A polymer composition curable at room temperature, produced from a polyaldehyde and a polycyanoacetate

Abstract

The present invention relates to a curable composition containing a first component containing an aldehyde group-containing compound containing at least one compound having two or more aldehyde groups, and a second component containing a cyanoacetate group-containing compound containing at least one compound having two or more cyanoacetate groups, wherein the average molecular weight Mn of the first component and the second component with respect to the compound containing an aldehyde group or a cyanoacetate group is in the range of 400 to 20,000 g / mol, and the average functionality of at least one of the two components with respect to the compound containing an aldehyde group or a cyanoacetate group is greater than 2.0. This composition contains almost no toxic components, cures in a rapid and problem-free manner under ambient conditions using a conventional catalyst, and forms a non-tacky elastic polymer having high strength, high elasticity, and high tear propagation resistance. This composition is particularly suitable for use as an elastic adhesive, sealant, or coating having high robustness during production, storage, and processing and high resistance after curing.

Description

Technical Field

[0001] The present invention relates to a two-component composition and its use as an adhesive, sealant, or coating that can be cured at room temperature.

Background Art

[0002] Reactive polymer compositions that are curable at room temperature and can be used as adhesives, sealants, or coatings having elastic properties are known. Polyurethane systems that cure by the reaction of isocyanate groups with polyols and / or moisture and form particularly highly elastic polymers are widely used. The formulation, manufacture, and use of polyurethane systems actually involve a series of problems. These usually contain a large amount of monomeric diisocyanates that can potentially irritate the eyes, skin, and mucous membranes. The sensitivity of isocyanate groups to moisture causes premature cross-linking reactions related to viscosity increase to gelation, which can consequently impair the shelf life and storage stability. In the case of systems formulated in one-component form, the moisture required for curing must penetrate from the outside in the form of atmospheric moisture, making use between thick layers or substrates impermeable to moisture cumbersome. In the case of two-component systems containing a polyol component and an isocyanate component, there is a problem that isocyanate groups can react not only with the hydroxyl groups of the polyol but also with any moisture present. Especially when the ambient humidity is high, this causes the formation of air bubbles, leading to incomplete polymerization with chain termination due to incompletely incorporated polyol, and there is a possibility that strength and elasticity are lost to some extent. These problems hardly occur when using mercury catalysts that very selectively catalyze the reaction with polyols. However, mercury catalysts are highly toxic and have not been usable for quite some time. As an alternative, two-component polyurethanes are often catalyzed with tin compounds and / or tertiary amines, but these have significantly low selectivity. This means that air bubbles may be formed, especially when the ambient humidity is high. Bismuth catalysts and zirconium catalysts have high selectivity, but these and other alternative metal catalysts are sensitive to hydrolysis. This means that the catalytic activity can be greatly lost, leading to curing defects.

[0003] Silane-functional polymers (SMP / STP) and silicone-based reactive polymer compositions are also widely used. These polymer systems cure by hydrolysis and condensation of silane groups, releasing alcohol, especially methanol or ethanol, or oxime. These are toxic and cause VOC emissions. In addition, they usually contain a large amount of low molecular weight silane as a crosslinking agent or desiccant, which is also harmful to health. Due to the sensitivity of silane groups to moisture, these polymer systems are demanding in terms of production and use, and do not always give desirable results.

[0004] Also, aqueous polymer systems are known, which are usually based on acrylate dispersions or polyurethane dispersions. These cure by evaporation and coalescence of water and contain few chemically reactive groups. However, these can only be used in relatively thin layers and only between open-cell substrates. The curing rate is highly dependent on the ambient humidity and has a high shrinkage rate. After curing, surfactants required for the production and stability of the dispersion are present, increasing the sensitivity to moisture and potentially reducing durability, especially for outdoor applications.

[0005] U.S. Patent No. 2020 / 0257202 describes the reaction of polymeric dicyanoacetate with aromatic dialdehyde in a solvent and the application of the resulting solution to glass to form a pressure-sensitive film. SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION

[0006] Accordingly, an object of the present invention is to provide a novel polymer composition that can be cured at room temperature and is suitable as an elastic adhesive, sealant, or coating, overcoming the drawbacks of known polymer systems. MEANS FOR SOLVING THE PROBLEM

[0007] Surprisingly, this object is achieved by the curable composition according to claim 1. This composition includes a first component containing a compound having an aldehyde group and a second component containing a compound having a cyanoacetate group, and the average molecular weight M of the first component and the second component with respect to the compound having an aldehyde group or a cyanoacetate group n is in the range of 400 to 20,000 g / mol, and the average functionality of at least one of the two components with respect to the compound having an aldehyde group or a cyanoacetate group is greater than 2.0. This composition has several advantageous and surprising properties over polymer systems curable at room temperature according to the prior art.

[0008] Compounds containing an aldehyde group and compounds containing a cyanoacetate group are both substances with low concern for toxicity, do not require hazard labeling, and can be handled without special precautions. The composition of the present invention is not sensitive to moisture and bubble formation and achieves a high degree of formulation freedom. This is because it is possible to use additives generally used in curable compositions for both components without causing problems in the storage stability of each component. This means that the mixing ratio of the two components can be adjusted almost infinitely, enabling a highly flexible processing method. The composition has excellent processability under ambient conditions without the need for an organic solvent for dissolution or dilution, or water for emulsification or dispersion of the components. The composition cures surprisingly quickly and perfectly under ambient conditions without generating emissions regardless of humidity. What is particularly advantageous here is that the curing rate can be very efficiently controlled by common catalysts, especially non-metallic bases such as tertiary amines, amidines, or guanidines. Upon curing, a non-sticky elastic polymer with high strength and surprisingly high elongation and excellent stability against heat and water is obtained. Of particular note is the very high tear propagation resistance of the cured polymer, which makes it particularly resistant to large mechanical stresses. Due to this combination of advantageous properties, the composition of the present invention can be handled particularly easily without special protective means and has high robustness and a long lifespan in any of the manufacture and storage of the components, its use under a wide range of ambient and application conditions, and after curing under mechanical, thermal, or chemical stress.

[0009] Therefore, the composition of the present invention is very well suited for use as a high-quality elastic adhesive, sealant, or coating.

[0010] A further aspect of the present invention is the subject matter of the further independent claims. Particularly preferred embodiments of the present invention are the subject matter of the dependent claims.

Mode for Carrying Out the Invention

[0011] The present invention relates to ·A first component containing an aldehyde group-containing compound including at least one compound having two or more aldehyde groups, ·A second component containing a cyanoacetate group-containing compound including at least one compound having two or more cyanoacetate groups, A curable composition containing the same, wherein the average molecular weight M of the first component and the second component with respect to the compound containing an aldehyde group or a cyanoacetate group n is in the range of 400 to 20,000 g / mol, and the average functionality of at least one of the two components with respect to the compound containing an aldehyde group or a cyanoacetate group is greater than 2.0, to provide a curable composition.

[0012] "Aldehyde group" refers to the functional group of the formula bonded by a dotted line

Chemical formula

[0013] "Cyanoacetate group" refers to the functional group of the formula bonded by a dotted line

Chemical formula

[0014] "Molecular weight" refers to the molar mass of a molecule (gram / mol). "Average molecular weight" refers to the number average molecular weight (M n ) of a polydisperse mixture of oligomer molecules or polymer molecules. This is determined by gel permeation chromatography (GPC) using polystyrene as a standard.

[0015] When the composition is "storage stable", it means that it can be stored in a suitable container at room temperature for a long period, typically at least 3 months to a maximum of 6 months or more, and no change occurs in its use and use characteristics to the extent related to its use due to this storage.

[0016] Substance names starting with "poly", such as polycyanoacetate, polyaldehyde, and polyol, formally refer to substances containing two or more functional groups per molecule included in their names.

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

[0018] All industry standards and benchmarks mentioned in this specification relate to the versions effective as of the first filing date.

[0019] Weight percent (wt%) refers to the mass fraction of the components of a composition or molecule based on the whole composition or whole molecule, unless otherwise specified. The terms "mass" and "weight" are used synonymously in this specification.

[0020] The first and second components of the curable composition are essentially storage-stable and are stored in separate containers until they are mixed with each other immediately before or during application.

[0021] The curable composition is preferably not aqueous. This preferably contains little or only a small amount of water. Such a composition cures rapidly regardless of the ambient humidity, can be used between thick layers and / or waterproof substrates, and shows little shrinkage upon curing.

[0022] Preferably, the curable composition contains less than 10 wt%, preferably less than 5 wt%, particularly less than 2 wt% of water based on the whole composition.

[0023] In a preferred embodiment of the present invention, the composition contains a small amount of water. The water here functions as an accelerator for curing. For this purpose, the water is in an amount of 0.05 wt% to 5 wt%, particularly 0.1 wt% to 2 wt% based on the whole composition.

[0024] The curable composition does not contain a compound having an aldehyde group or a cyanoacetate group, preferably in the form of an emulsion or a dispersion. Therefore, the compound having an aldehyde group or a cyanoacetate group present preferably contains few ionic groups or precursors thereof and few relatively long poly(oxyethylene) chains typical of surfactants. Such a composition has high resistance to water. In particular, the compound containing an aldehyde group in the first component and the compound containing a cyanoacetate group in the second component each have an acid group or ionic group content of less than 0.1% by weight, preferably less than 0.05% by weight, based on the compound containing an aldehyde group or the compound containing a cyanoacetate group. The ionic group is particularly a carboxylate group, an ammonium group, or a sulfonate group.

[0025] In the curable composition, the average molecular weight M of the first component and the second component with respect to the compound containing an aldehyde group or a cyanoacetate group n is in the range of 400 to 20,000 g / mol. This enables a polymer having high elongation.

[0026] Preferably, at least one of the two components has an average molecular weight M with respect to the compound having an aldehyde group or a cyanoacetate group in the range of 1000 to 20,000 g / mol, preferably 1500 to 15,000 g / mol, particularly 2000 to 10,000 g / mol. n This enables particularly high elongation.

[0027] In the curable composition, the average functionality of at least one of the two components with respect to the aldehyde group or the cyanoacetate group is greater than 2.0. Therefore, if the average aldehyde functionality of the first component is 2.0 or less, the average cyanoacetate functionality of the second component must be greater than 2.0. Also, if the average cyanoacetate functionality of the second component is 2.0 or less, the average aldehyde functionality of the first component must be greater than 2.0. Such a composition cures to give an elastic polymer having high strength and high stability.

[0028] More preferably, the average aldehyde functionality of the first component and the average cyanoacetate functionality of the second component are each greater than 2.0, particularly in the range of 2.2 to 3.0. This enables the formation of polymers having excellent elongation while having high strength and stability.

[0029] The compound having two or more aldehyde groups is preferably a liquid at room temperature. Specifically, this is measured with a cone plate viscometer having a cone diameter of 10 mm, a cone angle of 1°, a distance between the cone tip and the plate of 0.05 mm, a shear rate of 10 s -1 and, for viscosities less than 1 Pa·s, with a ball diameter of 50 mm, and has a viscosity of 0.2 to 700 Pa·s, preferably 0.3 to 500 Pa·s, more preferably 0.5 to 200 Pa·s, particularly 1 to 100 Pa·s at 20°C. Such compounds can be easily handled at ambient temperature without adding solvents or diluents.

[0030] Preferred compounds containing an aldehyde group are polymers having an aldehyde group.

[0031] Preferably, the average molecular weight M n of the first component with respect to the compound containing an aldehyde group, when measured by gel permeation chromatography (GPC) relative to polystyrene as a standard, is in the range of 1000 to 20000 g / mol, preferably 1500 to 15000 g / mol, particularly 2000 to 10000 g / mol. Such components can be easily handled at ambient temperature without adding solvents or diluents, enabling the formation of polymers having high elongation and elasticity.

[0032] Preferably, the average aldehyde functionality of the compound containing an aldehyde group is in the range of 1.6 to 4, preferably 1.8 to 3.5, more preferably 2.0 to 3.0, particularly 2.2 to 3.0. This enables the formation of cured compositions having high elongation, strength, and stability.

[0033] Compounds containing an aldehyde group preferably include polymers having a polymer backbone containing poly(oxyalkylene) units and / or polyester units.

[0034] Preferred poly(oxyalkylene)s are poly(oxyethylene), poly(oxy-1,2-propylene), poly(oxy-1,3-propylene), poly(oxy-1,4-butylene), poly(oxy-1,2-butylene), or a mixed form of these poly(oxyalkylene)s. Among these, poly(oxy-1,2-propylene), poly(oxy-1,3-propylene), or poly(oxy-1,4-butylene), particularly poly(oxy-1,2-propylene), is preferred, and the latter may contain poly(oxyethylene) units in a content of 0% to 25% by weight based on the poly(oxyalkylene) backbone, particularly at the chain ends. Aldehyde-functional polymers having such a backbone have a low viscosity and are thus particularly efficiently handleable and particularly hydrophobic. These enable compositions having particularly excellent processability, high elongation, and excellent water resistance.

[0035] Preferred polyesters are esters of dicarboxylic acids and diols or triols, triglycerides, or polyesters based on dimer fatty acids or trimer fatty acids. Polyesters of dimer fatty acids, or polyesters derived from castor oil, derivatives of castor oil, or vegetable oils are particularly preferred. Aldehyde-functional polymers having such a backbone are particularly hydrophobic and enable compositions having particularly high resistance to heat and water. Also, since these are based on renewable raw materials, they are particularly sustainable.

[0036] Compounds having two or more aldehyde groups preferably further contain urethane groups. Thereby, compositions having particularly high elongation and particularly high tear propagation resistance are obtained.

[0037] Preferably, the compound containing an aldehyde group is liquid at room temperature and has an average molecular weight M of 1000 to 20000 g / mol, preferably 1500 to 15000 g / mol, particularly 2000 to 10000 g / mol. n It contains a urethane group-containing polymer having an average aldehyde functionality of 1.8 to 3.5, more preferably 2.0 to 3.0, particularly 2.2 to 3.0.

[0038] Preferably, the compound having two or more aldehyde groups is obtained from the reaction of at least one hydroxyaldehyde with at least one isocyanate group-containing polymer or at least one polyisocyanate.

[0039] Suitable hydroxyaldehydes are, in particular, compounds having a molecular weight in the range of 60 to 500 g / mol, preferably 60 to 250 g / mol.

[0040] The following are particularly suitable: 2-hydroxyacetaldehyde, 3-hydroxybutanal, 3-hydroxypivalaldehyde, 5-hydroxypentanal, 2-(2-hydroxyethoxy)acetaldehyde, 3-(2-hydroxyethoxy)propanal, 5-hydroxymethylfurfural, alkoxylated o-, m-, or p-hydroxybenzaldehyde or alkoxylated vanillin ( "alkoxylated" preferably means (single or plural) "ethoxylated" or "propoxylated"), and 4,4'-(2-hydroxypropane-1,3-diyl)bis(oxy)bis(benzaldehyde) or 4,4'-(2-hydroxypropane-1,3-diyl)bis(oxy)bis(3-methoxybenzaldehyde).

[0041] Ethoxylated salicylaldehyde, especially 2-(2-hydroxyethoxy)benzaldehyde, ethoxylated vanillin, especially 4-(2-hydroxyethoxy)-3-methoxybenzaldehyde, or 5-hydroxymethylfurfural is preferred. These hydroxyaldehydes can be obtained by a simple method, which enables compounds containing an aldehyde group, having low viscosity, and thus excellent handleability, as well as compositions having very high elongation together with excellent processability and high strength.

[0042] A particularly preferred hydroxyaldehyde is 5-hydroxymethylfurfural. This hydroxyaldehyde is obtained from renewable raw materials and surprisingly enables a particularly low-viscosity compound having an aldehyde group, as well as a curable composition having particularly excellent processability, high strength, elongation, tear propagation resistance, heat resistance, and water resistance.

[0043] Isocyanate group-containing polymers suitable for the preparation of compounds having two or more aldehyde groups are especially reaction products of a polyol and a diisocyanate, especially those having an NCO / OH molar ratio of 1.5 / 1 to 10 / 1, and optionally those from which unreacted monomeric diisocyanate has been removed from the polymer.

[0044] The isocyanate group-containing polymer preferably has a free isocyanate group content in the range of 0.5% to 15% by weight, more preferably 1% to 10% by weight, especially 1.5% to 6% by weight, based on the polymer.

[0045] A very preferred isocyanate group-containing polymer is a reaction product obtained by reacting at least one diisocyanate and at least one polyol at an NCO / OH ratio of at least 3 / 1, preferably 3 / 1 to 10 / 1, especially 4 / 1 to 8 / 1, and then removing most of the monomeric diisocyanate by a suitable separation method so that the isocyanate group-containing polymer finally has a monomeric diisocyanate content of 0.2% by weight or less based on the polymer.

[0046] Such isocyanate group-containing polymers enable the production of aldehyde-functional polymers with a particularly low content of reaction products of monomeric diisocyanates and hydroxyaldehydes, specifically less than 0.5% by weight of these reaction products based on the aldehyde-functional polymer. This enables the production of curable compositions that have a long open time, rapid curing, and particularly excellent flexibility, and are particularly easy to process.

[0047] Suitable diisocyanates are, in particular, hexane 1,6-diisocyanate (HDI), 2,2(4),4-trimethylhexane 1,6-diisocyanate (TMDI), 1-methyl-2,4(6)-diisocyanatocyclohexane (H6TDI), isophorone diisocyanate (IPDI), 4,4'-diisocyanatodicyclohexylmethane (H 12 MDI), 4(2),4'-diphenylmethane diisocyanate (MDI), or toluene 2,4(6)-diisocyanate. HDI, IPDI, TDI, or MDI are preferred. Particularly preferred is IPDI. This gives a composition with particularly excellent processability that cures to give a polymer having high strength and high elongation.

[0048] Suitable polyols are, in particular, the following: · Polyether polyols, especially polyoxyalkylene diols or polyoxyalkylene triols, especially polymerization products of ethylene oxide or 1,2-propylene oxide or 1,2- or 2,3-butylene oxide or oxetane or tetrahydrofuran or mixtures thereof. These can be polymerized with the aid of starter molecules having two or more active hydrogen atoms, especially starter molecules such as water, ammonia, or compounds having two or more OH or NH groups, for example ethan-1,2-diol, propane-1,2- or -1,3-diol, neopentyl glycol, diethylene glycol, triethylene glycol, isomeric dipropylene glycols or tripropylene glycols, isomeric butanediols, pentanediols, hexanediols, heptanediols, octanediols, nonanediols, decanediols, undecanediols, cyclohexane-1,3- or -1,4-dimethanol, bisphenol A, hydrogenated bisphenol A, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, glycerol, aniline, or mixtures of the above-mentioned compounds.

[0049] Preferred polyether polyols are those called polyoxypropylene diols or polyoxypropylene triols, or ethylene oxide-terminated (EO end-capped or EO tipped) polyoxypropylene diols or triols. The latter are polyoxyethylene-polyoxypropylene copolyols, which are obtained in particular by further alkoxylating polyoxypropylene diols or triols with ethylene oxide at the end of the polypropoxylation reaction, so that they finally have primary hydroxyl groups.

[0050] Preferred polyether polyols have an unsaturation of less than 0.02 meq / g, especially less than 0.01 meq / g. · Polyester polyols, especially those obtained from polycondensation of hydroxycarboxylic acids or lactones, or polycondensation of aliphatic and / or aromatic polycarboxylic acids with dihydric or polyhydric alcohols. For example, polyester polyols based on amorphous, dimer, or trimer fatty acids commercially available from Croda are preferred. · Polycarbonate polyols, such as those obtained by reaction of diols with dialkyl carbonates, diaryl carbonates, or phosgene. · Block copolymers having at least two hydroxyl groups, especially polyether polyester polyols. · Polyacrylate polyols and polymethacrylate polyols. · Polyhydroxy-functional oils, especially natural oils, such as castor oil, derivatives of castor oil; or polyols obtained by chemically modifying natural oils (referred to as oleochemical polyols), such as hydroxylated vegetable oils available under the trade name Sovermol® (from BASF). · Polyhydrocarbon polyols, such as especially polyhydroxy-functional polyolefins, polyisobutylene, polyisoprene; polyhydroxy-functional ethylene / propylene, ethylene / butylene, or ethylene / propylene / diene copolymers, such as those manufactured by Kraton Polymers; polyhydroxy-functional polymers of dienes, especially 1,3-butadiene, which can be prepared especially from anionic polymerization; polyhydroxy-functional copolymers of dienes such as 1,3-butadiene or diene mixtures with vinyl monomers such as styrene, acrylonitrile, vinyl chloride, vinyl acetate, vinyl alcohol, isobutylene, and isoprene, such as polyhydroxy-functional acrylonitrile / butadiene copolymers, which can be prepared, for example, from epoxides or aminoalcohols and carboxyl-terminated acrylonitrile / butadiene copolymers (e.g., commercially available under the names Hypro® CTBN or CTBNX or ETBN from Emerald Performance Materials); and hydrogenated polyhydroxy-functional polymers or copolymers of dienes.

[0051] A liquid polyol at room temperature is preferred.

[0052] A polyol having an OH value in the range of 9 to 115 mgKOH / g, preferably 14 to 60 mgKOH / g, particularly 18 to 40 mgKOH / g is preferred.

[0053] Polyether polyols, polyester polyols based on dimeric or trimeric fatty acids, castor oil, derivatives of castor oil, or hydroxylated vegetable oils are particularly preferred. Polyether polyols are most preferred.

[0054] Also suitable as a compound having two or more aldehyde groups is a reaction product of at least one polyisocyanate and at least one hydroxyaldehyde, particularly the hydroxyaldehyde described above.

[0055] Suitable polyisocyanates are, in particular, oligomeric diisocyanates, especially HDI biuret, such as Desmodur® N100 or N3200 (from Covestro), Tolonate® HDB or HDB-LV (from Vencorex), or Duranate® 24A-100 (from Asahi Kasei Corporation); HDI isocyanurate, such as Desmodur® N3300, N3600, or N3790BA (all from Covestro), Tolonate® HDT, HDT-LV, or HDT-LV2 (from Vencorex), Duranate® TPA-100 or THA-100 (from Asahi Kasei Corporation), or Coronate® HX (from Nippon Polyurethane Industry Co., Ltd.); HDI uretdione, such as Desmodur® N3400 (from Covestro); HDI iminooxadiazinedione, such as Desmodur® XP2410 (from Covestro); HDI allophanate, such as Desmodur® VP LS2102 (from Covestro); IPDI isocyanurate, such as Desmodur® Z4470 (from Covestro) in solution form or Vestanat® T1890 / 100 (from Evonik) in solid form; TDI oligomer, such as Desmodur® IL (from Covestro); or mixed isocyanurate based on TDI / HDI, such as Desmodur® HL (from Covestro), where "HDI" represents hexane 1,6-diisocyanate, "IPDI" represents isophorone diisocyanate, and "TDI" represents tolylene 2,4-diisocyanate or a mixture thereof with tolylene 2,6-diisocyanate. Oligomeric diisocyanates derived from HDI, especially HDI biuret, are preferred.

[0056] Preferably, the isocyanate group-containing polymer or polyisocyanate and hydroxyaldehyde react at an OH / NCO ratio of 1 / 1 to 1.2 / 1, at a temperature of 40 to 140°C, preferably 60 to 120°C, optionally in the presence of a suitable catalyst.

[0057] The curable composition contains, as a constituent of the second component, at least one compound having two or more cyanoacetate groups.

[0058] The compound having two or more cyanoacetate groups is preferably liquid at room temperature. Specifically, this is when measured with a cone plate viscometer with a cone diameter of 10 mm, a cone angle of 1°, a distance between the cone tip and the plate of 0.05 mm, a shear rate of 10 s -1 and for viscosities less than 1 Pa·s, with a ball diameter of 50 mm, it has a viscosity of 0.1 to 100 Pa·s, preferably 0.2 to 50 Pa·s, particularly 0.5 to 20 Pa·s at 20°C. Such a compound can be easily handled at ambient temperature without adding solvents or diluents, enabling an efficiently processable composition.

[0059] Preferably, the average functionality of the second component with respect to the compound containing a cyanoacetate group is in the range of 1.6 to 4, preferably 1.8 to 3.5, more preferably 2.0 to 3.0, particularly 2.3 to 3.0. This enables a cured composition having high elongation, strength, and stability.

[0060] Preferably, the average molecular weight M of the second component with respect to the compound containing a cyanoacetate group n is in the range of 400 to 10000 g / mol, preferably 500 to 2000 g / mol.

[0061] In a preferred embodiment of the present invention, the average molecular weight M of the second component n is in the range of 500 to 2000 g / mol. Such a second component enables a high-strength composition that is particularly efficiently processable.

[0062] In a more preferred embodiment of the present invention, the average molecular weight M of the second component with respect to the compound containing a cyanoacetate group n is in the range of 2000 to 10000 g / mol. Similarly, for the compound containing an aldehyde group, a high average molecular weight Mn When combined with a first component having such, such a second component enables a composition in which the mixing ratio of the two components is in the range of 1:1 in a particularly simple manner, which is particularly advantageous for certain applications, especially in the case of treatment with a static mixer.

[0063] More preferably, the second component has an average molecular weight M of 400 to 10,000 g / mol, preferably 500 to 2,000 g / mol n and contains at least one cyanoacetate-functional polymer having an average cyanoacetate functionality of 1.8 to 3.5, more preferably 2.0 to 3.0, especially 2.5 to 3.0.

[0064] Preferably, the compound having at least two cyanoacetate groups is of formula (I)

Chemical formula

[0065] Preferably, R here is methyl, ethyl, or tert-butyl, especially ethyl.

[0066] The reaction is preferably carried out at a temperature in the range of 50 to 150 °C while distilling off the released alcohol R-OH, optionally under reduced pressure, and optionally in the presence of a catalyst.

[0067] Suitable polyfunctional alcohols are commercially available compounds or polymers having two or more OH groups, for example, in particular, ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, cyclohexane-1,3-dimethanol, cyclohexane-1,4-dimethanol, diethylene glycol, dipropylene glycol, 1,1,1-trimethylolpropane, glycerol, ethoxylated or in particular propoxylated glycerol, ethoxylated or in particular propoxylated 1,1,1-trimethylolpropane, castor oil, ethoxylated or in particular propoxylated castor oil, ketone resin-modified castor oil, hydroxylated vegetable oil, dimer fatty acid diol, trimer fatty acid triol, amorphous polyester diol or triol based on dimer or trimer fatty acid, and other polyols already mentioned above in the production of isocyanate group-containing polymers, in particular poly(oxy-1,2-propylene) diol or triol, or poly(oxy-1,2-propylene) diol or triol end-capped with ethylene oxide.

[0068] Particularly preferred polyfunctional alcohols are propoxylated 1,1,1-trimethylolpropane having an average molecular weight M n of 300 to 1700 g / mol.

[0069] Other particularly preferred polyfunctional alcohols are poly(oxy-1,2-propylene) diol or triol having an average molecular weight M n of 2000 to 10000 g / mol, which may optionally be end-capped with ethylene oxide.

[0070] Other particularly preferred polyfunctional alcohols are amorphous polyester diol based on dimer fatty acid or amorphous polyester triol based on trimer fatty acid having an average molecular weight M n of 800 to 4000 g / mol.

[0071] More preferably, the compound containing a cyanoacetate group has an average molecular weight M of 500 to 2000 g / mol n Propoxylated 1,1,1-trimethylolpropane tris(cyanoacetate) having an average molecular weight M of 2000 to 10000 g / mol n Poly(oxy-1,2-propylene) diol bis(cyanoacetate) having an average molecular weight M of 2000 to 10000 g / mol n Poly(oxy-1,2-propylene) triol tris(cyanoacetate) having an average molecular weight M of 2000 to 10000 g / mol and containing ethylene oxide units n Poly(oxy-1,2-propylene) diol bis(cyanoacetate) having an average molecular weight M of 2000 to 10000 g / mol and containing ethylene oxide units n Poly(oxy-1,2-propylene) triol tris(cyanoacetate) having an average molecular weight M of 1000 to 4000 g / mol n Polyester diol bis(cyanoacetate) based on dimer fatty acid having an average molecular weight M of 1000 to 4000 g / mol, and n At least one cyanoacetate-functional polymer selected from polyester triol tris(cyanoacetate) based on trimer fatty acid having an average molecular weight M of 1000 to 4000 g / mol.

[0072] Preferably, the average functionality of the entire composition regarding the compound containing an aldehyde group and a cyanoacetate group is at least 2.2. This means that, for example, a composition having an average aldehyde functionality of 1.8 for the first component is combined with a second component having an average cyanoacetate functionality of at least 2.4, preferably, so that the average functionality of the reactive groups as a whole becomes 2.2.

[0073] More preferably, the curable composition contains urethane groups and has an average molecular weight M of 1000 to 20000 g / mol, preferably 1500 to 15000 g / mol, particularly 2000 to 10000 g / mol nand at least one polymer that is liquid at room temperature and has an average aldehyde functionality of 1.8 to 3.5, more preferably 2.0 to 3.0, particularly 2.2 to 3.0, as a constituent of the first component, and also contains a cyanoacetate group and has an average molecular weight M of 400 to 10,000 g / mol, preferably 500 to 2,000 g / mol n and at least one polymer having an average cyanoacetate functionality of 1.8 to 3.5, preferably 2.0 to 3.0, particularly 2.5 to 3.0, as a constituent of the second component. The average reactive group functionality here is preferably at least 2.2 in total.

[0074] Furthermore, the first component of the curable composition may contain a low molecular weight polyaldehyde, such as particularly hexane-1,6-dialdehyde, heptane-1,7-dialdehyde, octane-1,8-dialdehyde, nonane-1,9-dialdehyde, 2-methyloctane-1,8-dialdehyde, decane-1,10-dialdehyde, undecane-1,11-dialdehyde, dodecane-1,12-dialdehyde, hexahydrophthalaldehyde, hexahydroisophthalaldehyde, hexahydroterephthalaldehyde, octahydro-4,7-methano-1H-indenedicarbaldehyde, 3,6,9-trioxaundecane-1,11-dial, 1,3-bis(2,2-dimethyl-3-oxopropyl)imidazolidin-2-one, N,N'-bis(2,2-dimethyl-3-oxopropyl)piperazine, N,N'-bis(2,2-dimethyl-3-oxopropyl)urea, phthalaldehyde, isophthalaldehyde, terephthalaldehyde, anthracene-9,10-dicarbaldehyde, or naphthalenedicarbaldehyde in a certain proportion.

[0075] In addition, the second component of the curable composition may contain, in a certain proportion, low molecular weight polycyanoacetates, for example, in particular, ethan-1,2-diol bis(cyanoacetate), propan-1,2-diol bis(cyanoacetate), propan-1,3-diol bis(cyanoacetate), butane-1,4-diol bis(cyanoacetate), hexane-1,6-diol bis(cyanoacetate), cyclohexane-1,4-dimethanol bis(cyanoacetate), dipropylene glycol bis(cyanoacetate), 1,1,1-trimethylolpropane tris(cyanoacetate), or glycerol tris(cyanoacetate).

[0076] The curable composition may additionally contain, in particular, the following additional constituents: · Fillers, in particular pulverized or precipitated calcium carbonate optionally coated with a fatty acid, in particular a stearate, barite, quartz powder, quartz sand, dolomite, wollastonite, kaolin, calcined kaolin, layered silicates such as mica or talc, zeolites, aluminum hydroxide, magnesium hydroxide, silica (including finely divided silica obtained from a pyrolysis process), industrially produced carbon black, graphite, metal powders (such as aluminum, copper, iron, silver, or steel), PVC powder, or hollow beads; · Fibers, in particular glass fibers, carbon fibers, metal fibers, ceramic fibers, hemp fibers, cellulose fibers, or plastic fibers (such as polyamide fibers or polyethylene fibers); · Nanofillers, for example graphene or carbon nanotubes; · Dyes; · Pigments, in particular titanium dioxide, chromium oxide, iron oxide, or organic pigments; · Plasticizers, especially phthalic acid esters, especially diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), or di(2-propylheptyl) phthalate (DPHP), hydrogenated phthalic acid esters, especially diisononyl cyclohexane-1,2-dicarboxylate (DINCH), terephthalic acid esters, especially bis(2-ethylhexyl) terephthalate or diisononyl terephthalate (DINT), hydrogenated phthalic acid esters, especially bis(2-ethylhexyl) cyclohexane-1,4-dicarboxylate or diisononyl cyclohexane-1,4-dicarboxylate, isophthalic acid esters, trimellitic acid esters, adipic acid esters, especially dioctyl adipate (DOA), azelaic acid esters, sebacic acid esters, benzoic acid esters, glycol ethers, glycol esters, plasticizers having a polyether structure, especially polypropylene oxide monools, diols, or triols, or polypropylene oxide monools, diols, or triols having blocked hydroxyl groups, especially in the form of acetate groups, and organic sulfonic acid esters or phosphoric acid esters, especially cresyl diphenyl phosphate (DPK), plasticizers derived from polybutene, polyisobutene, or natural oils (especially epoxidized soybean oil or linseed oil), especially phthalic acid esters, hydrogenated phthalic acid esters, adipic acid esters, or plasticizers having a polyether structure; · Solvents; · Modifiers such as hydrocarbon resins, natural or synthetic waxes, or bitumens; · Rheology modifiers, especially urea compounds, layered silicates such as bentonite, derivatives of castor oil, hydrogenated castor oil, polyamides, polyurethanes, fumed silica, or polyoxyethylene modified to be hydrophobic; · Desiccants, especially molecular sieves, calcium oxide, monooxazolidines such as Incozol (registered trademark) 2 (from Incorez), or orthoformic acid esters; adhesion promoters, in particular titanate esters or organoalkoxysilanes, such as aminosilanes, mercaptosilanes, epoxysilanes, vinylsilanes, (meth)acrylosilanes, carbamatosilanes, alkylsilanes, S-(alkylcarbonyl)mercaptosilanes or oligomeric forms of these silanes; catalysts, in particular non-metallic bases, for example tertiary amines, in particular 2-dimethylaminoethyl ether, 2,2'-dimorpholinodiethyl ether (DMDEE), or 1,4-diazabicyclo[2.2.2]octane (DABCO), amidines, in particular 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), or 1-(2-hydroxy-3-(3-trimethoxysilylpropoxy)prop-1-yl)-2-methyl-1,4,5,6-tetrahydropyrimidine, or guanidines, in particular 1,1,3,3-tetramethylguanidine, 1-hexyl-2,3-diisopropylguanidine, or an average molecular weight M of about 250 to 500 g / mol n and in particular the basic salts, such as in particular potassium acetate, potassium benzoate, potassium carbonate, potassium hydrogen carbonate, potassium phosphate and the corresponding salts which contain sodium or lithium instead of potassium, such basic salts being preferably used in the form of an aqueous solution, for example with a salt concentration of 10 to 30% by weight, based on the total weight of the solution; · non-reactive thermoplastic polymers, such as homopolymers or copolymers of unsaturated monomers, in particular from the group comprising ethylene, propylene, butylene, isobutylene, isoprene, vinyl acetate and alkyl (meth)acrylates, in particular polyethylene (PE), polypropylene (PP), polyisobutylene, ethylene-vinyl acetate copolymers (EVA) and atactic poly-α-olefins (APAO); flame-retardant substances, in particular the already mentioned aluminium or magnesium hydroxide fillers, organic phosphates, ammonium polyphosphate, melamine or its derivatives, boron compounds or antimony compounds; · Additives, in particular wetting agents, leveling agents, defoaming agents, degassing agents, stabilizers against oxidation or heat or light or ultraviolet rays, or biocides; and other substances commonly used in curable compositions.

[0077] Such additives can be present as constituents of the first or second component. Substances having reactivity with the cyanoacetate group are preferably constituents of the first component. Substances having reactivity with the aldehyde group are preferably constituents of the second component.

[0078] The curable composition preferably further contains at least one additional constituent selected from plasticizers, fillers, and catalysts. The curable composition preferably contains a plurality of such additional constituents.

[0079] The curable composition preferably contains at least one basic catalyst having a pKa of at least 8, preferably at least 8.5, in particular an aqueous solution of a nitrogen compound or a basic salt. Such compositions exhibit particularly rapid curing.

[0080] In a preferred embodiment of the present invention, the curable composition contains 10% to 95% by weight, preferably 20% to 90% by weight, in particular 30% to 80% by weight of filler based on the total composition. Fillers selected from calcium carbonate, barite, quartz powder, quartz sand, kaolin, aluminum hydroxide, titanium dioxide, and carbon black are preferred. Such compositions are particularly suitable for applications with a layer thickness of at least 1 mm, preferably 1 to 50 mm, in particular 1.5 to 25 mm. The cured composition exhibits significant elastic properties.

[0081] In a more preferred embodiment of the present invention, the curable composition contains 5% to 80% by weight, particularly 10% to 60% by weight, of a plasticizer based on the total composition. Plasticizers selected from DINP, DIDP, DPHP, DINCH, bis(2-ethylhexyl) terephthalate, DINT, bis(2-ethylhexyl) cyclohexane-1,4-dicarboxylate, diisononyl cyclohexane-1,4-dicarboxylate, DOA, polypropylene oxide monoalcohol, polypropylene oxide diol, polypropylene oxide triol, polypropylene oxide monoacetate, polypropylene oxide diol diacetate, polypropylene oxide triol triacetate, and DPK are preferred.

[0082] In a particularly preferred embodiment of the present invention, the curable composition contains a filler and a plasticizer, and particularly contains 20% to 90% by weight, particularly 30% to 80% by weight, of a filler and 5% to 60% by weight of a plasticizer based on the total composition.

[0083] The curable composition preferably contains less than 10% by weight, more preferably less than 5% by weight, particularly less than 1% by weight, of a volatile organic solvent having a boiling point of less than 250°C at standard pressure, based on the total composition. Such a composition produces particularly low levels of emissions.

[0084] The first component of the curable composition preferably contains no aldimine groups or only a low aldimine group content of less than 0.2 moles, particularly less than 0.1 mole, of aldimine groups per mole of cyanoacetate groups in the second component. This means that the first component contains almost no primary amines. Primary amino groups react with aldehydes to form aldimines. Converting aldehyde groups in the first component to aldimine groups is not within the scope of the present invention. The composition of the present invention cures mainly by the reaction of cyanoacetate groups with free aldehyde groups.

[0085] The curable composition preferably has a total of, based on the total composition, · Compounds having an aldehyde group or a cyanoacetate group are combined in an amount of 5 wt% to 100 wt%, preferably 10 wt% to 70 wt%, · Plasticizers are in an amount of 0 wt% to 50 wt%, preferably 10 wt% to 40 wt%, · Fillers are in an amount of 0 wt% to 90 wt%, preferably 20 wt% to 80 wt%, · Optional other substances, and are contained.

[0086] In the curable composition, the ratio of the number of cyanoacetate groups to the number of aldehyde groups is preferably in the range of 0.7 to 1.5, more preferably in the range of 0.8 to 1.2, and particularly in the range of 0.9 to 1.1. Such a ratio enables rapid and complete curing. Particularly preferably, the ratio of the number of cyanoacetate groups to the number of aldehyde groups is in the range of 0.9 to 1.5. Such a ratio enables a composition having particularly high strength.

[0087] The consistency of the first and second components of the curable composition is appropriate to the extent that the components can be efficiently mixed with each other by a simple method under ambient conditions. For this purpose, particularly liquid or paste-like components are suitable.

[0088] The first and second components of the curable composition are manufactured separately from each other. The constituents of each component are mixed with each other here so as to form a macroscopically homogeneous mass. Each component is stored in a separate container. Suitable containers are, in particular, drums, containers, hobbocks, buckets, canisters, cans, pouches, tube-like pouches, cartridges, or tubes. The components have storage stability.

[0089] For using the curable composition, the two components and any additional components present are mixed with each other immediately before or during application. The mixing ratio is here selected such that the ratio of the number of cyanoacetate groups to the number of aldehyde groups is within an appropriate range, particularly about 0.9 to 1.1. By weight, the mixing ratio of the first component to the second component is typically in the range of about 100:1 to 1:10, and particularly in the range of 50:1 to 1:5.

[0090] When the components are mixed with each other before application, care must be taken to ensure that not too much time elapses between the mixing of the components and the application. Otherwise, due to the initiation of the reaction and the associated increase in viscosity, problems such as insufficient leveling, delayed or incomplete adhesion to the substrate may occur. More specifically, it is necessary not to exceed the open time of the composition during application.

[0091] In this specification, the "open time" refers to the time interval from the mixing of the components to the end of the state of the composition suitable for processing.

[0092] The mixing is preferably carried out at a temperature in the range of ambient temperature, in particular -5 to 50 °C, especially 0 to 40 °C.

[0093] When two components are mixed, the curing of the composition is initiated by the start of a chemical reaction. Here, it is mainly the cyanoacetate group that reacts with the aldehyde group, and as a result, the composition gradually cures to give a solid polymer material. The curing reaction results in the formation of the structural unit of the following formula:

Chemical formula

[0094] The curing is preferably carried out at a temperature in the range of ambient temperature, in particular -5 to 50 °C, especially 0 to 40 °C.

[0095] The present invention further provides a cured composition obtained from the curable composition after mixing two components.

[0096] The cured composition preferably has elasticity and high strength together with high elongation and tear propagation resistance.

[0097] The cured composition preferably has a tensile strength determined according to DIN EN53504 described in the examples of at least 1 MPa, preferably at least 1.5 MPa, more preferably at least 2 MPa, more preferably at least 2.5 MPa, particularly at least 3 MPa.

[0098] The cured composition preferably has an elongation at break determined according to DIN EN53504 described in the examples of at least 100%, preferably at least 150%, more preferably at least 200%, more preferably at least 250%, particularly at least 300%.

[0099] The cured composition preferably has a tear propagation resistance determined according to DIN ISO34-1, Method B described in the examples of at least 3 N / mm, preferably at least 5 N / mm, more preferably at least 7 N / mm, particularly at least 10 N / mm.

[0100] The cured composition preferably has a Shore A hardness determined according to DIN53505 described in the examples in the range of 10 - 90, particularly 20 - 80.

[0101] Furthermore, the cured composition has excellent resistance to heat and water. The cured composition preferably has high strength, elongation, and hardness even after storage at 100 °C or 70 °C and 100% relative humidity for 7 days.

[0102] The curable composition is suitable for many applications. In particular, it can be used as an adhesive, sealant, coating, casting resin, or spackling compound.

[0103] The present invention further provides the use of a curable composition as an elastic adhesive, elastic sealant, or elastic coating, wherein the first and second components, and any additional components present, are mixed with each other, and the mixed composition is applied in a liquid state to at least one substrate.

[0104] When used as an elastic adhesive, elastic sealant, or elastic coating, the layer thickness of the cured composition is preferably at least 1 mm, preferably 1 - 50 mm, particularly 1.5 - 25 mm.

[0105] Suitable substrates specifically include · Glass, glass ceramics, concrete, mortar, cement screed, fiber cement, bricks, tiles, gypsum, or natural rocks such as granite and marble; · Repair compounds or leveling compounds based on PCC (polymer - modified cement mortar) or ECC (epoxy resin - modified cement mortar); · Metals or alloys such as aluminum, iron, steel, copper, and other non - ferrous metals (including surface - finished metals or alloys such as zinc - plated or chromium - plated metals or alloys); · Asphalt or bitumen; · Leather, fabric, paper, wood, wood - based materials joined with resins such as phenolic resin, melamine resin, or epoxy resin, resin - fabric composite materials, or other polymer composite materials; · 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 (either untreated in each case or surface - treated, for example, by plasma, corona, or flame); · Fiber - reinforced plastics such as carbon fiber - reinforced plastic (CFRP), glass fiber - reinforced plastic (GFRP), natural fiber - reinforced plastic (NFRP), and sheet molding compound (SMC); · Insulation foams, particularly those made of EPS, XPS, PUR, PIR, rock wool, glass wool, aerogel, or expanded glass; · Coated or painted substrates, particularly painted tiles, coated concrete, powder - coated metals or alloys, or painted metal sheets; · Coatings, paints, or varnishes; and so on.

[0106] The substrate can be pretreated before coating, if necessary, in particular by physical and / or chemical cleaning methods, or by application of an activator or a primer.

[0107] It is possible to join and / or seal two identical or two different substrates.

[0108] An article is obtained by use of the curable composition. The article is in particular joined, sealed or coated with the composition. The article may be a building or a part thereof, in particular a civil engineering structure, a bridge, a roof, a staircase or a facade constructed above or below ground, or an industrial product or a consumer good, in particular a window, a pipe, a rotor blade of a wind turbine, a household electrical appliance, or a means of transport, for example in particular a motor vehicle, a bus, a truck, a railway vehicle, a ship, an aircraft or a helicopter, or an attachable component thereof.

Examples

[0109] Examples are shown hereinafter which are intended to further illustrate the present invention described. It is clear that the present invention is not limited to these described examples.

[0110] "Standard climatic conditions" ("SCC") refer to a temperature of 23 ± 1 °C and a relative air humidity of 50 ± 5%.

[0111] Unless otherwise specified, the chemicals used are from Sigma-Aldrich Chemie GmbH.

[0112] Description of the measurement method: The viscosity was measured with a Rheotec RC30 cone-plate viscometer with thermostat (cone diameter 10 mm, cone angle 1°, cone tip-plate distance 0.05 mm, shear rate 10 s -1 )). Viscosities below 1 Pa·s were measured with a cone diameter of 50 mm.

[0113] The infrared spectrum (FT-IR) was measured as undiluted film using a Thermo Scientific Nicolet iS5 FT-IR instrument equipped with a horizontal ATR measurement unit having a diamond crystal. The absorption bands are reported at a wave number (cm -1 ).

[0114] Preparation of isocyanate group-containing polymers: Polymer P-1: 780 g of ethylene oxide-terminated polyoxypropylene triol (Desmophen® 5031BT, OH value 28.0 mg KOH / g, OH functionality approximately 2.3, from Covestro) and 303 g of isophorone diisocyanate (Vestanat® IPDI, from Evonik) were converted at 80 °C by a known method into a reaction mixture with an NCO content of 9.1 wt%. Subsequently, volatile components, especially unreacted isophorone diisocyanate, were removed by distillation in a short-path evaporator (jacket temperature 160 °C, pressure 0.1 - 0.005 mbar) to obtain a polymer with an NCO content of 1.84 wt% and a monomeric isophorone diisocyanate content of 0.02 wt%.

[0115] Polymer P-2: 590 g of polyoxypropylene diol (Acclaim® 4200, OH value 28 mg KOH / g, from Covestro), 1180 g of ethylene oxide-terminated polyoxypropylene triol (Caradol® MD34-02, OH value 35 mg KOH / g, from Shell), and 230 g of isophorone diisocyanate (Vestanat® IPDI, from Evonik) were converted at 80 °C by a known method into a polymer with an NCO content of 2.1 wt%.

[0116] Polymer P-3: 725 g of ethylene oxide-terminated polyoxypropylene triol (Desmophen® 5031BT, OH number 28.0 mg KOH / g, OH functionality approximately 2.3, from Covestro) and 275 g of diphenylmethane 4,4'-diisocyanate (Desmodur® 44MC L, from Covestro) were converted into a reaction mixture with an NCO content of 7.6 wt% by a known method at 80 °C. Subsequently, volatile components, especially unreacted diphenylmethane 4,4'-diisocyanate, were removed by distillation in a short-path evaporator (jacket temperature 180 °C, pressure 0.1 - 0.005 mbar, condensation temperature 47 °C) to obtain a polymer with an NCO content of 1.68 wt% and a monomeric diphenylmethane 4,4'-diisocyanate content of 0.04 wt%.

[0117] Polymer P-4: 513.3 g of polyoxypropylene diol (Acclaim® 4200, OH number 28 mg KOH / g, from Covestro), 256.7 g of ethylene oxide-terminated polyoxypropylene triol (Caradol® MD34-02, OH number 35 mg KOH / g, from Shell), and 64.2 g of toluene diisocyanate (Desmodur® T80P, from Covestro) were converted into a polymer with an NCO content of 1.5 wt% by a known method at 80 °C.

[0118] Polymer P-5: 818 g of polyoxypropylene diol (Acclaim® 4200, OH value 28.5 mg KOH / g, from Covestro) and 227 g of isophorone diisocyanate (Vestanat® IPDI, from Evonik) were converted into a reaction mixture with an NCO content of 6.6 wt% by a known method at 80 °C. Then, volatile components, especially unconverted isophorone diisocyanate, were removed by distillation using a short-path evaporator (jacket temperature 160 °C, pressure 0.1 - 0.005 mbar) to obtain a polymer with an NCO content of 1.91 wt% and a monomeric isophorone diisocyanate content of 0.03 wt%.

[0119] Polymer P-6: 600 g of polyoxypropylene diol (Voranol® 1010L, OH value 112 mg KOH / g, from Dow) and 533.3 g of isophorone diisocyanate (Vestanat® IPDI, from Evonik) were converted into a reaction mixture with an NCO content of 15.6 wt% by a known method at 80 °C. Then, volatile components, especially unconverted isophorone diisocyanate, were removed by distillation using a short-path evaporator (jacket temperature 160 °C, pressure 0.1 - 0.005 mbar) to obtain a polymer with an NCO content of 5.18 wt% and a monomeric isophorone diisocyanate content of 0.03 wt%.

[0120] Preparation of compounds having two or more aldehyde groups: Compounds A-1 to A-7: For each compound, the corresponding isocyanate group-containing polymer in the amounts (parts by weight) specified in Table 1 was reacted with the corresponding hydroxy-functional aldehyde in the specified amounts (parts by weight) at 110 °C while excluding moisture in the presence of 0.02 wt% of dibutyltin dilaurate until no isocyanate groups were detected by IR spectroscopy. For polymers P-3 and P-4 having aromatic isocyanate groups, the reaction was carried out at 80 °C without using dibutyltin dilaurate. In each case, a colorless transparent liquid was obtained.

[0121] The properties of Compounds A-1 to A-7 are shown in Table 1.

[0122]

Table 1

[0123] The average molecular weight M of Compound A-1 n was further determined by gel permeation chromatography (GPC) using tetrahydrofuran as the mobile phase and a refractive index detector, with polystyrene (474 - 2520000 g / mol) as the standard. The average molecular weight M n was 6100 g / mol.

[0124] Preparation of compounds having two or more cyanoacetate groups: Compounds C-1 to C-9: For each compound, a specified amount (parts by weight) of a specific polyfunctional alcohol was mixed with a specified amount (parts by weight) of ethyl cyanoacetate and 0.1% by weight of tetra-n-butyl titanate (Tyzor® TnBT, from Dorf Ketal), and the mixture was converted while removing volatile components at a temperature of 80 - 140 °C under reduced pressure. In each case, a colorless and transparent liquid was obtained, except for Compound C-9.

[0125]

Table 2

[0126] Preparation of compounds having an acetoacetate group (comparison): Compound R-1: To 50 g of polyoxypropylene triol (Desmophen® 4011T, OH value 550 mg KOH / g, from Covestro) initiated with trimethylolpropane, 67 g of ethyl acetoacetate and 0.12 g of tetra-n-butyl titanate (Tyzor® TnBT, from Dorf Ketal) were added, and the mixture was converted at a temperature of 140 °C while removing volatile components under reduced pressure. A colorless and transparent liquid with a viscosity of 0.8 Pa·s at 20 °C, an average acetoacetate functionality of 3, and an acetoacetate equivalent of 186 g / eq was obtained.

[0127] Production of curable composition: Examples E-1 to E-33 For each example, the raw materials of the first component (K1) specified in Tables 3 to 8 were mixed with each other in a specified amount (parts by weight) using a centrifugal mixer (SpeedMixer™ DAC150, Flack Tek Inc.) and stored in a sealed container.

[0128] The raw materials of the second component (K2) specified in Tables 3 to 8 were similarly treated and stored.

[0129] The “precipitated CaCO3” used was Socal® U1S2 (from Imerys), which is calcium carbonate precipitated and coated with stearate.

[0130] The “carbon black” used was Monarch® 570 (from Cabot).

[0131] Thereafter, the two components of each composition were treated using a centrifugal mixer to obtain a homogeneous paste. This was tested as described below. In the case of E-33 (reference), the component K2 consisting of compound C-9 was heated to 60 °C and melted before mixing.

[0132] The gel time was determined under standard climatic conditions by stirring a newly mixed amount of about 3 g at regular intervals using a spatula until the mass gelled and could no longer be stirred.

[0133] The mechanical properties were determined by applying the mixed composition to a silicone-coated release paper to obtain a film with a thickness of 2 mm, leaving this film to cure by standing for 7 days under standard climatic conditions, punching out several dumbbell-shaped test pieces with a bar length of 30 mm, a bar width of 4 mm and a length of 75 mm from the film, and testing the tensile strength, elongation at break, MoE 5% (at an elongation of 0.5% to 5%), and MoE 50% (at an elongation of 0.5% to 50%) at a strain rate of 200 mm / min in accordance with DIN EN 53504. Furthermore, to determine the tear propagation resistance, a plurality of test pieces were punched out and tested at a strain rate of 500 mm / min in accordance with DIN ISO 34-1, Method B (notched test piece).

[0134] The evaluation criterion used for the strength of the adhesive bond of the plurality of compositions was the lap shear strength on glass. For this purpose, a composite test piece was produced by joining two glass plates that had been degreased with isopropanol and pretreated with Sika® Aktivator-205 (from Sika Schweiz). This joining was carried out such that the dimensions of the overlapping adhesive bond were 12 × 25 mm, the thickness was 4 mm, and the glass plates protruded at the upper end. After storing the composite test piece under standard climatic conditions for 7 days, the lap shear strength was tested at a strain rate of 20 mm / min in accordance with DIN EN 1465. Subsequently, the failure profile was evaluated as to whether it was AF (adhesive failure) or CF (cohesive failure). In the absence of additional data, the failure profile described in the table was evaluated for 90% to 100% of the failure area.

[0135] The Shore A hardness was measured in accordance with DIN 53505 for specimens cured for 7 days under standard climatic conditions. These results were marked with "7d SCC". The heat resistance and water resistance were determined by measuring the Shore A hardness as described for each case after further storing the Shore A specimens for an additional 7 days in an air-circulating oven at 100 °C or for an additional 7 days at 70 °C and 100% relative humidity after curing for 7 days under standard climatic conditions and then cooling to room temperature. These results were marked with "+7d 100 °C" or "+7d 70 / 100".

[0136] In each case, a non-tacky elastic material was obtained by curing the examples of the present invention. The examples marked with "(reference)" are comparative examples that are not of the present invention.

[0137] The results are reported in Tables 3 to 8.

[0138]

Table 3

[0139] Comparing Example E-1 with Comparative Examples E-7 (reference) and E-8 (reference), it is shown that the compound C-1 having a cyanoacetate ester group enables much better mechanical values (especially with respect to high tensile strength, high elongation, and high tear propagation resistance) than the compound R-1 having an acetoacetate group. For Comparative Examples E-7 (reference) and E-8 (reference), DBU was used as a catalyst to achieve a similarly rapid gel time.

[0140]

Table 4

[0141]

Table 5

[0142]

Table 6

[0143]

Table 7

[0144]

Table 8

[0145] Examples E-32 (reference) and E-33 (reference) are comparative examples in which the first and second components each have an average functionality of only 2.0 with respect to compounds having an aldehyde group or a cyanoacetate group. Such compositions based on linear reactive compounds do not cure in any case to produce a solid elastic material, whereas Example E-31 of the present invention having a second component with an average cyanoacetate functionality of 3.0 cures to give an elastic material.

Claims

1. A first component comprising an aldehyde group-containing compound, the first component comprising at least one compound having two or more aldehyde groups, A second component comprising a cyanoacetate group-containing compound, the second component comprising at least one compound having two or more cyanoacetate groups, A curable composition containing, The average molecular weight M of the first and second components relating to the aldehyde group-containing compound or the cyanoacetate group-containing compound. ｎ A curable composition wherein the concentration is in the range of 400 to 20,000 g / mol, and the average functional value of at least one of the two components with respect to the aldehyde group-containing compound or the cyanoacetate group-containing compound is greater than 2.

0.

2. The composition according to claim 1, characterized in that it contains less than 10% by weight, preferably less than 5% by weight, and particularly less than 2% by weight of water based on the entire composition.

3. The composition according to claim 1 or 2, characterized in that the compound having two or more aldehyde groups is a liquid at room temperature.

4. The average molecular weight M of the first component relating to the aldehyde group-containing compound ｎ The composition according to claim 1 or 2, characterized in that, when measured against polystyrene as a standard by gel permeation chromatography (GPC), the amount is in the range of 1,000 to 20,000 g / mol, preferably 1,500 to 15,000 g / mol, and particularly 2,000 to 10,000 g / mol.

5. The composition according to claim 1 or 2, characterized in that the aldehyde group-containing compound comprises a polymer having a polymer backbone containing poly(oxyalkylene) units and / or polyester units.

6. The composition according to claim 1 or 2, characterized in that the compound having two or more aldehyde groups further comprises a urethane group.

7. The aldehyde group-containing compound comprises a urethane group-containing polymer, which is liquid at room temperature and has an average molecular weight M of 1,000 to 20,000 g / mol, preferably 1,500 to 15,000 g / mol, and particularly 2,000 to 10,000 g / mol. ｎ The composition according to claim 1 or 2, characterized in that it has an average aldehyde functional value of 1.8 to 3.5, more preferably 2.0 to 3.0, and particularly 2.2 to 3.

0.

8. The composition according to claim 1 or 2, characterized in that the compound having two or more aldehyde groups is obtained from the reaction of at least one hydroxyaldehyde with at least one isocyanate group-containing polymer or at least one polyisocyanate.

9. The composition according to claim 1 or 2, characterized in that the average functional value of the second component with respect to the cyanoacetate group-containing compound is in the range of 1.6 to 4, preferably 1.8 to 3.5, more preferably 2.0 to 3.0, and particularly 2.3 to 3.

0.

10. The average molecular weight M of the second component in the cyanoacetate group-containing compound ｎ The composition according to claim 1 or 2, characterized in that the amount is in the range of 400 to 10,000 g / mol, preferably 500 to 2,000 g / mol.

11. The cyanoacetate group-containing compound has an average molecular weight M of 500 to 2000 g / mol ｎ Propoxylated 1,1,1-trimethylolpropane tris(cyanoacetate) having an average molecular weight M of 2000 to 10000 g / mol ｎ Poly(oxy-1,2-propylene) diol bis(cyanoacetate) having an average molecular weight M of 2000 to 10000 g / mol ｎ Poly(oxy-1,2-propylene) triol tris(cyanoacetate) having an average molecular weight M of 2000 to 10000 g / mol and containing ethylene oxide units ｎ Poly(oxy-1,2-propylene) diol bis(cyanoacetate) having an average molecular weight M of 2000 to 10000 g / mol and containing ethylene oxide units ｎ Poly(oxy-1,2-propylene) triol tris(cyanoacetate) having an average molecular weight M of 1000 to 4000 g / mol ｎ Polyester diol bis(cyanoacetate) based on dimer fatty acid having an average molecular weight M of 1000 to 4000 g / mol, and ｎ The composition according to claim 1 or 2, characterized by comprising at least one cyanoacetate-functional polymer selected from polyester triol tris(cyanoacetate) based on trimer fatty acid

12. The composition according to claim 1 or 2, characterized in that it contains at least one additional component selected from plasticizers, fillers, and catalysts.

13. The composition according to claim 1 or 2, characterized in that a volatile organic solvent having a boiling point of less than 250°C at standard pressure is present in an amount of less than 10% by weight, more preferably less than 5% by weight, and particularly less than 1% by weight, based on the entire composition.

14. A cured composition obtained from the curable composition according to claim 1 or 2 after mixing the two components, characterized in that it has a tear propagation resistance of at least 7 N / mm, and more particularly at least 10 N / mm, as determined by DIN ISO 34-1, Method B, at a strain rate of 500 mm / min.

15. Use of the composition according to claim 1 or 2 as an elastic adhesive, elastic sealant, or elastic coating, wherein the first and second components, and any additional components present, are mixed together, and the mixed composition is applied in a liquid state to at least one substrate.