Curable polymer compositions containing isocyanates, aldimines and compounds with activated methylene groups

Abstract

The invention relates to a curable composition comprising at least one polymer containing isocyanate groups, at least one aldimine L with aldimine groups of the formula (I), and at least one compound V with activated methylene groups of the formula (II), where Y is a radical of the formula (A), R is a monovalent hydrocarbon radical having 1 to 10 carbon atoms and R1 is an alkyl radical having 1 to 6 carbon atoms, where, relative to the overall composition, the ratio of the number of aldimine groups of the formula (I) to the number of isocyanate groups is not more than 1 and the ratio of the number of activated methylene groups of the formula (II) to the number of aldimine groups of the formula (I) is at least 1. The composition is particularly suitable as an elastic adhesive or sealant. With readily available aldimines, even without exposure to moisture and without forming bubbles, the composition cures reliably to afford an elastic polymer; with aldimines derived from volatile aldehydes such as benzaldehyde, no odour is developed.

Description

[0001] Curable polymer compositions containing isocyanates, aldimines and compounds with activated methylene groups

[0002] Technical area

[0003] The invention relates to curable polymer compositions containing isocyanates, aldimines and compounds with activated methylene groups, as well as their use as elastic adhesives or sealants.

[0004] State of the art

[0005] Moisture-curing polymer compositions based on isocyanates and aldimines are known. They are used in particular as one-component moisture-curing elastic sealants, adhesives, or coatings, as described, for example, in US Pat. Nos. 7,625,993, 9,752,054, or 10,647,807. Upon contact with moisture, particularly in the form of atmospheric moisture, the hydrolyzing aldimines react with existing isocyanate groups to form urea bonds and release aldehydes. Special aldimines enable compositions with good storage stability that cure rapidly and without the formation of bubbles when exposed to atmospheric moisture and exhibit good mechanical properties, particularly high elasticity and extensibility.

[0006] However, these known compositions have several disadvantages. Either aldimines are used, which release highly volatile aldehydes. Upon curing, an undesirable odor and emissions occur. Or aldimines are used, which release low-volatility and largely odorless aldehydes that remain in the composition even after curing. However, such aldehydes can migrate from the composition, causing contamination and substrate damage. They typically have a strong plasticizing effect on the composition, which can be undesirable for applications where increased stiffness or a high modulus of elasticity is required.A further difficulty may be that curing occurs slowly or not at all inside the building due to insufficient moisture, whether due to dry climatic conditions or a lack of access to atmospheric moisture due to moisture-proof substrates or a thick-layer application, where moisture diffusion is hindered by the thickening cured polymer layer. This difficulty can be overcome by using a water-based booster component. This is mixed into an otherwise single-component composition, allowing curing to occur particularly quickly and independently of the prevailing ambient humidity.However, mixing a water-containing and thus hydrophilic booster component into a mostly pasty and hydrophobic polymer composition can lead to inhomogeneities and thus reduced strength due to incompatibility.

[0007] US 2015 / 0259465 describes compositions with a polyol and an isocyanate component, which additionally contain polyaldimines and special metal catalysts. Small amounts of metal catalysts with acetoacetate ligands can also be used. These compositions rely on water for curing, have only limited elongation, and the problems with odor and / or plasticizing and migration effects caused by the released aldehydes are not resolved.

[0008] WO 2022 / 219148 describes two-component anti-corrosive coatings containing a polyisocyanate, a polyol, and a special aldimine. These systems also rely on water for curing, have limited expansion, and do not address the problems of odor and / or plasticizing and migration effects caused by the released aldehydes.

[0009] US Pat. No. 5,288,804 describes curable polymer compositions containing polyacetoacetates and aldimines. These do not contain isocyanates and do not form elastic polymers, as is typical for polyurethanes.

[0010] US Pat. No. 5,714,563 describes one-component moisture-curing polymer compositions containing polyacetoacetates and polyisocyanates. These contain no aldimines, are mechanically inferior, and are prone to blistering.

[0011] WO 2017 / 044726 describes coatings, particularly anti-corrosive coatings, in which polyacetoacetates are cured with polyisocyanates. This does not produce elastic polymers, as is typical for polyurethanes. Description of the invention

[0012] The object of the invention is to provide a polymer composition which cures smoothly and without odor and is suitable as an elastic adhesive and / or sealant with high elasticity and strength.

[0013] This object is surprisingly achieved with the curable composition according to claim 1. The curable composition contains at least one polymer containing isocyanate groups, at least one aldimine L having aldimine groups of the formula (I) and at least one compound V having activated methylene groups of the formula (II). When the components are mixed, the composition cures without odor and without blistering to form a highly elastic product with high strength. This surprisingly also applies when aldimines derived from volatile aldehydes such as benzaldehyde are used. Particularly surprising is the fact that curing takes place even without the ingress of water and not from the outside in, but simultaneously across the entire cross-section of the material. It appears that the aldimine is not activated, i.e., becomes reactive towards isocyanate groups, by hydrolysis as is usual, but rather by reaction with the compound V.The curing reaction proceeds reliably without blistering or odor, as no aldehyde is released. This aldehyde remains permanently in the composition in derivatized form, presumably as an adduct with compound V or its derivatives, and shows no signs of migration. The mechanical properties of the cured composition largely correspond to those of a corresponding moisture-cured composition without compound V. The aldehyde derivatives therefore do not appear to have a plasticizing effect and thus do not weaken the composition.

[0014] The curable composition preferably contains a nitrogen-containing catalyst as an accelerator for the reaction of aldehyde groups with activated methylene groups of formula (I). It is particularly surprising that the composition cures without blistering even in the presence of such a catalyst, since nitrogen-containing catalysts such as triethylamine or DBU also accelerate the reaction of isocyanate groups with water and thus the release of CO2. The composition according to the invention cures independently of moisture, even in high layer thicknesses and between moisture-proof substrates, without emissions, without odor, and without blistering. Since no aldehydes are released, high isocyanate contents are also possible, and very high mechanical strengths and elastic moduli with high extensibility can be achieved.

[0015] In a preferred embodiment, the composition according to the invention is used as a two-component system with storage-stable components. Particular preference is given to an asymmetric two-component system with a first, quantitatively dominant component containing the isocyanate-containing polymer and the aldimine L, which is also curable with moisture alone; and a second, so-called "booster" component containing the compound V and optionally a catalyst. Due to its better compatibility, such a booster component is significantly easier to mix into the first component than is possible with a conventional water-based booster component, as is typically used for the accelerated curing of one-component moisture-curing compositions.

[0016] The curable composition is particularly suitable as an elastic adhesive or elastic sealant.

[0017] Further aspects of the invention are the subject of further independent claims. Particularly preferred embodiments of the invention are the subject of the dependent claims.

[0018] Ways to implement the invention

[0019] The invention relates to a curable composition comprising

[0020] - at least one polymer containing isocyanate groups,

[0021] - at least one aldimine L having aldimine groups of formula (I),

[0022] — N^Z 0) where Z is an organic radical with 1 to 25 C atoms, and

[0023] - at least one compound V having activated methylene groups of formula (II), where Y is a radical of the formula ■■ _ CN or --- C— R , ---C— OR 1 or O II

[0024] ---C— O—, R represents a monovalent hydrocarbon radical having 1 to 10 C atoms and R 1represents an alkyl radical having 1 to 6 C atoms, wherein, based on the total composition, the ratio of the number of aldimine groups of the formula (I) to the number of isocyanate groups is at most 1 and the ratio of the number of activated methylene groups of the formula (II) to the number of aldimine groups of the formula (I) is at least 1.

[0025] A dashed line in the formulas in this document represents the bond between a substituent and the corresponding molecular residue. Substance names beginning with "poly", such as polyisocyanate or polyol, refer to substances that formally contain two or more of the functional groups mentioned in their name per molecule.

[0026] The term “molecular weight” refers to the molar mass (in grams per mole) of a molecule or a moiety of a molecule. The term “average molecular weight” refers to the number average molecular weight (M n) a polydisperse mixture of oligomeric or polymeric molecules or molecular residues. It is determined by gel permeation chromatography (GPC) using polystyrene as a standard.

[0027] A composition is described as “storage-stable” if it can be stored at room temperature in a suitable container for a prolonged period, typically for at least 3 months up to 6 months or more, without its application or use properties being changed by storage to an extent relevant to its use.

[0028] The "NCO content" refers to the content of isocyanate groups in weight percent. "Room temperature" refers to a temperature of 23 °C.

[0029] All industry standards and norms mentioned in this document refer to the versions valid at the time of filing the initial application. Percentages by weight (wt%) refer to the mass fraction of a component of a composition or molecule relative to the entire composition or molecule, unless otherwise specified. The terms "mass" and "weight" are used synonymously in this document.

[0030] The isocyanate-containing polymer is preferably liquid at room temperature. It is preferably low-viscosity and in particular has a viscosity of 0.5 to 50 Pa s, preferably 1 to 30 Pa s, in particular 1 to 20 Pa s, determined at 20 °C using a cone-plate viscometer with a cone diameter of 10 mm, a cone angle of 1°, and a cone-plate distance of 0.05 mm at a shear rate of 10 s -1 .

[0031] The isocyanate-containing polymer preferably has an NCO content of 0.5 to 8% by weight, preferably 0.75 to 5% by weight, and in particular 1 to 3% by weight, based on the total polymer. Such a polymer enables high extensibility of the cured composition.

[0032] Preferably, the isocyanate group-containing polymer has an average isocyanate functionality of 1.7 to 4.0, in particular 1.8 to 3.0.

[0033] Preferably, the isocyanate group-containing polymer has an average molecular weight M n from 1,000 to 20,000 g / mol, 2,000 to 15,000 g / mol, in particular 4,000 to 10,000 g / mol.

[0034] Preferably, the isocyanate group-containing polymer is obtained from the reaction of at least one polyol with at least one diisocyanate.

[0035] The diisocyanate is preferably a commercially available aliphatic, cycloaliphatic or aromatic diisocyanate, such as in particular 1,5-pentane diisocyanate (PDI), 1,6-hexane diisocyanate (HDI), isophorone diisocyanate (IPDI), perhydro-4,4'-diphenylmethane diisocyanate (H12MDI), perhydro-2,4(6)-toluene diisocyanate (HeTDI), 2,2(4),4-trim ethyl-1,6-hexane diisocyanate (TMDI), cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, m-xylene diisocyanate, p-xylene diisocyanate, 2,4(6)-toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), 1,4-phenylene diisocyanate (PDI) or naphthalene-1,5-diisocyanate (NDI).

[0036] Particularly preferred is IPDI, HDI, H12MDI, MDI or TDI, in particular IPDI, MDI or TDI.

[0037] Preferred TDIs are mixtures containing 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, in particular mixtures of 80 parts by weight of 2,4-toluene diisocyanate and 20 parts by weight of 2,6-toluene diisocyanate.

[0038] Preferred MDIs are 4,4'-diphenylmethane diisocyanate, as well as commercially available mixtures containing 4,4'-diphenylmethane diisocyanate and portions of 2,4'- and / or 2,2'-diphenylmethane diisocyanate. 4,4'-diphenylmethane diisocyanate with a purity of at least 98% by weight is particularly preferred.

[0039] Suitable polyols are commercially available polyols or mixtures thereof, in particular

[0040] - polyether polyols, in particular polyoxyalkylene diols and / or polyoxyalkylene triols, wherein triols are preferably started on 1,1,1-trimethylolpropane or glycerol, as well as polyether polyols with polymer particles dispersed therein, in particular those with styrene-acrylonitrile particles (SAN) or polyurea or polyhydrazodicarbonamide particles (PHD),

[0041] - Polyester polyols, in particular from the polycondensation of hydroxycarboxylic acids or lactones or the polycondensation of aliphatic and / or aromatic polycarboxylic acids with di- or polyhydric alcohols,

[0042] - polycarbonate polyols,

[0043] - polyetherpolyesterpolyols,

[0044] - polyacrylate or polymethacrylate polyols,

[0045] - polyhydroxyfunctional fats or oils, for example natural fats and oils, in particular castor oil; or polyols obtained by chemical modification of natural fats and oils - so-called oleochemical polyols,

[0046] - Polyhydrocarbon polyols, in particular hydroxy-functional polyolefins, polyisobutylenes or polyisoprenes, furthermore hydroxy-functional ethylene-propylene copolymers, ethylene-butylene copolymers or ethylene-propylene-diene copolymers, as produced, for example, by Kraton Polymers, furthermore hydroxy-functional polymers of dienes, in particular of 1,3-butadiene, furthermore hydroxy-functional copolymers of dienes and vinyl monomers such as styrene, acrylonitrile, vinyl chloride, vinyl acetate, vinyl alcohol, isobutylene or isoprene, and hydrogenated hydroxy-functional polymers or copolymers of dienes.

[0047] Mixtures of polyols are also particularly suitable.

[0048] Polyols with an average OH functionality of 1.7 to 3 are preferred.

[0049] Preferred are polyether polyols, polyester polyols, polycarbonate polyols, or polyacrylate polyols. Particular preference is given to polyether polyols or polyester polyols, especially polyether polyols.

[0050] Preferred polyether polyols are those having repeating units selected from oxy-1,2-ethylene, oxy-1,2-propylene, oxy-1,3-propylene, oxy-1,4-butylene, oxy-1,2-butylene and oxyphenylethylene, with oxy-1,2-ethylene optionally additionally being present, in particular up to 25% by weight of oxy-1,2-ethylene units based on the polyether polyol.

[0051] Preferred are polyether polyols with a low unsaturation content (so-called "low monol" and "ultra low monol" polyols), in particular less than 0.02 mEq / g, preferably less than 0.01 mEq / g.

[0052] Particularly preferred are polyether polyols with oxy-1,2-propylene repeating units, optionally with up to 25% by weight, based on the total weight of the polyether polyol, of oxy-1,2-ethylene units at the chain ends (also called "ethylene oxide-terminated" or "EO-terminated" polyether polyols).

[0053] Particularly preferred are poly(oxy-1,2-propylene)diols or triols, which are optionally EO-terminated, having an OH number of 7 to 175 mg KOH / g, preferably 10 to 145 mg KOH / g, in particular 14 to 112 mg KOH / g, and / or having an average molecular weight M n from 1,000 to 12,000 g / mol, preferably 2,000 to 8,000 g / mol.

[0054] Also preferred are polyether polyols with oxy-1,4-butylene repeating units, in particular poly(oxy-1,4-butylene)diols with an OH number of 50 to 175 mg KOH / g and / or an average molecular weight M n from 650 to 2,000 g / mol.

[0055] The isocyanate-containing polymer preferably contains polyether chains with repeating units selected from the list consisting of oxy-1,2-propylene, oxy-1,3-propylene, oxy-1,4-butylene, oxy-1,2-butylene, and oxyphenylethylene. Oxy-1,2-ethylene units may also be present, in particular up to 25% by weight of oxy-1,2-ethylene units based on the total weight of the polyether chains, with the oxy-1,2-ethylene units preferably being located at the chain ends of the polyether chains.

[0056] Preferred polyether chains are poly(oxy-1,2-propylene) chains, which may be EO-terminated.

[0057] The curable composition particularly preferably contains a polymer containing isocyanate groups and having polyether chains and an NCO content, based on the total polymer, of 1 to 3% by weight.

[0058] The isocyanate group-containing polymer is preferably prepared by reacting at least one monomeric diisocyanate with at least one polyol in a molar ratio NCO / OH of at least 1.3, preferably at least 1.5, in particular at least 1.8, preferably with exclusion of moisture at 20 to 160 °C, in particular 40 to 140 °C, optionally in the presence of a suitable catalyst.

[0059] A particularly preferred isocyanate-containing polymer has a monomeric diisocyanate content of less than 0.5% by weight, preferably less than 0.3% by weight, and especially less than 0.2% by weight, based on the total polymer. This enables curable compositions with a monomeric diisocyanate content of less than 0.1% by weight, based on the total composition. Such compositions are particularly safe to use and do not require labeling.

[0060] An isocyanate group-containing polymer with a particularly low content of monomeric diisocyanates is preferably prepared with a molar NCO / OH ratio of 3 / 1 to 10 / 1, preferably 3 / 1 to 8 / 1, and subsequent removal of unreacted monomeric diisocyanate by distillation, preferably by thin film distillation or short path distillation, preferably under vacuum.

[0061] The curable composition may contain one or more isocyanate group-containing polymers.

[0062] The curable composition further contains at least one aldimine L having aldimine groups of the formula (I).

[0063] — N^Z 0)

[0064] The aldimine L preferably has two to three aldimine groups of formula (I). The aldimine L preferably has an aldimine equivalent weight of 110 to 500 g / eq. In particular, the aldimine L has two to three aldimine groups of formula (I) and an aldimine equivalent weight of 110 to 500 g / eq.

[0065] Z preferably represents an aliphatic hydrocarbon radical having 3 to 11 C atoms bonded via a primary or secondary C atom or an aromatic or heteroaromatic five- or six-membered ring which is optionally substituted and / or fused and comprises a total of 4 to 25 C atoms, in particular an aromatic or heteroaromatic five- or six-membered ring which is optionally substituted and / or fused and comprises a total of 4 to 25 C atoms.

[0066] Insbesondere ist Z ausgewählt aus der Liste bestehend aus 1 -Propyl, 2-Propyl, 1- Butyl, 1 -Pentyl, 1 -Heptyl, 3-Heptyl, 1 -Undecyl, Phenyl, 2-M ethyl phenyl, 3-Methyl- phenyl, 4-Methylphenyl, 4-Ethylphenyl, 4-lsopropylphenyl, 4-tert-Butylphenyl, 4- C -14-Alkylphenyl, 2,5-Dimethylphenyl, 2-Methoxyphenyl, 3-M ethoxy phenyl, 4-Me- thoxyphenyl, 2-Ethoxyphenyl, 3-Ethoxyphenyl, 4-Ethoxyphenyl, 4-Propoxyphenyl, 4-lsopropoxyphenyl, 4-Butoxyphenyl, 4-Pentoxyphenyl, 4-Decyloxyphenyl, 4-Do- decyloxyphenyl, 2,3-Dimethoxyphenyl, 2,4-Dimethoxyphenyl, 2,5-Dimethoxyphe- nyl, 3,4-Dimethoxyphenyl, 3,5-Dimethoxyphenyl, 2,4,6-Trimethylphenyl, 2,4,5-Tri- methoxyphenyl, 2,4,6-Trimethoxyphenyl, 3,4,5-Trimethoxyphenyl, 4-Methoxycar- bonylphenyl, 4-Ethoxycarbonylphenyl, 3-Nitrophenyl, 1 -Naphthyl, 2-Naphthyl, 2- Furyl, 5-Methyl-2-furyl, Thiophen, Pyridin, Pyrrol und Chinolin.

[0067] Of these, preference is given to phenyl, the isomeric methylphenyls, 4-Cw-14-alkylphenyl, 4-methoxyphenyl, 3,4-dimethoxyphenyl, 4-methoxycarbonylphenyl, 4-ethoxycarbonylphenyl, 3-nitrophenyl or 2-furyl.

[0068] Most preferably, Z is phenyl. Such aldimines are derived from benzaldehyde. They are particularly easily accessible and enable particularly fast and reliable curing.

[0069] Furthermore, Z preferably represents a 4-C10-14-alkylphenyl radical. Such aldimines are derived from a 4-C10-14-alkylbenzaldehyde mixture. They are odorless and thus enable asymmetric two-component compositions whose first component cures odorlessly upon exposure to moisture, even without the addition of the booster component containing compound V.

[0070] Aldimines derived from volatile aldehydes such as benzaldehyde produce a strong, unpleasant odor when used as latent curing agents in polyurethane compositions. This severely limits the applicability of such compositions, as the odor is present during application and persists long afterward. Surprisingly, the composition according to the invention does not produce any aldehyde odor, which is particularly advantageous because the composition can be used without restriction even in odor-sensitive applications, for example, in building interiors or in automobiles.

[0071] Preferred as aldimine L is an aldimine of formula (III), (Hl) where n is 2 or 3 and G is an n-valent organic radical with 2 to 25 C-

[0072] atoms and Z has the meanings already mentioned.

[0073] Preferably, G represents a divalent hydrocarbon radical having 2 to 15 C atoms, in particular 5 to 15 C atoms, or a di- or trivalent polyoxyalkylene radical having an average molecular weight M n from 160 to 500 g / mol.

[0074] The aldimine of formula (III) is typically derived from a primary

[0075] Amine and an aldehyde of the formula aus which it is obtainable by a condensation reaction.

[0076] Preferred primary amines are commercially available aliphatic or cycloaliphatic primary amines, in particular selected from the list consisting of 1,2-ethanediamine, 1,2-propanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 2,2-dimethyl-1,3-propanediamine, 1,3-pentanediamine (DAMP), 1,6-hexanediamine, 1,5-diamino-2-methylpentane (MPMD), 1,7-heptanediamine, 1,8-octanediamine, 2,5-dimethyl-1,6-hexanediamine, 1,9-nonanediamine, 2,2(4),4-trimethyl-1,6-hexanediamine (TMD), 1 ,10-decanediamine, 1,11-undecanediamine, 2-butyl-2-ethyl-1,5-pentanediamine (C11-neodiamine), 1,12-dodecanediamine, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1 ,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)benzene (MXDA), isophoronediamine (IPDA), 2(4)-methyl-1,3-diaminocyclohexane, bis(4-aminocyclohexyl)methane, 2,5(6)-Bis(aminomethyl)bicyclo[2.2.1]heptane (NBDA), 3(4),8(9)-Bis(ami- nomethyl)tricyclo[5.2.1 .0 2 ' 6]decane (TCD-diamine), 4,9-dioxadodecane-1 , 12-diamine, 4,7,10-trioxatridecane-1 ,13-diamine, polyoxypropylenediamines with an average molecular weight M n from 200 to 500 g / mol and polyoxypropylenetriamines with an average molecular weight M n from 300 to 500 g / mol. Preferred polyoxypropylene di- or triamines are Jeffamine® D-230, Jeffamine® D-400, or Jeffamine® T-403 (all from Huntsman), as well as corresponding grades from BASF or Nitroil.

[0077] As an aldehyde of the formula bevorzugt sind Butanal, Isobutyraldehyd, Valer- aldehyd, Hexanal, Octanal, 2-Ethylhexanal, Dodecanal, Benzaldehyd, 2-Tolual- dehyd, 3-Tolualdehyd, 4-Tolualdehyd, 4-Ethylbenzaldehyd, 4-lsopropyl-benzalde- hyd, 4-tert-Butylbenzaldehyd, 4-Cio-i4-Alkylbenzaldehyd, 2,5-Dimethylbenzalde- hyd, 2-Methoxybenzaldehyd, 3-Methoxybenzaldehyd, 4-Methoxybenzaldehyd, 2- Ethoxybenzaldehyd, 3-Ethoxybenzaldehyd, 4-Ethoxybenzaldehyd, 4-Propoxy- benzaldehyd, 4-lsopropoxybenzaldehyd, 4-Butoxybenzaldehyd, 4-Pentoxybenz- aldehyd, 4-Decyloxybenzaldehyd, 4-Dodecyloxybenzaldehyd, 2,3-Dimethoxy- benzaldehyd, 2,4-Dimethoxybenzaldehyd, 2,5-Dimethoxybenzaldehyd, 3,4-Dime- thoxybenzaldehyd, 3,5-Dimethoxybenzaldehyd, 2,4,6-T rimethylbenzaldehyd, 2,4,5-T rimethoxybenzaldehyd, 2,4,6-T rimethoxybenzaldehyd, 3,4,5-T rimethoxy- benzaldehyd, 4-Formylbenzoesäuremethylester, 4-Formylbenzoesäureethylester,

[0078] 3-Nitrobenzaldehyd, 1-Naphthaldehyd, 2-Naphthaldehyd, Furfural oder 5-Methyl- furfural.

[0079] Of these, aromatic or heteroaromatic aldehydes are preferred.

[0080] Particularly preferred are benzaldehyde, the isomeric tolualdehydes, a 4-C -i4-alkylbenzaldehyde mixture, 4-methoxybenzaldehyde, 3,4-dimethoxybenzaldehyde,

[0081] 4-Formylbenzoic acid methyl ester, 4-Formylbenzoic acid ethyl ester, 3-nitrobenzaldehyde or furfural.

[0082] Benzaldehyde is most preferred.

[0083] Aldimines of formula (III) derived from aromatic aldehydes, such as benzaldehyde in particular, sometimes exhibit a marked tendency to crystallize. Preferred aldimines of formula (III) are those which, as such or as mixtures with one another, are permanently liquid at room temperature without the addition of solvents or diluents. Such aldimines enable compositions with low emissions.

[0084] Particularly preferred aldimines of the formula (III) are selected from the list consisting of N,N'-dibenzylidene-1,5-pentanediamine, N,N'-dibenzylidene-1,6-hexanediamine, N,N'-dibenzylidene-2-methyl-1,5-pentanediamine, N,N'-dibenzylidene-2,2(4),4-trimethyl-1,6-hexanediamine, N,N'-dibenzylidene-1,3-bis(aminomethyl)cyclohexane, N,N'-dibenzylidene-1,3-bis(aminomethyl)benzene, N,N'-dibenzylideneisophoronediamine, N,N'-dibenzylidene-4,4'-methylene-bis(cyclohexylamine), N,N'-dibenzylidene-polyoxypropylenediamines with medium molecular weight M n from 350 to 750 g / mol and N,N',N"-tribenzylidenepolyoxypropylenetriamines with medium molecular weight M n from 450 to 700 g / mol, as well as the analogous aldimines derived from tolualdehyde, a 4-Cio-i4-alkylbenzaldehyde mixture, 4-methoxybenzaldehyde, 4-formylbenzoic acid methyl ester, 4-formylbenzoic acid ethyl ester, 3-nitrobenzaldehyde and furfural instead of benzaldehyde.

[0085] Of these, preferred are N,N'-dibenzylidene-1,5-pentanediamine, N,N'-dibenzylidene-2-methyl-1,5-pentanediamine, N,N'-dibenzylidene-1,6-hexanediamine, N,N'-dibenzylidene-2,2(4),4-trimethyl-1,6-hexanediamine, N,N'-dibenzylidenepolyoxypropylenediamines with medium molecular weight M n from 350 to 700 g / mol or N,N'-bis(4-C-14-alkylbenzylidene)isophoronediamine.

[0086] The curable composition further contains at least one compound V having activated methylene groups of the formula (II), oo

[0087] II II where Y is a radical of the formula "" _ CN , ---C— R , ---C— OR 1 or Preferably, the methylene groups of formula (II) are covalently bonded in compound V. In particular, the methylene groups of formula (II) are not present as a ligand on a metal atom.

[0088] R is preferably an alkyl radical having 1 to 6 carbon atoms or phenyl, particularly preferably methyl, ethyl, propyl, isopropyl, butyl, or phenyl. Most preferably, R is methyl.

[0089] Preferably R 1 for methyl, ethyl or tert-butyl, particularly preferably for ethyl or tert-butyl, in particular for ethyl.

[0090] The compound V preferably contains one to six activated methylene groups of the formula (II), particularly preferably two to four, in particular two to three, activated methylene groups of the formula (II).

[0091] Preferably, the compound V has a molecular weight, or in the case of an oligomeric or polymeric compound V average molecular weight M n , from 100 to 10,000 g / mol, preferably 196 to 5,000 g / mol, particularly preferably 240 to 2,500 g / mol, in particular 240 to 1,500 g / mol.

[0092] Preferably, compound V is liquid at room temperature. In particular, it has a viscosity at 20 °C of 0.01 to 50 Pa s, more preferably 0.01 to 25 Pa s, particularly preferably 0.01 to 10 Pa s, in particular 0.02 to 5 Pa s, measured using a cone-plate viscometer with a cone diameter of 10 mm, a cone angle of 1°, a cone tip-to-plate distance of 0.05 mm, and a shear rate of 10 s -1 , for viscosities of less than 0.5 Pa s with a cone diameter of 50 mm. Such a connection enables compositions that are easy to process at ambient temperature without the addition of solvents or thinners.

[0093] Preferably, the compound V has an equivalent weight, or in the case of an oligomeric or polymeric compound V, an average equivalent weight, of 100 to 2,100 g / eq, preferably 114 to 600 g / eq, in particular 114 to 400 g / eq, with respect to the activated methylene groups of the formula (II). Preferably, the compound V has a functionality, or in the case of an oligomeric or polymeric compound V, an average functionality, of 1 to 4, preferably 1.5 to 3.5, in particular 1.8 to 3, with respect to the activated methylene groups of the formula (II).

[0094] In particular, the compound V has, with respect to the activated methylene groups of the formula (II), an equivalent weight, or in the case of an oligomeric or polymeric compound V average equivalent weight, of 100 to 2,100 g / eq, preferably 114 to 600 g / eq, in particular 114 to 400 g, and a functionality, or in the case of an oligomeric or polymeric compound V average functionality, of 1 to 4, preferably 1.5 to 3.5, in particular 1.8 to 3.

[0095] The ratio of the number of activated methylene groups of formula (II) to the number of aldimine groups of formula (I) is preferably in the range of 1 to 4, preferably 1.2 to 3, particularly preferably 1.5 to 2.5. This enables the activation of the aldimine groups without the ingress of moisture, while the aldehyde underlying the aldimine is not released. As a result, no unpleasant aldehyde odor develops when the curable composition is used.

[0096] Preferably, the compound V is obtained from the transesterification of at least one hydroxyl-containing compound with at least one compound of the formula (IV), where Y 1 for a remainder of the formula ■ __ CN , ---C— R or ~-~C— OR 1 stands and R and R 1 have the meanings already described.

[0097] The transesterification is preferably carried out at a temperature of 50 to 150 °C with distillative removal of the released alcohol R 1 OH and optionally fragmentation products thereof, optionally under vacuum and optionally in the presence of catalysts.

[0098] It is also possible to prepare a compound V containing cyanoacetate groups by esterification of cyanoacetic acid with at least one compound containing hydroxyl groups.

[0099] It is also possible to prepare a compound V with acetoacetate groups by reacting the hydroxyl group-containing compound on which compound V is based with diketene or the adduct of diketene with acetone (= 2,2,6-trimethyl-4H-1,3-dioxin-4-one), whereby in the case of the acetone-diketene adduct, acetone is released.

[0100] It is also possible to produce a compound V with malonate groups by esterification of malonic acid with at least one hydroxyl group-containing compound.

[0101] Particularly suitable compounds of formula (IV) are methyl cyanoacetate, ethyl cyanoacetate, tert-butyl cyanoacetate, methyl acetoacetate, ethyl acetoacetate, tert-butyl acetoacetate, ethyl 3-oxohexanoate, ethyl benzoyl acetate, dimethyl malonate, diethyl malonate, diisopropyl malonate or di-(tert-butyl) malonate.

[0102] Preferred are ethyl cyanoacetate or tert-butyl cyanoacetate, ethyl acetoacetate or tert-butyl acetoacetate, and malonic acid diethyl ester.

[0103] Preferred hydroxyl-containing compounds are commercially available OH-functional compounds or polymers, such as in particular 1,2-ethanediol, diethylene glycol, triethylene glycol, 1,2-propanediol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, 1,2-pentanediol, neopentyl glycol, 2-methyl-1,4-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 2-ethyl-1,3-hexanediol, 1,10-decanediol, 1,12-dodecanediol, Polytetrahydrofurandiols, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, glycerol, pentaerythritol, ethoxylated or especially propoxylated glycerol, ethoxylated or especially propoxylated 1,1,1-trimethylolpropane, poly(oxy-1,2-propylene)diols with an average molecular weight of 400 to 4,000 g / mol, EO-terminated poly(oxy-1,2-propylene)diols with an average molecular weight of 1,000 to 4,000 g / mol,Poly(oxy-1,2-propylene)triols with an average molecular weight of 400 to 6,000 g / mol, EO-terminated poly(oxy-1,2-propylene)triols with an average molecular weight of 3,000 to 6,000 g / mol, di- or trimer fatty acid-based polyester polyols with an average molecular weight of 1,000 to 3,000 g / mol, castor oil, derivatives of castor oil or hydroxylated vegetable oils.

[0104] O II

[0105] Preferably, Y represents a radical of the formula --- CN or ---C— R . In particular, the activated methylene groups of formula (II) represent cyanoacetate groups or acetoacetate groups.

[0106] In a preferred embodiment of the invention, Y is a radical of the formula ■ __ CN and the activated methylene groups of formula (II) are therefore cyanoacetate groups.

[0107] Preferably, a compound V having cyanoacetate groups is selected from the list consisting of ethyl cyanoacetate, 2-methyl-1,3-propanediol dicyanoacetate, neopentylglycol dicyanoacetate, 1,6-hexanediol dicyanoacetate, 3-methyl-1,5-pentanediol dicyanoacetate, 2-ethyl-1,3-hexanediol dicyanoacetate, the tricyanoacetate of ethoxylated and / or propoxylated 1,1,1-trimethylolpropane, the tricyanoacetate of ethoxylated and / or propoxylated glycerol, poly(oxy-1,2-propylene)diol bis(cyanoacetate), ethylene oxide units-containing poly(oxy-1,2-propylene)diol bis(cyanoacetate), dimer fatty acid-based polyesterdiol bis(cyanoacetate) and trimer fatty acid-based Polyestertriol tris(cyanoacetate). In a further particularly preferred embodiment of the invention, Y

[0108] O II in the formula (II) represents a radical of the formula ---C— R , where R preferably represents methyl and the activated methylene groups of the formula (II) are thus acetoacetate groups.

[0109] Preferably, a compound V having acetoacetate groups is selected from the list consisting of ethyl acetoacetate, 1,2-propanediol diacetoacetate, dipropylene glycol diacetoacetate, tripropylene glycol diacetoacetate, 1,3-propanediol diacetoacetate, 1,4-butanediol diacetoacetate, 2-methyl-1,3-propanediol diacetoacetate, 1,5-pentanediol diacetoacetate, neopentyl glycol diacetoacetate, 1,6-hexanediol diacetoacetate, 3-methyl-1,5-pentanediol diacetoacetate, 2-ethyl-1,3-hexanediol diacetoacetate, glycerol diacetoacetate, glycerol triacetoacetate, 1,1,1-trimethylolethane diacetoacetate, 1,1,1-trimethylolethane triacetoacetate, 1,1,1-trimethylolpropane diacetoacetate, 1,1,1-trimethylolpropane triacetoacetate, the triacetoacetate of propoxylated and / or ethoxylated 1,1,1-trimethylolpropane, the triacetoacetate of propoxylated and / or ethoxylated glycerol, poly(oxy-1,2-propylene)diol bis(acetoacetate), poly(oxy-1,2-propylene)diol bis(acetoacetate) containing ethylene oxide units,Castor oil bis(acetoacetate), castor oil tris(acetoacetate), dimer fatty acid-based polyesterdiol bis(acetoacetate) and trimer fatty acid-based polyestertriol tris(acetoacetate).

[0110] Of these, 1,2-propanediol diacetoacetate, dipropylene glycol diacetoacetate, 2-methyl-1,3-propanediol diacetoacetate, neopentyl glycol diacetoacetate, 1,6-hexanediol diacetoacetate, 3-methyl-1,5-pentanediol diacetoacetate, 2-ethyl-1,3-hexanediol diacetoacetate, glycerol diacetoacetate, glycerol triacetoacetate, 1,1,1-trimethylolpropane diacetoacetate, 1,1,1-trimethylolpropane triacetoacetate, a triacetoacetate of propoxylated 1,1,1-trimethylolpropane with medium molecular weight M n from 500 to 1,000 g / mol or a poly(oxy-1,2-propylene)diol bis(acetoacetate) with an average molecular weight Mn of 550 to 5,000 g / mol.

[0111] In a further embodiment, Y is a radical of the formula ~-~C— OR 1O II or ---C— O--- and the activated methylene groups of formula (II) are thus malonate groups.

[0112] Preferably, a compound V having malonate groups is selected from the list consisting of diethyl malonate, diisopropyl malonate, 1,2-ethanediol bis(ethylmalonate), 1,2-propanediol bis(ethylmalonate), 1,3-propanediol bis(ethylmalonate), 1,4-butanediol bis(ethylmalonate), 2-methyl-1,3-propanediol bis(ethylmalonate), neopentyl glycol bis(ethylmalonate), 1,6-hexanediol bis(ethylmalonate), 3-methyl-1,5-pentanediol bis(ethylmalonate), 2-ethyl-1,3-hexanediol bis(ethylmalonate), 1,4-cyclohexanedimethanol bis(ethylmalonate), diethylene glycol bis(ethylmalonate), di- propylene glycol bis(ethylmalonate), glycerol tris(ethylmalonate), 1,1,1-trimethylolpropane tris(ethylmalonate), castor oil tris(ethylmalonate), poly(oxy-1,2-propylene)diol bis(ethylmalonate) with medium molecular weight M nfrom 500 to 2,000 g / mol, propoxylated 1,1,1-trimethylolpropane with three ethyl malonate end groups and an average molecular weight M n from 650 to 2,500 g / mol, corresponding oligomeric compounds of these reaction products, as well as polyesterdiols containing malonate groups from the reaction of diols such as 1,6-hexanediol and 1,4-cyclohexanedimethanol with malonic acid and diethyl malonate and optionally adipic acid or diethyl adipic acid.

[0113] Suitable compounds containing malonate groups are also commercially available, in particular as Acure® 510-200 (from Allnex).

[0114] The curable composition preferably contains at least one catalyst for the reaction between the methylene groups of formula (II) and the aldimine groups of formula (I), in particular a nitrogen-containing catalyst.

[0115] Preferred nitrogen-containing catalysts are compounds containing at least one tertiary amino group, amidine group, or guanidine group. The nitrogen-containing catalyst is preferably free of primary and secondary amino groups, as well as hydroxyl groups.

[0116] Suitable catalysts for the reaction between the methylene groups of formula (II) and the aldimine groups of formula (I) are in particular triethylamine, tripropylamine, tributylamine, tri(2-ethylhexyl)amine, N,N-dimethylisopropylamine, N-ethyldiisopropylamine, N,N-dimethylcyclohexylamine, N,N-dimethyl-Ci2-i4-alkylamine, N,N-dimethylbenzylamine, α-methylbenzyldimethylamine, tetramethyl-1,2-ethanediamine, tetramethyl-1,6-hexanediamine, pentamethyldiethylenetriamine, tris(3-dimethylaminopropyl)amine, N-methylpiperidine, N,N'-dimethylpiperazine, N-methyl-N'-dimethylaminoethylpiperazine, bis-(dimethylaminoethyl)piperazine, 1,4-diazabicyclo- [2.2.2]octane (DABCO), 1,3,5-trimethylhexahydrotriazine, 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine, 1,3-bis(dimethylaminopropyl)urea, bis(2-dimethylaminoethyl)ether, tris(2-(2-methoxyethoxy)ethyl)amine, N-methylmorpholine, N- Ethylmorpholine, 2,2'-dimorpholinodiethyl ether (DMDEE), N-methylimidazole, N-vinylimidazole, 1,2-dimethylimidazole, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), tetramethylguanidine (TMG) 1-Hexyl-2,3-diisopropylguanidine or 1, 1 '-( a,®-Polyoxypropylene)bis(2,3-diisopropylguanidine) with medium molecular weight M. n from 250 to 500 g / mol.

[0117] O

[0118] II

[0119] In the case of methylene groups of formula (I) where Y is ---C— R, OO

[0120] II II

[0121] ---C— OR 1 or ---C— O—, a catalyst is particularly preferred.

[0122] In the curable composition, the ratio of the number of aldimine groups to the number of isocyanate groups is not more than 1.

[0123] A preferred ratio of the number of aldimine groups to the number of isocyanate groups is 0.4 to 1, preferably 0.5 to 0.95, especially 0.6 to 0.9. Such a composition exhibits a low tendency to bubble formation during curing, and the cured composition has high strength with high extensibility. The curable composition may additionally contain other components, in particular:

[0124] - Oligomeric diisocyanates, in particular mixtures of MDI and MDI homologues (polymeric MDI or PMDI) which are liquid at room temperature, HDI biurets such as Desmodur® N 100 or N 3200 (from Covestro), Tolonate® HDB or HDB-LV (from Vencorex) or Duranate® 24A-100 (from Asahi Kasei), HDI isocyanurates such as Desmodur® N 3300, N 3600 or N 3790 BA (all from Covestro), Tolonate® HDT, HDT-LV or HDT-LV2 (from Vencorex), Duranate® TPA-100 or THA-100 (from Asahi Kasei) or Coronate® HX (from Nippon Polyurethane), HDI uretdiones such as Desmodur® N 3400 (from Covestro), HDI iminooxadiazinediones such as Desmodur® XP 2410 (from Covestro), HDI allophanates such as Desmodur® VP LS 2102 (from Covestro), IPDI isocyanurates such as in solution as Desmodur® Z 4470 (from Covestro) or in solid form as Vestanat® T1890 / 100 (from Evonik), TDI oligomers such as Desmodur® IL (from Covestro), or mixed isocyanurates based on TDI / HDI such as Desmodur® HL (from Covestro);

[0125] - crosslinking agents, in particular oxazolidines, ketimines or other aldimines;

[0126] - Fillers, in particular ground or precipitated calcium carbonates, which may be coated with fatty acids, in particular stearates, barytes (heavy spars), quartz flours, quartz sands, dolomites, wollastonites, calcined kaolins, layered silicates such as mica or talc, zeolites, aluminum hydroxides, magnesium hydroxides, silicas including highly dispersed silicas from pyrolysis processes, industrially produced carbon blacks, graphite, ground fillers from agricultural sources such as olive kernel flour or nutshell flour, metal powders, for example of aluminum, copper, iron, silver or steel, PVC powder or hollow spheres;

[0127] - pigments, in particular titanium dioxide, chromium oxide, iron oxides or organic pigments;

[0128] - dyes;

[0129] - fibres, in particular glass fibres, carbon fibres, metal fibres, ceramic fibres, hemp fibres, cellulose fibres or plastic fibres such as polyamide fibres or polyethylene fibres;

[0130] - Nanofillers or nanofibers such as graphene or carbon nanotubes; - Plasticizers, in particular phthalates, in particular diisononyl phthalate (DINP), diisodecyl phthalate (DIDP) or di(2-propylheptyl)phthalate (DPHP), hydrogenated phthalates, in particular diisononyl 1,2-cyclohexanedicarboxylate (DINCH), terephthalates, in particular bis(2-ethylhexyl)terephthalate or diisononyl terephthalate (DINT), hydrogenated terephthalates, in particular bis(2-ethylhexyl)-1,4-cyclohexanedicarboxylate or diisononyl 1,4-cyclohexanedicarboxylate, isophthalates, trimellitates, adipates, in particular dioctyl adipate (DOA), azelates, sebacates, citrates, benzoates, glycol ethers, glycol esters, plasticizers with polyether structure, in particular poly(oxy-1,2-propylene) monols, diols or triols with blocked hydroxyl groups, in particular in in the form of acetyl groups, organic sulfonates or phosphates, in particular diphenyl cresyl phosphate (DPK), polybutenes,Polyisobutenes or plasticizers derived from natural fats or oils, in particular epoxidized soy or linseed oil or rapeseed oil methyl ester, with phthalates, hydrogenated phthalates, adipates or plasticizers with a polyether structure being preferred;

[0131] - solvents;

[0132] - Modifiers such as hydrocarbon resins, natural or synthetic waxes or bitumen;

[0133] - Rheology modifiers, in particular urea compounds, layered silicates such as bentonites, derivatives of castor oil, hydrogenated castor oil, polyamides, polyurethanes, fumed silicas or hydrophobically modified polyoxyethylenes;

[0134] - drying agents, in particular molecular sieves, calcium oxide, highly reactive isocyanates such as p-tosyl isocyanate, mono-oxazolidines such as Incozol® 2 (from Incorez) or orthoesters;

[0135] - adhesion promoters, in particular titanates or organoalkoxysilanes such as in particular epoxysilanes, in particular 3-glycidoxypropyltrimethoxysilane or 3-glycidoxypropyltriethoxysilane, aminosilanes, iminosilanes, mercaptosilanes, vinylsilanes, (meth)acrylosilanes, carbamatosilanes, alkylsilanes, S-(alkylcarbonyl)mercaptosilanes or oligomeric forms of these silanes;

[0136] - further catalysts, in particular organotin(IV) compounds, in particular dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dibutyltin diacetylacetonate, dimethyltin dilaurate, dioctyltin diacetate, dioctyltin dilaurate or dioctyltin diacetylacetonate, or complex compounds of bismuth(III) or zirconium(IV), in particular with ligands selected from alkoxides, carboxylates, 1,3-diketonates, oxinate, 1,3-ketoesterates and 1,3-ketoamidates, and organic acids which accelerate the hydrolysis of aldimines, in particular carboxylic acids or sulfonic acids, in particular an aromatic carboxylic acid;

[0137] - non-reactive thermoplastic polymers, in particular homo- or copolymers of unsaturated monomers, in particular from the group comprising ethylene, propylene, butylene, isobutylene, isoprene, styrene, vinyl acetate and alkyl (meth)acrylates, in particular polyethylenes (PE), polypropylenes (PP), polyisobutylenes, ethylene-vinyl acetate copolymers (EVA) and atactic poly-α-olefins (APAO);

[0138] - flame-retardant substances, in particular the fillers already mentioned, aluminium hydroxide or magnesium hydroxide, organic phosphoric acid esters, ammonium polyphosphates, melamine or derivatives thereof, boron compounds or antimony compounds;

[0139] - Additives, in particular wetting agents, flow control agents, defoamers, deaerators, stabilizers against oxidation, heat, light or UV radiation or biocides; as well as other substances commonly used in curable compositions.

[0140] It may be useful to dry certain substances chemically or physically before mixing them into the composition.

[0141] The curable composition preferably contains at least one further component selected from fillers, pigments, plasticizers, and adhesion promoters. The curable composition preferably contains several such components.

[0142] The curable composition preferably contains less than 10% by weight, particularly preferably less than 5% by weight, in particular less than 1% by weight, of volatile organic compounds (VOCs) with a boiling point at atmospheric pressure of less than 250 °C, based on the total composition. Such a composition causes particularly low emissions. A preferred curable composition contains, based on the total composition

[0143] - 5 to 90% by weight, preferably 10 to 70% by weight, of polymers containing isocyanate groups,

[0144] - 0 to 80% by weight, preferably 20 to 70% by weight, of the sum of fillers, pigments and thickeners,

[0145] - 0 to 60% by weight, in particular 10 to 50% by weight, of plasticizer, as well as at least one aldimine L and at least one compound V, as described above, and optionally further components.

[0146] The curable composition is preferably formulated as a multi-component system, in particular as a two-component system.

[0147] The curable composition preferably comprises a component K1 and a component K2, each of which is individually stable and stored in separate containers, with isocyanate-containing polymers and aldimines L preferably being a component of component K1, and compounds V and optionally a catalyst for the reaction between the methylene groups of formula (II) and the aldimine groups of formula (I) preferably being a component of component K2. To use the composition, the two components K1 and K2 are mixed together shortly before or during application, which initiates curing.

[0148] Other ingredients of the composition may be present as components K1 and / or K2. Substances reactive with isocyanate groups are preferably part of component K2.

[0149] Particularly preferred is an asymmetric two-component system with a quantitatively dominant component K1 containing the isocyanate-containing polymer and the aldimine L, which can also be cured with moisture alone; and a second, so-called "booster" component containing the compound V and optionally a catalyst. In a particularly preferred embodiment, component K1 thus contains the isocyanate-containing polymer, the aldimine L and additionally at least one acid.

[0150] A particularly suitable acid is an organic acid, in particular a carboxylic acid such as 2-ethylhexanoic acid, lauric acid, stearic acid, isostearic acid, oleic acid, neodecanoic acid, benzoic acid, salicylic acid or 2-nitrobenzoic acid, an organic carboxylic acid anhydride, an organic sulfonic acid such as methanesulfonic acid, p-toluenesulfonic acid or 4-dodecylbenzenesulfonic acid, or a sulfonic acid ester, preferably an aromatic carboxylic acid such as benzoic acid, 2-nitrobenzoic acid or salicylic acid.

[0151] Such a component K1 can also cure solely by the ingress of moisture through reaction of the hydrolyzing aldimine groups with isocyanate groups and reaction of further isocyanate groups with moisture, whereby the acid accelerates the hydrolysis of the aldimine groups.

[0152] Component K2 can be used as needed to enable the curing of component K1 without moisture-induced hydrolysis and to prevent the release of the aldehyde from the aldimine L. Such a component K2 can also be referred to as a "booster" component.

[0153] In case the curable composition contains an acid and a nitrogen-containing catalyst, the nitrogen-containing catalyst is preferably dosed such that the composition is not acidic after mixing the ingredients or components, i.e. the acid is completely neutralized by the nitrogen-containing catalyst.

[0154] Component K2 may contain a small amount of water, in particular 0.05 to 5% by weight, preferably 0.1 to 2% by weight, of water based on the total composition.

[0155] The consistency of the components is preferably such that they can be easily mixed together under ambient conditions using simple methods. Liquid or pasty components are particularly suitable for this purpose. The components preferably have a similar viscosity and / or rheology. Such components are particularly easy to mix with each other.

[0156] Components K1 and K2 of the curable composition are manufactured separately. The ingredients of each component are mixed together to form a macroscopically homogeneous liquid or paste. Components K1 and K2 are each stored in separate containers. Suitable containers include drums, containers, hobbocks, buckets, canisters, cans, bags, tubular bags, cartridges, or tubes.

[0157] To apply the curable composition, all ingredients, particularly components K1 and K2, are mixed together shortly before or during application, with the mixing ratio being selected such that the ratio of the number of aldimine groups to the number of isocyanate groups and the ratio of the number of activated methylene groups of formula (II) to the number of aldimine groups are within the range according to the invention. In parts by weight, the mixing ratio is preferably 50:1 to 1:1, in particular 25:1 to 2:1.

[0158] Mixing is preferably carried out at ambient temperature, in particular at a temperature of -5 to 50 °C, preferably 0 to 40 °C, in particular 5 to 35 °C.

[0159] If the components are mixed together prior to application, care must be taken to ensure that the time between mixing and application is not too long, as otherwise the reaction and the associated increase in viscosity may cause problems such as insufficient flow or slow or incomplete adhesion to the substrate. In particular, the open time of the composition during application should not be exceeded.

[0160] The "open time" refers to the period of time between mixing the components and the end of a composition suitable for processing. The open time can also be referred to as the "processing time." The time until a tack-free surface forms is a measure of the open time.

[0161] When the ingredients or components are mixed, the composition begins to harden due to the chemical reaction that occurs.

[0162] Based on the observed effects, it can be assumed that the activated methylene groups of formula (II) react with aldimine groups of formula (I), thereby activating them, i.e., making them reactive towards isocyanate groups. The reaction of the activated aldimine groups with the isocyanate groups leads to crosslinking of the isocyanate-containing polymer with the formation of urea groups. Unlike the hydrolytic activation of aldimine groups, the aldehyde is not released but remains permanently in the composition in derivatized form, presumably as an adduct with compound V or its derivatives. Furthermore, isocyanate groups can react with existing moisture or with methylene groups of formula (II).

[0163] Curing preferably takes place at ambient temperature, in particular at a temperature of -5 to 50 °C, preferably 0 to 40 °C.

[0164] The curing reaction proceeds reliably without blistering or odor. The aldehyde derivatives remaining in the composition show no signs of migration, nor do they appear to have a plasticizing effect on the cured composition.

[0165] Another object of the invention is the cured composition obtained from the curable composition after mixing the ingredients or components and subsequent curing.

[0166] Preferably, the cured composition is elastic and has a high extensibility.

[0167] The cured composition preferably has an elongation at break of at least 50%, preferably 100%, in particular at least 200%, determined according to DIN EN 53504 on dumbbell-shaped test specimens (length 75 mm, web length 30 mm, web width 4 mm, thickness 2 mm) at a tensile speed of 200 mm / min.

[0168] The curable composition is suitable for a wide range of applications. It can be used, in particular, as an adhesive, sealant, coating, casting resin, or filler.

[0169] Preferred is the use as an elastic adhesive or elastic sealant, wherein the ingredients or components are mixed together and the mixed composition is applied in the liquid state to at least one substrate.

[0170] Suitable substrates include:

[0171] - Glass, glass ceramics, concrete, mortar, cement screed, fiber cement, brick, tile, plaster or natural stones such as granite or marble;

[0172] - Repair or levelling compounds based on PCC (polymer-modified cement mortar) or ECO (epoxy resin-modified cement mortar);

[0173] - Metals or alloys such as aluminum, iron, steel, copper, other non-ferrous metals, including surface-treated metals or alloys such as galvanized or chrome-plated metals;

[0174] - asphalt or bitumen;

[0175] - leather, textiles, paper, wood, wood materials bonded with resins, for example phenolic, melamine or epoxy resins, resin-textile composites or other so-called polymer composites;

[0176] - Plastics such as rigid and soft PVC, polycarbonate, polystyrene, polyester, polyamide, PMMA, ABS, SAN, epoxy resins, phenolic resins, PUR, POM, TPO, PE, PP, EPM or EPDM, each untreated or surface-treated, for example by means of plasma, corona or flames;

[0177] - fiber-reinforced plastics, such as carbon fiber-reinforced plastics (CFRP), glass fiber-reinforced plastics (GRP), natural fiber-reinforced plastics (NFRP) and sheet molding compounds (SMC); - insulating materials, in particular foams, in particular made of EPS, XPS, PUR, PIR, aerogel or foamed glass (foamglass), or fibers made of rock wool or glass wool,

[0178] - coated or painted substrates, in particular painted tiles, painted concrete, powder-coated metals or alloys or painted sheets;

[0179] - Coatings, paints or varnishes.

[0180] If necessary, the substrates may be pretreated before application, in particular by physical and / or chemical cleaning processes or the application of an activator or a primer.

[0181] Two similar or two different substrates can be bonded and / or sealed.

[0182] An article is obtained from the use of the curable composition. The article is in particular bonded or sealed with the composition. This article may be a building or a part thereof, in particular a building or civil engineering structure, a bridge, a roof, a staircase or a facade, or it may be an industrial or consumer good, in particular a window, a pipe, a rotor blade of a wind turbine, a household appliance or a means of transport such as in particular an automobile, a bus, a truck, a rail vehicle, a ship, an aircraft or a helicopter, or an attachment thereof.

[0183] A further object of the invention is the use of a booster component comprising at least one compound V having activated methylene groups of the formula (II) for curing a one-component composition comprising at least one polymer containing isocyanate groups and at least one aldimine L having aldimine groups of the formula (I), wherein the booster component is mixed with the one-component composition using a suitable method.

[0184] Preferably, in the one-component composition, the ratio of the number of aldimine groups of the formula (I) to the number of isocyanate groups is at most 1. Preferably, the booster component is used in an amount such that the ratio of the number of activated methylene groups of the formula (II) to the number of aldimine groups is at least 1.

[0185] The booster component preferably contains at least one nitrogen-containing catalyst, in particular a compound having at least one tertiary amino group, amidine group or guanidine group, which is free of primary and secondary amino groups and hydroxyl groups, in particular in such an amount that any acids contained in the one-component composition are completely neutralized when mixed with the booster component.

[0186] The booster component may also contain other ingredients, in particular plasticizers, fillers or pigments.

[0187] By using the booster component, the one-component composition cures even without the ingress of moisture from the environment, whereby undesirable effects of the aldehyde underlying the aldimine L, such as odor, plasticizing effect or migration effects, do not occur.

[0188] Examples

[0189] The following are exemplary embodiments intended to further illustrate the described invention. Of course, the invention is not limited to these described exemplary embodiments.

[0190] The “standard climate” (“NK”) is defined as a temperature of 23±1 °C and a relative humidity of 50±5%.

[0191] Unless otherwise stated, the chemicals used were from Merck.

[0192] The viscosity was measured on a thermostatted cone-plate viscometer Rheotec RC30 (cone diameter 10 mm, cone angle 1 °, cone tip-plate distance 0.05 mm, shear rate 10 s -1 ) was measured. For viscosities of less than 0.5 Pa s, measurements were taken with a cone diameter of 50 mm.

[0193] Polymer P1 :

[0194] 590 g of polyoxypropylene diol (Acclaim® 4200, OH number 28 mg KOH / g, from Covestro), 1180 g of ethylene oxide-terminated polyoxypropylene triol (Caradol® MD34-02, OH number 35 mg KOH / g, from Shell) and 230 g of isophorone diisocyanate (Vestanat® IPDI, from Evonik) were reacted at 80 °C according to a known method to form a polymer with an NCO content of 2.1 wt%.

[0195] Polymer P2:

[0196] 725 g of ethylene oxide-terminated polyoxypropylenetriol (Desmophen® 5031 BT, OH number 28.0 mg KOH / g, OH functionality approx. 2.3, from Covestro) and 275 g of 4,4'-diphenylmethane diisocyanate (Desmodur® 44 MC L, from Covestro) were reacted at 80 °C using a known method to form a reaction mixture with an NCO content of 7.6% by weight. The volatile components, particularly unreacted 4,4'-diphenylmethane diisocyanate, were then removed by distillation in a short-path evaporator, yielding a polymer with an NCO content of 1.68% by weight and a monomeric 4,4'-diphenylmethane diisocyanate content of 0.04% by weight.

[0197] Polymer P3:

[0198] 513.3 g of polyoxypropylenediol (Acclaim® 4200, OH number 28 mg KOH / g, from Covestro), 256.7 g of ethylene oxide-terminated polyoxypropylenetriol (Caradol® MD34-02, OH number 35 mg KOH / g, from Shell) and 64.2 g of toluene diisocyanate (Desmodur® T 80 P, from Covestro) were reacted at 80 °C according to a known method to form a polymer with an NCO content of 1.5 wt%.

[0199] Polymer P4:

[0200] 1,300 g of polyoxypropylenediol (Acclaim® 4200, OH number 28 mg KOH / g, from Covestro), 2,600 g of ethylene oxide-terminated polyoxypropylenetriol (Caradol® MD34-02, OH number 35 mg KOH / g, from Shell) and 600 g of 4,4'-diphenylmethane diisocyanate (Desmodur® 44 MC L, from Covestro) were reacted in the presence of 500 g of diisodecyl phthalate at 80 °C according to a known method to give a polymer with an NCO content based on the total weight of polymer and diisodecyl phthalate of

[0201] 2.1% by weight converted.

[0202] Production of aldimines:

[0203] Aldimine A1 :

[0204] 212.2 g (2 mol) of benzaldehyde were initially charged under a nitrogen atmosphere, mixed with 158.3 g (1 mol) of 2,2(4),4-trimethyl-1,6-hexanediamine (Vestamin® TMD, from Evonik) with vigorous stirring, and the volatile components were subsequently removed at 80 °C and a vacuum of 10 mbar. This yielded 333.6 g of N,N'-dibenzylidene-2,2(4),4-trimethyl-1,6-hexanediamine as a clear, yellowish liquid with an amine number of 335 mg KOH / g and an aldimine equivalent weight of 167.3 g / g.

[0205] Aldimine A2:

[0206] 106.1 g (1 mol) of benzaldehyde was initially charged under a nitrogen atmosphere, mixed with 124.0 g (1 mol NH2) of polyoxypropylenediamine (Jeffamine® D-230, from Huntsman) with vigorous stirring, and the volatile components were subsequently removed at 80 °C and a vacuum of 10 mbar. This yielded 210.7 g of a clear, yellowish liquid with a viscosity of 0.34 Pa s at 20 °C, an amine number of 265 mg KOH / g, and an aldimine equivalent weight of 212 g / g.

[0207] Aldimine A3:

[0208] 50.00 g of aldehyde-1 (0.17 mol of aldehyde groups) were placed in a round-bottomed flask under a nitrogen atmosphere. 13.93 g (0.08 mol) of isophoronediamine (Vestamin® IPD, from Evonik) were added with vigorous stirring. The volatile components were then removed at 80 °C and a vacuum of 10 mbar. A clear, yellowish liquid with an aldimine equivalent weight of 390 g / eq was obtained.

[0209] As aldehyde-1, a reaction mixture containing predominantly branched 4-(Cio-14-alkyl)benzaldehydes with an average aldehyde equivalent weight of 290 g / eg was used, obtained from HF-BF3 catalyzed formylation of Cio-14-alkylbenzene.

[0210] Preparation of compounds with activated methylene groups: Compound V-1 : (with cyanoacetate groups)

[0211] 555.2 g (5.4 mol OH) of propoxylated 1,1,1-trimethylolpropane (Desmophen® 4011 T, OH number 550 mg KOH / g, from Covestro) were treated with 633.5 g (5.6 mol) of ethyl cyanoacetate and 1.2 g of tetra-n-butyl titanate (Tyzor® TnBT, from Dorf Ketal) and reacted at a temperature of 80 to 140 °C under vacuum until the broad OH band in the range of 3,300 to 3,600 cm' was observed in the FT-IR. 1had disappeared and no more volatiles were deposited. 866.2 g of a clear, yellowish liquid with a viscosity of 1.72 Pa s at 20 °C, a cyanoacetate functionality of 3, and a cyanoacetate equivalent weight of 169 g / eq were obtained.

[0212] Compound V-2: (with acetoacetate groups)

[0213] 154.2 g (1.5 mol OH) of propoxylated 1,1,1-trimethylolpropane (Desmophen® 4011 T, OH number 550 mg KOH / g, from Covestro) were treated with 201.7 g (1.55 mol) of ethyl acetoacetate and 0.4 g of tetra-n-butyl titanate (Tyzor® TnBT, from Dorf Ketal) and reacted at a temperature of 80 to 140 °C under vacuum until the broad OH band in the range of 3,300 to 3,600 cm was observed in the FT-IR. -1had disappeared and no more volatiles were separated. 265.1 g of a clear, yellowish liquid with a viscosity of 0.8 Pa s at 20 °C, an acetoacetate functionality of 3, and an acetoacetate equivalent weight of 186 g / eq were obtained. Other substances and abbreviations used:

[0214] TEA Triethylamine

[0215] DMDEE 2,2'-dimorpholinodiethyl ether

[0216] DBU 1,8-Diazabicyclo[5.4.0]undec-7-ene (Lupragen® N700, from

[0217] BASF)

[0218] DAEE bis(2-dimethylaminoethyl)ether

[0219] Guanidine-1 1 ,1'-(α,®-polyoxypropylene)bis(2,3-diisopropylguanidine), prepared as described below

[0220] TMG Tetramethylguanidine

[0221] DIDP diisodecyl phthalate (Palatinol® 10-P, from BASF)

[0222] DBTDL Dibutyltin dilaurate

[0223] DBTDL 5% 5 wt% dibutyltin dilaurate in diisodecyl phthalate Salicylic acid 5% 5 wt% salicylic acid in dioctyl adipate Calcined kaolin Satintone® Whitetex, from HM Royal

[0224] Titanium dioxide Kronos® 2500, from Kronos Fumed silica Fumed silica (Aerosil® R 972, from Evonik) Thickener paste Urea adduct in diisodecyl phthalate, prepared as described below

[0225] The guanidine-1 was prepared by reacting 5.57 g of polyoxypropylenediamine with medium molecular weight M n approximately 430 g / mol (Jeffamine® D-400, from Huntsman) and 2.95 g of N,N'-diisopropylcarbodiimide for 18 h at 120 °C, followed by removal of the volatile components under vacuum. An odorless yellowish liquid was obtained.

[0226] The thickener paste was prepared by placing 300 g of diisodecyl phthalate and 48 g of 4,4'-diphenylmethane diisocyanate (Desmodur® 44 MC L, from Covestro) in a vacuum mixer, warming slightly, and then slowly adding 27 g of n-butylamine while stirring vigorously. Stirring was continued for one hour under vacuum and cooling. A homogeneous, finely divided, spreadable paste was obtained.

[0227] Production of curable compositions:

[0228] Examples Z-1 to Z-30:

[0229] For each example, the ingredients of the first component (K1) listed in Tables 1 to 6 were mixed together in the specified amounts (in parts by weight) using a centrifugal mixer (Thinky ARE-250), processed into a macroscopically homogeneous liquid, and the mixed component was stored in a moisture-proof container.

[0230] Likewise, the ingredients of the second component (K2) listed in Tables 1 to 7 were processed and stored.

[0231] The components of each composition were then processed into a homogeneous liquid or paste using a centrifugal mixer and tested as described below. The tack-free time (TFT) was determined by applying 20 g of the mixed composition to cardboard in a layer thickness of approximately 2 mm. The time taken for the first time to leave no residue on the pipette when lightly tapping the surface of the applied composition with an LDPE pipette was determined under standard conditions.

[0232] To determine the mechanical properties, the mixed composition was applied to a silicone-coated release paper to form a film of 2 mm thickness, which was allowed to cure for 7 days under standard climate conditions, some dumbbell-shaped test specimens with a length of 75 mm, a web length of 30 mm and a web width of 4 mm were punched out of the film and tested according to DIN EN 53504 at a tensile speed of 200 mm / min for tensile strength, elongation at break, E-modulus 5% (between 0.5-5% elongation) and E-modulus 50% (between 0.5-50% elongation).

[0233] The Shore A hardness was determined according to DIN 53505 on test specimens (diameter 20 mm, thickness 5 mm) cured for 7 days in standard climate.

[0234] Odor was assessed by nose-sniffing the freshly prepared films at a distance of 2 cm. "0" means no aldehyde odor was detectable. "+", "++", or "+++" indicate a slight, distinct, or intense aldehyde odor.

[0235] To monitor curing in the absence of atmospheric humidity, the freshly mixed composition was stored in an aluminum tube under exclusion of air for some compounds. After 1 day (24 hours), the test was carried out to determine whether the compound was still liquid or hardened (solid). If the compound was still liquid, the tube was sealed and reassessed after a total of 7 days of storage.

[0236] During curing, a bubble-free, non-sticky, polymeric material was created.

[0237] The results are shown in Tables 1 to 6.

[0238] The examples marked with “(Ref.)” are comparative examples.

[0239]

[0240] Table 1 : Composition and properties of Z-1 to Z-6.

[0241] 1 Ratio of the number of aldimine groups of formula (I) to the number of isocyanate groups

[0242] 2 Ratio of the number of activated methylene groups of formula (II) to the number of aldimine groups of formula (I)

[0243] 3 Viscosity (20°C) 15.7 Pa s

[0244] 4 Viscosity (20°C) 16.5 Pa s

[0245] Table 2: Composition and properties of 7.-7 to Z-12.

[0246] 1 Ratio of the number of aldimine groups of formula (I) to the number of isocyanate groups

[0247] 2 Ratio of the number of activated methylene groups of formula (II) to the number of aldimine groups of formula (I)

[0248]

[0249] Table 3: Composition and properties of Z-13 to Z-16.

[0250] 1 Ratio of the number of aldimine groups of formula (I) to the number of isocyanate groups

[0251] 2 Ratio of the number of activated methylene groups of formula (II) to the number of aldimine groups of formula (I)

[0252] 3 Viscosity (20°C) 13.8 Pa s

[0253] 4 Viscosity (20°C) 15.4 Pa s

[0254]

[0255] Table 4: Composition and properties of Z-17 to Z-21.

[0256] 1 Ratio of the number of aldimine groups of formula (I) to the number of isocyanate groups

[0257] 2 Ratio of the number of activated methylene groups of formula (II) to the number of aldimine groups of formula (I)

[0258] 3 Viscosity (20°C) 47.9 Pa s

[0259] 4 Viscosity (20°C) 54.1 Pa s

[0260]

[0261] Table 5: Composition and properties of Z-22 to Z-27.

[0262] 1 Ratio of the number of aldimine groups of formula (I) to the number of isocyanate groups

[0263] 2 Ratio of the number of activated methylene groups of formula (II) to the number of aldimine groups of formula (I)

[0264] 3 Viscosity (20°C) 41.8 Pa s

[0265] 4 Viscosity (20°C) 42.9 Pa s

[0266] 5 Viscosity (20°C) 25.4 Pa s

[0267] 6 Viscosity (20°C) 26.8 Pa s

[0268]

[0269] Table 6: Composition and properties of Z-28 to Z-30.

[0270] 1 Ratio of the number of aldimine groups of formula (I) to the number of isocyanate groups

[0271] 2 Ratio of the number of activated methylene groups of formula (II) to the number of aldimine groups of formula (I)

Claims

Patent claims: 1 . Curable composition comprising - at least one polymer containing isocyanate groups, - at least one aldimine L having aldimine groups of formula (I), — N^Z (D where Z is an organic radical with 1 to 25 C atoms, and - at least one compound V having activated methylene groups of formula (II), oo II II . where Y is a radical of the formula ---CN , — C— R , ---C— OR or O II ---C— O— -, R represents a monovalent hydrocarbon radical having 1 to 10 C atoms and R 1 represents an alkyl radical having 1 to 6 C atoms, wherein, based on the total composition, the ratio of the number of aldimine groups of the formula (I) to the number of isocyanate groups is at most 1 and the ratio of the number of activated methylene groups of formula (II) to the number of aldimine groups of formula (I) is at least 1.

2. Composition according to claim 1, characterized in that the isocyanate group-containing polymer has an NCO content based on the total polymer of 0.5 to 8% by weight, preferably 0.75 to 5% by weight, in particular 1 to 3% by weight.

3. Composition according to one of claims 1 or 2, characterized in that the isocyanate group-containing polymer contains polyether chains with repeating units selected from the list consisting of oxy-1,2-propylene, oxy-1,3-propylene, oxy-1,4-butylene, oxy-1,2-butylene and oxyphenylethylene.

4. Composition according to one of claims 1 to 3, characterized in that Z represents an aliphatic hydrocarbon radical having 3 to 11 C atoms bonded via a primary or secondary C atom or represents an aromatic or heteroaromatic five- or six-membered ring which is optionally substituted and / or fused and comprises a total of 4 to 25 C atoms, where Z is in particular selected from the list consisting of 1-propyl, 2-propyl, 1-butyl, 1-pentyl, 1-heptyl, 3-heptyl, 1-undecyl, phenyl, 2-methyl-phenyl, 3-methylphenyl, 4-methylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 4-C-i4-alkylphenyl, 2,5-Dimethylphenyl, 2-Methoxyphenyl, 3-Methoxyphenyl, 4-M ethoxy phenyl, 2-Ethoxyphenyl, 3-Ethoxyphenyl, 4- Ethoxyphenyl, 4-Propoxyphenyl, 4-lsopropoxyphenyl, 4-Butoxyphenyl, 4- Pentoxyphenyl, 4-Decyloxyphenyl, 4-Dodecyloxyphenyl, 2,3-Dimethoxy- phenyl, 2,4-Dimethoxyphenyl, 2,5-Dimethoxyphenyl, 3,4-Dimethoxyphenyl, 3,5-Dimethoxyphenyl, 2,4,6-Trimethylphenyl, 2,4,5-Trimethoxyphenyl, 2,4,6- Trimethoxyphenyl, 3,4,5-Trimethoxyphenyl, 4-Methoxycarbonylphenyl, 4- Ethoxycarbonylphenyl, 3-Nitrophenyl, 1 -Naphthyl, 2-Naphthyl, 2-Furyl, 5- Methyl-2-furyl, Thiophen, Pyridin, Pyrrol und Chinolin.

5. Zusammensetzung gemäss einem der Ansprüche 1 bis 4, dadurch gekenn- zeichnet, dass das Aldimin L ein Aldimin der Formel (III) ist, where n is 2 or 3 and G is an n-valent organic radical having 2 to 25 C atoms, wherein the aldimine of the formula (III) is in particular selected from the list consisting of N,N'-dibenzylidene-1,5-pentanediamine, N,N'-dibenzylidene-1,6-hexanediamine, N,N'-dibenzylidene-2-methyl-1,5-pentanediamine, N,N'-dibenzylidene-2,2(4),4-trimethyl-1,6-hexanediamine, N,N'-dibenzylidene-1,3-bis(aminomethyl)cyclohexane, N,N'-dibenzylidene-1,3-bis(aminomethyl)benzene, N,N'-dibenzylideneisophoronediamine, N,N'-Dibenzylidene-4,4'-methylene-bis(cyclohexylamine), N,N'-Dibenzylidenepolyoxypropylenediamines with medium molecular weight M n from 350 to 750 g / mol and N,N',N"-tribenzylidenepolyoxypropylenetriamines with medium molecular weight M nfrom 450 to 700 g / mol, as well as the analogous aldimines derived from tolualdehyde, a 4-Cw-i4-alkylbenzaldehyde mixture, 4-methoxybenzaldehyde, methyl 4-formylbenzoate, ethyl 4-formylbenzoate, 3-nitrobenzaldehyde and furfural instead of benzaldehyde.

6. Composition according to one of claims 1 to 5, characterized in that the compound V, with respect to the activated methylene groups of the formula (II), has an equivalent weight, or in the case of an oligomeric or polymeric compound V average equivalent weight, of 100 to 2,100 g / eq, preferably 114 to 600 g / eq, in particular 114 to 400 g, and a functionality, or in the case of an oligomeric or polymeric compound V average functionality, of 1 to 4, preferably 1.5 to 3.5, in particular 1.8 to 3.

7. Composition according to one of claims 1 to 6, characterized in that, based on the total composition, the ratio between the number of activated methylene groups of the formula (II) and the number of aldimine groups of the formula (I) is in the range from 1 to 4, preferably 1.2 to 3, particularly preferably 1.5 to 2.

5.

8. Composition according to one of claims 1 to 7, characterized in that Y is a radical of the formula " _"CN and the activated methylene groups of the formula (II) are thus cyanoacetate groups, wherein the compound V is in particular selected from the list consisting of ethyl cyanoacetate, 2-methyl-1,3-propanediol dicyanoacetate, neopentylglycol dicyanoacetate, 1,6-hexanediol dicyanoacetate, 3-methyl-1,5-pentanediol dicyanoacetate, 2-ethyl-1,3-hexanediol dicyanoacetate, the tricyanoacetate of ethoxylated and / or propoxylated 1,1,1-trimethylolpropane, the tricyanoacetate of ethoxylated and / or propoxylated glycerol, poly(oxy-1,2-propylene)diol bis(cyanoacetate), poly- (oxy-1,2-propylene)diol bis(cyanoacetate), dimer fatty acid-based polyester diol bis(cyanoacetate) and trimer fatty acid-based polyester triol tris(cyanoacetate).

9. Composition according to one of claims 1 to 7, characterized in O II indicates that Y represents a radical of the formula ■ _-C—R, where R preferably represents methyl and the activated methylene groups of formula (II) are thus acetoacetate groups, where the compound V is in particular selected from the list consisting of ethyl acetoacetate, 1,2-propanediol diacetoacetate, dipropylene glycol diacetoacetate, tripropylene glycol diacetoacetate, 1,3-propanediol diacetoacetate, 1,4-butanediol diacetoacetate, 2-methyl-1,3-propanediol diacetoacetate, 1,5-pentanediol diacetoacetate, neopentyl glycol diacetoacetate, 1,6-hexanediol diacetoacetate, 3-methyl-1,5-pentanediol diacetoacetate, 2-ethyl-1,3-hexanediol diacetoacetate, glycerol diacetoacetate, glycerol triacetoacetate, 1,1,1 -Trimethylol- ethane diacetoacetate, 1,1,1-trimethylolethane triacetoacetate, 1,1,1-trimethylol- propane diacetoacetate, 1,1,1-trimethylolpropane triacetoacetate, the triacetoacetate of propoxylated and / or ethoxylated 1,1,1-trimethylolpropane, the triacetoacetate of propoxylated and / or ethoxylated glycerol, poly(oxy-1,2-propylene)diol bis(acetoacetate), ethylene oxide-containing poly(oxy-1,2-propylene)diol bis(acetoacetate), castor oil bis(acetoacetate), castor oil tris(acetoacetate), dimer fatty acid-based polyesterdiol bis(acetoacetate) and trimer fatty acid-based polyester triol tris(acetoacetate).

10. Composition according to one of claims 1 to 9, characterized in that at least one catalyst for the reaction between the methylene groups of formula (II) and the aldimine groups of formula (I) is present, in particular a nitrogen-containing catalyst.

11. Composition according to one of claims 1 to 10, characterized in that at least one further component selected from fillers, pigments, plasticizers and adhesion promoters is present.

12. Composition according to one of claims 1 to 11, characterized in that the composition comprises a component K1 and a component K2, which are each storage-stable on their own and are stored in separate containers, wherein isocyanate group-containing polymers and aldimines L are preferably a component of component K1 and compounds V and optionally a catalyst for the reaction between the methylene groups of the formula (II) and the aldimine groups of the formula (I) are preferably a component of component K2.

13. Composition according to claim 12, characterized in that component K1 contains the isocyanate group-containing polymer, the aldimine L and additionally at least one acid.

14. Cured composition obtained from the curable composition according to any one of claims 1 to 13 after mixing the ingredients or components and subsequent curing.

15. Use of a booster component containing at least one compound V with activated methylene groups of the formula (II), oo where Y is a radical of the formula ■ __ CN or O II C— O— -, R represents a monovalent hydrocarbon radical having 1 to 10 C atoms and R 1 represents an alkyl radical having 1 to 6 C atoms, for curing a one-component composition comprising at least one polymer containing isocyanate groups and at least one aldimine L having aldimine groups of the formula (I), — N^^Z (I) where Z represents an organic radical having 1 to 25 carbon atoms, wherein the booster component is mixed with the single-component composition using a suitable method.

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