One-component moisture-curable composition

Abstract

The present invention describes a one-component moisture-curable composition comprising 100 parts by weight of a polymer P1 containing silane groups of formula (I), 5-50 parts by weight of at least one liquid epoxy resin, at least one polyketimine, 2-15 parts by weight of at least one epoxy silane, preferably glycidoxy silane, 0-500 parts by weight of a filler, and 0-500 parts by weight of a plasticizer. The composition of the present invention allows for adhesives and / or sealants with soft elastic properties, good adhesion to mortar or concrete after immersion in water, and high heat resistance.

Description

[Technical field]

[0001] An elastic one-component moisture-curable composition based on a combination of a silane group-containing polymer and an epoxy resin. [Background technology]

[0002] Elastic sealants and adhesives for architectural or industrial applications are well known and are used, for example, in joint sealers or adhesive joints in vehicle construction. In some applications, it is required that the elastic material has soft elastic properties with high elongation combined with moderate hardness and e-modulus. Such materials allow elastic joints that can compensate for some movements of the joined bodies and do not transfer stress to the joined surfaces. Soft elastic sealants and / or adhesives are typically based on polyurethane or silane functional polymers. Unfortunately, they have weaknesses in terms of adhesive properties and often require laborious pre-treatments to achieve reliable adhesion that is stable even after immersion in water and / or heat action. In some applications, soft elastic sealants and / or adhesives need to have high heat resistance, for example for joints on car bodies that are powder coated at 180°C in the later process, and even sealants for battery boxes of e-vehicles that must withstand temperatures of 80°C or more. Known soft elastic sealants and / or adhesives based on polyurethane polymers or silane-functional polymers are unable to meet this requirement.

[0003] US Patent Application Publication No. 2021 / 163667 describes soft elastic compositions based on silane-functional and / or isocyanate-functional polymers. These compositions have weaknesses in terms of adhesive performance and heat resistance.

[0004] Adhesives based on a combination of silane-functional polymers and epoxy resins are known. Such combinations allow the production of materials with high hardness and considerable elongation. They are typically packaged as two-component compositions in two separate containers, requiring a mixing step before or during application. This is inconvenient and the process is prone to mistakes in terms of the mixing ratio, incomplete mixing, or exceeding the waiting time between mixing the components and application, which can result in insufficient curing or poor adhesion. Such adhesives are described, for example, in US Pat. No. 9,856,374 or US Pat. No. 10,428,252. They typically contain a large amount of epoxy resin, have high hardness and limited flexibility.

[0005] One-component moisture-curing compositions based on a combination of a silane group-containing polymer and an epoxy resin are also known, for example from JP 2003-128755, JP 2003-128756 or US 2016 / 0122606. They describe ketimine-containing compositions stored in a single container and then applied without the need for a mixing step. The known compositions are based on silane group-containing polymers, which are reaction products by hydrosilylation of polyether glycol allyl ethers (so-called MS polymers). The compositions allow adhesives or sealants with adhesion to mortar or concrete under dry conditions. However, the adhesion obtained after immersion in water and the thermal stability after curing of the compositions are insufficient. Summary of the Invention [Problem to be solved by the invention]

[0006] The object of the present invention is to provide a one-component moisture-curing composition having soft elastic properties, good heat resistance and good adhesion, especially to mortar or concrete, especially after immersion in water and / or exposure to heat. [Means for solving the problem]

[0007] Surprisingly, this object is achieved by using the composition according to claim 1. The composition of the present invention comprises a specific silane group-containing polymer, a relatively small amount of epoxy resin, a large amount of epoxy silane, polyketimine, and possibly a filler and / or plasticizer. Surprisingly, the composition of the present invention shows a highly improved adhesion on mortar or concrete after immersion in water, as well as a surprisingly good adhesion on plastic substrates, such as PVC. Even more surprising, the cured composition shows an excellent thermal stability of up to 2 hours at 200°C, and even a long-term heat resistance of 28 days at 90°C or 24 hours at 180°C. This excellent thermal stability is quite surprising for a soft elastic material. Materials with soft elastic performance are based on a polymer network with a low degree of crosslinking, which is prone to depolymerization on heat exposure.

[0008] The compositions of the invention are particularly suitable for use as sealants and / or adhesives, in particular in the building industry, in manufacturing or in vehicle construction, in particular for sealing joints or cavities, for example for high-rise facades or ship decks, for adhering wall panels to facades or for module bonding, in particular for module bonding in vehicle construction or for sealing battery boxes in e-vehicles.

[0009] Further aspects of the invention are set out in the other independent claims. Preferred aspects of the invention are set out in the dependent claims. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The subject of the present invention is a one-component moisture-curing composition comprising: 100 parts by weight of a polymer P1 containing silane groups of formula (I), [ka] [In the formula, n is 2 or 3; R 1 is a linear or branched C1 to C5 alkyl group, R 2 is bifunctional C2~C 12 Bifunctional C3-C containing a hydrocarbon group, an amide group or a carbamate group 12 is a hydrocarbon group, X is O, S or NR 3 Here, R 3 is hydrogen or C1-C 10 Hydrocarbon group, or C3-C containing one or two ether groups or carboxylate groups 20 a hydrocarbon group or an alkoxysilane group, D is a divalent C4-C 15 is a hydrocarbon group. - 5 to 50 parts by weight of at least one liquid epoxy resin, at least one polyketimine, - 2 to 15 parts by weight of at least one epoxy silane, - 0 to 500 parts by weight of a filler, and - 0 to 500 parts by weight of plasticizer.

[0011] As used herein, the term "one-component moisture-curable composition" refers to a composition that is stored in a single, moisture-tight container, has shelf-life stability, and cures upon exposure to moisture without the need for additional components.

[0012] In this document, the term "shelf life stability" refers to the ability of a material or composition to be stored at room temperature in a suitable container protected from moisture for a period of time, specifically several months, without significant change in application performance or end use performance.

[0013] A dotted line in formulas herein represents a bond between a substituent and the remainder of the molecule to which it is connected.

[0014] The term "silane group" refers to a silyl group attached to an organic residue and having a hydrolyzable alkoxy group on the silicon atom.

[0015] Thus, the term "silane" or "organosilane" refers to an organic compound that contains at least one silane group.

[0016] The terms "epoxysilane," "aminosilane," or "hydroxysilane" refer to organosilanes that have epoxy, amine, or hydroxy groups on the organic residue in addition to the silane group.

[0017] Substance names beginning with "poly", such as polyamine, polyketimine, or polyepoxide, refer to substances that contain two or more of the functional groups represented by those names per molecule.

[0018] The term "amine hydrogen" refers to the hydrogen atoms of primary and secondary amine groups.

[0019] A "primary amine group" refers to an amine group that is bonded to a single organic residue and bears two hydrogen atoms; a "secondary amine group" refers to an amine group that is bonded to two organic residues (both of which may be part of a ring) and bears one hydrogen atom; and a "tertiary amine group" refers to an amine group that is bonded to three organic residues (two or three of which may be part of one or more rings) and bears no hydrogen atoms.

[0020] The term "molecular weight" refers to the molar mass (g / mol) of a molecule. The term "average molecular weight" refers to the number average molecular weight (M n It is measured by means of gel permeation chromatography (GPC) against polystyrene as standard, in particular with tetrahydrofuran as mobile phase and a refractive index detector.

[0021] The "open time" is the time interval during which an applied composition can be worked or reprocessed without any adverse effects. It is exceeded when, as a result of the curing process, the composition becomes too viscous, or at the latest when a skin forms on its surface. The time until a skin forms on the surface is called the "skin formation time" or "skinning time".

[0022] "Room temperature" refers to a temperature of 23°C.

[0023] The term "wt. %" refers to the mass fraction of a composition component based on the total composition, unless otherwise specified. The terms "weight" and "mass" are used synonymously in this document.

[0024] All industry standards and regulations referred to in this document refer to the latest editions in effect at the time of initial filing, unless otherwise noted.

[0025] The polymer P1 is preferably liquid at room temperature.

[0026] It is preferred that the polymer P1 has a poly(oxyalkylene) backbone, in particular a poly(oxy-1,4-butylene) or poly(oxy-1,2-butylene) or poly(oxy-1,3-propylene) or poly(oxy-1,2-propylene) or poly(oxyethylene) backbone, or mixtures thereof.

[0027] In particular, polymer P1 has a poly(oxy-1,2-propylene) backbone or a mixed poly(oxyethylene) and poly(oxy-1,2-propylene) backbone.

[0028] It is most preferred if the polymer P1 has a poly(oxy-1,2-propylene) backbone.

[0029] The polymer P1 preferably has an average molecular weight M of 4,000 to 30,000 g / mol, more preferably 6,000 to 25,000 g / mol, in particular 10,000 to 20,000 g / mol. n It has.

[0030] The polymer P1 preferably has an average silane functionality of 1.5-3, more preferably 1.6-2.3 and in particular 1.8-2.

[0031] Preferably, the polymer P1 contains no hydroxyl groups and no isocyanate groups.

[0032] The polymer P1 has a poly(oxyalkylene) backbone and an average molecular weight M of 6,000 to 25,000 g / mol. n and an average silane functionality of 1.8 to 2.

[0033] Such polymers allow for good paintability and cured materials with high flexibility.

[0034] In the silane group of formula (I), it is preferred that n is 3.

[0035] R 1 is preferably methyl or ethyl or isopropyl, in particular methyl or ethyl.

[0036] n is 2 and R 1 is methyl, or n is 3 and R 1 It is particularly preferred that is methyl or ethyl. Such compositions cure rapidly and are capable of high mechanical strength.

[0037] n=3, R 1 = Methyl, hardening is particularly fast.

[0038] R 1 = ethyl, the composition has toxicological advantages.

[0039] R2 is 1,3-propylene, 1,4-butylene, methyl-substituted 1,4-butylene, dimethyl-substituted 1,4-butylene, or a C6-C aryl group containing an amide group or a carbamate group. 12 Hydrocarbon groups are preferred, in particular groups of the formula [ka] (where X=O).

[0040] X is O or NR 3 It is preferable that:

[0041] R 3 is preferably hydrogen, n-butyl, phenyl, or succinate-2-yl. 3 It is particularly preferred that the aryl group is diethylsuccinate-2-yl.

[0042] R 2 is a C3-C6 alkylene group, preferably 1,3-propylene, and X is NR 3 and R 3 It is particularly preferred if is succinate-2-yl, preferably diethylsuccinate-2-yl. Such polymers P1 allow compositions with high elongation and flexibility, as well as good tear strength performance.

[0043] D is divalent C6~C 13 It is preferably a hydrocarbon group.

[0044] In particular, D is 1,6-hexane diisocyanate (HDI), isophorone diisocyanate (IPDI), 4,4'-diisocyanatodicyclohexylmethane (H 12 The divalent radical obtained after removing two isocyanate groups from diphenylmethane diisocyanate (MDI), diphenylmethane diisocyanate (MDI), and toluene diisocyanate (TDI).

[0045] It is most preferred if D is a divalent radical obtained after removal of two isocyanate groups from isophorone diisocyanate. Such polymers P1 allow compositions with particularly good coating properties and high light fastness.

[0046] n is 3, and R 1 is methyl and R 2 is 1,3-propylene and X is NR 3 and R 3 Most preferred are polymers P1 containing silane groups of formula (I), such that is diethylsuccinate-2-yl and D is a divalent radical obtained after removal of two isocyanate groups from isophorone diisocyanate.

[0047] Suitable polymers P1 are preferably obtained by reacting an isocyanate-functional polymer with at least one silane of formula (II), [ka] In the formula, n, R 1 , R 2 , and X have the meanings given above.

[0048] The reaction is preferably carried out under the exclusion of moisture at a temperature in the range from 20 to 140° C. and at a molar ratio of silane of formula (II) to isocyanate groups of 1 / 1 to 1.5 / 1, in particular 1 / 1 to 1.2 / 1.

[0049] Preferably, the isocyanate-functional polymer has an isocyanate group content of 0.4 to 3.5% by weight, preferably 0.6 to 1.5% by weight.

[0050] Suitable isocyanate-functional polymers are therefore obtainable in particular by reaction of at least one polyol with at least one diisocyanate of the formula OCN-D-NCO, in which D has the meaning already mentioned.

[0051] The reaction is preferably carried out under the exclusion of moisture at a temperature in the range from 20 to 160° C., in particular from 40 to 140° C., optionally in the presence of a suitable catalyst. The molar ratio NCO / OH is preferably from 1.3 / 1 to 2.5 / 1, in particular from 1.8 / 1 to 2.1 / 1.

[0052] Suitable polyols for preparing isocyanate-functional polymers are polyether polyols which are liquid at room temperature, in particular the polymerization reaction products of polyoxyalkylene diols and / or polyoxyalkylene triols, in particular ethylene oxide or 1,2-propylene oxide or 1,2-butylene oxide or oxetane or tetrahydrofuran, or mixtures thereof, which can be polymerized using starter molecules having two or three active hydrogen atoms, such as, for example, water, ammonia, or compounds having multiple OH or NH groups, such as, for example, ethane-1,2-diol. , propane-1,2-diol, propane-1,3-diol, neopentyl glycol, diethylene glycol, triethylene glycol, the various isomeric dipropylene glycols or tripropylene glycols, the various 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 or aniline, or mixtures of the above-mentioned compounds.

[0053] Preferred are poly(oxy-1,2-propylene) diols or triols, or so-called ethylene oxide-terminated (EO-capped) poly(oxy-1,2-propylene) diols or triols, which are obtained by further alkoxylation with ethylene oxide of poly(oxy-1,2-propylene) diols or triols which have been subjected to the complete polypropoxylation reaction, so that they contain primary hydroxyl groups.

[0054] Preferred polyether polyols have unsaturation levels of less than 0.02 meq / g, especially less than 0.01 meq / g.

[0055] Preference is given to poly(oxy-1,2-propylene)diols or poly(oxy-1,2-propylene)triols, optionally containing terminal oxyethylene groups, with an average OH functionality in the range from 1.6 to 3. Particular preference is given to poly(oxy-1,2-propylene)diols with an average OH functionality of 1.8 to 2.

[0056] Preferred are average molecular weights M in the range of 2,000 to 20,000 g / mol, preferably 4,000 to 18,000 g / mol, more preferably 8,000 to 15,000 g / mol. n It is a polyether polyol having the formula:

[0057] Preferred are polyether polyols having an OH value in the range of 6 to 58 mg KOH / g, preferably 8 to 20 mg KOH / g.

[0058] Suitable diisocyanates of the formula OCN-D-NCO are: 1,6-hexane diisocyanate (HDI), isophorone diisocyanate (IPDI), 4,4'-diisocyanatodicyclohexylmethane (H 12Diphenylmethane diisocyanate (MDI), in particular 4,4'-diphenylmethane diisocyanate or mixtures thereof with 2,4'-diphenylmethane diisocyanate and 2,2'-diphenylmethane diisocyanate, and toluene diisocyanate (TDI), in particular mixtures thereof with 2,4-toluene diisocyanate or 2,6-toluene diisocyanate.

[0059] Particularly preferred is IPDI.

[0060] Suitable silanes of formula (II) are: aminosilanes, in particular 3-aminopropyl-trimethoxysilane, 3-aminopropyldimethoxymethylsilane, 4-aminobutyltrimethoxysilane, 4-amino-3-methylbutyltrimethoxysilane, 4-amino-3,3-dimethylbutyltrimethoxysilane, N-butyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, adducts of primary aminosilanes, such as 3-aminopropyltrimethoxysilane or 3-aminopropyldimethoxymethylsilane, with Michael reaction acceptors, such as acrylonitrile, esters or amides of (meth)acrylic acid, diesters of maleic acid, fumaric acid, citraconic acid or itaconic acid, in particular diethyl N-(3-trimethoxy-silylpropyl)aminosuccinate or diethyl N-(3-dimethoxymethylsilylpropyl)aminosuccinate, and also the corresponding aminosilanes, in which ethoxysilane groups are substituted for the methoxysilane groups.

[0061] Further suitable silanes of formula (II) are mercaptosilanes, in particular 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane or 3-mercaptopropyl-dimethoxymethylsilane.

[0062] Further suitable silanes of formula (II) are hydroxysilanes, in particular N-(3-triethoxysilylpropyl)-2-hydroxypropanamide, N-(3-trimethoxysilylpropyl)-2-hydroxy-propanamide, N-(3-triethoxysilylpropyl)-4-hydroxypentanamide, N-(3-triethoxysilylpropyl)-4-hydroxyoctanamide, N-(3-triethoxysilylpropyl)-5-hydroxydecaneamide, or N-(3-triethoxysilylpropyl)-2-hydroxypropyl carbamate, in particular N-(3-triethoxysilylpropyl)-2-hydroxypropanamide.

[0063] Particularly preferred silanes of formula (II) are aminosilanes, most preferred being diethyl N-(3-trimethoxysilylpropyl)aminosuccinate or diethyl N-(3-triethoxysilylpropyl)aminosuccinate.

[0064] Suitable liquid epoxy resins include common industrial epoxy resins that are free-flowing at room temperature and have a glass transition temperature of less than 25° C. They are typically obtained by glycidylation of polyphenols, polyols or amines by reaction with epichlorohydrin.

[0065] Suitable liquid epoxy resins are in particular aromatic liquid epoxy resins, in particular the glycidyl reaction products of: bisphenol-A or bisphenol-F (where A represents acetone and F represents formaldehyde, which serve as reactants for the preparation of these bisphenols. In the case of bisphenol F, positional isomers may also be present, in particular those derived from 2,4'- or 2,2'-hydroxyphenylmethane); - dihydroxybenzene derivatives, such as resorcinol, hydroquinone or catechol; further bisphenols or polyphenols, such as bis(4-hydroxy-3-methylphenyl)methane, 2,2-bis(4-hydroxy-3-methylphenyl)propane (bisphenol-C), bis(3,5-dimethyl-4-hydroxyphenyl)methane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-tert-butylphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane (bisphenol-B), 3,3-bis(4-hydroxyphenyl)pentane, 3,4-bis(4-hydroxyphenyl)hexane, 4,4-bis(4-hydroxyphenyl)heptane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 2,4-bis(3,5-dimethyl-4-hydroxyphenyl)-2-methylbutane, 1,1- bis(4-hydroxyphenyl)cyclohexane (bisphenol-Z), 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (bisphenol-TMC), 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,4-bis[2-(4-hydroxyphenyl)-2-propyl]benzene (bisphenol-P), 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene (bisphenol-M), 4,4'-dihydroxydiphenyl (DOD), 4,4'-dihydroxybenzophenone, bis(2-hydroxynaphth-1-yl)methane, bis(4-hydroxynaphth-1-yl)methane, 1,5-dihydroxynaphthalene, tris(4-hydroxyphenyl)methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, bis(4-hydroxyphenyl)ether, or bis(4-hydroxyphenyl)sulfone; - condensation products of phenol with formaldehyde, obtained under acidic conditions, such as phenol novolacs or cresol novolacs (also called bisphenol-F novolacs); aromatic amines, such as aniline, toluidine, 4-aminophenol, 4,4'-methylenediphenyldiamine, 4,4'-methylenediphenyldi(N-methyl)amine, 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisaniline (bisaniline-P), or 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisaniline (bisaniline-M).

[0066] Further suitable liquid epoxy resins are aliphatic or cycloaliphatic polyepoxides, in particular: - Saturated or unsaturated, branched or unbranched, cyclic or open-ring, bifunctional, trifunctional or tetrafunctional C2-C 30 glycidyl ethers of alcohols, in particular ethylene glycol, propylene glycol, butylene glycol, hexanediol, octanediol, polypropylene glycol, dimethylolcyclohexane, neopentyl glycol, dibromoneopentyl glycol, castor oil, trimethylolpropane, trimethylolethane, pentaerythritol, sorbitol or glycerol, or alkoxylated glycerol or alkoxylated trimethylolpropane; - hydrogenated bisphenol-A or bisphenol-F liquid resins or glycidyl reaction products of hydrogenated bisphenol-A or bisphenol-F; - N-glycidyl derivatives of amide or heterocyclic nitrogen bases, such as triglycidyl cyanurate or triglycidyl isocyanurate, or the reaction products of epichlorohydrin with hydantoin; - epoxy resins obtained, for example, by oxidation of the following olefins: vinylcyclohexene, dicyclopentadiene, cyclohexadiene, cyclododecadiene, cyclododecatriene, isoprene, 1,5-hexadiene, butadiene, polybutadiene or divinylbenzene.

[0067] Preferred liquid epoxy resins are aromatic polyglycidyl ethers, preferably selected from bisphenol-A diglycidyl ether, bisphenol-F diglycidyl ether, and phenol-formaldehyde novolac glycidyl ether, with an average functionality of 2.3 to 4, preferably 2.5 to 3. Such liquid epoxy resins are highly hydrophobic and have relatively low viscosity. They are commercially available, for example, from Olin, Huntsman, or Momentive.

[0068] Particularly preferred is bisphenol-A diglycidyl ether.

[0069] Further particularly preferred are phenol-formaldehyde novolac glycidyl ethers, such as DEN® 431 (Olin), having an average functionality of 2.5 to 3. This gives particularly good adhesion on plastic substrates.

[0070] The liquid epoxy resin preferably has an average epoxy equivalent weight of 156 to 200 g / eq.

[0071] The amount of liquid epoxy resin in the one-component moisture-curable composition is preferably between 10 and 35 parts by weight, based on 100 parts by weight of polymer P1.

[0072] The one-component moisture curable composition further includes at least one polyketimine.

[0073] Suitable polyketimines are condensation products of primary polyamines with ketones. The condensation is preferably carried out with at least 1 mol of ketone per mol equivalent of primary amine groups at temperatures between 10 and 100° C., with removal of the released water, preferably either by direct distillation or by using a solvent such as toluene or cyclohexane as an entrainer. Primary polyamines further comprising secondary amine groups can also be further reacted with monoepoxides, such as phenyl glycidyl ether.

[0074] Preference is given to aliphatic, cycloaliphatic or araliphatic amines having two or three primary amine groups, in particular 2,2-dimethylpropane-1,3-diamine, pentane-1,3-diamine (DAMP), pentane-1,5-diamine, 1,5-diamino-2-methylpentane (MPMD), 2-butyl-2-ethylpentane-1,5-diamine (C11 neodiamine), hexane-1,6-diamine, 2,5-dimethylhexane-1,6-diamine. , 2,2(4),4-trimethylhexamethylenediamine (TMD), heptane-1,7-diamine, octane-1,8-diamine, nonane-1,9-diamine, decane-1,10-diamine, undecane-1,11-diamine, dodecane-1,12-diamine, diethylenetriamine (DETA), dipropylenetriamine (DPTA), 3-(2-aminoethyl)aminopropylamine, bis(hexamethylene)triamine (BHMT), N-(3-aminopropyl)- 2-Methylpentane-1,5-diamine, N3-(3-aminopentyl)pentane-1,3-diamine, N5-(3-amino-1-ethylpropyl)-2-methylpentane-1,5-diamine, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, isophoronediamine (IPDA), 2(4)-methyl-1,3-diaminocyclohexane Cyclohexane, bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane, bis(4-amino-3-ethylcyclohexyl)methane, bis(4-amino-3,5-dimethylcyclohexyl)methane, bis(4-amino-3-ethyl-5-methylcyclohexyl)methane, 2,5(2,6)-bis(aminomethyl)bicyclo[2.2.1]heptane (NBDA), 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.0]heptane (NBDA), 2,6]decane, 1,4-diamino-2,2,6-trimethylcyclohexane (TMCDA), menthane-1,8-diamine, 1,3-bis(aminomethyl)benzene (MXDA), 1,4-bis(aminomethyl)benzene, 3,6-dioxaoctane-1,8-diamine, 4,7-dioxadecane-1,10-diamine, 4,7-dioxadecane-2,9-diamine, 4,9-dioxadodecane-1,12-diamine, 5,8-dioxadodecane-3,10-diamine, 4,7,10-trioxatridecane-1,13-diamine, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, average molecular weight M of 200 to 5,000 g / mol, preferably 200 to 500 g / mol n Polyoxypropylene diamine or triamine having the formula:

[0075] Among them, the following are preferred: MPMD, C11 neodiamine, hexane-1,6-diamine, TMD, DETA, DPTA, 3-(2-aminoethyl)aminopropylamine, 1,2-diaminocyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, IPDA, 2(4)-methyl-1,3-diaminocyclohexane, bis(4-aminocyclohexyl)methane, NBDA, MXDA, or amines having an average molecular weight M of 200 to 500 g / mol. n Polyoxy-propylene-diamines or -triamines having the formula:

[0076] Particularly preferred are DETA, 1,2-diaminocyclohexane, IPDA, or cyclohexane having an average molecular weight M of 200 to 500 g / mol. n It is a polyoxypropylene diamine or triamine having the formula:

[0077] Suitable ketones are in particular ketones having 3 to 15 C atoms, preferably acetone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl pentyl ketone, methyl isopentyl ketone, methyl isoamyl ketone, diethyl ketone, dipropyl ketone, diisopropyl ketone, dibutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone or acetophenone.

[0078] Among them, methyl isobutyl ketone or cyclohexanone is preferred.

[0079] Particularly preferred polyketimines are (a) DETA, 1,2-diaminocyclohexane, IPDA, or polyketimines having an average molecular weight M of 200 to 500 g / mol. n with (b) methyl isobutyl ketone or cyclohexanone in a ratio of at least 1 mole of ketone per molar equivalent of primary amine groups, where the condensate is optionally further reacted with a monoepoxide, preferably phenyl glycidyl ether.

[0080] Particularly preferred is the bisketimine of DETA and methyl isobutyl ketone, which is preferably further reacted with phenyl glycidyl ether at the secondary amine groups.

[0081] More particularly preferred is a bisketimine from IPDA and methyl isobutyl ketone.

[0082] More particularly preferred is a bisketimine from 1,2-diaminocyclohexane and cyclohexanone.

[0083] The amount of polyketimine in the composition is preferably such that the number of ketimine groups in the composition is 0.5 to 1.5, preferably 0.8 to 1.2, based on the number of epoxy groups.

[0084] The one-component moisture-curable composition further comprises from 2 to 15 parts by weight of at least one epoxy silane per 100 parts by weight of polymer P1.

[0085] The preferred epoxy silane is glycidoxy silane.

[0086] Particularly preferred are 3-glycidoxypropyltrimethoxysilane or 3-glycidoxypropyltriethoxysilane. In the case of polymers P1 having methoxysilane groups, 3-glycidoxypropyltrimethoxysilane is preferred. In the case of polymers P1 having ethoxysilane groups, 3-glycidoxypropyltriethoxysilane is preferred.

[0087] The amount of epoxysilane in the composition is preferably from 2 to 10 parts by weight, in particular from 3 to 8 parts by weight, per 100 parts by weight of polymer P1.

[0088] Preferred epoxy silanes allow a long open time and particularly good adhesion on mortar or concrete after immersion in water, as well as on plastic substrates such as PVC or ABS.

[0089] The one-component moisture curable composition may include additional components.

[0090] It is preferred that the one-component moisture curable composition include at least one desiccant.

[0091] Suitable drying agents include, in particular, vinyltrimethoxysilane, vinyltriethoxysilane, tetraethoxysilane, methoxymethylsilane, orthoformates, organosilanes having a functional group alpha to the silane group, such as N-(methyldimethoxy-silylmethyl)-O-methylcarbamate or (methacryloyloxymethyl)silane, and also calcium oxide, or molecular sieves.

[0092] Preferred is vinyltrimethoxysilane or vinyltriethoxysilane.

[0093] In a preferred embodiment of the present invention, the one-component moisture curable composition comprises at least one ketiminosilane.Preferred ketiminosilane is the condensate of 3-aminopropyltrimethoxysilane or 3-aminopropyltriethoxysilane with at least one ketone, preferably methyl isobutyl ketone or methyl isoamyl ketone.Such ketiminosilane allows particularly fast curing and particularly good adhesion on plastic substrates such as ABS.

[0094] It is preferred that the one-component moisture curable composition include at least one accelerator.

[0095] Suitable accelerators are substances that accelerate the crosslinking of polymers containing silane groups. Particularly suitable are metal catalysts, preferably compounds of titanium, zirconium, aluminum or tin, in particular organotin compounds, organotitanates, organozirconates or organoaluminates. These metal catalysts preferably have alkoxy groups, aminoalkoxy groups, sulfonate groups, carboxylate groups, 1,3-diketonate groups, 1,3-ketoesterate groups, dialkylphosphate groups or dialkylpyrophosphate groups. Particularly suitable are dibutyltin dilaurate, dibutyltin diacetylacetonate, dibutyltin dineodecanoate or dioctyltin dilaurate.

[0096] Suitable further accelerators are substances which accelerate the reaction of epoxy groups with amine groups and / or which accelerate the hydrolysis of ketimine groups, in particular acids or compounds which can be hydrolyzed to acids, in particular organic carboxylic acids such as salicylic acid, organic sulfonic acids such as p-toluenesulfonic acid, sulfonic acid esters, phosphoric acids or nitrates, in particular calcium nitrate. Particularly suitable is salicylic acid.

[0097] It is preferred that the one-component moisture curable composition contains at least one filler.

[0098] Suitable fillers are in particular ground or precipitated calcium carbonate (optionally coated with fatty acids, such as stearic acid esters), also barite flour, quartz flour, silica sand, dolomite, wollastonite, calcined kaolin, sheet silicates, such as mica or talc, zeolites, aluminium hydroxide, magnesium hydroxide, silica (including finely divided silica from pyrogenic processes), cementing agents, gypsum, fly ash, industrially produced carbon black, graphite, metal powders, such as aluminium, copper, iron, silver or steel, PVC powder or light-weight fillers, such as hollow glass beads or gas-filled plastic spheres (microspheres), in particular of the type available under the trade name Expancel® (manufactured by Akzo Nobel).

[0099] Preferred are calcium carbonate, calcined kaolin, finely divided silica, or industrially produced carbon black.

[0100] The one-component moisture-curable composition contains from 0 to 500 parts by weight of filler per 100 parts by weight of polymer P1.

[0101] The amount of filler is preferably from 50 to 500 parts by weight, in particular from 100 to 300 parts by weight, based on 100 parts by weight of polymer P1.

[0102] It is preferred that the one-component moisture curable composition contains at least one plasticizer.

[0103] Suitable plasticizers are in particular carboxylic acid esters, such as phthalates, in particular isononyl phthalate (DINP), diisodecyl phthalate (DIDP) or di(2-propylheptyl)phthalate (DPHP), hydrogenated phthalates, i.e. cyclohexane-1,2-dicarboxylates, in particular hydrogenated diisononyl phthalates, i.e. diisononylcyclohexane-1,2-dicarboxylate (DINCH), terephthalates, in particular bis(2-ethylhexyl)terephthalate (DOTP) or diisononyl terephthalate (DINT), hydrogenated terephthalates, i.e. cyclohexane-1,4-dicarboxylates, in particular hydrogenated bis(2-ethylhexyl)terephthalate, i.e. bis(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, or hydrogenated diisononyl phthalates. Examples of suitable plasticizers include but are not limited to dioctyl adipate, isophthalate, trimellitate, adipate, especially dioctyl adipate, azelate, sebacate, citrate, benzoate, glycol ether, glycol ester, especially triethylene glycol bis(2-ethylhexanoate), plasticizers having a polyether structure, especially poly-(oxypropylene) monol or poly(oxypropylene) diol or poly(oxypropylene) triol, or poly(oxypropylene) mono-, di- or triols having blocked hydroxyl groups, especially in the form of acetates, organic phosphates or sulfonates, polybutenes, polyisobutenes, or plasticizers derived from natural fats and oils, especially epoxidized soybean oil or linseed oil.

[0104] Preferably, the plasticizer is selected from the group consisting of DINP, DIDP, DPHP, DINCH, DOTP, DINT, bis(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, diisononylcyclohexane-1,4-dicarboxylate, dioctyl adipate, poly(oxypropylene) monols, poly(oxypropylene) diols, poly(oxypropylene) triols, and poly(oxypropylene) monols, diols, and triols with blocked hydroxyl groups in the acetate form.

[0105] The one-component moisture-curable composition preferably contains plasticizers in an amount of 10 to 500 parts by weight, preferably 20 to 300 parts by weight, based on 100 parts by weight of polymer P1.

[0106] In a preferred embodiment of the invention, the composition does not contain any or only small amounts of plasticizer, preferably 0 to 50 parts by weight of plasticizer, based on 100 parts by weight of polymer P1, and additionally at least one ketiminosilane. Such compositions have particularly good adhesion, in particular to plastic substrates such as ABS or PVC.

[0107] The one-component moisture-curable composition may contain further additives, in particular: - solvents or diluents other than plasticizers (not including alcohols and ketones released by hydrolysis of silane groups and ketimines) in an amount preferably less than 5% by weight, in particular less than 1% by weight, based on the total composition; inorganic or organic pigments, in particular titanium dioxide, chromium oxide or iron oxide; - dye; - rheology modifiers, in particular thickeners, in particular layered silicates, such as bentonite, derivatives of castor oil, hydrogenated castor oil, polyamides, polyurethanes, urea compounds, polyvinyl chloride, fumed silica, cellulose ethers or hydrophobically modified poly(oxyethylene); - natural resins, oils and fats, such as rosin, shellac, linseed oil, castor oil or soybean oil; non-reactive polymers, in particular homopolymers or copolymers of unsaturated monomers such as ethylene, propylene, butylene, isobutylene, isoprene, vinyl acetate or alkyl (meth)acrylates, in particular polyethylene (PE), polypropylene (PP), polyisobutylene, ethylene / vinyl acetate copolymers (EVA) or atactic poly-α-olefins (APAO); fibres, in particular glass, carbon, metal, ceramic, hemp, cellulose or polymer fibres, such as polyamide or polyethylene fibres; - nanofillers such as graphene or carbon nanotubes; - flame retardant substances, in particular the above-mentioned aluminium hydroxide or magnesium hydroxide fillers, and more particularly organic phosphates, such as, in particular, triethyl phosphate, tricresyl phosphate, triphenyl phosphate, diphenylcresyl phosphate, isodecyldiphenyl phosphate, tris(1,3-dichloro-2-propyl) phosphate, tris(2-chloroethyl) phosphate, tris(2-ethylhexyl) phosphate, tris(chloroisopropyl) phosphate, tris(chloropropyl) phosphate, isopropylated triphenyl phosphate of various degrees of isopropylation, mono-, bis- or tris-(isopropylphenyl) phosphate, resorcinol bis(diphenyl phosphate), bisphenol-A bis(diphenyl phosphate) or ammonium polyphosphate; Further additives, such as emulsifiers, wetting agents, levelling agents, defoamers, degassing agents or stabilizers against oxidation, heat, light or UV radiation, or insecticides.

[0108] It may be desirable to chemically or physically dry certain components before incorporating them into the composition.

[0109] The composition of the present invention is prepared by mixing all the ingredients while excluding moisture to obtain a macroscopically homogeneous fluid or paste, and stored in a moisture-tight container at ambient temperature. A suitable moisture-tight container is preferably made of metal or plastic, optionally coated. It is preferably a bucket, barrel, hob, pouch, sausage, cartridge, can, bottle, or cylinder. With proper packaging and storage, the composition of the present invention has good shelf life stability.

[0110] The curing process begins when the packaging is opened and the composition of the present invention is applied, thereby coming into contact with moisture, particularly atmospheric moisture. During the curing process, the silane group undergoes moisture decomposition to release an alcohol, for example, methanol in the case of a methoxysilane group, or ethanol in the case of an ethoxysilane group, to form a silanol group (Si-OH group), which is then condensed to produce a siloxane group (Si-O-Si group). Furthermore, the ketimine group also undergoes moisture decomposition to release the corresponding ketone, which reacts with the epoxy group. As a result of these reactions, the composition cures and forms an elastic material.

[0111] The moisture for curing the composition is preferably atmospheric moisture that has penetrated into the composition from the surrounding air via a diffusion process. Upon curing, a thin skin of cured composition is initially formed on the surface of the applied composition, which continues to increase in thickness as the curing process proceeds until the entire applied composition is cured. Additional moisture contributing to the curing process may come from the substrate to which the composition is applied and / or from water-containing or water-releasing accelerator components that are mixed into the composition before or during application, or sprayed or brushed onto the surface of the applied composition.

[0112] The compositions of the invention are preferably applied under ambient conditions, preferably at temperatures in the range of from 0 to 50°C, especially from 5 to 40°C.

[0113] Curing of the composition is preferably also carried out under ambient conditions. Curing typically takes several days to several weeks to become nearly complete under prevailing conditions. Under certain conditions, it may be advantageous to further cure the partially cured composition at elevated temperatures, for example, 50-130° C. or higher.

[0114] Another subject of the invention is the cured composition obtained after contacting the one-component moisture-curable composition described above with moisture.

[0115] The one-component moisture curable compositions are preferably used as elastic adhesives and / or sealants or as elastic coatings.

[0116] Particularly preferred is the use as an elastic adhesive and / or sealant, especially in the building industry, or in manufacturing, or in vehicle construction, in particular for sealing joints or cavities, e.g. for high-rise facades or ship decks, for adhering wall panels to facades, or for module bonding, especially in vehicle construction, or for sealing battery boxes in e-vehicles.

[0117] The one-component moisture-curable composition may be formulated so that it has a paste-like consistency with pseudoplastic properties. Such a composition is preferably applied in the form of a bead having, for example, a circular or triangular cross-sectional shape from a cartridge, barrel, or hob.

[0118] The one-component moisture-curable composition may further be formulated so that it has a fluid consistency with self-leveling properties, possibly with slight thixotropy. Such compositions may also be applied by spraying or pouring onto flat or slightly inclined surfaces or into cavities. The composition may then be spread to the desired layer thickness using a suitable tool, such as a squeegee, toothed trowel, spatula, roller, brush, or drawdown bar.

[0119] The one-component moisture-curable composition of the present invention has advantageous properties. It has good coating performance, especially low viscosity and long open time, together with good shelf life stability. When in contact with moisture, it cures quickly at ambient conditions to form a non-tacky, highly elastic material with high tensile strength, high tear strength and soft elastic performance. The composition of the present invention shows particularly good adhesion, especially on mortar or concrete in dry and wet conditions, without pre-treatment of the substrate, so that the good adhesion is maintained even after the bond is immersed in water. Most surprising is the excellent heat resistance of the cured material, which shows long-term heat resistance up to 2 hours at 200°C, even 4 weeks at 90°C, or 24 hours at 180°C. This heat resistance allows applications such as, for example, the use for bonding wall panels on buildings, sealing battery boxes of e-vehicles, or bonding to vehicle parts that are heated in a later process, for example to cure heat-curable varnishes or powder coatings.

[0120] Preferably, the cured composition has a Shore A hardness (according to DIN 53505) of less than 55 after curing for 7 days at 23° C. and 50% relative humidity.

[0121] Preferably, the cured composition has an elongation at break of more than 150%, measured at a crosshead speed of 200 mm / min according to DIN EN 53504, after curing for 7 days at 23° C. and 50% relative humidity.

[0122] Preferably, the cured composition has an e-modulus of less than 5 MPa between 0.5 and 5% elongation, measured according to DIN EN 53504 at a crosshead speed of 200 mm / min, after curing for 7 days at 23° C. and 50% relative humidity.

[0123] Preferably, the cured composition has a tear strength of more than 3 N / mm after curing for 7 days at 23° C. and 50% relative humidity, measured according to DIN ISO 34 using angle-shaped test specimens at a crosshead speed of 500 mm / min.

[0124] The low e-modulus and low Shore A hardness combined with high elongation ensure a soft elastic performance of the cured material, which allows some movement of the adhesive and / or sealing bond without transmitting high forces to the substrate, while the high tear strength gives the bond high durability.

[0125] Another subject of the invention is a method for providing an elastic adhesive or sealing bond, comprising the following steps: (i) a one-component moisture-curable composition - applied onto a first substrate and contacting the composition with a second substrate; or - applied onto a first substrate and onto a second substrate to bond the two substrates together; or - applying between two substrates; (ii) subsequently curing the composition by contact with moisture.

[0126] Application of the one-component moisture curable composition is suitably carried out as described above.

[0127] Substrates which may be joined by the method of the present invention preferably include: - concrete, lightweight concrete, mortar, cement, fibre cement, brick, adobe, tiles, slate, gypsum, gypsum panels or natural stone, such as granite or marble; - glass or glass ceramic; - Repair or levelling compounds based on PCC (polymer modified cement) or ECC (epoxy modified cement); - Metals and alloys, such as aluminium, copper, iron, steel, non-ferrous metals (including finished metals and alloys, such as galvanised or chrome-plated metals); - Asphalt; - Asphalt felt; - plastics, such as rigid or flexible PVC, polycarbonate, polystyrene, polyester, polyamide, PMMA, ABS, SAN, epoxide resins, phenolic resins, PUR, POM, TPO, PE, PP, EPM or EPDM (in untreated form or with a surface treatment by means of plasma, corona or flame); - fibre-reinforced plastics, such as carbon fibre-reinforced plastics, glass fibre-reinforced plastics, natural fibre-reinforced plastics or sheet moulding compounds; - wood or plywood, paper, paperboard, wood substances glued with organic resins, resin-textile composites or so-called polymer composites; - insulating foams, in particular those made from EPS, XPS, PUR, PIR, rock wool, glass wool or foam glass; - Coated substrates, such as varnished tiles, painted concrete, coated metals or varnished metal sheets.

[0128] It is possible to bond two identical substrates or two different substrates.

[0129] These substrates are optionally pretreated before the composition is applied, in particular by physical and / or chemical cleaning processes or by applying an activator or primer.

[0130] It is preferred not to pretreat the substrate with an activator or primer because the compositions of the present invention exhibit excellent adhesion even without pretreatment.

[0131] Porous substrates such as concrete or mortar can also be bonded in moist or wet conditions.

[0132] The one-component moisture-curable compositions of the present invention have sufficient open time to allow for precise positioning and application to large surfaces, and rapid cure progression, such that the compositions are immediately tack-free and exhibit rapid onset of mechanical strength and elasticity.

[0133] As a result of the method of the invention, an article is obtained, which is bonded and / or sealed by the composition of the invention, which is preferably a building or infrastructure object or part thereof, preferably a facade, a roof, a balcony, a terrace, a staircase, a floor or a bridge, or it is an industrial or household item, in particular a window, a pipe, a household machine, a car, a bus, a truck, a rail vehicle, an aircraft or a helicopter, or part thereof, such as the battery box of an e-vehicle. EXAMPLES

[0134] The following examples illustrate the invention without, however, limiting it.

[0135] The term "standard conditions" means a temperature of 23±1° C. and an atmospheric relative humidity of 50±5%, and is abbreviated as "SC".

[0136] "EEW" stands for "epoxy equivalent weight."

[0137] Unless otherwise stated, chemicals were from Sigma-Aldrich Chemie GmbH and were used as received.

[0138] Diethyl N-(3-trimethoxysilylpropyl)aminosuccinate was prepared by reacting maleic acid diethyl ester with 3-aminopropyltrimethoxysilane.

[0139] Preparation of silane-functional polymer: Polymer ST-1: 1000 g of poly(oxypropylene) glycol (Acclaim® 12200 from Covestro; OH number 11 mg KOH / g) was reacted with 43.6 g of isophorone diisocyanate (Vestanat® IPDI from Evonik) in the presence of dibutyltin dilaurate at 80° C. with the exclusion of moisture to give an isocyanate-functional polymer with an NCO content of 0.7% by weight, determined by titration.

[0140] Then, 61.8 g of diethyl N-(3-trimethoxysilylpropyl)aminosuccinate was added and the polymer was kept under stirring at 80° C. until no isocyanate groups were detectable by means of FT-IR spectroscopy. The silane-functional polymer thus obtained was then cooled to room temperature and stored with the exclusion of moisture. It was clear and liquid at room temperature.

[0141] Preparation of polyketimines: Ketimine K1: 785.2 g (8 mol) cyclohexanone and 422.5 g (3.7 mol) 1,2-cyclohexanediamine (Dytek® DCH-99, Invista) were mixed and reacted in a rotary evaporator at 80° C. under vacuum while removing volatile components. The so obtained bis-ketimine had an amine number of 452 mg KOH / g and a theoretical ketimine-equivalent weight of 137 g / eq.

[0142] Ketimine K2: 90.1 g (0.9 mol) methyl isobutyl ketone and 51.1 g (0.3 mol) isophorone diamine (Vestamin® IPD, Evonik) were mixed and reacted in a rotary evaporator at 80° C. under vacuum while removing the volatile components. The bisketimine so obtained had an amine number of 367 mg KOH / g and a theoretical ketimine-equivalent weight of 165 g / eq.

[0143] Ketimine K3: 360.6 g (3.6 mol) methyl isobutyl ketone and 137.0 g (1.2 mol) 1,2-cyclohexanediamine (Dytek® DCH-99, Invista) were mixed and reacted in a rotary evaporator at 80° C. under vacuum while removing volatile components. The so obtained bisketimine had an amine number of 466 mg KOH / g and a theoretical ketimine-equivalent weight of 139 g / eq.

[0144] Ketimine K4: 647.8 g (6.6 mol) cyclohexanone and 510.9 g (3 mol) isophoronediamine (Vestamin® IPD, Evonik) were mixed and reacted in a rotary evaporator at 80° C. under vacuum while removing the volatile components. The bisketimine so obtained had an amine number of 351 mg KOH / g and a theoretical ketimine-equivalent weight of 167 g / eq.

[0145] Ketimine K5: 103.1 g (1.05 mol) cyclohexanone and 153.0 g (0.50 mol) of 306 g / mol average molecular weight M n (a mixture of 84.1 g Jeffamine® D-230 and 68.9 g Jeffamine® D-400, Huntsman) and reacted in a rotary evaporator at 80° C. under vacuum while removing the volatile components. The so obtained bisketimine had an amine number of 253 mg KOH / g and a theoretical ketimine-equivalent weight of 221.7 g / eq.

[0146] One-component moisture curable composition: Compositions C1-C6: For each composition, the components listed in Table 1 were mixed in the amounts listed (units, parts by weight) in a sealed polypropylene beaker by means of a centrifugal mixer (SpeedMixer™ DAC150, FlackTek Inc.) with the exclusion of moisture until a homogeneous mixture was obtained, which was then stored in a moisture-tight container.

[0147] Each composition was tested according to the following procedure.

[0148] The adhesion was tested by applying two beads of 10x150 mm and 5 mm thickness on each substrate as shown in Table 1, without any pretreatment other than wiping with isopropanol for non-porous substrates and removing dust for porous substrates, and leaving them to cure for 7 days under standard conditions. The adhesion of the first bead was then tested (first number) by cutting off a few millimeters from the end of the bead from the substrate, then pinching the floating end of the bead with pliers and pulling the cured bead in a perpendicular direction from the substrate. The specimen with the remaining bead was then immersed in water at room temperature for 7 days, dried with a cloth and the adhesion test was repeated with the remaining bead (second number). This means that the first number indicates the adhesion after 7 days under standard conditions and the second number indicates the adhesion after another immersion in water for 7 days. The adhesion was evaluated on the following scale: 1 = Very good adhesion (cohesive failure >95%) 2 = Good adhesion (70% < cohesive failure ≤ 95%) 3 = Some adhesion (50% < cohesive failure ≤ 70%) 4 = Poor adhesion (5% < cohesive failure ≤ 50%) 5 = no adhesion (0% < cohesive failure ≦ 5%, i.e. adhesive failure > 95%).

[0149] The cure speed was tested by applying the compositions in a layer thickness of 10 mm under standard conditions and measuring the thickness of the cured skin after 1 day ("1dSC") and after 3 days ("3dSC").

[0150] The Shore A hardness was determined according to DIN 53505 on test specimens cured for 7 days under standard conditions.

[0151] The ultimate tensile strength, the elongation at break and the strength at 50%, 100% and 150% elongation (el.) were determined according to DIN EN 53504 at a crosshead speed of 200 mm / min on flat dumbbell-shaped test specimens (length 75 mm, gauge length 30 mm, gauge width 4 mm) prepared by punching from 2 mm thick films of the compositions cured for 7 days under standard conditions.

[0152] The tear strength was determined according to DIN ISO 34 at a crosshead speed of 500 mm / min using angle-shaped test specimens prepared by punching out of the coating as described for the determination of the tensile strength.

[0153] As a measure of thermal stability, measurements of tensile strength and strength at 150% elongation were repeated on specimens stored in an oven at 90°C for a given time, followed by a further 24 hours at standard conditions. A significant loss in strength indicates poor thermal stability.

[0154] The results are shown in Tables 1 and 2.

[0155] Reference examples are marked with "(Ref.)".

[0156] [Table 1]

[0157] [Table 2]

[0158] Tables 1 and 2 show that: Reference composition C4 without epoxy silane shows poor adhesion to concrete after immersion in water, Reference composition C5 without epoxy resin and polyketimine shows poor adhesion to mortar and concrete after immersion in water, poor hardening speed after the first day of application, and poor thermal stability, while Reference composition C6 with MS polymer instead of polymer ST-1 shows poor adhesion to mortar and concrete after immersion in water.

[0159] Compositions C7-C16: For each composition, the components listed in Tables 3 or 5 were mixed in the amounts listed (units, parts by weight) in a sealed polypropylene beaker by means of a centrifugal mixer (SpeedMixer™ DAC150, FlackTek Inc.) with the exclusion of moisture until a homogeneous mixture was obtained, which was then stored in a moisture-tight container.

[0160] The compositions were tested as follows:

[0161] The adhesion was tested on AlMg3 (aluminium with low silicone content, from Rocholl, Germany), AlMgSi1 (aluminium with high silicone content, also from Rocholl), ABS (acrylonitrile-butadiene-styrene polymer, from Rocholl), FRP (fiberglass reinforced plastic, POLYDET® performancePlus-WR, from Optiplan, Germany), PVC (rigid PVC, from Rocholl) and concrete without pretreatment other than wiping with isopropanol for the non-porous substrates and removing dust from the concrete. For each adhesion test, four beads were applied and left to cure for 7 days under standard conditions. The first adhesion test was then carried out with the first bead (first number). The specimen with the remaining bead was then immersed in water for 7 days at room temperature, dried with a cloth and tested for adhesion with the next bead (second number). The specimens with the remaining beads were then stored in an oven at 80° C. for 24 hours, allowed to cool at room temperature and tested for adhesion with the next bead (third number). The specimens with the remaining beads were then stored at 70° C. and 100% relative humidity for 7 days, allowed to cool at room temperature and tested for adhesion with the last bead (fourth number). This means that: the first number indicates the adhesion after 7 days at standard conditions, the second number indicates the adhesion after another 7 days immersed in water, the third number indicates the adhesion after another 24 hours at 80° C. and the fourth number indicates the adhesion after another 7 days at 70° C. / 100% rh. The beads were tested and their adhesion was determined as described for composition C1. The adhesion on concrete was discontinued after the third test (80° C., 24 hours).

[0162] The skinning time (skin formation time) was measured by applying a few grams of the composition to a paperboard in a layer thickness of approximately 2 mm and gently touching the surface from time to time under standard conditions with an LDPE pipette until no residue remained on the pipette when touched.

[0163] Tensile strength, elongation, tear strength, and Shore A hardness were measured as described for composition C1.

[0164] The e-modulus 5% was calculated from tensile strength tests between 0.5 and 5% elongation.

[0165] As a measure for thermal stability, measurements of Shore A hardness were repeated on specimens after further storage in an oven at 180° C. or 200° C. for a given time and then after a further 24 hours at standard conditions. A significant decrease in hardness indicates poor thermal stability.

[0166] The results are shown in Tables 3 to 6.

[0167] Reference examples are marked with "(Ref.)".

[0168] [Table 3]

[0169] [Table 4]

[0170] [Table 5]

[0171] [Table 6]

Claims

1. 1. A one-component moisture-curable composition comprising: 100 parts by weight of a polymer P1 containing silane groups of formula (I), 【Chemistry 1】 [In the formula, n is 2 or 3; R １ is a linear or branched C １ ~C ５ is an alkyl group, R ２ is a bifunctional C ２ ~C １２ Bifunctional C containing a hydrocarbon group, an amide group or a carbamate group ３ ~C １２ is a hydrocarbon group, X is O, S or NR ３ However, here R ３ is hydrogen or C １ ~C １０ C containing a hydrocarbon group or one or two ether groups or carboxylic acid ester groups ３ ~C ２０ a hydrocarbon group or an alkoxysilane group, D is a divalent C ４ ~C １５ a hydrocarbon group] - 5 to 50 parts by weight of at least one liquid epoxy resin, at least one polyketimine, - 2 to 15 parts by weight of at least one epoxy silane, 0 to 500 parts by weight of a filler, and 0 to 500 parts by weight of a plasticizer, 1. A one-component moisture-curable composition comprising:

2. The polymer P1 has a poly(oxyalkylene) backbone, an average molecular weight M ｎ and an average silane functionality of 1.8 to 2.

3. n is 2 and R １ is methyl, or n is 3 and R １ 3. The composition of claim 1, wherein is methyl or ethyl.

4. R ２ But C ３ ~C ６ an alkylene group, preferably 1,3-propylene, and X is NR ３ and R ３ 3. The composition according to claim 1 or 2, wherein is succinate-2-yl, preferably diethylsuccinate-2-yl.

5. 3. The composition of claim 1, wherein D is selected from the group consisting of divalent radicals obtained after removal of two isocyanate groups from 1,6-hexane diisocyanate, isophorone diisocyanate, 4,4'-diisocyanatodicyclohexylmethane, diphenylmethane diisocyanate, and toluene diisocyanate.

6. 3. The composition according to claim 1 or 2, wherein the liquid epoxy resin is selected from aromatic polyglycidyl ethers, preferably bisphenol-A diglycidyl ether, bisphenol-F diglycidyl ether, and phenol-formaldehyde novolac glycidyl ether, having an average functionality of 2.3 to 4, preferably 2.5 to 3.

7. 3. The composition according to claim 1, wherein the amount of said liquid epoxy resin is 10 to 35 parts by weight, based on 100 parts by weight of said polymer P1.

8. The polyketimine is (a) diethylenetriamine, 1,2-diaminocyclohexane, isophoronediamine, or a polyketimine having an average molecular weight M of 200 to 500 g / mol ｎ and (b) methyl isobutyl ketone or cyclohexanone in a ratio of at least 1 mol of ketone per 1 mol equivalent of primary amine groups, said condensate optionally being further reacted with a monoepoxide, preferably phenyl glycidyl ether.

9. 3. The composition of claim 1, wherein the amount of said polyketimine in said composition is such that the number of said ketimine groups based on the number of epoxy groups in said composition is 0.5 to 1.

5.

10. 3. The composition according to claim 1, wherein the amount of said filler is between 50 and 500 parts by weight, preferably between 100 and 300 parts by weight, based on 100 parts by weight of said polymer P1.

11. 3. The composition of claim 1, wherein the plasticizer is selected from the group consisting of diisononyl phthalate, diisodecyl phthalate, di(2-propylheptyl)phthalate, diisononyl cyclohexane-1,2-dicarboxylate, bis(2-ethylhexyl)terephthalate, diisononyl terephthalate, bis(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, diisononyl cyclohexane-1,4-dicarboxylate, dioctyl adipate, poly(oxypropylene)monols, poly(oxypropylene)diols, poly(oxypropylene)triols, and poly(oxypropylene)monols, diols, and triols having blocked hydroxyl groups in the form of acetate groups.

12. 3. The composition according to claim 1, wherein the amount of said plasticizer is between 10 and 500 parts by weight, preferably between 20 and 300 parts by weight, based on 100 parts by weight of said polymer P1.

13. 3. The composition according to claim 1, wherein the amount of said plasticizer is from 0 to 50 parts by weight, based on 100 parts by weight of said polymer P1, and said composition further comprises at least one ketiminosilane.

14. A cured composition obtained from the composition of claim 1 or 2 after contacting it with moisture.

15. 1. A method for forming an elastic adhesive or sealing bond, comprising: (i) a composition according to claim 1 or 2, - applying onto a first substrate and contacting said composition with a second substrate, or - onto a first substrate and onto a second substrate and laminating the two substrates together; or - applying between two substrates, (ii) subsequently curing the composition by contact with moisture; A method comprising:

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