Two-component composition based on epoxide mixtures

Abstract

The present invention relates to a two-component (2K) composition comprising: (I) a first component comprising: a) at least one epoxy silane oligomer according to formula (AI) wherein: Re is a C1-C6 alkyl group; rf is an epoxy substituted alkyl group with 1 to 12 carbon atoms, a cycloalkyl group with 3 to 18 carbon atoms or an alkoxy alkyl group with 2 to 18 carbon atoms; rg is H or a C1-C6 alkyl group; rh is a C1-C6 alkyl group; i is an integer greater than or equal to 1; and j is an integer > = 1; b) at least one polyepoxy compound having at least three epoxy groups per molecule; and optionally c) at least one compound selected from the group consisting of monoepoxy compounds and diepoxy compounds; wherein the compounds of part b) and part c) do not conform to formula (AI); (II) a second component comprising: d) a curing agent consisting of at least two compounds having at least two epoxy-reactive groups per molecule, said curing agent being characterized by comprising: at least one Mannich base; and at least one alicyclic amine wherein the two-component (2K) composition further comprises: e) core-shell rubber particles; and wherein the two-component (2K) composition is further characterized in that the molar ratio of epoxy reactive groups to epoxy groups is from 0.95: 1 to 1.5: 1. The compositions are curable at room temperature and exhibit advantageous adhesive strength under conditions of both room temperature and at elevated temperatures. And the cured reaction product of the composition can be used as a coating, an adhesive or a sealant. # imgabs0 #

Description

Technical Field

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

[0002] Epoxy resins have found a wide range of applications primarily on the basis that specific selection of resin, modifier, and crosslinker (or curing agent) can allow the properties of the cured epoxy resin to be tailored to achieve specific performance characteristics.

[0003] Its versatility is well recognized, and properly cured epoxy resins also possess many other attributes, including, among others: excellent chemical resistance, especially to alkaline environments; high tensile and compressive strength; high fatigue strength; low shrinkage upon cure; and electrical insulation properties, and their retention after aging or environmental exposure. However, cured epoxy resin systems can also be disadvantageously characterized by reduced fracture resistance and impact strength, low thermal stability, low pigment retention capacity, poor flexibility, and poor hydrophobicity.

[0004] The present disclosure relates to "two-component (2K) compositions", which are to be understood as compositions in which the binder component (I) - here based on one or more epoxy compounds - and the hardener component (II) are stored in separate containers due to their reactivity. The two components are mixed only shortly before application and then react and form bonds, thereby forming a polymer network.

[0005] While two-component (2K) compositions based on epoxy compounds are sometimes capable of rapid initial cure, this rapid cure is typically achieved by using elevated temperatures, which may not be suitable or practical for all substrates that may come into contact with the composition. Furthermore, utilizing elevated temperatures to promote rapid cure rates can also accelerate other problems. First, it can prevent adequate leveling in certain coating, adhesive, or sealant applications. Second, it can also restrict the respiration of the material: upon high temperature cure, any moisture trapped beneath the surface of the coating, adhesive, or sealant composition can evaporate and lead to blistering or warping in the cured composition, or at least nanoscale material failure. Material failure, of course, begins at the nanoscale, which expands to the microscale and then to the macroscale: exposure to abrasive conditions accelerates this failure sequence.

[0006] The problem is that at room temperature, two-component (2K) epoxy compositions generally tend to cure slowly over time and may require 6 to 8 hours of cure before handling, with full cure being achieved in one, two, or up to seven days. Such long handling times can be detrimental to many industrial applications. And in fact, the slow cure rate can prevent such two (2) 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 provide rapid strength build-up but are curable at room temperature, thereby not incurring the energy cost of heating the composition and / or the substrate to which it is applied. A prevalent approach has been to accelerate the cure time by conventionally adding specific low molecular weight additives (cure accelerators) to the hardener component of the 2K epoxy composition.

[0008] US2005 / 0143496 (Mueller) discloses a two-component epoxy resin composition comprising: as component A, at least one epoxy resin having an epoxy functionality greater than 1; and as component B, a liquid or pasty hardener containing an amine, a polyetheramine, a polyaminoamide, a Mannich base and / or a compound containing a mercapto group, the composition additionally containing a non-volatile and non-corrosive accelerator. The two-component composition is intended for use as a structural adhesive for vehicle body components.

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

[0010] WO2019115110A1 (Hilti AG) discloses a hardener component for a multi-component epoxy resin material to be cured at room temperature, the hardener component comprising a benzoxazine amine adduct as an accelerator and an amine as a hardener. The benzoxazine amine adduct is present in the hardener component in a proportion of 8.5 to 75% by weight.

[0011] However, the necessary inclusion of accelerators in room temperature curable compositions can be detrimental because they can increase the brittleness of the cured composition and reduce dynamic strength properties. In addition, in some cases, low molecular weight additives - which are not added to the polymer matrix - can promote excessive plasticization of the curing composition.

[0012] It has also been observed that room temperature curable epoxy resin compositions, after curing, exhibit a decrease in their bond strength when subjected to temperatures above room temperature. This limits their usefulness in low temperature adhesive applications. Summary of the invention

[0013] According to a first aspect of the present invention, there is provided a two-component (2K) composition comprising:

[0014] (I) a first component, the first component comprising:

[0015] a) at least one epoxysilane oligomer according to formula (AI);

[0016]

[0017] Where: R e C 1 -C 6 alkyl;

[0018] R f For epoxy-substituted C 1 -C 12 Alkyl, C 3 -C 18 Cycloalkyl or C 2 -C 18 Alkoxyalkyl;

[0019] R g H or C 1 -C 6 alkyl;

[0020] R h C 1 -C 6 alkyl;

[0021] i is an integer ≥ 1; and

[0022] j is an integer ≥ 1;

[0023] b) at least one polyepoxide having at least three epoxy groups per molecule; and

[0024] Optionally present c) at least one compound selected from monoepoxides and diepoxides;

[0025] Wherein, the compounds of part b) and part c) do not conform to formula (AI);

[0026] (II) a second component, the second component comprising:

[0027] d) a curing agent consisting of at least two compounds having at least two epoxy-reactive groups per molecule, characterized in that it contains: at least one Mannich base; and at least one alicyclic amine,

[0028] Wherein, the two-component (2K) composition further comprises:

[0029] e) core-shell rubber particles; and

[0030] The two-component (2K) composition is further characterized in that the molar ratio of epoxy-reactive groups to epoxy groups is from 0.95:1 to 1.5:1.

[0031] The core-shell rubber particles - indicated as part e) - may be contained in the first component, the second component or both components. However, it is preferred that at least a portion of the core-shell rubber particles, preferably at least 60% by weight or at least 70% by weight, is provided in the first component.

[0032] In certain embodiments, the two-component (2K) composition comprises, based on the weight of the composition:

[0033] 0.1 to 5 wt. %, preferably 0.5 to 4 wt. %, more preferably 0.5 to 2 wt. % of a) at least one epoxysilane oligomer according to formula (AI);

[0034] 10 to 80 wt. %, preferably 15 to 75 wt. %, more preferably 20 to 70 wt. % of b) at least one polyepoxide having at least three epoxy groups per molecule;

[0035] 0 to 20 wt %, preferably 0 to 15 wt %, more preferably 0 to 10 wt % of c) at least one compound selected from monoepoxides and diepoxides;

[0036] 10 to 30 wt %, preferably 15 to 30 wt % of d) the curing agent; and

[0037] 5 to 30 wt %, preferably 5 to 25 wt %, more preferably 10 to 25 wt % of e) the core-shell rubber particles,

[0038] The two-component (2K) composition is further characterized in that the molar ratio of epoxy-reactive groups to epoxy groups is from 0.95:1 to 1.1:1.

[0039] The composition as defined above has been shown to be curable at room temperature. Furthermore, when cured at room temperature, the cured composition exhibits advantageous bond strengths both at room temperature and at elevated temperatures.

[0040] The or each 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 or consists of at least one compound according to formula (AII):

[0041]

[0042] Wherein: L is an integer from 0 to 20, preferably an integer from 1 to 10; and

[0043] R k C 1 -C 6 Alkyl, preferably C 1 -C 4 Alkyl, more preferably C 2 -C 3 alkyl.

[0044] Preferably, b) the at least one polyepoxide having at least three epoxy groups per molecule is selected from the group consisting of: glycidyl ethers of polyols; glycidyl ethers of polyphenols; glycidyl esters of polycarboxylic acids; polyfunctional glycidyl amines; and epoxidized polyethylenically unsaturated hydrocarbons. For example, good results were obtained when 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'methylenedianiline; p-aminophenol triglycidyl ether; m-aminophenol triglycidyl ether; tetraglycidyl di(aminomethyl)cyclohexane; and N,N,N',N'-tetraglycidyl-m-xylene diamine.

[0045] Part c) of the composition is optional. However, when added, it is preferred that part c) comprises or consists of at least one diepoxide having an epoxy equivalent weight of 100 to 700 g / eq. The at least one diepoxide may preferably be selected from: glycidyl ethers of diols; glycidyl ethers of diphenols; glycidyl esters of dicarboxylic acids; and epoxidized polyethylenically unsaturated hydrocarbons.

[0046] In this context, it is preferred that the Mannich base or each Mannich base of the curing agent of the composition is a phenalkamine. Independently of or in addition to this preference, the alicyclic amine or each alicyclic amine of the curing agent should preferably be selected from: 1,2-, 1,3- and 1,4-diaminocyclohexane; di(4-aminocyclohexyl)methane; di(4-amino-3-methylcyclohexyl)methane; di(4-amino-3-ethylcyclohexyl)methane; di(4-amino-3,5-dimethylcyclohexyl)methane; di(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- Alkanediamine.

[0047] According to a second aspect of the present invention, there is provided a cured product obtained from a two-component (2K) composition as defined herein above and in the appended claims. The present invention also provides the use of the cured reaction product as a coating, adhesive or sealant.

[0048] limited

[0049] As used herein, the singular form "a," "an," and "the" include plural referents unless the context clearly dictates otherwise.

[0050] As used herein, the terms "comprising," "comprises," and "comprised of" are synonymous with "including," "includes," or "containing," and are inclusive or open-ended and do not exclude additional, unrecited members, elements, or method steps.

[0051] As used herein, the term "consisting of excludes any elements, ingredients, members or method steps not specified.

[0052] When amounts, concentrations, sizes and other parameters are expressed in the form of ranges, preferred ranges, upper values, lower values ​​or preferred upper and lower values, it should be understood that any range obtainable by combining any upper value or preferred value with any lower value or preferred value is also specifically disclosed, regardless of whether the obtained range is explicitly mentioned in the context.

[0053] Furthermore, according to standard understandings, weight ranges expressed as "0 to x" specifically include 0 wt %: the ingredient defined by the range may not be present in the composition or may be present in the composition in an amount of up to x wt %.

[0054] As used herein, the term "at least a portion" may mean any non-zero percentage of the entire amount, up to and including 100%. For example, "at least a portion" may mean 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 entire amount.

[0055] The words "preferred", "preferably", "desirably" and "particularly" are generally used herein to refer to embodiments of the present disclosure that may provide particular benefits under particular circumstances. However, the listing of one or more preferred, desired or particular embodiments does not mean that other embodiments are not useful, and is not intended to exclude those other embodiments from the scope of the present disclosure.

[0056] "Exemplary" is used herein to mean used as an example, instance, or illustration. Any aspect or design described herein as "exemplary" is not necessarily to be construed as preferred or superior to other aspects or designs. On the contrary, the use of exemplary is intended to present concepts in a concrete way.

[0057] As used throughout this application, the words "may" or "may" are used in a permissive sense—meaning having the possibility—rather than in a mandatory sense.

[0058] As used herein, "room temperature" is 23° C.±2° C. As used herein, "ambient conditions" refers to the temperature and pressure of the surrounding environment in which the composition is located or the coating or the substrate of the coating is located.

[0059] The term "Mannich base" is used herein according to its standard definition in the art, as a ketoamine obtainable by condensation of ammonia, a diamine or a polyamine with an active hydrogen component selected from aldehydes, ketones, esters or aromatics (e.g. phenols) and / or heteroaromatics. Phenalkamines - used herein as curing agents - are Mannich base compounds that are the reaction product of an aldehyde, an amine and a phenolic compound.

[0060] The term "monomer" as used herein refers to a substance that can undergo polymerization to contribute a constituent unit to the chemical structure of a polymer. The term "monofunctional" as used herein refers to having one polymerizable moiety. The term "multifunctional" as used herein refers to having more than one polymerizable moiety.

[0061] As used herein, the term "equivalent (eq.)" refers, as usual in chemical notation, to the relative number of reactive groups present in a reaction.

[0062] As used herein, “(meth)acryl” is a shorthand term meaning “acryl” and / or “methacryl.” Thus, the term “(meth)acrylamide” collectively means acrylamide and methacrylamide.

[0063] As used in this article, “C 1 -C n An "alkyl" group refers to a monovalent group containing 1 to n carbon atoms, which is a radical of an alkane and includes straight-chain and branched organic groups. Thus, an "alkyl" group refers to a monovalent group containing 1 to n carbon atoms, which is a radical of an alkane and includes straight-chain and branched organic groups. 1 -C 18 An "alkyl" group refers to a monovalent group containing 1 to 18 carbon atoms, which is a radical of an alkane and includes straight-chain and branched organic groups. In general, it should be noted that alkyl groups (C 1 -C 12 Alkyl), for example, an alkyl group containing 1 to 8 carbon atoms (C 1 -C 8 Alkyl). Examples of alkyl 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 may be substituted with one or more halogens. Where applicable to a given group (R), the permissibility of one or more non-halogen substituents within the alkyl group will be noted in the specification.

[0064] As used herein, the term "C 1 -C 18 "Hydroxyalkyl" refers to a HO-(alkyl) group having from 1 to 18 carbon atoms, wherein the point of attachment of the substituent is through the oxygen atom, and the alkyl group is as defined above.

[0065] "Alkoxy" refers to a monovalent group represented by -OA, where A is an alkyl group: non-limiting examples of which are methoxy, ethoxy, and iso-propoxy. As used herein, the term "C 2 -C 18"Alkoxyalkyl" refers to an alkyl group having an alkoxy substituent as defined above and wherein the (alkyl-O-alkyl) moiety contains a total of 2 to 18 carbon atoms: such groups include methoxymethyl (-CH 2 OCH 3 ), 2-methoxyethyl (-CH 2 CH 2 OCH 3 ) and 2-ethoxyethyl. Similarly, as used herein, the term "C 7 -C 18 "Alkoxyaryl" refers to an aryl group having an alkoxy substituent as defined above and wherein the (aryl-O-alkyl) portion has a total of 7 to 18 carbon atoms.

[0066] As used herein, the term "C 2 -C 4 "Alkylene" is defined as a saturated divalent hydrocarbon radical having 2 to 4 carbon atoms.

[0067] The term "C 3 -C 18 "Cycloalkyl" is understood to mean a saturated monocyclic or polycyclic hydrocarbon radical having from 3 to 18 carbon atoms. In the present invention, such cycloalkyl radicals may be unsubstituted or may be substituted by one or more halogens. The permissibility of one or more non-halogen substituents within the cycloalkyl radical will be noted in the specification where applicable to a given radical (R). Examples of cycloalkyl radicals include: cyclopropyl; cyclobutyl; cyclopentyl; cyclohexyl; cycloheptyl; cyclooctyl; adamantane; and norbornane.

[0068] As used in this article, “C 6 -C 18 "Aryl", used alone or as part of a larger moiety - such as in "aralkyl", refers to monocyclic, bicyclic and tricyclic ring systems, wherein the monocyclic ring system is aromatic, or at least one ring of the bicyclic or tricyclic ring system is aromatic. The bicyclic and tricyclic ring systems include benzo-fused 2-3 membered carbon rings. In the present invention, such aryl groups may be unsubstituted or may be substituted with one or more halogens. Where applicable to a given group (R), the permissibility of one or more non-halogen substituents within the aryl group will be noted in the specification. Exemplary aryl groups include: phenyl; (C1-C4) alkylphenyls, such as tolyl and ethylphenyl; indenyl; naphthyl, tetrahydronaphthyl, tetrahydroindenyl; tetrahydroanthracenyl; and anthracenyl. And it can be noted that phenyl is preferred.

[0069] As used in this article, “C 2 -C 20"Alkenyl" refers to a hydrocarbon group having 2 to 20 carbon atoms and at least one ethylenically unsaturated unit. The alkenyl group may be straight chain, branched or cyclic, and may be optionally substituted with one or more halogens. The permissibility of one or more non-halogen substituents within the alkenyl group will be noted in the specification where applicable to a given portion (R). As understood by those of ordinary skill in the art, the term "alkenyl" also encompasses groups having "cis" and "trans" configurations or alternatively "E" and "Z" configurations. However, it should generally be noted that alkenyl groups containing 2 to 10 (C 2-10 ) or 2 to 8 (C 2-8 ) carbon atom. 2 -C 12 Examples of alkenyl groups include, but are not limited to: -CH═CH 2 ; -CH═CHCH 3 ; -CH 2 CH═CH 2 ; -C(═CH 2 )(CH 3 ); -CH═CHCH 2 CH 3 ; -CH 2 CH═CHCH 3 ; -CH 2 CH 2 CH═CH 2 ; -CH═C(CH 3 ) 2 ; -CH 2 C(═CH 2 )(CH 3 ); -C(═CH 2 )CH 2 CH 3 ; -C(CH 3 )═CHCH 3 ; -C(CH 3 )CH═CH 2 ; -CH═CHCH 2 CH 2 CH 3 ; -CH 2 CH═CHCH 2 CH 3 ; -CH 2 CH 2 CH═CHCH 3 ; -CH 2 CH 2 CH 2 CH═CH 2 ; -C(═CH 2 )CH 2 CH 2 CH3 ; -C(CH 3 )═CHCH 2 CH 3 ; -CH(CH 3 )CH═CHCH; -CH(CH 3 )CH 2 CH═CH 2 ; -CH 2 CH═C(CH 3 ) 2 ; 1-cyclopent-1-enyl; 1-cyclopent-2-enyl; 1-cyclopent-3-enyl; 1-cyclohex-1-enyl; 1-cyclohex-2-enyl; and 1-cyclohex-3-enyl.

[0070] As used herein, "alkaryl" refers to an aryl group substituted with an alkyl group, both groups being as defined above. Additionally, "aralkyl" as used herein refers to an alkyl group substituted with an aryl group, as defined above.

[0071] As used herein, the term "hetero" refers to a group or moiety that contains one or more heteroatoms, such as N, O, Si and S. Thus, for example, "heterocycle" 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, respectively, as defined above, containing N, O, Si or S as part of their structure.

[0072] As used herein, the term "equivalent weight" refers to the molecular weight divided by the number of associated functional groups. Thus, "epoxy equivalent weight" (EEW) refers to the weight (in grams) of a resin containing one equivalent of epoxy.

[0073] The term "epoxide" as used herein means a compound characterized by the presence of at least one cyclic ether group, i.e., a compound in which an ether oxygen atom is attached to two adjacent carbon atoms to form a cyclic structure. The term is intended to include monoepoxides, diepoxides, higher polyepoxides having more than two epoxy groups, and epoxy-terminated prepolymers. The term "monoepoxide" is intended to mean an epoxy compound having one epoxy group. The term "polyepoxide" is intended to mean an epoxy compound having at least two epoxy groups. The term "diepoxide" is intended to mean an epoxy compound having two epoxy groups.

[0074] The epoxide may be unsubstituted, but may also be inertly substituted. Exemplary inert substituents include chlorine, bromine, fluorine and phenyl.

[0075] Molecular weights referred to in this specification can be measured by gel permeation chromatography (GPC) using polystyrene calibration standards, for example according to ASTM 3536.

[0076] The Shore A hardness of a given material referred to herein is determined using a durometer according to ISO 868 entitled "Plastics and Ebonite-Determination of Indentation Hardness by Means of aDurometer (Shore Hardness)", the contents of which are incorporated herein by reference in their entirety. In this specification, all standard Shore A hardness measurements are performed on injection molded plaques using a Type A durometer at 10 seconds.

[0077] Unless otherwise stated, the viscosities of the compositions described herein are measured using an Anton Paar viscometer model MCR 301 at standard conditions of 25°C and 50% relative humidity (RH). The viscometer is calibrated once a year and checked by the service department. The calibration is done using standard liquids with known viscosities of 1 to 50,000 cps (parallel plate PP20, and at 23°C at 1 s -1 The measurements on the compositions according to the invention were carried out using a parallel plate PP20 at a shear rate of 1.5 to 100 s. -1 This was done at different shear rates. DETAILED DESCRIPTION

[0078] a) Epoxy silane oligomer

[0079] The composition of the present invention comprises a) at least one epoxysilane oligomer according to formula (AI).

[0080]

[0081] Where: R e C 1 -C 6 alkyl;

[0082] R f For epoxy-substituted C 1 -C 12 Alkyl, C 3 -C 18 Cycloalkyl or C 2 -C 18 Alkoxyalkyl;

[0083] R g H or C 1 -C 6 alkyl;

[0084] R h C 1 -C 6 alkyl;

[0085] i is an integer ≥ 1; and

[0086] j is an integer ≥1.

[0087] The composition should generally contain 0.1 to 5 wt % a) of the 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 the at least one epoxy silane oligomer, based on the weight of the composition.

[0088] In a specific embodiment of the oligomer of formula (A1): R e C 1 -C 2 Alkyl; R f For epoxy-substituted C 1 -C 6 Alkyl, C 3 -C 12 Cycloalkyl or C 2 -C 12 Alkoxyalkyl; R g H or C 1 -C 2 Alkyl; R h C 1 -C 2 alkyl; i is an integer from 1 to 20, for example, an integer from 1 to 10; and j is an integer from 1 to 20, for example, an integer from 1 to 10. For R f Preferably, the epoxy-substituted C 2 -C 12 Alkoxyalkyl.

[0089] For the sake of completeness, part a) may comprise a single compound according to formula (AI) or may comprise a mixture of compounds according to formula (AI) which may or may not have different substituents and / or different parameters "i" and "j".

[0090] Independently or in addition to the preferred limitations of the above substituents, it is preferred that the or each epoxy silane oligomer present in the composition is characterized by a number average molecular weight (Mn) of 200 to 3000 Daltons, such as 200 to 2000 Daltons or 300 to 1500 Daltons.

[0091] In an exemplary embodiment, part a) of the composition comprises or consists of at least one compound according to formula (AII):

[0092]

[0093] Wherein: L is an integer from 0 to 20; and

[0094] R k C 1 -C 6 alkyl.

[0095] It is particularly preferred that: L is an integer from 1 to 10, for example an integer from 1 to 5; and R k C 1 -C 4 Alkyl groups, such as C 2 -C 3 For the sake of completeness, part a) in this exemplary embodiment may comprise or consist of a single compound according to formula (AII), or may comprise a mixture of compounds according to formula (AII), which may or may not have different values ​​of the parameter L and / or different substituents R k .

[0096] The oligomers according to formula (AI) or (AII) can be prepared by reacting a glycidoxy silane and / or an alicyclic epoxy silane having 2 or 3 alkoxy (OR) groups, and optionally, a copolymerizable silane other than the glycidoxy silane and the alicyclic epoxy silane, in the presence of a catalyst: the reaction is carried out in the presence of water, which is generally fed continuously to the reaction mixture.

[0097] Exemplary reactant glycidyloxysilane monomers include, but are not limited to: γ-glycidyloxypropyltrimethoxysilane; γ-glycidyloxypropyltriethoxysilane; γ-glycidyloxypropylmethyldimethoxysilane; and γ-glycidyloxypropylmethyldiethoxysilane. Exemplary reactant alicyclic 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. Any copolymerizable monomers present in the reaction mixture - other than the glycidyloxysilane and / or cycloaliphatic epoxysilane monomers - should also not be reactive toward epoxy groups under the polymerization conditions: Exemplary comonomers that can improve the stability of epoxysilane oligomers are disclosed in particular: U.S. Pat. No. 3,337,496; U.S. Pat. No. 3,341,469; and U.S. Pat. No. 5,073,195.

[0098] Exemplary catalysts for the synthesis process include: ion exchange resins such as those available from Rohm & Haas IRA 400 or available from Bayer M-500; alkylammonium salts such as hexadecyltrimethylammonium chloride, tetra-n-butylammonium chloride, or benzyltrimethylammonium halide; and quaternary ammonium organofunctional silanes.

[0099] In addition to the above-mentioned synthesis process, one or more epoxysilane oligomers can also be obtained from commercial sources. In this regard, CoatOSil MP200 (CAS No. 68611-45-0) available from Momentive Performance Materials Inc. can be mentioned.

[0100] b) Polyepoxides

[0101] The composition of the present invention comprises b) at least one polyepoxide having at least three epoxy groups per molecule: of course, the polyepoxide (b)) is different from the compound or compounds contained in part a) of the composition. Typically, the composition should comprise 10 to 80% by weight of the at least one polyepoxide of b), based on the weight of the composition. For example, the composition may comprise 15 to 75% by weight or 20 to 70% by weight of the at least one polyepoxide of b), based on the weight of the composition.

[0102] The polyepoxide may be a pure compound, but may also be a mixture of epoxy-functional compounds, including mixtures of compounds having different numbers of epoxy groups per molecule. The polyepoxide may be saturated or unsaturated, aliphatic, alicyclic, aromatic or heterocyclic, and may be substituted. Furthermore, the polyepoxide may also be monomeric or polymeric.

[0103] Without intending to limit the invention, suitable polyepoxides may be liquids, solids or solutions in solvents. In addition, such polyepoxides should have an epoxy equivalent weight of 100 to 700 g / eq, such as 120 to 320 g / eq. And generally, polyepoxides having an epoxy equivalent weight of less than 500 g / eq or even less than 400 g / eq are preferred: this is mainly from a cost point of view, because lower molecular weight epoxy resins require more limited purification processing in their production.

[0104] As examples of types or groups of polyepoxides that may be included in the composition, mention may be made of: glycidyl ethers of polyols; glycidyl ethers of polyphenols; glycidyl esters of polycarboxylic acids; polyfunctional glycidyl amines; and epoxidized polyethylenically unsaturated hydrocarbons.

[0105] 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; trihydroxyphenylmethane triglycidyl ether; trisphenol triglycidyl ether; trihydroxybiphenyl triglycidyl ether; tetrahydroxyphenylethane triglycidyl ether; tetraglycidyl ether of tetrahydroxyphenylethane; 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 glycerol triglycidyl ether. In addition, the following glycidyl ethers can be used in the present disclosure: phenol-formaldehyde novolac resin, cresol-formaldehyde novolac resin, brominated phenol-formaldehyde novolac resin, brominated cresol-formaldehyde novolac resin, 3,3',5,5'-tetramethyl-(1,1',-biphenyl)-2,4,4'-triol and pyrogallol. And it can also be mentioned that 2,2'-[(1-methylethylidene)bis[[6-(2-oxiranylmethoxy)-3,1-phenylene]methylene]]bis-oxirane (CAS No. 1799411-80-5) can be used herein.

[0106] The glycidyl esters of polycarboxylic acids useful in the present invention are derived from polycarboxylic acids containing three or more carboxylic acid groups and containing no other groups reactive toward epoxy groups. The polycarboxylic acids may be aliphatic, alicyclic, aromatic or heterocyclic. Preferred polycarboxylic acids are those containing no more than 18 carbon atoms per carboxylic acid group, suitable examples of which include, but are not limited to: aconitic acid; propane-1,2,3-tricarboxylic acid (β-carboxyglutaric acid); trimer acids of unsaturated fatty acids, such as trimer acids of linseed fatty acids; trimellitic acid; trimesic acid; and polymers and copolymers of (meth)acrylic acid.

[0107] Exemplary polyglycidylamines that can be used alone or in combination include, but are not limited to: N,N,N',N'-tetraglycidyl-4,4'methylenedianiline; p-aminophenol triglycidyl ether; m-aminophenol triglycidyl ether; tetraglycidylbis(aminomethyl)cyclohexane; and N,N,N',N'-tetraglycidyl-m-xylenediamine.

[0108] Examples of highly preferred commercial polyepoxides include: 2,2'-[(1-methylethylene)bis[[6-(2-oxiranylmethoxy)-3,1-phenylene]methylene]]bis-oxirane, available as SHOFREE BATG from ShowaDenko; castor oil triglycidyl ether, such as ERISYS TM GE-35H; Polyglycerol-3-polyglycidyl ether, such as ERISYS TM GE-38; sorbitan glycidyl ether, such as ERISYS TM GE-60; Epikote 1032H60 (manufactured by Japan Epoxy Resins Co., Ltd.); Epikote 1031S (manufactured by Japan Epoxy Resins Co., Ltd.); TECHMORE VG3101 (manufactured by Mitsui Chemicals, Inc.); polyfunctional glycidylamines such as Kane Ace414 (available from Kaneka Corporation), ELM-100 (manufactured by Sumitomo Chemical Co., Ltd.), MY721 and MY0510 (manufactured by Ciba Specialty Chemicals Inc.), MY0600-CH (available from Hunstman) and available from Mitsubushi Gas Chemicals Co. X and C; 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).

[0109] c) Other epoxy compounds

[0110] Based on the weight of the first component of the composition of the present disclosure, the first component of the composition of the present disclosure may include 0 to 20 wt% of c) at least one compound selected from monoepoxides and diepoxides that do not meet the definition of section a) above. For example, based on the weight of the first component of the composition, the first component of the composition may contain 0 to 15 wt% or 0 to 10 wt% of c) at least one epoxy compound.

[0111] Thus, part c) of the composition may comprise: one or more monoepoxides; one or more diepoxides; or combinations thereof. Thus, part c) may be a mixture of epoxy-functional compounds, including mixtures of compounds having different numbers of epoxy groups per molecule. The monoepoxides or diepoxides may be saturated or unsaturated, aliphatic, alicyclic, aromatic or heterocyclic, and may be substituted. Furthermore, the monoepoxides or diepoxides may also be monomeric or polymeric.

[0112] Without intending to limit the present invention, illustrative monoepoxides include: alkylene oxides; epoxy-substituted alicyclic hydrocarbons, such as cyclohexene oxide, vinylcyclohexene monooxide; 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 monohydric 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, in which one or more other carboxyl groups are esterified with alkanols; alkyl esters and alkenyl esters of epoxy-substituted monocarboxylic acids; epoxy alkyl ethers of polyols, in which one or more other OH groups are esterified or etherified with carboxylic acids or alcohols; and monoesters of polyols and epoxy monocarboxylic acids, in which one or more other OH groups are esterified or etherified with carboxylic acids or alcohols.

[0113] By way of example, the following glycidyl ethers may be mentioned as monoepoxides particularly suitable 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.

[0114] In important embodiments, the monoepoxide conforms to Formula (CI) below:

[0115]

[0116] Where: R w , R x , R y and R z may be the same or different and are independently selected from hydrogen, halogen atoms, C 1 -C 8 Alkyl, C 3 -C 10 Cycloalkyl, C 2 -C 12 Alkenyl, C 6 -C 18 Aryl or C 7 -C 18 Arylalkyl, provided that R y and R z At least one of them is not hydrogen.

[0117] Preferably, R w , R x and R y is hydrogen, and R z Phenyl or C 1 -C 8 Alkyl, more preferably C 1 -C 4 In view of this embodiment, exemplary monoepoxides include: ethylene oxide; 1,2-propylene oxide (propylene oxide); 1,2-butylene oxide; cis-2,3-butylene oxide; trans-2,3-butylene oxide; 1,2-pentene oxide; 1,2-hexene oxide; 1,2-heptane oxide; decane oxide; butadiene oxide; isoprene oxide; and styrene oxide.

[0118] In the present invention, it is mentioned to use 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.

[0119] Again, without intending to limit part c) of the present invention, suitable diepoxides may be liquids, solids or solutions in solvents. Furthermore, such diepoxides should have an epoxy equivalent weight of 100 to 700 g / eq, such as 120 to 320 g / eq. And generally, diepoxides having an epoxy equivalent weight of less than 500 g / eq or even less than 400 g / eq are preferred: this is primarily from a cost perspective, since lower molecular weight epoxy resins require more limited purification processing in their production.

[0120] As examples of types or groups of diepoxides that may be included in the composition, mention may be made of: glycidyl ethers of diols; glycidyl ethers of diphenols; glycidyl esters of dicarboxylic acids; and epoxidized diethylenically unsaturated hydrocarbons.

[0121] Suitable diglycidyl ether compounds may be aromatic, aliphatic or cycloaliphatic in nature and may thus be derived from dihydric phenols and diols. And useful classes of such diglycidyl ethers are: diglycidyl ethers of aliphatic and cycloaliphatic diols (e.g. 1,2-ethanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,12-dodecanediol, cyclopentanediol, cyclohexanediol and isosorbide); diglycidyl ethers based on bisphenol A; bisphenol F diglycidyl ethers; diglycidyl ethers based on polyalkylene glycols, in particular polypropylene glycol diglycidyl ethers; and glycidyl ethers based on polycarbonate diols.

[0122] The glycidyl esters of dicarboxylic acids useful in the present invention are derived from carboxylic acids containing two carboxylic acid groups and containing no other groups reactive toward epoxy groups. The dicarboxylic acids may be aliphatic, alicyclic, aromatic or heterocyclic. Preferred dicarboxylic acids are those containing no more than 18 carbon atoms per carboxylic acid group, suitable examples of which 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 dimer acids of linseed fatty acids; phthalic acid; isophthalic acid; terephthalic acid; phenylene-diacetic acid; chlorendic acid; hexahydrophthalic acid, in particular hexahydrophthalic acid (1,2-cyclohexanedicarboxylic acid); biphenyl dicarboxylic acid; naphthalene dicarboxylic acid; esters of dicarboxylic acids terminated with polyacids of aliphatic polyols; and polymers and copolymers of (meth) acrylic acid.

[0123] Other suitable diepoxides which may be mentioned include: diunsaturated fatty acids C 1 -C 18 Alkyl ester diepoxides; butadiene diepoxide; polybutadiene diglycidyl ether; vinyl cyclohexene diepoxide; and limonene diepoxide.

[0124] And highly preferred examples of diepoxides include: bisphenol-A epoxy resins, such as DER TM 331、DER TM 332、DER TM 383、JER TM 828 and Epotec YD 128; bisphenol-F epoxy resins such as DER TM 354; Bisphenol-A / F epoxy resin blends, such as DER TM 353; Polypropylene glycol diglycidyl ether, such as DER TM 732; Solid bisphenol-A epoxy resins, such as DER TM 661 and DER TM 664UE; Solutions of bisphenol-A solid epoxy resins, such as DER TM 671-X75; Brominated epoxy resin, such as DER TM 542; and di(2,3-epoxypropyl)cyclohexane-1,2-dicarboxylate available as Lapox Arch-11.

[0125] In a particular embodiment, the composition may comprise, in addition to the epoxysilane oligomer in part a) above, a monomeric epoxysilane, more particularly a glycidyloxyalkylalkoxysilane having the formula:

[0126]

[0127] wherein: each R is independently selected from methyl or ethyl; and

[0128] n is 1 to 10.

[0129] 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, the monomeric epoxy-functional silane should comprise less than 10 wt%, preferably less than 5 wt% or less than 2 wt%, based on the total weight of the epoxy-functional compounds in the first component ((a), b) and c)).

[0130] Although it does not represent a preferred embodiment, the present invention does not exclude that the first component of the curable composition further comprises one or more cyclic monomers selected from the group consisting of oxetanes; cyclic carbonates; cyclic anhydrides; and lactones. The disclosure of the following citations may be helpful 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; British Patent No. GB-A-1,485,925; and EP-A-0119 840. However, such cyclic comonomers should account for less than 10% by weight, preferably less than 5% by weight or less than 2% by weight, based on the total weight of the epoxy functional compounds in the first component (a), b) and c)).

[0131] d) Curing agent

[0132] The curing agent d) in the second component of the composition must consist of at least two compounds, each compound having at least two epoxy-reactive groups per molecule, wherein the curing agent is characterized by comprising: 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, in particular a phenalkamine obtained by condensation of cardanol (CAS No.: 37330-39-5), an aldehyde and an amine. The reactant amine in the condensation reaction is ideally ethylenediamine or diethyltriamine.

[0133] Mannich bases and phenalkamines are known in the art, and suitable examples include commercially available phenalkamines NC-541, NC-557, NC-558, NC-566, Lite 2001, and Lite 2002 (available from Cardolite); 3440, 3441, 3442 and 3460 (available from Huntsman); and EH 614, EH 621, EH 624, EH 628 and EH 629 (available from Cytec).

[0134] The term "alicyclic amine" refers to a molecule having an amine group attached to an aliphatic carbon atom of the alicyclic moiety. The term "alicyclic" means a saturated or unsaturated but non-aromatic carbocyclic group containing one or more fused rings, which may be optionally fused. The alicyclic group may be unsubstituted or may be optionally substituted with one or more halogens. The term "alicyclic" also includes "heterocycloaliphatic" groups, which are non-aromatic monocyclic or polycyclic rings, wherein one or more carbon atoms of the one or more rings have been replaced by heteroatoms. In this article, the alicyclic group is preferably C 3 -C 18As the cycloalkyl group, specifically, there can be mentioned cycloheptyl, cyclohexyl and cyclopentyl.

[0135] It is preferred herein that the alicyclic amine is a primary amine and contains at least one primary amine group (-NH 2 The alicyclic group is preferably present at the α-position directly linked to the amine group or at the β-position adjacent to the α-position.

[0136] Exemplary alicyclic amines useful in the present invention include, but are not limited to: 1,2-, 1,3-, and 1,4-diaminocyclohexane; di(4-aminocyclohexyl)methane; di(4-amino-3-methylcyclohexyl)methane; di(4-amino-3-ethylcyclohexyl)methane; di(4-amino-3,5-dimethylcyclohexyl)methane; di(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 (norbornane diamine, 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- alkylenediamine; N-cyclohexyl-1,2-ethylenediamine; N-cyclohexyl-1,3-propylenediamine; 3-cyclohexylamino-1-pentylamine; 4-aminomethyl-piperidine; N-(2-aminoethyl)piperazine; and mixtures thereof.

[0137] Commercial 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.

[0138] Preferably, the curing agent d) consists or consists essentially 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 - in an amount of up to 10 mol %, based on the total moles of the curing agent - a further compound having at least two epoxy-reactive groups per molecule. Such supplementary compounds may in particular include one or both of the following: i) at least one polyamine having at least two amine hydrogens reactive toward epoxy groups, but which is not a cycloaliphatic amine; and ii) at least one mercapto compound having at least two mercapto groups reactive toward epoxy groups.

[0139] The at least one polyamine having at least two amine hydrogens reactive toward epoxy groups should in particular contain primary and / or secondary amine groups and have an equivalent weight per primary or secondary amine group of not more than 150 g / eq, more preferably not more than 125 g / eq.

[0140] Suitable polyamines that may be used alone or in combination include, but are not limited to, the following:

[0141] i) aliphatic or arylaliphatic primary diamines, among which the following may be mentioned as examples: 2,2-dimethyl-1,3-propylenediamine; 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-hexanediamine; 2,2,4- and / or 2,4,4-trimethylhexamethylenediamine; 1,7-heptanediamine; 1,8-octanediamine; 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).

[0142] ii) tertiary amino group-containing polyamines having two or three aliphatic primary amino groups, among which 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 of 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)tallowalkylamine, which are Y12D and YT (from Akzo Nobel) is commercially available.

[0143] iii) aliphatic primary polyamines containing ether groups, among which the following specific examples may be mentioned: 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)polytetrahydrofurans and other polytetrahydrofuran diamines; diamines containing alicyclic ether groups obtained by propoxylation of 1,4-dimethylolcyclohexane and subsequent amination, for example RFD-270 (from Huntsman) is a commercially available material; polyoxyalkylene diamines or triamines are available as products of amination of polyoxyalkylene diols and triols, and they are The name of the polyetheramine (from Huntsman), the name of the polyetheramine (from BASF) or the name of PC It is commercially available under the name of (from Nitroil). It should be noted that it is particularly preferred to use D-230, D-400, D-600, D-2000, D-4000, T-403, T-3000, T-5000, EDR-104, EDR-148 and EDR-176, and the corresponding amines from BASF or Nitroil.

[0144] iv) primary diamines with secondary amine groups, among which the following examples may be mentioned: 3-(2-aminoethyl)aminopropylamine, di(hexamethylene)triamine (BHMT); diethylenetriamine (DETA); triethylenetetramine (TETA); tetraethylenepentamine (TEPA); pentaethylenehexamine (PEHA); higher homologues of linear polyethyleneamines, for example polyethylenepolyamines with 5 to 7 ethyleneamine units (so-called “higher ethylenepolyamines”, HEPA); products from multiple cyanoethylation or cyanobutylation of primary diamines and polyamines with at least two primary amine groups and subsequent hydrogenated products, for example dipropylenetriamine (DPTA), N-(2-aminoethyl)-1,3-propylenediamine (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.

[0145] v) polyamines having one primary and at least one secondary amino group, among which the following examples may be mentioned: N-butyl-1,2-ethylenediamine; N-hexyl-1,2-ethylenediamine; N-(2-ethylhexyl)-1,2-ethylenediamine; N-methyl-1,3-propylenediamine; N-butyl-1,3-propylenediamine; N-(2-ethylhexyl)-1,3-propylenediamine; 3-methylamino-1-pentylamine; 3-ethylamino-1-pentylamine; aliphatic diamines, for example N-cocoalkyl-1,3-propylenediamine; aliphatic primary diamines reacted in a molar ratio of 1:1 with acrylonitrile, maleic acid or fumaric acid diesters, citraconic acid diesters, acrylic acid esters and methacrylic acid esters, acrylic acid amides and methyl products of the Michael-type addition reaction of acrylic acid amides and itaconic acid diesters; products from the partial reductive alkylation of primary polyamines with aldehydes or ketones, in particular N-monoalkylation products of the aforementioned polyamines having two primary amino 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-amine and N4-amine, wherein preferred alkyl groups are benzyl, isobutyl, hexyl and 2-ethylhexyl; and partially styrenated polyamines, for example 240 (from Mitsubishi Gas Chemical) are those commercially available.

[0146] vi) N,N′-dialkylation products of secondary diamines, in particular the aforementioned polyamines having two primary amino 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 2-phenylethyl, benzyl, isobutyl, hexyl and 2-ethylhexyl.

[0147] vii) Aromatic polyamines, among which may be mentioned: 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; mixtures of 3,5-dimethylthio-2,4- and -2,6-tolylenediamine (as 300 available from Albermarle); a mixture of 3,5-diethyl-2,4- and -2,6-toluenediamine (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′-diaminodiphenylmethane (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′-methylenedi-o-aminobenzoic acid; dimethyl-(5,5′-methylenedi-o-aminobenzoate); 1,3-propylene-bis(4-aminobenzoate); 1,4-butylene-bis(4-aminobenzoate); polyoxytetramethylene-bis(4-aminobenzoate) (with Available from Air Products); 1,2-bis(2-aminophenylthio)ethane, 2-methylpropyl-(4-chloro-3,5-diaminobenzoate); and tert-butyl-(4-chloro-3,5-diaminobenzoate).

[0148] viii) Polyamidoamines, representative members of which include the reaction products of mono- or polycarboxylic acids or their esters or anhydrides, especially dimerized fatty acids, with aliphatic, cycloaliphatic or aromatic polyamines, for example polyalkyleneamines such as DETA or TETA. Commercially available polyamidoamines include: 100, 125, 140 and 150 (from Cognis); 223, 250 and 848 (from Huntsman); 3607 and 530 (from Huntsman); and EH 651, EH 654, EH 655, EH 661 and EH 663 (from Cytec).

[0149] As mentioned above, the composition of the present invention may optionally include at least one compound having at least two reactive thiol groups per molecule. Suitable thiol-containing compounds that may be used alone or in combination include, but are not limited to, the following.

[0150] Liquid mercaptan-terminated polysulfide polymers, of which commercial examples include: 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 thereof; and Polymers (from Akzo Nobel), in particular types G10, G112, G131, G1, G12, G21, G22, G44 and G4.

[0151] - Mercaptan-terminated polyoxyalkylene ethers, obtainable by reacting polyoxyalkylene diols and triols with epichlorohydrin or with alkylene oxides and subsequent reaction with sodium hydrosulfide.

[0152] Thiol-terminated compounds in the form of polyoxyalkylene derivatives, which are marketed under the trade name (from Cognis), in particular its WR-8, LOF and 3-800 types.

[0153] Polyesters of thiocarboxylic acids, of which specific examples include: pentaerythritol tetrathioglycolate (PETMP); trimethylolpropane trimercaptoacetate (TMPMP); ethylene 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.

[0154] 2,4,6-Trimercapto-1,3,5-triazine, 2,2'-(ethylenedioxy)-diethanethiol (triethylene glycol dithiol) and / or ethanedithiol.

[0155] Preference is given to using polyesters of thiocarboxylic acids, in particular at least one of pentaerythritol tetrathioglycolate (PETMP), trimethylolpropane trimercaptoacetate (TMPMP) and ethylene glycol dimercaptoacetate.

[0156] When formulating the curable composition, it is preferred that the curing agent is included in an amount such that the overall composition is characterized by a molar ratio of epoxy-reactive groups to epoxy groups of 0.95:1 to 1.5:1, such as 0.95:1 to 1.1:1. Notably, a molar ratio of epoxy-reactive groups to epoxy groups of 1:1 is included within these stated ranges and itself represents a highly preferred molar ratio.

[0157] In the case where the above molar ratio terms are met, the composition can also be characterized as comprising 10 to 30 weight percent, such as 15 to 30 weight percent, of d) the curing agent, based on the weight of the composition.

[0158] d) Toughening agent

[0159] The composition of the present invention comprises a toughened rubber in the form of core-shell particles. Although such particles can in principle be included in either the first component or the second component, it will typically be that the core-shell particles are added dispersed in the epoxy resin of the first component.

[0160] The term "core-shell rubber" or CSR is used in accordance with its standard meaning in the art to denote a rubber particle core formed by a polymer comprising an elastomer or rubbery polymer as a major component and a shell formed by a polymer graft polymerized onto the core. The shell partially or completely covers the surface of the rubber particle core during the graft polymerization process. By weight, the core should account for at least 50% by weight of the core-shell rubber particle.

[0161] The polymer material of the core should have a glass transition temperature (T g ), preferably -20°C or lower, more preferably -40°C or lower, even more preferably -60°C or lower. g The polymer of the shell has a glass transition temperature (T g ) is a non-elastomeric, thermoplastic or thermosetting polymer having a temperature greater than room temperature, preferably greater than 30°C, and more preferably greater than 50°C.

[0162] Without intending to limit the invention, the core may comprise: a diene homopolymer, such as a homopolymer of butadiene or isoprene; a diene copolymer, such as a copolymer of butadiene or isoprene with one or more ethylenically unsaturated monomers, such as vinyl aromatic monomers, (meth)acrylonitrile or (meth)acrylates; a polymer based on (meth)acrylate monomers, such as polybutyl acrylate; and a polysiloxane elastomer, such as polydimethylsiloxane and cross-linked polydimethylsiloxane.

[0163] Similarly, without intending to limit the invention, the shell may comprise 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)acrylamide. The polymer or copolymer used in the shell may have acid groups that are ionically crosslinked by metal carboxylate formation, in particular by forming 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.

[0164] Preferably, any included core-shell rubber particles have an average particle size (d50) of 10 nm to 300 nm, such as 50 nm to 200 nm: the particle size refers to the diameter or largest dimension of a particle in a particle distribution and is measured by dynamic light scattering.

[0165] The present application does not exclude the presence of two types of core-shell rubber (CSR) particles having different particle sizes in the composition to provide a balance of key properties of the resulting cured product, including shear strength, peel strength and resin fracture toughness. In this embodiment, the smaller particles (first CSR type) contained may have an average particle size of 10 to 100 nm, and the larger particles (second CSR type) contained may have an average particle size of 120 to 300 nm, such as 150 to 300 nm. On a weight basis, the amount of smaller core-shell rubber particles should generally exceed the larger core-shell rubber particles: for example, a weight ratio of smaller CSR particles to larger CSR particles of 3:1 to 5:1 may be used.

[0166] The core-shell rubber may be selected from commercially available products, examples of which include: Paraloid EXL 2650A, EXL2655 and EXL2691 A available from The Dow Chemical Company; Kane available from Kaneka Corporation; MX series, in particular MX 120, MX 125, MX 130, MX 136, MX 551, MX553; and METABLEN SX-006 available from Mitsubishi Rayon.

[0167] 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.

[0168] f) Additives and auxiliary ingredients

[0169] The compositions obtained in the present invention generally additionally contain adjuvants and additives which can impart improved properties to these compositions. For example, the adjuvants and additives can impart one or more of the following properties: improved elastic properties; improved elastic recovery; longer permissible processing time; faster curing time; and lower residual viscosity. Such adjuvants and additives, which can be contained independently of one another in a single component or in both components of a two-component (2K) composition, include: catalysts; plasticizers; stabilizers, including UV stabilizers; antioxidants; toughening agents; fillers; reactive diluents; desiccants; adhesion promoters; bactericides; flame retardants; rheological adjuvants; colored pigments, such as titanium dioxide, iron oxide or carbon black; color pastes; dyes; and / or, optionally, to a small extent, non-reactive diluents.

[0170] For the sake of completeness, it should be noted that auxiliary materials and additives containing epoxy-reactive groups are typically blended into the hardener component of a two (2K) component composition. Materials containing epoxy groups or reactive toward one or more hardeners are typically formulated as the epoxide-containing component of a two (2K) component composition. Non-reactive materials may be formulated into either component A or component B or both.

[0171] The use of a catalyst is not required in the present application, and in fact, in a preferred embodiment, the composition may be characterized as being substantially free of a catalyst. However, in certain circumstances, it may be advantageous to add one or more substances that act as catalysts to promote the reaction between epoxy groups and epoxy-reactive groups, such as the reaction between amine groups and epoxy groups.

[0172] Without intending to limit the catalyst used in the present invention, the following suitable catalysts may be mentioned: i) acids or compounds which can be hydrolyzed into 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 BF 3 Amine complex, SbF 6sulfonium compounds, di-aromatic hydrocarbon iron complexes; f) Bronsted acid compounds, such as pentafluoroantimonic acid complex; and e) mixtures of the above acids and acid esters; ii) tertiary amines, such as 1,4-diazabicyclo[2.2.2]octane, benzyldimethylamine, α-methylbenzyldimethylamine, triethanolamine, dimethylaminopropylamine, imidazoles (including N-methylimidazole, N-vinylimidazole and 1,2-dimethylimidazole) and salts of such tertiary amines; iii) quaternary ammonium salts, 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) phenol resins; and vii) phosphites, such as diphenyl phosphite and triphenyl phosphite.

[0173] In an embodiment, the amine catalyst used to cure the epoxy resin-based composition may be a photobase generator: upon exposure to UV radiation (generally in the wavelength range of 320 to 420 nm), the photobase generator releases an amine that catalyzes the addition of epoxy-reactive groups to epoxides. There is no particular restriction on the photobase generator, as long as it can generate amines directly or indirectly by light irradiation. However, suitable photobase generators that may be mentioned include: benzyl carbamates; benzoin carbamates; o-carbamoyl hydroxylamines; O-carbamoyl oximes; aromatic sulfonamides; α-lactams; N-(2-allylethenyl)amides; aromatic azides, N-arylformamides, and 4-(o-nitrophenyl)dihydropyridines.

[0174] In an alternative embodiment, the acid catalyst may be selected from a photoacid generator (PAG): upon irradiation with light energy, an ionic photoacid generator undergoes a cleavage reaction and releases one or more Lewis acid or Bronsted acid molecules that catalyze the ring opening and addition of pendant epoxy groups to form crosslinks. Useful photoacid generators are thermally stable, do not undergo heat-induced reactions with the copolymer being formed, and are readily dissolved or dispersed in the curable composition.

[0175] Exemplary cations useful as the cationic portion of the ionic PAGs of the present invention include organic onium cations such as those described in U.S. Pat. Nos. 4,250,311, 3,113,708, 4,069,055, 4,216,288, 5,084,586, 5,124,417, and 5,554,664. These references specifically encompass aliphatic or aromatic onium salts centered on Groups IVA and VIIA (CAS version), with preference being given to I-, S-, P-, Se-, N-, and C-centered onium salts, such as those selected from sulfoxonium, iodonium, sulfonium, selenonium, pyridinium, carbonium, and phosphonium.

[0176] As is known in the art, the nature of the counter-anion in the ionic photoacid generator (PAG) affects the rate and extent of cationic addition polymerization of the epoxy group. For example, the reactivity of commonly used nucleophilic anions is in the order of SbF 6 >AsF 6 >PF 6 >BF 4 The effect of the anion on reactivity has been attributed to three major factors, which one skilled in the art should compensate for in the present invention: (1) the acidity of the protic or Lewis acid generated; (2) the extent of ion pair separation in the growing cationic chain; and (3) the susceptibility of the anion to fluoride abstraction and subsequent chain termination.

[0177] It is not excluded that the composition of the present invention comprises a photoinitiator compound which can replace the above-mentioned photobase generator and photoacid generator compounds, and the one or more photoinitiator compounds will initiate polymerization or hardening of the composition when irradiated with actinic radiation. It should be noted that the photo-polymerizable composition of the present invention can be cationically polymerizable or free radical polymerizable: although the epoxy group is cationically active, the choice of free radical polymerization mechanism requires that the composition must contain a compound with a free radical 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 choice, the preferred photoinitiator will be a photoactive compound that undergoes Norrish I-type cleavage to generate a free radical, which can be initiated by addition to the acrylic double bond.

[0178] The total photoinitiator should be present in the composition in an amount of 0 to 1.0 weight percent based on the weight of the composition.

[0179] The use of photoinitiators - as well as the photobase generators and photoacid generators mentioned above - can produce residual compounds from the photochemical reaction. The residues can be detected by conventional analytical techniques, such as infrared, ultraviolet and NMR spectroscopy; gas chromatography or liquid chromatography; and mass spectrometry. Therefore, the present invention can include a cured (epoxy) matrix copolymer and a detectable amount of residues of a photobase / acid generator. Such residues are present in small amounts and generally do not interfere with the desired physicochemical properties of the product.

[0180] Without intending to limit the invention, a mixture containing one or more photoinitiators can be irradiated with activating radiation to polymerize one or more monomer components. The purpose of this irradiation is to produce an active species from the photoinitiator that initiates the curing reaction. Once this species is produced, the curing chemistry will follow the same thermodynamic rules as any chemical reaction: the reaction rate can be accelerated by heating. The practice of using thermal treatment to enhance cationic UV curing of monomers is generally known in the art, and the reference for illustrative guidance is: Crivello et al., "Dual Photo-and thermallyinitiated cationic polymerization of epoxy monomers," Journal of Polymer Science A, Polymer Chemistry., Vol. 44, Issue: 23, pp. 6750-6764, (Dec. 1, 2006).

[0181] As will be appreciated by those skilled in the art, a photosensitizer may be added to the composition to improve the efficiency with which any photoinitiator present utilizes the delivered energy. The photosensitizer is typically used in an amount of 5 to 25 wt % based on the weight of the photoinitiator.

[0182] A "plasticizer" for the purposes of the present invention is a substance which reduces the viscosity of the composition and thus promotes its processability. In this context, the plasticizer may represent up to 10% by weight or up to 5% by weight, based on the total weight of the composition, and is preferably selected from: polydimethylsiloxane (PDMS); diurethanes; ethers of monofunctional, linear or branched C4-C16 alcohols, such as Cetiol OE (available from Cognis Deutschland GmbH, Düsseldorf); esters of rosin acid, butyric acid, thiobutyric acid, acetic acid, propionic acid and citric acid; esters based on nitrocellulose and polyvinyl acetate; fatty acid esters; dicarboxylic acid esters; esters of fatty acids carrying OH groups or epoxidized; glycolates; benzoates; phosphates; sulfonates; trimellitates; epoxidized plasticizers; polyether plasticizers, such as end-capped polyethylene glycols or polypropylene glycols; polystyrene; hydrocarbon plasticizers; chlorinated paraffins; and mixtures thereof. Note that in principle phthalates can 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).

[0183] "Stabilizer" for the purposes of the present invention is understood to be an antioxidant, a UV stabilizer or a hydrolysis stabilizer. In this context, the stabilizer may constitute a total of 0 to 10% by weight or up to 5% by weight, based on the total weight of the composition. Standard commercial examples of stabilizers suitable for use herein include: hindered phenols; thioethers; benzotriazoles; benzophenones; benzoates; cyanoacrylates; acrylates; amines of the hindered amine light stabilizer (HALS) type; phosphorus; sulfur; and mixtures thereof.

[0184] As mentioned above, the composition according to the invention may additionally contain fillers. Suitable here are, for example, chalk, lime powder, precipitated and / or pyrolyzed silicic acid, zeolite, bentonite, magnesium carbonate, diatomaceous earth, aluminum oxide, clay, talc, titanium oxide, iron oxide, zinc oxide, sand, quartz, flint, mica, glass powder and other ground minerals. Organic fillers may also be used, in particular carbon black, graphite, wood fiber, wood powder, sawdust, cellulose, cotton, pulp, cotton, wood chips, chopped straw, husks, ground walnut shells and other chopped fibers. Short fibers may also be added, for example glass fibers, glass fibers, polyacrylonitrile, carbon fibers, Kevlar fibers or polyethylene fibers. Aluminum powder is also suitable as a filler.

[0185] The pyrogenic and / or precipitated silica may advantageously have a particle size of 10 to 90 m 2 / g BET surface area: when they are used, such silicas do not cause any additional increase in the viscosity of the composition according to the invention, but do contribute to strengthening the cured composition. It is also conceivable to use silicas with a higher BET surface area, advantageously between 100 and 250 m 2 / g, especially 110 to 170m 2 / g of pyrogenic and / or precipitated silicic acid as filler: Due to the greater BET surface area, the effect of reinforcing the cured composition is achieved with a smaller weight proportion of silicic acid.

[0186] Also suitable as fillers are hollow spheres with a mineral shell or a plastic shell. For example, these may be hollow glass spheres, which are marketed under the trade name Glass Commercially available. Plastic based hollow spheres can be used, e.g. or And they are described in EP 0 520 426 B1: They are made of inorganic or organic substances and each have a diameter of 1 mm or less, preferably 500 μm or less.

[0187] Fillers which impart thixotropy to the composition may be preferred for many applications: such fillers are also described as rheology adjuvants, for example hydrogenated castor oil, fatty acid amides or swellable plastics such as PVC.

[0188] The total amount of filler present in the composition of the invention will preferably be 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 will generally be determined by the total amount of filler added, and it is believed that in order to be easily extrudable from a suitable dispensing device, such as a tube, the curable composition should have a viscosity of 3000 to 150,000 mPas, preferably 40,000 to 80,000 mPas, or even 50,000 to 60,000 mPas.

[0189] With respect to component c) above, it is worth noting that other compounds having metal chelating properties may also be used in the compositions of the present invention to help enhance the adhesion of the cured adhesive to the substrate surface. Also suitable for use as an adhesion promoter is the acetoacetate functionalized modified resin sold by King Industries under the trade name K-FLEX XM-B301.

[0190] In order to extend the shelf life even further, it is generally advisable to further stabilize the composition according to the invention with respect to moisture penetration by using a desiccant. Occasionally there is also a need to reduce the viscosity of the adhesive or sealant composition according to the invention for a specific application by using one or more reactive diluents. The total amount of reactive diluent present is generally up to 15% by weight, preferably 1 to 5% by weight, based on the total weight of the composition.

[0191] The presence of non-reactive diluents in the composition of the invention is not excluded insofar as it is effective to adjust the viscosity thereof. For example, but for illustration only, the composition may contain one or more of the following: 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; propylene glycol phenyl ether; dipropylene glycol; dipropylene glycol monomethyl ether; dipropylene glycol dimethyl ether; dipropylene glycol di-n-butyl ether; N-methylpyrrolidone; diphenylmethane; diisopropylnaphthalene; petroleum fractions, such as 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.

[0192] In addition to the above, it is preferred that the non-reactive diluent accounts for less than 10 wt%, in particular less than 5 wt% or less than 2 wt%, based on the total weight of the composition.

[0193] Illustrative Embodiments of Two-Component Compositions

[0194] According to an illustrative embodiment of the present invention, there is provided a two-component (2K) composition comprising, based on the weight of the composition:

[0195] (I) a first component, the first component comprising:

[0196] 0.5 to 4 wt. % of a) at least one epoxysilane oligomer according to formula (AII):

[0197]

[0198] Wherein: L is an integer from 1 to 10; and

[0199] R k C 1 -C 4 alkyl;

[0200] 15 to 75 weight percent of b) at least one polyepoxide having at least three epoxy groups per molecule, wherein the at least one polyepoxide is selected from the group consisting of: glycidyl ethers of polyols; glycidyl ethers of polyphenols; glycidyl esters of polycarboxylic acids; polyfunctional glycidyl amines; and epoxidized polyethylenically unsaturated hydrocarbons; and

[0201] 0 to 15% by weight of c) at least one compound selected from monoepoxides and diepoxides;

[0202] Wherein, the compounds of part b) and part c) do not conform to formula (AI);

[0203] (II) a second component, the second component comprising:

[0204] 15 to 30% by weight of d) a curing agent consisting of at least two compounds having at least two epoxy-reactive groups per molecule, characterized in that it contains: at least one phenalkamine; and at least one alicyclic amine selected from the group consisting of 1,2-, 1,3- and 1,4-diaminocyclohexane; di(4-aminocyclohexyl)methane; di(4-amino-3-methylcyclohexyl)methane; di(4-amino-3-ethylcyclohexyl)methane; di(4-amino-3,5-dimethylcyclohexyl)methane; di(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 (norbornanediamine, 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- Alkanediamine,

[0205] Wherein, the two-component (2K) composition further comprises:

[0206] e) core-shell rubber particles, at least a portion of which are provided in the first component (I); and

[0207] The two-component (2K) composition is further characterized by a molar ratio of epoxy-reactive groups to epoxy groups of 0.95:1 to 1.1:1.

[0208] Methods and Applications

[0209] For two-component (2K) curable compositions, the reactive components are brought together and mixed in a manner that causes them to harden: The reactive compounds should be mixed under sufficient shear to produce a homogeneous mixture. It is believed that this can be achieved without special conditions or special equipment. That is, suitable mixing devices may include: static mixing devices; magnetic stir bar devices; whisk devices; helical stirrers; batch mixers; planetary mixers; CW Brabender or type mixers; and high shear mixers, such as blade mixers and rotary impellers.

[0210] For small-scale lining applications, where volumes of less than 2 litres will usually be used, the preferred packaging for the two-component (2K) composition will be a side-by-side double cartridge or a 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 cartridges, advantageously through a closely mounted static or dynamic mixer. For larger volume applications, the two components of the composition can advantageously be stored in pails or drums: in this case, the two components are extruded by a hydraulic press, in particular through a follower plate, and supplied by pipes to a mixing device which ensures a fine and highly uniform mixing of the hardener and adhesive components. In any case, for any packaging, it is important that the adhesive component is handled in an airtight and moisture-tight form so that the two components can be stored for a long time, ideally for 12 months or more.

[0211] Non-limiting examples of two-component dispensing apparatus and methods that may be suitable for use with the present invention include those described in US Pat. No. 6,129,244 and US Pat. No. 8,313,006.

[0212] Two-component (2K) curable compositions should generally be formulated to exhibit an initial viscosity at 25° C. of less than 200,000 mPa.s—measured immediately after mixing, for example, up to two minutes after mixing—e.g., less than 100,000 mPa.s. Independently of or in addition to said viscosity properties, the two-component (2K) composition should be formulated to be free of bubbles (foam) upon mixing and subsequent curing. Furthermore, the two-component (2K) composition should additionally be formulated to exhibit at least one, desirably at least two, and most desirably all of the following properties: i) a long pot life, typically of at least 30 minutes, often of at least 60 minutes or 120 minutes, which pot life is understood herein as the time after which the viscosity of the mixture will rise to more than 50,000 mPas at 20°C; ii) a maximum exotherm temperature of not more than 120°C, preferably not more than 100°C, more preferably not more than 80°C; and iii) a Shore A hardness of at least 50, preferably at least 60, more preferably at least 70 after curing and storage for 7 days at room temperature and 50% relative humidity.

[0213] The curing of the composition of the invention generally takes place at temperatures of -10°C to 120°C, preferably 0°C to 70°C, in particular 20°C to 60°C. Suitable temperatures depend on the specific compounds present and the desired curing rate and can be determined by the person skilled in the art in the individual case, if necessary using simple preliminary tests. Of course, curing at temperatures of 10°C to 35°C or 20°C to 30°C is particularly advantageous, since this avoids the need to heat or cool the mixture significantly from the usual ambient temperature. However, where applicable, the temperature of the mixture formed from the individual components of the two (2K) component composition can be raised to above the mixing temperature and / or application temperature using conventional methods including microwave induction.

[0214] The curable compositions according to the invention can be used in particular for: varnishes; inks; binders for fibers and / or particles; coating of glass; coating of mineral building materials, such as lime- and / or cement-bound plasters, gypsum-containing surfaces, fiber cement building materials and concrete; coating and sealing of wood and wood materials (such as particleboard, fiberboard and paper); coating of metal surfaces; coating of bituminous and asphalt-containing pavements; coating and sealing of various plastic surfaces; and coating of leather and textiles.

[0215] Due to the fact that the composition of the present invention is generally capable of developing high bond strength in a short time at room temperature, the composition is most suitable for forming composite structures by surface-to-surface bonding of the same or different materials to each other. It can be mentioned that bonding wood to wood materials and bonding metal materials together are exemplary adhesive applications of the present invention.

[0216] The compositions of the present invention are also believed to be suitable as pourable sealing compounds for electrical building components such as cables, optical fibers, covering strips or plugs. The sealants can be used to protect these components from the intrusion of water and other contaminants, from heat exposure, temperature fluctuations and thermal shock, and from mechanical damage.

[0217] In a particularly preferred embodiment, the compositions of the present invention are used as adhesives or sealants for forming and joining metal parts such as those found in vehicles, particularly doors, trunks, hood hoods and panels of automobiles. The sealant can be used during the manufacture or repair of such parts and will effectively serve to seal these parts and prevent corrosion thereof.

[0218] In each of the above applications, the composition can be applied by conventional application methods, such as brushing; roller coating, such as roller coating using a 4-application roller device in which the composition is solvent-free or a 2-application roller device for a solvent-containing composition; blade application; printing; and spraying, including but not limited to air atomization 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 provides a reduced possibility of thick cured areas, which may require grinding for coating applications. However, strict control must be performed when applying thinner coatings or layers to avoid the formation of discontinuous cured films.

[0219] For the sake of completeness, it should be noted that the present invention does not exclude the preparation of epoxy adhesives in the form of "film adhesives." A prepolymer mixture of epoxy resin, hardener, and other desired components is applied as a coating to a polymer film substrate, rolled up, and stored at a sufficiently low temperature to inhibit chemical reactions between the components. When desired, the film adhesive is removed from this low temperature environment and applied to a metal or composite part, the backing is peeled off, the assembly is completed, and it is cured in an oven or autoclave.

[0220] The following examples are illustrative of the present invention and are not intended to limit the scope of the present invention in any way.

[0221] Example

[0222] The following materials were used in the examples:

[0223] Kane Ace 414: An epoxy resin based on N,N,N',N'-tetraglycidyl-4,4'-methylenedianiline (75 wt%) in which core-shell beads (25 wt%) are dispersed, available from Kaneka Corporation.

[0224] Kane Ace 154: Bisphenol A epoxy resin (60 wt%) in which core shell beads (40 wt%) are dispersed, available from Kaneka Corporation.

[0225] CoatOSil MP 200: Multifunctional epoxy silane oligomer available from Momentive Performance.

[0226] Ancamine 2264: A modified cycloaliphatic amine curing agent available from Evonik Industries AG.

[0227] Acamine 2914UF: an aliphatic curing agent with an accelerator, available from Evonik Industries AG.

[0228] Cardolite NX 5608: a phenalkamine curing agent available from Cardolite Corporation.

[0229] SHOFREE BATG: a multifunctional epoxy resin, (2,2'-[1-methylethylene)bis[6-(2-oxiranylmethoxy)-3,1-phenylene]methylene]]bis-oxirane (CAS No. 1799411-80-5)), available from Showa Denko.

[0230] Loctite PC 7303: A two component high temperature epoxy wear resistant compound available from Henkel.

[0231] The first and second components of the exemplary curable composition are prepared by simply mixing the ingredients listed below in Table 1. For the finished product, the weight percentages in Table 1 are the weight percentages of the entire composition, not the weight percentages of its individual components.

[0232] Table 1

[0233] Element Example 1 Example 2 Example 3 Comparative Example 1 Component 1 Kane Ace 414 68.6 68.6 Kane Ace 154 45.0 CoatOSil MP 200 1.4 1.4 1.5 SHOFREE BATG 28.5 Loctite PC 7303 resin 80.0 Second component Ancamine 2264 19.5 18.0 15.0 Ancamine 2914UF 6.0 5.0 Cardolite NX 5608 10.5 6.0 5.0 Loctite PC 7303 Hardener 20.0

[0234] The two listed components of each example were combined to form the curable composition. The following tests were then performed to characterize each composition.

[0235] Initial bond strength, tensile lap shear (TLS) testing:The substrate tested was stainless steel (1.4301, thickness 1.5 mm). The substrate was cut into 2.5 cm × 10 cm plates for tensile testing. The bonding overlap area of ​​each plate was 2.5 cm × 1.0 cm (1 "x 0.4"), with a bonding thickness of 150 microns. For the initial bonding operation, the applied adhesive composition in the overlapping area was cured at 23 ° C for 168 hours. The comparative example Loctite PC 7303 was additionally cured at 148 ° C for 2 hours. Then, tensile lap shear (TLS) tests were performed at 23 ° C, 150 ° C and 200 ° C based on EN 1465:2009 (German version) Adhesives-Determination of Tensile Lap-shear Strength of Bonded Assemblies. The test sample was placed in the fixture of a universal testing machine and stretched at 10 mm / min until failure occurred. The fixtures used to fix the ends of the assembly are aligned so that the applied force is applied through the center line of the sample. The type of failure observed can be adhesive—wherein the adhesive separates from one of the substrates—or cohesive, where the adhesive breaks within itself.

[0236] The results of this testing are provided in Table 2 below.

[0237] Table 2

[0238]

[0239] In view of the above description and embodiments, it will be obvious to those skilled in the art that equivalent modifications may be made thereto without departing from the scope of the appended claims.

Claims

1. A two-component (2K) composition comprising: (I) a first component, the first component comprising: a) at least one epoxysilane oligomer according to formula (AI): in: R e is a C1-C6 alkyl group; R f is an epoxy-substituted C1-C 12 Alkyl, C3-C 18 Cycloalkyl or C2-C 18 Alkoxyalkyl; R g is H or C1-C6 alkyl; R h is a C1-C6 alkyl group; i is an integer ≥ 1; and j is an integer ≥ 1; b) at least one polyepoxide having at least three epoxy groups per molecule; and, Optionally present c) at least one compound selected from monoepoxides and diepoxides; Wherein, the compounds of part b) and part c) do not conform to formula (AI); (II) a second component, the second component comprising: d) a curing agent consisting of at least two compounds having at least two epoxy-reactive groups per molecule, characterized in that it contains: at least one Mannich base; and at least one alicyclic amine, Wherein, the two-component (2K) composition further comprises: e) core-shell rubber particles; and The two-component (2K) composition is further characterized by a molar ratio of epoxy-reactive groups to epoxy groups of 0.95:1 to 1.5:

1.

2. The two-component (2K) composition according to claim 1, comprising, based on the weight of the composition: 0.1 to 5 wt. % of a) at least one epoxysilane oligomer according to formula (AI); 10 to 80 wt. % of b) at least one polyepoxide having at least three epoxy groups per molecule; 0 to 20 wt % of c) at least one compound selected from monoepoxides and diepoxides; 10 to 30 wt % of d) the curing agent; and 5 to 30 wt % of e) the core-shell rubber particles, in, The two-component (2K) composition is also characterized by a molar ratio of epoxy-reactive groups to epoxy groups of 0.95:1 to 1.1:

1.

3. The two-component (2K) composition according to claim 1, comprising, based on the weight of the composition: 0.5 to 4 wt. %, preferably 0.5 to 2 wt. % of a) at least one epoxysilane oligomer according to formula (AI); 15 to 75% by weight, preferably 20 to 70% by weight, of b) at least one polyepoxide having at least three epoxy groups per molecule; 0 to 15 wt %, preferably 0 to 10 wt % of c) at least one compound selected from monoepoxides and diepoxides; 10 to 30 wt %, preferably 15 to 30 wt % of d) the curing agent; and 5 to 25 wt %, preferably 10 to 25 wt % of e) the core-shell rubber particles, in, The two-component (2K) composition is also characterized by a molar ratio of epoxy-reactive groups to epoxy groups of 0.95:1 to 1.1:

1.

4. A two-component (2K) composition according to any one of claims 1 to 3, wherein: a) The at least one epoxysilane oligomer is characterized by a number average molecular weight (Mn) of 200 to 3000 Daltons.

5. The two-component (2K) composition according to any one of claims 1 to 4, wherein: Part a) of the composition comprises or consists of at least one compound according to formula (AII) composition: Wherein: L is an integer from 0 to 20; and R k It is a C1-C6 alkyl group.

6. The two-component (2K) composition according to claim 5, wherein: L is an integer from 1 to 10; and R k It is a C1-C4 alkyl group.

7. A two-component (2K) composition according to any one of claims 1 to 6, wherein: b) the at least one polyepoxide having at least three epoxy groups per molecule is selected from the group consisting of: glycidyl ethers of polyols; Glycidyl ethers of polyphenols; glycidyl esters of polycarboxylic acids; polyfunctional glycidyl amines; and epoxidized polyethylenically unsaturated hydrocarbons.

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 glycidylamine selected from: N,N,N',N'-tetraglycidyl-4,4'methylenedianiline; p-aminophenol triglycidyl ether; m-aminophenol triglycidyl ether; tetraglycidylbis(aminomethyl)cyclohexane; and N,N,N',N'-tetraglycidyl-m-xylenediamine.

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

10. The two-component composition according to claim 9, wherein: The at least one diepoxide is selected from the group consisting of: glycidyl ethers of diols; glycidyl ethers of diphenols; 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 curing agent is a phenalkamine.

12. A two-component (2K) composition according to any one of claims 1 to 11, wherein: The or each alicyclic amine of the curing agent is selected from: 1,2-, 1,3- and 1,4-diaminocyclohexane; di(4-aminocyclohexyl)methane; di(4-amino-3-methylcyclohexyl)methane; di(4-amino-3-ethylcyclohexyl)methane; di(4-amino-3,5-dimethylcyclohexyl)methane; di(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 (norbornane diamine, 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- Alkanediamine.

13. A two-component (2K) composition according to any one of claims 1 to 12, wherein: At least a portion of the core-shell rubber particles are provided in the first component of the composition.

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

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

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