Two-component (2K) epoxy formulations

Abstract

The present invention comprises, based on the weight of the first component, a) i) 80 to 100 wt. % of at least one partially (meth)acrylated epoxy resin; a)ii) 0 to 20% by weight of at least one epoxy resin different from said resin a)i). A first component including b) a second component comprising at least one polyamine having at least two amine hydrogens reactive towards epoxy groups; Including, The present invention relates to a two-component (2K) curable composition, characterized in that the ratio of the amine hydrogen equivalent of the at least one polyamine (b) to the total equivalent of epoxy groups and acrylate groups of the first component (a) is 0.5:1 to 1.05:1.

Description

[Technical field]

[0001] The present invention relates to a two-component (2K) curable composition based on a partially (meth)acrylated epoxy resin. More particularly, the present invention is directed to a two-component (2K) curable composition having a fast gel time, characterized in that it comprises a partially (meth)acrylated epoxy resin in the first component and an amine-functional hardener in the second component. [Background technology]

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

[0003] Recognized for their versatility, properly cured epoxy resins possess several other properties including, among others, excellent chemical resistance, especially to alkaline environments; high tensile and compressive strength; high fatigue strength; low shrinkage upon cure; cure performance over a wide temperature range; electrical insulating properties and their retention upon aging or environmental exposure.

[0004] Although in certain circumstances the use of epoxy resins to obtain the above-mentioned advantages may be beneficial, known epoxy resin systems can be difficult to use in practice because they do not gel, i.e. transition from liquid to solid-like behavior, quickly enough. For example, rapid gelation is required when an epoxy resin system is deposited on a vertical substrate or on the underside of a horizontal substrate, otherwise the resin system will drip or run off the substrate surface before it has cured sufficiently to support its own weight. Similarly, additive manufacturing processes in which a curable composition is deposited on a substrate in layers require a sufficiently fast gelation to prevent the collapse of the layered structure obtained after deposition.

[0005] In such cases, the gel time of the curable composition may be shortened by increasing the temperature of the epoxy resin system and / or the substrate. However, the application of heat or the high temperatures required to obtain a sufficiently short gel time may not always be practical. Therefore, the present inventors have focused on shortening the gel time by selecting a specific epoxy resin and curing agent that react quickly at low temperatures.

[0006] For such curable compositions, gelation is believed to be a heterogeneous process. As the polymerization proceeds, microgels can be obtained in the form of crosslinked polymer coils swollen with unreacted monomers. The size and concentration of these polymer coils increase until the growing molecules reach a mass sufficient to interconnect all the boundaries of the system, a process called macro-gelation. Curable compositions that are said to have a curing schedule characterized by short gelation times have already been presented by certain authors.

[0007] European Patent Application Publication No. 0502611 (Morton International Incorporated) describes a two-component (2K) curable epoxy composition comprising (a) 100 parts by weight of an epoxy-containing resin having an epoxy functionality of 2 or greater, (b) 1-100 parts by weight of a Lewis base curing agent for said epoxy-containing resin, (c) 10-100 parts by weight of a component having an acrylate functionality of 2 or greater, and (d) 5-100 parts by weight of a component having a mercaptan functionality of 2 or greater, said components (c) and (d) having a sum of the acrylate functionality and the mercaptan functionality of at least 4.5 or greater, said components (c) and (d) rapidly gel in the presence of said Lewis base (b) prior to substantial curing of said component (a) in the presence of said Lewis base (b). In the composition, components (a) and (c) are packaged together and said components (b) and (d) are packaged together.

[0008] U.S. Patent Application Publication No. 2017 / 369635 (Colson et al.) discloses a first component comprising: a1) an epoxy resin having an average of 1.8 to 6 epoxy groups per molecule and an epoxy equivalent of 150 to 300; a2) 3 to 20 parts by weight per 100 parts by weight of component a1) of a polyacrylate having an average of 2 to 8 acrylate groups per molecule and an acrylate group equivalent of 80 to 250; and a3) 0 to 10 parts by weight per 100 parts by weight of component a1). and, in the second component, b1) an amine hardener having an average of 2-8 amine hydrogens per molecule and an amine hydrogen equivalent of 15-100; and b2) a thiol hardener having an average of 2-8 thiol groups per molecule and a thiol group equivalent of 50-300. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] European Patent Application Publication No. 0502611 [Patent Document 2] US Patent Application Publication No. 2017 / 369635 Summary of the Invention [Problem to be solved by the invention]

[0010] All the above mentioned documents present complex formulations. It is believed that there is a need in the art to prepare alternative, ideally less complex, curable compositions based on epoxy resins, which present short curing times, but which do not compromise the cured products with regard to their physicochemical properties. [Means for solving the problem]

[0011] According to a first aspect of the present invention, based on the weight of the first component, a) i) 80-100% by weight, preferably 90-100% by weight, of at least one partially (meth)acrylated epoxy resin; a)ii) 0 to 20% by weight, preferably 0 to 10% by weight, of at least one epoxy resin different from said resin a)i). A first component including b) a second component comprising at least one polyamine having at least two amine hydrogens reactive towards epoxy groups; Including, There is provided a two-component (2K) curable composition, characterized in that the ratio of the amine hydrogen equivalent of the at least one polyamine (b) to the total equivalent of epoxy groups and acrylate groups of the first component (a) is from 0.5:1 to 1.05:1, preferably from 0.8:1 to 1.0:1.

[0012] The curable compositions defined herein may achieve gel times of less than 10 minutes, such as less than 5 minutes, measured at 25°C.

[0013] In one embodiment, the ratio of epoxy groups to (meth)acrylate groups in the or each partially (meth)acrylated epoxy resin a)i) is from 1:1 to 1:3, such as from 1:1 to 1:2. Additionally or alternatively, the partially (meth)acrylated epoxy resin a)i) is preferably a liquid having a viscosity in the range of 1000 to 1,000,000 centipoise (cps), such as 2500 to 750,000 cps, measured at 25°C.

[0014] It is preferred that component a)i) of the composition comprises at least one partially (meth)acrylated epoxy resin, the epoxy resin being selected from diepoxide compounds having an epoxy equivalent of less than 500 g / eq. In particular, fast gel times are achieved when component a)i) comprises at least one partially (meth)acrylated epoxy resin, the epoxy resin being selected from the group consisting of bisphenol A based diglycidyl ethers; hydrogenated bisphenol A based diglycidyl ethers; bisphenol A epichlorohydrin based epoxy resins; bisphenol F diglycidyl ethers; and hydrogenated bisphenol F based diglycidyl ethers.

[0015] According to a second aspect of the present invention there is provided a cured product obtainable from a two-component (2K) curable composition as defined hereinbefore and in the accompanying claims. The present invention also provides the use of the cured reaction product as a coating, adhesive or sealant. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] <Definition> As used herein, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise.

[0017] As used herein, the terms "comprising," "comprises," and "comprised of" are synonymous with "including," "includes," "containing," or "contains," and are inclusive or open-ended and do not exclude additional, unrecited materials, elements, or method steps. When used, the phrase "consisting of" is closed and excludes all additional elements. Furthermore, the phrase "consisting essentially of" excludes additional material elements, but allows for the inclusion of non-material elements that do not materially alter the nature of the invention.

[0018] When an amount, concentration, dimension, or other parameter is expressed in the form of a range, preferred range, upper limit, lower limit, or preferred upper limit and limit, any range obtained by combining any upper limit or preferred value with any lower limit or preferred value is to be understood as also specifically disclosed, whether or not the resulting range is expressly referred to in the context.

[0019] Furthermore, in accordance with standard understanding, a weight range expressed as "0 to x" specifically includes 0 wt.%. A component defined by the range may be absent from the composition or may be present in the composition in an amount up to x wt.%. Similarly, a weight range expressed as "y to 100 wt.%" specifically includes 100 wt.% and the component defined by the range may be the only component present.

[0020] The words "preferred," "preferably," "desirably," and "particularly," and their synonyms, are used frequently herein to direct attention to embodiments of the present disclosure that may afford particular advantages, under certain circumstances. However, the recitation of one or more preferred, preferred, desirable, or particular embodiments does not imply that other embodiments are not useful, and is not intended to exclude such other embodiments from the scope of the present disclosure.

[0021] As used in this application, the word "may" is used in its permissive rather than obligatory sense, i.e., it means there is a possibility.

[0022] As used herein, room temperature is 23° C. plus or minus 2° C. As used herein, "ambient conditions" refers to the temperature and pressure surrounding the composition or coating layer or substrate on which the coating layer is disposed.

[0023] As used herein, the term "equivalents (eq.)," as is often the case in chemical notation, relates to the relative numbers of reactive groups present in a reaction.

[0024] The term "equivalent weight" as used herein means molecular weight divided by the corresponding functionality. Thus, "epoxy equivalent weight" (EEW) means the weight in grams of a resin containing one equivalent of epoxy. Similarly, "amine hydrogen equivalent weight" (AHEW) is the weight in grams of an organic amine containing one amine hydrogen.

[0025] As used herein, the term "monofunctional" means having one polymerizable site. As used herein, the term "multifunctional" means having two or more polymerizable sites.

[0026] As used herein, the term "epoxide" refers to a compound characterized by the presence of at least one cyclic ether group, i.e., a group in which an ether oxygen atom is bonded to two adjacent carbon atoms, thereby forming a cyclic structure. The term is intended to encompass monoepoxide compounds, polyepoxide compounds (having two or more epoxide groups), and epoxide-terminated prepolymers. The term "monoepoxide compound" is meant to refer to an epoxide compound having one epoxy group. The term "polyepoxide compound" is meant to refer to an epoxide compound having at least two epoxy groups. The term "diepoxide compound" is meant to refer to an epoxide compound having two epoxy groups.

[0027] The epoxides may be unsubstituted or inertly substituted. Exemplary inert substituents include chlorine, bromine, fluorine and phenyl.

[0028] As used herein, "(meth)acrylic" is a contraction that refers to "acrylic" and / or "methacrylic." Thus, the term "(meth)acrylate" refers collectively to acrylates and methacrylates.

[0029] As used herein, "C1-C n An "alkyl" group refers to a monovalent group containing 1 to n carbon atoms. It is an alkane group, including linear and branched organic groups. Thus, a "C1-C8 alkyl" group refers to a monovalent group containing 1 to 8 carbon atoms, which is an alkane group, including linear and branched organic groups. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, and 2-ethylhexyl. In the present invention, such alkyl groups may be unsubstituted or substituted with one or more substituents selected from halogen, hydroxy, nitrile (-CN), amido, and amino (-NH2). When applicable, the specification will specify the selection of the given substituents.

[0030] "C3-C 30 The term "cycloalkyl" is understood to mean an optionally substituted, saturated, monocyclic, bicyclic or tricyclic hydrocarbon group having 3 to 30 carbon atoms. Generally, cycloalkyl groups (C3-C4) containing 3 to 10 carbon atoms are 18 It is particularly noted that a cycloalkyl group is selected. Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantane, and norbornane. In the present invention, such a cycloalkyl group may be unsubstituted or substituted with one or more substituents selected from halogen, C1-C6 alkyl, and C1-C6 alkoxy.

[0031] As used herein, "aralkyl group" refers to a C6-C 18"Aryl" refers to optionally substituted monocyclic, bicyclic and tricyclic ring systems in which the monocyclic ring system is aromatic or at least one of the rings of the bicyclic or tricyclic ring system is aromatic. Bicyclic and tricyclic ring systems include benzo-fused 2-3 membered carbocyclic rings. In the present invention, such aryl groups may be unsubstituted or substituted with one or more substituents selected from halogen, C1-C6 alkyl and C1-C6 alkoxy. Exemplary aryl groups include phenyl; (C1-C4)alkoxyphenyl, such as methoxyphenyl; (C1-C4)alkylphenyl, such as tolyl and ethylphenyl; indenyl; naphthalenyl, tetrahydronaphthyl, tetrahydroindenyl; tetrahydroanthracenyl; and anthracenyl. The choice of phenyl group may be noted.

[0032] As used herein, "C2-C 12 "Alkenyl" refers to a hydrocarbyl group having from 2 to 12 carbon atoms and at least one unit of ethylenic unsaturation. Alkenyl groups may be straight chained, branched chain or cyclic, and may be substituted. The term "alkenyl" also embraces groups having "cis" and "trans" configurations, or "E" and "Z" configurations, as will be understood by those of skill in the art. In general, however, groups having from 2 to 10 (C 2-10 ) or 2 to 8 (C 2-8 Of particular note is the preference for unsubstituted alkenyl groups containing C2-C 12Examples of alkenyl groups are -CH=CH2;-CH=CHCH3;-CH2CH=CH2;-C(=CH2)(CH3);-CH=CHCH2CH3;-CH2CH=CHCH3;-CH2CH2CH=CH2;-CH=C(CH3)2;-CH2C(=CH2)(CH3);-C(=CH2)CH2CH3;-C(CH3)=CHC H3;-C(CH3)CH=CH2;-CH=CHCH2CH2CH3;-CH2CH=CHCH2CH3;-CH2CH2CH=CHCH3;-CH2CH2CH2CH=CH2;-C(=CH2)CH2CH2CH3;-C(CH3)=CHCH2CH3;-CH(CH3)CH=CHCH;-CH(CH3)CH2CH=CH2; These include, but are not limited to, -CH2CH=C(CH3)2; 1-cyclopent-1-enyl; 1-cyclopent-2-enyl; 1-cyclopent-3-enyl; 1-cyclohex-1-enyl; 1-cyclohex-2-enyl; and 1-cyclohexyl-3-enyl.

[0033] As used herein, "alkylaryl" refers to an alkyl-substituted aryl group, and "substituted alkylaryl" refers to an alkylaryl group further bearing one or more substituents as defined above. Additionally, as used herein, "aralkyl" refers to an alkyl group substituted with an aryl group as defined above. Exemplary aralkyl groups include benzyl, 4-methoxybenzyl, and phenethyl.

[0034] The term "hetero" as used herein refers to groups or moieties that contain one or more heteroatoms, such as N, O, Si, and S. Thus, for example, "heterocyclic" refers to cyclic groups having, for example, N, O, Si, or S as part of the ring structure. "Heteroalkyl" and "heterocycloalkyl" moieties are alkyl and cycloalkyl groups, as defined above, that contain N, O, Si, or S, respectively, as part of their structure.

[0035] As used herein, the term "catalytic amount" refers to a sub-stoichiometric amount of catalyst relative to a reactant, unless expressly stated.

[0036] As used herein, a "primary amino group" refers to an NH group bonded to an organic group, and a "secondary amino group" refers to an NH group bonded to two organic groups, both of which may also be part of a ring. Thus, the term "tertiary amine" refers to a nitrogen having a moiety where the nitrogen atom is not bonded to a hydrogen atom. As used herein, the term "amine hydrogen" refers to the hydrogen atom of primary and secondary amino groups.

[0037] As used herein, "anhydrous" means that the relevant composition contains less than 0.25% by weight of water. For example, the composition may contain less than 0.1% by weight of water or may be completely free of water. The term "essentially solvent-free" should be inferred by analogy to mean that the relevant composition contains less than 0.25% by weight of solvent.

[0038] Molecular weights referred to herein can be determined by gel permeation chromatography (GPC) according to ASTM 3536 using polystyrene calibration standards.

[0039] The viscosity of the coating compositions described herein is measured using a Brookfield viscometer at standard conditions of 25° C. and 50% relative humidity (RH) unless otherwise specified. The calibration method, spindle type and rotation speed of the Brookfield viscometer are selected according to the manufacturer's instructions to suit the composition being measured.

[0040] As used herein, unless otherwise specified, "gel time" means the time required for mixed components to reach the gel point at 25° C. As used herein, the "gel point" is the point at which the storage modulus of a mixture exceeds its loss modulus.

[0041] Unless otherwise specified, the term "particle size" refers to the largest axis of the particle. For spherical particles, the largest axis is generally the diameter.

[0042] As used herein, the term "average particle size" (D50) refers to the particle size at which 50% of the sample particles' volume is greater than the stated D50 value and 50% of the sample particles' volume is less than the stated D50 value. Similarly, as used, the term "D90" refers to the particle size at which 90% of the sample particles' volume is less than the stated D90 value and 10% of the sample particles' volume is greater than the stated D90 value.

[0043] All documents cited herein are incorporated by reference in their entirety.

[0044] <First component> a)i) Partially acrylated epoxy resin The first component of the composition comprises 80-100 wt. % of a)i) the at least one partially (meth)acrylated epoxy resin, based on the weight of the first component. The first component may, for example, comprise 85-100 wt. % or 90-100 wt. % of a)i) the at least one partially (meth)acrylated epoxy resin.

[0045] Each of the partially (meth)acrylated epoxy resins contained in this component should be characterized by at least one, and preferably both, of the following: the ratio of epoxide groups to (meth)acrylate groups is from 1:1 to 1:3, preferably from 1:1 to 1:2; and the resin is a liquid having a viscosity in the range of 1000 to 1,000,000 centipoise (cps), e.g., 2500 to 750,000 cps, measured at 25°C.

[0046] As is known in the art, partially (meth)acrylated epoxy resins a)i) can be obtained by reacting a suitable epoxide compound with acrylic or methacrylic acid, and therefore such resins necessarily contain (meth)acryloxy groups at the ends of the molecule and β-hydroxyl groups in the main chain of the molecule.

[0047] The epoxide compound, which is the reactant, must have two or more epoxy groups in its molecule. Although not intended to limit the present invention, a suitable polyepoxide compound may be liquid and preferably has an epoxy equivalent weight of 100 to 700 g / eq, for example 120 to 320 g / eq. Also, generally, diepoxide compounds having an epoxy equivalent weight of less than 500 g / eq, or even 400 g / eq, are preferred. This is mainly advantageous in terms of cost, since the purification process is more limited in the production of low molecular weight epoxy resins.

[0048] Examples of classes or groups of polyepoxide compounds which may be reacted to form component a)i) include glycidyl ethers of polyhydric alcohols and polyhydric phenols; glycidyl esters of polycarboxylic acids; and epoxidized polyethylenically unsaturated hydrocarbons.

[0049] Suitable diglycidyl ether compounds may be aromatic, aliphatic or cycloaliphatic in nature and such may be derived from dihydric phenols and dihydric alcohols. Useful classes of such diglycidyl ethers are as follows: diglycidyl ethers of aliphatic and cycloaliphatic diols, such as 1,2-ethanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 1,8-octanediol, 1,12-dodecanediol, cyclopentanediol, cyclohexanediol, cyclohexanedimethanol; resorcinol diglycidyl ether; pyrocatechol diglycidyl ether; hydroquinone diglycidyl ether; diglycidyl ethers; bisphenol A diglycidyl ethers; hydrogenated bisphenol A diglycidyl ethers; bisphenol A epichlorohydrin-based epoxy resins; bisphenol F diglycidyl ethers; hydrogenated bisphenol F diglycidyl ethers; 4,4'-dihydroxydiphenyl sulfone (bisphenol S) diglycidyl ethers; polyalkylene glycol diglycidyl ethers, especially polypropylene glycol diglycidyl ether; and polycarbonate diol glycidyl ethers. Other suitable diepoxides that may also be mentioned are: diepoxides of doubly unsaturated fatty acid C1-C18 alkyl esters; dimer acid diglycidyl esters; O-phthalic acid diglycidyl; isophthalic acid diglycidyl ester; terephthalic acid diglycidyl ester; tetrahydrophthalic acid diglycidyl ester; hexahydrophthalic acid diglycidyl ester; adipic acid diglycidyl ester; butadiene dipoxide; polybutadiene diglycidyl ether; vinylcyclohexene dipoxide; and limonene dipoxide.

[0050] Further exemplary polyepoxide compounds having utility in the present invention include: phenol novolac type epoxy resins; cresol novolac type epoxy resins; diglycidyl ethers; glycidyl glycidate; glycerol polyglycidyl ether; bis(2,3-epoxy-2-methylpropyl)ether; trimethylolethane triglycidyl ether; trimethylolpropane polyglycidyl ether; pentaerythritol polyglycidyl ether; diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether; sorbitol polyglycidyl ether; propoxylated glycerol polyglycidyl ether; polyglycidyl ethers of castor oil, epoxidized propylene glycol diolate, 1,2-tetradecane oxide, internally epoxidized 1,3-butadiene homopolymer.

[0051] Exemplary commercially available polyepoxide compounds that can be used in preparing the partially (meth)acrylated epoxy resins a)i) include, but are not limited to, novolac resins such as the EPIKOTE™ and EPON™ series of resins available from Hexion, and DEN™ 438 available from Dow Chemical Company; bisphenol A epoxy resins such as DER™ 331 and DER™ 383; bisphenol F epoxy resins such as DER™ 354; and bisphenol A / F epoxy resin blends such as DER™ 353.

[0052] The reaction with the epoxide compound or the compound containing acrylic or methacrylic acid is preferably carried out in bulk, but can be carried out in a suitable inert solvent, examples of which include butyl acetate, toluene, cyclohexane, or mixtures thereof. In general, the reaction temperature is 60-150° C., and heating is carried out for 30 minutes to 3 hours. However, a person skilled in the art can select suitable heating conditions depending on the molecular weight of the epoxide compound to be reacted. Furthermore, the reaction is carried out in the presence of a suitable catalyst, which can be mentioned in particular as follows: tertiary amines; quaternary ammonium salts such as tetraethylammonium chloride, tetraethylammonium bromide, tetrabutylammonium chloride and tetrabutylammonium bromide; alkali metal hydroxides; alkali metal salts of carboxylic acids; mercaptans; dialkyl sulfides; sulfonium compounds; phosphonium compounds; and phosphines. The amount of catalyst of such compounds can also be determined by a person skilled in the art, but will typically be in the range of 0.01-5% by weight, based on the weight of the epoxide compound.

[0053] To prevent undesired polymerization of the partially (meth)acrylated epoxy resin, the above reaction may be carried out in the presence of at least one polymerization inhibitor. The at least one polymerization inhibitor may typically be 0.0005 to 0.25 wt.% of the total reaction mixture. Exemplary polymerization inhibitors that may be used alone or in combination also include, but are not limited to, those described in EP 1935860 A1; EP 0965619 A; DE 10 201 1 077 248 B1; DE 199 56 509; and DE 19531649 A1. The epoxide compound and (meth)acrylic acid should be reacted in approximately stoichiometric ratios based on the desired degree of (meth)acrylation. Thus, in this specification, the reactants should provide 0.50 to 0.75 equivalents of (meth)acrylic acid per epoxy equivalent. The conversion of epoxy groups during the reaction is in any case continuously measured by titration of the epoxy groups according to DIN 16945 Resins, hardeners and accelerators, and catalyst resins tests (1989-03), and the reaction should be continued until at least 50% of said epoxy groups have reacted.

[0054] Apart from the above reactions, compound a)i) can be obtained commercially. Examples of commercially available partially (meth)acrylated epoxy resins include, but are not limited to, 4HBAGE (4-hydroxybutyl (meth)acrylate glycidyl ether) from Nippon Kasei Chemical Industry Co., Ltd. In addition, examples of the commercially available products include, but are not limited to, EA-1010N, EA-1010LC, and EA-1010NT (partially (meth)acrylated bisphenol A type epoxy resins) manufactured by Shin-Nakamura Chemical Co., Ltd.; EBECRYL (registered trademark) resins such as UVACURE1561 manufactured by Daicel Allnex and EBECRYL (registered trademark) 600, 605, 608, 3700, 3701, 3701-20T, 3708, 3720, 3720-HD20, 3720-TM20, 3720-TM40, 3720-TP25, 3720-TP40, 3605, and 3730-TP20 manufactured by UCB Radcure; and ENA or ENC (partially (meth)acrylated novolac type epoxy resins) manufactured by Kagawa Chemical Co., Ltd.

[0055] a)ii) Other ingredients The first component of the two-component (2K) composition may optionally comprise a supplementary epoxide compound to those defined above as compound a)i), in an amount of up to 20% by weight based on the weight of said first component. Said supplementary epoxy compound a)ii) may for example constitute 0-15% by weight, preferably 0-10% by weight, more preferably 0-5% by weight of the first component of the composition.

[0056] Epoxy resins as used herein can include monofunctional epoxy resins, multifunctional (multi- or polyfunctional) epoxy resins, and combinations thereof. Epoxy resins can be pure compounds, but also mixtures of epoxy-functional compounds, such as mixtures of compounds having different numbers of epoxy groups per molecule. Epoxy resins can be saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or heterocyclic, and can be substituted. Furthermore, epoxy resins can be monomeric or polymeric.

[0057] Without intending to limit the invention, exemplary monoepoxide compounds include the following: alkylene oxides; epoxy-substituted alicyclic hydrocarbons such as cyclohexene oxide, vinylcyclohexene monoxide, (+)-cis-limonene oxide, (+)-cis,trans-limonene oxide, (-)-cis,trans-limonene oxide, cyclooctene oxide, cyclododecene oxide and α-pinene oxide; epoxy-substituted aromatic hydrocarbons; monoepoxy-substituted alkyl ethers of monohydric alcohols or phenols such as the glycidyl ethers of aliphatic, alicyclic and aromatic alcohols; monoepoxy-substituted alkyl esters of monocarboxylic acids such as the glycidyl esters of aliphatic, alicyclic and aromatic monocarboxylic acids; monoepoxy-substituted alkyl esters of polycarboxylic acids in which the other carboxy group is esterified with an alkanol; alkyl and alkenyl esters of epoxy-substituted monocarboxylic acids; epoxy alkyl ethers of polyhydric alcohols in which the other OH group is esterified or etherified with a carboxylic acid or alcohol; and monoesters of polyhydric alcohols and epoxy monocarboxylic acids in which the other OH group is esterified or etherified with a carboxylic acid or alcohol.

[0058] By way of example, the following glycidyl ethers may be mentioned as particularly suitable monoepoxide compounds for use herein: methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, cyclohexyl glycidyl ether, octyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, benzyl glycidyl ether, phenyl glycidyl ether, 4-tert-butylphenyl glycidyl ether, 1-naphthyl glycidyl ether, 2-naphthyl glycidyl ether, 2-chlorophenyl glycidyl ether, 4-chlorophenyl glycidyl ether, 4-bromophenyl glycidyl ether, 2,4,6-trichlorophenyl glycidyl ether, 2,4,6-tribromophenyl glycidyl ether, pentafluorophenyl glycidyl ether, o-cresyl glycidyl ether, m-cresyl glycidyl ether, and p-cresyl glycidyl ether.

[0059] In one important embodiment, the monoepoxide compound conforms to formula (III) herein below. TIFF2024500835000001.tif30141 (in the formula, R 2 , R 3 , R 4 and R 5 may be the same or different and are independently hydrogen, a halogen atom, a C1-C8 alkyl group, a C3-C 10 Cycloalkyl groups, C2-C 12 Alkenyl, C6-C 18 Aryl group or C7-C 18 aralkyl groups, where R 3 and R 4 At least one of is not hydrogen.)

[0060] R 2 , R 3 and R 5 is hydrogen, and R 4is preferably a phenyl group or a C1-C8 alkyl group, more preferably a C1-C4 alkyl group.

[0061] With regard to this embodiment, exemplary monoepoxides include ethylene oxide, 1,2-propylene oxide (propylene oxide); 1,2-butylene oxide; cis-2,3-epoxybutane; trans-2,3-epoxybutane; 1,2-epoxypentane; 1,2-epoxyhexane; 1,2-heptylene oxide; decene oxide; butadiene oxide; isoprene oxide; and styrene oxide.

[0062] In the present invention, reference is made to the use of at least one monoepoxide compound selected from the group consisting of ethylene oxide; propylene oxide; cyclohexene oxide; (+)-cis-limonene oxide; (+)-cis, trans-limonene oxide; (-) cis, trans-limonene oxide; cyclooctene oxide; and cyclododecene oxide.

[0063] Again, without intending to limit the invention, suitable polyepoxide compounds can be liquid, solid, or in solution in a solvent. Moreover, such polyepoxide compounds should have an epoxide equivalent weight of 100-700 g / eq, for example, 120-320 g / eq. Furthermore, diepoxide compounds having an epoxide equivalent weight of less than 500 g / eq, even less than 400 g / eq, are generally preferred. This is mainly from the standpoint of cost, as in their manufacture, low molecular weight epoxy resins require more limited processing in purification.

[0064] Examples of types or groups of polyepoxy compounds which may be polymerized in the present invention include glycidyl ethers of polyhydric alcohols and polyhydric phenols; glycidyl esters of polycarboxylic acids; and epoxidized polyethylenically unsaturated hydrocarbons.

[0065] Suitable diglycidyl ether compounds may be aromatic, aliphatic, or cycloaliphatic in nature, and may be derived from dihydric phenols and dihydric alcohols. Useful classes of such diglycidyl ethers are the diglycidyl ethers of aliphatic and cycloaliphatic diols, such as 1,2-ethanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 1,8-octanediol, 1,12-dodecanediol, cyclopentanediol, cyclohexanediol, cyclohexanedimethanol; resorcinol diglycidyl ether; pyrocatechol diglycidyl ether; hydroquinone diglycidyl ether; bisphenol A-based diglycidyl ethers; bisphenol A epichlorohydrin-based epoxy resins; bisphenol F diglycidyl ether; polyalkylene glycol-based diglycidyl ethers, particularly polypropylene glycol diglycidyl ether; and polycarbonate diol-based glycidyl ethers. Further suitable diepoxides which may be mentioned include diunsaturated fatty acid C1-C 18 dimer acid diglycidyl ester; diglycidyl o-phthalate; diglycidyl isophthalate; terephthalic acid diglycidyl ester; tetrahydrophthalic acid diglycidyl ester; hexahydrophthalic acid diglycidyl ester; adipic acid diglycidyl ester; butadiene diepoxide; polybutadiene diglycidyl ether; vinylcyclohexene diepoxide; and limonene diepoxide.

[0066] Further exemplary polyepoxide compounds having utility in the present invention include diglycidyl ethers; glycidyl glycidate; glycerol polyglycidyl ether; bis(2,3-epoxy-2-methylpropyl)ether; trimethylolethane triglycidyl ether; trimethylolpropane polyglycidyl ether; pentaerythritol polyglycidyl ether; diglycerol polyglycidyl ether; polyglycerol polyglycidyl ether; sorbitol polyglycidyl ether; propoxylated glycerol polyglycidyl ether; polyglycidyl ether of castor oil; epoxidized propylene glycol diolate; 1,2-tetradecane oxide; and internally epoxidized 1,3-butadiene homopolymer.

[0067] Also highly preferred examples of polyepoxy compounds include flexible epoxy resins available as Heloxy™ Modifier Numbers 32, 44, 56, 67, 68, 69, 71, 84, 107 and 505 available from Shell Chemical Company; epoxy novolac resins such as the EPIKOTE™ and EPON™ series of resins available from Hexion, and DEN™ 438 available from Dow Chemical Company; bisphenol A epoxy resins such as DER™ 331 and DER™ 383; bisphenol F epoxy resins such as DER™ 354; bisphenol A / F epoxy resin blends such as DER™ 353; aliphatic glycidyl ethers such as DER™ 736; polypropylene glycol diglycidyl ethers such as DER™ 732; solid bisphenol A epoxy resins such as DER™ 661 and DER™ 664. UE, etc.; solutions of bisphenol A solid epoxy resins, such as DER™ 671-X75; castor oil triglycidyl ethers, such as ERISYS™ GE-35H; polyglycerol-3-polyglycidyl ethers, such as ERISYS™ GE-38; sorbitol glycidyl ethers, such as ERISYS™ GE-60; and Poly BD 600, Poly BD 650, Vikoflex™ 4050 and Vikoflex™ 5075 available from Elf Atochem.

[0068] Alternatively, in certain embodiments, the composition may include a glycidoxyalkylalkoxysilane having the formula: TIFF2024500835000002.tif18104 (wherein each R is independently selected from methyl or ethyl, and n is 1 to 10.)

[0069] Exemplary epoxy-functional silanes include, but are not limited to, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxyethyltrimethoxysilane, gamma-glycidoxymethyltrimethoxysilane, gamma-glycidoxymethyltriethoxysilane, gamma-glycidoxyethyltriethoxysilane, gamma-glycidoxypropyltriethoxysilane, and 8-glycidoxyoctyltrimethoxysilane. If present, the epoxy-functional silanes should comprise 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 compound.

[0070] Based on the above composition ranges, it is clear that the first component of the composition may be composed of compound a)i) independently or may be composed of a combination of compound a)i) and epoxide compound a)ii). However, in some embodiments, further resin components and / or auxiliary components may be present in the first component, as long as the composition ranges defined above for components a)i) and a)ii) are met. In this respect, 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 disclosures of the following references may be of reference in disclosing suitable cyclic carbonate-functional compounds: U.S. Pat. No. 3,535,342, U.S. Pat. No. 4,835,289, U.S. Pat. No. 4,892,954, GB Patent Publication No. 1,485,925, and EP Patent Publication No. 0119840. However, such cyclic comonomers should constitute less than 10 weight percent, preferably less than 7.5 weight percent, or even less than 5 weight percent, based on the total weight of epoxide-functional compounds in the first component.

[0071] <Second component> The curable component comprises b) at least one polyamine having at least two amine hydrogen atoms reactive towards epoxy groups, the at least one polyamine having at least two amine hydrogen atoms reactive towards epoxy groups in particular comprising primary and / or secondary amine groups and having an amine hydrogen equivalent weight of 150 g / eq or less, preferably 125 g / eq or less, more preferably 100 g / eq or less.

[0072] Suitable polyamines, which may be used alone or in combination, include, but are not limited to, the following:

[0073] i) aliphatic, cycloaliphatic or arylaliphatic primary diamines, examples of which include: 2,2-dimethyl-1,3-propanediamine; 1,3-pentanediamine (DAMP); 1,5-pentanediamine; 1,5-diamino-2-methylpentane (MPMD); 2-butyl-2-ethyl-1,5-pentanediamine (C11-neodiamine); 1,6-hexanediamine (hexamethylenediamine, HMDA); 2,5-dimethyl-1,6-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; 1,2-, 1,3- and 1,4-diaminocyclohexanediamine. San;Bis(4-aminocyclohexyl)methane;Bis(4-amino-3-methylcyclohexyl)methane;Bis(4-amino-3-ethylcyclohexyl)methane;Bis(4-amino-3,5-dimethylcyclohexyl)methane;Bis(4-amino-3-ethyl-5-methylcyclohexyl)methane;1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (isophoronediamine, IPDA);2- and / or 4-methyl-1,3-diaminocyclohexane;1,3-Bis(aminomethyl)-cyclohexane;1,4-Bis(aminomethyl)cyclohexane;2,5(2,6)-Bis(aminomethyl)-bicyclo[2.2.1]heptane (norbornanediamine, NBDA);3(4),8(9)-Bis(aminomethyl)tricyclo[5.2.1.0 2,6 ]-decane (TCD-diamine); 1,4-diamino-2,2,6-trimethylcyclohexane (TMCDA); 1,8-menthanediamine; 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5.5]undecane; and 1,3-bis(aminomethyl)benzene (MXDA).

[0074] ii) tertiary amine group-containing polyamines having two or three primary aliphatic amine groups, of 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)cyclohexylamine; N,N-bis(3-aminopropyl)-2-ethyl-hexylamine; tris(2-aminoethyl)amine; tris(2-aminopropyl)amine; tris(3-aminopropyl)amine; and products from the double cyanoethylation and subsequent reduction of fatty amines derived from natural fatty acids, such as N,N-bis(3-aminopropyl)dodecylamine and N,N-bis(3-aminopropyl)tallow alkylamine, commercially available as Triameen® Y12D and Triameen® YT (Akzo Nobel).

[0075] iii) Ether group-containing aliphatic primary polyamines, of 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)polytetrahydrofuran and other polytetrahydrofuran diamines; 1,4-dimethylaminoethylamine; alicyclic ether group-containing diamines obtained from the propoxylation and subsequent amination of arylcyclohexane, such as the material commercially available as Jeffamine® RFD-270 (Huntsman); polyoxyalkylene diamines or triamines obtained as products from the amination of polyoxyalkylene diols and triols, available under the name Jeffamine® (Huntsman), Polyetheramines (BASF), or PCAmines® (Nitroil). Particularly suitable may be the use of Jeffamine® D-230, Jeffamine® D-400, Jeffamine® D-600, Jeffamine® D-2000, Jeffamine® D-4000, Jeffamine® T-403, Jeffamine® T-3000, Jeffamine® T-5000, Jeffamine® EDR-104, Jeffamine® EDR-148 and Jeffamine® EDR-176, as well as the corresponding amines from BASF or Nitroil.

[0076] iv) primary diamines containing secondary amine groups, examples of which include: 3-(2-aminoethyl)aminopropylamine, bis(hexamethylene)triamine (BHMT); diethylenetriamine (DETA); triethylenetetramine (TETA); tetraethylenepentamine (TEPA); pentaethylenehexamine (PEHA); higher homologues of linear polyethyleneamines, such as polyethylenepolyamines containing 5 to 7 ethyleneamine units (the so-called "high ethylenepolyamines", HEP A) and the like; products from multi-step cyanoethylation or cyanobutylation of primary diamines and polyamines having at least two primary amine groups followed by hydrogenation, such as dipropylenetriamine (DPTA), N-(2-aminoethyl)-1,3-propanediamine (N3-amine), N,N'-bis(3-aminopropyl)ethylenediamine (N4-amine), N,N'-bis(3-aminopropyl)-1,4-diaminobutane, N5-(3-aminopropyl)-2-methyl-1,5-pentanediamine, N3-(3-aminopentyl)-1,3-pentanediamine, N5-(3-amino-1-ethylpropyl)-2-methyl-1,5-pentanediamine, or N,N'-bis(3-amino-1-ethylpropyl)-2-methyl-1,5-pentanediamine.

[0077] v) Polyamines having one primary amino group and at least one secondary amino group, examples of which may be mentioned: N-butyl-1,2-ethanediamine; N-hexyl-1,2-ethanediamine; N-(2-ethylhexyl)-1,2-ethanediamine; N-cyclohexyl-1,2-ethanediamine; 4-aminomethyl-piperidine; N-(2-aminoethyl)piperazine (N-AEP); N-methyl-1,3-propanediamine; N-butyl- 1,3-propanediamine; N-(2-ethylhexyl)-1,3-propanediamine; N-cyclohexyl-1,3-propanediamine; 3-methylamino-1-pentylamine; 3-ethylamino-1-pentylamine; 3-cyclohexylamino-1-pentylamine; fatty diamines, such as N-cocoalkyl-1,3-propanediamine; primary aliphatic diamines reacted in a 1:1 molar ratio with acrylonitrile, maleic acid or fluorocarbons. Products from Michael-type addition reactions with malic acid diesters, citraconic acid diesters, acrylic and methacrylic acid esters, acrylic and methacrylic acid amides and itaconic acid diesters; products from partial reductive alkylation of primary polyamines with aldehydes or ketones, in particular the N-monoalkylation products of the aforementioned polyamines having two primary amine groups, in particular 1,6-hexanediamine, 1,5-diamino-2-methylpentane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)benzene, BHMT, DETA, TETA, TEPA, DPTA, N3-amines and N4-amines, where preferred alkyl groups are benzyl, isobutyl, hexyl, 2-ethylhexyl; and partially styrenated polyamines, such as those commercially available as Gaskamine® 240 (Mitsubishi Gas Chemical).

[0078] vi) Secondary diamines, in particular the aforementioned polyamines having two primary amine groups, in particular 1,6-hexanediamine, 1,5-diamino-2-methylpentane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)-cyclohexane, 1,3-bis(aminomethyl)benzene, BHMT, DETA, TETA, TEPA, DPTA, N,N'-dialkylation products of N3-amines or N4-amines, where preferred alkyl groups are 2-phenylethyl, benzyl, isobutyl, hexyl and 2-ethylhexyl.

[0079] vii) aromatic polyamines which may include: m- and p-phenylenediamine, 4,4'-, 2,4'- and 2,2'-diaminodiphenylmethane; 3,3'-dichloro-4,4'-diaminodiphenylmethane (MOCA); 2,4- and 2,6-tolylenediamine; a mixture of 3,5-dimethylthio-2,4- and -2,6-tolylenediamine (available from Albermarle as Ethacure® 300); a mixture of 3,5-diethyl-2,4- and -2,6-tolylenediamine (DETDA); 3,3',5,5'-tetraethyl-4,4'-diaminodiphenylmethane (M-DEA); 3,3',5,5'-tetraethyl-2,2'-dichloro-4,4'-diaminodiphenylmethane (M-CDEA); 3,3'-diisopropyl-5,5'-dimethyl-4,4'-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'-methylenedianthranilic acid; dimethyl-(5,5'-methylenedianthranilate); 1,3-propylene-bis(4-aminobenzoate); 1,4-butylene-bis(4-aminobenzoate); polytetramethylene oxide-bis(4-aminobenzoate) (available as Versalink® from AirProducts); 1,2-bis(2-aminophenylthio)ethane, 2-methylpropyl-(4-chloro-3,5-diaminobenzoate); and tert-butyl-(4-chloro-3,5-diaminobenzoate).

[0080] viii) Polyamidoamines comprising the reaction product of a mono- or polycarboxylic acid, or an ester or anhydride thereof, in particular a dimeric fatty acid, and an aliphatic, cycloaliphatic or aromatic polyamine, such as a polyalkyleneamine, for example DETA or TETA. Commercially available polyamidoamines include: Versamid® 100, 125, 140, and 150 (Cognis); Aradur® 223, 250, and 848 (Huntsman); Euretek® 3607 and 530 (Huntsman); and Beckopox® EH651, EH654, EH655, EH661, and EH663 (Cytec).

[0081] Among the aforementioned polyamines having at least two primary aliphatic amine groups, preferred are isophoronediamine (IPDA); hexamethylenediamine (HMDA); 1,3-bis(amino-methyl)cyclohexane; 1,4-bis(aminomethyl)cyclohexane; bis(4-amino-cyclohexyl)methane; bis(4-amino-3-methylcyclohexyl)methane; NBDA; and ether-containing polyamines having a number average molecular weight (Mn) of up to 500 g / mol. Among the aforementioned ether-containing polyamines, Jeffamine® D-230 and D-600 (available from Huntsman) are particularly preferred.

[0082] Among said polyamines having one primary amino group and at least one secondary amino group, preferred are 4-aminomethyl-piperidine and N-(2-aminoethyl)piperazine (N-AEP).

[0083] When preparing a curable composition, generally: the active hydrogen equivalents of said at least one polyamine (b); the total equivalents of the epoxy groups and acrylate groups of the first component (a), It is characterized by a ratio of 0.5:1 to 1.05:1, for example 0.8:1 to 1.0:1.

[0084] <Additives and auxiliary ingredients> The compositions obtained in the present invention usually further comprise auxiliaries and additives that can provide these compositions with improved properties. For example, the auxiliaries and additives can provide one or more of the following: improved elastic properties; improved elastic recovery; faster curing time; and low residual tack. Such auxiliaries and additives can be included, independently of one another, in one or both parts (parts) of the two-component (2K) composition: catalysts, plasticizers; stabilizers, such as UV stabilizers; antioxidants; reinforcing agents; conductive fillers; non-conductive fillers; reactive diluents; drying agents; adhesion promoters; fungicides; flame retardants; rheological auxiliaries; color pigments or color pastes; and / or, optionally, also in small amounts, non-reactive diluents.

[0085] For completeness, it is noted that auxiliary materials and additives that contain epoxy-reactive groups are generally incorporated into the second component, the hardener component, of a two-component (2K) composition. Materials that contain epoxy groups or react with the hardener are generally incorporated into the first component, the epoxide-containing component, of a two-component (2K) composition. Non-reactive materials can be incorporated into either or both of the first and second components.

[0086] Suitable catalysts are substances that, when present in catalytic amounts, promote the reaction between epoxy groups and amine groups. Although it is not intended to limit the catalysts used in the present invention, the following suitable catalysts can be mentioned: i) acids or compounds hydrolyzable to acids, in particular a) organic carboxylic acids, such as acetic acid, benzoic acid, salicylic acid, 2-nitrobenzoic acid and lactic acid; b) organic sulfonic acids, such as methanesulfonic acid, p-toluenesulfonic acid and 4-dodecylbenzenesulfonic acid; c) sulfonic acid esters; d) inorganic acids, such as phosphoric acid; e) Lewis acid compounds, such as BF3 amine complexes, SbF6 sulfonium compounds, bisarene iron complexes; f) Bronsted acid compounds, such as pentafluoroantimonate complexes; and e) mixtures of the aforementioned acids and acid esters; ii) tertiary amines, such as 1,4-diazabicyclo[2.2.2]. ]octane, benzyldimethylamine, α-methylbenzyldimethylamine, triethanolamine, dimethylaminopropylamine, imidazole (including N-methylimidazole, N-vinylimidazole and 1,2-dimethylimidazole), and the salts of these tertiary amines; iii) quaternary ammonium salts, for example, benzyltrimethylammonium chloride; iv) amidines, for example, 1,8-diazabicyclo[5.4.0]undec-7-ene; v) guanidines, for example, 1,1,3,3-tetramethylguanidine; vi) phenols, especially bisphenols; vii) phenolic resins; viii) Mannich bases; and, ix) phosphites, for example, di- and triphenylphosphite.

[0087] For purposes of the present invention, a "plasticizer" is a substance that reduces the viscosity of the composition and promotes its processability. As used herein, the plasticizer may comprise up to 10% by weight or up to 5% by weight based on the total weight of the composition, and is preferably selected from the group consisting of polydimethylsiloxane (PDMS); diurethane; monofunctional, linear or branched C4-C 16The plasticizers are selected from the group consisting of ethers of alcohols, such as Cetiol OE (available from Cognis Deutschland Gmbh, Düsseldorf); esters of abietic, butyric, thiobutyric, acetic, propionic and citric acids; esters based on nitrocellulose and polyvinyl acetate; fatty acid esters; dicarboxylic acid esters; esters of fatty acids bearing OH groups or epoxidized; glycolic acid esters; benzoic acid esters; phosphoric acid esters; sulfonic acid esters; trimellitic acid esters; epoxidized plasticizers; polyether plasticizers, such as end-capped polyethylene or polypropylene glycols; polystyrene; hydrocarbon plasticizers; chlorinated paraffins; and mixtures thereof. It should be noted that, in principle, phthalic acid esters can be used as plasticizers, but these are not preferred due to their possible toxicity. The plasticizer preferably comprises or consists of one or more polydimethylsiloxanes (PDMS).

[0088] "Stabilizer" for the purpose of the present invention should be understood as antioxidant, UV stabilizer or hydrolysis stabilizer. In this specification, stabilizers may constitute up to 10% by weight or up to 5% by weight in total, based on the total weight of the composition.Standard commercial examples of stabilizers suitable for use herein include sterically hindered phenols; thioethers; benzotriazoles; benzophenones; benzoates; cyanoacrylates; acrylates; amines of the hindered amine light stabilizer (HALS) type; phosphorus; sulfur; and mixtures thereof.

[0089] These compositions of the present invention may optionally contain reinforced rubber in the form of core-shell particles dispersed in an epoxy resin matrix. The term "core-shell rubber" or CSR is used according to its standard meaning in the art to indicate a rubber particle core formed by a polymer containing mainly elastomeric or rubbery polymers and a shell layer formed by graft-polymerized polymers on the core. The shell layer partially or completely covers the surface of the rubber particle core in the graft polymerization step. By weight, the core must constitute at least 50% by weight of the core-shell rubber particle.

[0090] The polymeric material of the core has a glass transition temperature (Tg) of 0° C. or less, preferably −20° C. or less, more preferably −40° C. or less, even more preferably −60° C. or less. The polymer of the shell is a non-elastomeric, thermoplastic or thermosetting polymer having a glass transition temperature (Tg) above room temperature, preferably above 30° C., more preferably above 50° C.

[0091] Without intending to limit the invention, the core may be composed of diene homopolymers, such as homopolymers of butadiene or isoprene; diene copolymers, such as copolymers of butadiene or isoprene with one or more ethylenically unsaturated monomers, such as vinyl aromatic monomers, (meth)acrylonitrile or (meth)acrylates; polymers based on (meth)acrylic acid ester monomers, such as polybutyl acrylate; and polysiloxane elastomers, such as polydimethylsiloxane and crosslinked polydimethylsiloxane.

[0092] Similarly, without intending to limit the invention, the shell may be composed of a polymer or copolymer of one or more monomers selected from (meth)acrylates, such as methyl methacrylate; vinyl aromatic monomers, such as styrene; vinyl cyanides, such as acrylonitrile; unsaturated acids and anhydrides, such as acrylic acid; and (meth)acrylamides. The polymers or copolymers used in the shell may have acid groups ionically crosslinked via the formation of metal carboxylates, particularly salts of divalent metal cations. The shell polymer or copolymer may also be covalently crosslinked by monomers having two or more double bonds per molecule.

[0093] The core-shell rubber particles contained therein preferably have an average particle size (d50) of from 10 nm to 300 nm, for example from 50 nm to 200 nm, which refers to the diameter or largest dimension of a particle in a particle size distribution, as measured by dynamic light scattering.

[0094] The present application does not exclude the presence of two types of core-shell rubber (CRS) particles having different particle sizes in the composition to provide a balance of important properties of the resulting cured product, such as shear strength, peel strength, and resin fracture toughness. In this embodiment, the smaller inclusion particles (1 st CSR type) may have an average particle size of 10 nm to 100 nm, and larger contained particles (2 nd The CSR type may have an average particle size of 120 nm to 300 nm, for example 150 nm to 300 nm. The small core-shell rubber particles should typically be used in excess of the larger particles on a weight basis. For example, a weight ratio of small CSR particles to large CSR particles of 3:1 to 5:1 may be employed.

[0095] The core-shell rubber can be selected from commercially available products, examples of which include Paraloid EXL2650A, EXL2655 and EXL2691A available from The Dow Chemical Company; the Kane Ace® MX series available from Kaneka Corporation, particularly MX120, MX125, MX130, MX136, MX551, MX553; and METABLEN SX-006 available from Mitsubishi Rayon.

[0096] The core shell rubber particles may be present in the composition in an amount of 0 to 10% by weight, such as 0 to 5% by weight, based on the total weight of the composition.

[0097] As mentioned above, the composition of the present invention may further comprise a filler. Suitable fillers in the present invention include, for example, chalk, lime powder, precipitated and / or pyrogenic silicic acid, zeolite, bentonite, magnesium carbonate, diatomite, alumina, clay, talc, titanium oxide, iron oxide, zinc oxide, sand, quartz, flint, mica, glass powder and other ground mineral substances. Organic fillers may also be used, in particular carbon black, graphite, wood fiber, wood flour, sawdust, cellulose, cotton, pulp, cotton, wood chips, chopped straw, chaff, crushed walnut shells and other chopped fibers. Short fibers, such as glass fibers, glass filaments, polyacrylonitrile, carbon fibers, Kevlar fibers, polyethylene fibers, etc., may also be added. Aluminum powder is also suitable as a filler.

[0098] The pyrogenic and / or precipitated silicic acid is advantageously from 10 to 90 m 2 / g. When used, they do not cause a further increase in the viscosity of the composition of the invention, but contribute to the strengthening of the cured composition.

[0099] Similarly, higher, advantageously 100-250 m 2 / g, especially 110-170m 2It is conceivable to use pyrogenic and / or precipitated silicic acids with a BET specific surface area of ​​0.1 g / g as fillers. Due to the larger BET specific surface area, the effect of strengthening the setting composition is achieved with a smaller weight proportion of silicic acid.

[0100] Also suitable as fillers are hollow spheres with a mineral or plastic shell. These may be, for example, hollow glass spheres available under the trade name Glass Bubbles®. Plastic-based hollow spheres, such as Expancel® or Dualite®, may also be used and are described in EP 0 520 426. They are composed of inorganic or organic materials and have a diameter of less than or equal to 1 mm, preferably less than or equal to 500 μm, respectively.

[0101] Fillers that impart thixotropy to the composition may be suitable for many applications. Such fillers are also described as rheological aids, for example hydrogenated castor oil, fatty acid amides, or swellable plastics such as PVC.

[0102] The total amount of filler present in the composition of the present invention is preferably 0-30% by weight, more preferably 0-20% by weight, based on the total weight of the composition. The desired viscosity of the curable composition usually determines the total amount of filler added, and it is proposed that the curable composition should have a viscosity of 3000-1000000, preferably 5000-250000 mPas in order to be easily extrudable from a suitable dispensing device such as a tube.

[0103] It should be noted that the compositions of the present invention may employ compounds having metal chelating properties that aid in enhancing adhesion of the cured adhesive to the substrate surface. Additionally, suitable adhesion promoters include acetoacetate functional modified resins sold by King Industries under the trade name K-FLEX XM-B301.

[0104] Examples of suitable pigments include titanium dioxide, iron oxide, or carbon black.

[0105] To further extend the shelf life, it is often recommended to further stabilize the composition of the present invention against moisture penetration using a desiccant. There is also sometimes a need to reduce the viscosity of the adhesive or sealing composition of the present invention for certain applications by using a reactive diluent. The total amount of reactive diluents present is usually not more than 15% by weight, preferably 1-5% by weight, based on the total weight of the composition.

[0106] The presence of solvents and non-reactive diluents in the compositions of the present invention is also not excluded if this can effectively reduce their viscosity. For example, and by way of illustration only, the compositions 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-butyryl ether; propylene glycol butyl ether; propylene glycol diisopropyl ... glycol phenyl ether; dipropylene glycol; dipropylene glycol monomethyl ether; dipropylene glycol dimethyl ether; dipropylene glycol di-n-butyl ether; N-methylpyrrolidone; diphenylmethane; diisopropylnaphthalene; petroleum distillates, such as Solvesso® products (available from Exxon Corporation); 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.

[0107] Alternatively, said solvents and non-reactive diluents together preferably constitute less than 10% by weight, especially less than 5% by weight or less than 2% by weight, based on the total weight of the composition.

[0108] Exemplary embodiments of two-component compositions In an exemplary embodiment of the present invention, the two-component (2K) composition comprises: Based on the weight of the first component, a) i) 80-100% by weight of at least one partially (meth)acrylated epoxy resin selected from the group consisting of bisphenol A based diglycidyl ether, hydrogenated bisphenol A based diglycidyl ether, bisphenol A epichlorohydrin based epoxy resin, bisphenol F diglycidyl ether and hydrogenated bisphenol F based diglycidyl ether, wherein the ratio of epoxy groups to (meth)acrylate groups in the partially (meth)acrylated epoxy resin is 1:1 to 1:2, and a)ii) 0 to 20% by weight of at least one epoxy resin different from said resin a)i). a first component comprising: b) a second component comprising at least one polyamine having at least two amine hydrogens reactive towards epoxy groups; Including, The curable composition is characterized in that the ratio of the amine hydrogen equivalent of at least one polyamine (b) to the total equivalent of epoxy groups and acrylate groups of the first component is 0.8:1 to 1.0:1.

[0109] The composition of this exemplary embodiment has been demonstrated to have a fast gel time of less than 5 minutes when measured at 25°C.

[0110] Methods and Applications To form a two-component (2K) curable composition, the reactive components are brought together and mixed in a manner that induces curing thereof. The reactive compounds must be mixed under sufficient shear to produce a homogeneous mixture. It is believed that this can be accomplished without special conditions or special equipment. However, suitable mixing devices may include magnetic stir bar devices; wire whisks; augers; batch mixers; planetary mixers; CW Brabender or Banburry® type mixers; and high shear mixers such as blade mixers and rotary impellers.

[0111] For small-scale applications, where volumes of less than 2 liters are usually used, the preferred packaging of two-component (2K) compositions is 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 by pistons. By driving these pistons, the components can be pushed out of the cartridge advantageously using closely mounted static or dynamic mixers. For larger scale applications, the two components of the composition can be advantageously stored in drums or pails. In this case, the two components can be pushed out using a hydraulic press, in particular via a follower plate, and fed through a pipeline to a mixing device, which ensures a fine and highly homogeneous mixture of the hardener and binder components. In any case, it is important for any package to have the first component placed in a hermetically sealed position with an air-tight and moisture-proof seal, so that both components can be stored for a long period of time, ideally for more than 12 months.

[0112] Non-limiting examples of two-component dispensing devices and methods that may be suitable for the present invention include those described in US Pat. No. 6,129,244 and US Pat. No. 8,313,006.

[0113] Two-component (2K) curable compositions should be formulated extensively to have an initial viscosity (viscosity measured immediately after mixing, e.g. up to 2 minutes after mixing) of less than 1,000,000 mPa·s, e.g. less than 500,000 mPa·s at 25° C. Apart from or in addition to the above viscosity characteristics, two-component (2K) compositions should be formulated to be free of air bubbles (foam) upon mixing and subsequent curing.

[0114] Curing of the compositions of the invention can be carried out at temperatures ranging from -10°C to 120°C, preferably from 0°C to 70°C, in particular from 20°C to 60°C. The appropriate temperature depends on the particular compounds present and the desired rate of curing, and can be determined individually by the skilled artisan, if necessary using simple preliminary tests. Naturally, curing at temperatures between 10°C and 35°C, or even between 20°C and 30°C, is particularly advantageous, since it does not require significant heating or cooling from normal ambient temperatures. However, where applicable, the temperature of the mixture formed from the individual components of the two-component (2K) composition may be elevated above the mixing and / or application temperatures using conventional means, including microwave induction.

[0115] The curable compositions according to the invention may find utility in, inter alia, varnishes; inks; binders for fibres and / or particles; coatings on glass; coating, sealing and bonding of mineral building materials such as lime and / or cement-bonded plaster, gypsum-containing surfaces, fibre cement building materials and concrete; coating, sealing and bonding of wood and wooden materials such as chipboard, fibre board and paper; coatings on metal surfaces; coatings on asphalt and asphalt-containing pavement; coating, sealing and bonding of various plastic surfaces; and coatings on leather and textiles.

[0116] In a particularly preferred embodiment, the composition of the present invention is applied to a substrate to produce a highly adherent wear-resistant coating.Adhesion can often be performed at room temperature, and can provide effective wear resistance after curing.Furthermore, when applied to mechanical structures, or to the surfaces of floors or pavements, the coating composition can provide corrosion protection to the surfaces, and prevent the surfaces from coming into contact with compounds that are harmful to the operation or efficiency of the particular structure.

[0117] In each of the above mentioned applications, the composition can be applied by conventional application methods, including but not limited to brush application; roll coating using a four applicator roll set when the composition is solvent-free or a two applicator roll set for solvent-borne compositions; doctor blade application; printing methods; and spraying methods such as air-atomized spray, air-assisted spray, airless spray, and high volume low pressure spray. For coating and adhesive applications, it is recommended that the composition be applied to the surface at a wet film thickness of 10-500 μm. Applying thinner layers within this range is more economical and reduces the chance of thick cured areas requiring sanding in coating applications. However, precise control must be exercised when applying thinner coatings or layers to avoid the formation of discontinuous cured films.

[0118] For 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 polymeric film substrate, rolled up, and stored at a temperature low enough to inhibit chemical reaction between the components. When required, the film adhesive is removed from the cold environment and applied to metal or composite components, the backing is peeled off to complete the assembly, and cured in an oven or autoclave.

[0119] Various features and embodiments of the present disclosure are illustrated in the following examples, which are intended to be representative and not limiting. EXAMPLES

[0120] In the examples, the following commercially available products were used: HCT-1: 50% acrylated bisphenol A type epoxy resin available from Kagawa Chemical Co., Ltd. (CAS No. 55127-80-5, Oxirane, 2,2'-((1-methylethylidene)bis(4,1-phenyleneoxymethylene)bis-, homopolymer, di-2-propenoate). Uvacure 1561: 50% acrylated bisphenol A type epoxy resin (CAS No. 55127-80-5, Oxirane, 2,2'-((1-methylethylidene)bis(4,1-phenyleneoxymethylene)bis-, homopolymer, di-2-propenoate) available from Daicel Allnex. JER 828: Bisphenol A type epoxy resin available from Mitsubishi Chemical. Ancamine 2678: Amine hardener available from Evonik (AHEW 30g / eq.). N-AEP: N-(2-aminoethyl)piperazine (AHEW 43 g / eq.) available from Nouryon.

[0121] Using the ingredients described above, six formulations were prepared as shown in Table 1 below. The weight percentages listed in the table are based on the total weight of the composition.

[0122] [Table 1]

[0123] The properties of the two-component formulations were then evaluated using the following test methods.

[0124] Gel time test method: A total of 10 g of the first component, resin component, and second component of each ratio was weighed into a disposable beaker and mixed thoroughly to start measuring the gel time. The gel time was measured at 25°C according to ASTM D 2471 (Standard Test Method for Gel Time of Thermosetting Resins). The results are shown in Table 2.

[0125] [Table 2]

[0126] As shown, the two-component composition according to the invention is characterized by a gel time at 25° C. of less than 5 minutes.

[0127] In view of the above description and examples, it will be apparent to one skilled in the art that equivalent modifications may be made without departing from the scope of the appended claims.

Claims

1. Based on the weight of the first component, a) i) 80 to 100 wt. % of at least one partially (meth)acrylated epoxy resin; a)ii) 0-20% by weight of at least one epoxy resin different from said resin a)i). A first component comprising: b) a second component comprising at least one polyamine having at least two amine hydrogens reactive with epoxy groups; Including, 1. A two-component (2K) curable composition, characterized in that the ratio of the amine hydrogen equivalents of said at least one polyamine (b) to the total equivalents of epoxy groups and acrylate groups of said first component (a) is from 0.5:1 to 1.05:

1.

2. the first component comprising, based on the weight of the component, a) i) 85 to 100 wt. % of at least one partially (meth)acrylated epoxy resin; a)ii) 0-15% by weight of at least one epoxy resin different from said resin a)i). The two-component (2K) curable composition of claim 1, comprising:

3. the first component comprising, based on the weight of the component, a) i) 90 to 100 wt. % of at least one partially (meth)acrylated epoxy resin; a)ii) 0-10% by weight of at least one epoxy resin different from said resin a)i). The two-component (2K) curable composition of claim 1, comprising:

4. 4. The two-component (2K) curable composition according to claim 1, wherein the ratio of epoxy groups to (meth)acrylate groups in the partially (meth)acrylated epoxy resin is from 1:1 to 1:

3.

5. 5. The two-component (2K) curable composition according to claim 4, wherein the ratio of epoxy groups to (meth)acrylate groups in the partially (meth)acrylated epoxy resin is from 1:1 to 1:

2.

6. 6. The two-component (2K) curable composition according to any of claims 1 to 5, wherein the partially (meth)acrylated epoxy resin is a liquid having a viscosity in the range of 1000 to 1,000,000 centipoise (cps), preferably 2500 to 750,000 cps, measured at 25°C.

7. 7. The two-component (2K) curable composition according to claim 1, wherein component a)i) comprises at least one partially (meth)acrylated resin selected from diepoxide compounds having an epoxy equivalent weight of less than 500 g / eq.

8. 8. The two-component (2K) curable composition according to any of claims 1 to 7, wherein component a)i) comprises at least one partially (meth)acrylated resin selected from the group consisting of bisphenol A based diglycidyl ethers; hydrogenated bisphenol A based diglycidyl ethers; bisphenol A epichlorohydrin based epoxy resins; bisphenol F diglycidyl ethers; and hydrogenated bisphenol F based diglycidyl ethers.

9. The two-component (2K) curable composition according to any of claims 1 to 8, wherein said at least one polyamine has an amine hydrogen equivalent weight of 150 g / eq or less.

10. The two-component (2K) curable composition according to any of claims 1 to 9, wherein said at least one polyamine has one primary amino group and at least one secondary amino group.

11. Based on the weight of the first component, a) i) 80 to 100 wt. % of at least one partially (meth)acrylated epoxy resin; a)ii) 0-20% by weight of at least one epoxy resin different from said resin a)i). A first component comprising: b) a second component comprising at least one polyamine having at least two amine hydrogens reactive towards epoxy groups; It consists of:

11. The two-component (2K) curable composition according to any of claims 1 to 10, characterized in that the ratio of the amine hydrogen equivalents of the at least one polyamine (b) to the total equivalents of epoxy and acrylate groups of the first component (a) is from 0.5:1 to 1.05:

1.

12. 12. The two-component (2K) curable composition according to any of claims 1 to 11, characterized in that the ratio of the amine hydrogen equivalents of the at least one polyamine (b) to the total equivalents of epoxy and acrylate groups of the first component (a) is from 0.8:1 to 1.0:

1.

13. A cured product obtained from the two-component (2K) curable composition according to any one of claims 1 to 12.

14. 14. Use of the cured reaction product of claim 13 as a coating, adhesive or sealant.