Moisture-curable polyurethane compositions having reduced surface tack - Patents.com

Abstract

The present invention relates to a moisture-curable composition comprising: (a) at least one polyurethane polymer P having isocyanate groups; (b) at least one blocked polyamine BA having a blocked hydrolytically activatable amino group; and (c) at least one monoamine MA of formula (V): In the formula, R a represents a linear, cyclic or branched alkyl or alkenyl group or an optionally substituted aryl group having 1 to 12 C atoms and optionally containing an ether oxygen atom; R b and R c are independently a group R a or a hydrogen atom, provided that R b and R c At least one of R is a hydrogen atom or b and R c combines with the N atom of the monoamine MA to form the aldehyde and amine R under the influence of water. a Forms an aldimine group that hydrolyzes to -NH2; wherein the polymer P is a reaction product of 2,4- and / or 2,6-toluylene diisocyanate (TDI) with at least one polyol, the polyol having an average functionality of >2; and the amount of monoamine MA in the composition is 0.2 to 25 parts by weight per 100 parts by weight of the polymer P. The compositions are highly suitable as low modulus sealants and exhibit excellent mechanical properties in terms of low modulus and high migration capacity, and exhibit particularly low surface tack. TIFF2022543549000014.tif24160

Description

[Technical field]

[0001] The present invention relates to the field of moisture-curable polyurethane compositions, and in particular to their use as low modulus sealants. [Background technology]

[0002] One-component compositions based on moisture-reactive polyurethanes with free isocyanate groups have been used for a long time as adhesives, sealants and coating materials. Such systems are easy to use, since they do not require mixing operations and the open time allows for a comfortable application process in both construction and do-it-yourself applications.

[0003] In particular, for joint sealant applications, such one-component polyurethane compositions must in most cases have certain properties in the cured state in order to perform their tasks efficiently. On the one hand, a suitable adhesion on the joint substrate is required, and on the other hand, the sealant material must have sufficient elasticity, including a low modulus, so that it can counteract the movement of the substrate without breaking the sealant body. In general, such joint sealants require a modulus of elasticity of less than about 0.7 MPa at an elongation in the range of 0.5-25% and a modulus of elasticity of less than about 0.35 MPa at an elongation in the range of 0.5-100% in the stress-strain test according to DIN 53504.

[0004] One major problem associated with such low modulus moisture-curing one-part polyurethane compositions is the inherent surface tackiness that these compositions exhibit after curing. The lower the modulus of the composition, the more pronounced this phenomenon is usually. Surface tackiness leads to aesthetically unpleasing surfaces, for example due to the accumulation of dirt or dust. In particular, for one-part polyurethane compositions that contain latent water-activatable curing agents with blocked amino groups, this phenomenon is known, and is particularly pronounced in low modulus sealants. The use of blocked amines in moisture-curing compositions based on conventional isocyanate group-containing polymers is known, for example, from US Pat. No. 7,625,993 or US Pat. No. 8,252,859.

[0005] Strategies to overcome this problem are known in the art. For example, EP 3315528 (Sika Technology AG) uses crystalline monofunctional alcohols to reduce the surface tack of polyurethane-based hot melt adhesives. However, for low modulus sealants, this approach is not sufficient. Summary of the Invention [Problem to be solved by the invention]

[0006] Thus, there is a need for one-component polyurethane compositions useful as elastomeric sealants that exhibit not only a very low elastic modulus, but also low surface tack. [Means for solving the problem]

[0007] It is an object of the present invention to provide a one-component polyurethane composition which is particularly suitable as a joint sealant having a low modulus and therefore a particularly high migration capacity, and which simultaneously exhibits exceptionally low surface tack.

[0008] The compositions according to the invention are particularly suitable for sealing joints or surfaces, but may also be used, in particular as elastic adhesives or coatings.

[0009] Surprisingly, it has been found that the above object can be achieved by adding a defined amount of at least one monofunctional amine to a composition comprising an isocyanate-functional polyurethane polymer and a latent amine curing agent according to claim 1. The compositions according to the invention exhibit, in the stress-strain test according to DIN 53504, a modulus of elasticity of less than about 0.7 MPa at an elongation range of 0.5-25% and a modulus of elasticity of less than about 0.35 MPa at an elongation range of 0.5-100%. Moreover, while maintaining a low modulus of elasticity, their surface tackiness is significantly reduced compared to compositions that do not contain said monofunctional amine or that contain other additives from the prior art, such as alcohols.

[0010] According to another aspect of the invention, a method for sealing a joint is provided. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] Substance names beginning with "poly", such as polyamines, polyols, or polyisocyanates, refer to substances that formally contain two or more of the functional groups appearing in their names per molecule. For example, polyols refer to compounds having at least two hydroxyl groups. Polyethers refer to compounds having at least two ether groups. A "primary polyamine" refers to a compound having at least two primary amino groups. Thus, substances beginning with "mono", such as monoamines, formally contain only one of each functional group, such as amine.

[0012] On the one hand, the term "polymer" in this document encompasses chemically homogeneous ensembles of macromolecules that also differ in terms of degree of polymerization, molar mass and chain length, which ensembles have been prepared by polymerization reactions (chain-propagating addition polymerization, radical polymerization, polyaddition, polycondensation). On the other hand, the term also encompasses derivatives of such ensembles of macromolecules from polymerization reactions, in other words compounds that are obtained, for example, by reactions, for example addition or substitution, of functional groups on existing macromolecules, and that can be chemically homogeneous or chemically non-homogeneous.

[0013] "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 using gel permeation chromatography (GPC) against polystyrene as a standard.

[0014] The term "(meth)acrylic" refers to methacrylic or acrylic. Thus, the term "(meth)acrylate" refers to methacrylate or acrylate.

[0015] "Aromatic isocyanate" or "aliphatic isocyanate" refers to an isocyanate in which the isocyanate group is attached directly to an aromatic or aliphatic carbon atom. This type of isocyanate group is therefore referred to as an "aromatic isocyanate group" or an "aliphatic isocyanate group."

[0016] The term "nominal functionality" (f) refers to the average or actual functionality of a given material or polymer with respect to a particular functional group. For example, a pure polyether diol has a nominal hydroxyl functionality of f=2. Similarly, glycerin has a nominal functionality of 3 with respect to hydroxyl groups.

[0017] The term "viscosity" refers to the dynamic or shear viscosity, which is determined by the ratio of the shear stress to the shear rate (velocity gradient) and is determined as described in DIN EN ISO 3219.

[0018] A substance or composition is said to be "storage-stable" or "storable" when it 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 change in its application or use characteristics to the extent relevant for its use as a result of storage.

[0019] The term "shelf life" refers to the period of time after which the dispersion adhesive composition has substantially solidified, separated or set, and the composition cannot be readily applied (spread) as a uniform, uniform film or bead onto the surface of a substrate.

[0020] The unit term "wt. %" means weight percent based on the weight of the respective total composition, unless otherwise specified. The terms "weight" and "mass" are used interchangeably throughout this document.

[0021] All industry standards and standard procedures mentioned in this document refer to their latest versions at the time of filing.

[0022] The term "room temperature" (abbreviated "RT") refers to a temperature of 23°C.

[0023] The term "standard pressure" refers to an absolute pressure of 1 bar.

[0024] In a first aspect of the present invention, (a) at least one polyurethane polymer P having isocyanate groups; (b) at least one blocked polyamine BA having a blocked hydrolytically activatable amino group; and (c) at least one monoamine MA of formula (V): [ka] The moisture-curable composition comprises: During the ceremony, R a teeth, having 1 to 12 C atoms, preferably 2 to 10 C atoms, more preferably 3 to 8 C atoms, and optionally containing an ether oxygen atom,Linear, cyclic or branched alkyl or alkenyl groups, or It is represents an optionally substituted aryl group; R b and R c each independently represents a group R a or a hydrogen atom, provided that R b and R c At least one of R b and R c combines with the N atom of the monoamine MA to form the aldehyde and amine R under the influence of water. a - forms an aldimine group which hydrolyzes to NH2; Where: Polymer P is a reaction product of 2,4- and / or 2,6-toluylene diisocyanate (TDI) with at least one polyol, the polyol having an average functionality of >2; and The amount of the monoamine MA in the composition is 0.2 to 25 parts by weight per 100 parts by weight of the polymer P.

[0025] Polyurethane polymer P having isocyanate groups The composition comprises at least one polyurethane polymer P having isocyanate groups, where the polymer P is a reaction product of 2,4- and / or 2,6-toluylene diisocyanate (TDI) and at least one polyol, where the polyol has an average functionality of >2.

[0026] It is necessary that TDI is used as the polyisocyanate for the production of polymer P. Other aromatic polyisocyanates, such as diphenylmethane 4,4'- or 2,4'- or 2,2'-diisocyanate, or any mixture of these isomers (MDI), or aliphatic polyisocyanates, such as 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (IPDI), do not produce the desired effect of the present invention.

[0027] The polyurethane polymer P is obtained in particular from the reaction of at least one polyol with a superstoichiometric amount of MDI. The reaction is preferably carried out at a temperature in the range of 50 to 160° C., optionally in the presence of a suitable catalyst, with the exclusion of moisture (water). The NCO / OH ratio is preferably in the range of 1.3 / 1 to 2.5 / 1. The polyisocyanates, in particular the monomeric diisocyanates, remaining after the conversion of the OH groups in the reaction mixture can be removed, if necessary, in particular by means of distillation, which may be preferred in the case of high NCO / OH ratios. The polyurethane polymer obtained preferably has a content of free isocyanate groups in the range of 0.5% to 10% by weight, in particular 1% to 5% by weight, more preferably 1% to 3% by weight. The polyurethane polymer can optionally be prepared with the additional use of a plasticizer or a solvent, in which case the plasticizer or solvent used does not contain any groups that are reactive towards isocyanates.

[0028] Suitable polyols for the synthesis of isocyanate-functional polymers suitable as polymer P are commercially available polyols or mixtures thereof, in particular - polyether polyols, in particular polyoxyalkylene diols and / or polyoxyalkylene triols, in particular the polymerization products of ethylene oxide or 1,2-propylene oxide or 1,2- or 2,3-butylene oxide or oxetane or tetrahydrofuran or mixtures thereof, which are polymerized on the polymerization platform of initiator molecules having two or more active hydrogen atoms, in particular initiator molecules such as water, ammonia or compounds having several OH or NH groups, for example 1,2-ethanediol, 1,2- or 1,3-propanediol, neopentyl glycol, The polyether polyols may be polymerized with the aid of ethanol, diethylene glycol, triethylene glycol, isomeric dipropylene glycols or tripropylene glycols, isomeric butanediols, pentanediols, hexanediols, heptanediols, octanediols, nonanediols, decanediols, undecanediols, 1,3- or 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, glycerol or aniline, or mixtures of the abovementioned compounds. Also suitable are polyether polyols having polymer particles dispersed therein, in particular those having styrene-acrylonitrile particles (SAN) or polyurea or polyhydrazodicarbonamide particles (PHD).

[0029] Preferred polyether polyols are polyoxypropylene diols or triols, or so-called ethylene oxide-terminated (EO end-capped) polyoxypropylene diols or triols, the latter being mixed polyoxyethylene-polyoxypropylene polyols, which are obtained in particular in that the polyoxypropylene diols or triols are further alkoxylated with ethylene oxide at the end of the polypropoxylation reaction and thus ultimately have primary hydroxyl groups.

[0030] Preferred polyether polyols have an unsaturation level 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 to polyesterdiols formed from dihydric alcohols, such as, in particular, 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 abovementioned 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 or hexahydrophthalic acid, or mixtures of the abovementioned acids, or lactones, such as, in particular, ε-caprolactone. Particular preference is given to polyesterpolyols formed from adipic acid or sebacic acid or dodecanedicarboxylic acid and hexanediol or neopentyl glycol. - polycarbonate polyols, such as may be obtained, for example, by reaction of the abovementioned alcohols (used to form the polyester polyols) with dialkyl carbonates, diaryl carbonates or phosgene. - block copolymers having at least two different blocks carrying at least two hydroxyl groups and having a polyether, polyester and / or polycarbonate structure of the type described above, in particular polyether polyester polyols. - Polyacrylate polyols and 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), such as epoxy polyesters or epoxy polyethers obtained by oxidation of natural fats and oils with carboxylic acids or alcohols and subsequent ring opening, or polyols obtained by hydroformylation and hydrogenation of unsaturated oils; or polyols obtained from natural fats and oils by degradation processes, such as alcoholysis or ozonolysis, followed by chemical linking, for example by transesterification or dimerization, of the degradation products thus obtained or their derivatives. Suitable degradation products of natural fats and oils are in particular fatty acids and fatty alcohols, and also 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 polyhydroxy-functional polyolefins, polyisobutylene, polyisoprene; 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 can also be prepared in particular from anionic polymerization; polyhydroxy-functional copolymers of dienes, for example 1,3-butadiene or mixtures of dienes, and polyhydroxy-functional acrylonitrile / butadiene copolymers, such as can be prepared from vinyl monomers, for example styrene, acrylonitrile, vinyl chloride, vinyl acetate, vinyl alcohol, isobutylene and isoprene, for example 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); and hydrogenated polyhydroxy-functional polymers or copolymers of dienes.

[0031] Also particularly suitable are mixtures of polyols, in which the average functionality of the polyol is calculated as a total average using the average functionality of the individual polyols. Thus, it is possible to use mixtures of polyols with a functionality of ≦2, as long as a sufficient amount of polyols with a functionality of >2 are contained in the mixture so that the overall average functionality is >2.

[0032] If the average functionality of all polyols is ≦2, the desired technical effect cannot be obtained in a sufficient manner.

[0033] In a preferred embodiment, the overall average OH functionality of the polyols used for the production of the polymer P is >2.25, in particular >2.5, in particular >2.75.

[0034] In a preferred embodiment of the moisture-curable composition according to the invention, the polyol used for the synthesis of the polymer P has an average OH functionality of 2.1 to 3.5, preferably 2.5 to 3, and / or said polymer P is prepared from said polyol and TDI using a molar ratio of NCO groups to OH groups of 1.8 to 2.2.

[0035] As regards the polyols, polyether polyols, polyester polyols, polycarbonate polyols, poly(meth)acrylate polyols or polybutadiene polyols are preferred.

[0036] Particularly preferred are polyether polyols, polyester polyols, especially aliphatic polyester polyols, or polycarbonate polyols, especially aliphatic polycarbonate polyols.

[0037] Most preferred are polyether polyols, especially polyoxypropylene diols or triols or ethylene oxide-terminated polyoxypropylene diols or triols.

[0038] Polyols having an average molecular weight in the range of 400 to 20,000 g / mol, preferably 1,000 to 15,000 g / mol, are preferred.

[0039] Polyols having an average OH functionality in the range of 2.1 to 3.5, preferably 2.5 to 3, are preferred.

[0040] Polyols that are liquid at room temperature are preferred.

[0041] In the preparation of polyurethane polymers containing isocyanate groups, fractions of di- or polyfunctional alcohols are used, in particular 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,3-pentanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, dibromoneopentyl glycol, 1,2-hexanediol, 1,6-hexanediol, 1,7-heptanediol, 1,2-octanediol, 1,8-octanediol, 2-ethyl-1,3-hexanediol, It is also possible to use glycerol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, 1,3- or 1,4-cyclohexanedimethanol, ethoxylated bisphenol A, propoxylated bisphenol A, cyclohexanediol, hydrogenated bisphenol A, dimer fatty acid alcohols, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, glycerol, pentaerythritol, sugar alcohols, such as, in particular, xylitol, sorbitol and mannitol, or sugars, such as, in particular, sucrose, or alkoxylated derivatives of the alcohols mentioned, or mixtures of the alcohols mentioned.

[0042] Suitable polyurethane polymers containing isocyanate groups as polymer P preferably have an average molecular weight M in the range from 1,500 to 20,000 g / mol, in particular from 2,000 to 15,000 g / mol. n has.

[0043] It is preferably a liquid at room temperature.

[0044] The amount of polymer P in the composition preferably ranges from 10 to 50% by weight, preferably from 15 to 40% by weight, based on the total composition.

[0045] Monoamine MA The composition comprises at least one monoamine MA of formula (V): [ka] During the ceremony, R a teeth, having 1 to 12 C atoms, preferably 2 to 10 C atoms, more preferably 3 to 8 C atoms, and optionally containing an ether oxygen atom, Linear, cyclic or branched alkyl or alkenyl groups, or It is represents an optionally substituted aryl group; R b and R c each independently represents a group R a or a hydrogen atom, provided that R b and R c At least one of R b and R c combines with the N atom of the monoamine MA to form the aldehyde and amine R under the influence of water. a Forms an aldimine group which hydrolyzes to -NH2.

[0046] The amount of the monoamine MA in the composition is 0.2 to 25, preferably 0.3 to 10, more preferably 0.4 to 5 parts by weight per 100 parts by weight of the polymer P.

[0047] In a preferred embodiment of the composition, R b and R c each independently represents a group R a or a hydrogen atom, provided that R b and R c At least one of the is a hydrogen atom.

[0048] In a particularly preferred embodiment of the composition, R b is the group R a and R c is a hydrogen atom. In this embodiment, R a and R b are preferably, independently of one another, a linear, cyclic or branched alkyl or alkenyl group or an optionally substituted aryl group having 1 to 12 C atoms, preferably having 2 to 10 C atoms, more preferably having 3 to 8 C atoms. Most preferably, R a and R b is a linear or branched alkyl group having 3 to 8 C atoms.

[0049] In another preferred embodiment of the composition, R b and R c combines with the N atom of the monoamine MA to form the aldehyde and amine R under the influence of water. a The blocked polyamine BA forms an aldimine group that hydrolyzes to -NH2. Suitable aldehydes are the same as those discussed further below for the blocked polyamine BA. This embodiment is particularly preferred when used in combination with a non-drying component, such as a filler. In this case, the aldimine made from the monoamine MA may act as an internal desiccant while releasing the monoamine MA. In this embodiment, R b and R c is a hydrogen atom, and R a teeth, having 1 to 12 C atoms, preferably 2 to 10 C atoms, more preferably 3 to 8 C atoms, and optionally containing an ether oxygen atom, linear, cyclic or branched alkyl or alkenyl groups, It is Preferably, R represents an optionally substituted aryl group. a is a linear or branched alkyl group having 3 to 8 C atoms.

[0050] Polyamine BA The composition comprises at least one blocked polyamine BA having blocked hydrolytically activatable amino groups.

[0051] The role of the blocked polyamine BA is to provide a latent curing agent for the isocyanate-functional polymer P. Under the influence of moisture (water), e.g., from the air, the blocked polyamine BA hydrolyzes and releases an amine crosslinker, which readily reacts with the isocyanate groups of the polymer P to form a crosslinked structure. Curing of polyurethanes using such latent curing agents is well known in the art and results in a controlled, bubble-free cure of the polyurethane composition.

[0052] In a preferred embodiment of the moisture-curable composition according to the invention, the blocked polyamine BA and the polymer P carrying isocyanate groups are present in the curable composition in an amount such that the ratio of blocked amino groups to isocyanate groups is between 0.1 and 1.1, preferably between 0.2 and 1.1, particularly preferably between 0.3 and 1.0.

[0053] The blocked amines in the form of polyamines BA used as curing coagents preferably have at least one aldimino or oxazolidinino group. These blocked amino groups together with the isocyanate groups are particularly storage stable with the exception of moisture.

[0054] Suitable as blocked amines are in particular bis-oxazolidines, in particular bis-oxazolidines of the formula (Ia) or (Ib) below: [ka] During the ceremony, D is a divalent hydrocarbon radical having 6 to 15 carbon atoms, in particular 1,6-hexylene or (1,5,5-trimethylcyclohexan-1-yl)methane-1,3 or 4(2)-methyl-1,3-phenylene, G is a monovalent organic group having 3 to 26 C atoms, in particular a 2-propyl, 3-heptyl, phenyl or substituted phenyl group.

[0055] Particularly preferred is D for 1,6-hexylene, where G is a substituted phenyl group having 12 to 26 carbon atoms, especially a phenyl group substituted in the para position with an optionally branched decylphenyl, undecylphenyl, dodecylphenyl, tridecylphenyl or tetradecylphenyl group. Such bis-oxazolidines are liquid and odorless at room temperature, stable in storage with isocyanate groups, and allow rapid curing.

[0056] In a preferred embodiment, the polyamine BA is an aldimine of formula (I): [ka] In formula (I), A is the remainder of the amine after removal of the n primary amino groups and m HX groups; n is 2 or 3 or 4; m is 0 or 1 or 2, with the proviso that m+n is 2 or 3 or 4; R 1 and R 2 are each independently a monovalent hydrocarbon radical having 1 to 12 C atoms or together form a divalent hydrocarbon radical having 4 to 12 C atoms which is part of an optionally substituted carbocyclic ring having 5 to 8, preferably 6 C atoms; R 3 is a hydrogen atom or an alkyl group, a cycloalkyl group, an arylalkyl group or an alkoxycarbonyl group having 1 to 12 C atoms; R 4 is a hydrogen atom, or an alkyl-, cycloalkyl-, arylalkyl-, aryl-, -OR 5 ',-SR 5 ', and -NR 5 'R 5 '' is a monovalent radical having 1 to 20 C atoms selected from, where R 5 ' and R 5" are each independently a hydrocarbon group or together form an alkylene group that is part of a 5-, 6-, or 7-membered ring; and X is O, S or NR 6 where R 6 is a hydrocarbon group having 1 to 20 C atoms which is optionally substituted with a carbonate group, a nitrile group, a nitro group, a phosphonate group, a sulfone group or a sulfonate group.

[0057] Preferably, A is 2-methyl-1,5-pentylene; 1,6-hexylene; 2,2(4),4-trimethyl-1,6-hexamethylene; 1,8-octylene; 1,10-decylene; 1,12-dodecylene; (1,5,5-trimethylcyclohexan-1-yl)methane-1.3; 1,3-cyclohexylene-bis(methylene); 1,4-cyclohexylene-bis(methylene); 1,3-phenylene-bis(methylene); 2- and / or 4-methyl-1,3-cyclohexylene; 3-oxa-1,5-pentylene; 3,6-dioxa-1,8-octylene; 4,7-dioxa-1,10-decylene; α,ω-polyoxypropylene having a molecular weight in the range of 170 to 450 g / mol; and trimethylolpropane-initiated tris(ω-polyoxypropylene) having an average molecular weight in the range of 330 to 450 g / mol.

[0058] Particularly preferably, A is 1,6-hexylene; (1,5,5-trimethylcyclohexan-1-yl)methane-1,3; 3-oxa-1,5-pentylene; α,ω-polyoxypropylene having an average molecular weight of about 200 g / mol, or trimethylolpropane tris(ω-polyoxypropylene) having an average molecular weight of about 390 g / mol.

[0059] Most preferably, A is 1,6-hexylene or (1,5,5-trimethylcyclohexan-1-yl)methane-1,3.

[0060] Preferably, R 1 and R 2are each methyl.

[0061] Preferably, R 3 is hydrogen.

[0062] R 4 is preferably a linear alkyl group having 11 to 20 C atoms, in particular a linear alkyl group having 11 C atoms.

[0063] These aldimines are low viscosity and substantially odorless before, during, and after hydrolytic activation and crosslinking with isocyanates.

[0064] Preferably, m is 0 and n is 2 or 3, in particular 2.

[0065] When m is 1, n is preferably 1.

[0066] When m is 1, X is preferably O.

[0067] Aldimines of formula (I) can in particular result from a condensation reaction between at least one primary amine of formula (II) below and at least one aldehyde of formula (III) below. [ka]

[0068] In formulas (II) and (III), the parameters m, n, A, X, R 1 , R 2 , R 3 , and R 4 has the same meaning as defined above.

[0069] For this condensation reaction, the aldehyde of formula (III) is preferably used stoichiometrically or superstoichiometrically based on the primary amino groups of the amine of formula (II). The reaction is advantageously carried out at a temperature in the range of 15 to 120° C., where appropriate in the presence or absence of a solvent. The released water is preferably removed azeotropically, for example with a suitable solvent or directly from the reaction mixture by applying a vacuum.

[0070] Preferred amines of formula (II) are 1,5-diamino-2-methylpentane, 1,6-hexanediamine, 2,2,4- and 2,4,4-trimethyl-hexamethylenediamine, 1,8-octanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)benzene. and polyoxypropyleneamines having an average molecular weight in the range from 200 to 500 g / mol, in particular Jeffamine® D-230, Jeffamine® D-400 and Jeffamine® T-403.

[0071] In some preferred embodiments of the moisture-curable composition according to the invention, the blocked polyamine BA is a polymeric blocked polyamine PBA, which is a polymer having at least two blocked hydrolytically activatable amino groups.

[0072] This means that A in formula (I) is a polymeric residue, preferably a polyether residue. Aldimines of this type can be prepared using amines of formula (II) that have a polymeric backbone, in particular a polyether backbone. Examples of such amines are polyoxypropyleneamines with average molecular weights in the range of 200 to 500 g / mol, in particular Jeffamine® D-230, Jeffamine® D-400 and Jeffamine® T-403.

[0073] The moisture-curable composition of the present invention preferably comprises at least one filler, preferably in an amount of 5 to 60% by weight, in particular 25 to 50% by weight, based on the total composition.

[0074] The term "filler" in this disclosure refers to solid particulate materials commonly used as fillers in polyurethane-based single-component compositions.

[0075] Fillers affect the rheological properties of the uncured composition, and also the mechanical properties and surface properties of the fully cured composition.Suitable fillers are inorganic and organic fillers, such as natural, ground or precipitated chalk (which consists entirely or mainly of calcium carbonate), which is optionally coated with fatty acid, more particularly stearic acid; barium sulfate (BaSO4, also called barite or barite), calcined kaolin, aluminum oxide, aluminum hydroxide, silica, especially finely divided silica from pyrolysis process, carbon black, especially industrially produced carbon black, titanium dioxide, PVC powder, or hollow beads.Preferred fillers are calcium carbonate, calcined kaolin, carbon black, finely divided silica, and flame retardant fillers, such as hydroxides or hydrates, especially hydroxides or hydrates of aluminum, preferably aluminum hydroxide.

[0076] It is entirely possible, and even may be advantageous, to use mixtures of different fillers.

[0077] Highly preferred as a filler for the compositions of the invention is chalk (calcium carbonate). Particularly preferred is coated or uncoated chalk, available, for example, under the name ranges Omyacarb® (Omya AG, Switzerland) or Socal® (Solvay).

[0078] The type and amount of filler is not particularly limited in the present invention. Examples of suitable fillers include calcium carbonate, calcium sulfate, and calcium containing minerals such as limestone, calcite, chalk, dolomite, wollastonite, gypsum, apatite, rock phosphate, and mixtures thereof.

[0079] Preferably, the filler has a median particle size d in the range of 1.0 to 100.0 μm, more preferably 1.0 to 60.0 μm, and most preferably 2.0 to 50.0 μm. 50 has.

[0080] The term "median particle size d 50 " means, in this disclosure, that less than 50% by volume of all particles are d 50 The term "particle size" refers to a particle size smaller than the area equivalent spherical diameter of the particle. The particle size distribution can be measured by laser diffraction by the method described in the standard ISO13320:2009. A Mastersizer2000 instrument (trademark of Malvern Instruments Ltd, GB) can be used to measure the particle size distribution.

[0081] In a preferred embodiment, the composition according to the invention comprises at least one filler chosen from calcium carbonate and / or titanium dioxide and / or carbon black.

[0082] In particular, many fillers contain significant amounts of chemisorbed or physisorbed water, which may be detrimental to the storage stability of the composition, and therefore it may be advantageous to dry the filler prior to formulation of the composition. b and R ccombines with the N atom of monoamine MA to form aldehydes and amines R under the influence of water. a When using a monoamine MA that forms an aldimine group that hydrolyzes to -NH2, drying may be reduced or eliminated entirely because the aldimine, the monoamine MA, may act as a desiccant in situ by chemically binding water and releasing the free amine of the monoamine MA. Thus, this embodiment has the advantage that dried fillers or other components may be used less stringently, which facilitates raw material storage and formulation processes.

[0083] The composition according to the invention may further comprise at least one additive, preferably selected from the list consisting of thixotropic agents, fillers, plasticizers, catalysts and adhesion promoters.

[0084] Suitable catalysts are in particular catalysts for the hydrolysis of oxazolidinyl and / or aldimino groups, in particular organic acids, in particular carboxylic acids such as 2-ethylhexanoic acid, lauric acid, stearic acid, isostearic acid, oleic acid, neodecanoic acid, benzoic acid, salicylic acid or 2-nitrobenzoic acid, organic carboxylic acid anhydrides such as phthalic anhydride, hexahydrophthalic anhydride or hexahydromethylphthalic anhydride, silyl esters of carboxylic acids, organic sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid or 4-dodecylbenzenesulfonic acid, sulfonic acid esters, other organic or inorganic acids, or mixtures of the aforementioned acids and acid esters. Particular preference is given to carboxylic acids, in particular aromatic carboxylic acids such as benzoic acid, 2-nitrobenzoic acid, or in particular salicylic acid.

[0085] Further suitable catalysts are catalysts for accelerating the reaction of isocyanate groups, in particular organotin(IV) compounds, such as, in particular, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dibutyltin diacetylacetonate, dimethyltin dilaurate, dioctyltin diacetate, dioctyltin dilaurate or dioctyltin diacetylacetonate, complex compounds of bismuth(III) or zirconium(IV) with ligands selected from alcoholates, carboxylates, 1,3-diketonates, oxinates, 1,3-ketoesterates and 1,3-keto-amidates, or compounds containing tertiary amino groups, in particular 2,2'-dimorpholinodiethyl ether (DMDEE).

[0086] In particular, combinations of different catalysts are also suitable.

[0087] In this case, catalysts for accelerating the reaction of isocyanate groups are in particular only present in amounts such that the stability of the cured composition is not excessively impaired.

[0088] The composition preferably further optionally contains one or more plasticizers having at least one ester or ether group.

[0089] Suitable plasticizers are liquid or solid inert organic substances having a low vapor pressure and preferably a boiling point, measured at standard pressure, above 200° C. The plasticizer may be selected from the group consisting of adipic and sebacic acid plasticizers, phosphoric acid plasticizers, citric acid plasticizers, fatty acid esters and epoxidized fatty acid esters, polypropylene glycols, polyethylene glycols, benzoates, and phthalates or esters of 1,2-dicarboxycyclohexane.

[0090] Suitable fatty acid esters include alkyl esters of fatty acids containing more than about 14 or more than about 16 carbon atoms, such as the alkyl esters of lauric acid, myristic acid, stearic acid, arachidic acid and behenic acid and mixtures thereof. Suitable as fatty alcohols are the alcohols of the above fatty acids, such as those obtainable from fatty acids or esters thereof by using processes known to those skilled in the art.

[0091] Particularly suitable plasticizers are carboxylic acid esters, such as phthalic acid esters, in particular diisononyl phthalate (DINP), diisodecyl phthalate (DIDP) or di(2-propylheptyl)phthalate (DPHP), hydrogenated phthalates, in particular hydrogenated diisononyl phthalate or diisononyl-1,2-cyclohexanedicarboxylate (DINCH), terephthalates, in particular bis(2-ethylhexyl) terephthalate or diisononyl terephthalate, hydrogenated terephthalates, in particular , hydrogenated bis(2-ethylhexyl) terephthalate or diisononyl terephthalate or bis(2-ethylhexyl)-1,4-cyclohexanedicarboxylate, trimellitates, adipates, in particular dioctyl adipate, azelates, sebacates, benzoates, glycol ethers, glycol esters, organic phosphoric or sulfonic acid esters, polybutenes, polyisobutenes, or plasticizers derived from natural fats or oils, in particular epoxidized soybean oil or linseed oil.

[0092] Preferably, the one or more plasticizers having at least one ester or ether group, if any, may be present in the single-component sealant or adhesive composition in a total amount of from 0.5 to 40.0 wt.-%, for example from 1.0 to 35 wt.-%, in particular from 10.0 to 30.0 wt.-%, based on the total weight of the composition.

[0093] The moisture curable composition may contain other additives, in particular - inorganic or organic pigments, in particular titanium dioxide, chromium oxide or iron oxide; fibres, in particular glass fibres, carbon fibres, metal fibres, ceramic fibres, plastic fibres, for example polyamide fibres or polyethylene fibres, or natural fibres, for example wool, cellulose, hemp or sisal; - nanofillers, such as graphene or carbon nanotubes; - dye; - desiccants, in particular molecular sieve powder, calcium oxide, highly reactive isocyanates such as p-tosylisocyanate, mono-oxazolidines such as Incozol® 2 (from Incorez) or orthoformates; adhesion promoters or adhesives, in particular organoalkoxysilanes, in particular epoxysilanes, such as, in particular, 3-glycidoxypropyltrimethoxysilane or 3-glycidoxypropyl-triethoxysilane, (meth)acrylosilanes, anhydrides, carbamatosilanes, alkylsilanes or iminosilanes, or oligomeric forms of these silanes, or titanates; further catalysts which accelerate the reaction of isocyanate groups, in particular salts, soaps or complexes of tin, zinc, bismuth, iron, aluminium, molybdenum, dioxomolybdenum, titanium, zirconium or potassium, in particular stannous 2-ethylhexanoate, tin(II) neodecanoate, zinc(II) acetate, zinc(II) 2-ethylhexanoate, zinc(II) laurate, zinc(II) acetylacetonate, aluminium lactate, aluminium oleate, diisopropoxytitanium bis(ethylacetoacetate) or potassium acetate; compounds containing tertiary amino groups, in particular N-ethyldiisopropylamine, N,N,N',N'-tetramethylalkylenediamine, pentamethyl-alkylene-triamine and their higher homologues. , bis(N,N-diethylaminoethyl)adipate, tris(3-dimethylaminopropyl)amine, 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), N-alkylmorpholines, N,N'-dimethylpiperazines; nitrogen aromatic compounds, such as 4-dimethylaminopyridine, N-methylimidazole, N-vinylimidazole or 1,2-dimethylimidazole; organic ammonium compounds, such as benzyltrimethylammonium hydroxide or alkoxylated tertiary amines; the so-called "slow-acting" catalysts, which are modifications of known metal or amine catalysts; rheology modifiers, in particular thickeners, in particular layered silicates, for example bentonite, derivatives of castor oil, hydrogenated castor oil, polyamides, polyamide waxes, polyurethanes, urea compounds, pyrogenic silicic acid, cellulose ethers or hydrophobically modified polyoxyethylenes; 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-tetraxoundecane (TOU), toluene, xylene, heptane, octane, naphtha, white spirit, petroleum ether or gasoline, in particular Solvesso™ type (formerly Exxon Mobile), and also propylene carbonate, dimethyl carbonate, butyrolactone, N-methylpyrrolidone, N-ethylpyrrolidone, p-chlorobenzotrifluoride or benzotrifluoride; natural resins, fats or oils, such as rosin, shellac, linseed oil, castor oil or soybean oil; - non-reactive polymers, in particular homopolymers or copolymers, of unsaturated monomers, in particular 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 fillers already mentioned, aluminium hydroxide or magnesium hydroxide, and in particular organic phosphates, in particular triethyl phosphate, tricresyl phosphate, triphenyl phosphate, diphenylcresyl phosphate, isodecyldiphenyl 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 different 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, stabilizers against oxidation, heat, light or UV light or biocides; or other materials commonly used in moisture curable compositions. may contain

[0094] It may be useful to chemically or physically dry certain materials prior to incorporation into the composition.

[0095] Biocides (preservatives) may be added to the sealant composition according to the invention in an amount of 0% to 2% by weight, preferably 0.2% to 1.8% by weight, more preferably 0.4% to 1.5% by weight, based on the total composition of biocides.

[0096] In general, any known type of biocide, also referred to as a preservative, can be used in the compositions of the present invention.

[0097] Suitable as preservatives are the customary preservatives, such as, for example, benzoisothiazolinone (BIT), methylisothiazolinone (MIT), octylisothiazolinone (OIT), chloromethylisothiazolinone (CMIT), etc.

[0098] According to one or more embodiments, the total amount of further additives is preferably 0.1-15.0 wt. %, more preferably 0.2-5.0 wt. %, based on the total weight of the single-component sealant or adhesive composition.

[0099] Particularly preferred embodiments of the moisture-curable composition according to the invention are - from 10 to 40% by weight, preferably from 15 to 35% by weight, of a polyurethane polymer P containing isocyanate groups, relative to the composition; - from 1 to 5% by weight, preferably from 2 to 4% by weight, of blocked polyamines BA having blocked hydrolytically activatable amino groups, relative to the composition; - from 5 to 40% by weight, preferably from 10 to 30% by weight, of at least one plasticizer, relative to the composition; - 0 to 40% by weight, preferably 2.5 to 10% by weight, based on the composition, of at least one thixotropic additive; - from 0.05 to 2% by weight, and preferably from 0.1 to 1% by weight, of said monoamine MA, relative to the composition; - from 0 to 60% by weight, preferably from 10 to 50% by weight, of at least one filler, relative to the composition; - 0 to 5% by weight, preferably 0.1 to 2.5% by weight, of at least one further additive selected from the group consisting of adhesion promoters, drying agents, catalysts and stabilizers, relative to the composition. Includes.

[0100] The composition according to the present invention can be prepared by mixing the components together at room temperature. Any suitable mixing equipment can be used for the preparation of the adhesive composition, with no particular restrictions other than preferably excluding moisture during preparation.

[0101] In particular, the polyurethane composition is produced with the exclusion of moisture and storage in a moisture-tight container at ambient temperature. Suitable moisture-proof containers are in particular made of metal and / or plastic, optionally coated, and in particular represent cylindrical cylinders, containers, buckets, canisters, cans, bags, tubular bags, cartridges or tubes.

[0102] The composition is applied as a one-part composition by itself, without the need for mixing, and begins to harden under the influence of moisture or water. To accelerate hardening, the composition can, however, be mixed with an accelerating component that contains or releases water.

[0103] Under curing conditions, i.e. in contact with water, the isocyanate groups react with the blocked amino groups under the influence of moisture. A portion of the isocyanate groups, in particular those in excess of the blocked amino groups, react with each other and / or with further reactive groups optionally present in the composition, in particular hydroxyl groups or free amino groups, under the influence of moisture. The totality of these reactions of the isocyanate groups, which result in the curing of the composition, is also called crosslinking.

[0104] The moisture required to cure the moisture-curable composition passes from the air (atmospheric moisture), preferably by diffusion into the composition. At the same time, a solid layer of the cured composition ("skin") is formed on the surface of the composition that is in contact with the air. The cure proceeds from the outside to the inside along the direction of diffusion, and the skin progressively thickens and eventually surrounds the entire applied composition. The moisture can also or completely come from the substrate or substrates to which the composition is applied, enter the composition, and / or come from facilitating components that are mixed with the composition during or after application and come into contact with it, for example, by brushing or spraying.

[0105] The moisture-curable composition is preferably applied at ambient temperatures, in particular in the range of about -10 to 50°C, preferably in the range of -5 to 45°C, particularly preferably in the range of 0 to 40°C.

[0106] Curing of the moisture curable composition is also preferably carried out at ambient temperature.

[0107] The compositions according to the invention have a long processing time (open time) and rapid hardening.

[0108] "Open time" refers to the period during which a composition can be processed or post-processed without loss of functionality. In one-component compositions, the open time is exceeded at the latest when a skin forms.

[0109] "Cure rate" is the amount of polymer formation in a composition within a given period of time after application, for example, by determining the thickness of the skin formed.

[0110] During crosslinking, the aldehyde used to block the amino groups is liberated. As the aldehyde is largely non-volatile and odorless, it remains largely in the cured composition and acts as a plasticizer.

[0111] Preferably, the moisture-curable composition according to the invention is used as an elastic adhesive or an elastic sealant or an elastic coating, in particular as a sealant.

[0112] As sealants, the moisture-curing compositions are particularly suitable for elastic sealing of all kinds of joints, seams or gaps, in particular joints in construction, such as expansion joints or connection joints between components, or soil joints in civil engineering. In particular, sealants with soft elasticity and high low-temperature flexibility are particularly suitable for sealing expansion joints in structures.

[0113] As coatings, the moisture-curing compositions are particularly suitable for protecting and / or sealing structures or parts thereof, in particular on balconies, terraces, roofs, especially for flat or slightly sloping roofs or roof gardens, or under tiles or ceramic tiles in bathrooms or kitchens in buildings, or in drip pans, water channels, manholes, silos, docks or sewage treatment plants.

[0114] It can also be used for restoration purposes, for example as a seal or coating from leaky roof membranes or flooring that is no longer suitable, or as a restoration compound for highly reactive spray seals.

[0115] The moisture-curable composition may be formulated to have a paste-like consistency having pseudoplastic properties. Such compositions are applied using a suitable pre-applied device, for example from a commercially available cartridge or bucket or hob, in the form of a bead which may have, for example, a substantially circular or triangular cross-sectional area.

[0116] The moisture-curing composition can be further formulated to be liquid and so-called self-leveling or only slightly thixotropic, and can be poured out for application. As a coating, for example, it can then be distributed over the entire surface to the desired layer thickness, for example, using a roller, slider, serrated trowel or spatula. In this case, layer thicknesses in the range of 0.5 to 3 mm, in particular 1.0 to 2.5 mm, are typically applied in one operation.

[0117] Suitable substrates which can be bonded or sealed or coated with the moisture curable composition are, in particular: glass, glass ceramics, concrete, mortar, cement screed, fibre cement, in particular fibre cement boards, brick, bricks, plaster, in particular gypsum boards or anhydrous screeds, or natural stone, for example granite or marble; - repair or levelling compounds based on PCC (polymer modified cement mortar) or ECC (epoxy resin modified cement mortar); - metals or alloys, for example aluminium, copper, iron, steel, surface-finished metals or alloys, for example non-ferrous metals, including galvanised or chromium-plated metals; - Asphalt or bitumen; - leather, textiles, paper, wood, resins, for example wood-based materials bound with phenolic, melamine or epoxy resins, resin-textile composites or other so-called polymer composites; - plastics, such as hard and soft PVC, polycarbonate, polystyrene, polyester, polyamide, PMMA, ABS, SAN, epoxy resins, phenolic resins, PUR, POM, TPO, PE, PP, EPM or EPDM, each of which is untreated or surface-treated, for example by means of plasma, corona or flame light; - fibre reinforced plastics, such as carbon fibre reinforced plastics (CFRP), glass fibre reinforced plastics (GRP) and sheet moulding compounds (SMC); - Insulation materials, in particular EPS, XPS, PUR, PIR, rock wool, mineral wool or cellular glass (foam glass); - coated or painted substrates, in particular painted tiles, painted concrete, powder-coated metals or alloys or painted sheets; - Paints or varnishes, in particular automotive finishes It is.

[0118] If necessary, the substrate can be pretreated prior to application, especially by physical and / or chemical cleaning methods or by application of activators or primers.

[0119] Two identical or similar, or two different substrates can be bonded and / or sealed.

[0120] The single-component composition according to the invention, when intended for use as an elastic sealant, preferably has, after drying in air, a Shore A hardness of 5 to 25, preferably 9 to 21, at 23° C. and 50% relative humidity for 7 days.

[0121] According to another aspect of the present invention, there is provided a method for sealing a joint between a substrate S1 and a substrate S2, the method comprising the steps of: (i) applying a moisture-curable composition according to the above description to the gap between substrate S1 and substrate S2, thereby bringing the composition into contact with both substrates S1 and S2; And, subsequently, (ii) hardening of the applied composition by moisture, particularly moisture from the air; Here, the substrate S2 is formed from the same or different material as the substrate S1.

[0122] According to another aspect of the present invention there is provided the use of the moisture curable composition of the present invention as a joint sealant.

[0123] Yet another aspect of the present invention is the use of monoamines MA of formula (V) for reducing the surface tack and / or the elastic modulus of cured moisture-curing compositions comprising at least one polyurethane polymer P having isocyanate groups: [ka] During the ceremony, R a teeth, having 1 to 12 C atoms, preferably 2 to 10 C atoms, more preferably 3 to 8 C atoms, and optionally containing an ether oxygen atom, linear, cyclic or branched alkyl or alkenyl groups, It is represents an optionally substituted aryl group; R b and R c each independently represents a group R a or a hydrogen atom, provided that R b and R c At least one of R band R c combines with the N atom of the monoamine MA to form the aldehyde and amine R under the influence of water. a - forms an aldimine group which hydrolyzes to NH2; wherein said polymer P is a reaction product of 2,4- and / or 2,6-toluylene diisocyanate (TDI) with at least one polyol, wherein the polyol has an average functionality of >2; The amount of the monoamine MA in the composition is 0.2 to 25 parts by weight per 100 parts by weight of the polymer P.

[0124] In a preferred embodiment of said use, R b and R c each independently represents a group R a or a hydrogen atom, provided that R b and R c At least one of is a hydrogen atom. All other preferred embodiments for the monoamine MA and the polymer P are the same as those generally discussed further above in the description.

[0125] Yet another aspect of the present invention is a dried and / or cured single-component sealant or adhesive composition according to the present invention. EXAMPLES

[0126] The invention is further illustrated in the following experimental part, which should not, however, be construed as a limitation to the scope of the invention.

[0127] Test Method The tensile strength, elongation at break and modulus at 0.5-25% elongation and 0.5-100% elongation, respectively, were determined according to DIN 53504 (tensile speed: 200 mm / min) on films with a layer thickness of 2 mm cured for 7 days at 23 °C and 50% relative humidity.

[0128] The Shore A hardness was determined according to DIN 53505 on samples with a layer thickness of 6 mm cured for 7 days at 23° C. and 50% relative humidity.

[0129] Surface tack (grams of sand adhered to the surface) was determined by filling 30 g of each sealant composition into a plastic cup, followed by mixing in a speedmixer for 1 minute to obtain a smooth surface. The compositions were cured in the cup for 3 days at 23° C. and 50% relative humidity. After this, sand was poured onto the exposed surface of the cured sealant, and the cup was turned upside down to allow the unadhered sand to fall off. The adhered portion of the sand was determined by weighing using a laboratory balance. Surface tack was determined by the difference in weight of the cup before and after sand treatment.

[0130] raw material The ingredients used for the example sealant compositions and their descriptions of important properties are shown in Table 1.

[0131] [Table 1]

[0132] Preparation of thixotropic agents, aldimines, and polyurethane polymers Thixotropic Agent The thixotropic agent was prepared by charging 300 g of diisodecyl phthalate and 48 g of 4,4'-diphenylmethane diisocyanate (Desmodur® 44MC L, ex Covestro) in a vacuum mixer, followed by slight pre-heating, then slowly adding 27 g of monobutylamine dropwise under vigorous stirring. The paste thus obtained was further stirred under vacuum and external cooling for 1 hour.

[0133] Aldimine N,N'-Bis(2,2-dimethyl-3-lauroyloxypropylidene)-3-aminomethyl-3,5,5-trimethylcyclohexylamine 598g (2.1mol) of 2,2-dimethyl-3-lauroyloxy-propanal is placed in a round-bottom flask under nitrogen atmosphere. 170.3g (1mol) of 3-aminomethyl-3,5,5-trimethylcyclohexylamine (Vestamin® IPD from Evonik) solution (70% by weight in water) is added while stirring, and then volatile components are removed at 80°C and 10mbar vacuum. 732g of almost colorless liquid is obtained with an amine content of 2.73mmol N / g, which corresponds to a calculated equivalent weight of about 367g / Eq.

[0134] Preparation of polymer P1 The isocyanate-functional polyurethane-based polymer P1 was prepared by known polyurethane synthesis processes by synthesizing ethylene oxide-capped polyoxypropylene triol (M) at a molar ratio of NCO groups to OH groups of 1.95 at 80° C. under nitrogen until the reaction was complete. W The polymer was prepared by reacting 2,4-toluene diisocyanate (2,4-toluene diisocyanate) with toluene diisocyanate (TDI) at 6000 g / mol. The TDI used was a blend of 80% by weight of 2,4-toluene diisocyanate and 20% by weight of 2,6-toluene diisocyanate.

[0135] Preparation of polymer P2 3241 g of polyoxypropylene diol (Acclaim® 4200N, Bayer MaterialScience AG, OH number 28.5 mg KOH / g), 1351 g of polyoxypropylene polyoxyethylene triol (Caradol® MD34-02, Shell Chemicals Ltd., UK, OH number 35.0 mg KOH / g) and 395 g of tolylene diisocyanate (TDI, Desmodur® T80P, Bayer MaterialScience AG) were reacted at 80° C. to obtain an NCO-terminated polyurethane polymer with a content of free isocyanate groups of 1.47% by weight.

[0136] Preparation of polymer P3 4051 g of polyoxypropylene polyoxyethylene triol (Caradol® MD34-02, Shell Chemicals Ltd., UK, OH number 35.0 mg KOH / g), 675 g of 4,4'-methylenediphenyl diisocyanate (4,4'-MDI; Desmodur® 44MC L, Bayer MaterialScience AG) and 1172 g of diisodecyl phthalate (DIDP, Palatinol® Z, BASF SE, Germany) were reacted at 80°C by known methods to obtain an NCO-terminated polyurethane polymer with a content of free isocyanate groups of 2.38% by weight.

[0137] Preparation of polymer P4 1632 g of polyoxypropylene diol (Acclaim® 4200, ex Covestro, OH number 28.5 mg KOH / g), 4410 g of polyoxypropylene polyoxyethylene triol (Caradol® MD34-02, ex Shell, OH number 35.0 mg KOH / g) and 800 g of isophorone diisocyanate (Vestanat® IPDI, Degussa) were reacted at 80° C. by known methods with a liquid (at room temperature) NCO-terminated polyurethane polymer having a content of free isocyanate groups of 2.1% by weight.

[0138] [Table 2]

[0139] Compositions E1 to E3 and R1 to R5 of the Examples For each composition, the ingredients shown in Table 1 were thoroughly mixed in the amounts (parts by weight) shown in Table 2 with the exclusion of moisture under vacuum using a planetary mixer and stored with the exclusion of moisture. Several non-inventive reference (labeled "Reference") and inventive example compositions were made from the raw materials in Table 1 using the respective amounts as shown in Table 2.

[0140] Test results The results of the test methods used on each example composition are detailed in Table 3.

[0141] [Table 3]

[0142] The results in Table 3 show that the sealant compositions E1 to E3 of the invention show a low modulus of <0.7 MPa in the elongation range of 0.5 to 25% and <0.35 MPa in the elongation range of 0.5 to 100%, while at the same time showing only low to moderate surface tack. In an otherwise identical composition without monoamine MA (R1), the surface tack increases significantly. The same is true when using another TDI-based polymer P without monoamine MA (R5). If alcohol is used instead (R2), the surface tack is low but the modulus increases significantly, reducing the suitability for elastic sealants. Other references (R3 and R4), which used different polyisocyanates for polymer P, show a modulus and / or surface tack that are too high for the intended use as elastic sealants. The present disclosure also includes the following: [1] 1. A moisture curable composition comprising: (a) at least one polyurethane polymer P having isocyanate groups; (b) at least one blocked polyamine BA having a blocked hydrolytically activatable amino group; and (c) at least one monoamine MA of formula (V): [ka] During the ceremony, R a represents a linear, cyclic or branched alkyl or alkenyl group or an optionally substituted aryl group having 1 to 12 C atoms and optionally containing an ether oxygen atom; R b and R c each independently represents a group R a or a hydrogen atom, provided that R b and R c At least one of R b and Rc combines with the N atom of the monoamine MA to form an aldehyde and an amine R under the influence of water. a -NH 2 to form an aldimine group which hydrolyzes to; Where: Polymer P is a reaction product of 2,4- and / or 2,6-toluylene diisocyanate (TDI) with at least one polyol, said polyol having an average functionality of >2; and the amount of the monoamine MA in the composition is 0.2 to 25 parts by weight per 100 parts by weight of the polymer P; Moisture curable compositions. [2] R b and R c independently represents a group R a or a hydrogen atom, provided that R b and R c The moisture-curable composition of embodiment 1, wherein at least one of is a hydrogen atom. [3] R b Group R a and R c is a hydrogen atom. [4] R b and R c together with the N atom of the monoamine MA to form an aldehyde and an amine R under the influence of water. a -NH 2 2. The moisture-curable composition of claim 1, wherein the moisture-curable composition forms an aldimine group that hydrolyzes to give: [5] 5. The moisture-curable composition according to any one of aspects 1 to 4, wherein the blocked polyamine BA and the polymer P having isocyanate groups are present in the curable composition in amounts such that the ratio of blocked amino groups to isocyanate groups is 0.1 to 1.1, preferably 0.2 to 1.1, and particularly preferably 0.3 to 1.0. [6] 6. The moisture-curable composition according to any one of the first to fifth aspects, characterized in that the blocked polyamine BA is an aldimine of formula (I):

change

[10] 10. The moisture-curable composition according to any of the preceding aspects, characterized in that the polyol used for the synthesis of polymer P has an average OH functionality of 2.1 to 3.5, preferably 2.5 to 3, and / or the polymer P is prepared from polyol and TDI using a molar ratio of NCO groups to OH groups of 1.8 to 2.2.

[11] A moisture-curable composition according to any one of aspects 1 to 10, characterized in that it comprises: - from 10 to 40% by weight, preferably from 15 to 35% by weight, of said polyurethane polymer P containing isocyanate groups, relative to said composition; - from 1 to 5% by weight, preferably from 2 to 4% by weight, relative to the composition, of said blocked polyamine BA having blocked hydrolytically activatable amino groups; - from 5 to 40% by weight, preferably from 10 to 30% by weight, relative to the composition, of at least one plasticizer; - from 0 to 40% by weight, preferably from 2.5 to 10% by weight, relative to the composition, of at least one thixotropic additive; - from 0.05 to 2% by weight, preferably from 0.1 to 1% by weight, of said monoamine MA relative to said composition; - from 0 to 60% by weight, preferably from 10 to 50% by weight, relative to the composition, of at least one filler; - 0 to 5% by weight, preferably 0.1 to 2.5% by weight, relative to the composition, of at least one further additive selected from the group consisting of adhesion promoters, drying agents, catalysts and stabilizers.

[12] A method for sealing a joint between a substrate S1 and a substrate S2, comprising the steps of: (i) applying the moisture-curable composition according to any one of embodiments 1 to 11 to a gap between substrate S1 and substrate S2, thereby bringing the composition into contact with both substrates S1 and S2; And, subsequently, (ii) hardening of the applied composition by moisture, in particular moisture from the air; Here, the substrate S2 is formed from the same or different material as the substrate S1.

[13] 12. Use of the moisture-curable composition according to any one of aspects 1 to 11 as a joint sealant.

[14] Use of monoamines MA of formula (V) for reducing the surface tack and / or elastic modulus of cured moisture-curing compositions comprising at least one polyurethane polymer P having isocyanate groups:

change

[15] R b and R c independently represents a group R a or a hydrogen atom, provided that R b and R c The use according to embodiment 14, characterized in that at least one of is a hydrogen atom.

Claims

1. 1. A moisture curable composition comprising: (a) at least one polyurethane polymer P having isocyanate groups; (b) at least one blocked polyamine BA having a blocked hydrolytically activatable amino group; and (c) at least one monoamine MA of formula (V): 【Chemistry 1】 During the ceremony, R ａ represents a linear, cyclic or branched alkyl or alkenyl group having 1 to 12 C atoms, optionally containing an ether oxygen atom, or an optionally substituted aryl group having 6 to 12 C atoms; R ｂ and R ｃ are independently a group R ａ or a hydrogen atom, provided that R ｂ and R ｃ At least one of R ｂ and R ｃ together with the N atom of the monoamine MA to form an aldehyde and an amine R under the influence of water. ａ -NH ２ to form an aldimine group which hydrolyzes to Where: Polymer P is a reaction product of 2,4- and / or 2,6-toluylene diisocyanate (TDI) with at least one polyol, said polyol having an average functionality of >2; and the amount of said monoamine MA in said composition is from 0.2 to 25 parts by weight per 100 parts by weight of said polymer P; Moisture curable compositions.

2. R ｂ and R ｃ are independently a group R ａ or a hydrogen atom, with the proviso that R ｂ and R ｃ The moisture-curable composition according to claim 1, wherein at least one of the following is a hydrogen atom:

3. R ｂ is a group R ａ and R ｃ The moisture-curable composition according to claim 2 , wherein is a hydrogen atom.

4. R ｂ and R ｃ together with the N atom of the monoamine MA to form an aldehyde and an amine R under the influence of water. ａ -NH ２ 2. The moisture-curable composition according to claim 1, which forms an aldimine group which hydrolyzes to give:

5. 5. The moisture-curing composition according to claim 1, wherein the blocked polyamine BA and the polymer P carrying isocyanate groups are present in the curable composition in an amount such that the ratio of blocked amino groups to the isocyanate groups is between 0.1 and 1.

1.

6. The moisture-curable composition according to any one of claims 1 to 5, characterized in that the blocked polyamine BA is an aldimine of formula (I): 【Chemistry 2】 During the ceremony, A is the remainder of the amine after removal of the n primary amino groups and m HX groups; n is 2 or 3 or 4; m is 0 or 1 or 2, with the proviso that m+n is 2 or 3 or 4; R １ and R ２ are each independently a monovalent hydrocarbon radical having 1 to 12 C atoms or together form a divalent hydrocarbon radical having 4 to 12 C atoms which is part of an optionally substituted carbocyclic ring having 5 to 8 C atoms; R ３ is a hydrogen atom or an alkyl group, a cycloalkyl group, an arylalkyl group or an alkoxycarbonyl group having 1 to 12 C atoms; R ４ is a hydrogen atom, or an alkyl-, cycloalkyl-, arylalkyl-, aryl-, -OR ５ ', -SR ５ ' and -NR ５ 'R ５ '' is a monovalent radical having 1 to 20 C atoms selected from, where R ５ ' and R ５ " are each independently a hydrocarbon group or together form an alkylene group that is part of a 5-, 6-, or 7-membered ring; and X is O, S or NR ６ where R ６ is a hydrocarbon group having 1 to 20 C atoms which is optionally substituted with a carbonate group, a nitrile group, a nitro group, a phosphonate group, a sulfone group or a sulfonate group.

7. R １ and R ２ are each methyl, and / or R ３ is a hydrogen atom, and / or R ４ The moisture-curable composition according to claim 6, characterized in that is a linear alkyl group having 11 to 20 C atoms.

8. 8. The curable composition according to claim 6, wherein m is 0 and n is 2 or 3.

9. 9. The moisture-curable composition according to claim 1, wherein the blocked polyamine BA is a blocked polyamine PBA polymer, which is a polymer having at least two blocked hydrolytically activatable amino groups.

10. 10. The moisture-curing composition according to claim 1, characterized in that the polyol used for the synthesis of polymer P has an average OH functionality of 2.1 to 3.5 and / or that polymer P is prepared from said polyol and TDI using a molar ratio of NCO groups to OH groups of 1.8 to 2.

2.

11. The moisture-curable composition according to any one of claims 1 to 10, characterized in that it comprises: - 10 to 40% by weight, relative to the composition, of said polyurethane polymer P containing isocyanate groups; - 1 to 5% by weight, relative to the composition, of said blocked polyamine BA having blocked hydrolytically activatable amino groups; from 5 to 40% by weight, relative to the composition, of at least one plasticizer; - from 0 to 40% by weight, relative to the composition, of at least one thixotropic additive; from 0.05 to 2% by weight of said monoamine MA, relative to said composition; - from 0 to 60% by weight, relative to the composition, of at least one filler; - 0-5% by weight of at least one further additive selected from the group consisting of adhesion promoters, driers, catalysts and stabilizers, relative to said composition.

12. A method for sealing a joint between a substrate S1 and a substrate S2, comprising the steps of: (i) applying a moisture-curable composition according to any one of claims 1 to 11 into a gap between substrate S1 and substrate S2, thereby bringing said composition into contact with both substrates S1 and S2; And, subsequently, (ii) hardening the applied composition by moisture; Here, the substrate S2 is formed from the same or different material as the substrate S1.

13. Use of the moisture-curable composition according to any one of claims 1 to 11 as a joint sealant.

14. Use of monoamines MA of formula (V) for reducing the surface tack and / or elastic modulus of cured moisture-curing compositions comprising at least one polyurethane polymer P having isocyanate groups: 【Chemistry 3】 During the ceremony, R ａ represents a linear, cyclic or branched alkyl or alkenyl group having 1 to 12 C atoms, optionally containing an ether oxygen atom, or an optionally substituted aryl group having 6 to 12 C atoms; R ｂ and R ｃ are independently a group R ａ or a hydrogen atom, provided that R ｂ and R ｃ At least one of R ｂ and R ｃ together with the N atom of the monoamine MA to form an aldehyde and an amine R under the influence of water. ａ -NH ２ to form an aldimine group which hydrolyzes to wherein the polymer P is a reaction product of 2,4- and / or 2,6-toluylene diisocyanate (TDI) with at least one polyol, the polyol having an average functionality of >2; and The amount of said monoamine MA in said composition is between 0.2 and 25 parts by weight per 100 parts by weight of said polymer P.

15. R ｂ and R ｃ are independently a group R ａ or a hydrogen atom, with the proviso that R ｂ and R ｃ The use according to claim 14, characterized in that at least one of the is a hydrogen atom.

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