Moisture-curable polyurethane compositions with reduced surface tack

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 Art

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

[0003] Particularly for joint sealant applications, such one-component polyurethane compositions generally need to have certain properties in the cured state in order to fulfill the tasks efficiently. On the one hand, proper adhesion on the joint substrate is required, and on the other hand, the sealant material needs to have sufficient elasticity, including a low modulus of elasticity, so that it can compensate for the movement of the substrate without breaking the sealant body. Generally, such joint sealants require a modulus of elasticity of less than about 0.7 MPa at elongations in the range of 0.5 to 25% and less than about 0.35 MPa at elongations in the range of 0.5 to 100% in a stress-strain test according to DIN 53504.

[0004] One of the main problems associated with such low modulus moisture-curing one-component polyurethane compositions is the inherent surface tackiness exhibited by these compositions after curing. The lower the modulus of the composition, the more pronounced this phenomenon usually is. Surface tackiness results in an aesthetically unpleasant surface, for example, due to the accumulation of dirt or dust. In particular, this phenomenon is known for one-component polyurethane compositions containing a latent moisture-activated curative with blocked amino groups, 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 U.S. Patent No. 7,625,993 or U.S. Patent No. 8,252,859.

[0005] Strategies for overcoming this problem are known in the art. For example, European Patent No. 3315528 (Sika Technology AG) uses crystalline monofunctional alcohols to reduce the surface tackiness of polyurethane-based hot melt adhesives. However, this approach is not sufficient for low modulus sealants. SUMMARY OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION

[0006] Therefore, there is a need for a one-component polyurethane composition that exhibits not only a very low modulus but also low surface tackiness and is useful as an elastic sealant. MEANS FOR SOLVING THE PROBLEM

[0007] It is an object of the present invention to provide a one-component polyurethane composition that is particularly suitable as a joint sealant having a particularly low modulus and thus particularly high movement capabilities, and that simultaneously exhibits exceptionally low surface tackiness.

[0008] The composition according to the invention is particularly suitable for sealing joints or surfaces, but can also be used, in particular, as an elastic adhesive or coating.

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

[0010] According to another aspect of the present invention, a method for sealing a joint is provided. [Modes for carrying out the invention]

[0011] Substance names beginning with "poly," such as polyamine, polyol, or polyisocyanate, indicate substances that formally contain two or more functional groups per molecule as appearing in their names. For example, polyol refers to a compound having at least two hydroxyl groups. Polyether refers to a compound having at least two ether groups. Primary polyamine refers to a compound having at least two primary amino groups. Therefore, substances beginning with "mono," such as monoamine, formally contain only one of each functional group, such as an amine.

[0012] On the one hand, the term “polymer” in this literature encompasses a collection of chemically homogeneous macromolecules that differ in degree of polymerization, molar mass, and chain length, which have been prepared by polymerization reactions (chain growth addition polymerization, radical polymerization, polyaddition, polycondensation). On the other hand, the term also encompasses derivatives of such macromolecular collections from polymerization reactions, in other words, compounds obtained, for example, by the reaction of functional groups on existing macromolecules, e.g., addition or substitution, and which may be chemically homogeneous or chemically heterogeneous.

[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) of a polydisperse mixture of oligomer molecules, polymer molecules, or molecular residues. n This refers to the standard. This is typically determined using gel permeation chromatography (GPC) with respect to polystyrene as a standard substance.

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

[0015] "Aromatic isocyanates" or "aliphatic isocyanates" refer to isocyanates in which the isocyanate group is directly bonded to an aromatic or aliphatic carbon atom. Therefore, this type of isocyanate group is called an "aromatic isocyanate group" or an "aliphatic isocyanate group."

[0016] The term "nominal functional group number" (f) refers to the average or actual number of functional groups in a given substance or polymer with respect to a particular functional group. For example, pure polyetherdiol has a nominal hydroxyl functional group number of f=2. Similarly, glycerol has a nominal functional group number of 3 with respect to hydroxyl groups.

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

[0018] A substance or composition is described as "storage-stable" or "storable" if, as a result of storage, it can be stored in a suitable container at room temperature for an extended period, typically at least three to six months or more, without any change in its application or use characteristics to a degree relevant to its use.

[0019] The term "storage life" refers to the period after which the dispersion adhesive composition has substantially solidified, separated, or fixed, and the composition cannot be easily applied (coated) to the surface of the substrate as a homogeneous and uniform film or beads.

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

[0021] All industrial standards and standard methods described herein refer to their respective latest versions at the time of filing.

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

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

[0024] In a first embodiment of the present invention, (a) At least one polyurethane polymer P having an isocyanate group; (b) at least one blocked polyamine BA having a blocked hydrolyzable amino group; and (c) at least one monoamine MA of formula (V): [ka] Regarding moisture-curing compositions, including, During the ceremony, R arepresents a linear, cyclic, or branched alkyl or alkenyl group, or an optionally substituted aryl group 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; R b and R c each independently represents either the group R a or a hydrogen atom, provided that at least one of R b and R c is a hydrogen atom, or R b and R c together with the N atom of the monoamine MA form an aldimine group that hydrolyzes to an aldehyde and the amine R a -NH2 under the influence of water; Here, the polymer P is a reaction product of 2,4- and / or 2,6-toluene diisocyanate (TDI) and at least one polyol, which has an average functionality > 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 above.

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

[0026] It is necessary for TDI to be used as the polyisocyanate for the production of the 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 bring about the desired effects of the present invention.

[0027] Polyurethane polymer P is particularly obtained 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, with moisture (water) excluded in the presence of a suitable catalyst, which is optional. The NCO / OH ratio is preferably in the range of 1.3 / 1 to 2.5 / 1. The polyisocyanate remaining after the conversion of OH groups in the reaction mixture, in particular the diisocyanate of the monomer, can be removed as needed, particularly by distillation, which may be preferred in the case of a high NCO / OH ratio. The resulting polyurethane polymer preferably has a free 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. The polyurethane polymer can be optionally prepared with the further use of plasticizers or solvents, in which case the plasticizers or solvents used do not contain any groups that are reactive with isocyanates.

[0028] Suitable polyols for the synthesis of isocyanate-functionalized polymers suitable as polymer P are commercially available polyols or mixtures thereof, in particular, - Polyether polyols, in particular polyoxyalkylenediols and / or polyoxyalkylentriols, 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 polymerization products of such, initiating molecules having two or more active hydrogen atoms, in particular initiating molecules such as water, ammonia, or compounds having multiple OH or NH groups, such as 1,2-ethanediol, 1,2- or 1,3-propanediol, neopentylglyceride Polyether polyols may be polymerized with the help of chol, diethylene glycol, triethylene glycol, isomer dipropylene glycol or tripropylene glycol, isomer butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, undecanediol, 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 above compounds. Equally suitable are polyether polyols having polymer particles dispersed therein, in particular styrene-acrylonitrile particles (SAN) or polyurea or polyhydrazodicarbonamide particles (PHD).

[0029] Preferred polyether polyols are polyoxypropylenediol or polyoxypropylenetriol, or so-called ethylene oxide-terminated (EO-end capped) polyoxypropylenediol or polyoxypropylenetriol. The latter is a mixed polyoxyethylene-polyoxypropylene polyol, which is particularly obtained in that the polyoxypropylenediol or polyoxypropylenetriol is further alkoxylated with ethylene oxide at the end of the polypropoxylation reaction, and therefore ultimately has a primary hydroxyl group.

[0030] Preferred polyether polyols have a degree of unsaturation of less than 0.02 meq / g, and in particular less than 0.01 meq / g. - Polyester polyols, also known as oligoesterols, prepared by known processes, particularly by polycondensation of hydroxycarboxylic acids or lactones with dihydric or polyhydric alcohols, or by polycondensation of aliphatic and / or aromatic polycarboxylic acids. Polyester diols are preferred from the reaction of a dihydric alcohol, for example, particularly 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 a mixture of the above alcohols, with an organic dicarboxylic acid or its anhydride or ester, for example, particularly 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 a mixture of the above acids, or a lactone, for example, particularly ε-caprolactone, to form a polyester polyol. Polyester polyols formed from adipic acid or sebacic acid or dodecanedicarboxylic acid and hexanediol or neopentyl glycol are particularly preferred. - For example, a polycarbonate polyol that can be obtained by the reaction of the above-mentioned alcohol (used to form a polyester polyol) with a dialkyl carbonate, diaryl carbonate, or phosgene. - A block copolymer having at least two different blocks supporting at least two hydroxyl groups and having the above-described polyether, polyester and / or polycarbonate structure, in particular a polyether polyester polyol. - Polyacrylate polyols and polymethacrylate polyols. - Polyhydroxy functional fats and oils, for example, natural fats and oils, in particular castor oil; or polyols obtained by chemical modification of natural fats and oils (referred to as oleochemical polyols), for example 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 decomposition processes, for example alcohol decomposition or ozonolysis, and subsequent chemical linkage, for example, by transesterification or dimerization of the decomposition products or derivatives thus obtained. Suitable decomposition products of natural fats and oils are particularly fatty acids and fatty alcohols, and also fatty acid esters, in particular methyl esters (FAMEs) that can be derivatized to hydroxy fatty acid esters by hydroformylation and hydrogenation, for example. - Also referred to as oligohydrocarbonols, polyhydrocarbon polyols, e.g., polyhydroxy-functional polyolefins, polyisobutylene, polyisoprene; polyhydroxy-functional ethylene-propylene, ethylene-butylene, or ethylene-propylene-diene copolymers, e.g., those produced by Kraton Polymers; dienes, particularly polyhydroxy-functional polymers of 1,3-butadiene, which can be prepared in particular from anionic polymerization; polyhydroxy-functional copolymers of dienes, e.g., 1,3-butadiene, or mixtures of dienes; and polyhydroxy-functional acrylonitrile / butadiene copolymers, e.g., those prepared from vinyl monomers, e.g., styrene, acrylonitrile, vinyl chloride, vinyl acetate, vinyl alcohol, isobutylene, and isoprene, e.g., epoxides or amino alcohols, and carboxyl-terminated acrylonitrile / butadiene copolymers (e.g., commercially available from Emerald Performance Materials under the names Hypro® CTBN, CTBNX, or ETBN); and hydrogenated polyhydroxy-functional polymers or copolymers of dienes.

[0031] Polyol mixtures are particularly suitable. In the case of a mixture, the average number of functional groups of the polyols is calculated as a grand average using the average number of functional groups of the individual polyols. Thus, it is possible to use a mixture of polyols with ≤2 functional groups, as long as a sufficient amount of polyols with >2 functional groups are contained in the mixture, so that the overall average number of functional groups is >2.

[0032] If the average number of functional groups for all polyols is ≤2, the desired technical effect cannot be obtained in a sufficient manner.

[0033] In preferred embodiments, the overall average number of OH functional groups in the polyol used for the production of polymer P is >2.25, in particular >2.5, and in particular >2.75.

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

[0035] With regard to polyols, polyether polyols, polyester polyols, polycarbonate polyols, poly(meth)acrylate polyols, or polybutadiene polyols are preferred.

[0036] Polyether polyols, polyester polyols, especially aliphatic polyester polyols, or polycarbonate polyols, especially aliphatic polycarbonate polyols, are particularly preferred.

[0037] Most preferred are polyether polyols, particularly polyoxypropylenediol or triol, or ethylene oxide-terminated polyoxypropylenediol or triol.

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

[0039] A polyol having an average number of OH functional groups in the range of 2.1 to 3.5, preferably 2.5 to 3, is preferred.

[0040] A polyol that is liquid at room temperature is preferred.

[0041] In the preparation of polyurethane polymers containing isocyanate groups, fractions of difunctional or polyfunctional alcohols, particularly 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, dibromo-neopentyl 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 diethylene glycol, triethylene glycol, dipropylene glycol, tripylene glycol, 1,3- or 1,4-cyclohexanedimethanol, ethoxylated bisphenol A, propoxylated bisphenol A, cyclohexanediol, hydrogenated bisphenol A, dimer fatty acid alcohol, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, glycerol, pentaerythritol, sugar alcohols, for example, xylitol, sorbitol and mannitol in particular, or sugars, for example, sucrose in particular, or alkoxylated derivatives of the alcohols described, or mixtures of the alcohols described.

[0042] A polyurethane polymer containing an isocyanate group suitable as polymer P is preferably an average molecular weight M in the range of 1,500 to 20,000 g / mol, particularly 2,000 to 15,000 g / mol. n It holds.

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

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

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

[0046] The amount of monoamine MA in the composition is 0.2 to 25 parts by weight, preferably 0.3 to 10 parts by weight, and 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 Independently, base R a or represents a hydrogen atom, however, R b and R c At least one of them is a hydrogen atom.

[0048] In a particularly preferred embodiment of the composition, R b is based on R a And R c R is a hydrogen atom. In this embodiment, R a and R b Preferably, these are linear, cyclic, or branched alkyl or alkenyl groups, or optionally substituted aryl groups having 1 to 12 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 3 to 8 carbon atoms, independently of each other. Most preferably, R a and R b It is a linear or branched alkyl group having 3 to 8 carbon atoms.

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

[0050] Polyamine BA The composition comprises at least one blocked polyamine BA having a blocked, hydrolyzably activatable amino group.

[0051] The role of the blocked polyamine BA is to provide a latent curing agent for isocyanate-functionalized polymers P. For example, under the influence of moisture from the air, the blocked polyamine BA hydrolyzes and releases the amine crosslinking agent, which readily reacts with the isocyanate groups of polymer P to form a crosslinked structure. Curing of polyurethanes using such latent curing agents is well known in this field and results in controlled, bubble-free curing of the polyurethane composition.

[0052] In a preferred embodiment of the moisture-curable composition according to the present invention, the blocked polyamine BA and the polymer P having isocyanate groups are present in the curable composition in such an amount 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.

[0053] Blocked amines in the form of polyamine BA used as curing aids preferably have at least one aldimino group or oxazolidino group. These blocked amino groups, together with moisture-free isocyanate groups, are particularly storage stable.

[0054] Suitable blocked amines are, in particular, bis-oxazolidines, especially those of the following formula (Ia) or (Ib): [ka] During the ceremony, D is a divalent hydrocarbon group having 6 to 15 carbon atoms, in particular representing 1,6-hexylene or (1,5,5-trimethylcyclohexane-1-yl)methane-1,3 or 4(2)-methyl-1,3-phenylene, and G is a monovalent organic group having 3 to 26 carbon atoms, particularly 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 at 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 for rapid curing.

[0056] In a preferred embodiment, the polyamine BA is an aldimine of the following formula (I): [ka] In equation (I), A is the residue of the amine after the removal of n primary amino groups and m HX groups; n is 2, 3, or 4; m is 0, 1, or 2, where m+n is 2, 3, or 4; R 1 and R 2 Each is independently a monovalent hydrocarbon group having 1 to 12 carbon atoms, or together they form a divalent hydrocarbon group having 4 to 12 carbon atoms, which is an optionally substituted portion of a carbocyclic ring having 5 to 8, preferably 6, carbon atoms; R 3 This is an alkyl group, cycloalkyl group, arylalkyl group, or alkoxycarbonyl group having a hydrogen atom or 1 to 12 carbon atoms; R 4 is a hydrogen atom, or alkyl-, cycloalkyl-, arylalkyl-, aryl-, -OR 5 ',-SR 5 ', and -NR 5 'R 5 A monovalent group having 1 to 20 C atoms selected from '', where R 5 'and R 5Each of these groups is either independently a hydrocarbon group or together forms an alkylene group which is a 5-membered, 6-membered, or 7-membered ring; and X is O, S, or NR 6 And here, R 6 This refers to a hydrocarbon group having 1 to 20 carbon atoms that is optionally substituted with a carbonate ester group, a nitrile group, a nitro group, a phosphonic acid ester group, a sulfonate group, or a sulfonic acid ester 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-trimethylcyclohexane-1-yl)methane-1,3; 1,3-cyclohexylene-bis(methylene); 1,4-cyclohexylene-bis(methylene); 1,3-phenylene-bis(methylene); 2- The group is selected from the group consisting of 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-starting tris(ω-polyoxypropylene) having an average molecular weight in the range of 330 to 450 g / mol.

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

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

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

[0061] Preferably, R 3 It is hydrogen.

[0062] R 4 Preferably, it is a linear alkyl group having 11 to 20 carbon atoms, and more particularly, a linear alkyl group having 11 carbon 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, particularly 2.

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

[0066] When m is 1, X is preferably 0.

[0067] Aldimines of formula (I) can be obtained, in particular, from the condensation reaction of at least one primary amine of formula (II) below and at least one aldehyde of formula (III) below. [ka]

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

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

[0070] Preferred amines of formula (II) are 1,5-diamino-2-methylpentane, 1,6-hexanediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, 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, and 1,3-bis(aminomethyl)benzene. The following are selected from the group consisting of 2- and / or 4-methyl-1,3-diaminocyclohexane, 2-(2-aminoethoxy)ethanol, 3,6-dioxaoctane-1,8-diamine, 4,7-dioxadecane-1,10-diamine, and polyoxypropyleneamines having an average molecular weight in the range of 200 to 500 g / mol, particularly Jeffamine® D-230, Jeffamine® D-400, and Jeffamine® T-403.

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

[0072] This means that in formula (I), A is the polymer residue, preferably the polyether residue. This type of aldimine can be prepared using amines of formula (II) having a polymer backbone, particularly a polyether backbone. Examples of such amines are polyoxypropylene amines having an average molecular weight in the range of 200 to 500 g / mol, in particular Jeffamine® D-230, Jeffamine® D-400, and Jeffamine® T-403.

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

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

[0075] The fillers affect the rheological properties of the uncured composition, as well as the mechanical properties and surface properties of the fully cured composition. Suitable fillers include inorganic and organic fillers, such as fatty acids, more specifically, natural, crushed, or precipitated chalk (consisting entirely or primarily of calcium carbonate) optionally coated with stearic acid; barium sulfate (also known as BaSO4, barite or barite); calcined kaolin, aluminum oxide, aluminum hydroxide, silica, in particular, pulverized silica from a pyrolysis process; carbon black, in particular, industrially produced carbon black; titanium dioxide; PVC powder; or hollow beads. Preferred fillers include calcium carbonate, calcined kaolin, carbon black, pulverized silica, and flame-retardant fillers, such as hydroxides or hydrates, in particular, aluminum hydroxide or hydrate, preferably aluminum hydroxide.

[0076] Using a mixture of different fillers is entirely possible, and may even be advantageous.

[0077] A very preferred filler for the compositions of the present invention is chalk (calcium carbonate). Particularly preferred is coated or uncoated chalk, for example, available under the designation range Omyacarb® (Omya AG, Switzerland) or Socal® (Solvay).

[0078] The type and amount of filler are not particularly limited in the present invention. Suitable fillers include calcium carbonate, calcium sulfate, and mineral-containing calcium, such as limestone, calcite, chalk, dolomite, wollastonite, gypsum, apatite, phosphate rock, 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 It holds.

[0080] The term "median particle size d" 50 In this disclosure, " means that 50% of all particles are less than d 50 This refers to particle size smaller than the specified value. The term "particle size" refers to the area equivalent spherical diameter of a particle. The particle size distribution can be measured by laser diffraction using methods such as those described in the standard ISO 13320:2009. The Mastersizer 2000 instrument (a trademark of Malvern Instruments Ltd, GB) can be used in measuring the particle size distribution.

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

[0082] In particular, many fillers contain a considerable amount of chemically or physically adsorbed water, which can be detrimental to the storage stability of the composition; therefore, it may be advantageous to dry the filler before preparing the composition. However, in the case of monoamine MA, R b and R cHowever, together with the N atom of the monoamine MA, under the influence of water, it forms an aldehyde and an amine R a When using a monoamine MA that forms an aldimine group that hydrolyzes to -NH2, this aldimine, being a monoamine MA, can act as a drying agent in situ by chemically binding to water and releasing the free amine of the monoamine MA, thus reducing or completely eliminating drying. Thus, this embodiment has the advantage of allowing the use of dried fillers or other components with less strictness, which facilitates raw material storage and compounding processes.

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

[0084] Suitable catalysts include, in particular, catalysts for the hydrolysis of oxazolidino and / or algimino groups, in particular organic acids, in particular carboxylic acids, e.g., 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, e.g., phthalic anhydride, hexahydrophthalic anhydride or hexahydromethylphthalic anhydride, silyl esters of carboxylic acids, organic sulfonic acids, e.g., methanesulfonic acid, p-toluenesulfonic acid or 4-dodecylbenzenesulfonic acid, sulfonic acid esters, other organic or inorganic acids, or mixtures of the above acids and acid esters. Carboxylic acids, in particular aromatic carboxylic acids, e.g., benzoic acid, 2-nitrobenzoic acid, or especially salicylic acid are particularly preferred.

[0085] Further suitable catalysts are catalysts for accelerating the reaction of isocyanate groups, in particular organotin(IV) compounds, for example, in particular dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dibutyltin diacetylacetonate, dimethyltin dilaurate, dioctyltin diacetate, dioctyltin dilaurate or dioctyltin diacetylacetonate, in particular bismuth(III) or zirconium(IV) complex compounds having ligands selected from alkoxide, carboxylate, 1,3-diketonate, oxinate, 1,3-ketoesterate and 1,3-ketoamide, or compounds containing a tertiary amino group, in particular 2,2'-dimorpholinodiethyl ether (DMDEE).

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

[0087] In this case, the catalyst for promoting the reaction of the isocyanate group is present only in an amount that does not excessively impair the stability of the cured composition.

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

[0089] A suitable plasticizer is an inert organic substance in liquid or solid form having a low vapor pressure and, preferably, a boiling point greater than 200°C as measured at standard pressure. The plasticizer can be selected from the group consisting of adipic acid and sebaciate plasticizers, phosphate plasticizers, citrate plasticizers, fatty acid esters and epoxide fatty acid esters, polypropylene glycol, polyethylene glycol, benzoate, and phthalate or ester of 1,2-dicarboxycyclohexane.

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

[0091] Particularly suitable plasticizers include carboxylic acid esters, for example, phthalate 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, and The following are also included: hydrogenated bis(2-ethylhexyl) terephthalate or diisononyl terephthalate or bis(2-ethylhexyl)-1,4-cyclohexanedicarboxylate, trimellitates, adipates, especially dioctyl adipate, azelate, sebacate, benzoate, glycol ether, glycol ester, organophosphoric acid or sulfonic acid ester, polybutene, polyisobutene, or plasticizers derived from natural fats or oils, especially epoxide-treated soybean oil or linseed oil.

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

[0093] Moisture-curing compositions include other additives, particularly, - Inorganic or organic pigments, particularly titanium dioxide, chromium oxide, or iron oxide; - Fibers, especially glass fibers, carbon fibers, metal fibers, ceramic fibers, plastic fibers, such as polyamide fibers or polyethylene fibers, or natural fibers, such as wool, cellulose, hemp or sisal; - Nanofillers, such as graphene or carbon nanotubes; - dye; - Desiccants, in particular molecular sieve powders, calcium oxide, highly reactive isocyanates, such as p-tosyl isocyanates, mono-oxazolidines, such as Incozol® 2 (from Incorez) or orthoformate esters; - Adhesion promoters or adhesives, in particular organoalkoxysilanes, in particular epoxysilanes, for example, in particular 3-glycidoxypropyltrimethoxysilane or 3-glycidoxypropyl-triethoxysilane, (meth)acrylosilane, anhydrous silane, carbamatosilane, alkylsilane or iminosilane, or oligomeric forms of these silanes, or titanates; - Further catalysts to accelerate the reaction of isocyanate groups, in particular salts, soaps, or complexes of tin, zinc, bismuth, iron, aluminum, 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) acetylacetoneate, aluminum lactate, aluminum oleate, diisopropoxytitanium bis(ethylacetate) or potassium acetate; tertiary amino group-containing compounds, in particular N-ethyldiisopropylamine, N,N,N',N'-tetramethylalkylenediamine, pentamethylalkylenetriamine and its 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]undeca-7-ene (DBU), 1,5-diazabicyclo[4.3.0]nona-5-ene (DBN), N-alkylmorpholine, N,N'-dimethylpiperazine; nitrogen aromatic compounds, e.g., 4-dimethylaminopyridine, N-methylimidazole, N-vinylimidazole or 1,2-dimethylimidazole; organic ammonium compounds, e.g., benzyltrimethylammonium hydroxide or alkoxylated tertiary amines; so-called "slow-acting" catalysts, which are modifications of known metal or amine catalysts; - Rheological modifiers, in particular thickeners, in particular layered silicates, such as bentonite, castor oil derivatives, hydrogenated castor oil, polyamides, polyamide waxes, polyurethanes, urea compounds, pyrogenic silicic acid, cellulose ethers, or hydrophobically modified polyoxyethylenes; - Solvents, particularly 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 propyral, butyral, 2-ethylhexylal, dioxolane, glycerol formal or 2,5,7,10-tetraxoundecane (TOU), toluene, xylene, heptane, octane, naphtha, white spirit, petroleum ether or gasoline, particularly Solvesso® type (formerly Exxon Mobile), and 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 of unsaturated monomers, particularly homopolymers or copolymers, from the group including ethylene, propylene, butylene, isobutylene, isoprene, vinyl acetate or alkyl (meth)acrylate, and especially polyethylene (PE), polypropylene (PP), polyisobutylene, ethylene vinyl acetate copolymer (EVA) or atactic poly-α-olefin (APAO); - Flame retardant substances, in particular aluminum hydroxide or magnesium hydroxide, which are fillers already described, and in particular organic phosphate esters, in particular triethyl phosphate, tricresyl phosphate, triphenyl phosphate, diphenylcresil 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) phosphate of different degrees of isopropylation, resorcinol bis(diphenyl phosphate), bisphenol A bis(diphenyl phosphate), or ammonium polyphosphate; - Additives, particularly wetting agents, leveling agents, defoaming agents, deaeration agents, stabilizers against oxidation, heat, light or ultraviolet light, or biocides; or other substances commonly used in moisture-curing compositions It may contain.

[0094] It may be useful to chemically or physically dry certain substances before mixing them into a composition.

[0095] A biocide (preservative) can be added to the sealant composition according to the present invention in an amount of 0% to 2% by weight, preferably 0.2% to 1.8% by weight, and more preferably 0.4% to 1.5% by weight, relative to the total composition of the biocide.

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

[0097] Suitable preservatives include common preservatives such as benzoisothiazolinone (BIT), methylisothiazolinone (MIT), octylisothiazolinone (OIT), and chloromethylisothiazolinone (CMIT).

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

[0099] A particularly preferred embodiment of the moisture-curing composition according to the present invention is: - 10 to 40% by weight, preferably 15 to 35% by weight, of a polyurethane polymer P having isocyanate groups in this composition; - 1 to 5% by weight, preferably 2 to 4% by weight, of blocked polyamine BA having blocked hydrolyzable amino groups in this composition; - 5 to 40% by weight, preferably 10 to 30% by weight, of at least one plasticizer relative to this composition; - A composition based on 0 to 40% by weight, preferably 2.5 to 10% by weight, of at least one thixotropic additive; - 0.05 to 2% by weight, preferably 0.1 to 1% by weight of the monoamine MA in this composition; - At least one filler in an amount of 0 to 60% by weight, preferably 10 to 50% by weight, relative to this composition; - To this 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. Includes.

[0100] The composition according to the present invention can be prepared by mixing the components together at room temperature. Preferably, any suitable mixing apparatus can be used for preparing the adhesive composition, without any special restrictions other than the exclusion of moisture during the mixing process.

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

[0102] The composition, as a one-component composition, is applied as is without the need for mixing and begins to cure under the influence of moisture or water. To accelerate curing, however, the composition may be mixed with a curing component that contains or releases water.

[0103] Under curing conditions, i.e., in contact with water, isocyanate groups react with blocked amino groups under the influence of moisture. Some of the isocyanate groups, particularly those in excess of the blocked amino groups, react with each other and / or with any further reactive groups optionally present in the composition, in particular hydroxyl groups or free amino groups, under the influence of moisture. The entirety of these reactions of the isocyanate groups that result in the curing of the composition is also referred to as crosslinking.

[0104] The moisture required to cure a moisture-curable composition preferably passes through the composition from the air (moisture in the atmosphere) by diffusion. Simultaneously, a solid layer ("skin") of the cured composition forms on the surface of the composition that is in contact with the air. Curing proceeds from the outside inward along the direction of diffusion, and the skin progressively thickens, eventually enveloping the entire applied composition. The moisture may also originate from one or more substrates to which the composition is applied, enters the composition, and / or is mixed with the composition during or after application, and may originate from accelerating components that come into contact with it, for example, by brushing or spraying.

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

[0106] The curing of the moisture-curable composition is preferably carried out at ambient temperature.

[0107] The composition according to the present invention has a long processing time (open time) and rapid curing.

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

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

[0110] During crosslinking, the aldehyde used to block the amino group is released. If the aldehyde is mostly non-volatile and odorless, it will largely remain in the cured composition and act as a plasticizer.

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

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

[0113] As a coating, moisture-curing compositions are particularly suitable for protecting and / or sealing structures or their parts, especially for balconies, terraces, roofs, especially flat roofs or slightly sloped roofs or roof gardens, or under tiles or ceramic tiles in bathrooms or kitchens within buildings, or in drip trays, waterways, manholes, silos, docks or sewage treatment plants.

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

[0115] Moisture-curing compositions can be formulated to have a paste-like consistency with pseudoplastic properties. Such compositions are applied (coated) using appropriate pre-treatment equipment, for example, from commercially available cartridges, buckets, or hovocs, in the form of beads, which may have substantially circular or triangular cross-sectional areas.

[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 (coating). As a coating, for example, it can then be distributed over the entire surface to the desired thickness using, for example, a roller, slider, serrated trowel or spatula. In this case, layer thicknesses in the range of 0.5 to 3 mm, and especially 1.0 to 2.5 mm, are typically applied (coated) in a single operation.

[0117] Suitable substrates that can be bonded, sealed, or coated with moisture-curing compositions include, in particular, - Glass, glass ceramics, concrete, mortar, cement screed, fiber cement, especially fiber cement board, brick, plaster, especially gypsum board or anhydrous screed, or natural stone, such as granite or marble; - Repair or leveling compounds based on PCC (polymer-modified cement mortar) or ECC (epoxy resin-modified cement mortar); - Metals or alloys, such as aluminum, copper, iron, steel, and non-ferrous metals, including surface-refined metals or alloys, such as galvanized or chromium-plated metals; - Asphalt or bitumen; - Leather, textiles, paper, wood, resins, for example, wood-based materials bonded with phenolic resins, melamine resins, 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 resin, phenolic resin, PUR, POM, TPO, PE, PP, EPM, or EPDM, either untreated or surface-treated, for example, using plasma, corona, or flame light; - Fiber-reinforced plastics, such as carbon fiber reinforced plastics (CFRP), glass fiber reinforced plastics (GRP), and sheet-forming compounds (SMC); - In particular, insulation materials such as EPS, XPS, PUR, PIR, rock wool, glass wool, or bubble glass; - Coated or painted substrates, in particular painted tiles, painted concrete, powder-coated metals or alloys, or painted sheets; - Paints or varnishes, especially automotive finishes. That is the case.

[0118] If necessary, the substrate may be pre-treated before application, particularly by physical and / or chemical cleaning methods, or by the application of activators or primers.

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

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

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

[0122] According to another aspect of the present invention, the use of the moisture-curing composition of the present invention as a joint sealant (joint filler) is provided.

[0123] Another aspect of the present invention is the use of a monoamine MA of formula (V) below to reduce the surface tackiness and / or modulus of a cured moisture-curable composition comprising at least one polyurethane polymer P having an isocyanate group: [ka] During the ceremony, R a This represents a linear, cyclic, or branched alkyl or alkenyl group, or an optionally substituted aryl group having 1 to 12 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 3 to 8 carbon atoms, and optionally containing an ether oxygen atom; R b and R c Independently, base R a It represents either a hydrogen atom or R b and Rc At least one of them is a hydrogen atom, or R b and R c It combines with the N atom of the monoamine MA to form an aldehyde and amine R under the influence of water. a -Forms an aldimine group that hydrolyzes to NH2; Here, 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 number of functional groups >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 the preferred embodiment of the above use, R b and R c Independently, base R a or represents a hydrogen atom, however, R b and R c At least one of these is a hydrogen atom. All other preferred embodiments for monoamine MA and polymer P are the same as those generally discussed above in the description.

[0125] 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 present invention will be further described in the experimental section below, but this should not be construed as a limitation on the scope of the invention.

[0127] Test method The tensile strength, elongation at break, and modulus of elasticity at elongations of 0.5–25% and 0.5–100% were determined using DIN53504 (tensile speed: 200 mm / min) on a 2 mm thick film cured for 7 days at 23°C and 50% relative humidity.

[0128] Shore A hardness was determined by DIN53505 on a sample with a layer thickness of 6 mm that was cured for 7 days at 23°C and 50% relative humidity.

[0129] Surface tackiness (grams of sand adhered to the surface) was determined by filling 30g of each sealant composition into a plastic cup and then mixing it in a speed mixer for 1 minute to obtain a smooth surface. The composition was cured in the cup at 23°C and 50% relative humidity for 3 days. After this, sand was poured onto the exposed surface of the cured sealant, and the cup was inverted to remove the non-adhering sand. The amount of sand adhered was determined by weighing using a laboratory balance. Surface tackiness was determined by the difference in weight of the cup before and after sand treatment.

[0130] raw material Table 1 shows the raw materials used for the sealant compositions of the examples and their important properties.

[0131] [Table 1]

[0132] Preparation of thixotropic agents, aldimines, and polyurethane polymers Thixotropic agents The thixotropic agent was prepared by loading 300 g of diisodecyl phthalate and 48 g of 4,4'-diphenylmethane diisocyanate (Desmodur® 44MC L, from Covestro) into a vacuum mixer, followed by slight preheating. Then, 27 g of monobutylamine was slowly added dropwise while vigorously stirring. The resulting paste was further stirred under vacuum and external cooling for 1 hour.

[0133] Aljimin :N,N'-bis(2,2-dimethyl-3-lauroyloxypropyridene)-3-aminomethyl-3,5,5-trimethylcyclohexylamine 598 g (2.1 mol) of 2,2-dimethyl-3-lauroyloxypropanal was placed in a round-bottom flask under a nitrogen atmosphere. With stirring, 170.3 g (1 mol) of 3-aminomethyl-3,5,5-trimethylcyclohexylamine (Vestamin® IPD from Evonik) solution (70 wt% in water) was added, and then volatile components were removed at 80°C and under a vacuum of 10 millibars. 732 g of a nearly colorless liquid with an amine content of 2.73 mmol N / g, corresponding to the calculated equivalent volume of approximately 367 g / Eq, was obtained.

[0134] Preparation of polymer P1 Polymer P1, based on polyurethane having isocyanate functional groups, is subjected to a known polyurethane synthesis process until the reaction is complete, and is ethylene oxide-capped polyoxypropylene triol (M) at 80°C under nitrogen with a molar ratio of NCO groups to OH groups of 1.95. W It was prepared by reacting 6000 g / mol of toluene diisocyanate (TDI) with toluene diisocyanate. The TDI used was a mixed 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, 28.5 mg KOH / g), 1351 g of polyoxypropylene polyoxyethylene triol (Caradol® MD34-02, Shell Chemicals Ltd., UK, 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 having a free isocyanate group content of 1.47% by weight.

[0136] Preparation of polymer P3 4051 g of polyoxypropylene polyoxyethylene triol (Caradol® MD34-02, Shell Chemicals Ltd., UK, 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 a known method to obtain an NCO-terminated polyurethane polymer having a free isocyanate group content of 2.38% by weight.

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

[0138] [Table 2]

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

[0140] Test results The results of the test methods used on the compositions of each example are described in detail in Table 3.

[0141] [Table 3]

[0142] The results in Table 3 show that sealant compositions E1 to E3 of the present invention exhibit a low modulus of elasticity of <0.7 MPa with elongation in the range of 0.5 to 25%, and <0.35 MPa with elongation in the range of 0.5 to 100%, while simultaneously exhibiting only low to moderate surface tackiness. In the otherwise identical composition (R1) without the monoamine MA, surface tackiness is significantly increased. The same is true when using a different TDI-based polymer P without the monoamine MA (R5). When using an alcohol instead (R2), surface tackiness is low, but the modulus of elasticity is significantly increased, reducing suitability for use as an elastic sealant. Other reference examples using different polyisocyanates for polymer P (R3 and R4) exhibit modulus of elasticity and / or surface tackiness that are too high for their intended use as elastic sealants.

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.

Images