Two-component compositions based on blends of epoxide compounds

Abstract

The present disclosure: (I) a first component comprising: a) Formula (AI): TIFF2025530806000013.tif3776[in the formula, R e is a C1-C6 alkyl group; R f Epoxide-substituted C1-C 12 Alkyl groups, C3-C 18 Cycloalkyl groups or C2-C 18 an alkoxyalkyl group; R g is H or a C1-C6 alkyl group; R h is a C1-C6 alkyl group; i is an integer greater than or equal to 1; and j is an integer greater than or equal to 1. at least one epoxy silane oligomer represented by the formula: b) at least one polyepoxide compound having at least three epoxide groups per molecule; and optionally, c) at least one compound selected from the group consisting of monoepoxide compounds and diepoxide compounds; wherein the compounds of parts b) and c) do not satisfy formula (AI); (II) a second component comprising: d) a curing agent consisting of at least two compounds having at least two epoxide-reactive groups per molecule, characterized in that the curing agent comprises at least one Mannich base and at least one cycloaliphatic amine; A two-component (2K) composition comprising: The two-component (2K) composition further comprises e) Core-shell rubber particles and Furthermore, the present invention relates to a two-component (2K) composition characterized in that the molar ratio of epoxide-reactive groups to epoxide groups is 0.95:1 to 1.5:1.

Description

[Technical Field]

[0001] The present disclosure relates to a two-component (2K) composition based on a blend of epoxide compounds. More specifically, the present disclosure relates to a two-component (2K) composition in which a first component comprises a multifunctional epoxide compound and a silane oligomer containing epoxide groups, and a second component comprises a curing agent having epoxide-reactive groups. [Background technology]

[0002] Epoxy resins have found a wide range of uses, based primarily on the ability to tailor the properties of the cured epoxy resin to achieve specific performance characteristics through the specific selection of resins, modifiers, and crosslinkers (or hardeners).

[0003] Recognizing their versatility, properly cured epoxy resins also possess several other attributes, including, inter alia: excellent chemical resistance, especially to alkaline environments; high tensile and compressive strength; high fatigue strength; low shrinkage upon cure; and electrical insulating properties and their retention with aging or environmental exposure. However, cured epoxy resin systems can also be disadvantageously characterized by reduced fracture resistance and impact strength, poor thermal stability, poor pigment retention, poor flexibility, and poor hydrophobicity.

[0004] The present disclosure is directed to "two-component (2K) compositions," which should be understood as compositions in which the binder component (I) (here based on an epoxide compound) and the hardener component (II) are stored in separate containers due to their reactivity. The two components are mixed only immediately before application and then react by bond formation, thereby forming a polymer network.

[0005] While two-component (2K) compositions based on epoxide compounds are sometimes capable of rapid initial cure, such rapid cure is usually achieved by using high temperatures that may not be suitable or practical for all substrates that may come into contact with the composition. Furthermore, using high temperatures to promote fast cure rates can also cause other problems. First, it can prevent proper leveling in certain coating, adhesive, or sealant applications. Second, it can limit the breathing of the material: during high-temperature cure, moisture trapped beneath the surface of the coating, adhesive, or sealant composition can evaporate, causing bubbles or buckling in the cured composition, or at least nanoscale material failure. Of course, material failure begins at the nanoscale, then expands to the microscale and then to the macroscale; exposure to abrasive conditions can accelerate this process.

[0006] The problem is that at room temperature, two-component (2K) epoxy compositions often tend to cure slowly over time, sometimes requiring 6-8 hours of curing before handling, with full cure achieved in 1, 2, or even 7 days. Such long processing times can be disadvantageous for many industrial applications. In fact, the slow cure rate can prevent such two-component epoxy compositions from being used in room-temperature, assembly-line processing, or other low-temperature applications requiring high throughput.

[0007] Many authors have attempted to address the need to develop two-component (2K) epoxy compositions that can provide a rapid build-up of strength, but that can be cured at room temperature, thus avoiding the energy costs of heating the composition and / or the substrate to which it is applied. A common approach has traditionally been to speed up the cure time by adding certain low molecular weight additives (cure accelerators) to the hardener component of the 2K epoxy composition.

[0008] US2005 / 0143496 (Mueller) discloses a two-component epoxide resin composition comprising, as component A, at least one epoxide resin having an epoxy functionality greater than 1; and, as component B, a liquid or paste-like curing agent containing an amine, polyetheramine, polyaminoamide, Mannich base, and / or mercapto group, further containing a non-volatile and non-corrosive accelerator. The two-component composition is intended to be used as a structural adhesive for the assembly of car bodies.

[0009] WO2004092244A2 (Huntsman Advanced Materials Americas Inc.) discloses a composition useful as a curing accelerator for epoxy resin compositions at low temperatures, the accelerator composition comprising: a first component, a 1-imidazolyl[methyl-substituted 2-naphthol compound; and a second component, a phenol that is liquid at room temperature, the weight ratio of the first component to the second component being 10:90 to 80:20.

[0010] WO2019115110A1 (Hilti AG) discloses a curing agent component for a multi-component epoxy resin material that cures at room temperature, the curing agent component comprising a benzoxazine amine adduct as an accelerator and an amine as a curing agent, the benzoxazine amine adduct being present in the curing agent component in an amount of 8.5% to 75% by weight. [Prior art documents] [Patent documents]

[0011] [Patent Document 1] US Patent Application Publication No. 2005 / 0143496 [Patent Document 2] International Publication No. 2004 / 092244 [Patent Document 3] International Publication No. 2019 / 115110 Summary of the Invention [Problem to be solved by the invention]

[0012] However, the necessary inclusion of accelerators in room temperature vulcanizable compositions can be detrimental in that they can increase the brittleness of the cured composition and reduce dynamic strength performance. Additionally, low molecular weight additives that are not incorporated into the polymer matrix can promote overplasticization of the curable composition in some circumstances.

[0013] It has also been observed that room temperature curable epoxy resin compositions lose adhesive strength when exposed to temperatures above room temperature after curing, which limits their usefulness to low temperature adhesive applications. [Means for solving the problem]

[0014] In a first aspect of the present invention, (I) a first component comprising: a) Formula (AI): [ka] [In the formula, R e is a C1-C6 alkyl group; R f Epoxide-substituted C1-C 12 Alkyl groups, C3-C 18 Cycloalkyl groups or C2-C 18 an alkoxyalkyl group; R g is H or a C1-C6 alkyl group; R h is a C1-C6 alkyl group; i is an integer greater than or equal to 1; and j is an integer greater than or equal to 1. at least one epoxy silane oligomer represented by the formula: b) at least one polyepoxide compound having at least three epoxide groups per molecule; and optionally c) at least one compound selected from the group consisting of monoepoxide compounds and diepoxide compounds; wherein the compounds of parts b) and c) do not satisfy formula (AI); (II) a second component comprising: d) a curing agent consisting of at least two compounds having at least two epoxide-reactive groups per molecule, characterized in that the curing agent comprises at least one Mannich base and at least one cycloaliphatic amine; A two-component (2K) composition comprising: The two-component (2K) composition further comprises e) Core-shell rubber particles and A two-component (2K) composition is provided, characterized in that the molar ratio of epoxide-reactive groups to epoxide groups is between 0.95:1 and 1.5:1.

[0015] The core-shell rubber particles described in part e) may be included in the first component, the second component, or both components, however, it is preferred that at least a portion, preferably at least 60% or at least 70% by weight, of the core-shell rubber particles be provided in the first component.

[0016] In certain embodiments, the two-component (2K) composition comprises, based on the weight of the composition: 0.1 to 5 wt. %, preferably 0.5 to 4 wt. %, and more preferably 0.5 to 2 wt. % of a) said at least one epoxy silane oligomer represented by formula (AI); 10 to 80 wt. %, 15 to 75 wt. %, and more preferably 20 to 70 wt. % of b) said at least one polyepoxide compound having at least three epoxide groups per molecule; 0-20 wt. %, preferably 0-15 wt. % and more preferably 0-10 wt. % of c) said at least one compound selected from the group consisting of monoepoxide compounds and diepoxide compounds; 10 to 30% by weight, preferably 15 to 30% by weight, of d) the curing agent; and 5 to 30 wt. %, preferably 5 to 25 wt. %, and more preferably 10 to 25 wt. % of e) said core-shell rubber particles; wherein the two-component (2K) composition is characterized in that the molar ratio of epoxide-reactive groups to epoxide groups is from 0.95:1 to 1.1:1.

[0017] The compositions defined above have been demonstrated to be curable at room temperature, and furthermore, when cured at room temperature, the cured compositions exhibit good adhesive strength at both room temperature and elevated temperature conditions.

[0018] The epoxy silane oligomer contained in the composition is preferably characterized by a number average molecular weight (Mn) of 200 to 3000 Daltons. Independently of or in addition to this characteristic, part a) of the composition preferably comprises a compound represented by formula (AII): [ka] [wherein L is an integer of 0 to 20, preferably 1 to 10; and R k is C1-C6 alkyl, preferably C1-C4 alkyl, and more preferably C2-C3 alkyl. The compound may comprise or consist of at least one compound represented by the formula:

[0019] Preferably, the at least one polyepoxide compound b) having at least three epoxide groups per molecule is selected from the group consisting of glycidyl ethers of polyhydric alcohols, glycidyl ethers of polyhydric phenols, glycidyl esters of polycarboxylic acids, polyfunctional glycidyl amines, and epoxidized polyethylenically unsaturated hydrocarbons. For example, good results have been obtained when b) comprises or consists of at least one polyfunctional glycidyl amine selected from the group consisting of N,N,N',N'-tetraglycidyl-4,4'methylenebisbenzenamine, p-aminophenol triglycidyl ether, m-aminophenol triglycidyl ether, tetraglycidyl bis(aminomethyl)cyclohexane, and N,N,N',N'-tetraglycidyl-m-xylenediamine.

[0020] Part c) of the composition is optional. However, if added, it is preferred that part c) comprises or consists of at least one diepoxide compound having an epoxide equivalent weight of 100 to 700 g / eq. The at least one diepoxide compound may preferably be selected from the group consisting of glycidyl ethers of dihydric alcohols; glycidyl ethers of dihydric phenols; glycidyl esters of dicarboxylic acids; and epoxidized polyethylenically unsaturated hydrocarbons.

[0021] Preferably, the or each Mannich base of the curing agent is a phenalkamine. Independently of or in addition to this preference, the or each cycloaliphatic amine of the curing agent is preferably 1,2-, 1,3-, and 1,4-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; 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (isophoronediamine, IPDA); 2- and / or or 4-methyl-1,3-diaminocyclohexane; 1,3-bis(aminomethyl)cyclohexane; 1,4-bis(aminomethyl)cyclohexane; 2,5(2,6)-bis(aminomethyl)-bicyclo[2.2.1]heptane (norboranediamine, NBDA); 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.02,6]decane (TCD-diamine); 1,4-diamino-2,2,6-trimethylcyclohexane (TMCDA); N,N-bis(3-aminopropyl)cyclohexylamine; and 1,8-menthanediamine.

[0022] In accordance with a second aspect of the present invention, there is provided a cured product obtained from a two-component (2K) composition as defined above and in the appended claims. The present invention also provides the use of the cured reaction product as a coating, adhesive or sealant. DETAILED DESCRIPTION OF THE INVENTION

[0023] (definition) As used herein, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise.

[0024] As used herein, the terms "comprising," "comprises," and "comprised of" are synonymous with "including," "includes," "containing," or "contains" and are inclusive or open-ended and do not exclude additional, unrecited members, elements, or method steps.

[0025] As used herein, the term "consisting of" excludes elements, components, materials or method steps not specified.

[0026] When amounts, concentrations, dimensions, and other parameters are expressed in the form of ranges, preferred ranges, upper values, lower values, or preferred upper values ​​and limits, it is understood that any range obtained by combining any upper value or preferred value with any lower value or preferred value is also specifically disclosed, regardless of whether the resulting range is expressly stated in the context.

[0027] Furthermore, in accordance with standard understanding, a weight range expressed as being "0 to x" specifically includes 0 wt. %. A component defined by said range may be absent from the composition, or may be present in the composition in an amount up to x wt. %.

[0028] As used herein, the term "at least a portion" can refer to any non-zero percentage of a total amount up to and including 100%. For example, "at least a portion" can refer to at least about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 99%, 99.9%, or 100% of the total amount.

[0029] The terms "preferred," "preferably," "desirably," and "particularly" are frequently used herein to refer to embodiments of the present disclosure that may provide particular benefits, under particular circumstances. However, the recitation of one or more preferred, desirable, or particular embodiments does not imply that other embodiments are not useful, and is not intended to exclude such other embodiments from the scope of the present disclosure.

[0030] As used herein, the term "exemplary" means serving as an example, instance, or illustration. Any aspect or design described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other aspects or designs. Rather, use of the word "exemplary" is intended to present concepts in a concrete manner.

[0031] As used in this application, the term "may" is used in a permissive (i.e., possible) rather than obligatory sense.

[0032] As used herein, room temperature is 23° C. plus or minus 2° C. As used herein, "ambient conditions" means the temperature and pressure surrounding the composition or coating layer or substrate on which the coating layer is disposed.

[0033] As used herein, the term "Mannich base" is used in accordance with the standard definition in the art as a ketone amine resulting from the condensation of ammonia, a diamine, or a polyamine with an aldehyde, a ketone, an ester, or an active hydrogen component selected from aromatics (such as phenols) and / or heteroaromatic compounds. The phenalkamines that act as curing agents herein are Mannich base compounds that are the reaction products of aldehydes, amines, and phenolic compounds.

[0034] As used herein, the term "monomer" means a substance that can undergo a polymerization reaction to provide a building block for the chemical structure of a polymer. As used herein, the term "monofunctional" means having one polymerizable site. As used herein, the term "multifunctional" means having two or more polymerizable sites.

[0035] As used herein, the term "equivalents (eq.)," as common in chemical notation, relates to the relative number of reactive groups present in a reaction.

[0036] As used herein, "(meth)acryl" is an abbreviation for "acrylic" and / or "methacrylic." Thus, the term "(meth)acrylamide" refers collectively to acrylamide and methacrylamide.

[0037] As used herein, "C1-C n An "alkyl" group refers to a monovalent group containing 1 to n carbon atoms, i.e., an alkane group, and includes straight-chain and branched-chain organic groups. Thus, "C1 to C 18 An "alkyl" group refers to a monovalent group, i.e., an alkane group, containing 1 to 18 carbon atoms and includes straight-chain and branched-chain organic groups. Generally, alkyl groups (C1-C2) containing 1 to 12 carbon atoms are used. 12It should be noted that preference is given to alkyl groups, such as alkyl groups containing 1 to 8 carbon atoms (C1-C8 alkyl). Examples of alkyl groups include, but are not limited to: methyl; ethyl; propyl; isopropyl; n-butyl; isobutyl; sec-butyl; tert-butyl; n-pentyl; n-hexyl; n-heptyl; and 2-ethylhexyl. In the present invention, such alkyl groups may be unsubstituted or substituted with one or more halogens. If applicable to a given moiety (R), the permissible range of one or more non-halogen substituents in an alkyl group is described herein.

[0038] As used herein, "C1-C 18 The term "hydroxyalkyl" refers to a HO-(alkyl) group having from 1 to 18 carbon atoms, where the point of attachment of the substituent is through the oxygen atom and the alkyl group is as defined above.

[0039] "Alkoxy" refers to a monovalent group represented by -OA, where A is an alkyl group; non-limiting examples of which are methoxy, ethoxy, and isopropyloxy. As used herein, "C-C 18 The term "alkoxyalkyl" refers to an alkyl group having an alkoxy substituent, as defined above, where the portion (alkyl-O-alkyl) contains a total of 2 to 18 carbon atoms; such groups include methoxymethyl (-CHOCH), 2-methoxyethyl (-CHCHOCH), and 2-ethoxyethyl. Similarly, as used herein, the term "C-C 18 "Alkoxyaryl" refers to an aryl group having an alkoxy substituent, as defined above, where the moiety (aryl-O-alkyl) has a total of 7 to 18 carbon atoms.

[0040] The term "C2-C4 alkylene," as used herein, is defined as a saturated divalent hydrocarbon radical having from two to four carbon atoms.

[0041] "C3-C 18The term "cycloalkyl" is understood to mean a saturated monocyclic or polycyclic hydrocarbon group having 3 to 18 carbon atoms. In the present invention, such cycloalkyl groups may be unsubstituted or substituted with one or more halogens. If applicable for a given moiety (R), the permissible range of one or more non-halogen substituents in a cycloalkyl group is described herein. Examples of cycloalkyl groups include cyclopropyl; cyclobutyl; cyclopentyl; cyclohexyl; cycloheptyl; cyclooctyl; adamantane; and norbornane.

[0042] As used herein, the term "C-C alkyl group" used alone or as part of a larger moiety (as in "aralkyl group") refers to a C-C alkyl group. 18 An "aryl" group refers to a monocyclic, bicyclic, or tricyclic ring system in which the monocyclic ring system is aromatic or at least one of the rings in the bicyclic or tricyclic ring system is aromatic. Bicyclic and tricyclic ring systems include benzo-fused 2- to 3-membered carbocyclic rings. In the present invention, such aryl groups can be unsubstituted or substituted with one or more halogens. Where applicable for a given moiety (R), the tolerance of one or more non-halogen substituents in an aryl group is described herein. Exemplary aryl groups include the following: phenyl; (C1-C4) alkylphenyl, such as tolyl and ethylphenyl; indenyl; naphthalenyl, tetrahydronaphthyl, tetrahydroindenyl; tetrahydroanthracenyl; and anthracenyl. It can also be mentioned that the phenyl group is preferred.

[0043] As used herein, "C2-C 20"Alkenyl" refers to a hydrocarbyl group having 2 to 20 carbon atoms and at least one unit of ethylenic unsaturation. Alkenyl groups may be straight-chained, branched, or cyclic and may optionally be substituted with one or more halogens. If applicable to a given moiety (R), the permissible range of one or more non-halogen substituents within an alkenyl group is described herein. The term "alkenyl" also encompasses groups having "cis" and "trans" configurations, or "E" and "Z" configurations, as understood by those skilled in the art. However, generally, alkenyl groups having 2 to 10 (C 2-10 ) or 2 to 8 (C 2-8 Of particular note is the preference for unsubstituted alkenyl groups containing C2-C 12 Examples of alkenyl groups are -CH=CH2;-CH=CHCH3;-CH2CH=CH2;-C(=CH2)(CH3);-CH=CHCH2CH3;-CH2CH=CHCH3;-CH2CH2CH=CH2;-CH=C(CH3)2 ;-CH2C(=CH2)(CH3);-C(=CH2)CH2CH3;-C(CH3)=CHCH3;-C(CH3)CH=CH2;-CH=CHCH2CH2CH3;-CH2CH=CHCH2CH3;-CH2CH2CH=CHCH 3; -CH2CH2CH2CH=CH2; -C(=CH2)CH2CH2CH3; -C(CH3)=CHCH2CH3; -CH(CH3)CH=CHCH; -CH(CH3)CH2CH=CH2; -CH2CH=C(CH3)2; 1-cyclopent-1-enyl; 1-cyclopent-2-enyl; 1-cyclopent-3-enyl; 1-cyclohex-1-enyl; 1-cyclohex-2-enyl; and 1-cyclohexyl-3-enyl.

[0044] As used herein, "alkylaryl" refers to an alkyl-substituted aryl group, both of which are defined above. Additionally, as used herein, "aralkyl" refers to an alkyl group substituted with an aryl group, as defined above.

[0045] As used herein, "hetero" refers to groups or moieties that include one or more heteroatoms, such as N, O, Si, and S. Thus, for example, "heterocyclic" refers to a cyclic group having, for example, N, O, Si, or S as part of the ring structure. "Heteroalkyl," "heterocycloalkyl," and "heteroaryl" moieties are alkyl, cycloalkyl, and aryl groups, as defined above, that include N, O, Si, or S as part of their structure, respectively.

[0046] As used herein, the term "equivalent weight" refers to the molecular weight divided by the number of functional groups involved. Thus, "epoxide equivalent weight" (EEW) means the weight (in grams) of a resin containing one equivalent of epoxide.

[0047] As used herein, the term "epoxide" refers to a compound characterized by the presence of at least one cyclic ether group, i.e., a compound in which the ether oxygen atom is bonded to two adjacent carbon atoms to form a ring structure. The term is intended to encompass monoepoxide compounds, diepoxide compounds, and higher polyepoxide compounds having two or more epoxide groups and epoxide-terminated prepolymers. The term "monoepoxide compound" is intended to refer to an epoxide compound having one epoxide group. The term "polyepoxide compound" is intended to refer to an epoxide compound having at least two epoxide groups. The term "diepoxide compound" is intended to refer to an epoxide compound having two epoxide groups.

[0048] The epoxide may be unsubstituted or may be inertly substituted. Examples of inert substituents include chlorine, bromine, fluorine, and phenyl.

[0049] Molecular weights referred to herein can be determined by gel permeation chromatography (GPC) according to ASTM 3536 using polystyrene calibration standards.

[0050] The Shore A hardness of a given material referred to herein is determined using a durometer in accordance with ISO 868, entitled "Plastics and Ebonite - Determination of Indentation Hardness with a Hardness Tester (Shore Hardness)," the contents of which standard are incorporated herein by reference in their entirety. Throughout this specification, all standard Shore A hardness measurements were made on injection molded plates in 10 seconds using a Type A durometer.

[0051] The viscosity of the compositions described herein is measured using an Anton Paar Viscometer, Model MCR 301, at standard conditions of 25°C and 50% relative humidity (RH), unless otherwise specified. The viscometer is calibrated annually and checked by service. Calibration is performed using standard solutions of known viscosity between 1 and 50,000 cps (parallel plate PP20, shear rate 1 s). -1 The composition of the present invention is measured using a parallel plate PP20 at 1.5 to 100 s. -1 The process is carried out at different shear rates.

[0052] (Detailed Description of the Invention) a) Epoxy silane oligomer The composition of the present invention comprises a) a compound of formula (AI): [ka] [In the formula, R e is a C1-C6 alkyl group; R f Epoxide-substituted C1-C 12 Alkyl groups, C3-C 18 Cycloalkyl groups or C2-C 18 an alkoxyalkyl group; R g is H or a C1-C6 alkyl group; R h is a C1-C6 alkyl group; i is an integer greater than or equal to 1; and j is an integer greater than or equal to 1. The epoxy silane oligomer comprises at least one epoxy silane oligomer represented by the formula:

[0053] The composition should typically contain 0.1 to 5 wt. % of a) said at least one epoxy silane oligomer, based on the weight of the composition. For example, the composition may contain 0.5 to 4 wt. %, or 0.5 to 2 wt. % of said at least one epoxy silane oligomer, based on the weight of the composition.

[0054] In particular embodiments of the oligomer of formula (A1): R e is a C1-C2 alkyl group; R f is an epoxide-substituted C1-C6 alkyl group, C3-C 12 Cycloalkyl groups or C2-C 12 is an alkoxyalkyl group; R g is H or a C1-C2 alkyl group; R h is a C1-C2 alkyl group; i is an integer of 1 to 20, for example, 1 to 10; and j is an integer of 1 to 20, for example, 1 to 10. R f Preferred are epoxide-substituted C2-C 12 It may be mentioned that the alkyl group is an alkoxyalkyl group.

[0055] For completeness, part a) may comprise a single compound of formula (AI) or may comprise a mixture of compounds of formula (AI) which may or may not have different substituents and / or different parameters "i" and "j".

[0056] Independently of or in addition to the preferred definitions of the substituents above, the or each epoxy silane oligomer present in the composition is preferably characterized by a number average molecular weight (Mn) of 200 to 3000 Daltons, e.g., 200 to 2000 Daltons or 300 to 1500 Daltons.

[0057] In an exemplary embodiment, part a) of the composition has the formula (AII): [ka] [In the formula, L is an integer from 0 to 20; and R k is C1-C6 alkyl] The compound may comprise or consist of at least one compound represented by the formula:

[0058] Particularly preferably, L is an integer of 1 to 10, for example, 1 to 5; R k is C1-C4 alkyl, for example C2-C3 alkyl. For completeness, part a) may in this exemplary embodiment comprise or consist of a single compound of formula (AII), or may comprise multiple compounds with different values ​​for parameter L and / or different substituents R k The compound may comprise a mixture of compounds of formula (AII) with or without

[0059] The oligomers represented by formula (AI) or (AII) may be prepared by reacting a glycidoxysilane and / or a cycloaliphatic epoxysilane having two or three alkoxy (OR) groups, and, optionally, a copolymerizable silane other than the glycidoxysilane and the cycloaliphatic epoxysilane, in the presence of a catalyst, the reaction usually being carried out in the presence of water, which is continuously fed to the reaction mixture.

[0060] Exemplary reactive glycidoxysilane monomers include, but are not limited to, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and γ-glycidoxypropylmethyldiethoxysilane. Exemplary reactive cycloaliphatic epoxysilane monomers include, but are not limited to, β-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)-ethylmethyldimethoxysilane, β-(3,4-epoxycyclohexyl)-ethylmethyldiethoxysilane, and β-(3,4-epoxycyclohexyl)-ethyltriethoxysilane. In addition to the glycidoxysilane and / or cycloaliphatic epoxysilane monomers, any copolymerizable monomers present in the reaction mixture should not be reactive with epoxide groups under the polymerization conditions. Exemplary comonomers that may improve the stability of epoxy silane oligomers are disclosed in, among others, US Patent No. 3,337,496; US Patent No. 3,341,469; and US Patent No. 5,073,195.

[0061] Exemplary catalysts for the synthesis process include: ion exchange resins such as Amberlite® IRA 400 available from Rohm & Haas or Lewatit® M-500 available from Bayer; alkylammonium salts such as hexadecyltrimethylammonium chloride, tetra-n-butylammonium chloride, or benzyltrimethylammonium halide; and quaternary ammonium organofunctional silanes.

[0062] Aside from the above synthesis process, one or more epoxy silane oligomers may be obtained commercially. In this regard, they may be made from CoatOSil MP200 (CAS No. 68611-45-0) available from Momentive Performance Materials Inc.

[0063] b) Polyepoxide compounds The compositions of the present invention include b) at least one polyepoxide compound having at least three epoxide groups per molecule; for clarity, this polyepoxide compound (b)) is distinct from the compound or compounds contained in part a) of the composition. Typically, the composition should contain 10 to 80 weight percent of b) said at least one polyepoxide compound, based on the weight of the composition. For example, the composition may contain 15 to 75 weight percent, or 20 to 70 weight percent, of b) said at least one polyepoxide compound, based on the weight of the composition.

[0064] The polyepoxide compounds may be pure compounds, as well as mixtures of epoxide-functional compounds, including mixtures of compounds with different numbers of epoxide groups per molecule. The polyepoxide compounds may be saturated or unsaturated, aliphatic, cycloaliphatic, aromatic, or heterocyclic, and may be substituted. Furthermore, the polyepoxide compounds may be monomeric or polymeric.

[0065] Although not intended to limit the present invention, suitable polyepoxide compounds may be liquid, solid, or dissolved in a solvent. Furthermore, such polyepoxide compounds should have an epoxide equivalent weight of 100 to 700 g / eq, e.g., 120 to 320 g / eq. Generally, polyepoxide compounds having an epoxide equivalent weight of less than 500 g / eq, or even less than 400 g / eq, are preferred. This is primarily due to cost considerations, and because lower molecular weight epoxy resins require more limited purification processing during production.

[0066] Examples of types or groups of polyepoxide compounds that can be included in the composition include glycidyl ethers of polyhydric alcohols; glycidyl ethers of polyhydric phenols; glycidyl esters of polycarboxylic acids; polyfunctional glycidyl amines; and epoxidized polyethylenically unsaturated hydrocarbons.

[0067] Exemplary polyglycidyl ethers that can be used alone or in combination include, but are not limited to, glycerol polyglycidyl ether, trimethylolmethane triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, triphenylolmethane triglycidyl ether, trisphenol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, tetraphenylolethane triglycidyl ether, tetraglycidyl ether of tetraphenylolethane, 1,2,6-hexanetriol triglycidyl ether, glycerol triglycidyl ether, diglycerol triglycidyl ether, glycerol ethoxylate triglycidyl ether, castor oil triglycidyl ether, fluoroglycinol triglycidyl ether, and propoxylated glycerin triglycidyl ether. Additionally, phenol-formaldehyde novolac resins, cresol-formaldehyde novolac resins, brominated phenol-formaldehyde novolac resins, brominated cresol-formaldehyde novolac resins, 3,3',5,5'-tetramethyl-(1,1'-biphenyl)-2,4,4'-triol, and pyrogallol glycidyl ethers may be used in the present disclosure. Also useful in the present disclosure is 2,2'-[(1-methylethylidene)bis[[6-(2-oxiranylmethoxy)-3,1-phenylene]methylene]]bis-oxirane (CAS No. 1799411-80-5).

[0068] The glycidyl ester of polycarboxylic acid useful in the present invention is derived from a polycarboxylic acid containing three or more carboxylic acid groups and not containing any other groups reactive with epoxide groups. The polycarboxylic acid can be aliphatic, alicyclic, aromatic, or heterocyclic. Preferred polycarboxylic acids contain 18 or fewer carbon atoms per carboxylic acid group, and suitable examples include, but are not limited to, aconitic acid; propane-1,2,3-tricarboxylic acid (β-carboxyglutaric acid); unsaturated fatty acid trimer acid, such as linseed fatty acid trimer acid; trimellitic acid; trimesic acid; and (meth)acrylic acid polymers and copolymers.

[0069] Exemplary polyglycidyl amines that can be used alone or in combination include, but are not limited to, N,N,N',N'-tetraglycidyl-4,4'methylenebisbenzenamine, p-aminophenol triglycidyl ether, m-aminophenol triglycidyl ether, tetraglycidyl bis(aminomethyl)cyclohexane, and N,N,N',N'-tetraglycidyl-m-xylylenediamine.

[0070] More preferred examples of commercially available polyepoxide compounds include 2,2'-[(1-methylethylidene)bis[[6-(2-oxiranylmethoxy)-3,1-phenylene]methylene]]bisoxirane available from Showa Denko as SHOFREE BATG; castor oil triglycidyl ether such as ERISYS™ GE-35H; polyglycerol-3-polyglycidyl ether such as ERISYS™ GE-38; sorbitol glycidyl ether such as ERISYS™ GE-60; Epikote 1032H60 (manufactured by Japan Epoxy Resins Co., Ltd.); Epikote 1031 S (manufactured by Japan Epoxy Resins Co., Ltd.); TECHMORE VG3101 (manufactured by Mitsui Chemicals, Inc.); and Kane Ace 414 (available from Kaneka Corporation); ELM-100 (manufactured by Sumitomo Chemical Co., Ltd.); MY721 and MY0510 (manufactured by Ciba Specialty Chemicals Inc.); Araldite® MY0600-CH (available from Hunstman); and Tetrad® X and Tetrad® C available from Mitsubishi Gas Chemical Company, Inc.; and dicyclopentadiene-type epoxy resins such as ZX-1257 (manufactured by Tohto Kasei Co., Ltd.) and HP-7200 (manufactured by Dainippon Ink and Chemicals Incorporated).

[0071] c) further epoxide compounds The first component of the composition of the present disclosure may comprise 0 to 20 wt. % of c) at least one compound selected from the group consisting of monoepoxide compounds and diepoxide compounds that do not meet the definition of part a) above, based on the weight of the composition. For example, the first component of the composition may contain 0 to 15 wt. % or 0 to 10 wt. % of c) said at least one epoxide compound, based on the weight of the component.

[0072] Thereby, part c) of the composition may comprise one or more monoepoxide compounds, one or more diepoxide compounds, or a combination thereof. Thus, part c) may be a mixture of epoxide-functional compounds, including a mixture of compounds having different numbers of epoxide groups per molecule. The monoepoxide or diepoxide compounds may be saturated or unsaturated, aliphatic, cycloaliphatic, aromatic, or heterocyclic, and may be substituted. Furthermore, the monoepoxide or diepoxide compounds may be monomeric or polymeric.

[0073] Although not intended to limit the invention, exemplary monoepoxide compounds include: alkylene oxides; epoxy-substituted alicyclic hydrocarbons such as cyclohexene oxide, vinylcyclohexene monoxide, (+)-cis-limonene oxide, (+)-cis,trans-limonene oxide, (-)-cis,trans-limonene oxide, cyclooctene oxide, cyclododecene oxide, and α-pinene oxide; epoxy-substituted aromatic hydrocarbons; monoepoxy-substituted alkyl ethers of monohydric alcohols or phenols, such as glycidyl ethers of aliphatic, alicyclic, and aromatic alcohols. monoepoxy-substituted alkyl esters of monocarboxylic acids, such as glycidyl esters of aliphatic, alicyclic, and aromatic monocarboxylic acids; monoepoxy-substituted alkyl esters of polycarboxylic acids, where the other carboxy group is esterified with an alkanol; alkyl and alkenyl esters of epoxy-substituted monocarboxylic acids; epoxy alkyl ethers of polyhydric alcohols, where the other OH group is esterified or etherified with a carboxylic acid or alcohol; and monoesters of polyhydric alcohols and epoxy monocarboxylic acids, where the other OH group is esterified or etherified with a carboxylic acid or alcohol.

[0074] By way of example, the following glycidyl ethers may be mentioned as being particularly suitable monoepoxide compounds for use herein: methyl glycidyl ether; ethyl glycidyl ether; propyl glycidyl ether; butyl glycidyl ether; pentyl glycidyl ether; hexyl glycidyl ether; cyclohexyl glycidyl ether; octyl glycidyl ether; 2-ethylhexyl glycidyl ether; allyl glycidyl ether; benzyl glycidyl ether; phenyl glycidyl ether; 4-tert-butylphenyl glycidyl ether; 1-naphthyl glycidyl ether; 2-naphthyl glycidyl ether; 2-chlorophenyl glycidyl ether; 4-chlorophenyl glycidyl ether; 4-bromophenyl glycidyl ether; 2,4,6-trichlorophenyl glycidyl ether; 2,4,6-tribromophenyl glycidyl ether; pentafluorophenyl glycidyl ether; o-cresyl glycidyl ether; m-cresyl glycidyl ether; and p-cresyl glycidyl ether.

[0075] In important embodiments, the monoepoxide compound has the following formula (CI) herein: [ka] [In the formula, R w ,R x ,R y and R z may be the same or different and independently represent hydrogen, a halogen atom, a C1 to C8 alkyl group, a C3 to C 10 Cycloalkyl groups, C2-C 12 Alkenyl groups, C6-C 18 Aryl group or C7-C 18 aralkyl groups, provided that R 3 and R 4 at least one of which is not hydrogen] Fits.

[0076] R w ,R x and R y is hydrogen and R zis preferably either a phenyl group or a C1-C8 alkyl group, more preferably a C1-C4 alkyl group. In view of this embodiment, exemplary monoepoxides include: ethylene oxide; 1,2-propylene oxide (propylene oxide); 1,2-butylene oxide; cis-2,3-epoxybutane; trans-2,3-epoxybutane; 1,2-epoxypentane; 1,2-epoxyhexane; 1,2-heptylene oxide; decene oxide; butadiene oxide; isoprene oxide; and styrene oxide.

[0077] The present invention refers to the use of at least one monoepoxide compound selected from the group consisting of ethylene oxide, propylene oxide; cyclohexene oxide; (+)-cis-limonene oxide; (+)-cis,trans-limonene oxide; (-)-cis,trans-limonene oxide; cyclooctene oxide; and cyclododecene oxide.

[0078] Again, without intending to limit part c) of the present invention, suitable diepoxide compounds can be liquid, solid, or in solution in a solvent. Furthermore, such diepoxide compounds should have an epoxide equivalent weight of 100 to 700 g / eq, for example, 120 to 320 g / eq. Generally, diepoxide compounds having an epoxide equivalent weight of less than 500 g / eq, or even less than 400 g / eq, are preferred: this is primarily due to cost considerations, and in their production, low molecular weight epoxy resins require more limited processing, particularly in terms of purification.

[0079] Examples of types or groups of diepoxide compounds that may be included in the composition may include glycidyl ethers of dihydric alcohols, glycidyl ethers of dihydric phenols, glycidyl esters of dicarboxylic acids; and epoxidized diethylenically unsaturated hydrocarbons.

[0080] Suitable diglycidyl ether compounds may be aromatic, aliphatic, or cycloaliphatic in origin and thus may be derived from dihydric phenols and dihydric alcohols. Useful classes of such diglycidyl ethers include: diglycidyl ethers of aliphatic and cycloaliphatic diols such as 1,2-ethanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,12-dodecanediol, cyclopentanediol, cyclohexanediol, and isosorbide; bisphenol A diglycidyl ethers; bisphenol F diglycidyl ethers; polyalkylene glycol diglycidyl ethers, particularly polypropylene glycol diglycidyl ether; and polycarbonate diol diglycidyl ethers.

[0081] The glycidyl esters of dicarboxylic acids useful in the present invention are derived from carboxylic acids containing at least two carboxylic acid groups and no other groups reactive with epoxide groups. The dicarboxylic acids can be aliphatic, alicyclic, aromatic, or heterocyclic. Preferred dicarboxylic acids contain 18 or fewer carbon atoms per carboxylic acid group, and suitable examples include, but are not limited to, oxalic acid; sebacic acid; adipic acid; succinic acid; pimelic acid; suberic acid; glutaric acid; dimer acids of unsaturated fatty acids, such as dimers of linseed fatty acids; phthalic acid; isophthalic acid; terephthalic acid; phenylene diacetic acid; chlorendic acid; hexahydrophthalic acid, especially hexahydroorthophthalic acid (1,2-cyclohexanedicarboxylic acid); diphenic acid; naphthalic acid; polyacid-terminated esters of dibasic acids and aliphatic polyols; and polymers and copolymers of (meth)acrylic acid.

[0082] Other suitable diepoxides that may also be mentioned include: diepoxides of doubly unsaturated fatty acid C1-C18 alkyl esters; butadiene diepoxide; polybutadiene diglycidyl ether; vinylcyclohexene diepoxide; and limonene diepoxide.

[0083] Also highly preferred examples of diepoxide compounds include bisphenol A epoxy resins such as DER™ 331, DER™ 332, DER™ 383, JER™ 828 and Epotec YD 128; bisphenol F epoxy resins such as DER™ 354; bisphenol A / F epoxy resin blends such as DER™ 353; polypropylene glycol diglycidyl ethers, for example DER™ 732; solid bisphenol A epoxy resins such as DER™ 661 and DER™ 664 UE; bisphenol A solid epoxy resin solutions such as DER™ 671-X75; brominated epoxy resins such as DER™ 542; and bis(2,3-epoxypropyl)cyclohexane-1,2-dicarboxylate, available as Lapox Arch-11.

[0084] In addition to the epoxy silane oligomers described in part a) above, in certain embodiments, the composition comprises monomeric epoxy silanes and, more specifically, epoxy silanes having the following formula: [ka] [In the formula, each R is independently selected from methyl or ethyl; and n is 1 to 10] The glycidoxyalkylalkoxysilane may include a glycidoxyalkylalkoxysilane having the formula:

[0085] Exemplary monomeric epoxy silanes include, but are not limited to, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxymethyltrimethoxysilane, γ-glycidoxymethyltriethoxysilane, γ-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, and 8-glycidoxyoctyltrimethoxysilane. When present, monomeric epoxy-functional silanes should constitute less than 10 wt. %, preferably less than 5 wt. %, or less than 2 wt. %, based on the total weight of the epoxide-functional compounds in the first component ((a), b), and c)).

[0086] Although not representing a preferred embodiment, the present invention does not exclude the first component of the curable composition further comprising one or more cyclic monomers selected from the group consisting of oxetanes, cyclic carbonates, cyclic anhydrides, and lactones. The disclosures of the following references may be useful in disclosing suitable cyclic carbonate-functional compounds: U.S. Pat. No. 3,535,342; U.S. Pat. No. 4,835,289; U.S. Pat. No. 4,892,954; GB 1,485,925; and EP 0 119 840. However, such cyclic comonomers should constitute less than 10 wt. %, preferably less than 5 wt. %, or less than 2 wt. %, based on the total weight of the epoxide-functional compounds in the first components (a), b), and c).

[0087] d) Hardener The curing agent d) incorporated into the second component of the composition must consist of at least two compounds, each having at least two epoxide-reactive groups per molecule, characterized in that the curing agent contains at least one Mannich base and at least one alicyclic amine. Furthermore, in a preferred embodiment, the at least one Mannich base is a phenalkamine, particularly a phenalkamine obtained by condensation of cardanol (CAS No.: 37330-39-5), an aldehyde, and an amine. The reacting amine in the condensation reaction is preferably ethylenediamine or diethyltriamine.

[0088] Mannich bases and phenalkamines are known in the art, and suitable examples include the commercially available phenalkamines Cardolite® NC-541, NC-557, NC-558, NC-566, Lite 2001 and Lite 2002 (available from Cardolite), Aradur® 3440, 3441, 3442 and 3460 (available from Huntsman), and Beckopox® EH 614, EH 621, EH 624, EH 628 and EH 629 (available from Cytec).

[0089] The term "alicyclic amine" refers to a molecule having an amine group attached to an aliphatic carbon atom of a cyclic aliphatic moiety. The term "alicyclic" refers to a saturated or unsaturated, but non-aromatic, carbocyclic group containing one or more fused rings, which may be optionally fused together. An alicyclic group may be unsubstituted or may be optionally substituted with one or more halogens. The term "alicyclic" also includes "heteroalicyclic" groups, which are non-aromatic monocyclic or polycyclic rings in which one or more carbon atoms of the ring are replaced by a heteroatom. As used herein, alicyclic groups are preferably C3-C6 18 The cycloalkyl group includes, specifically, a cycloheptyl group, a cyclohexyl group, and a cyclopentyl group.

[0090] As used herein, alicyclic amines are preferably primary amines and contain at least one primary amine group (—NH), and the alicyclic group is preferably located either at the α-position directly attached to the amine group or at the β-position adjacent to the α-position.

[0091] Exemplary alicyclic amines useful in the present invention include 1,2-, 1,3-, and 1,4-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; 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (isophoronediamine, IPDA); 2- and / or 4-methyl-1,3-diaminocyclohexane; 1,3-bis(aminomethyl)cyclohexane; 1,4-bis(aminomethyl)cyclohexane; 2 ,5(2,6)-bis(aminomethyl)-bicyclo[2.2.1]heptane (norboranediamine, NBDA); 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.02,6]-decane (TCD-diamine); 1,4-diamino-2,2,6-trimethylcyclohexane (TMCDA), N,N-bis(3-aminopropyl)cyclohexylamine; 1,8-menthanediamine; N-cyclohexyl-1,2-ethanediamine, N-cyclohexyl-1,3-propanediamine; 3-cyclohexylamino-1-pentylamine; 4-aminomethyl-piperidine; N-(2-aminoethyl)piperazine, and mixtures thereof.

[0092] Commercially available examples of cycloaliphatic amines useful in the present invention include Ancamine 2264, Ancamine 2280, and Ancamine 2286 available from Air Product and Chemical Inc., Baxxodur EC331 available from BASF, Versamine C31 available from Cognis; and Epicure 3300 available from Momentive Specialty Chemicals.

[0093] Preferably, curing agent d) consists of or essentially consists of the at least one Mannich base and the at least one cycloaliphatic amine. However, it is not excluded that the curing agent may contain an additional compound having at least two epoxide-reactive groups per molecule in an amount of up to 10 mole % based on the total moles of the curing agent. Such additional compounds may include, in particular, one or both of i) at least one polyamine having at least two amine hydrogens reactive with epoxide groups but which is not a cycloaliphatic amine, and ii) at least one mercapto compound having at least two mercapto groups reactive with epoxide groups.

[0094] The at least one polyamine having at least two amine hydrogens reactive with epoxide groups should in particular contain primary and / or secondary amine groups and have an equivalent weight per primary or secondary amine group of 150 g / eq or less, more preferably 125 g / eq or less.

[0095] Suitable polyamines that may be used alone or in combination include, but are not limited to:

[0096] i) As aliphatic or arylaliphatic primary diamines, the following examples may be mentioned: 2,2-dimethyl-1,3-propanediamine; 1,3-pentanediamine (DAMP); 1,5-pentanediamine; 1,5-diamino-2-methylpentane (MPMD); 2-butyl-2-ethyl-1,5-pentanediamine (C11-neodiamine); 1,6-hexanediamine (hexamethylenediamine, HMDA); 2,5-dimethyl-1,6- 1,9-nonanediamine; 1,10-decanediamine; 1,11-undecanediamine; 1,12-dodecanediamine; 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5.5]undecane; and 1,3-bis(aminomethyl)benzene (MXDA).

[0097] ii) As tertiary amine group-containing polyamines having two or three primary aliphatic amine groups, the following specific examples may be mentioned: N,N'-bis(aminopropyl)-piperazine; N,N-bis(3-aminopropyl)methylamine; N,N-bis(3-aminopropyl)ethylamine; N,N-bis(3-aminopropyl)propylamine; N,N-bis(3-aminopropyl)-2-ethyl-hexylamine; tris(2-aminoethyl)amine; tris(2-aminopropyl)amine; tris(3-aminopropyl)amine; and products from double cyanoethylation and subsequent reduction of fatty amines derived from natural fatty acids, such as N,N-bis(3-aminopropyl)dodecylamine and N,N-bis(3-aminopropyl)tallow alkylamine (commercially available as Triameen® Y12D and Triameen® YT (manufactured by Akzo Nobel)).

[0098] iii) Specific examples of ether group-containing aliphatic primary polyamines include bis(2-aminoethyl)ether; 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 and higher oligomers of these diamines; bis(3-aminopropyl)poly Tetrahydrofuran and other polytetrahydrofuran diamines; alicyclic ether group-containing diamines obtained from the propoxylation and subsequent amination of 1,4-dimethylolcyclohexane, such as the material commercially available as Jeffamine® RFD-270 (manufactured by Huntsman); polyoxyalkylene di- or -triamines obtained as products from the amination of polyoxyalkylene di- and -triols and sold commercially under the name Jeffamine® (manufactured by Huntsman), under the name Polyetheramines (manufactured by BASF), or under the name PC Amines® (manufactured by Nitroil). It should be noted that particular preference is given to using Jeffamine® D-230, Jeffamine® D-400, Jeffamine® D-600, Jeffamine® D-2000, Jeffamine® D-4000, Jeffamine® T-403, Jeffamine® T-3000, Jeffamine® T-5000, Jeffamine® EDR-104, Jeffamine® EDR-148 and Jeffamine® EDR-176, as well as the corresponding amines from BASF or Nitroil.

[0099] iv) As primary diamines having secondary amine groups, the following may be mentioned as examples: 3-(2-aminoethyl)aminopropylamine, bis(hexamethylene)triamine (BHMT); diethylenetriamine (DETA); triethylenetetramine (TETA); tetraethylenepentamine (TEPA); pentaethylenehexamine (PEHA); higher homologues of linear polyethyleneamines, such as polyethylenepolyamines having 5 to 7 ethyleneamine units (so-called "higher ethylenepolyamines," HEPA); multiple cyanoethylation of primary di- and polyamines having at least two primary amine groups followed by Products from hydrogenation, such as dipropylenetriamine (DPTA), N-(2-aminoethyl)-1,3-propanediamine (N3-amine), N,N'-bis(3-aminopropyl)ethylenediamine (N4-amine), N,N'-bis(3-aminopropyl)-1,4-diaminobutane, N5-(3-aminopropyl)-2-methyl-1,5-pentanediamine, N3-(3-aminopentyl)-1,3-pentanediamine, N5-(3-amino-1-ethylpropyl)-2-methyl-1,5-pentanediamine or N,N'-bis(3-amino-1-ethylpropyl)-2-methyl-1,5-pentanediamine.

[0100] v) Examples of polyamines having one primary amino group and at least one secondary amino group include: N-butyl-1,2-ethanediamine; N-hexyl-1,2-ethanediamine; N-(2-ethylhexyl)-1,2-ethanediamine; N-methyl-1,3-propanediamine; N-butyl-1,3-propanediamine; N-(2-ethylhexyl)-1,3-propanediamine; 3-methylamino-1-pentylamine; 3-ethylamino-1-pentylamine; fatty diamines such as N-cocoalkyl-1,3-propanediamine; and Michael-type addition reactions of primary aliphatic diamines with acrylonitrile, maleic or fumaric acid diesters, citraconic acid diesters, acrylic and methacrylic acid esters, acrylic and methacrylic acid amides, and itaconic acid diesters. products from the partial reductive alkylation of primary polyamines with aldehydes or ketones, especially the N-monoalkylation products of the aforementioned polyamines having two primary amine groups, in particular 1,6-hexanediamine, 1,5-diamino-2-methylpentane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)benzene, BHMT, DETA, TETA, TEPA, DPTA, N3-amines and N4-amines (wherein preferred alkyl groups are benzyl, isobutyl, hexyl and 2-ethylhexyl); and partially styrenated polyamines such as those commercially available as Gaskamine® 240 (Mitsubishi Gas Chemical).

[0101] vi) Secondary diamines and, in particular, the N,N′-dialkylation products of the aforementioned polyamines having two primary amine groups, in particular 1,6-hexanediamine, 1,5-diamino-2-methylpentane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)benzene, BHMT, DETA, TETA, TEPA, DPTA, N3-amines or N4-amines, preferred alkyl groups being 2-phenylethyl, benzyl, isobutyl, hexyl and 2-ethylhexyl.

[0102] vii) As aromatic polyamines, mention may be made of m- and p-phenylenediamine; 4,4'-, 2,4'- and 2,2'-diaminodiphenylmethane; 3,3'-dichloro-4,4'-diaminodiphenylmethane (MOCA); 2,4- and 2,6-tolylenediamine; a mixture of 3,5-dimethylthio-2,4- and -2,6-tolylenediamine (available from Albermarle as Ethacure® 300); a mixture of 3,5-diethyl-2,4- and -2,6-tolylenediamine (DETDA); 3,3',5,5'-tetraethyl-4,4'-diaminodiphenylmethane (M-DEA); 3,3',5,5'-tetraethyl-2,2'-dichloro-4,4'-diaminodiphenylmethane (M-CDEA); 3,3'-diisopropyl-5,5'-dimethyl-4,4'-diamino Diphenylmethane (M-MIPA); 3,3',5,5'-tetraisopropyl-4,4'-diaminodiphenylmethane (M-DIPA); 4,4'-diaminodiphenyl sulfone (DDS); 4-amino-N-(4-aminophenyl)benzenesulfonamide; 5,5'-methylenedianthranilic acid; dimethyl-(5,5'-methylenedianthranilate); 1,3-propylene-bis(4-aminobenzoic acid); 1,4-butylene-bis(4-aminobenzoic acid); polytetramethyleneoxide-bis(4-aminobenzoic acid) (available from AirProducts as Versalink®); 1,2-bis(2-aminophenylthio)ethane, 2-methylpropyl-(4-chloro-3,5-diaminobenzoate); and tert.butyl-(4-chloro-3,5-diaminobenzoate).

[0103] viii) Its representative polyamidoamines include the reaction products of mono- or polycarboxylic acids or their esters or anhydrides, especially dimeric fatty acids, with aliphatic, cycloaliphatic, or aromatic polyamines, such as polyalkyleneamines, for example, DETA or TETA. Commercially available polyamidoamines include Versamid® 100, 125, 140, and 150 (manufactured by Cognis); Aradur® 223, 250, and 848 (manufactured by Huntsman); Euretek® 3607 and 530 (manufactured by Huntsman); and Beckopox® EH 651, EH 654, EH 655, EH 661, and EH 663 (manufactured by Cytec).

[0104] As noted above, the compositions of the present invention may optionally contain at least one compound having at least two reactive mercapto groups per molecule. Suitable mercapto-containing compounds that may be used alone or in combination include, but are not limited to, the following: Commercially available examples of liquid mercaptan-terminated polysulfide polymers include: Thiokol® polymers (available from Morton Thiokol), particularly types LP-3, LP-33, LP-980, LP-23, LP-55, LP-56, LP-12, LP-31, LP-32, and LP-2; and Thioplast® polymers (manufactured by Akzo Nobel), particularly types G10, G112, G131, G1, G12, G21, G22, G44, and G4. Mercaptan-terminated polyoxyalkylene ethers obtained by reacting polyoxyalkylene- and -triols with epichlorohydrin or alkylene oxides, followed by reaction with sodium hydrogen sulfide. Mercaptan-terminated compounds in the form of polyoxyalkylene derivatives known under the trade name Capcure® (manufactured by Cognis), in particular the WR-8, LOF and 3-800 types. Specific examples of polyesters of thiocarboxylic acids include: pentaerythritol tetramercaptoacetate (PETMP); trimethylolpropane trimercaptoacetate (TMPMP); glycol dimercaptoacetate; and the esterification products of polyoxyalkylene diols and triols, ethoxylated trimethylolpropane and polyester diols with thiocarboxylic acids such as thioglycolic acid and 2- or 3-mercaptopropionic acid. 2,4,6-trimercapto-1,3,5-triazine, 2,2'-(ethylenedioxy)-diethanethiol (triethylene glycol dimercaptan) and / or ethanedithiol.

[0105] Preference has been given to the use of polyesters of thiocarboxylic acids, in particular at least one of pentaerythritol tetramercaptoacetate (PETMP), trimethylolpropane trimercaptoacetate (TMPMP) and glycol dimercaptoacetate.

[0106] When curable compositions are formulated, they are preferably characterized by the inclusion of curing agent in an amount such that the composition as a whole has a molar ratio of epoxide-reactive groups to epoxide groups of 0.95:1 to 1.5:1, e.g., 0.95:1 to 1.1:1. In particular, a molar ratio of epoxide-reactive groups to epoxide groups of 1:1 is included within these recited ranges and as such represents a highly preferred molar ratio.

[0107] Provided that the above molar ratio conditions are met, the composition may further be characterized by comprising 10 to 30% by weight, for example 15 to 30% by weight, of d) said curing agent, based on the weight of the composition.

[0108] d) Reinforcement The compositions of the present invention contain reinforced rubber in the form of core-shell particles. While such particles may in principle be included in either the first or second component, the core-shell particles are typically added dispersed in the epoxy resin of the first component.

[0109] The term "core-shell rubber" or CSR is used according to its standard meaning in the art to refer to a rubber particle core formed from a polymer primarily containing an elastomeric or rubbery polymer and a shell layer formed from a grafted polymer onto the core. The shell layer partially or completely covers the surface of the rubber particle core during the graft polymerization process. The core must constitute at least 50% by weight of the core-shell rubber particle.

[0110] The polymeric material of the core has a glass transition temperature (Tg) of 0° C. or less, preferably −20° C. or less, more preferably −40° C. or less, and even more preferably −60° C. or less. The polymer of the shell is a non-elastomeric, thermoplastic or thermosetting polymer with a glass transition temperature (Tg) above room temperature, preferably above 30° C., and more preferably above 50° C.

[0111] Without intending to limit the invention, the core may be composed of diene homopolymers, such as homopolymers of butadiene or isoprene; diene copolymers, such as copolymers of butadiene or isoprene with one or more ethylenically unsaturated monomers, such as vinyl aromatic monomers, (meth)acrylonitrile, or (meth)acrylates; polymers based on (meth)acrylic acid ester monomers, such as polybutyl acrylate; and polysiloxane elastomers, such as polydimethylsiloxane and crosslinked polydimethylsiloxane.

[0112] Similarly, without intending to limit the present invention, the shell may be composed of a polymer or copolymer of one or more monomers selected from (meth)acrylates, such as methyl methacrylate; vinyl aromatic monomers, such as styrene; vinyl cyanides, such as acrylonitrile; unsaturated acids and anhydrides, such as acrylic acid; and (meth)acrylamides. The polymer or copolymer used in the shell may have acid groups ionically crosslinked via the formation of metal carboxylates, particularly salts of divalent metal cations. The shell polymer or copolymer may also be covalently crosslinked by monomers having two or more double bonds per molecule.

[0113] The core-shell rubber particles contained therein preferably have an average particle size (d50) of 10 nm to 300 nm, for example 50 nm to 200 nm, where the particle size refers to the diameter or largest dimension of the particle in the particle size distribution, as measured by dynamic light scattering.

[0114] The present application does not exclude the presence of two types of core-shell rubber (CRS) particles having different particle sizes in the composition to provide a balance of important properties of the resulting cured product, such as shear strength, peel strength, and resin fracture toughness. In this embodiment, the smaller contained particles (first CSR type) may have an average particle size of 10 nm to 100 nm, and the larger contained particles (second CSR type) may have an average particle size of 120 nm to 300 nm, for example, 150 nm to 300 nm. The small core-shell rubber particles should typically be used in excess of the larger particles on a weight basis. For example, a weight ratio of the small CSR particles to the large CSR particles of 3:1 to 5:1 may be employed.

[0115] The core-shell rubber can be selected from commercially available products, examples of which include Paraloid EXL2650A, EXL2655, and EXL2691A available from The Dow Chemical Company; the Kane Ace® MX series, particularly MX120, MX125, MX130, MX136, MX551, and MX553 available from Kaneka Corporation; and METABLEN SX-006 available from Mitsubishi Rayon.

[0116] The core-shell rubber particles should be included in the composition in an amount of 5 to 30 wt. %, such as 5 to 25 wt. % or 10 to 25 wt. %, based on the total weight of the composition.

[0117] f) Additives and auxiliary ingredients The compositions obtained by the present invention typically further contain adjuvants and additives that can impart improved properties to these compositions. For example, the adjuvants and additives can impart one or more of the following: improved elastic properties; improved elastic recovery; longer effective processing times; faster cure times; and lower residual tack. Included among such adjuvants and additives (which may be contained, independently of one another, in a single component or both components of a two-component (2K) composition) are catalysts; plasticizers; stabilizers, including UV stabilizers; antioxidants; toughening agents; fillers; reactive diluents; driers; adhesion promoters; fungicides; flame retardants; rheology aids; color pigments, such as titanium dioxide, iron oxide, or carbon black; color pastes; dyes; and / or, optionally, small amounts of non-reactive diluents.

[0118] For the sake of completeness, it should be noted that auxiliary materials and additives containing epoxide-reactive groups are generally incorporated into the hardener component of a two-(2K)-component composition. Materials that contain epoxide groups or are reactive with the hardener are generally incorporated into the epoxide-containing component of a two-(2K)-component composition. Non-reactive materials may be incorporated into either or both of the A and B components.

[0119] The use of a catalyst is not required in this application, and in fact, in preferred embodiments, the composition may be characterized as being substantially catalyst-free. However, in certain circumstances, it may be advantageous to add one or more substances as catalysts that promote the reaction between epoxide groups and epoxide-reactive groups, such as the reaction between amine groups and epoxide groups.

[0120] Without intending to limit the catalysts used in the present invention, the following suitable catalysts may be mentioned: i) acids or compounds hydrolyzable to acids, in particular a) organic carboxylic acids such as acetic acid, benzoic acid, salicylic acid, 2-nitrobenzoic acid and lactic acid; b) organic sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid and 4-dodecylbenzenesulfonic acid; c) sulfonic acid esters; d) inorganic acids such as phosphoric acid; e) Lewis acid compounds such as BF3 amine complexes, SbF6 sulfonium compounds, bis-arene iron complexes; f) Bronsted acid compounds such as pentafluoroantimonate complexes; and e) mixtures of the aforementioned acids and acid esters; ii) 1,4-diazabicyclo[2.2.2] tertiary amines such as octane, benzyldimethylamine, α-methylbenzyldimethylamine, triethanolamine, dimethylaminopropylamine, imidazole (including N-methylimidazole, N-vinylimidazole, and 1,2-dimethylimidazole), and salts of such tertiary amines; iii) quaternary ammoniums such as benzyltrimethylammonium chloride; iv) amidines such as 1,8-diazabicyclo[5.4.0]undec-7-ene; v) guanidines such as 1,1,3,3-tetramethylguanidine; vi) phenols, especially bisphenols; vii) phenolic resins; and vii) phosphites such as di- and triphenyl phosphites.

[0121] In one embodiment, the amine catalyst for curing an epoxy resin-based composition may be a photobase generator. Upon exposure to UV radiation, typically at a wavelength of 320 to 420 nm, the photobase generator releases an amine that catalyzes the addition of an epoxide-reactive group to an epoxide. The photobase generator is not particularly limited, as long as it generates an amine directly or indirectly upon irradiation with light. However, suitable photobase generators that may be mentioned include benzyl carbamate; benzoin carbamate; o-carbamoylhydroxyamine; O-carbamoyloxime; aromatic sulfonamide; alpha-lactam; N-(2-allylethenyl)amide; aryl azide compounds, N-arylformamide, and 4-(ortho-nitrophenyl)dihydropyridine.

[0122] In an alternative embodiment, the acid catalyst may be selected from photoacid generators (PAGs). Upon irradiation with light energy, ionic photoacid generators undergo a cleavage reaction that releases one or more molecules of Lewis or Bronsted acids that catalyze ring opening and the addition of pendant epoxide groups to form crosslinks. Useful photoacid generators are thermally stable, do not undergo heat-induced reactions with the forming copolymer, and are readily dissolved or dispersed in the curable composition.

[0123] Exemplary cations that can be used as the cationic portion of the ionic PAGs of the invention include organic onium cations such as those described in U.S. Patent No. 4,250,311, U.S. Patent No. 3,113,708, U.S. Patent No. 4,069,055, U.S. Patent No. 4,216,288, U.S. Patent No. 5,084,586, U.S. Patent No. 5,124,417, and U.S. Patent No. 5,554,664. These references specifically include aliphatic or aromatic Group IVA and Group VIIA (CAS-type) centered onium salts, with it being noted that I-, S-, P-, Se-N-, and C-centered onium salts, such as those selected from sulfoxonium, iodonium, sulfonium, selenonium, pyridinium, carbonium, and phosphonium, are preferred.

[0124] As is known in the art, the nature of the counteranion in an ionic photoacid generator (PAG) can affect the rate and extent of cationic addition polymerization of epoxide groups. For example, the order of reactivity among commonly used nucleophilic anions is SbF > AsF > PF > BF. The effect of the anion on reactivity is due to three fundamental factors that one skilled in the art must account for in this invention: (1) the acidity of the generated protonic or Lewis acid; (2) the degree of ion-pair separation in the propagating cationic chain; and (3) the susceptibility of the anion to fluoride abstraction and resulting chain termination.

[0125] It is not excluded that the compositions of the present invention include alternative photoinitiator compounds to the photobase generator and photoacid generator compounds described herein, which initiate polymerization or curing of the composition upon exposure to actinic radiation. It should be noted that the photopolymerizable compositions of the present invention may be cationically polymerizable or free-radically polymerizable. While epoxide groups are cationically active, the selection of a free-radical polymerization mechanism imposes the requirement that the composition contain a compound with a free-radically active unsaturated group, such as an acrylate compound, a (meth)acrylate compound, an epoxy-functional acrylate, an epoxy-functional (meth)acrylate, or a combination thereof. Applying this selection, preferred photoinitiators are photoactive compounds that undergo Norrish I cleavage to generate free radicals that can be initiated by addition to an acrylic double bond.

[0126] Overall, the photoinitiator should be present in the composition in an amount of 0 to 1.0 weight percent, based on the weight of the composition.

[0127] The use of photoinitiators, as well as the photobase generators and photoacid generators described herein above, may generate residual compounds from the photochemical reaction. The residues can be detected by conventional analytical techniques, such as infrared, ultraviolet, and NMR spectroscopy; gas or liquid chromatography; and mass spectrometry. Thus, the present invention may contain detectable amounts of residues from the cured (epoxy) matrix copolymer and photobase / acid generator. Such residues are present in small amounts and typically do not interfere with the desired physicochemical properties of the product.

[0128] Although not intended to limit the present invention, a mixture containing one or more photoinitiators can be irradiated with activating radiation to polymerize the monomer components. The purpose of irradiation is to generate active species from the photoinitiator, which initiate the curing reaction. Once the species is generated, the curing chemistry follows the same thermodynamic rules as any chemical reaction: the reaction rate can be accelerated by heat. The practice of using thermal treatment to enhance cationic UV curing of monomers is commonly known in the art; an exemplary reference is Crivello et al., "Dual Photo- and Thermally Initiated Cationic Polymerization of Epoxy Monomers," Journal of Polymer Science A, Polymer Chemistry, Vol. 44, Issue 23, pp. 6750-6764, (Dec. 1, 2006).

[0129] As will be appreciated by those skilled in the art, a photosensitizer can be incorporated into the composition to improve the efficiency with which any photoinitiator present uses the supplied energy. The photosensitizer is typically used in an amount of 5 to 25% by weight, based on the weight of the photoinitiator.

[0130] For the purposes of the present invention, a plasticizer is a substance that reduces the viscosity of the composition and thus promotes its processability. The plasticizer may comprise up to 10% by weight, or up to 5% by weight, based on the total weight of the composition, and is preferably selected from polydimethylsiloxanes (PDMS), diurethanes, ethers of monofunctional, linear or branched C4-C16 alcohols such as Cetiol OE (available from Cognis Deutschland GmbH, Duesseldorf), esters of abietic, butyric, thiobutyric, acetic, propionic and citric acids, esters based on nitrocellulose and polyvinyl acetate, fatty acid esters, dicarboxylic acid esters, esters of OH-bearing or epoxidized fatty acids, glycolic acid esters, benzoic acid esters, phosphate esters, sulfonic acid esters, trimellitic acid esters, epoxidized plasticizers, polyether plasticizers such as end-capped polyethylene or polypropylene glycols, polystyrene, hydrocarbon plasticizers, chlorinated paraffins, and mixtures thereof. It should be noted that, in principle, phthalates could be used as plasticizers, but these are not preferred due to their toxicological potential. Preferably, the plasticizer comprises or consists of one or more polydimethylsiloxanes (PDMS).

[0131] For purposes of the present invention, stabilizers are to be understood as antioxidants, UV stabilizers, or hydrolysis stabilizers. As used herein, the stabilizers may collectively constitute 0-10% by weight, or up to 5% by weight, based on the total weight of the composition. Common commercially available examples of stabilizers suitable for use herein include: sterically hindered phenols; thioethers; benzotriazoles; benzophenones; benzoates; cyanoacrylates; acrylates; amines of the hindered amine light stabilizer (HALS) type; phosphorus; sulfur; and mixtures thereof.

[0132] As mentioned above, the composition according to the present invention can further contain a filler. Suitable fillers include, for example, chalk, lime powder, precipitated and / or calcined silicic acid, zeolite, bentonite, magnesium carbonate, diatomaceous earth, alumina, clay, talc, titanium oxide, iron oxide, zinc oxide, sand, quartz, flint, mica, glass powder, and other ground minerals. Organic fillers, in particular carbon black, graphite, wood fiber, wood flour, sawdust, cellulose, cotton, pulp, cotton, wood chips, shredded straw, rice husks, crushed walnut shells, and other shredded fibers, can also be used. Short fibers such as glass fiber, glass filament, polyacrylonitrile, carbon fiber, Kevlar fiber, or polyethylene fiber can also be added. Aluminum powder is also suitable as a filler.

[0133] The pyrogenic and / or precipitated silica is advantageously from 10 to 90 m 2 / g: when used, such silicas do not cause a further increase in the viscosity of the composition according to the invention, but contribute to the strengthening of the cured composition. Similarly, as fillers, silicas with a larger BET surface area, advantageously 100 to 250 m 2 / g, especially 110-170m 2 It is conceivable to use calcined and / or precipitated silicic acids with a higher BET surface area of ​​0.1g / g: due to the higher BET surface area, the effect of strengthening the setting composition is achieved with a lower weight proportion of silica.

[0134] Also suitable as fillers are hollow spheres with a mineral or plastic shell. These can be, for example, hollow glass spheres commercially available under the trade name Glass Bubbles®. Plastic-based hollow spheres such as Expancel® or Dualite® can also be used, as described in EP 0 520 426 B1; they are composed of inorganic or organic materials and have a diameter of 1 mm or less, preferably 500 μm or less.

[0135] Fillers that impart thixotropy to the composition may be preferred for many applications: such fillers are also described as rheological aids, e.g., hydrogenated castor oil, fatty acid amides, or swellable plastics such as PVC.

[0136] The total amount of filler present in the compositions of the present invention is preferably 0 to 30 wt.%, more preferably 0 to 20 wt.%, based on the total weight of the composition. The desired viscosity of the curable composition typically determines the total amount of filler added, and it is believed that in order to be easily extrudable from an appropriate dispensing device, such as a tube, the curable composition should have a viscosity of 3000 to 150,000, preferably 40,000 to 80,000 mPas, or even 50,000 to 60,000 mPas.

[0137] With respect to component c) above, it should be noted that other compounds having metal chelating properties may also be used in the compositions of the present invention to help enhance adhesion of the cured adhesive to the substrate surface. Additionally, an acetoacetate-functionalized modified resin sold by King Industries under the trade name K-FLEX XM-B301 is also suitable for use as an adhesion promoter.

[0138] To further improve shelf life, it is often recommended to further stabilize the compositions of the present invention against moisture penetration by using a desiccant. For specific applications, it is sometimes necessary to reduce the viscosity of the adhesive or sealant compositions of the present invention by using a reactive diluent. The total amount of reactive diluent present is typically up to 15 wt. %, preferably 1 to 5 wt. %, based on the total weight of the composition.

[0139] The presence of a non-reactive diluent in the composition of the present invention is not excluded if it can effectively optimize its viscosity. For example, and by way of example only, the composition may be prepared using xylene, 2-methoxyethanol, dimethoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-isopropoxyethanol, 2-butoxyethanol, 2-phenoxyethanol, 2-benzyloxyethanol, benzyl alcohol, ethylene glycol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol diphenyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-butyl ether, propylene glycol butyl ether, ethers; propylene glycol phenyl ether; dipropylene glycol; dipropylene glycol monomethyl ether; dipropylene glycol dimethyl ether; dipropylene glycol di-n-butyl ether; N-methylpyrrolidone; diphenylmethane; diisopropyl naphthalene; petroleum fractions such as Solvesso® products (available from Exxon); alkylphenols such as tert-butylphenol, nonylphenol, dodecylphenol, and 8,11,14-pentadecatrienylphenol; styrenated phenols; bisphenols; aromatic hydrocarbon resins, especially those containing phenolic groups such as ethoxylated or propoxylated phenols; adipates; sebacates; phthalates; benzoates; organic phosphates or sulfonates; and sulfonamides.

[0140] Alternatively, the non-reactive diluent preferably constitutes less than 10% by weight, in particular less than 5% by weight, or even less than 2% by weight, relative to the total weight of the composition.

[0141] Exemplary Embodiments of Two-Component Compositions According to an exemplary embodiment of the present invention, based on the weight of the composition: (I) a first component comprising: 0.5 to 4% by weight of a) a compound of formula (AII): [ka] [In the formula, L is an integer from 1 to 10; and R k is C1-C4 alkyl] at least one epoxy silane oligomer represented by the formula: 15 to 75% by weight of b) at least one polyepoxide compound having at least three epoxide groups per molecule, selected from the group consisting of glycidyl ethers of polyhydric alcohols, glycidyl ethers of polyhydric phenols, glycidyl esters of polycarboxylic acids, polyfunctional glycidyl amines, and epoxidized polyethylenically unsaturated hydrocarbons; and 0-15 wt. % of c) at least one compound selected from the group consisting of monoepoxide compounds and diepoxide compounds; and the compound of parts b) and c) does not satisfy formula (AI); (II) a second component comprising: 15 to 30% by weight of at least one phenalkamine and 1,2-, 1,3-, and 1,4-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, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (isophoronediamine, IPDA), 2- and / or 4-methyl-1,3-diaminocyclohexane, 1,3-bis(aminomethyl)cyclohexyl d) a curing agent comprising at least one alicyclic amine selected from the group consisting of 1,4-bis(aminomethyl)cyclohexane, 2,5(2,6)-bis(aminomethyl)-bicyclo[2.2.1]heptane (norboranediamine, NBDA), 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.02,6]decane (TCD-diamine), 1,4-diamino-2,2,6-trimethylcyclohexane (TMCDA), N,N-bis(3-aminopropyl)cyclohexylamine, and 1,8-menthanediamine; A two-component (2K) composition comprising: moreover, e) core-shell rubber particles, at least a portion of which is provided in the first component (I); and Further provided is a two-component (2K) composition characterized in that the molar ratio of epoxide-reactive groups to epoxide groups is from 0.95:1 to 1.1:1.

[0142] Methods and Uses For two-component (2K) curable compositions, the reactive components are combined and mixed to induce their cure: the reactive compounds should be mixed under sufficient shear to produce a homogeneous mixture. This is believed to be achievable without special conditions or special equipment. Thus, suitable mixing devices may include: static mixers; magnetic stir bar devices; wire whisks; augers; batch mixers; planetary mixers; CW Brabender or Banburry® style mixers; blade blenders and high shear mixers such as rotating impellers.

[0143] For small-scale liner applications, where volumes of less than 2 liters are typically used, the preferred packaging for two-component (2K) compositions is a parallel double cartridge or coaxial cartridge in which two tubular chambers are arranged side by side or inside each other and sealed with pistons; the actuation of these pistons allows the components to be extruded from the cartridge, advantageously through a closely mounted static or dynamic mixer. For larger-volume applications, the two components of the composition can be advantageously stored in drums or pails, where they can be extruded through a hydraulic press, particularly through a follower plate, and fed via a pipeline to a mixing device, ensuring a fine and highly homogeneous mixture of the hardener and binder components. In any case, it is important that the binder component be placed with an airtight and moisture-proof seal so that both components can be stored for a long period of time, ideally for 12 months or more.

[0144] Non-limiting examples of two-component dispensing devices and methods that may be suitable for the present invention include those described in US Pat. No. 6,129,244 and US Pat. No. 8,313,006.

[0145] Two-component (2K) curable compositions should generally be prepared to exhibit an initial viscosity of less than 200,000 mPa·s, e.g., less than 100,000 mPa·s, at 25° C., determined immediately after mixing, e.g., up to 2 minutes after mixing. Regardless of, or in addition to, the viscosity characteristics described above, two-component (2K) compositions should be prepared so as to be free of bubbles (foam) upon mixing and subsequent curing. Furthermore, the two-component (2K) composition should further be formulated to exhibit at least one, preferably at least two, and most preferably all of the following properties: i) a long pot life, which shall be understood herein as the time after which the viscosity of the mixture at 20°C rises above 50,000 mPas, typically at least 30 minutes, generally at least 60 or 120 minutes; ii) a maximum exotherm temperature of 120°C or less, preferably 100°C or less, more preferably 80°C or less; and iii) a Shore A hardness of at least 50, preferably 60, more preferably at least 70, after curing and storage at room temperature and 50% relative humidity for 7 days.

[0146] Curing of the compositions of the present invention is typically carried out at temperatures ranging from -10°C to 120°C, preferably from 0°C to 70°C, and especially from 20°C to 60°C. The appropriate temperature will depend on the particular compounds present and the desired cure rate and can be determined in each case by those skilled in the art using simple preliminary tests, if necessary. Of course, curing at temperatures between 10°C and 35°C or between 20°C and 30°C is particularly advantageous, as it eliminates the need to substantially heat or cool the mixture from the usual prevailing ambient temperature. However, where applicable, conventional means, including microwave induction, can be used to raise the temperature of the mixture formed from each component of the two-component (2K) composition above the mixing and / or application temperature.

[0147] The curable compositions according to the invention may find utility in, inter alia: varnishes; inks; binders for fibres and / or particles; coatings on glass; coatings on mineral building materials such as lime and / or cement-bound gypsum, gypsum-containing surfaces, fibre cement building materials and concrete; coatings and sealings on wood and wood-based materials such as chipboard, fibreboard and paper; coatings on metal surfaces; coatings on asphalt and bitumen-containing paving; coatings and sealings on various plastic surfaces; and coatings on leather and textiles.

[0148] Due to the fact that the compositions of the present invention can produce high adhesive strength in a short time, often at room temperature, they are best used to form composite structures by surface-to-surface bonding of the same or different materials. Exemplary adhesive applications of the compositions of the present invention include bonding wood and wood-based materials and bonding metal materials.

[0149] The compositions of the present invention are also believed to be suitable as injectable sealing compounds for electrical building components such as cables, optical fibers, cover strips or plugs, etc. The sealants can help protect these components from the ingress of water and other contaminants, heat exposure, temperature fluctuations and thermal shock, and mechanical damage.

[0150] In a particularly preferred embodiment, the compositions of the present invention are used as adhesives or sealants for molded and bonded metal components such as those found in vehicles, particularly automobile doors, trunks, hood shields and panels. The sealants can be used during the manufacture or repair of such components and effectively function to seal and protect the components from corrosion.

[0151] For each of the above applications, the composition can be applied by conventional application methods, such as brushing; roll coating, for example, using a four-roll applicator if the composition is solvent-free, or a two-roll applicator for solvent-borne compositions; doctor blade application; printing; and spraying (including, but not limited to, air-atomized spraying, air-assisted spraying, airless spraying, and high-volume, low-pressure spraying). For coating and adhesive applications, it is recommended that the composition be applied to a wet film thickness of 10 to 500 μm. Applying thinner layers within this range is more economical and reduces the likelihood of thick cured areas that may require sanding for coating applications. However, careful control must be exercised when applying thinner coatings or layers to avoid the formation of discontinuous cured films.

[0152] For completeness, it should be noted that the present invention does not exclude the preparation of epoxide adhesives in the form of "film adhesives." A prepolymer mixture of epoxy resin, hardener, and other desired components is applied as a coating onto a polymeric film substrate, rolled up, and stored at a temperature low enough to inhibit chemical reaction between the components. When desired, the film adhesive is removed from the cold environment, applied to a metal or composite part, the backing is stripped off, the assembly is completed, and cured in an oven or autoclave.

[0153] The following examples are illustrative of the present invention and are not intended to limit the scope of the invention in any way. [Example]

[0154] The following raw materials were used in the examples: Kane Ace 414: N,N,N',N'-tetraglycidyl-4,4'-methylenebisbenzeneamine-based epoxy resin (75 wt%) with dispersed core-shell beads (25 wt%), available from Kaneka Corporation. Kane Ace 154: Bisphenol A epoxy resin (60 wt%) dispersed with core-shell beads (40 wt%), available from Kaneka Corporation CoatOSil MP 200: A multifunctional epoxy resin silane oligomer available from Momentive Performance Ancamine 2264: A modified cycloaliphatic amine curing agent available from Evonik Industries AG Acamine 2914 UF: An aliphatic curing agent with accelerator, available from Evonik Industries AG Cardolite NX 5608: A phenalkamine hardener available from Cardolite Corporation SHOFREE BATG: A multifunctional epoxy resin, (2,2'-[1-methylethylidene)bis[6-(2-oxiranylmethoxy)-3,1-phenylene]methylene]]bis-oxirane (CAS No. 1799411-80-5), available from Showa Denko. Loctite PC 7303: A two-component, high-temperature resistant epoxy coating compound available from Henkel.

[0155] Exemplary first and second components were prepared by simple mixing of the ingredients listed below in Table 1. For completeness, the weight percentages in Table 1 are for the overall composition, not for the components.

[0156] [Table 1]

[0157] The two components of each example listed in the table were combined to form a cured composition, and the following tests were then performed to characterize each composition.

[0158] Initial adhesive strength, tensile lap shear (TLS) test: The substrates tested were stainless steel (1.4301, 1.5 mm thick). For tensile testing, the substrates were cut into 2.5 cm x 10 cm plates. The adhesive overlap area for each plate was 2.5 cm x 1.0 cm (1" x 0.4"), with an adhesive thickness of 150 microns. For the initial adhesive run, the applied adhesive composition was cured in the overlap area at 23°C for 168 hours. The comparative Loctite PC 7303 adhesive was further cured at 148°C for 2 hours. Tensile lap shear (TLS) tests were then performed at 23°C, 150°C, and 200°C according to EN 1465:2009 (German version) Adhesives - Determination of Tensile Lap-shear Strength of Bonded Assemblies. The specimens were placed in the grips of a universal testing machine and pulled at 10 mm / min until failure. The grips holding both ends of the assembly were positioned so that the applied force was through the centerline of the specimen. The type of failure observed could be either adhesive (the adhesive peeled away from one substrate) or cohesive (the adhesive itself ruptured).

[0159] The results of this test are shown in Table 2 below.

[0160] [Table 2]

[0161] In view of the foregoing description and examples, it will be apparent to one skilled in the art that equivalent modifications can be made without departing from the scope of the appended claims.

Claims

1. (I) a first component comprising: a) Formula (AI): 【Chemical 1】 [In the formula, R ｅ is C １ -C ６ is an alkyl group; R ｆ is an epoxide-substituted C １ -C １２ Alkyl group, C ３ -C １８ Cycloalkyl group or C ２ -C １８ an alkoxyalkyl group; R ｇ is H or C １ -C ６ is an alkyl group; R ｈ is C １ -C ６ is an alkyl group; i is an integer greater than or equal to 1; and, j is an integer of 1 or greater. at least one epoxy silane oligomer represented by the formula: b) at least one polyepoxide compound having at least three epoxide groups per molecule; and optionally c) at least one compound selected from the group consisting of monoepoxide compounds and diepoxide compounds; wherein the compounds of parts b) and c) do not satisfy formula (AI); (II) a second component comprising: d) a curing agent consisting of at least two compounds having at least two epoxide-reactive groups per molecule, characterized in that it contains at least one Mannich base and at least one cycloaliphatic amine; A two-component (2K) composition comprising: The two-component (2K) composition further comprises e) Core-shell rubber particles Including; and, Further, a two-component (2K) composition characterized in that the molar ratio of epoxide-reactive groups to epoxide groups is from 0.95:1 to 1.5:

1.

2. Based on the weight of the composition, 0.1 to 5 wt. % of a) the at least one epoxy silane oligomer represented by formula (AI); 10 to 80% by weight of b) said at least one polyepoxide compound having at least three epoxide groups per molecule; 0-20 wt. % of c) the at least one compound selected from the group consisting of monoepoxide compounds and diepoxide compounds; 10 to 30 wt. % of d) said curing agent; and 5 to 30 wt. % of e) the core-shell rubber particles; 2. The two-component (2K) composition according to claim 1, characterized in that it comprises a molar ratio of epoxide-reactive groups to epoxide groups of from 0.95:1 to 1.1:

1.

3. Based on the weight of the composition, 0.5 to 4 wt. %, preferably 0.5 to 2 wt. % of a) said at least one epoxy silane oligomer of formula (AI); 15 to 75% by weight, preferably 20 to 70% by weight, of b) said at least one polyepoxide compound having at least three epoxide groups per molecule; 0 to 15% by weight, preferably 0 to 10% by weight, of c) said at least one compound selected from the group consisting of monoepoxide compounds and diepoxide compounds; 10 to 30% by weight, preferably 15 to 30% by weight, of d) said curing agent; and 5 to 25 wt. %, preferably 10 to 25 wt. % of e) said core-shell rubber particles; 2. The two-component (2K) composition according to claim 1, characterized in that it comprises a molar ratio of epoxide-reactive groups to epoxide groups of from 0.95:1 to 1.1:

1.

4. 4. Two-component (2K) composition according to claim 1, characterized in that the at least one epoxy silane oligomer a) has a number average molecular weight (Mn) of 200 to 3000 Daltons.

5. Part a) of the composition is a compound of formula (AII): 【Chemistry 2】 wherein L is an integer from 0 to 20; and R ｋ is C １ -C ６ alkyl] A two-component (2K) composition according to any one of claims 1 to 4, comprising or consisting of at least one compound represented by the formula:

6. L is an integer from 1 to 10; and R ｋ is C １ -C ４ 6. The two-component (2K) composition of claim 5, wherein the alkyl is alkyl.

7. 7. The two-component (2K) composition according to claim 1, wherein the at least one polyepoxide compound having at least three epoxide groups per molecule is selected from the group consisting of glycidyl ethers of polyhydric alcohols; glycidyl ethers of polyhydric phenols; glycidyl esters of polycarboxylic acids; polyfunctional glycidyl amines; and epoxidized polyethylenically unsaturated hydrocarbons.

8. 8. The two-component (2K) composition according to any one of claims 1 to 7, wherein part b) comprises or consists of at least one polyfunctional glycidyl amine selected from the group consisting of N,N,N',N'-tetraglycidyl-4,4'methylenebisbenzenamine; p-aminophenol triglycidyl ether; m-aminophenol triglycidyl ether; tetraglycidyl bis(aminomethyl)cyclohexane; and N,N,N',N'-tetraglycidyl-m-xylylenediamine.

9. 9. Two-component (2K) composition according to any of claims 1 to 8, wherein part c) comprises or consists of at least one diepoxide compound having an epoxide equivalent weight of 100 to 700 g / eq.

10. 10. The two-component composition of claim 9, wherein the at least one diepoxide compound is selected from the group consisting of glycidyl ethers of dihydric alcohols; glycidyl ethers of dihydric phenols; glycidyl esters of dicarboxylic acids; and epoxidized polyethylenically unsaturated hydrocarbons.

11. A two-component (2K) composition according to any one of claims 1 to 10, wherein the or each Mannich base of the hardener is a phenalkamine.

12. The or each cycloaliphatic amine of the curing agent may be 1,2-, 1,3-, and 1,4-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; 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (isophoronediamine, IPDA); 2- and / or 4-methyl-1,3-diaminocyclohexane; 1, 12. The two-component (2K) composition of any of claims 1 to 11, wherein the diamine is selected from the group consisting of 3-bis(aminomethyl)cyclohexane; 1,4-bis(aminomethyl)cyclohexane; 2,5(2,6)-bis(aminomethyl)-bicyclo[2.2.1]heptane (norboranediamine, NBDA); 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.02,6]-decane (TCD-diamine); 1,4-diamino-2,2,6-trimethylcyclohexane (TMCDA); N,N-bis(3-aminopropyl)cyclohexylamine; and 1,8-menthanediamine.

13. A two-component (2K) composition according to any of the preceding claims, wherein at least a portion of the core-shell rubber particles are provided in the first component of the composition.

14. A cured product obtained from a two-component (2K) composition according to any one of claims 1 to 13.

15. 15. Use of the cured reaction product of claim 14 as a coating, adhesive or sealant.

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