Curable polymer compositions containing aldehyde imines, polyisocyanates, and compounds with activated methylene groups.

Abstract

The present invention provides a curable composition comprising at least one aldehyde imine L having an aldehyde imine group of formula (I), optionally at least one polyol, at least one polyisocyanate, and at least one compound V having an activated methylene group of formula (II), wherein Y is a group of formula (III) or (IV), R is a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R 1 It is an alkyl group having 1 to 6 carbon atoms, wherein the ratio of the number of isocyanate groups to the total number of aldehyde imine groups plus hydroxyl groups is at least 0.9 based on the total composition, and wherein the ratio of the number of activated methylene groups of formula (II) to the number of aldehyde imine groups of formula (I) is at least 1. This composition is particularly suitable as an elastic coating with high strength, as a viscoelastic coating with a particularly low tendency to bubble formation, or as a viscoelastic adhesive. It is cured with readily available aldehyde imines derived from volatile aldehydes such as benzaldehyde without odor, and yields a high-quality polymer with high tear resistance.

Description

Technical Field

[0001] This invention relates to curable compositions comprising aldehyde imines, polyisocyanates and compounds having activated methylene groups, and their use as elasto-viscoelastic coatings or adhesives.

[0002] Existing technology

[0003] Typical polyurethane coatings and adhesives consist of polyol and isocyanate components, which are mixed and applied for use. The curing reaction (urethane formation) is typically catalyzed by tertiary amines and / or organometallic compounds. Especially in coating applications, due to the low layer thickness and large surface area, the curing material comes into strong contact with moisture from the environment. During this process, moisture can react with isocyanate groups to compete with the polyol, leading to bubble formation and curing defects due to incomplete crosslinking. This can be improved by using more selective metal catalysts, but mercury-based catalysts are unavailable due to toxicity, and complexes of bismuth, zinc, or zirconium are difficult to use due to their high reactivity and high hydrolytic sensitivity.

[0004] Furthermore, the moisture sensitivity of such polyurethane coatings can be improved by using a certain proportion of amine curing agents in the polyol component. However, in their free form, most amine curing agents are too reactive and cause difficulties during application, such as due to uneven mixing, insufficient open time, or inadequate wetting of the substrate surface when forming adhesion through an adhesive. To improve this, amine curing agents can be used in a closed, hydrolyzed activated form, such as so-called latent curing agents, for example, in the form of ketimines or aldehyde imines. However, during curing, these release ketones or aldehydes, which cause undesirable odors and emissions or remain in the cured composition as plasticizers, which can significantly reduce the strength of the cured composition or cause problems such as migration, exudation, or substrate contamination.

[0005] US 2015 / 0259465 describes compositions having a polyol component and an isocyanate component, which further contain a polyaldehyde imide and a specific metal catalyst. Small amounts of a metal catalyst with an acetoacetate ligand may also be used herein. The problems of odor and / or plasticizer effects and migration effects caused by the released aldehydes are not addressed herein.

[0006] WO 2022 / 219148 describes two-component anti-corrosion coatings comprising polyisocyanates, polyols, and specific aldehyde imides. The problems of plasticizer effects and migration effects caused by released aldehydes remain unresolved.

[0007] US 5,288,804 describes curable compositions comprising polyacetoacetate and aldehyde imide. They do not contain polyisocyanate and do not form elastic polymers as typically found in polyurethanes.

[0008] WO 2017 / 044726 describes coatings, particularly anti-corrosion coatings, in which polyacetoacetate is cured with polyisocyanate. This also does not produce the elastic polymer typically found in polyurethanes. Invention Overview

[0010] One object of the present invention is to provide a polymer composition that can be applied defectively and has a sufficiently long open time, without bubble formation, odor, emission or plasticizer cracking products, and is suitable as a coating or adhesive.

[0011] This objective is achieved by the curable composition as described in claim 1. The composition comprises at least one aldimine L having an aldimine group of formula (I), optionally at least one polyol, at least one polyisocyanate, and at least one compound V having an activated methylene group (particularly a cyanoacetate group, acetoacetate group, or malonate group) of formula (II). Surprisingly, the aldimine L is activated by compound V, making the aldimine group available for reaction with the polyisocyanate to form a urea bond. Surprisingly, there is no hydrolysis of the aldimine, meaning that no water is needed to activate the aldimine groups to make them readily react with the isocyanate groups. Furthermore, there is clearly no aldehyde release, as no aldehyde odor is detected during curing, even in the case of aldimines based on volatile aldehydes such as benzaldehyde. It can be assumed that the adduct of compound V and the aldehyde group remains in the cured composition during curing, without observed odor emission, plasticizer effect, or migration effect. The compositions of the present invention enable the use of aldimines derived from widely available, inexpensive aldehydes (e.g., particularly benzaldehyde) without undesirable odor problems. Surprisingly, the compositions of the present invention not only cure without odor, but also exhibit a significantly reduced tendency to bubble formation and / or particularly good mechanical properties, especially higher strength and hardness, as well as higher tear resistance and consistently good ductility.

[0012] The curable compositions of this invention enable the creation of elastic coatings with high strength and high ductility, viscoelastic high-strength coatings with a particularly low tendency to bubble formation, and viscoelastic adhesives with good phase separation and a particularly low glass transition temperature. This means that the mechanical properties of such adhesives are particularly low in dependence on ambient temperature over a wide temperature range. This is advantageous for the use of such adhesives in load-bearing bonding, for example, in vehicles that are subjected to large temperature fluctuations during use.

[0013] Other aspects of the invention are the subject of the other independent claims. Particularly preferred embodiments of the invention are the subject of the dependent claims.

[0014] Embodiments of the present invention

[0015] This invention provides a curable composition comprising:

[0016] – At least one aldimine L having an aldimine group of formula (I),

[0017]

[0018] Where Z is an organic group having 1 to 25 carbon atoms.

[0019] – Optionally at least one polyol,

[0020] – At least one polyisocyanate, and

[0021] – At least one compound V having an activated methylene group of formula (II)

[0022]

[0023] Where Y is the expression , , or The group R is a monovalent hydrocarbon group having 1 to 10 carbon atoms and R 1 It is an alkyl group having 1 to 6 carbon atoms.

[0024] In this composition, the ratio of the number of isocyanate groups to the total number of aldehyde imine groups plus hydroxyl groups is at least 0.9, and the ratio of the number of activated methylene groups in formula (II) to the number of aldehyde imine groups in formula (I) is at least 1.

[0025] In the formulas in this article, the dashed lines in each case represent the bonds between the substituents and the relevant molecular groups.

[0026] Substances whose names begin with "poly / poly" (e.g., polyisocyanates or polyols) are substances that, in form, each molecule contains two or more functional groups that appear in their name.

[0027] "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 (Mn) of a polydisperse mixture of oligomers or polymers or molecular groups. It is determined by gel permeation chromatography (GPC) using polystyrene as a standard.

[0028] A composition is said to be "storage stable" when it can be stored at room temperature in a suitable container for an extended period, typically at least three to six months or longer, without causing any change in its application or use properties to the extent relevant to its use.

[0029] "NCO content" refers to the content of isocyanate groups, expressed as a percentage by weight.

[0030] "Room temperature" refers to a temperature of 23°C.

[0031] All industry standards and specifications mentioned in this document refer to the versions that were valid on the date of initial submission.

[0032] Unless otherwise stated, weight percentage (wt%) refers to the proportion of components of a composition or molecules based on the total composition or total molecules. The terms “mass” and “weight” are used synonymously herein.

[0033] Aldehydeimine L preferably has 2-3 aldehydeimine groups of formula (I).

[0034] Aldehydeimine L preferably has an aldehyde imine equivalent of 110 to 2500 g / eq, or in the case of oligomeric or polymeric aldehyde imine L, an average aldehyde imine equivalent of 110 to 2500 g / eq.

[0035] In particular, the aldimine L has 2 to 3 aldimine groups of formula (I) and an aldimine equivalent of 110 to 2500 g / eq, or in the case of oligomeric or polymeric aldimine L, an average aldimine equivalent of 110 to 2500 g / eq.

[0036] Z is preferably an aliphatic hydrocarbon group, which is bonded via primary or secondary carbon atoms and has 3 to 11 carbon atoms, or optionally substituted and / or fused aromatic or heteroaromatic five- or six-membered rings containing a total of 4 to 25 carbon atoms, particularly optional substituted and / or fused aromatic or heteroaromatic five- or six-membered rings containing a total of 4 to 25 carbon atoms.

[0037] Specifically, Z is selected from the list consisting of: 1-propyl, 2-propyl, 1-butyl, 1-pentyl, 1-heptyl, 3-heptyl, 1-undecyl, phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 4-C 10-14 -alkylphenyl, 2,5-dimethylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-ethoxyphenyl, 3-ethoxyphenyl, 4-ethoxyphenyl, 4-propoxyphenyl, 4-isopropoxyphenyl, 4-butoxyphenyl, 4-pentoxyphenyl, 4-decoxyphenyl, 4-dodecyloxyphenyl, 2,3-dimethoxyphenyl, 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-furanyl, 5-methyl-2-furanyl, thiophene, pyridine, pyrrole, and quinoline.

[0038] Among them, phenyl, isomerized methylphenyl, and 4-C are preferred. 10-14 -alkylphenyl, 4-methoxyphenyl, 3,4-dimethoxyphenyl, 4-methoxycarbonylphenyl, 4-ethoxycarbonylphenyl, 3-nitrophenyl, 5-methyl-2-furanyl or 2-furanyl.

[0039] Z is preferably phenyl. Such aldehydes and imides are derived from benzaldehyde. They are particularly readily available and can be cured particularly quickly and reliably.

[0040] Aldehydes derived from volatile aldehydes such as benzaldehyde, when used as latent curing agents in compositions containing isocyanate groups, produce a strong, unpleasant odor. This greatly limits the usability of such compositions because the odor is already present during application and persists for a long time afterward. Surprisingly, the compositions of the present invention, on the contrary, do not produce an aldehyde odor, which is particularly advantageous because the compositions can also be used without limitation in odor-sensitive applications, such as indoor or automotive applications.

[0041] The preferred aldehyde imine L is an aldehyde imine of formula (IIIa) or (IIIb).

[0042]

[0043] in

[0044] n is 2 or 3

[0045] G 1 It consists of divalent or trivalent polyoxyalkylene groups with an average molecular weight Mn of 800 to 6000 g / mol.

[0046] G 2 It is an n-valent organic group having 2 to 25 carbon atoms.

[0047] Furthermore, Z has the given definition.

[0048] In a preferred embodiment of the invention, the aldehyde imine L is an aldehyde imine of formula (IIIa).

[0049]

[0050] Where n is 2 or 3, G 1 Z is a divalent or trivalent polyoxyalkylene group having an average molecular weight Mn of 800 to 6000 g / mol, and Z has the given definition.

[0051] Aldehydeimides of formula (IIIa) are typically derived from polyoxyalkylene diamines or polyoxyalkylene triamines and the following formula Aldehydes can be obtained through condensation reactions.

[0052] Preferred polyoxyalkylene diamines or polyoxyalkylene triamines are polyoxypropylene diamines or polyoxypropylene triamines, especially Jeffamine. ® D-2000, Jeffamine ® D-4000 or Jeffamine ® T-5000 (all from Huntsman), or corresponding products from BASF or Nitroil.

[0053] Specifically, the aldehyde imine of formula (IIIa) is selected from N,N'-dibenzylpolyoxypropylene diamine and N,N',N''-tribenzylpolyoxypropylene triamine, as well as those derived from toluene, 4-C 10-14 α-alkylbenzaldehyde mixtures, 4-methoxybenzaldehyde, methyl 4-formylbenzoate, ethyl 4-formylbenzoate, 3-nitrobenzaldehyde, and furfural, but not benzaldehyde, are similar aldehyde imines.

[0054] Curable compositions containing aldehydes and imides of formula (IIIa) can be formulated entirely without polyols. Polyurea is produced upon curing. This results in coatings with, for example, high heat resistance, moisture resistance, and abrasion resistance.

[0055] In another preferred embodiment of the invention, the aldehyde imine L is an aldehyde imine of formula (IIIb).

[0056]

[0057] Where n is 2 or 3, G 2 Z is an n-valent organic group having 2 to 25 carbon atoms, and Z has the given definition.

[0058] G 2 Preferably, it is a divalent hydrocarbon group having 2 to 15 carbon atoms, especially 5 to 15 carbon atoms, or a divalent or trivalent polyoxyalkylene group having an average molecular weight Mn of 160 to 500 g / mol.

[0059] Aldehydes of formula (IIIb) are typically derived from primary amines and formulas... Aldehydes can be obtained through condensation reactions.

[0060] Preferred primary amines are commercially available aliphatic or alicyclic primary amines, particularly those selected from the list of the following compositions: ethane-1,2-diamine, propane-1,2-diamine, propane-1,3-diamine, butane-1,4-diamine, pentane-1,5-diamine, 2,2-dimethylpropane-1,3-diamine, pentane-1,3-diamine (DAMP), hexane-1,6-diamine, 1,5-diamino-2-methylpentane (MPMD), heptane-1,7-diamine, octane-1,8-diamine, 2,5-dimethylhexane-1,6-diamine, nonane-1,9-diamine, 2,2(4),4-trimethylhexane-1,6-diamine (TMD), decane-1,10-diamine, undecane -1,11-diamine, 2-butyl-2-ethylpentane-1,5-diamine (C11-neo-diamine), dodecane-1,12-diamine, 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), isophorone diamine (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(aminomethyl)tricyclo[5.2.1.0] 2,6 Decane (TCD-diamine), 4,9-dioxadodecane-1,12-diamine, 4,7,10-trioxatridecane-1,13-diamine, polyoxypropylene diamines with an average molecular weight Mn of 200 to 500 g / mol, and polyoxypropylene triamines with an average molecular weight Mn of 300 to 500 g / mol.

[0061] The preferred polyoxypropylene diamine or polyoxypropylene triamine is Jeffamine. ® D-230, Jeffamine ® D-400 or Jeffamine ® T-403 (all from Huntsman), and corresponding products from BASF or Nitroil.

[0062] Preferred formula The aldehydes include butyraldehyde, isobutyraldehyde, pentaldehyde, hexanal, octaldehyde, 2-ethylhexanal, dodecanal, benzaldehyde, 2-tolualdehyde, 3-tolualdehyde, 4-tolualdehyde, 4-ethylbenzaldehyde, 4-isopropylbenzaldehyde, 4-tert-butylbenzaldehyde, and 4-C 10-14alkylbenzaldehyde, 2,5-dimethylbenzaldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, 4-methoxybenzaldehyde, 2-ethoxybenzaldehyde, 3-ethoxybenzaldehyde, 4-ethoxybenzaldehyde, 4-propoxybenzaldehyde, 4-isopropoxybenzaldehyde, 4-butoxybenzaldehyde, 4-pentoxybenzaldehyde, 4-decyloxybenzaldehyde, 4-dodecyloxybenzaldehyde, 2,3-dimethoxybenzaldehyde, 2,4-dimethoxybenzaldehyde Benzaldehyde, 2,5-dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 3,5-dimethoxybenzaldehyde, 2,4,6-trimethylbenzaldehyde, 2,4,5-trimethoxybenzaldehyde, 2,4,6-trimethoxybenzaldehyde, 3,4,5-trimethoxybenzaldehyde, methyl 4-formylbenzoate, ethyl 4-formylbenzoate, 3-nitrobenzaldehyde, 1-naphthaldehyde, 2-naphthaldehyde, furfural, or 5-methylfurfural.

[0063] Among them, aromatic or heteroaromatic aldehydes are preferred.

[0064] Particularly preferred are benzaldehyde, isomerized toluene-formaldehyde, and 4-C 10-14 1-alkylbenzaldehyde mixtures, 4-methoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, methyl 4-formylbenzoate, ethyl 4-formylbenzoate, 3-nitrobenzaldehyde, or furfural.

[0065] Benzaldehyde is the preferred choice.

[0066] Aldehydeimides of formula (IIIb) derived from aromatic aldehydes such as benzaldehyde exhibit a particularly pronounced tendency to crystallize in certain situations. Preferably, aldehydeimides of formula (IIIb) are permanent liquids on their own or as mixtures of each other at room temperature without the addition of solvents or diluents. Such aldehydeimides result in compositions with low emissions.

[0067] Particularly preferably, the aldehyde imine of formula (IIIb) is selected from N,N'-dibenzylpentane-1,5-diamine, N,N'-dibenzylhexane-1,6-diamine, N,N'-dibenzyl-2-methylpentane-1,5-diamine, N,N'-dibenzyl-2,2(4),4-trimethylhexane-1,6-diamine, N,N'-dibenzyl-1,3-bis(aminomethyl)cyclohexane, N,N'-dibenzyl-1, 3-Bis(aminomethyl)benzene, N,N'-dibenzylisophorone diamine, N,N'-dibenzyl-4,4'-methylenebis(cyclohexylamine), N,N'-dibenzylpolyoxypropylene diamine with an average molecular weight Mn of 350 to 750 g / mol, and N,N',N''-tribenzylpolyoxypropylene triamine with an average molecular weight Mn of 450 to 700 g / mol, as well as derivatives derived from toluene, 4-C 10-14α-alkylbenzaldehyde mixtures, 4-methoxybenzaldehyde, methyl 4-formylbenzoate, ethyl 4-formylbenzoate, 3-nitrobenzaldehyde, and furfural rather than benzaldehyde-like aldehyde imines.

[0068] Preferred are N,N'-dibenzylpentane-1,5-diamine, N,N'-dibenzyl-2-methylpentane-1,5-diamine, N,N'-dibenzylhexane-1,6-diamine, N,N'-dibenzyl-2,2(4),4-trimethylhexane-1,6-diamine, N,N'-dibenzylpolyoxypropylene diamine or N,N'-bis(4-C) 10-14 -alkylbenzyl)isophorone diamine.

[0069] In a preferred embodiment of the invention, the curable composition comprises at least one polyol P with an OH value of 14-280 mg KOH / g, preferably 28-112 mg KOH / g.

[0070] The polyol P preferably has an average molecular weight Mn of 400 to 10000 g / mol, particularly 1000 to 6000 g / mol.

[0071] The polyol P preferably has an average OH functionality of 1.6 to 3, more preferably 1.8 to 3, and especially 2.2 to 3.

[0072] The polyol P preferably has at least some primary hydroxyl groups. This polyol reacts particularly well with isocyanates.

[0073] The polyol P is preferably a liquid at room temperature.

[0074] The suitable polyol P is a commercially available polyol, especially

[0075] – Polyether polyols, particularly polyoxyalkylene glycols and / or polyoxyalkylene triols, wherein the triol is preferably derived from 1,1,1-trimethylolpropane or glycerol, and polyether polyols having polymer particles dispersed therein, particularly those having styrene-acrylonitrile particles (SAN) or polyurea or polyhydrazodicarbonamide particles (PHD).

[0076] – Polyester polyols, especially condensation products derived from hydroxycarboxylic acids or lactones, or condensation products of aliphatic and / or aromatic polycarboxylic acids with diols or polyols, or esterification products of dimer or trimer fatty acids.

[0077] - Polycarbonate polyols,

[0078] – Polyether polyester polyols

[0079] – Polyacrylate or polymethacrylate polyol,

[0080] – Polyhydroxy functional fats or oils, especially natural fats, oils or their derivatives, particularly transformation products of castor oil.

[0081] – Polyhydrocarbon polyols, particularly hydroxyl-functionalized polyolefins, polyisobutylene or polyisoprene, and hydroxyl-functionalized ethylene-propylene copolymers, ethylene-butene copolymers or ethylene-propylene-diene copolymers, such as those produced by Kraton Polymers, as well as hydroxyl-functionalized polymers of dienes, particularly 1,3-butadiene, and hydroxyl-functionalized copolymers of dienes and vinyl monomers such as styrene, acrylonitrile, vinyl chloride, vinyl acetate, vinyl alcohol, isobutylene or isoprene, and hydrogenated hydroxyl-functionalized polymers or copolymers of dienes.

[0082] Polyether polyols or polyester polyols are preferred.

[0083] Polyether polyols are particularly capable of achieving high elasticity over a wide temperature range, while polyester polyols can achieve exceptionally high strength.

[0084] Particularly preferred polyether polyols are polyoxypropylene polyols, ethylene oxide-terminated polyoxypropylene polyols, or polyether polyols in which polymer particles are dispersed, especially those having styrene-acrylonitrile particles (SAN) or polyurea or polydiurea particles (PHD).

[0085] Particularly preferred are ethylene oxide-terminated polyoxypropylene triols or ethylene oxide-terminated polyoxypropylene triols containing styrene-acrylonitrile particles (SAN) dispersed therein.

[0086] Also preferred are polyether polyols with low unsaturation content (so-called "low monohydric alcohol content" and "ultra-low monohydric alcohol content" polyols), especially those less than 0.02 meq / g, preferably less than 0.01 meq / g.

[0087] Particularly preferred polyester polyols are reaction products of castor oil, such as Setathane. ®D 1150 (from Allnex), or amorphous saturated polyester diols or triols, particularly from the reaction of dicarboxylic acids (e.g., especially succinic acid, glutaric acid, adipic acid, pimelic acid, octanoic acid, azelaic acid, sebacic acid, or dodecanedicarboxylic acid) with alcohols (e.g., especially ethane-1,2-diol, diethylene glycol, propane-1,2-diol, propane-1,3-diol, 2-methylpropane-1,3-diol, dipropylene glycol, butane-1,4-diol, pentane-1,5-diol, 3-methylpentane-1,5-diol, hexane-1,6-diol, neopentyl glycol, cyclohexane-1,3-diethanol, cyclohexane-1,4-diethanol, trimethylolpropane, or glycerol).

[0088] If the aldolimide L contains at least one aldolimide of formula (IIIb), the curable composition preferably contains at least one polyol P or at least one aldolimide of formula (IIIa), particularly at least one polyol P.

[0089] The weight ratio between the aldehyde imide L, particularly the aldehyde imide of formula (IIIb), and the polyol P is preferably in the range of 2 / 98-50 / 50, particularly preferably 3 / 97-40 / 60, and especially 4 / 96-30 / 70. This curable composition has a sufficiently long processing time, high strength, and good ductility after curing.

[0090] The curable composition further comprises at least one polyisocyanate.

[0091] Preferably, the polyisocyanate has an NCO content of 8% to 35% by weight, more preferably 10% to 33% by weight, based on the polyisocyanate.

[0092] The polyisocyanate preferably has an NCO functionality of 2.1 to 4.0 or an average NCO functionality.

[0093] Preferred polyisocyanates are oligomers or derivatives of commercially available diisocyanates, such in particular pentane-1,5-diisocyanate (PDI), hexane-1,6-diisocyanate (HDI), isophorone diisocyanate (IPDI), perhydrotoluene-2,4(6)-diisocyanate (H6TDI), and perhydrodiphenylmethane-4,4'-diisocyanate (H6TDI). 12MDI), 2,2(4),4-trimethylhexane-1,6-diisocyanate (TMDI), cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, 1,3-bis(isocyanate-methyl)cyclohexane, 1,4-bis(isocyanate-methyl)cyclohexane, m-xylene diisocyanate, p-xylene diisocyanate, toluene-2,4(6)-diisocyanate (TDI), diphenylmethane diisocyanate (MDI), benzene-1,4-diisocyanate (PDI) or naphthalene-1,5-diisocyanate (NDI), and so-called polymeric diphenylmethane diisocyanate (polymeric MDI or pMDI), which is a room-temperature liquid mixture of MDI and MDI homologues having more than two isocyanate-substituted benzene rings, wherein each may contain a certain proportion of the reaction product with a polyol.

[0094] Polyisocyanates containing a certain proportion of the reaction product with polyols can also be called "quasi-prepolymers". Polyether polyols with an average molecular weight (Mn) of 300-2000 g / mol are particularly suitable for this purpose, especially those selected from poly(oxy-1,2-ethylene) glycol, poly(oxy-1,2-ethylene) glycol containing ethylene oxide units, ethoxylated and / or propoxylated 1,1,1-trimethylolpropane, and ethoxylated and / or propoxylated glycerol.

[0095] The polyisocyanates are particularly preferred from oligomers and derivatives of HDI, IPDI, TDI and MDI, as well as room-temperature liquids of polymeric MDI (pMDI), each of which may contain reaction products with polyols.

[0096] Particularly preferred are polymeric MDIs and oligomers containing urea diketone, isocyanurate, or iminooxadiazine diketone groups, or different groups thereof, as well as derivatives containing ester, urea, carbamate, biuret, urethane, carbodiimide, urea ketimide, or oxadiazine triketone groups, or different groups thereof. In practice, such polyisocyanates are typically mixtures of substances with different degrees of oligomerization and / or chemical structures.

[0097] Particularly preferred are room-temperature liquid mixtures of MDI and MDI homologues (polymeric MDI or pMDI), and HDI biuret 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 N3790 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 urea diketone such as Desmodur ® N 3400 (from Covestro), HDI iminooxadiazine dione such as Desmodur ® XP 2410 (from Covestro), HDI urea esters such as Basonat BA products (BASF), TDI oligomers such as Desmodur ® IL (from Covestro), or TDI / HDI-based mixed isocyanurates such as Desmodur ® HL (from Covestro), where each of these may contain reaction products with polyols.

[0098] Based on the total composition, the ratio of the number of isocyanate groups to the total number of aldehyde imine groups plus hydroxyl groups is at least 0.9.

[0099] This is the ratio of all isocyanate groups contained in the composition to the sum of all aldehyde-imine groups contained in the composition and all hydroxyl groups contained in the composition. The hydroxyl groups are particularly derived from polyol P, and optionally from other polyols, especially chain extenders.

[0100] Preferably, the ratio of the number of isocyanate groups to the total number of aldehyde-imine groups plus hydroxyl groups is 0.9-1.2, particularly 1-1.1. Such compositions, when cured, yield polymers with high strength and good ductility.

[0101] The curable composition further comprises at least one compound V having an activated methylene group of formula (II).

[0102]

[0103] Where Y is the expression , , or . group.

[0104] Preferably, the methylene group of formula (II) is covalently bonded in compound V. In particular, the methylene group of formula (II) does not exist as a ligand on a metal atom.

[0105] R is preferably an alkyl or phenyl group having 1-6 carbon atoms, and is particularly preferably methyl, ethyl, propyl, isopropyl, butyl, or phenyl.

[0106] Most preferably, R is a methyl group.

[0107] R 1 Preferably methyl, ethyl or tert-butyl, more preferably ethyl or tert-butyl, especially ethyl.

[0108] Compound V is preferably a liquid at room temperature. Specifically, its viscosity at 20°C is 0.01-50 Pa·s, more preferably 0.01-25 Pa·s, particularly preferably 0.01-10 Pa·s, and especially 0.02-5 Pa·s, obtained by passing through a cone with a diameter of 10 mm, a cone angle of 1°, a cone tip-plate distance of 0.05 mm, and a shear rate of 10 s. -1 Viscosities less than 0.5 Pa·s were measured using a cone-plate viscometer and a cone-plate viscometer with a ball diameter of 50 mm. This compound allows the composition to have good processability at ambient temperature without the need for the addition of solvents or diluents.

[0109] Preferably, compound V contains 1 to 6 activated methylene groups of formula (II), particularly preferably 2 to 4, especially 2 to 3 activated methylene groups of formula (II).

[0110] Preferably, compound V has a molecular weight of 100 to 10,000 g / mol, more preferably 196 to 5,000 g / mol, more preferably 240 to 2,500 g / mol, particularly 240 to 1,500 g / mol, or in the case of oligomeric or polymeric compound V, an average molecular weight Mn of 100 to 10,000 g / mol, more preferably 196 to 5,000 g / mol, more preferably 240 to 2,500 g / mol, particularly 240 to 1,500 g / mol.

[0111] Preferably, compound V has an equivalent of 100 to 2100 g / eq, preferably 114 to 600 g / eq, particularly 114 to 400 g / eq, relative to the activated methylene group of formula (II), or in the case of oligomeric or polymeric compound V, an average equivalent of 100 to 2100 g / eq, preferably 114 to 600 g / eq, particularly 114 to 400 g / eq.

[0112] Preferably, with respect to the activated methylene group of formula (II), compound V has a functionality of 1 to 4, preferably 1.5 to 3.5, particularly 1.8 to 3, or in the case of oligomeric or polymeric compound V, an average functionality of 1 to 4, preferably 1.5 to 3.5, particularly 1.8 to 3.

[0113] In particular, compound V, relative to the activated methylene group of formula (II), has an equivalent of 100 to 2100 g / eq, preferably 114 to 600 g / eq, particularly 114 to 400 g, or in the case of oligomeric or polymeric compound V, an average equivalent of 100 to 2100 g / eq, preferably 114 to 600 g / eq, particularly 114 to 400 g, and a functionality of 1 to 4, preferably 1.5 to 3.5, particularly 1.8 to 3, or in the case of oligomeric or polymeric compound V, an average functionality of 1 to 4, preferably 1.5 to 3.5, particularly 1.8 to 3.

[0114] Preferably, based on the total composition, the ratio of the number of activated methylene groups of formula (II) to the number of aldehyde imine groups of formula (I) is 1 to 4, more preferably 1.2 to 3, and particularly 1.5 to 2.5.

[0115] Compound V is preferably obtained by transesterification of at least one hydroxyl-containing compound with at least one compound of formula (IV).

[0116]

[0117] Where Y 1 This is the formula , or The groups, and R and R 1 It has the definition that has already been described.

[0118] Ester exchange is preferably carried out at a temperature of 50-150°C, wherein the released alcohol R is removed by distillation. 1 OH and any of its decomposition products are optionally processed under reduced pressure and optionally in the presence of a catalyst.

[0119] Compound V, which has a cyanoacetic acid ester group, can also be prepared by esterifying cyanoacetic acid with at least one compound containing a hydroxyl group.

[0120] Compound V, which has an acetoacetate group, can also be prepared by reacting the parent compound containing a hydroxyl group of compound V with a diene or a diene-acetone adduct (=2,2,6-trimethyl-4H-1,3-dioxane-4-one), in the case of an acetone-diene adduct, in which acetone is released.

[0121] Compound V, which has a malonic acid ester group, can also be prepared by esterifying malonic acid with at least one compound containing a hydroxyl group.

[0122] Suitable compounds of formula (IV) are especially 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 ditert-butyl malonate.

[0123] Preferred ingredients include ethyl cyanoacetate or tert-butyl cyanoacetate, ethyl acetoacetate or tert-butyl acetoacetate, and diethyl malonate.

[0124] Preferred compounds containing hydroxyl groups are commercially available OH-functionalized compounds or polymers, such particularly ethane-1,2-diol, diethylene glycol, triethylene glycol, propane-1,2-diol, dipropylene glycol, tripropylene glycol, propane-1,3-diol, butane-1,4-diol, butane-1,2-diol, 2-methylpropane-1,3-diol, pentane-1,5-diol, and pentane-1,2-diol. Neopentyl glycol, 2-methylbutane-1,4-diol, hexane-1,6-diol, 3-methylpentane-1,5-diol, octane-1,8-diol, 2-ethylhexane-1,3-diol, decane-1,10-diol, dodecane-1,12-diol, polytetrahydrofurandiol, cyclohexane-1,3-diethanol, cyclohexane-1,4-diethanol, 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-propylidene) glycol with an average molecular weight of 400 to 4000 g / mol, EO-terminated poly(oxy-1,2-propylidene) glycol with an average molecular weight of 1000 to 4000 g / mol, poly(oxy-1,2-propylidene) triol with an average molecular weight of 400 to 6000 g / mol, EO-terminated poly(oxy-1,2-propylidene) triol with an average molecular weight of 3000 to 6000 g / mol, polyester polyols based on dimer or trimer fatty acids with an average molecular weight of 1000 to 3000 g / mol, castor oil, derivatives of castor oil, or hydroxylated vegetable oils.

[0125] In a preferred embodiment of the present invention, Y is the formula... Therefore, the activated methylene group in formula (II) is a cyanoacetic acid ester group.

[0126] Preferably, the compound V having a cyanoacetate group is selected from ethyl cyanoacetate, 2-methylpropane-1,3-diol dicyanoacetate, neopentyl glycol dicyanoacetate, hexane-1,6-diol dicyanoacetate, 3-methylpentane-1,5-diol dicyanoacetate, 2-ethylhexane-1,3-diol dicyanoacetate, ethoxylated and / or propoxylated 1,1,1-trimethylolpropane tricyanoacetate, ethoxylated and / or propoxylated glycerol tricyanoacetate, poly(oxy-1,2-propylene)diol bis(cyanoacetate), poly(oxy-1,2-propylene)diol bis(cyanoacetate) containing ethylene oxide units, polyester diol bis(cyanoacetate) based on dimeric fatty acids, and polyester triol tri(cyanoacetate) based on trimeric fatty acids.

[0127] In a particularly preferred embodiment of the invention, Y in formula (II) is a formula... The group, wherein R is preferably methyl, so the activated methylene group of formula (II) is an acetoacetate group.

[0128] Preferably, compound V having an acetoacetate group is selected from ethyl acetoacetate, propane-1,2-diol diacetoacetate, dipropylene glycol diacetoacetate, tripropylene glycol diacetoacetate, propane-1,3-diol diacetoacetate, butane-1,4-diol diacetoacetate, 2-methylpropane-1,3-diol diacetoacetate, pentane-1,5-diol diacetoacetate, neopentyl glycol diacetoacetate, hexane-1,6-diol diacetoacetate, 3-methylpentane-1,5-diol diacetoacetate, 2-ethylhexane-1,3-diol diacetoacetate, glycerol diacetoacetate, glycerol triacetoacetate, and 1,1,1-tris(hydroxymethyl)ethanediacetate. Acetates, 1,1,1-trimethylolethane triacetate, 1,1,1-trimethylolpropane diacetate, 1,1,1-trimethylolpropane triacetate, propoxylated and / or ethoxylated 1,1,1-trimethylolpropane triacetate, propoxylated and / or ethoxylated glycerol triacetate, poly(oxy-1,2-propylene)diol bis(acetate), poly(oxy-1,2-propylene)diol bis(acetate) containing ethylene oxide units, castor oil bis(acetate), castor oil tri(acetate), dimeric fatty acid polyester diol bis(acetate), and trimeric fatty acid polyester triol tri(acetate).

[0129] Preferred ingredients include propane-1,2-diol diacetyl acetate, dipropylene glycol diacetyl acetate, 2-methylpropane-1,3-diol diacetyl acetate, neopentyl glycol diacetyl acetate, hexane-1,6-diol diacetyl acetate, 3-methylpentane-1,5-diol diacetyl acetate, 2-ethylhexane-1,3-diol diacetyl acetate, glycerol diacetyl acetate, glycerol triacetyl acetate, 1,1,1-trimethylolpropane diacetyl acetate, 1,1,1-trimethylolpropane triacetyl acetate, propoxylated 1,1,1-trimethylolpropane triacetyl acetate with an average molecular weight Mn of 500 to 1000 g / mol, or poly(oxy-1,2-propylene)diol bis(acetyl acetate) with an average molecular weight Mn of 550 to 5000 g / mol.

[0130] In another implementation, Y is a formula or Therefore, the activated methylene group in formula (II) is a malonate ester group.

[0131] Preferably, compound V has a malonate group, selected from diethyl malonate, diisopropyl malonate, ethane-1,2-diol bis(ethyl malonate), propane-1,2-diol bis(ethyl malonate), propane-1,3-diol bis(ethyl malonate), butane-1,4-diol bis(ethyl malonate), 2-methylpropane-1,3-diol bis(ethyl malonate), neopentyl glycol bis(ethyl malonate), hexane-1,6-diol bis(ethyl malonate), 3-methylpentane-1,5-diol bis(ethyl malonate), 2-ethylhexane-1,3-diol bis(ethyl malonate), cyclohexane-1,4-dimethylethanol bis(ethyl malonate), diethylene glycol bis(ethyl malonate), dipropylene ... Diol bis(ethyl malonate), glyceryl tri(ethyl malonate), 1,1,1-trimethylolpropane tri(ethyl malonate), castor oil tri(ethyl malonate), poly(oxy-1,2-propylene)diol bis(ethyl malonate) having an average molecular weight Mn of 500 to 2000 g / mol, propoxylated 1,1,1-trimethylolpropane having three ethyl malonate end groups and an average molecular weight Mn of 650 to 2500 g / mol, the corresponding oligomers of these reaction products, and polyester diols containing malonic acid ester groups from the reaction of diols such as hexane-1,6-diol and cyclohexane-1,4-diethanol with malonic acid and diethyl malonate and optionally adipic acid or diethyl adipic acid.

[0132] Suitable compounds with malonic acid ester groups are also commercially available, especially as Acure. ® 510-200 (from Allnex).

[0133] The curable composition preferably contains at least one other component selected from crosslinking agents, catalysts, drying agents, fillers, and pigments. The curable composition preferably contains several such components.

[0134] Preferred crosslinking agents are so-called chain extenders or low molecular weight polyols, such in particular propane-1,3-diol, butane-1,4-diol, butane-1,2-diol, 2-methylpropane-1,3-diol, pentane-1,5-diol, neopentane glycol, 2-methylbutane-1,4-diol, hexane-1,6-diol, 3-methylpentane-1,5-diol, cyclohexane-1,3-diethanol, cyclohexane-1,4-diethanol, and ethoxylated and / or propoxylated glycerol or ethoxylated and / or propoxylated 1,1,1-trimethylolpropane, each with an OH value of 300-650 mg KOH / g.

[0135] It is preferable to use this crosslinking agent in combination with polyol P.

[0136] The preferred catalyst is

[0137] – Metal compounds, particularly organotin (IV) compounds, such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dibutyltin diacetylacetone, dimethyltin dilaurate, dioctyltin diacetate, dioctyltin dilaurate or dioctyltin diacetylacetone, and complexes of bismuth (III) or zirconium (IV), especially complexes with ligands selected from alkoxides, carboxylates, 1,3-diketones, hydroxyquinolineates, 1,3-keto esters and 1,3-keto amidates, and / or

[0138] – Compounds containing an amine group, such in particular triethylamine, tripropylamine, tributylamine, tri(2-ethylhexyl)amine, N,N-dimethylisopropylamine, N-ethyldiisopropylamine, N,N-dimethylcyclohexylamine, N,N-dimethyl-C 12-14 -alkylamines, N,N-dimethylbenzylamine, α-methylbenzylmethylamine, 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-bis(dimethylaminopropyl)urea, bis(2-dimethylaminoethyl) ether, tris(2-(2-methoxyethoxy)ethyl)amine, N-methylmorpholine, N-ethylmorpholine or 2,2'-dimorpholinodiethyl ether (DMDEE).

[0139] Here, metal compounds catalyze the reaction of isocyanate groups, and are preferably used in curable compositions comprising polyisocyanates having aliphatic isocyanate groups. Compounds containing amine groups catalyze the reaction of isocyanate groups and the reaction of compound V with aldehyde imine L.

[0140] If the curable composition contains an acid, it preferably also contains at least one base, particularly a compound containing an amine group, in an amount such that the curable composition is not acidic overall.

[0141] The curable composition preferably contains at least one zeolite (also known as a molecular sieve) as a desiccant.

[0142] Preferred fillers are ground or precipitated calcium carbonate, optionally coated with fatty acids, especially stearates, barite, quartz powder, quartz sand, dolomite, wollastonite, kaolin, calcined kaolin, flake silicates such as mica or talc, zeolite, aluminum hydroxide, magnesium hydroxide, silica, including highly dispersed silica from pyrolysis processes, industrially produced carbon black, graphite, ground fillers from agricultural sources, such as, in particular, olive kernel powder or nut shell powder, metal powders such as aluminum, copper, iron, silver or steel powders, PVC powder or hollow beads. Particularly preferred are calcium carbonate, barite, quartz powder, quartz sand or kaolin.

[0143] Preferred pigments are titanium dioxide, chromium oxide, iron oxide, or organic pigments.

[0144] Curable compositions may additionally contain other components, especially:

[0145] - Polymers containing isocyanate groups,

[0146] – Other crosslinking agents, such as oxazolidin, ketimine, or other aldehyde imines,

[0147] – Dyes,

[0148] – Fibers, especially glass fibers, carbon fibers, metal fibers, ceramic fibers, Hanf fibers, cellulose fibers, or plastic fibers such as polyamide fibers or polyethylene fibers.

[0149] – Nanofillers or nanofibers, such as graphene or carbon nanotubes,

[0150] – Plasticizers, especially phthalates, particularly diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), or di(2-propylheptyl) phthalate (DPHP), hydrogenated phthalates, especially diisononyl cyclohexane-1,2-dicarboxylate (DINCH), terephthalates, especially bis(2-ethylhexyl) terephthalate or diisononyl terephthalate (DINT), hydrogenated terephthalates, especially bis(2-ethylhexyl) cyclohexane-1,4-dicarboxylate or diisononyl cyclohexane-1,4-dicarboxylate, isophthalates, trimellitates, Adipate esters, especially dioctyl adipate (DOA), azelaate, sebacic acid ester, citrate, benzoate, glycol ether, glycol ester, plasticizers having a polyether structure, especially poly(oxy-1,2-propylene) monohydric alcohols, glycols or trihydric alcohols, organic sulfonates or phosphates having blocked hydroxyl groups (especially in the acetyl form), especially diphenyltolyl phosphate (DPK), polybutene, polyisobutylene, or plasticizers derived from natural fats or oils (especially epoxidized soybean oil, linseed oil or rapeseed oil methyl esters), wherein phthalates, hydrogenated phthalates, adipate esters or plasticizers having a polyether structure are preferred.

[0151] – Solvent,

[0152] – Rheology modifiers, especially urea compounds, flake silicates such as bentonite, castor oil derivatives, hydrogenated castor oil, polyamides, polyurethanes, pyrolytic silica, or hydrophobically modified polyoxyethylene.

[0153] Other desiccants, such as calcium oxide, highly reactive isocyanates such as p-toluenesulfonyl isocyanate, and monooxazolidines such as Incozol ® 2 (from Incorez) or orthoester,

[0154] – Adhesion promoters, especially titanates or organoalkoxysilanes, such as, in particular, epoxysilanes, especially 3-glycidoxypropyltrimethoxysilane or 3-glycidoxypropyltriethoxysilane, aminosilanes, iminosilanes, mercaptosilanes, vinylsilanes, (meth)acryloylsilanes, carbamate silanes, alkylsilanes, S-(alkylcarbonyl)mercaptosilanes, or oligomeric forms of these silanes.

[0155] - Flame retardants, especially aluminum hydroxide or magnesium hydroxide fillers already mentioned, organophosphates, ammonium polyphosphates, melamine or its derivatives, boron compounds or antimony compounds;

[0156] - Non-reactive thermoplastic polymers, especially homopolymers or copolymers of unsaturated monomers, particularly those selected from ethylene, propylene, butene, isobutylene, isoprene, styrene, vinyl acetate and (meth)acrylate alkyl esters, especially polyethylene (PE), polypropylene (PP), polyisobutylene, ethylene-vinyl acetate copolymer (EVA) and atactic poly-α-olefin (APAO).

[0157] – Modifiers, such as hydrocarbon resins, natural or synthetic waxes or asphalt;

[0158] – Additives, especially wetting agents, leveling agents, defoamers, degassing agents, antioxidants, stabilizers for heat, light or UV radiation, or biocides;

[0159] And other substances that are commonly used in curable compositions.

[0160] It may be meaningful to chemically or physically dry certain substances before mixing them into a composition.

[0161] The curable composition preferably contains less than 10% by weight, more preferably less than 5% by weight, and particularly less than 1% by weight of volatile organic compounds (VOCs) with a boiling point of less than 250°C at standard pressure, based on the total composition. This composition produces particularly low levels of emissions.

[0162] The curable composition is preferably formulated as a multi-component system, particularly a two-component or three-component system.

[0163] The curable composition preferably comprises components K1 and K2, and optionally component K3, each of which is individually storage stable and stored in separate containers.

[0164] The components are preferably distributed between the components, such that

[0165] – Aldehydeimine L and optional polyol are part of component K1, polyisocyanate is part of component K2, and compound V is part of component K2 or exists as a separate component K3, or

[0166] – Compound V and optional polyol are part of component K1, and aldehyde imine L and polyisocyanate are part of component K2.

[0167] Other components of the composition may be present as part of components K1 and / or K2 and / or K3. Care should be taken to ensure that the components are formulated such that each component is itself storage stable in a suitable container.

[0168] In a preferred embodiment of the invention, the curable composition comprises component K1, component K2, and optionally component K3, wherein component K1 comprises at least one aldehyde imine of formula (IIIa), component K2 comprises at least one polyisocyanate, and compound V is part of component K2 or present as a separate component K3. Preferred polyisocyanates are those having aliphatic isocyanate groups, particularly trimers of HDI. Such a curable composition cures into a polyurea and enables the production of particularly high-quality coatings with exceptionally high strength and resistance to UV, heat, moisture, and friction.

[0169] In another preferred embodiment of the invention, the curable composition comprises component K1 and component K2, wherein component K1 comprises at least one aldehyde imine of formula (IIIa) and at least one polyisocyanate, and component K2 comprises at least one compound V.

[0170] In another preferred embodiment of the invention, the curable composition comprises component K1, component K2, and optional component K3, wherein component K1 comprises at least one polyol P and at least one aldehyde imine of formula (IIIb), component K2 comprises at least one polyisocyanate, and compound V is part of component K2 or exists as a separate component K3. Such compositions are particularly inexpensive and can achieve high strength and good ductility.

[0171] In another preferred embodiment of the invention, the curable composition comprises component K1 and component K2, wherein component K1 comprises at least one polyol P and at least one compound V, and component K2 comprises at least one polyisocyanate and at least one aldehyde imine of formula (IIIb).

[0172] The preferred consistency of the components allows them to mix well with each other under ambient conditions using simple methods. Liquid or paste-like components are particularly suitable for this purpose. The components preferably have similar viscosity and / or rheological properties. These components are particularly miscible with each other.

[0173] The curable composition is prepared separately from its components K1, K2, and optional K3. This involves mixing the components together to obtain a macroscopically homogeneous liquid or paste. Components K1, K2, and optional K3 are stored separately in separate containers. Suitable containers include, in particular, barrels, containers, buckets, cans, cylinders, bags, bladders, tubular bags, tins, or tubes.

[0174] For the use of curable compositions, all components, especially in the form of components K1, K2, and optionally K3, are mixed together shortly before or during application. In the case of three components, the mixing order is arbitrary. All three components may be mixed simultaneously, or two of the three components may be mixed first, followed by the addition of the third component. Preferably, the aldehyde imine L and compound V are not premixed separately, but rather mixed in the presence of the polyisocyanate. The mixing ratio is chosen such that the ratio of the number of aldehyde imine groups to the number of isocyanate groups and the ratio of the number of activated methylene groups in formula (II) to the number of aldehyde imine groups are within the scope of this invention.

[0175] The mixing is preferably carried out at ambient temperature, particularly at temperatures ranging from -5 to 50°C, preferably from 0 to 40°C, and especially from 5 to 35°C.

[0176] If the components are mixed before application, it must be ensured that no excessive time elapses between mixing and application; otherwise, the onset of the reaction and the associated increase in viscosity can lead to problems such as insufficient leveling or delayed or incomplete adhesion to the substrate. More specifically, the open time of the composition should not be exceeded during application.

[0177] "Open time" here refers to the time between the mixing of the components and the completion of the process to a state suitable for processing. Open time can also be called "processing time". The time until a non-sticky surface is formed ("non-sticky time") is a measure of open time.

[0178] As the ingredients or components are mixed, the composition begins to solidify through the initiation of a chemical reaction.

[0179] Based on the observed effects, it can be assumed that the activated methylene group of formula (II) reacts with the aldehyde imine group of formula (I), thus becoming activated and reactive to the isocyanate group. The reaction of the activated aldehyde imine group with the isocyanate group leads to crosslinking of the polymer containing the isocyanate group to form a urea group. Unlike the case of hydrolytic activation of the aldehyde imine group, the aldehyde is not released but is permanently retained in the composition in a derivatized form (presumably as an adduct with compound V or its transformation product). Furthermore, the isocyanate group can react with the water present, or especially with the methylene group of formula (II) in the case of aromatic isocyanate groups.

[0180] Curing is preferably carried out at ambient temperature, particularly at temperatures ranging from -5 to 50°C, and preferably from 0 to 40°C.

[0181] The curing reaction proceeds reliably without bubble formation or odor. The aldehyde derivatives retained in the composition show no signs of migration, and they do not have any plasticizing effect on the cured composition.

[0182] The present invention also provides a cured composition obtained from a curable composition after mixing and then curing the components or parts.

[0183] The cured composition preferably has high strength, good ductility and high tear resistance.

[0184] The cured composition preferably has a tensile strength of at least 5 MPa, particularly at least 7 MPa, and—for certain hard compositions with a Shore D hardness greater than 60—particularly a tensile strength of at least 15 MPa, which is determined according to DIN EN 53504 on dumbbell-shaped specimens (75 mm in length, 30 mm in beam length, 4 mm in beam width, and 2 mm in thickness) at a tensile rate of 200 mm / min.

[0185] The cured composition preferably has an elongation at break of at least 50%, particularly at least 100%, as determined according to DIN EN 53504 on dumbbell-shaped specimens (75 mm in length, 30 mm in beam length, 4 mm in beam width, and 2 mm in thickness) at a tensile rate of 200 mm / min.

[0186] The cured composition preferably has a tear resistance of at least 7 N / mm, more preferably at least 10 N / mm, and for certain hard compositions with a Shore D hardness greater than 60, a tear resistance of at least 25 N / mm, especially at least 50 N / mm, which is determined according to DIN ISO 34-1 Method B (angular specimen) with a specimen thickness of 2 mm and a tensile rate of 500 mm / min.

[0187] This curable composition is suitable for a variety of applications. In particular, it can be used as a coating, adhesive, sealant, casting resin, or scraping coating, especially as an elastic to viscoelastic coating or adhesive.

[0188] The present invention also provides the use of curable compositions as elastic or viscoelastic coatings or adhesives, wherein the ingredients or components are mixed with each other and the mixed composition is applied in a liquid state to at least one substrate.

[0189] Suitable substrates, especially:

[0190] – Glass, glass ceramics, concrete, mortar, cement flooring (Zementestrich), fiber cement, brick, tile, plaster or natural stone such as granite or marble;

[0191] – Repair or leveling compounds based on PCC (polymer-modified cement mortar) or ECC (epoxy resin-modified cement mortar);

[0192] - Metals or alloys, such as aluminum, iron, steel, copper, and other non-ferrous metals, including surface-finished metals or alloys, such as galvanized or chromium-plated metals;

[0193] – Asphalt or tar;

[0194] – Leather, textiles, paper, wood, wood-based materials bonded with resins (such as phenolic resins, melamine resins, or epoxy resins), resin-fabric composites, or other so-called polymer composites;

[0195] - Plastics, such as rigid and flexible PVC, polycarbonate, polystyrene, polyester, polyamide, PMMA, ABS, SAN, epoxy resin, phenolic resin, PUR, POM, TPO, PE, PP, EPM or EPDM, in each case untreated or surface-treated, for example by plasma, corona or flame.

[0196] - Fiber-reinforced plastics, such as carbon fiber reinforced plastics (CFK), glass fiber reinforced plastics (GFK), natural fiber reinforced plastics (NFK), and sheet molding compounds (SMC);

[0197] – Insulation materials, especially foams, particularly EPS, XPS, PUR, PIR, aerogel, or foamed glass (foamed glass), or fibers of asbestos or glass wool,

[0198] - Coated or painted substrates, especially painted ceramic tiles, coated concrete, powder-coated metals or alloys, or painted metal sheets.

[0199] – Paint, varnish or varnish.

[0200] If necessary, the substrate can be pretreated before application, especially by physical and / or chemical cleaning methods or by applying an activator or primer.

[0201] It can bond and / or seal two identical or different types of substrates.

[0202] The use of the curable composition provides an article. The article can be a building structure or part thereof, particularly a building structure, bridge, roof, stairwell or facade of a building above or below ground, or it can be an industrial or consumer product, particularly windows, pipes, rotor blades of wind turbines, household appliances or modes of transport, such as, in particular, automobiles, buses, trucks, rail vehicles, ships, airplanes or helicopters, or their mounting components.

[0203] Example

[0204] Examples are given below, which are intended to further illustrate the invention described herein, but the invention is by no means limited to these described examples.

[0205] "Standard climatic conditions" ("NK") refer to a temperature of 23±1℃ and a relative humidity of 50%±5%.

[0206] Unless otherwise stated, the chemicals used are from Merck.

[0207] Using a constant-temperature Rheotec RC30 cone-plate viscometer (cone diameter 10 mm, cone angle 1°, cone tip-plate distance 0.05 mm, shear rate 10 s), -1 Viscosity was measured using a cone with a diameter of 50 mm and a 100s pulse. -1 The shear rate was measured for viscosity less than 0.5 Pa·s.

[0208] Infrared spectroscopy (FT-IR) of an undiluted film was measured on a Nicolet iS5 FT-IR instrument from Thermo Scientific equipped with a horizontal ATR measurement unit with a diamond crystal.

[0209] Preparation of aldehyde imine:

[0210] Aldehydeimine A-1:

[0211] 212.2 g (2 mol) of benzaldehyde was pre-placed under a nitrogen atmosphere, and 158.3 g (1 mol) of 2,2(4),4-trimethylhexane-1,6-diamine (Vestamin) was added with good stirring. ® TMD (from Evonik) was then removed under reduced pressure at 80 °C and 10 mbar to remove volatile components. 333.6 g of N,N'-dibenzyl-2,2(4),4-trimethylhexane-1,6-diamine was obtained as a transparent pale yellow liquid with an amine value of 335 mg KOH / g and an aldehyde imine equivalent of 167.3 g / eq.

[0212] Aldehydeimine A-2:

[0213] 106.1 g (1 mol) of benzaldehyde was pre-placed under a nitrogen atmosphere, and 124.0 g (1 mol NH2) of polyoxypropylene diamine (Jeffamine) was added under good stirring. ® D-230 (from Huntsman), and then the volatile components were removed under reduced pressure of 80 °C and 10 mbar. 210.7 g of a clear, pale yellow liquid was obtained, with a viscosity of 0.34 Pa·s at 20 °C, an amine value of 265 mgKOH / g, and an aldehyde-imine equivalent of 212 g / eq.

[0214] Aldehydeimine A-3:

[0215] Under a nitrogen atmosphere, 50.00 g of aldehyde-1 (0.17 mol aldehyde group) was pre-placed, and 13.93 g (0.08 mol) of isophorone diamine (Vestamin® IPD, from Evonik) was added with good stirring. Volatile components were then removed at 80 °C and a reduced pressure of 10 mbar. A clear, pale yellow liquid was obtained with an amine value of 144 mg KOH / g and an aldehyde imine equivalent of 390 g / eq.

[0216] Aldehyde-1 is mainly composed of branched 4-(C 10-14 The reaction mixture of alkylbenzaldehyde, with an average aldehyde equivalent of 290 g / eq, was produced by C24-catalyzed by Hf-BF3. 10-14 - It is obtained by the formylation of alkylbenzene.

[0217] Aldehydeimine A-4:

[0218] 212.2 g (2 mol) of benzaldehyde was pre-placed under a nitrogen atmosphere. A mixture of 51.1 g (0.5 mol) pentane-1,5-diamine (from Cathay Biotech) and 58.1 g (0.5 mol) hexane-1,6-diamine was added with good stirring. Volatile components were then removed under reduced pressure of 10 mbar and 80 °C. 289.8 g of a clear, pale yellow liquid was obtained, with a viscosity of 0.09 Pa·s at 20 °C, an amine value of 393 mg KOH / g, and an aldehyde-imine equivalent of 142.7 g / eq.

[0219] Preparation of compounds with activated methylene groups:

[0220] Compound B-1:

[0221] 522.1 g (3.3 mol) of tert-butyl acetoacetate was added to 134.2 g (1 mol) of 1,1,1-trimethylolpropane, and the mixture was reacted under reduced pressure at 140 °C until the FT-IR readings were within the range of 3300–3600 cm⁻¹. -1 The broad OH band disappeared within the range, and no more volatile substances separated out. 367.3 g of 1,1,1-trimethylolpropane triacetate was obtained, which was a clear, pale yellow liquid with a viscosity of 0.27 Pa·s at 20 °C and a theoretical acetate equivalent of 129 g / eq.

[0222] Compound B-2:

[0223] 348.0 g (2.2 mol) of tert-butyl acetoacetate was added to 146.1 g (1 mol) of isosorbide, and the mixture was reacted under reduced pressure at 140 °C until the FT-IR readings were within the range of 3300–3600 cm⁻¹. -1The broad OH band disappeared within the range, and no more volatile substances separated. 310.6 g of isosorbide diacetate was obtained, which was a clear, pale yellow liquid with a viscosity of 0.91 Pa·s at 20 °C and a theoretical acetate equivalent of 157 g / eq.

[0224] Compound B-3:

[0225] 506.2 g (3.2 mol) of tert-butyl acetoacetate was added to 92.1 g (1 mol) of glycerol (=1,2,3-trihydroxypropane), and the mixture was reacted under reduced pressure at 140 °C until the FT-IR output reached 3300–3600 cm⁻¹. -1 The broad OH band disappeared within the range, and no more volatile substances separated out. 327.6 g of glycerol triacetyl acetate was obtained, which was a clear, pale yellow liquid with a viscosity of 0.12 Pa·s at 20 °C and a theoretical acetyl acetate equivalent of 114.7 g / eq.

[0226] Compound B-4:

[0227] 348.0 g (2.2 mol) of ethyl acetoacetate and 0.45 g of tetrabutyl titanate were added to 104.1 g (1 mol) of neopentyl glycol (=2,2-dimethylpropane-1,3-diol). The mixture was reacted under reduced pressure at 140 °C until the FT-IR readings were within the range of 3300–3600 cm⁻¹. -1 The broad OH band disappeared within the range, and no more volatile substances separated out. 254.1 g of neopentyl glycol diacetate was obtained, which was a clear, pale yellow liquid with a viscosity of <0.05 Pa·s at 20 °C and a theoretical acetate equivalent of 136 g / eq.

[0228] Other substances and abbreviations used:

[0229]

[0230] Preparation of curable compositions:

[0231] Examples Z-1 to Z-30:

[0232] For each embodiment, the components of the first component (K1) specified in Tables 1 to 4 are mixed in a specified amount (in parts by weight) and stored in a sealed container.

[0233] The components of the second component (K2) are also mixed in the amounts (by weight) described in Tables 1 to 4 and stored in a sealed container.

[0234] If present, the composition of the third component (K3) is used in the amounts described in Tables 1 to 4.

[0235] Subsequently, the components of each composition were processed using a centrifugal mixer to obtain a homogeneous liquid, which was then tested as described below.

[0236] The gelation time (the time between mixing components and gelation) is determined by stirring 10g of the mixed composition with a spatula at regular intervals until the substance gels.

[0237] Mechanical properties were determined by pouring the composition onto a PTFE-coated membrane to obtain a 2 mm thick membrane, which was cured by storage under standard climatic conditions for 14 days. Multiple dumbbell-shaped test specimens (75 mm in length, 30 mm in beam length, and 4 mm in beam width) were stamped from the membrane and tested according to DIN EN 53504 at a tensile rate of 200 mm / min for maximum tensile strength, elongation at break, and 5% modulus of elasticity (between 0.5% and 5% elongation). Additionally, multiple test specimens were stamped to determine tear resistance and tested according to DIN ISO 34-1, Method B (angular test specimens) at a tensile rate of 500 mm / min.

[0238] Shore hardness was determined according to DIN 53505 on cylindrical specimens (20 mm in diameter and 5 mm in thickness) after storage under standard climatic conditions for 14 days.

[0239] Odor was evaluated by smelling the freshly prepared membrane at a distance of 2 cm. "0" indicates no detectable aldehyde odor. "+", "++", or "++++" indicates a detectable slight, noticeable, or strong aldehyde odor.

[0240] The tendency for bubble formation was determined by applying a freshly mixed composition to a glass plate in a 500 μm thick layer, immediately followed by storage in a climate-controlled chamber at 30°C and 80% relative humidity for 24 hours, and then evaluating the results. "0" indicates no bubbles. "+", "++", or "++++" indicates few, some, or many bubbles.

[0241] In each case, curing yields a non-sticky polymer material.

[0242] The results are reported in Tables 1 to 4.

[0243] Examples marked "(Ref.)" are comparative examples.

[0244]

[0245]

[0246]

[0247]

Claims

1. A curable composition comprising: – At least one aldimine L having an aldimine group of formula (I) Where Z is an organic group having 1 to 25 carbon atoms. –Optionally, at least one polyol – at least one polyisocyanate, and – At least one compound V having an activated methylene group of formula (II) Where Y is the expression , , or The group R is a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R 1 It is an alkyl group having 1 to 6 carbon atoms. Based on the total composition, the ratio of the number of isocyanate groups to the total number of aldehyde imine groups plus hydroxyl groups is at least 0.9, and the ratio of the number of activated methylene groups in formula (II) to the number of aldehyde imine groups in formula (I) is at least 1.

2. The composition according to claim 1, characterized in that The aldimine L has 2-3 aldimine groups of formula (I) and an aldimine equivalent of 110-2500 g / eq, or an average aldimine equivalent of 110-2500 g / eq in the case of oligomeric or polymeric aldimine L.

3. The composition according to any one of claims 1 or 2, characterized in that, Z is an aliphatic hydrocarbon group having 3 to 11 carbon atoms bonded via primary or secondary carbon atoms, or an aromatic or heteroaromatic five- or six-membered ring optionally substituted and / or fused and containing a total of 4 to 25 carbon atoms. Z is specifically selected from the list of the following compositions: 1-propyl, 2-propyl, 1-butyl, 1-pentyl, 1-heptyl, 3-heptyl, 1-undecyl, phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 4-C 10-14 -alkylphenyl, 2,5-dimethylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-ethoxyphenyl, 3-ethoxyphenyl, 4-ethoxyphenyl, 4-propoxyphenyl, 4-isopropoxyphenyl, 4-butoxyphenyl, 4-pentoxyphenyl, 4-decoxyphenyl, 4-dodecyloxyphenyl, 2,3-dimethoxyphenyl, 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-furanyl, 5-methyl-2-furanyl, thiophene, pyridine, pyrrole, and quinoline.

4. The composition according to any one of claims 1 to 3, characterized in that The aldehyde imine L is an aldehyde imine of formula (IIIa) or (IIIb). in n is 2 or 3 G 1 It consists of divalent or trivalent polyoxyalkylene groups with an average molecular weight Mn of 800 to 6000 g / mol, and G 2 It is an n-valent organic group having 2 to 25 carbon atoms.

5. The composition according to any one of claims 1 to 4, characterized in that It contains at least one polyol P with an OH value of 14-280 mg KOH / g, preferably 28-112 mg KOH / g.

6. The composition according to claim 5, characterized in that... The weight ratio of the aldehyde imine L, especially the aldehyde imine of formula (IIIb), to the polyol P is in the range of 2 / 98 to 50 / 50, preferably 3 / 97 to 40 / 60, especially 4 / 96 to 30 / 70.

7. The composition according to any one of claims 1 to 6, characterized in that, The polyisocyanate has an NCO content of 8% to 35% by weight, preferably 10% to 33% by weight, based on the polyisocyanate. The polyisocyanates are particularly selected as room-temperature liquid oligomers and derivatives of acetylene-1,6-diisocyanate, isophorone diisocyanate, toluene-2,4(6)-diisocyanate and diphenylmethane diisocyanate, as well as polymeric diphenylmethane diisocyanate, each of which may contain reaction products with polyols.

8. The composition according to any one of claims 1 to 7, characterized in that Compound V has an equivalent of 100 to 2100 g / eq, preferably 114 to 600 g / eq, particularly 114 to 400 g relative to the activated methylene group of formula (II), or in the case of oligomeric or polymeric compound V, an average equivalent of 100 to 2100 g / eq, preferably 114 to 600 g / eq, particularly 114 to 400 g, and a functionality of 1 to 4, preferably 1.5 to 3.5, particularly 1.8 to 3, or in the case of oligomeric or polymeric compound V, an average functionality of 1 to 4, preferably 1.5 to 3.5, particularly 1.8 to 3.

9. The composition according to any one of claims 1 to 8, characterized in that, Based on the total composition, the ratio of the number of activated methylene groups in formula (II) to the number of aldehyde imine groups in formula (I) is in the range of 1 to 4, preferably 1.2 to 3, more preferably 1.5 to 2.

5.

10. The composition according to any one of claims 1 to 9, characterized in that, Y is a formula The group, wherein R is preferably methyl and the activated methylene group of formula (II) is therefore an acetoacetate group, Compound V is specifically selected from ethyl acetoacetate, propane-1,2-diol diacetoacetate, dipropylene glycol diacetoacetate, tripropylene glycol diacetoacetate, propane-1,3-diol diacetoacetate, butane-1,4-diol diacetoacetate, 2-methylpropane-1,3-diol diacetoacetate, pentane-1,5-diol diacetoacetate, neopentane glycol diacetoacetate, hexane-1,6-diol diacetoacetate, 3-methylpentane-1,5-diol diacetoacetate, 2-ethylhexane-1,3-diol diacetoacetate, glycerol diacetoacetate, glycerol triacetoacetate, 1,1,1-tris(hydroxymethyl)ethane diacetoacetate, 1, 1,1-Trimethylolethane triacetate, 1,1,1-Trimethylolpropane diacetate, 1,1,1-Trimethylolpropane triacetate, propoxylated and / or ethoxylated 1,1,1-trimethylolpropane triacetate, propoxylated and / or ethoxylated glycerol triacetate, poly(oxy-1,2-propylene) glycol bis(acetate), poly(oxy-1,2-propylene) glycol bis(acetate) containing ethylene oxide units, castor oil bis(acetate), castor oil tri(acetate), polyester glycol bis(acetate) based on dimeric fatty acids, and polyester triol tri(acetate) based on trimeric fatty acids.

11. The composition according to any one of claims 1-10, characterized in that It contains at least one other component selected from crosslinking agents, catalysts, desiccants, fillers, and pigments.

12. The composition according to any one of claims 1 to 11, characterized in that The composition comprises components K1 and K2, and optional component K3, each of which is individually storage-stable and stored in separate containers.

13. The composition according to claim 12, characterized in that, – Aldehydeimine L and optional polyol are part of component K1, polyisocyanate is part of component K2, and compound V is part of component K2 or exists as a separate component K3, or – Compound V and optional polyol are part of component K1, and aldehyde imine L and polyisocyanate are part of component K2.

14. A cured composition, said cured composition being obtained from a curable composition according to any one of claims 1 to 13 after mixing the ingredients or components and then curing.

15. Use of the curable composition as an elastic or viscoelastic coating or adhesive according to any one of claims 1 to 13, wherein the ingredients or components are mixed with each other, and the mixed composition is applied to at least one substrate in a liquid or paste state.

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