A polymer composition curable at room temperature, produced from a polyaldehyde and a 1,3-ketoester

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 1,3-ketoester group-containing compound containing at least one compound having two or more 1,3-ketoester groups of formula (I), wherein the average molecular weight M of at least one of the two components containing a compound containing an aldehyde group or a 1,3-ketoester group n is in the range of 400 to 20,000 g / mol. This composition contains almost no toxic components, cures rapidly and problem-free under ambient conditions using a conventional catalyst, and forms a non-tacky elastic polymer having high strength and high elasticity. 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 a room-temperature curable elastic adhesive, sealant, or coating.

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 a cross-linking reaction that is too fast, related to an increase in viscosity up to gelation, and as a result, the shelf life and storage stability may be impaired. In the case of systems formulated in a one-component form, the moisture required for curing must penetrate from the outside in the form of atmospheric moisture, which complicates its use between thick layers and substrates that do not allow moisture to pass through. 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 and incomplete polymerization with chain termination due to incompletely incorporated polyols, and the strength and elasticity may be lost to some extent. These problems hardly occur when using a mercury catalyst that very selectively catalyzes the reaction with the polyol. However, since mercury catalysts are highly toxic, they 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 may be greatly lost, and as a result, curing defects may occur.

[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 not necessarily desirable results can be obtained.

[0004] In addition, aqueous polymer systems are also 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, they can only be used in relatively thin layers and only between open-pored substrates, the curing rate depends greatly on the ambient humidity, and they have a high shrinkage rate. After curing, surfactants necessary for the production and stability of the dispersion are present, resulting in increased sensitivity to moisture and a possible decrease in durability, especially for outdoor applications.

[0005] U.S. Patent No. 5,452,653 describes crosslinking a compound containing an acetoacetate group with an aromatic aldimine. This involves using an acrylate polymer containing an acetoacetate group and having a high solvent content, or an aqueous polyurethane acrylate dispersion containing an acetoacetate group. 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, is suitable as an elastic adhesive, sealant, or coating, and overcomes the disadvantages of known polymer systems. MEANS FOR SOLVING THE PROBLEMS

[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 1,3-ketoester group, and the average molecular weight M of at least one of the two components related to the compound having an aldehyde group or a 1,3-ketoester group n is in the range of 400 to 20,000 g / mol. This composition has several advantageous and surprising properties compared to polymer systems curable at room temperature according to the prior art.

[0008] Compounds containing an aldehyde group and compounds containing a 1,3-ketoester group are both substances with low concerns about 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 realizes a high degree of freedom in formulation. 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. Surprisingly, this composition is very tolerant with respect to the stoichiometric ratio of the reactive groups, and in each case, a cured non-sticky material with high elongation and strength, as well as excellent stability against heat and water, is formed over the entire range where the ratio of the number of 1,3-ketoester groups to the number of aldehyde groups is from 1 to 2 and above. Considering that in reaction systems according to the prior art, it is typical to show a significant decrease in mechanical quality when deviating greatly from the optimal stoichiometric ratio of the reactive groups (usually around 1:1), this is very surprising. For these reasons, the mixing ratio of the two components can be adjusted almost as desired, which provides a high degree of freedom in the coating method and enables a simple and very reliable process with a high error tolerance. The composition has excellent processability under ambient conditions without the need for organic solvents for dissolution or dilution, or water for emulsification or dispersion of the components. The composition cures rapidly and perfectly under ambient conditions without generating emissions regardless of humidity. Particularly advantageous here is that the curing rate can be very efficiently controlled by common catalysts, especially non-metal bases such as tertiary amines, amidines, or guanidines. Upon curing, a non-sticky elastic polymer with high strength and elongation, excellent tear propagation resistance, and excellent stability against heat and water is obtained. Due to this combination of advantageous properties, the composition of the present invention can be handled particularly easily without special protection means, in the manufacture and storage of the components, its use under a wide range of ambient and application conditions, when the mixing ratio varies, and in any of the cases after curing under mechanical, thermal, or chemical stress, and has high robustness and a long lifespan.

[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.

BRIEF DESCRIPTION OF THE INVENTION

[0011] The subject matter of the present invention is ·a first component comprising an aldehyde group-containing compound containing at least one compound having two or more aldehyde groups, ·at least one compound having two or more 1,3-ketoester groups of the following formula (I)

CHEMICAL FORMULA

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

CHEMICAL FORMULA

[0013] In the formulas herein, the dotted line represents a bond between a substituent and the remaining part of the molecule in each case.

[0014] "Molecular weight" refers to the molar mass of a molecule (grams / mole). "Average molecular weight" refers to the number average molecular weight (M nrefers to . This is determined by gel permeation chromatography (GPC) using polystyrene as the standard.

[0015] A composition having "storage stability" can be stored in a suitable container at room temperature for a long period, typically at least 3 months to up to 6 months or more, without any change in its use and performance characteristics to the extent related to its use during 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 in their names.

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

[0018] All industry standards and references mentioned in this specification relate to the version effective on 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 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 non-aqueous. This preferably contains little or only a small amount of water. Such a composition cures rapidly regardless of the ambient humidity and can be used between thick layers and / or water-tight substrates and shows little shrinkage upon curing.

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

[0023] The curable composition preferably does not contain a compound having an aldehyde group or a 1,3 - ketoester group in the form of an emulsion or dispersion. Therefore, the compound having an aldehyde group or a 1,3 - ketoester group present preferably contains few ionic groups or their precursors and few relatively long poly(oxyethylene) chains common to 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 1,3 - ketoester 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 1,3 - ketoester group. The ionic group is particularly a carboxylate group, an ammonium group, or a sulfonate group.

[0024] In the curable composition, the average molecular weight M of at least one of the two components regarding the compound containing an aldehyde group or a 1,3 - ketoester group n is in the range of 400 to 20,000 g / mol. Such a composition cures to give a highly strong elastic polymer.

[0025] Preferably, at least one of the two components has an average molecular weight M regarding the compound containing an aldehyde group or a 1,3 - ketoester group in the range of 1,000 to 20,000 g / mol, preferably 1,500 to 15,000 g / mol, particularly 2,000 to 10,000 g / mol. n This enables particularly high elongation.

[0026] The compound having two or more aldehyde groups is preferably liquid at room temperature. Specifically, this is at a cone 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 -1For viscosities of less than 1 Pa·s, when measured with a cone-plate viscometer with a ball diameter of 50 mm, it has a viscosity of 0.2 to 700 Pa·s at 20°C, preferably 0.3 to 500 Pa·s, more preferably 0.5 to 200 Pa·s, and particularly 1 to 100 Pa·s. Such compounds can be easily handled at ambient temperature without adding solvents or diluents.

[0027] Preferred compounds having two or more aldehyde groups are polymers having aldehyde groups.

[0028] Preferably, the average molecular weight M of the first component regarding the compound containing an aldehyde group n 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 when measured by gel permeation chromatography (GPC) with respect to polystyrene as a standard. Such components can be easily handled at ambient temperature without adding solvents or diluents, enabling polymers with high elongation and elasticity.

[0029] 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, and particularly 2.2 to 3.0. This enables a cured composition having high elongation, strength, and stability.

[0030] The compound containing an aldehyde group preferably includes a polymer having a polymer backbone containing poly(oxyalkylene) units and / or polyester units.

[0031] 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 mixed forms 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 low viscosity and are thus particularly efficiently handleable and particularly hydrophobic. These enable compositions having particularly excellent processability, high elongation, and excellent water resistance.

[0032] 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.

[0033] Compounds having two or more aldehyde groups preferably further contain urethane groups. Thereby, a composition having particularly high elongation is obtained.

[0034] Preferably, the compound containing an aldehyde group is liquid at room temperature and has an average molecular weight M n of 1,000 to 20,000 g / mol, preferably 1,500 to 15,000 g / mol, particularly 2,000 to 10,000 g / mol, 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, and contains a urethane group-containing polymer.

[0035] 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.

[0036] 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.

[0037] Particularly suitable are the following: 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 (where "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).

[0038] Ethoxylated salicylaldehyde, in particular 2-(2-hydroxyethoxy)benzaldehyde, ethoxylated vanillin, in particular 4-(2-hydroxyethoxy)-3-methoxybenzaldehyde, 5-hydroxymethylfurfural, N'-2-hydroxyethyl-N-piperazinyl-2,2-dimethylpropanal, or N'-3-hydroxypropyl-N-piperazinyl-2,2-dimethylpropanal are preferred. These hydroxyaldehydes can be obtained in a simple manner, thereby enabling compounds containing aldehyde groups, having low viscosity and thus excellent handleability, as well as compositions having very high elongation together with excellent processability and high strength.

[0039] 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, and water resistance.

[0040] An isocyanate group-containing polymer suitable for the preparation of a compound having two or more aldehyde groups is particularly a reaction product of a polyol and a diisocyanate, particularly one having an NCO / OH molar ratio of 1.5 / 1 to 10 / 1, and optionally one from which unreacted monomeric diisocyanate has been removed from the polymer.

[0041] 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, and particularly 1.5% to 6% by weight, based on the polymer.

[0042] A very preferred isocyanate group-containing polymer is 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, particularly 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.

[0043] Such an isocyanate group-containing polymer enables an aldehyde-functional polymer in which the content of the reaction product of the monomeric diisocyanate and the hydroxyaldehyde is particularly low, particularly less than 0.5% by weight based on the aldehyde-functional polymer. This enables a curable composition having a long open time, rapid curing, and particularly excellent flexibility, and which is particularly easy to process.

[0044] 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. In particular, IPDI is preferred. Thereby, a composition having particularly excellent processability is obtained which, upon curing, gives a polymer having high strength and high elongation.

[0045] Suitable polyols are, in particular, the following: · Polyether polyols, in particular polyoxyalkylene diols or polyoxyalkylene triols, in particular 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, in particular starter molecules such as water, ammonia, or compounds having two or more OH or NH groups, for example ethane - 1,2 - diol, propane - 1,2 - or - 1,3 - diol, neopentyl glycol, diethylene glycol, triethylene glycol, isomeric dipropylene glycol or tripropylene glycol, isomeric butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, undecanediol, 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.

[0046] Preferred polyether polyols are polyoxypropylene diols or triols, or ethylene oxide-terminated (EO end-capped or EO tipped) polyoxypropylene diols or triols. The latter are polyoxyethylene-polyoxypropylene copolyols, which are obtained by further alkoxylating polyoxypropylene diols or triols with ethylene oxide, especially at the completion of the propoxylation reaction, and as a result, they finally have primary hydroxyl groups.

[0047] 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 by polycondensation of hydroxycarboxylic acids or lactones, or by polycondensation of aliphatic and / or aromatic polycarboxylic acids with dihydric or polyhydric alcohols. For example, polyester polyols based on amorphous, dimeric, or trimeric fatty acids commercially available from Croda are preferred. · Polycarbonate polyols, for example 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 especially castor oil, derivatives of castor oil; or polyols obtained by chemically modifying natural oils (referred to as oleochemical polyols), for example hydroxylated vegetable oils available under the trade name Sovermol® (from BASF). · Polyhydrocarbon polyols, such as especially polyhydroxy-functionalized polyolefins, polyisobutylene, polyisoprene; polyhydroxy-functionalized ethylene / propylene, ethylene / butylene, or ethylene / propylene / diene copolymers, such as those from Kraton Polymers; polyhydroxy-functionalized polymers of dienes, especially 1,3-butadiene, which can be prepared especially from anionic polymerization; polyhydroxy-functionalized 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-functionalized acrylonitrile / butadiene copolymers, such as those which can be prepared from epoxides or amino alcohols and carboxyl-terminated acrylonitrile / butadiene copolymers (e.g., commercially available from Emerald Performance Materials under the name Hypro® CTBN or CTBNX or ETBN); and hydrogenated polyhydroxy-functionalized polymers or copolymers of dienes.

[0048] Polyols that are liquid at room temperature are preferred.

[0049] Polyols having an OH number in the range of 9 to 115 mg KOH / g, preferably 14 to 60 mg KOH / g, particularly 18 to 40 mg KOH / g are preferred.

[0050] 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.

[0051] Also suitable as compounds having two or more aldehyde groups are reaction products of at least one polyisocyanate and at least one hydroxyaldehyde, especially the hydroxyaldehydes described above.

[0052] 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.

[0053] 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.

[0054] The curable composition contains, as a constituent of the second component, at least one compound having two or more 1,3 - ketoester groups of the formula (I) [Chemical formula] (wherein R 1 is a monovalent hydrocarbyl radical having 1 to 6 carbon atoms). and includes at least one compound having two or more 1,3 - ketoester groups of

[0055] Preferably, R 1 is methyl, ethyl, propyl, isopropyl, butyl, or phenyl.

[0056] More preferably, R 1 is methyl or phenyl.

[0057] Most preferably, R 1 is methyl. Such 1,3 - ketoester groups are also called acetoacetate groups.

[0058] The compound having two or more 1,3 - ketoester groups is preferably liquid at room temperature. Specifically, when measured with a cone - plate viscometer at 20°C 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 0.01 to 100 Pa·s, preferably 0.02 to 50 Pa·s, particularly 0.05 to 20 Pa·s. 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 the 1,3 - ketoester group is in the range of 1.6 to 4, preferably 1.8 to 3.5, more preferably 2.0 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 1,3-ketoester group n is in the range of 230 to 10,000 g / mol, preferably 250 to 2,000 g / mol.

[0061] In a preferred embodiment of the present invention, the average molecular weight M of the second component with respect to the compound containing a 1,3-ketoester group n is in the range of 500 to 2,000 g / mol. Such a second component enables a high-strength composition that can be processed particularly efficiently.

[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 1,3-ketoester group n is in the range of 2,000 to 10,000 g / mol. When combined with the first component having a similarly high average molecular weight M with respect to the compound containing an aldehyde group n such a second component enables, in a particularly simple manner, a composition in which the mixing ratio of the two components is in the range of 1:1, which is particularly advantageous in the case of specific applications, especially for processing with a static mixer.

[0063] Preferably, the second component contains at least one polymer having a 1,3-ketoester group and an average molecular weight M of 500 to 10,000 g / mol, preferably 500 to 2,000 g / mol n and an average 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 two or more 1,3-ketoester groups of formula (I) is of formula (II)

Chemical formula

[0065] Preferably, R 2 here is methyl, ethyl, or tert - butyl, especially ethyl.

[0066] The reaction is preferably carried out at a temperature in the range of 50 - 150 °C, while distilling off the released alcohol R 2 OH, optionally under reduced pressure, and optionally in the presence of a catalyst.

[0067] Preferred 1,3 - ketoesters of formula (II) are methyl acetoacetate, ethyl acetoacetate, tert - butyl acetoacetate, ethyl propionylacetate, ethyl 3 - oxohexanoate, ethyl isobutyrylacetate, or ethyl benzoate, especially ethyl acetoacetate.

[0068] Similarly, it is also possible to prepare a compound having two or more 1,3 - ketoester groups by the reaction of diketene or an adduct of diketene and acetone (= 2,2,6 - trimethyl - 4H - 1,3 - dioxin - 4 - one) with at least one kind of polyfunctional alcohol, and in the case of the acetone - diketene adduct, acetone is released.

[0069] Suitable polyfunctional alcohols are commercially available compounds or polymers having two or more OH groups, such as, 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.

[0070] Particularly preferred polyfunctional alcohols are ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, butane-1,4-diol, hexane-1,6-diol, cyclohexane-1,4-dimethanol, dipropylene glycol, or 1,1,1-trimethylolpropane.

[0071] Even more particularly preferred polyfunctional alcohols are propoxylated 1,1,1-trimethylolpropane having an average molecular weight M n of from 300 to 1,700 g / mol.

[0072] Even more particularly preferred polyfunctional alcohols are poly(oxy-1,2-propylene) diol having an average molecular weight M n of from 400 to 10,000 g / mol or poly(oxy-1,2-propylene) diol having an average molecular weight M nIt is a poly(oxy-1,2-propylene) triol, and these poly(oxy-1,2-propylene) diols or triols may optionally be end-capped with ethylene oxide.

[0073] Other particularly preferred polyfunctional alcohols are amorphous polyester diols based on dimer fatty acids having an average molecular weight M of 800 to 3,000 g / mol or amorphous polyester triols based on trimer fatty acids. n

[0074] More preferably, the compound containing a 1,3-ketoester group is ethan-1,2-diol bis(acetoacetate), propan-1,2-diol bis(acetoacetate), propan-1,3-diol bis(acetoacetate), butan-1,4-diol bis(acetoacetate), hexan-1,6-diol bis(acetoacetate), cyclohexane-1,4-dimethanol bis(acetoacetate), dipropylene glycol bis(acetoacetate), 1,1,1-trimethylolpropane tris(acetoacetate), glycerol tris(acetoacetate), propoxylated 1,1,1-trimethylolpropane tris(acetoacetate) having an average molecular weight M of 500 to 2,000 g / mol, poly(oxy-1,2-propylene) diol bis(acetoacetate) having an average molecular weight M of 600 to 10,000 g / mol, poly(oxy-1,2-propylene) triol tris(acetoacetate) having an average molecular weight of 2,000 to 10,000 g / mol, poly(oxy-1,2-propylene) triol tris(acetoacetate) containing ethylene oxide units and having an average molecular weight of 2,000 to 10,000 g / mol, polyester diol bis(acetoacetate) based on dimer fatty acids, and polyester triol tris(acetoacetate) based on trimer fatty acids, and is selected from the group consisting of. n It is propoxylated 1,1,1-trimethylolpropane tris(acetoacetate) having an average molecular weight M of 600 to 10,000 g / mol. n It is selected from the group consisting of poly(oxy-1,2-propylene) diol bis(acetoacetate) having an average molecular weight M of 14 to 10,000 g / mol, poly(oxy-1,2-propylene) triol tris(acetoacetate) having an average molecular weight of 2,000 to 10,000 g / mol, poly(oxy-1,2-propylene) triol tris(acetoacetate) containing ethylene oxide units and having an average molecular weight of 2,000 to 10,000 g / mol, polyester diol bis(acetoacetate) based on dimer fatty acids, and polyester triol tris(acetoacetate) based on trimer fatty acids.

[0075] ​Most preferably, the compound containing a 1,3-ketoester group is a polyester diol diacetoacetate based on a dimer fatty acid that is liquid at room temperature, or a polyester triol triacetoacetate based on a trimer fatty acid that is liquid at room temperature. This enables a cured composition having particularly high elongation.

[0076] Suitable compounds having two or more acetoacetate groups are also commercially available, and are particularly available as K-Flex7301 (registered trademark) or K-Flex (registered trademark) M-B301 (both from King Industries).

[0077] Preferably, the average functionality of the entire composition with respect to the reactive aldehyde group and 1,3-ketoester group is at least 1.9, particularly at least 2.0. This means that, in order for the average functionality of the reactive groups as a whole to be 1.9, preferably 2.0, a composition with an average aldehyde functionality of 1.8 for the first component is combined, for example preferably with a second component having an average 1,3-ketoester functionality of at least 2.0, preferably at least 2.1.

[0078] More preferably, the curable composition contains a urethane group and has an average molecular weight M of 1,000 to 20,000 g / mol, preferably 1,500 to 15,000 g / mol, particularly 2,000 to 10,000 g / mol n and 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 component of the first component, and also contains at least one polymer that contains an acetoacetate group and has an average molecular weight M of 500 to 10,000 g / mol, preferably 500 to 2,000 g / mol n and an average cyanoacetate functionality of 1.8 to 3.5, more preferably 2.0 to 3.0, particularly 2.5 to 3.0, as a constituent component of the second component. The overall average functionality of the reactive groups here is preferably at least 1.9, particularly at least 2.0.

[0079] Furthermore, the first component of the curable composition may contain a low molecular weight polyaldehyde, for example, especially 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 ratio.

[0080] The curable composition may particularly additionally contain the following additional components: · Fillers, especially fatty acid, especially pulverized or precipitated calcium carbonate optionally coated with stearate, barite, quartz powder, quartz sand, dolomite, wollastonite, kaolin, calcined kaolin, layered silicates such as mica or talc, zeolite, aluminum hydroxide, magnesium hydroxide, silica (including fine silica powder obtained from a thermal decomposition process), industrially produced carbon black, graphite, metal powders (such as aluminum, copper, iron, silver, or steel), PVC powder, or hollow beads; · Fibers, especially glass fibers, carbon fibers, metal fibers, ceramic fibers, hemp fibers, cellulose fibers, or plastic fibers (such as polyamide fibers or polyethylene fibers); · Nanofillers, such as graphene or carbon nanotubes; · Dyes; · Pigments, especially 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 hydrophobically modified polyoxyethylene; · 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 generally used in curable compositions.

[0081] Such additives can be present as constituents of the first or second component. Substances having reactivity with the 1,3-ketoester group are preferably constituents of the first component. Substances having reactivity with the aldehyde group are preferably constituents of the second component.

[0082] 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.

[0083] 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.

[0084] In a preferred embodiment of the 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, ground quartz, silica 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 500 mm, in particular 1.5 to 250 mm. The cured composition exhibits remarkable elastic properties.

[0085] 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.

[0086] 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.

[0087] The curable composition preferably contains less than 10% by weight, 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 the standard pressure present, based on the total composition. Such a composition produces particularly low levels of emissions.

[0088] 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 1,3-ketoester groups in the second component. This means that the first component contains little primary amine. The primary amino group reacts with an aldehyde to form an aldimine. Converting the aldehyde groups in the first component to aldimine groups is not within the scope of the present invention. The curable composition of the present invention cures mainly by the reaction of 1,3-ketoester groups and free aldehyde groups.

[0089] The curable composition preferably has a total of, based on the total composition, · A compound having an aldehyde group or a 1,3 - ketoester group of formula (I) is combined in an amount of 5% to 100% by weight, preferably 10% to 70% by weight, · A plasticizer in an amount of 0% to 50% by weight, preferably 10% to 40% by weight, · A filler in an amount of 0% to 90% by weight, preferably 20% to 80% by weight, · Optional other substances, are contained.

[0090] In the curable composition, the ratio of the number of 1,3 - ketoester groups to the number of aldehyde groups is preferably in the range of 0.5 to 2.5, more preferably 0.8 to 2.2, and particularly 1 to 2. Such a ratio enables rapid and complete curing, giving a mechanically high - quality polymer with high strength, elongation, and stability. The fact that the ratio can be varied within such a range and a non - sticky material with always excellent mechanical properties can be obtained is particularly surprising. This means that the composition is particularly robust against variations in the mixing ratio of the two components during processing.

[0091] 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.

[0092] The first and second components of the curable composition are manufactured separately from each other. The constituent components 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 - shaped pouches, cartridges, or tubes. The components have storage stability.

[0093] For using the hardening composition, two components and any additional components present are mixed with each other immediately before or during application. The mixing ratio is selected here such that the ratio of the number of 1,3-ketoester groups to the number of aldehyde groups is within an appropriate range, particularly about 1 to 2. In parts by weight, the mixing ratio of the first component to the second component is typically in the range of about 100:1 to 1:5, and particularly in the range of 50:1 to 1:2.

[0094] When mixing the components with each other before application, care must be taken that not too much time elapses between mixing of the components and application. Otherwise, due to the start of the reaction and the associated increase in viscosity, problems such as, for example, insufficient leveling or 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.

[0095] In this specification, the "open time" refers to the time interval from mixing of the components to the end of the state of the composition suitable for processing.

[0096] Mixing is preferably carried out at a temperature in the range of ambient temperature, particularly -5 to 50 °C, particularly 0 to 40 °C.

[0097] When the two components are mixed, the hardening of the composition is initiated by the start of a chemical reaction. Here, it is mainly the 1,3-ketoester groups that react with the aldehyde groups, and as a result, the composition hardens to ultimately give a solid polymer material. By the hardening reaction, the following formula:

Chemical formula

[0098] Hardening is preferably carried out at a temperature in the range of ambient temperature, particularly -5 to 50 °C, particularly 0 to 40 °C.

[0099] The present invention further provides a cured composition obtained from a curable composition after mixing two components.

[0100] The cured composition preferably has elasticity and has high strength together with high elongation.

[0101] For this purpose, the cured composition preferably has a tensile strength determined according to DIN EN 53504 described in the examples of at least 1 MPa, preferably at least 1.5 MPa, particularly at least 2 MPa.

[0102] The cured composition preferably has an elongation at break determined according to DIN EN 53504 described in the examples of at least 50%, preferably at least 75%, more preferably at least 100%, particularly preferably at least 150%, particularly at least 200%.

[0103] The cured composition preferably has a Shore A hardness determined according to DIN 53505 described in the examples in the range of 10 to 90, particularly 20 to 80.

[0104] Furthermore, the cured composition has excellent resistance to heat and water. The cured composition preferably has high strength, elongation, and hardness even after being stored at 100 °C or 70 °C and 100% relative humidity for 7 days.

[0105] The curable composition is suitable for many applications. In particular, it can be used as an adhesive, a sealant, a coating, a casting resin, or a spackling compound.

[0106] The present invention further provides the use of a curable composition as an elastic adhesive, an elastic sealant, or an 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.

[0107] 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 to 50 mm, particularly 1.5 to 25 mm.

[0108] Suitable substrates specifically include · Glass, glass ceramic, concrete, mortar, cement screed, fiber cement, brick, tile, 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 metals or alloys with surface finishes such as galvanized metals or chromium-plated metals); · Asphalt or bitumen; · Leather, fabric, paper, wood, and wood-based materials joined with resins such as phenolic resin, melamine resin, or epoxy resin, resin-fabric composites, or polymer composites; · 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 by, for example, 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); · Thermal 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; It is as follows.

[0109] The substrate can be pretreated before coating, if necessary, particularly by physical and / or chemical cleaning methods, or by applying an activator or a primer.

[0110] It is possible to join and / or seal two identical or two different substrates.

[0111] An article is obtained by using the curable composition. This article is particularly joined, sealed, or coated with the composition. This article may be a building or a part thereof, particularly a civil structure, bridge, roof, staircase, or facade constructed above or below the ground, or an industrial product or a consumer good, particularly a window, pipe, rotor blade of a wind turbine, household electrical appliance, or means of transportation, such as in particular an automobile, bus, truck, railway vehicle, ship, aircraft, or helicopter, or an attachable component thereof.

Examples

[0112] Examples intended to further illustrate the present invention described are shown hereinafter. It is clear that the present invention is not limited to these described examples.

[0113] "Standard climatic conditions" ("SCC") refer to a temperature of 23 ± 1°C and a relative air humidity of 50 ± 5%.

[0114] Unless otherwise specified, the chemicals used are from Sigma - Aldrich Chemie GmbH.

[0115] Explanation of the measurement method: The viscosity was measured with a Rheotec RC30 cone - plate viscometer equipped with a thermostat (cone diameter 10 mm, cone angle 1°, cone tip - plate distance 0.05 mm, shear rate 10 s -1 )). Viscosities less than 1 Pa·s were measured with a cone diameter of 50 mm.

[0116] 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 with a diamond crystal. Absorption bands are reported at a wave number (cm -1 ).

[0117] Preparation of isocyanate group-containing polymers: Polymer P-1: 780 g of ethylene oxide-terminated polyoxypropylene triol (Desmophen® 5031BT, OH number 28.0 mg KOH / g, OH functionality approximately 2.3, from Covestro) and 303 g of isophorone diisocyanate (Vestanat® IPDI, from Evonik) were converted into a reaction mixture with an NCO content of 9.1 wt% by a known method at 80 °C. 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%.

[0118] Polymer P-2: 590 g of polyoxypropylene diol (Acclaim® 4200, OH number 28 mg KOH / g, from Covestro), 1180 g of ethylene oxide-terminated polyoxypropylene triol (Caradol® MD34-02, OH number 35 mg KOH / g, from Shell), and 230 g of isophorone diisocyanate (Vestanat® IPDI, from Evonik) were converted into a polymer with an NCO content of 2.1 wt% by a known method at 80 °C.

[0119] Polymer P-3: 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. Subsequently, volatile components, especially unreacted isophorone diisocyanate, were removed by distillation using a short-path evaporator (jacket temperature 160 °C, pressure 0.1 - 0.005 mbar), obtaining a polymer with an NCO content of 1.91 wt% and a monomeric isophorone diisocyanate content of 0.03 wt%.

[0120] Polymer P-4: 727.0 g of polyoxypropylene diol (Acclaim® 4200, OH value 28 mg KOH / g, from Covestro) and 273.0 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 using a short-path evaporator (jacket temperature 180 °C, pressure 0.1 - 0.005 mbar, condensation temperature 47 °C), obtaining a polymer with an NCO content of 1.7 wt% and a monomeric diphenylmethane 4,4'-diisocyanate content of 0.08 wt%.

[0121] Polymer P-5: 513.3 g of polyoxypropylene diol (Acclaim® 4200, OH value 28 mg KOH / g, from Covestro), 256.7 g of ethylene oxide-terminated polyoxypropylene triol (Caradol® MD34-02, OH value 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.

[0122] 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. Subsequently, volatile components, particularly unreacted 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%.

[0123] Preparation of compounds having two or more aldehyde groups: Compounds D-1 to D-7: For each compound, the corresponding isocyanate group-containing polymer in the amount (parts by weight) specified in Table 1 was reacted with the corresponding hydroxy-functional aldehyde in the specified amount (parts by weight) in the presence of 0.02 wt% of dibutyltin dilaurate at 110°C while excluding moisture until the isocyanate groups were no longer detected by IR spectroscopy. In the case of polymers P-4 and P-5 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.

[0124] The properties of Compounds D-1 to D-7 are shown in Table 1.

[0125]

Table 1

[0126] The average molecular weight M of Compound D-1 n was further determined by gel permeation chromatography (GPC) using tetrahydrofuran as the mobile phase and a refractive index detector, with polystyrene (474 - 2,520,000 g / mol) as the standard. The average molecular weight M nIt was 6,100 g / mol.

[0127] Preparation of compounds having two or more 1,3 - ketoester groups: Compounds B - 1 to B - 5: For each compound, a specific polyfunctional alcohol in the amount (parts by weight) specified in Table 2 was mixed with an appropriate amount of 1,3 - ketoester in the specified amount (parts by weight) 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 140 °C under reduced pressure. In each case, a colorless and transparent liquid was obtained.

[0128] [Table 2]

[0129] Production of the curable composition: Examples E - 1 to E - 29 For each example, the raw materials of the first component (K1) specified in Tables 3 to 7 were mixed with each other in the specified amount (parts by weight) using a centrifugal mixer (SpeedMixer™ DAC150, Flack Tek Inc.) and stored in a sealed container.

[0130] The raw materials of the second component (K2) specified in Tables 3 to 7 were treated and stored in the same manner.

[0131] The "precipitated CaCO3" used was Socal® U1S2 (from Imerys), which is calcium carbonate precipitated and coated with stearate.

[0132] The "carbon black" used was Monarch® 570 (from Cabot).

[0133] Thereafter, the two components of each composition were treated using a centrifugal mixer to obtain a homogeneous paste. This was tested as described below.

[0134] The gel time was determined by stirring an approximately 3 g freshly mixed amount at regular intervals with a spatula in standard climatic conditions until the mass gelled and could no longer be stirred.

[0135] 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, allowing this film to cure by leaving it in standard climatic conditions for 7 days, 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, and modulus of elasticity MoE5% (at an elongation of 0.5% - 5%) and MoE50% (at an elongation of 0.5% - 50%) at a strain rate of 200 mm / min according to DIN EN53504. Furthermore, to determine the tear propagation resistance, a plurality of test pieces were punched out and tested according to DIN ISO34-1, Method B (angled test piece) at a strain rate of 500 mm / min.

[0136] The Shore A hardness was measured according to DIN53505 for test pieces cured in standard climatic conditions for 7 days. These results were marked with "7d SCC". The heat resistance and water resistance were determined by further storing the Shore A test pieces in an air-circulating oven at 100 °C for an additional 7 days, or at 70 °C and 100% relative humidity for an additional 7 days after curing in standard climatic conditions for 7 days, cooling them to room temperature, and then measuring the Shore A hardness as described in each case. These results were marked with "+7d 100 °C" or "+7d 70 / 100".

[0137] In each case, a non-tacky elastic material was obtained by curing the examples of the present invention.

[0138] The results are reported in Tables 3 to 7.

[0139]

Table 3

[0140]

Table 4

[0141]

Table 5

[0142]

Table 6

[0143]

Table 7

Claims

1. A curable composition, the following: - A first component comprising an aldehyde group-containing compound, which includes at least one compound having two or more aldehyde groups, A second component comprising a 1,3-ketoester group-containing compound, comprising at least one compound having two or more 1,3-ketoester groups of the following formula (I), 【Chemistry 1】 Includes R １ This is a monovalent hydrocarbyl group having 1 to 6 carbon atoms, The average molecular weight M of at least one of the two components relating to the aldehyde group-containing compound or the 1,3-ketoester group-containing compound. ｎ A curable composition having a concentration in the range of 400 to 20,000 g / mol.

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

3. The compound having two or more aldehyde groups is liquid at room temperature, and in particular, the cone diameter is 10 mm, the cone angle is 1°, the distance between the cone tip and the plate is 0.05 mm, and the shear rate is 10 s. －１ The composition according to claim 1 or 2, characterized in that, for viscosities less than 1 Pa·s, when measured with a cone plate viscometer with a ball diameter of 50 mm, the liquid has a viscosity of 0.2 to 700 Pa·s, preferably 0.3 to 500 Pa·s, and more preferably 0.5 to 200 Pa·s at 20°C.

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 aldehyde group-containing compound is a urethane group-containing polymer that 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 by comprising a urethane group-containing polymer having an average aldehyde functional value of 1.8 to 3.5, preferably 2.0 to 3.0, and particularly 2.2 to 3.

0.

7. In the 1,3-ketoester group of formula (I), R １ The composition according to claim 1 or 2, characterized in that is methyl, ethyl, propyl, isopropyl, butyl, or phenyl, preferably methyl or phenyl, and particularly methyl.

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

0.

9. The average molecular weight M of the second component in the 1,3-ketoester group-containing compound. ｎ The composition according to claim 1 or 2, characterized in that the amount is in the range of 230 to 10,000 g / mol, preferably 250 to 2,000 g / mol.

10. The composition according to claim 1 or 2, characterized in that a filler is present in an amount of 10% to 95% by weight, preferably 20% to 90% by weight, and particularly 30% to 80% by weight, based on the entire composition.

11. The composition according to claim 1 or 2, characterized in that a plasticizer is present in an amount of 5% to 80% by weight, particularly 10% to 60% by weight, based on the entire composition.

12. 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, preferably less than 5% by weight, and particularly less than 1% by weight, based on the entire composition.

13. A cured composition obtained from the curable composition according to claim 1 or 2 after the two components have been mixed, wherein the cured composition has a tensile strength of at least 1 MPa, preferably at least 1.5 MPa, particularly at least 2 MPa, and / or elongation at break of at least 75%, preferably at least 100%, particularly at least 150%, as measured by DIN EN 53504 at a strain rate of 200 mm / min in a dumbbell-shaped test specimen having a thickness of 2 mm, a length of 75 mm, a rod length of 30 mm, and a rod width of 4 mm, and / or elongation at break of at least 75%, preferably at least 100%, particularly at least 150%.

14. 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.

15. The use according to claim 14, wherein the cured composition has a layer thickness of at least 1 mm, preferably 1 to 50 mm, and particularly 1.5 to 25 mm.

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