Two-component composition with high degree of strength

Abstract

To provide a high-strength composition that cures rapidly under moist conditions.SOLUTION: The present invention relates to a composition comprising at least one silane group-containing polymer having a silicon content in the range of 0.6 to 2 wt.% obtained by reacting at least one isocyanate group-containing polymer with at least one aminosilane, mercaptosilane, or hydroxysilane, at least one liquid epoxy resin, and at least one polyamine having at least three amine hydrogens reactive toward epoxy groups. The composition provides adhesives, coatings, or sealing compounds that exhibit good storage stability, a fast curing time even in the presence of moisture or humidity, a surprisingly high degree of strength while maintaining high elasticity, a high resistance to further tearing, a high resistance particularly against glycol / water mixtures, and a high adhesion to many substrates. When used on metals such as steel or aluminum, the composition protects them against corrosion.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a composition which is curable at room temperature and which is based on a combination of a polymer containing silane groups and an epoxy resin, and to its use as a viscoelastic adhesive, coating or casting compound, having, inter alia, high strength, extensibility and stability. [Background technology]

[0002] Adhesives, casting compounds, and coatings based on polyurethane or epoxy resins are known and have a variety of uses. Polyurethane-based materials have high extensibility but are limited in terms of achievable strength. Furthermore, they tend to be damaged when used in moist or humid environments and exhibit weaknesses in stability to glycol / water, such as those used as cooling fluids for batteries in electric vehicles, and in adhesion to metals under corrosive conditions. Epoxy-based materials enable very high strength, bond strength, and stability, but are limited in terms of extensibility and exhibit weaknesses in adhesion to aluminum under corrosive conditions, such as in the case of saltwater stress.

[0003] Materials combining silane-functional polymers with epoxy resins are also known. These achieve much higher strength than silane-functional polymers alone. Such compositions based on so-called MS polymers, commercially available from Kaneka, are known. These are silane-functional polymers obtained by hydrosilylation of polyols with allyl ether end groups. Such compositions are described, for example, in EP 370464 or U.S. Pat. No. 6,737,482. However, the combination of MS polymers with epoxy resins achieves only very limited strength.

[0004] Compositions containing an epoxy resin and a silane-functional polymer, either from the reaction of a polyol with an isocyanatosilane or from the reaction of a polyol with a diisocyanate to give an isocyanate-functional polymer that is then further reacted with an aminosilane to give a silane-functional polymer, are also known. Such systems are described, for example, in U.S. Patent Application Publication No. 2017 / 0292050 or WO 2017 / 140688. The highest strength is achieved with silane-functional polymers derived from a polymer containing isocyanate groups and an aminosilane. The silane-containing polymer used here has an average molecular weight M of about 12,000 g / mol. n They are derived from long chain polyether diols having the formula:

[0005] However, for certain applications, such as bonding battery boxes in electric vehicles, significantly higher strength is desired in combination with high bond strength, high tear resistance and high stability. Particular requirements are therefore high stability of adhesion to aluminum substrates under corrosive conditions, especially salt water stress, and high stability to glycol / water mixtures, which are difficult to achieve with adhesives based on acrylates, polyurethanes and / or epoxy resins. Summary of the Invention [Problem to be solved by the invention]

[0006] It is therefore an object of the present invention to provide a composition that cures quickly and reliably at room temperature, even under moist or humid conditions, and allows high strength combined with high extensibility, high bond strength, good stability, especially to glycol / water mixtures, and corrosion-resistant adhesion to metals. [Means for solving the problem]

[0007] This object is surprisingly achieved by the composition described in claim 1. The composition comprises at least one polymer containing silane groups and having a silicon content ranging from 0.6% to 2% by weight, obtained by reacting at least one polymer containing isocyanate groups with at least one amino-, mercapto-, or hydroxysilane. In the prior art, such polymers have not been used in combination with epoxy resins to date. Compared to comparable compositions containing polymers containing silane groups and having a lower silicon content, as known from the prior art, the compositions of the present invention surprisingly exhibit significantly higher strength, especially on metals under corrosive conditions, as well as high extensibility, much higher tear resistance, and excellent bond strength, combined with excellent stability to hydrolysis and glycol / water mixtures.

[0008] The compositions of the present invention enable adhesives, coatings or casting compounds to cure rapidly and largely odorlessly after mixing, even in the presence of water or moisture, and have good storage stability as two-component products that combine high extensibility, high tear resistance and high stability, especially for glycol / water mixtures, to form surprisingly high strength materials, as well as very high bond strength on many substrates, including on damp or wet substrates, where the compositions can protect metals such as steel or aluminum from corrosion when used on these.

[0009] More specifically, the compositions allow for viscoelastic adhesives capable of bonding metals, especially aluminum, without pretreatment, so that the bond is stable under corrosive conditions, especially in the case of saltwater stress. Furthermore, the compositions allow for coatings that can protect metals, such as steel or aluminum, from corrosion. Finally, the compositions allow for casting compounds that can permanently fill and thus repair cracks in concrete, asphalt, or bitumen, with excellent adhesion even on wet substrates. Thus, it is possible in a simple way to permanently repair heavily trafficked roads or parks with damage to their surfaces or to curbs, edges, or borders. Finally, these products do not contain isocyanates in the process, which is advantageous for toxicological reasons.

[0010] Further aspects of the invention are the subject matter of further independent claims. Particularly preferred embodiments of the invention are the subject matter of the dependent claims. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention provides a composition comprising: - at least one polymer containing silane groups and having a silicon content ranging from 0.6% to 2% by weight, which is obtained from the reaction of at least one polymer containing isocyanate groups with at least one aminosilane, mercaptosilane or hydroxysilane, - at least one liquid epoxy resin, and - at least one polyamine having at least three amine hydrogens reactive towards epoxy groups;

[0012] In this document, the short term "alkoxysilane group" or "silane group" refers to a silyl group attached to an organic radical and having 1 to 3, especially 2 or 3, hydrolyzable alkoxy groups on the silicon atom.

[0013] Accordingly, the short term "organosilane" or "silane" refers to an organic compound containing at least one silane group.

[0014] "Aminosilane," "mercaptosilane," or "hydroxysilane" refers to an organosilane having an amino, mercapto, or hydroxyl group, respectively, on the organic radical in addition to the silane group.

[0015] The "silicon content" of a polymer containing silane groups refers to the silicon content of the polymer in weight percent, based on 100 weight percent of the polymer. Dilution with solvent or plasticizer is not counted as part of the polymer herein. Silane-functional additives, such as adhesion-promoting organosilanes, which may optionally be further present in the composition, are also not counted as part of the silicon content of the polymer containing silane groups. Such materials are not considered to be polymers containing silane groups in the context of the present invention.

[0016] The "NCO content" of a polymer refers to the isocyanate group content of the polymer in weight percent.

[0017] An "aromatic" isocyanate group refers to one attached directly to an aromatic carbon atom.

[0018] Substance names beginning with "poly", such as polyamine or polyol, formally refer to substances containing two or more of the functional groups appearing in their names per molecule.

[0019] "Amine hydrogen" refers to the hydrogen atoms of primary and secondary amino groups.

[0020] A "primary amino group" refers to an amino group that is bonded to one organic group and has two hydrogen atoms; a "secondary amino group" refers to an amino group that is bonded to two organic groups that may together be part of a ring and has one hydrogen atom; and a "tertiary amino group" refers to an amino group that is bonded to three organic groups, two or three of which may together be part of one or more rings, and does not have any hydrogen atoms.

[0021] "Molecular weight" refers to the molar mass (in g / mole) of a molecule or molecular residue. "Average molecular weight" refers to the number average molecular weight (M n It is measured by gel permeation chromatography (GPC) against polystyrene as a standard, using inter alia tetrahydrofuran as the mobile phase and a refractive index detector.

[0022] A "storage-stable" or "storable" substance or composition is one that can be stored at room temperature in a suitable container for an extended period of time, typically at least 3 months, and up to 6 months or more, without this storage resulting in any change in its application or use characteristics to the extent relevant to its use.

[0023] "Room temperature" refers to a temperature of 23°C.

[0024] All industry standards and norms mentioned in this document relate to the versions that were valid as of the date of first filing.

[0025] Weight percentage (% by weight or wt%) refers to the proportion by mass of a polymer or composition constituent based on the total polymer or total composition, unless otherwise specified. The terms "mass" and "weight" are used interchangeably in this document.

[0026] The dashed lines in the formulae in this document represent in each case a bond between a substituent and the associated molecular radical.

[0027] The polymer containing silane groups is preferably liquid at room temperature.

[0028] The silane group-containing polymer preferably has an average of 1.3 to 4, more preferably 1.5 to 3, and especially 1.7 to 2.8 silane groups per molecule, and most preferably has an average of 1.7 to 2.3 silane groups per molecule.

[0029] The polymer containing silane groups preferably has a silicon content in the range of 0.7% to 1.5% by weight, especially 0.8% to 1.2% by weight, such compositions allowing a particularly advantageous combination of high strength and high extensibility.

[0030] The polymer containing silane groups preferably has an average molecular weight M in the range of 2,000 to 10,000 g / mol, more preferably 3,000 to 8,000 g / mol, especially 4,000 to 7,000 g / mol. n It has.

[0031] The polymer containing silane groups preferably has predominantly polyoxyalkylene units, especially polyoxypropylene units.

[0032] The polymer containing silane groups preferably has the formula (I) [ka] (In the formula, n is 1 or 2 or 3, in particular 2 or 3; R 1 is a linear or branched monovalent hydrocarbyl group having 1 to 5 carbon atoms, R 2 is a linear or branched divalent hydrocarbyl group having 1 to 12 carbon atoms and optionally containing cyclic and / or aromatic moieties and optionally one or more heteroatoms, especially amide, carbamate or morpholino groups; X is O, S, or NR 3 where R 3 is a hydrogen atom or a linear or branched hydrocarbyl group having 1 to 20 carbon atoms and optionally containing a cyclic moiety and optionally containing an alkoxysilyl group or an ether group or a carboxylic acid ester group. The silane group is

[0033] Preferably, n is 3. Such compositions cure particularly quickly and allow for particularly high strength.

[0034] Preferably, R 1 is methyl, ethyl or isopropyl.

[0035] More preferably, R 1 is methyl. Polymers of this type containing silane groups are particularly reactive.

[0036] More preferably, further R 1 is ethyl. Polymers of this type containing silane groups are particularly stable on storage and have toxicological advantages.

[0037] Preferably, X is O or NR 3 is.

[0038] Preferably, R 3 is H, butyl, phenyl, or a branched aliphatic group having 6 to 20 carbon atoms and optionally having an ether group or a carboxylic acid ester group.

[0039] Most preferably, X is NR 3 and R 3 teeth, [ka] (In the formula, each R 4 is methyl or ethyl, especially ethyl) Such polymers containing silane groups are easy to obtain and allow particularly high strength combined with high extensibility and stability.

[0040] X=NR 3 If R 2 is preferably 1,3-propylene or 1,4-butylene (wherein the butylene may be substituted with one or two methyl groups), more preferably 1,3-propylene.

[0041] When X=O, R 2 preferably has 6 to 12 carbon atoms and an amide, carbamate or morpholino group, especially of the formula [ka] is a divalent hydrocarbyl group having the group

[0042] Preferred polymers containing silane groups enable compositions with a particularly attractive combination of high strength coupled with high extensibility.

[0043] The polymers containing silane groups result from the reaction of at least one polymer containing isocyanate groups with at least one amino-, mercapto- or hydroxysilane.

[0044] The polymer containing isocyanate groups preferably has an NCO content in the range of 1.2% to 4% by weight, especially 1.2% to 2.8% by weight. Such polymers containing isocyanate groups allow the silane group content of the present invention upon reaction with the preferred silane.

[0045] The polymer containing isocyanate groups is then obtained, inter alia, from the reaction of at least one polyol with at least one diisocyanate.

[0046] The reaction is preferably carried out with the exclusion of moisture at a temperature in the range of 20 to 160° C., especially 40 to 140° C., optionally in the presence of a suitable catalyst.

[0047] The molar NCO / OH ratio is preferably in the range from 1.3 / 1 to 2.5 / 1.

[0048] Suitable polyols for the preparation of polymers containing isocyanate groups are polyols that are liquid at room temperature, especially the following commercially available polyols or any mixtures thereof: - polymerization products of polyether polyols, especially polyoxyalkylene diols and / or polyoxyalkylene triols, especially ethylene oxide or 1,2-propylene oxide or 1,2- or 2,3-butylene oxide or oxetane or tetrahydrofuran or mixtures thereof (wherein these are in turn polymerized with starter molecules having two or three active hydrogen atoms, especially water, ammonia or compounds having a large number of OH or NH groups, such as ethane-1,2-diol, propane-1,2- or -1,3-diol, neopentyl glycol, diethylene The polymerization may be carried out with the aid of starter molecules such as glycol, triethylene glycol, the isomeric dipropylene glycols or tripropylene glycols, the 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 aforementioned compounds.

[0049] Preferred polyether polyols are those called polyoxypropylene diols or triols, or ethylene oxide-capped (EO-capped) polyoxypropylene diols or triols, the latter being polyoxyethylene / polyoxypropylene copolymers obtained, inter alia, by further alkoxylating polyoxypropylene diols or triols with ethylene oxide at the end of the polypropoxylation reaction, so that they contain primary hydroxyl groups.

[0050] Preferred polyether polyols have a level of unsaturation of less than 0.02 meq / g, especially less than 0.01 meq / g. - polyether polyester polyols, - polyacrylate polyols and polymethacrylate polyols, - polyacrylate or polymethacrylate polyols, polyhydroxy-functional fats and oils, such as natural fats and oils, especially castor oil, or polyols obtained by chemical modification of natural fats and oils, known as oleochemical polyols; - polyhydrocarbon polyols, also called oligohydrocarbonols, such as, in particular, polyhydroxy-functional polyolefins, polyisobutylene, polyisoprene; polyhydroxy-functional ethylene / propylene, ethylene / butylene or ethylene / propylene / diene copolymers, such as those produced, for example, by Kraton Polymers; polyhydroxy-functional polymers of dienes, in particular of 1,3-butadiene, which can also be produced, in particular, from anionic polymerization; polyhydroxy-functional copolymers of dienes, such as 1,3-butadiene, or mixtures of dienes, with vinyl monomers, such as styrene, acrylonitrile, vinyl chloride, vinyl acetate, vinyl alcohol, isobutylene or isoprene, in particular carboxyl-terminated acrylonitrile / butadiene copolymers with epoxides or amino alcohols (for example, Emerald Performance Polymers). and polyhydroxy-functional acrylonitrile / butadiene copolymers, among others, such as can be prepared from hydroxypropyl acrylate / butadiene copolymers (commercially available from Materials under the name Hypro® CTBN or CTBNX or ETBN); or hydrogenated polyhydroxy-functional polymers or copolymers of dienes.

[0051] Polyether polyols, especially polyoxyalkylene diols or triols, are preferred.

[0052] Polyoxypropylene diols or polyoxypropylene triols, optionally having terminal oxyethylene groups, are particularly preferred.

[0053] Polyols with an average OH functionality in the range of 1.6 to 3, especially diols with an average OH functionality in the range of 1.8 to 2, are preferred.

[0054] an average molecular weight M in the range of 1,000 to 8,000 g / mol, in particular 2,000 to 6,000 g / mol, more preferably 3,000 to 5,000 g / mol; n Preferred are polyols, especially diols, having the formula:

[0055] In the preparation of polymers containing isocyanate groups, it is also possible to include a proportion of di- or polyfunctional alcohols.

[0056] The polymer containing isocyanate groups is preferably obtained from the reaction of at least one polyoxypropylene diol having an OH number in the range of 18 to 58 mg KOH / g, in particular 22 to 40 mg KOH / g, and optionally having terminal oxyethylene groups, with at least one diisocyanate.

[0057] At least one further polyol, especially a polyoxypropylene triol optionally having terminal oxyethylene groups, is optionally included in the preparation of the polymer containing isocyanate groups.

[0058] Suitable diisocyanates for the preparation of polymers containing isocyanate groups are diisocyanates with aliphatic isocyanate groups, especially hexane 1,6-diisocyanate (HDI), 2,2(4),4-trimethylhexamethylene 1,6-diisocyanate (TMDI), cyclohexane 1,3- or 1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate or IPDI), perhydro(diphenylmethane 2,4'- or 4,4'-diisocyanate) (HMDI), 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane or m- or p-xylylene diisocyanate (XDI).

[0059] For the preparation of polymers containing isocyanate groups, preference is given to diisocyanates with aromatic isocyanate groups, especially diphenylmethane 4,4'-diisocyanate, tolylene 2,4-diisocyanate or mixtures thereof with tolylene 2,6-diisocyanate (TDI), phenylene 1,4-diisocyanate (PDI) or naphthalene 1,5-diisocyanate (NDI), optionally with fractional proportions of diphenylmethane 2,4'- and / or 2,2'-diisocyanate (MDI), as well as mixtures of the diisocyanates mentioned.

[0060] HDI, IPDI, MDI or TDI is preferred, especially IPDI, MDI or TDI, most preferably MDI or TDI.

[0061] In a preferred embodiment of the present invention, the polymer containing isocyanate groups has aromatic isocyanate groups, so that the resulting polymer containing silane groups allows for inexpensive compositions with particularly high strength.

[0062] More specifically, the aromatic isocyanate groups are derived from diphenylmethane 4,4'-diisocyanate, optionally with a fractional proportion of diphenylmethane 2,4'- and / or 2,2'-diisocyanate (MDI), or tolylene 2,4-diisocyanate or mixtures thereof with tolylene 2,6-diisocyanate (TDI).

[0063] The diisocyanate is therefore more preferably selected from the group consisting of diphenylmethane 4,4'-diisocyanate, diphenylmethane 2,4'-diisocyanate, tolylene 2,4-diisocyanate and tolylene 2,6-diisocyanate.

[0064] The amino- or mercapto- or hydroxysilanes for reaction with the polymers containing isocyanate groups preferably have the formula (II) [ka] (In the formula, n, R 1 , R 2 and X has the definition already given) It has.

[0065] Suitable aminosilanes for reaction with polymers containing isocyanate groups are primary or secondary aminosilanes. Preferred are adducts formed from primary aminosilanes such as 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, 4-aminobutyltrimethoxysilane, 4-amino-3-methylbutyltrimethoxysilane, 4-amino-3,3-dimethylbutyltrimethoxysilane, N-butyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane; 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, or N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, and Michael acceptors such as acrylonitrile, (meth)acrylic acid esters, (meth)acrylamide, maleic or fumaric acid diesters, citraconic acid diesters, or itaconic acid diesters, in particular diethyl N-(3-trimethoxysilylpropyl)aminosuccinate or diethyl N-(3-dimethoxymethylsilylpropyl)aminosuccinate. Analogs of the listed aminosilanes which have ethoxy groups instead of methoxy groups on the silicon are also suitable.

[0066] Suitable mercaptosilanes for reaction with polymers containing isocyanate groups are especially 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyldimethoxymethylsilane or those mercaptosilanes which have an ethoxy group instead of a methoxy group on the silicon atom.

[0067] Suitable hydroxysilanes for reaction with polymers containing isocyanate groups are obtained, inter alia, from the addition of aminosilanes to lactones, lactides or to cyclic carbonates.

[0068] Preferred hydroxysilanes of this type are N-(3-triethoxysilylpropyl)-2-hydroxypropanamide, N-(3-trimethoxysilylpropyl)-2-hydroxypropanamide, N-(3-triethoxysilylpropyl)-4-hydroxypentanamide, N-(3-triethoxysilylpropyl)-4-hydroxyoctanamide, N-(3-triethoxysilylpropyl)-5-hydroxydecanamide or N-(3-triethoxysilylpropyl)-2-hydroxypropylcarbamate.

[0069] Further suitable hydroxysilanes are obtained from the addition of aminosilanes to epoxides or from the addition of amines to epoxysilanes.

[0070] Preferred hydroxysilanes of this type are 2-morpholino-4(5)-(2-trimethoxysilylethyl)cyclohexan-1-ol, 2-morpholino-4(5)-(2-triethoxysilylethyl)cyclohexan-1-ol or 1-morpholino-3-(3-(triethoxysilyl)propoxy)propan-2-ol.

[0071] Aminosilanes, especially diethyl N-(3-trimethoxysilylpropyl)aminosuccinate, diethyl N-(3-dimethoxymethylsilylpropyl)aminosuccinate or diethyl N-(3-triethoxysilylpropyl)aminosuccinate, are most preferred for reaction with polymers containing isocyanate groups.

[0072] The composition further comprises at least one liquid epoxy resin.

[0073] Suitable liquid epoxy resins include conventional industrial epoxy resins that are free-flowing at room temperature and have a glass transition temperature below 25° C. They are obtained in known manner from the glycidylation of compounds having at least two active hydrogen atoms, more particularly polyphenols, polyols or amines, more particularly by reaction with epichlorohydrin.

[0074] Suitable liquid epoxy resins are especially aromatic liquid epoxy resins, especially bisphenol A, bisphenol F or bisphenol A / F (where A stands for acetone and F for formaldehyde, which serve as reactants for the preparation of these bisphenols. In the case of bisphenol F, positional isomers derived from 2,4'- or 2,2'-hydroxyphenylmethane may also be present); dihydroxybenzene derivatives such as resorcinol, hydroquinone or catechol; - 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 (bis further bisphenols or polyphenols such as 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 phenols with formaldehyde, obtained under acidic conditions, such as phenol novolac or cresol novolac, also known as bisphenol F novolac; - 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) It is a glycidylation product of

[0075] Further suitable liquid epoxy resins are aliphatic or cycloaliphatic polyepoxides, especially - saturated or unsaturated, branched or unbranched, cyclic or open-chain di-, tri- or tetrafunctional C2-C 30 glycidyl ethers of alcohols, especially 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, F or A / F liquid resins or glycidylation products of hydrogenated bisphenol A, F or A / F; - N-glycidyl derivatives of amide or heterocyclic nitrogen bases, such as triglycidyl cyanurate or triglycidyl isocyanurate, or reaction products of epichlorohydrin with hydantoin; - epoxy resins from the oxidation of olefins, such as, in particular, vinylcyclohexene, dicyclopentadiene, cyclohexadiene, cyclododecadiene, cyclododecatriene, isoprene, 1,5-hexadiene, butadiene, polybutadiene or divinylbenzene is.

[0076] Bisphenol-based liquid epoxy resins are preferred.

[0077] Liquid epoxy resins based on diglycidyl ethers of bisphenol A, bisphenol F, or bisphenol A / F, such as those commercially available from Dow, Huntsman, or Momentive, are particularly preferred. These liquid epoxy resins have easily manageable viscosities and allow for high strength and resistance. Such liquid resins may also contain portions of solid bisphenol A resin or phenol novolac.

[0078] The weight ratio between the silane group-containing polymer and the liquid epoxy resin in the composition is preferably in the range of 20 / 80 to 70 / 30, especially 25 / 75 to 50 / 50. This type of composition exhibits high strength combined with good extensibility.

[0079] The composition further comprises at least one polyamine having at least three amine hydrogens reactive with epoxy groups.

[0080] Suitable polyamines are especially: aliphatic, cycloaliphatic or arylaliphatic primary diamines, 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, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (isophoronediamine or IPDA), 2(4)-methyl-1,3-diaminocyclohexane, 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 2,6 ]decane, 1,4-diamino-2,2,6-trimethylcyclohexane (TMCDA), menthane-1,8-diamine, 1,3-bis(aminomethyl)benzene (MXDA) or 1,4-bis(aminomethyl)benzene; aliphatic primary di- or triamines containing ether groups, in particular 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 or higher oligomers of these diamines, bis(3-aminopropyl)polytetrahydrofuran or other polytetrahydrofuran diamines, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5,5]undecane, in particular 1,4-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5,5]undecane, available as Jeffamine® RFD-270 (Huntsman), cycloaliphatic diamines containing ether groups from the propoxylation and subsequent amination of dimethylolcyclohexane, or polyoxyalkylene diamines or triamines, especially Jeffamine® D-230, Jeffamine® D-400, Jeffamine® D-2000, Jeffamine® EDR-104, Jeffamine® EDR-148, Jeffamine® EDR-176, Jeffamine® T-403, Jeffamine® T-3000, Jeffamine® T-5000 (all from Huntsman), or the corresponding amines from BASF or Nitroil; In particular, 3-(2-aminoethyl)aminopropylamine, bis(hexamethylene)triamine (BHMT), diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA) or higher analogues of linear polyethyleneamines, dipropylenetriamine (DPTA), N-(2-aminoethyl)propane-1,3-diamine (N3-amine), N,N'-bis(3-aminopropyl)ethylenediamine ( polyamines having a secondary amino group and two primary amino groups, such as N4 amine), N,N'-bis(3-aminopropyl)-1,4-diaminobutane, N5-(3-aminopropyl)-2-methylpentane-1,5-diamine, N3-(3-aminopentyl)pentane-1,3-diamine, N5-(3-amino-1-ethylpropyl)-2-methylpentane-1,5-diamine or N,N'-bis(3-amino-1-ethylpropyl)-2-methylpentane-1,5-diamine; - polyamines containing tertiary amino groups, such as, in particular, 2-aminoethylpiperazine, 3-dimethylaminopropylamine (DMAPA), N,N-dimethyldi(1,3-propylene)triamine (DMAPAPA), N,N'-bis(aminoethyl)piperazine, N,N'-bis(aminopropyl)piperazine, N,N-bis(3-aminopropyl)methylamine, N,N-bis(3-aminopropyl)ethylamine; aliphatic, cycloaliphatic or arylaliphatic primary triamines, in particular 4-aminomethyloctane-1,8-diamine, 1,3,5-tris(aminomethyl)benzene, 1,3,5-tris(aminomethyl)cyclohexane, tris(2-aminoethyl)amine, tris(2-aminopropyl)amine or tris(3-aminopropyl)amine; or diamines containing one primary and one secondary amino group, in particular N-benzylethane-1,2-diamine, N-benzylpropane-1,2-diamine, N-benzyl-1,3-bis(aminomethyl)benzene, N-2-ethylhexyl-1,3-bis(aminomethyl)benzene, N-(2-phenylethyl)-1,3-bis(aminomethyl)benzene (constituent of styrenated 1,3-bis(aminomethyl)benzene available from Mitsubishi Gas Chemical Company as Gaskamine® 240), especially products resulting from the reductive alkylation of primary aliphatic polyamines with aldehydes or ketones; or adducts of the amines listed or of small amines, such as ethane-1,2-diamine or propane-1,2-diamine, with mono- or diepoxides, especially cresyl glycidyl ether or bisphenol A diglycidyl ether; or polyamidoamines, in particular reaction products of monobasic or polybasic carboxylic acids or their esters or anhydrides, in particular dimerized fatty acids, with polyamines, in particular polyalkyleneamines such as, for example, DETA or TETA, used in stoichiometric excess; or Mannich bases, especially phenalkamines, i.e. reaction products of phenols, especially cardanol, with aldehydes, especially formaldehyde, and polyamines. is.

[0081] Aliphatic, cycloaliphatic or arylaliphatic polyamines are preferred.

[0082] MPMD, TMD, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, IPDA, 2(4)-methyl-1,3-diaminocyclohexane, bis(4-aminocyclohexyl)methane, NBDA, MXDA, average molecular weight M in the range of 200 to 500 g / mol nPreferred polyamines are selected from the group consisting of polyoxypropylene diamines and polyoxypropylene triamines having the formula: BHMT, TETA, TEPA, N4 amine, DMAPAPA, N-benzylethane-1,2-diamine, N-benzylpropane-1,2-diamine, N-benzyl-1,3-bis(aminomethyl)benzene, N-(2-phenylethyl)-1,3-bis(aminomethyl)benzene, and MPMD or an adduct of propane-1,2-diamine with cresyl glycidyl ether.

[0083] Of these, 1,2-diaminocyclohexane is particularly preferred, as it provides particularly high strength.

[0084] Of these, IPDA is particularly preferred, as it provides a particularly inexpensive composition with high strength.

[0085] Among these, the average molecular weight M in the range of 200 to 500 g / mol n Also particularly preferred are polyoxypropylene di- or triamines having the formula:

[0086] Among these, the adduct of propane-1,2-diamine with cresyl glycidyl ether, especially ortho-cresyl glycidyl ether, is also particularly preferred, where the adduct is preferably formed using an excess of propane-1,2-diamine over cresyl glycidyl ether, and the unadducted propane-1,2-diamine is removed by distillation after the reaction, which gives a glossy surface even under humid conditions.

[0087] It may be advantageous to use a mixture of two or more polyamines, with mixtures comprising at least one polyoxypropylene di- or triamine and at least one further polyamine being preferred.

[0088] The polyamine or mixture of two or more polyamines is preferably present in an amount such that the ratio of the number of amine hydrogens to the number of epoxy groups is in the range of from 0.5 / 1 to 1.5 / 1, especially from 0.8 / 1 to 1.2 / 1.

[0089] The compositions of the present invention are preferably two-component compositions, comprising a first component and a second component that are manufactured, packaged, and stored separately, wherein the polyamine is not in the same component as the liquid epoxy resin.

[0090] In a preferred embodiment of the present invention, the composition comprises: - at least one polymer containing silane groups, as described above, and - at least one liquid epoxy resin a first component including - at least one polyamine having at least three amine hydrogen atoms reactive towards epoxy groups; and a second component comprising:

[0091] In a further preferred embodiment of the present invention, the composition comprises: - at least one polymer containing silane groups, as described above, and - at least one polyamine having at least three amine hydrogen atoms reactive towards epoxy groups; a first component including - at least one liquid epoxy resin and a second component comprising:

[0092] In both of these embodiments, the components are themselves stable upon storage in the absence of moisture. When the two components are mixed, the primary and / or secondary amino groups react with the epoxide groups present. The silane groups react when they come into contact with water, releasing alcohol.

[0093] The composition preferably further comprises at least one additional component selected from aminosilanes, drying agents, accelerators, water, fillers, and plasticizers.

[0094] Suitable aminosilanes are, among others, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-N'-[3-(trimethoxysilyl)propyl]ethylenediamine, and their analogs with ethoxy groups instead of methoxy groups on the silicon.

[0095] The aminosilane is preferably in the same component as the polyamine.

[0096] The composition preferably contains the aminosilane in an amount ranging from 0.1% to 5% by weight, especially from 0.2% to 2% by weight, and such a composition has particularly high strength.

[0097] Suitable desiccants are, inter alia, tetraethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, organosilanes having a functional group in the α-position of the silane group, in particular N-(methyldimethoxysilylmethyl)-O-methylcarbamate or (methacryloyloxymethyl)silane, methoxymethylsilane, orthoformates, and also calcium oxide or molecular sieves.

[0098] The composition more preferably comprises vinyltrimethoxysilane or vinyltriethoxysilane, where vinyltrimethoxysilane is preferred when the silane group-containing polymer has methoxysilane groups, while vinyltriethoxysilane is preferred when the silane group-containing polymer has ethoxysilane groups.

[0099] The desiccant is preferably in the same component as the polymer containing silane groups.

[0100] Suitable (curing) accelerators are, inter alia, substances which accelerate the crosslinking of polymers containing silane groups. Metal catalysts and / or nitrogen-containing compounds are particularly suitable for this purpose.

[0101] Suitable metal catalysts are compounds of titanium, zirconium, aluminum, or tin, especially organotin compounds, organotitanates, organozirconates, or organoaluminates, which contain, inter alia, alkoxy, aminoalkoxy, sulfonate, carboxyl, 1,3-diketonate, 1,3-ketoesterate, dialkylphosphate, or dialkylpyrophosphate groups. The following are particularly suitable: dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin diacetylacetonate, dioctyltin oxide, dioctyltin dichloride, dioctyltin diacetate, dioctyltin dilaurate, or dioctyltin diacetylacetonate, and organotitanates or organozirconates.

[0102] Suitable nitrogen-containing compounds are, inter alia, reaction products of amidines such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 6-dibutylamino-1,8-diazabicyclo[5.4.0]undec-7-ene, or guanidines such as tetramethylguanidine, 2-guanidinobenzimidazole, acetylacetoneguanidine, or carbodiimides with amines, in particular polyetheramines or aminosilanes.

[0103] Suitable accelerators are also substances that accelerate the reaction between epoxy groups and amino groups, particularly acids or compounds that 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 acid, or nitrates, in particular calcium nitrate, or tertiary amines, in particular 1,4-diazabicyclo[2.2.2]octane, triethanolamine, imidazoles, in particular N-methylimidazole, N-vinylimidazole, or 1,2-dimethylimidazole, the listed amidines or guanidines, phenols, or Mannich bases, in particular 2,4,6-tris(dimethylaminomethyl)phenol, or compounds containing a mercapto group.

[0104] The composition preferably includes at least one accelerator selected from dialkyltin compounds, organic titanates, amidines, guanidines, acids, calcium nitrate, and Mannich bases.

[0105] More preferably, the composition comprises 2,4,6-tris(dimethylaminomethyl)phenol and at least one additional accelerator.

[0106] In a preferred embodiment of the present invention, the composition comprises water or a water-releasing substance. This type of composition has the advantage that it only needs to absorb a portion of the water required for cross-linking of the silane groups from the environment.

[0107] The composition preferably contains a total of no more than 5% by weight, especially no more than 2% by weight, of free or releasable water.

[0108] The free water is preferably not in the same component as the polymer containing silane groups.

[0109] Suitable fillers are especially lightweight fillers such as ground or precipitated calcium carbonate, optionally coated with fatty acids, especially stearates, barite, quartz flour, silica sand, dolomite, wollastonite, calcined kaolin, mica or talc, layered silicates, zeolites, aluminum hydroxide, magnesium hydroxide, silica such as finely divided silica from pyrolysis processes, cement, gypsum, fly ash, industrially produced carbon black, graphite, metal powders, for example of aluminum, copper, iron, silver or steel, PVC powder or hollow glass beads or gas-filled plastic spheres (microspheres), especially the types available under the brand name Expancel® (from Akzo Nobel).

[0110] Calcium carbonate, calcined kaolin, micronized silica or industrially produced carbon black are preferred.

[0111] Suitable plasticizers are, inter alia, phthalates, especially diisononyl phthalate (DINP), diisodecyl phthalate (DIDP) or di(2-propylheptyl) phthalate (DPHP), hydrogenated phthalates, i.e., cyclohexane-1,2-dicarboxylates, especially hydrogenated diisononyl phthalate, i.e., diisononylcyclohexane-1,2-dicarboxylate (DINCH), terephthalates, especially bis(2-ethylhexyl) terephthalate (DOTP) or diisononyl terephthalate (DINT), hydrogenated terephthalates, i.e., cyclohexane-1,4-dicarboxylates, especially hydrogenated bis(2-ethylhexyl) terephthalate, i.e., bis(2-ethylhexyl)cyclohexane-1,4-dicarboxylate. or hydrogenated diisononyl terephthalate, i.e. diisononylcyclohexane-1,4-dicarboxylate, isophthalate, trimellitate, adipate, especially dioctyl adipate, azelate, sebacate, benzoate, carboxylic acid esters, glycol ethers, in particular glycol esters, such as triethylene glycol bis(2-ethylhexanoate), plasticizers with a polyether structure, especially polypropylene oxide mono-, di- or triols with blocked hydroxyl groups, especially in the form of acetate groups, organic phosphates or sulfonates, polybutene, polyisobutene, or plasticizers derived from natural fats and oils, especially epoxidized soybean or linseed oil.

[0112] Preferred plasticizers are those having a phthalate, glycol ester or polyether structure.

[0113] The compositions of the present invention may contain further additives, in particular further crosslinkers, especially further silanes such as epoxysilanes or mercaptosilanes, or compounds containing mercapto groups, such as mercaptan-terminated polysulfide polymers or mercapto-terminated polyoxyalkylene ethers; - solvents or diluents; inorganic or organic pigments, in particular titanium dioxide, chromium oxide or iron oxide; - dye; rheology modifiers, especially 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 polyoxyethylene; - natural resins, oils, such as rosin, shellac, linseed oil, castor oil or soybean oil; - non-reactive polymers, in particular homopolymers or copolymers of unsaturated monomers from the group comprising ethylene, propylene, butylene, isobutylene, isoprene, vinyl acetate or alkyl (meth)acrylates, in particular polyethylene (PE), polypropylene (PP), polyisobutylene, ethylene / vinyl acetate copolymer (EVA) or atactic poly-α-olefins (APAO); - fibres, in particular glass fibres, carbon fibres, metal fibres, ceramic fibres, polymer fibres such as polyamide fibres or polyethylene fibres, or natural fibres such as wool, cellulose, hemp or sisal; - nanofillers such as graphene or carbon nanotubes; - flame retardant substances, especially the already mentioned aluminum hydroxide or magnesium hydroxide fillers, and also, especially, organic phosphate esters, such as, in particular, triethyl phosphate, tricresyl phosphate, triphenyl phosphate, diphenyl cresyl phosphate, isodecyl diphenyl 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, mono-, bis- or tris(isopropylphenyl)phosphates of different degrees of isopropylation, resorcinol bis(diphenyl phosphate), bisphenol A bis(diphenyl phosphate), or ammonium polyphosphate; additives, in particular emulsifiers, wetting agents, levelling agents, antifoaming agents, degassing agents, stabilizers against oxidation, heat, light or UV radiation, or biocides may contain

[0114] It may be advisable to chemically or physically dry certain components before incorporating them into the composition, especially if they are stored together with a polymer containing silane groups.

[0115] Preferably, the composition of the present invention is substantially solvent-free, in particular containing less than 5% by weight, preferably less than 2.5% by weight, of solvent, and most preferably it is essentially solvent-free.

[0116] The composition of the present invention preferably has a content of polymer containing silane groups in the range of 10% to 50% by weight, in particular 12% to 40% by weight.

[0117] The composition of the present invention preferably has a liquid epoxy resin content in the range of 10% to 60% by weight, especially 20% to 50% by weight.

[0118] The composition of the present invention preferably has a total content of liquid epoxy resin and reactive diluent containing epoxy groups in the range of 20% to 70% by weight, in particular 25% to 65% by weight.

[0119] The composition of the present invention preferably comprises: - 12% to 40% by weight of a polymer containing silane groups, - 20% to 50% by weight of liquid epoxy resin, - 0% to 20% by weight of a reactive diluent containing epoxy groups, - 5% to 40% by weight of a polyamine, - 0% to 50% by weight of filler, and optionally further components Contains:

[0120] The compositions of the present invention are preferably prepared and used as two-component compositions. The first and second components of the composition are prepared separately from each other and stored in moisture-tight containers. Suitable containers are, inter alia, drums, hobbocks, pouches, buckets, cans, cartridges or tubes.

[0121] For use of the described composition, the two components are mixed together immediately before or during application. The mixing ratio is preferably selected so that the epoxy-reactive groups are present in a suitable ratio to the epoxy groups, as described above. In parts by weight, the mixing ratio is typically in the range of 1:10 to 10:1.

[0122] The two components are mixed by any suitable method; mixing can be achieved continuously or batchwise using a static mixer or by a dynamic mixer. If mixing precedes application, care must be taken to ensure that application occurs within the pot life of the composition, as otherwise there may be complications, such as delayed or incomplete adhesion to the substrate or premature crusting.

[0123] "Pot life" refers to the time within which a composition should be applied after it is mixed.

[0124] The ingredients are preferably mixed at ambient temperature, typically in the range of about 0-50°C, preferably about 5-35°C.

[0125] Curing by chemical reaction begins with the mixing of the two components. The epoxy groups then react with the amine hydrogen, and the silane groups undergo hydrolysis with the release of alcohol to form silanol groups (Si-OH groups), and subsequent condensation reactions to form siloxane groups (Si-O-Si groups). As a result of these and possibly further reactions, the composition cures to give a crosslinked polymer. If water for hydrolysis of the silane groups is not already present in the composition, it can come from the air (atmospheric humidity) or from the substrate, or the composition can be brought into contact with a water-containing component, for example, by coating, spraying, or mixing.

[0126] Curing typically proceeds at temperatures ranging from 0 to 150° C. It can be accomplished at ambient temperature, typically continuing for several days to several weeks until it is largely complete under prevailing conditions. In some cases, it may be advantageous to subject a composition that has partially cured at ambient temperature to further curing at elevated temperatures.

[0127] The compositions described are applied to at least one substrate, including the following substrates: - Metals or alloys such as aluminium, iron, steel, copper and other non-ferrous metals, including surface-modified metals or alloys such as galvanised or chrome-plated metals; - Concrete, mortar, cement screed, fibre cement, brick, tile, plaster and natural stone such as granite or marble; - Asphalt or bitumen; - coated or painted substrates, in particular painted tiles, coated concrete, powder-coated metals or alloys or painted metal sheets; - Repair or leveling compounds based on PCC (polymer modified cement mortar) or ECC (epoxy resin modified cement mortar); leather, textiles, paper, wood, wood-based materials bonded with resins, such as phenolic, melamine or epoxy resins, resin-textile composites or further so-called polymer composites; plastics, such as rigid and flexible PVC, polycarbonate, polystyrene, polyester, polyamide, PMMA, ABS, SAN, epoxy resins, phenolic resins, PUR, POM, TPO, PE, PP, EPM or EPDM, in each case untreated or surface-treated, for example by plasma, corona or flame; - Fiber reinforced plastics, such as carbon fiber reinforced plastics (CFP), glass fiber reinforced plastics (GFP) and sheet molding compounds (SMC); - glass or glass ceramic; - insulating foam, especially made of EPS, XPS, PUR, PIR, rock wool, glass wool or foam glass is particularly preferred.

[0128] If necessary, the substrate can be pretreated before application, inter alia, by physical and / or chemical cleaning methods or by application of an activator or primer.

[0129] Curing of the described compositions provides a cured composition.

[0130] The cured composition has very high strength, high extensibility and high tear resistance.

[0131] More specifically, it has a tensile strength of at least 15 MPa, preferably at least 20 MPa, measured on dumbbell-shaped test specimens having a length of 75 mm, a specimen length of 30 mm, a specimen width of 4 mm and a thickness of about 2 mm as described in accordance with DIN EN 53504 at a strain rate of 2 mm / min, and an elongation at break of at least 10%, preferably at least 15%, in particular at least 20%, most preferably at least 25%.

[0132] More particularly, it has a tear resistance of at least 10 N / mm, preferably at least 15 N / mm, especially at least 20 N / mm, measured according to DIN ISO 34 at a strain rate of 500 mm / min.

[0133] The composition also has high stability to heat, light, and hydrolysis. More specifically, the composition also has high stability to glycol / water mixtures such as those used as cooling fluids or antifreeze in automotive or electric vehicle batteries, such as a mixture of 50% by weight of Glysantin® G64® Concentrate (BASF) and 50% by weight of water.

[0134] Furthermore, the composition has very high bonding strength to various substrates, especially to wet or moist substrates. More specifically, metals such as aluminum or steel can be bonded with the composition of the present invention without a primer, and the bond is highly resistant to corrosion, for example, in the case of saltwater stress. Furthermore, it is possible to permanently bond concrete, asphalt, or bitumen without a primer, even under moist or damp conditions.

[0135] Additionally, the composition has anti-corrosion properties when used on metals such as aluminum or steel.

[0136] This composition is also advantageous when using isocyanate-free products, particularly for industrial and health protection reasons.

[0137] The compositions described are preferably used, inter alia, as adhesives, sealants, coatings or casting compounds, in particular on at least one metal such as steel or aluminum, preferably aluminum.

[0138] When used on at least one metal, the composition has the advantage that the metal is protected from corrosion. Therefore, the adhesive strength is not weakened by metal corrosion, even in the case of stress in salt water, for example. More particularly, it is possible to bond non-anodized aluminum without the use of a primer, without weakening the adhesive strength due to corrosion, even in the case of stress in salt water.

[0139] The described compositions are more preferably used as viscoelastic adhesives. In this case, after the components are mixed, they typically have a liquid or paste-like consistency with structurally viscous properties. During application, the mixed adhesive is applied within its pot life to at least one of the substrates to be bonded, and the substrates are joined to form an adhesive bond within the adhesive's open time.

[0140] The "open time" of an adhesive refers to the maximum period of time possible for a cohesive bond between application of the adhesive and joining of the parts to be bonded.

[0141] The mixed adhesive is applied using a brush, roll, spatula, doctor blade or trowel, among others, or from a tube, cartridge or metering device.

[0142] The adhesive is particularly suitable for use in the construction industry or for bonding components in the manufacturing industry.

[0143] A preferred use is the bonding of battery boxes, especially in electric vehicles. Advantageous features here are high strength combined with high extensibility, high bonding strength, and high stability, especially with respect to glycol / water mixtures used as coolants for such batteries. The components to be bonded here are especially those made of aluminum, with corrosion-resistant adhesion, especially advantageous under saltwater stress.

[0144] The present invention therefore further provides a bonding method, characterized in that the mixed composition is applied to at least one of the substrates to be bonded within the pot life, and the substrates are joined to provide bonding within the open time, followed by curing of the mixed composition, wherein at least one of the substrates here is preferably metal, in particular aluminum or steel, more preferably aluminum.

[0145] The compositions described are preferably also used as coatings, especially as coatings for metals such as steel or aluminum, in which case the compositions protect the metal from corrosion.

[0146] The compositions described are also preferably used as casting compounds for filling cavities such as cracks, gaps or drilled holes, where the mixed composition is poured or injected into the cavity and fills it after hardening, causing the sides of the cavity to adhere to each other in a viscoelastic manner, giving excellent adhesion even on wet substrates.It is therefore possible in a simple way to permanently repair roads, parks or terraces, as well as walls or other solid structures that are damaged on their surface or at curbs, edges or borders, with the repaired areas being very stable even under severe stress.

[0147] If necessary, during filling of the cavity it is possible to introduce into the cavity what are called anchors, for example reinforcing rods, threaded rods or bolts.

[0148] The present invention therefore further provides a method for coating a substrate or filling cavities, in particular cracks or gaps, characterized in that the mixed composition is applied to the substrate within the pot life or used to fill a cavity and hardens in situ, whereby in filling the cavity it is optionally possible to insert an anchor into the cavity while the composition is still free-flowing.

[0149] The application and curing of the described compositions or methods of adhering or coating a substrate or filling a cavity provides an article, which may be a solid structure or part thereof, especially a road, park, terrace, curb, edging, boundary or wall, or it may be an industrial or consumer good, especially a motor vehicle or part thereof, especially a motor vehicle battery box.

[0150] The present invention therefore further provides an article resulting from the described use or the described method of joining or filling cavities.

[0151] The compositions of the present invention have advantageous properties, among them good storage stability, rapid cure, surprisingly high strength even under moist or humid conditions, combined with high extensibility, high tear resistance, high stability, and high bond strength to many substrates, while protecting metals such as steel or aluminum from corrosion when the compositions are used thereon. The compositions therefore enable reliable adhesion of untreated aluminum under corrosive conditions. [Example]

[0152] Examples are presented herein below that are intended to clarify the invention as described, but the invention is of course not limited to these described examples.

[0153] "Standard Climatic Conditions" ("SCC") refers to a temperature of 23±1°C and a relative air humidity of 50±5%.

[0154] Unless otherwise stated, chemicals used were from Sigma-Aldrich Chemie GmbH.

[0155] Diethyl N-(3-trimethoxysilylpropyl)aminosuccinate was prepared from the reaction of diethyl maleate with 3-trimethoxysilylpropylamine.

[0156] Diisodecyl phthalate was used in the form of Palatinol® 10-P (manufactured by BASF).

[0157] Comparative examples are identified by (Ref.).

[0158] Preparation of polymers containing silane groups: Polymer ST-1 With the exclusion of moisture, 400 g of polyoxypropylene diol (Acclaim® 4200, OH value 28 mg KOH / g, from Covestro) and 52 g of diphenylmethane 4,4′-diisocyanate (Desmodur® 44 MC L, from Covestro) were heated to 80° C. with constant stirring and left at that temperature until the NCO content reached a value of 1.85% by weight.

[0159] Then, 70.7 g of N-(3-trimethoxysilylpropyl)diethylaminosuccinate was added, and the mixture was stirred at 60° C. until no isocyanate groups could be detected by FT-IR spectroscopy. The resulting polymer containing silane groups was cooled to room temperature and stored with the exclusion of moisture. It was clear, colorless, and liquid at room temperature, with a calculated silicon content of 1.08 wt %.

[0160] Polymer ST-2 With the exclusion of moisture, 513.3 g of polyoxypropylene diol (Acclaim® 4200, OH value 28 mg KOH / g, ex Covestro), 256.7 g of ethylene oxide-terminated polyoxypropylene triol (Caradol® MD34-02, OH value 35 mg KOH / g, ex Shell) and 64.2 g of toluene diisocyanate (Desmodur® T 80 P, ex Covestro) were heated with constant stirring to 80° C. and left at that temperature until the NCO content reached a value of 1.5% by weight.

[0161] Then, 105.8 g of N-(3-trimethoxysilylpropyl)diethylaminosuccinate was added, and the mixture was stirred at 60° C. until no isocyanate groups could be detected by FT-IR spectroscopy. The resulting polymer containing silane groups was cooled to room temperature and stored with the exclusion of moisture. It was clear, colorless, and liquid at room temperature, with a calculated silicon content of 0.90 wt %.

[0162] Polymer ST-3 With the exclusion of moisture, 400 g of polyoxypropylene diol (Acclaim® 4200, OH value 28 mg KOH / g, from Covestro), 44.4 g of isophorone diisocyanate (Vestanat® IPDI, from Evonik) and 0.05 g of dibutyltin dilaurate were heated to 80° C. with constant stirring and left at that temperature until the NCO content reached a value of 1.9% by weight.

[0163] Then, 74.8 g of N-(3-trimethoxysilylpropyl)diethylaminosuccinate was added, and the mixture was stirred at 60° C. until no isocyanate groups could be detected by FT-IR spectroscopy. The resulting polymer containing silane groups was cooled to room temperature and stored with the exclusion of moisture. It was clear, colorless, and liquid at room temperature, with a calculated silicon content of 1.15 wt %.

[0164] Polymer ST-4 With the exclusion of moisture, 500.0 g of polyoxypropylene diol (Voranol® 2000 L, OH value 55.5 mg KOH / g, from Dow) and 88.7 g of toluene diisocyanate (Desmodur® T 80 P, from Covestro) were heated to 80° C. with constant stirring and left at that temperature until the NCO content reached a value of 3.4% by weight.

[0165] Then, 167.5 g of N-(3-trimethoxysilylpropyl)diethylaminosuccinate was added, and the mixture was stirred at 60° C. until no isocyanate groups could be detected by FT-IR spectroscopy. The resulting polymer containing silane groups was cooled to room temperature and stored with the exclusion of moisture. It was clear, colorless, and liquid at room temperature, with a calculated silicon content of 1.8% by weight.

[0166] Polymer ST-5 (Ref.) With the exclusion of moisture, 250.0 g of polyoxypropylene diol (Voranol® 2000 L, OH value 55.5 mg KOH / g, ex Dow), 250.0 g of polyoxypropylene diol (Voranol® P1010, OH value 110 mg KOH / g, ex Dow) and 130.4 g of toluene diisocyanate (Desmodur® T 80 P, ex Covestro) were heated to 80° C. with constant stirring and left at that temperature until the NCO content reached a value of 4.9% by weight.

[0167] Then, 258.5 g of N-(3-trimethoxysilylpropyl)diethylaminosuccinate was added, and the mixture was stirred at 60° C. until no isocyanate groups could be detected by FT-IR spectroscopy. The resulting polymer containing silane groups was cooled to room temperature and stored with the exclusion of moisture. It was clear, colorless, and liquid at room temperature, with a calculated silicon content of 2.3% by weight.

[0168] Polymer ST-6 (Ref.) With the exclusion of moisture, 1000 g of polyoxypropylene diol (Acclaim® 12200 from Covestro; OH value 11.0 mg KOH / g), 122.8 g of diisodecyl phthalate, 43.6 g of isophorone diisocyanate (Vestanat® IPDI from Evonik) and 0.12 g of dibutyltin dilaurate were heated to 90° C. with constant stirring and left at that temperature until the NCO content reached a value of 0.63% by weight.

[0169] Then, 61.8 g of N-(3-trimethoxysilylpropyl)diethylaminosuccinate was added, and the mixture was stirred at 90°C until no isocyanate groups could be detected by FT-IR spectroscopy. The resulting polymer (90 wt% in diisodecyl phthalate) containing silane groups was cooled to room temperature and stored with the exclusion of moisture. It was clear, colorless, and liquid at room temperature, with a calculated silicon content of 0.45 wt% (calculated relative to 100 wt% of the polymer, without diisodecyl phthalate).

[0170] Polymers ST-1 to ST-4 have silicon contents according to the invention. Polymer ST-5 (Ref.) has a higher silicon content than the invention, and polymer ST-6 (Ref.) has a lower silicon content. They serve as a comparison.

[0171] Preparation of the two-component composition Examples Z-1 to Z-7: For each composition, the components specified in Table 1 were mixed in the specified amount (in parts by weight) of component 1 using a centrifugal mixer (SpeedMixer™ DAC 150, FlackTek Inc.) and stored with the exclusion of moisture.

[0172] Similarly, the components of Component 2 specified in Table 1 were processed and stored.

[0173] The two components of each composition were then processed in a centrifugal mixer at the specified mixing ratio (0.6 / 1 by weight) to obtain a homogeneous liquid, which was immediately tested as follows: For pot life measurements, a 300 g quantity of the freshly mixed composition was stirred in a 500 ml beaker with a spatula at 5 minute intervals until it felt as if the composition had thickened to such an extent that it no longer had good workability.

[0174] For the measurement of mechanical properties, the mixed composition was poured onto a PTFE-coated film to obtain a 2 mm-thick film and stored under standard climatic conditions. After one day, a number of 75 mm-long dumbbell-shaped test specimens with a 30 mm specimen length and a 4 mm specimen width were punched out of the film and stored under standard climatic conditions for an additional six days. These were then measured for tensile strength (load at break), elongation at break, and modulus of elasticity at 0.5% to 1% elongation (MoE 0.5-1%) and at 0.5% to 5% elongation (MoE 0.5-5%) as specified in DIN EN 53504 at a strain rate of 2 mm / min. Similarly, a number of test specimens were punched out, stored, and tested for tear resistance according to DIN ISO 34 at a strain rate of 500 mm / min.

[0175] After 7 days under SCC, the appearance of all films was visually rated. All films were black in color after curing, had a silky matte surface with absolutely zero tack, were homogeneous, and were blister-free. Such films were referred to as "good."

[0176] These results are reported in Table 2.

[0177] Examples Z-1 to Z-3 and Z-5 to Z-6 are inventive examples in which the silane group-containing polymer has a silicon content in accordance with the present invention. Example Z-4 is a comparative example in which the silane group-containing polymer has a silicon content lower than that of the present invention. Example Z-7 is a comparative example in which the silane group-containing polymer has a silicon content higher than that of the present invention.

[0178] [Table 1]

[0179] [Table 2]

[0180] Additionally, the corrosion resistance or stability of the bond between two aluminum sheets (5754 alloy, AlMg3, shiny) was tested with the composition from Example Z-1 under saltwater stress. For comparison, the same test was carried out with a commercial two-component epoxy resin adhesive (2K epoxy adhesive) (= impact-resistant structural adhesive 07333, manufactured by 3M).

[0181] For this purpose, multi-adhesion test specimens were prepared by applying the freshly mixed adhesive between two shiny, heptane-degreased aluminum sheets (AlMg3, 100 x 25 x 1 mm) in a layer thickness of 0.3 mm with an overlapping adhesive area of 10 x 25 mm. After a storage time of 7 days under standard climatic conditions, the lap shear strength was measured in accordance with DIN EN 1465 at a strain rate of 10 mm / min. This value is reported in Table 3 as week 0 (starting value).

[0182] Further test specimens of this type were subjected to various cycles of saltwater stress, as described later in this specification. On the first day, the test specimens were placed in a salt solution (5% by weight NaCl in deionized water) at room temperature for 15 minutes, then suspended and dried without wringing under standard climatic conditions for 95 minutes, followed by 22 hours of storage in a climate-controlled cabinet at 50°C / 90% relative humidity (=1 cycle). This was followed by four more days in the same sequence, followed by 48 hours in a climate-controlled cabinet at 50°C / 90% relative humidity (weekend). This resulted in a one-week storage time with five cycles of saltwater stress. The test specimens were stored in this manner for two weeks (10 cycles), four weeks (20 cycles), or six weeks (30 cycles), and then the lap shear strength was measured in each case as described above. Upon completion of the lap shear strength test, the test specimens were visually evaluated for their fracture profile and the condition (appearance) of the aluminum sheet beneath the bond. "cf" means cohesion failure; "af" means adhesion failure. "No corrosion" means the aluminum sheet has an unchanged shine directly below the bond. "2-3mm corrosion" means the aluminum has a matte white color within 2-3mm of the edge directly below the bond. In areas not covered by the bond, all sheets have a mottled matte white appearance after saltwater stress.

[0183] These results are reported in Table 3.

[0184] [Table 3]

[0185] Adhesion on dry and wet concrete and bitumen was also measured for the composition from Example Z-1. For this purpose, three concrete slabs (500 x 500 x 40 mm) and three bitumen slabs (approximately 300 x 200 x 30 mm) were provided. Two slabs were each coated in the dry state with a freshly mixed composition in a layer thickness of approximately 3-4 mm. The third slab was placed in deionized water for 24 h and then, in the wet state with a residual of standing water on the surface, similarly coated with the freshly mixed composition in a layer thickness of approximately 3-4 mm. A steel cylinder with a diameter of 20 mm, which had been washed several times with acetone, was applied to each of the freshly coated slabs so that adhesion was formed between the steel cylinder and the composition (coating). After a storage time of 7 days of the coated slabs under standard climatic conditions, the adhesive strength values were measured in each case for one of the two dry slabs and for the wet slab. Further slabs coated in the dry state were placed in deionized water for 7 days to dry the surface and only then were the adhesive strength values measured, which were determined in each case in accordance with DIN EN 4624 by pulling the bonded steel cylinder at a test speed of 2 mm / min until it broke free from the slab.

[0186] These results are reported in Table 4.

[0187] [Table 4]

Claims

1. A composition comprising: at least one polymer containing silane groups and having a silicon content ranging from 0.6% to 2% by weight, resulting from the reaction of at least one polymer containing isocyanate groups with at least one aminosilane, mercaptosilane or hydroxysilane; at least one liquid epoxy resin, and - at least one polyamine having at least three amine hydrogens reactive towards epoxy groups;

2. 2. The composition according to claim 1, wherein the polymer containing silane groups has a silicon content ranging from 0.7% to 1.5% by weight, in particular from 0.8% to 1.2% by weight.

3. 3. The composition according to claim 1 or 2, characterized in that the polymer containing silane groups has silane groups of formula (I): 【Chemical Formula 1】 (In the formula, n is 1 or 2 or 3, especially 2 or 3; R １ is a linear or branched monovalent hydrocarbyl group having 1 to 5 carbon atoms; R ２ is a linear or branched divalent hydrocarbyl group having 1 to 12 carbon atoms and optionally containing cyclic and / or aromatic moieties and optionally one or more heteroatoms, especially amide, carbamate or morpholino groups; X is O, S or NR ３ where R ３ is a hydrogen atom or a linear or branched hydrocarbyl group having from 1 to 20 carbon atoms and optionally containing cyclic moieties, and optionally containing alkoxysilyl groups or ether or carboxylic acid ester groups.

4. 4. Composition according to any one of claims 1 to 3, characterized in that the polymer containing isocyanate groups has an NCO content ranging from 1.2% to 4% by weight, in particular from 1.2% to 2.8% by weight.

5. 5. Composition according to any one of claims 1 to 4, characterized in that the polymer containing isocyanate groups is a polymer obtained from the reaction of at least one polyoxypropylene diol having an OH number in the range from 18 to 58 mg KOH / g, in particular from 22 to 40 mg KOH / g, and optionally having terminal oxyethylene groups, with at least one diisocyanate.

6. 6. The composition according to claim 1, wherein the polymer containing isocyanate groups has aromatic isocyanate groups.

7. 7. The composition according to claim 1, wherein the aminosilane, mercaptosilane, or hydroxysilane is an aminosilane, in particular diethyl N-(3-trimethoxysilylpropyl)aminosuccinate, diethyl N-(3-dimethoxymethylsilylpropyl)aminosuccinate, or diethyl N-(3-triethoxysilylpropyl)aminosuccinate.

8. The polyamine may be 1,5-diamino-2-methylpentane, 2,2(4),4-trimethylhexamethylenediamine, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 2(4)-methyl-1,3-diaminocyclohexane, bis(4-aminocyclohexyl)methane, 2,5(2,6)-bis(aminomethyl)bicyclo[2.2.1]heptane, 1,3-bis(aminomethyl)benzene, or an average molecular weight M in the range of 200 to 500 g / mol. ｎ 8. The composition according to claim 1, wherein the diamine is selected from the group consisting of polyoxypropylenediamines and polyoxypropylenetriamines listed above, bis(hexamethylene)triamine, triethylenetetramine, tetraethylenepentamine, N,N'-bis(3-aminopropyl)ethylenediamine, N,N-dimethyldi(1,3-propylene)triamine, N-benzylethane-1,2-diamine, N-benzylpropane-1,2-diamine, N-benzyl-1,3-bis(aminomethyl)benzene, N-(2-phenylethyl)-1,3-bis(aminomethyl)benzene, and adducts of 1,5-diamino-2-methylpentane or propane-1,2-diamine with cresyl glycidyl ether.

9. 9. The composition of any one of claims 1 to 8, comprising a first component and a second component that are manufactured, packaged, and stored separately, wherein the polyamine is not in the same component as the liquid epoxy resin.

10. The composition according to any one of claims 1 to 9, characterized in that it further comprises at least one further constituent selected from aminosilanes, drying agents, accelerators, water, fillers and plasticizers.

11. Use of a composition according to any one of claims 1 to 10 as an adhesive, sealant, coating or casting compound, especially on at least one metal, preferably aluminium.

12. 12. Use according to claim 11, characterized in that the composition is used for bonding battery boxes.

13. 11. A method of bonding, characterized in that the mixed composition according to any one of claims 1 to 10 is applied to at least one of the substrates to be bonded within the pot life and the substrates are joined to provide bonding within the open time, followed by curing of the mixed composition.

14. 11. A method for coating a substrate or for filling cavities, especially cracks or gaps, characterized in that the mixed composition according to any one of claims 1 to 10 is applied to the substrate or used to fill the cavities within the pot life and cured in situ.

15. 15. An article obtained from the use according to claim 11 or 12 or the method according to claim 13 or 14.

Images