirring. The resulting paste was stirred for an additional hour under reduced pressure while cooling. A white, finely divided, homogeneous spreadable paste was obtained.

[0211] Thixotropic agent T-2: Thixotropic agent T-1 was prepared as described, except that 300 g of Polyether-2 was used instead of Polyether-1. A white, finely divided, homogeneous, spreadable paste was obtained.

[0212] Thixotropic agent T-3: Thixotropic agent T-1 was prepared as described, except that 300 g of diisodecyl phthalate (Palatinol® 10-P, from BASF SE) was used instead of polyether-1. A white, finely divided, homogeneous, spreadable paste was obtained.

[0213] Thixotropic agent T-4: Thixotropic agent T-1 was prepared as described, except that 300 g of diisononylcyclohexane-1,2-dicarboxylate (Hexamoll® DINCH, from BASF SE) was used instead of polyether-1. A white, finely divided, homogeneous, spreadable paste was obtained.

[0214] Manufacturing of mortar columns: A dry mix was prepared using 1300 parts by weight (PW) of 0-1 mm quartz sand, 200 PW of ground limestone (uncalcined) and 900 PW of CEMI 42.5N Portland cement. Separately, 400 PW of water was mixed with 6.3 PW of Sika® ViscoCrete®-3082 (retarder / plasticizer; from Sika Schweiz AG) and this mixture was thoroughly mixed with the dry mix in a mechanical mixer for 3 minutes. The resulting mortar was poured into 80 x 40 x 40 mm moulds, covered with plastic film and stored under standard climatic conditions.

[0215] After 24 hours, the plastic film was removed and the hardened but still fresh mortar prism was removed from the mold and the exterior was brushed with a steel brush to remove dust. The fresh (green) mortar prism thus produced was immediately coated with the hardenable composition described below.

[0216] Preparation of the curable (one-part) composition: Compositions Z1~Z5 For each composition, the ingredients specified in Table 1 were mixed in the amounts (parts by weight) specified using a centrifugal mixer (SpeedMixer™ DAC150, FlackTek Inc.) at 3000 rpm for 1 minute with exclusion of moisture.

[0217] Each composition was tested as follows: The skin time (ST) was determined as a measure of the open time. For this purpose, a few grams of the composition were applied to a cardboard board in a layer thickness of about 2 mm and the first time was determined at which, under standard climatic conditions, no residues were left on an LDPE pipette used to gently tap the surface of the composition.

[0218] The Shore A hardness was determined according to DIN 53505 on test specimens cured for 14 days under standard climatic conditions.

[0219] To determine the mechanical properties, the composition was applied to a PTFE-coated film to obtain a film of 2 mm thickness, which was then stored under standard climatic conditions for 14 days, and several dumbbells of 75 mm length with a bar length of 30 mm and a bar width of 4 mm were punched out of the film and tested according to DIN EN53504 for tensile strength (breaking load), elongation at break, modulus of elasticity 5% (elongation from 0.5% to 5%) and modulus of elasticity 25% (elongation from 0.5% to 25%) at a strain rate of 200 mm / min.

[0220] The appearance of the produced films was visually evaluated, with "good" being used to indicate a tack-free film with no blistering.

[0221] Odor was assessed by sniffing the freshly produced film with the nose at a distance of 2 cm. "None" means that no odor was perceived.

[0222] The results are reported in Table 1.

[0223] Compositions designated with "(Ref.)" do not contain the polyethers of the present invention having blocked hydroxyl groups.

[0224] [Table 1]

[0225] Use of the hardening composition on fresh mortar: Examples 1 to 5 Each of the compositions Z1 to Z5 prepared as described above was applied to two fresh (green) mortar prisms prepared as described above in a layer thickness of 2 mm over an area of ​​30 x 80 mm. The first prism coated in this way was stored in a closed aluminum can in an air-circulating oven at 80 ° C for 24 hours and then tested for odor development. These results are indicated as "(1d80 ° C)". The second coated prism was stored in a closed aluminum can under standard climatic conditions for 7 days and then similarly tested for odor development. These results are indicated as "(7dSCC)". The odor development was determined by carefully opening the aluminum can under standard climatic conditions and immediately detecting the odor by sniffing the aluminum can and the headspace of the composition with the nose. "None" means that no odor was perceived. "Weak" refers to a slight odor typical of the composition in the warm state as an inherent odor. "Clear" refers to a clearly perceptible mold odor. "Strong" refers to a strong mold odor.

[0226] The results are reported in Table 2.

[0227] The examples marked with (Ref.) are comparative examples.

[0228] [Table 2] The invention according to the present disclosure includes the following aspects: <Aspect 1> 1. Use of a curable composition comprising at least one polyether having blocked hydroxyl groups as a plasticizer on at least one alkaline substrate having a pH of at least 10 when wetted with water. <Aspect 2> 2. Use according to aspect 1, characterized in that the alkaline substrate is fresh concrete, fresh cement mortar, fresh lime mortar or fresh lime, or a silicate paint. <Aspect 3> 3. The use according to aspect 1 or 2, characterized in that the blocked hydroxyl group is selected from the group consisting of acetal groups, ester groups, acetoester groups, carbonate groups and urethane groups. <Aspect 4> 4. The use according to any one of aspects 1 to 3, characterized in that 70% by weight to 100% by weight of the repeating units in the polyether are composed of 1,2-propyleneoxy groups, and 0% by weight to 30% by weight of the repeating units in the polyether are composed of 1,2-ethyleneoxy groups. <Aspect 5> The polyethers with blocked hydroxyl groups have average molecular weights M ranging from 600 to 10,000 g / mol, as determined by gel permeation chromatography (GPC) against polystyrene as standard, using tetrahydrofuran as the mobile phase, a refractive index detector, and an evaluation from 200 g / mol. n 5. Use according to any one of aspects 1 to 4, characterized in that it comprises <Aspect 6> Use according to any one of aspects 1 to 5, characterized in that the polyether having blocked hydroxyl groups is derived from at least one hydroxy-functional polyether selected from the group consisting of: polyoxypropylene monools starting from alcohols, in particular starting from n-butanol, having an OH value in the range from 25 to 90 mg KOH / g; - polyoxypropylene diols having an OH value ranging from 12 to 155 mg KOH / g, - polyoxypropylene triols, optionally ethylene oxide terminated, starting from trimethylolpropane or in particular glycerol, having an average OH functionality ranging from 2.2 to 3 and an OH number ranging from 22 to 230 mg KOH / g, and - polyoxypropylene polyols starting from sugar alcohols, in particular starting from threitol, erythritol, xylitol, mannitol or sorbitol molecules, and having an average OH functionality ranging from 3 to 6. <Aspect 7> 7. Use according to any one of the preceding aspects, characterized in that the curable composition comprises at least one polymer containing isocyanate groups and / or silane groups. <Aspect 8> 8. Use according to any one of the preceding aspects, characterized in that the curable composition comprises at least one polymer containing isocyanate groups and at least one latent hardener. <Aspect 9> 9. Use according to any one of the preceding aspects, characterized in that the hardenable composition comprises at least one filler based on calcium carbonate. <Aspect 10> Use according to any one of aspects 1 to 9, characterized in that the curable composition comprises: - 10% to 50% by weight of polymers containing isocyanate groups and / or silane groups, - 20 to 60% by weight of a filler, and - 10% to 40% by weight of polyethers with blocked hydroxyl groups. <Aspect 11> 11. The use according to any one of aspects 1 to 10, characterized in that the curable composition is a one-component moisture-curable composition. <Aspect 12> 1. A method of bonding, sealing or coating comprising the steps of: (i) providing a curable composition according to any one of aspects 1 and 3 to 11; (ii) providing at least one alkaline substrate according to embodiment 1 or 2; (iii) contacting the curable composition with the alkaline substrate; (iv) curing the composition. <Aspect 13> 13. An article obtained from the method according to embodiment 12. <Aspect 14> 14. The article of claim 13, wherein the parquet floor is adhered to a screed of concrete or cement mortar. <Aspect 15> 13. An adhesive bond resulting from the use according to any one of aspects 1 to 11 or the method according to aspect 12, comprising the cured composition and at least one substrate adhering to the composition, the surface of the substrate being alkaline on contact with the composition and having a pH of at least 10 when wetted with water.

Claims

1. 1. Use of a curable composition comprising at least one polyether with blocked hydroxyl groups as a plasticizer on at least one alkaline substrate having a pH of at least 10 when wetted with water, The alkaline substrate is fresh concrete, fresh cement mortar, fresh lime mortar or fresh lime, or a silicate paint; the blocked hydroxyl group is selected from the group consisting of an ester group and an acetoester group; and The curable composition comprises at least one polymer containing isocyanate groups and / or silane groups. Characterized by, use.

2. 2. The use according to claim 1, characterized in that from 70% to 100% by weight of the repeating units in the polyether consist of 1,2-propyleneoxy groups and from 0% to 30% by weight of the repeating units in the polyether consist of 1,2-ethyleneoxy groups.

3. The polyethers with blocked hydroxyl groups have average molecular weights M ranging from 600 to 10,000 g / mol, as determined by gel permeation chromatography (GPC) against polystyrene as standard, using tetrahydrofuran as the mobile phase, a refractive index detector, and an evaluation from 200 g / mol. ｎ 3. Use according to claim 1 or 2, characterized in that it has

4. Use according to any one of claims 1 to 3, characterized in that the polyether having blocked hydroxyl groups is derived from at least one hydroxy-functional polyether selected from the group consisting of: polyoxypropylene monols starting from alcohols, in particular starting from n-butanol, having an OH number in the range from 25 to 90 mg KOH / g; - polyoxypropylene diols having an OH number ranging from 12 to 155 mg KOH / g, - polyoxypropylene triols, optionally ethylene oxide terminated, starting from trimethylolpropane or especially glycerol, having an average OH functionality in the range from 2.2 to 3 and an OH number in the range from 22 to 230 mg KOH / g, and Polyoxypropylene polyols starting from sugar alcohols, in particular starting from threitol, erythritol, xylitol, mannitol or sorbitol, and having an average OH functionality ranging from 3 to 6.

5. Use according to any one of claims 1 to 4, characterized in that the curable composition comprises at least one polymer containing isocyanate groups and at least one latent hardener.

6. Use according to any one of claims 1 to 5, characterized in that the hardenable composition comprises at least one filler based on calcium carbonate.

7. Use according to any one of claims 1 to 6, characterized in that the curable composition comprises: - 10% to 50% by weight of polymers containing isocyanate groups and / or silane groups, - 20 to 60% by weight of a filler, and - 10% to 40% by weight of polyethers with blocked hydroxyl groups.

8. Use according to any one of claims 1 to 7, characterized in that the curable composition is a one-component moisture-curable composition.

9. 1. A method of bonding, sealing or coating comprising the steps of: (i) providing a curable composition according to any one of claims 1 to 8, (ii) providing at least one alkaline substrate according to claim 1; (iii) contacting the curable composition with the alkaline substrate; (iv) curing the composition.

10. 10. An article obtained from the method of claim 9.

11. 11. An article according to claim 10, characterized in that it is a parquet floor bonded to a screed of concrete or cement mortar.

12. An adhesive bond resulting from the use according to any one of claims 1 to 8 or the method according to claim 9, comprising the cured composition and at least one substrate adhering to said composition, the surface of said substrate being alkaline on contact with said composition and having a pH of at least 10 when wetted with water.

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