One-component (1k) composition based on epoxy resin

Abstract

This invention provides a liquid one-component (1K) composition comprising, based on the weight of the composition: 10 to 90 wt% of a) at least one epoxy resin; 0.5 to 30 wt% of b) at least one organoboron compound selected from a tetrasubstituted borate of a monovalent tertiary amine cation; 10 to 50 wt% of c) at least one (meth)acrylamide monomer of formula (VII); and 0.05 to 10 wt% of d) at least one free radical photoinitiator, wherein R a H or Me; G is selected from -NH2, -NHR b and -N(R) b (R) c ); R b and R c Independently selected from C1-C 18 Alkyl, C1-C 18 Hydroxyalkyl, C1-C 18 Alkylalkoxy, C6-C 18 Aryl and –(CH2) n –N(R d (R) e ); n is an integer from 1 to 4; and R d and R e It is independently selected from H and C1-C6 alkyl groups.

Description

Technical Field

[0001] This invention relates to a one-component (1K) composition based on an epoxy resin. More specifically, this invention relates to a curable liquid one-component (1K) composition comprising an epoxy resin, an organoborate compound, a (meth)acrylamide monomer, and a free radical photoinitiator. Background Technology

[0002] Epoxy resins have been found to have a wide range of applications, mainly because specific choices of resins, modifiers, and crosslinking agents (or curing agents) allow for the customization of the properties of cured epoxy resins, thereby achieving specific performance characteristics.

[0003] In addition to its well-known versatility, properly cured epoxy resins also possess a variety of other properties, including: excellent chemical resistance (especially to alkaline environments); high tensile and compressive strength; high fatigue strength; low shrinkage during curing; and electrical insulation properties and their retention during aging or environmental exposure.

[0004] Epoxy resins are known for their utility in so-called "dual-curing" or hybrid resin systems, which can be both photochemically and thermally cured. These systems – typically based on combinations of epoxy resins with (meth)acrylate resins, (meth)acrylated bismaleimide (BMI) resins, or (meth)acrylated polyurethane resins – arose because photochemical curing of the composition itself may not be suitable for coating certain substrates or bonding or sealing certain components: areas within the substrate or between components may experience limited or no light exposure. In hybrid resin systems, the light-exposed portions of the curable composition can be photochemically cured (e.g., with ultraviolet light) to fix the components to be adhered, sealed, or coated within desired tolerances; then the remaining portions of the curable composition arranged in shaded areas are heat-treated to complete the curing process.

[0005] This invention relates to the development of dual-curing systems based on one-component (1K) compositions containing epoxy resin. Given that the epoxy resin and the hardener or curing agent are packaged together, the one-component (1K) composition must exhibit latent curing: curing cannot begin under normal storage and transport conditions, but must be delayed until the composition is exposed to specific curing conditions, such as elevated temperature or radiation.

[0006] According to a conventional method, a one-component (1K) epoxy composition may comprise a suspension of a solid curing agent in an epoxy resin, said curing agent being latent due to its low solubility in the epoxy material. Examples of this method are particularly described in U.S. Patent Nos. 3,519,576, 3,520,905, and 4,866,133. Various epoxy-dicyandiamide-based one-component compositions have been commercialized: for example, WO2014 / 165423 (Air Products and Chemicals Inc.) discloses a one-component composition comprising: at least one tertiary amine salt, said salt being a product of at least one carboxylic acid and at least one tertiary amine selected from the group consisting of: N-hydroxyethylpiperidine, N-hydroxyethylmorpholine, 1,4-bis(2-hydroxyethyl)piperazine, 1-ethylpiperidine, N,N-dimethylcyclohexane, and dimethylethanolamine; at least one epoxy resin; and at least one dicyandiamide.

[0007] The problem lies in the limitations imposed by systems using such solid particulate hardeners, which often have high viscosity and relatively long curing times. Furthermore, any uneven distribution of the particulate hardener within the composition can result in uncured areas in the formed product: this would certainly be extremely detrimental to users choosing hybrid systems specifically designed to avoid uncured areas in coatings, adhesives, or sealants.

[0008] These definite problems with solid particulate curing agents used in epoxy resins have driven many authors to seek a more uniform distribution of the curing agent in one-component compositions. For example, Japanese Patent Publication No. 2004-27159 describes a one-component epoxy resin composition in which a liquid phenol resin is used primarily as a curing agent in conjunction with a solid latent curing agent: although the composition is claimed to provide excellent storage stability, using a liquid phenol resin as the primary curing agent reduces the physical strength of the cured resin.

[0009] Other authors have sought to dissolve dicyandiamide, and in this regard, it is worth mentioning: U.S. Patent No. 4,859,761, U.S. Patent No. 4,621,128, U.S. Patent No. 3,420,794, and EP2180012A1.

[0010] Chemical blocking is considered an alternative to using particulate hardeners to modulate the latency of epoxy resin curing agents. An example of this can be found in US2007149727 (Okuhira et al.), where modified amines exhibit low curing efficiency because crosslinking depends on the hydrolysis of imine groups to produce amines. Furthermore, EP 2999730A (Inst.fürTextil und faserforschung dekendorf deustche) describes protected N-heterocyclic carbenes that are stable for several days at room temperature when stored under inert conditions. However, the development of protected functionalities, such as those exemplified, can be complex and uneconomical. Moreover, the application of such latent hardeners in hybrid resin systems is not disclosed in these cited documents.

[0011] The inventors believe that there is still a need in the art to develop stable, one-component (1K) liquid compositions based on epoxy resins that offer good processability and economical manufacturing, as well as effective utility in dual-curing systems. Summary of the Invention

[0012] According to a first aspect of the invention, a liquid single-component (1K) composition is provided, comprising, based on the weight of the composition:

[0013] 10 to 90% by weight of a) at least one epoxy resin;

[0014] 0.5 to 30% by weight of b) at least one organoboron compound selected from a tetrasubstituted borate of a monovalent tertiary amine cation;

[0015] 10 to 50% by weight of c) at least one (meth)acrylamide monomer of formula (VII):

[0016]

[0017] Among them, R a For H or Me;

[0018] G is selected from -NH2, -NHR b and -N(R) b (R) c );

[0019] R b and R c Independently selected from C1-C 18 Alkyl, C1-C 18 Hydroxyalkyl, C1-C 18 Alkylalkoxy, C6-C 18 Aryl and -(CH2) n -N(R d (R)e );

[0020] n is an integer from 1 to 4; and

[0021] R d and R e Independently selected from H and C1-C6 alkyl groups;

[0022] as well as,

[0023] d) At least one free radical photoinitiator, ranging from 0.05 to 10% by weight.

[0024] In a key embodiment, the liquid single-component (1K) composition comprises, by weight:

[0025] 20 to 80% by weight, preferably 30 to 70% by weight of a) at least one epoxy resin;

[0026] 1 to 25% by weight, preferably 5 to 15% by weight of b) at least one organoboron compound selected from a tetrasubstituted borate of a monovalent tertiary amine cation;

[0027] c) at least one (meth)acrylamide monomer of formula (VII): 15 to 45% by weight, preferably 25 to 40% by weight

[0028]

[0029] Among them, R a For H or Me;

[0030] G is selected from -NH2, -NHR b and -N(R) b (R) c );

[0031] R b and R c Independently selected from C1-C 18 Alkyl, C1-C 18 Hydroxyalkyl, C1-C 18 Alkylalkoxy, C6-C 18 Aryl and -(CH2) n -N(R d (R) e );

[0032] n is an integer from 1 to 4; and

[0033] R d and R e Independently selected from H and C1-C6 alkyl groups;

[0034] d) at least one free radical photoinitiator, 0.1 to 5% by weight, preferably 0.1 to 2.5% by weight.

[0035] 0 to 15% by weight, preferably 0 to 10% by weight of e1) at least one (meth)acrylate monomer represented by formula M:

[0036] H2C=CQCO2R 1 (M)

[0037] Wherein: Q is hydrogen, halogen, or C1-C4 alkyl; and

[0038] R 1 Selected from C1-C 30 Alkyl, C3-C 30 cycloalkyl, C2-C 20 alkenyl, C2-C 12 alkynyl group, C6-C 18 Aryl, C7-C 18 Alkyl and C7-C 18 Aryl alkyl groups;

[0039] 0 to 10% by weight, preferably 0 to 5% by weight, of at least one (meth)acrylate-functionalized oligomer, said oligomer having no epoxy groups.

[0040] The liquid compositions as defined above exhibit advantageous storage stability at room temperature. Furthermore, the liquid compositions as defined above advantageously have low viscosity at room temperature but can be fully irradiated at high temperatures for an operable duration. Because the compositions of the present invention combine radiation and heat curing, when using photocurable (meth)acrylate-based compositions, the compositions do not have the problem of poor shadow curing.

[0041] In certain exemplary embodiments of the liquid composition, component a) comprises at least one epoxy resin selected from: glycidyl ethers of polyols and polyphenols; glycidyl esters of polycarboxylic acids; and epoxidized polyene-bonded unsaturated hydrocarbons, esters, ethers, and amides. Independent of such preferred epoxy resins or other than such preferred epoxy resins, component a) of the liquid composition may ideally comprise an epoxy-functionalized polymer having both epoxy and (meth)acrylate functional groups. In component a) of the liquid composition, the following combinations may be mentioned: glycidyl ethers of polyols or polyphenols; and epoxy-functionalized polymers having both epoxy and (meth)acrylate functional groups.

[0042] Ideally, the anion of salt b) is a tetra(C1-C6 alkyl)borate, tetraphenylborate, or a substituted tetraphenylborate anion; tetraphenylborate anion is preferred. While the monovalent cation of salt b) may be a tetraalkylammonium ion, it is preferred that the cation be a heterocyclic moiety, which may be monocyclic, bicyclic, or polycyclic, wherein the charged nitrogen atom is part of an alicyclic or aromatic heterocyclic system. Therefore, in a particular embodiment, component b) of the composition comprises a cycloamidinium tetrasubstituted borate and / or an imidazole N,N-dimethylaminoethyl(meth)acrylamide tetrasubstituted borate. For example, good results have been obtained when component c) includes at least one salt selected from the group consisting of: imidazole tetraphenylborate; methylimidazolium tetraphenylborate; 2-ethyl-4-methylimidazolium tetraphenylborate; 2-ethyl-1,4-dimethylimidazolium tetraphenylborate; 8-benzyl-1,8-diazabicyclo[5.4.0]undecyl-7-ene tetraphenylborate; 1,8-diazabicyclo[5.4.0]undecyl-7-ene tetraphenylborate; and 1,5-diazabicyclo[4.3.0]nonyl-5-ene tetraphenylborate.

[0043] According to a second aspect of the invention, a cured product obtained from a liquid one-component (1K) composition as defined above and in the appended claims is provided. The cured product of the invention does not exhibit undesirable curing shrinkage.

[0044] The present invention also provides the use of the cured reaction products as defined above and in the appended claims as coatings, sealants or adhesives.

[0045] definition

[0046] As used herein, the singular forms “a,” “one,” and “the” include plural indicators unless the context clearly indicates otherwise.

[0047] As used herein, the term “comprising” is synonymous with “including” or “containing” and is inclusive or open-ended, excluding additional unlisted members, elements or method steps.

[0048] As used herein, the term “composes of” excludes any unspecified element, component, member, or method step.

[0049] When quantities, concentrations, dimensions, and other parameters are expressed in the form of ranges, preferred ranges, upper limits, lower limits, or preferred upper and lower limits, it should be understood that any range obtainable by combining any upper or preferred value with any lower or preferred value is also specifically disclosed, regardless of whether the obtained range is explicitly mentioned in the context.

[0050] Furthermore, according to the standard understanding, a weight range expressed as "0 to" explicitly includes 0% by weight: the component defined by the range may or may not be present in the composition.

[0051] The terms “preferred,” “preferred,” “desired,” and “particularly” are frequently used herein to refer to embodiments of this disclosure that may provide particular benefits in certain circumstances. However, the description of one or more preferred, preferred, desired, or particular embodiments does not imply that other embodiments are unavailable and is not intended to exclude those other embodiments from the scope of this disclosure.

[0052] The word “may” as used throughout this application is used in a permissive sense – meaning it is possible, not mandatory.

[0053] As used in this article, the room temperature was 23℃±2℃.

[0054] As used herein, the term "monofunion" refers to having one aggregateable part. As used herein, the term "multifunctional" refers to having more than one aggregateable part.

[0055] As used in this article, the term “equivalent (eq.)”, commonly found in chemical symbols, refers to the relative number of reactive groups present in a reaction.

[0056] As used in this article, the term "equivalent weight" refers to the molecular weight divided by the number of related functional groups. Therefore, "epoxy equivalent weight" (EEW) means the weight, in grams, of a resin containing one equivalent of epoxy groups.

[0057] As used herein, the term "epoxide" refers to a compound characterized by the presence of at least one cyclic ether group, i.e., a cyclic ether group in which an ether oxygen atom is bonded to two adjacent carbon atoms to form a cyclic structure. This term is intended to include monoepoxides, polyepoxides (having two or more epoxy groups), and epoxide-terminated prepolymers. The term "monoepoxide" refers to an epoxy compound having one epoxy group. The term "polyepoxide" refers to an epoxy compound having at least two epoxy groups. The term "diepoxide" refers to an epoxy compound having two epoxy groups.

[0058] Epoxides can be unsubstituted or inertly substituted. Exemplary inert substituents include chlorine, bromine, fluorine, and phenyl.

[0059] As used herein, “(meth)acryloyl” is an abbreviation of “acryloyl” and / or “methacryloyl”. Therefore, the term “(meth)acrylamide” refers to both acrylamide and methacrylamide.

[0060] As used in this article, "C1-C" n The "alkyl" group refers to a monovalent group containing 1 to n carbon atoms, which is an alkane group and includes both straight-chain and branched organic groups. Therefore, "C1-C30 "Alkyl" refers to a monovalent group containing 1 to 30 carbon atoms, which is an alkane group and includes both straight-chain 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 this invention, such alkyl groups may be unsubstituted or substituted with one or more substituents, such as halogens, nitro groups, cyano groups, amide groups, amino groups, sulfonyl groups, sulfinyl groups, mercapto groups, thiooxy groups, urea groups, thiourea groups, aminosulfonyl groups, sulfonamide groups, and hydroxyl groups. Where appropriate, the preferred substituents will be indicated in the specification. However, it should generally be noted that unsubstituted alkyl groups (C1-C1) containing 1 to 18 carbon atoms are preferred. 18 Alkyl groups, such as unsubstituted alkyl groups (C1-C1) containing 1 to 12 carbon atoms. 12 Alkyl) An unsubstituted alkyl group containing one to six carbon atoms (C1-C6 alkyl).

[0061] The term "C1-C" used in this article 18 "Hydroxyalkyl" refers to a HO-(alkyl) group having 1 to 18 carbon atoms, wherein the substituents are connected by oxygen atoms, and the alkyl group is as defined above.

[0062] "Alkoxy" refers to a monovalent group represented by -OA, where A is an alkyl group; non-limiting examples are methoxy, ethoxy, and isopropoxy. The term "C1-C" as used herein... 18 "alkylalkoxy" refers to an alkyl group having an alkoxy substituent as defined above, wherein the (alkyl-O-alkyl) moiety contains a total of 1 to 18 carbon atoms: such groups include methoxymethyl (-CH2OCH3), 2-methoxyethyl (-CH2CH2OCH3) and 2-ethoxyethyl.

[0063] The term “C2-C4 alkylene” as used in this article is defined as a saturated divalent hydrocarbon group having 2 to 4 carbon atoms.

[0064] The term "C3-C" 30 "Cycloalkyl" should be understood to refer to optionally substituted, saturated mono, di, or tricyclic hydrocarbon groups having 3 to 30 carbon atoms. Generally, attention should be paid to cycloalkyl groups containing 3–18 carbon atoms (C3–C4). 18 Cycloalkyl groups. Examples of cycloalkyl groups include: cyclopropyl; cyclobutyl; cyclopentyl; cyclohexyl; cycloheptyl; cyclooctyl; adamantane; and norbornane.

[0065] As used herein, "C6-C" is used alone or as part of a larger body—such as in "araneyl"— 18"Aryl" refers to optionally substituted monocyclic, bicyclic, and tricyclic systems, wherein the monocyclic system is aromatic, or at least one ring in the bicyclic or tricyclic system is aromatic. Bicyclic and tricyclic systems include benzofused 2- to 3-membered carbon rings. Exemplary aryl groups include: phenyl; (C1-C4)alkylphenyl, such as tolyl and ethylphenyl; indenyl; naphthyl, tetrahydronaphthyl, tetrahydroindenyl; tetrahydroanthrayl; and anthracel. It should be noted that phenyl is preferred.

[0066] As used in this article, "C2-C" 20 "Alkenyl" refers to a hydrocarbon group having 2 to 20 carbon atoms and at least one olefinic unsaturated unit. The alkenyl group can be straight-chain, branched, or cyclic, and can optionally be substituted. As will be understood by those skilled in the art, the term "alkenyl" also encompasses groups having "cis" and "trans" configurations or "E" and "Z" configurations. However, it should generally be noted that groups containing 2 to 10 carbon atoms are preferred. 2-10 ) or 2 to 8 (C 2-8 The unsubstituted alkenyl group of the carbon atom. The C2-C 12 Examples of alkenyl groups include, but are not limited to: -CH=CH2; —CH═CHCH3; —CH2CH═CH2; —C(═CH2)(CH3); —CH═CHCH2CH3; —CH2CH═CHCH3; —CH2CH2CH═CH2; —CH═C(CH3)2; —CH2C(═CH2)(CH3); —C(═CH2)CH2CH3; —C(CH3)═CHCH3; —C(CH3)CH═CH2; —CH═CHCH2CH2CH3; —CH2CH ═CHCH2CH3; —CH2CH2CH═CHCH3; —CH2CH2CH2CH═CH2; —C(═CH2)CH2CH2CH3; —C(CH3)═CHCH2CH3; —CH(CH3)CH═CHCH; —CH(CH3)CH2CH═CH2; —CH2CH═C(CH3)2; 1-cyclopent-1-enyl; 1-cyclopent-2-enyl; 1-cyclopent-3-enyl; 1-cyclohex-1-enyl; 1-cyclohex-2-enyl; and 1-cyclohex-3-enyl.

[0067] As used herein, “alkylaryl” refers to an alkyl-substituted aryl group, and “substituted alkylaryl” refers to an alkylaryl group that further contains one or more of the above-described substituents. Furthermore, as used herein, “aralkyl group” refers to an alkyl group substituted with an aryl group as defined above.

[0068] As used herein, the term "hetero" refers to a group or part containing one or more heteroatoms such as N, O, Si, and S. Thus, for example, "heterocyclic" refers to a cyclic group having, for example, N, O, Si, or S as part of its ring structure. The terms "heteroalkyl" and "heterocyclic alkyl" refer to alkyl and cycloalkyl groups as defined above, respectively, containing N, O, Si, or S as part of their structure.

[0069] As used herein, the term “catalytic amount” means a substoichiometric amount of catalyst relative to the reactants, unless otherwise explicitly stated.

[0070] As used herein, "primary amine" refers to an NH2 group attached to an organic group, and "secondary amine" refers to an NH group attached to two organic groups, which may also be part of a ring. Therefore, the term "tertiary amine" refers to the nitrogen-containing portion of the amine whose nitrogen atom is not bonded to a hydrogen atom. The term "amine hydrogen" as used refers to the hydrogen atom in both primary and secondary amines.

[0071] As used herein, the term "photoinitiator" refers to a compound that can be activated by an energy-carrying activating light beam, such as electromagnetic radiation, upon irradiation with it. This term is intended to include both photoacid generators and photobase generators. Specifically, the term "photoacid generator" refers to a compound or polymer that, upon exposure to photochemical radiation, produces an acid for catalyzing the curing of an acid-curing resin system. The term "photobase generator" refers to any substance that, upon exposure to suitable radiation, produces one or more bases.

[0072] The term "Lewis acid" as used in this article refers to any molecule or ion that can bind to a second molecule or ion by forming a covalent bond with two electrons from that molecule or ion, and is usually called an electrophile: thus, a Lewis acid is an electron acceptor.

[0073] The molecular weights mentioned in this specification can be measured using gel permeation chromatography (GPC) with polystyrene calibration standards, for example, as described in ASTM 3536.

[0074] As used herein, "anhydrous" means that the relevant composition or reaction mixture contains less than 0.25% by weight of water. For example, the composition may contain less than 0.1% by weight of water or be completely anhydrous.

[0075] Unless otherwise stated, the viscosity of the coating compositions described herein was measured using an RVT Brookfield viscometer under standard conditions of 23°C and 50% relative humidity (RH). The viscometer was calibrated using silicone oil of known viscosity, ranging from 5000 cps to 50000 cps. A set of RV spindles connected to the viscometer was used for calibration. Measurements of the coating compositions were performed using a No. 6 spindle at 20 rpm for 1 minute until the viscometer was balanced. The viscosity corresponding to the balanced reading was then calculated using the calibration. Detailed Implementation

[0076] a) Epoxy compounds

[0077] The compositions of the present invention, based on the weight of the composition, contain 10 to 90% by weight, preferably 20 to 80% by weight, of epoxy resin a. For example, the compositions of the present invention, based on the weight of the composition, contain 25 to 75% by weight or 30 to 70% by weight of said epoxy resin a.

[0078] The epoxy resins used herein may include monofunctional epoxy resins, polyfunctional epoxy resins, and combinations thereof. Epoxy resins may be pure compounds, but may also be mixtures of epoxy-functional compounds, including mixtures of compounds with different numbers of epoxy groups per molecule. Epoxy resins may be saturated or unsaturated, aliphatic, alicyclic, aromatic, or heterocyclic, and may be substituted. Furthermore, epoxy resins may be monomeric or polymeric.

[0079] This invention is not intended to limit the scope of the invention. Exemplary monoepoxide compounds include: epoxide alkanes; epoxide-substituted alicyclic hydrocarbons, such as cyclohexene oxide, vinylcyclohexene monooxide, (+)-cis-limonene oxide, (+)-cis-trans-limonene oxide, (-)-cis-trans-limonene oxide, cyclooctene oxide, cyclododecene oxide, and α-pinene oxide; epoxide-substituted aromatic hydrocarbons; monoepoxide-substituted alkyl ethers of monohydric alcohols or phenols, such as glycidyl ethers of aliphatic, alicyclic, and aromatic alcohols; monoepoxide-substituted alkyl esters of monocarboxylic acids, such as glycidyl esters of aliphatic, alicyclic, and aromatic monocarboxylic acids; monoepoxide-substituted alkyl esters of polycarboxylic acids, wherein other carboxyl groups are esterified with alkyl alcohols; alkyl esters and alkenyl esters of epoxide-substituted monocarboxylic acids; epoxide alkyl ethers of polyols, wherein other OH groups are esterified or etherified with carboxylic acids or alcohols; and monoesters of polyols and epoxide monocarboxylic acids, wherein other OH groups are esterified or etherified with carboxylic acids or alcohols.

[0080] For example, the following glycidyl ethers may be mentioned as monoepoxide compounds 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-tolyl glycidyl ether; m-tolyl glycidyl ether; and p-tolyl glycidyl ether.

[0081] In one important implementation, the monoepoxide compound conforms to the following formula (I):

[0082]

[0083] Where: R w R x R y and R z They can be the same or different, and are independently selected from hydrogen, halogen atoms, C1-C8 alkyl groups, and C3-C4 atoms. 10 cycloalkyl, C2-C 12 alkenyl, C6-C 18 Aryl or C7-C 18 Aryl alkyl group, under the condition that R y and R z At least one of them is not hydrogen.

[0084] Preferred R w R x and R y It is hydrogen, and R z It is phenyl or C1-C8 alkyl, more preferably C1-C4 alkyl.

[0085] Regarding this implementation, exemplary monoepoxides include: ethylene oxide; 1,2-epoxypropane (propylene oxide); 1,2-epoxybutane; cis-2,3-epoxybutane; trans-2,3-epoxybutane; 1,2-epoxypentane; 1,2-epoxyhexane; 1,2-epoxyheptane; epoxydecane; butadiene oxide; isoprene oxide; and styrene oxide.

[0086] In this invention, reference is made to 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.

[0087] Similarly, this is not intended to limit the invention; suitable polyepoxides can be liquids or solutions in solvents. Furthermore, such polyepoxides should have an epoxy equivalent of 100 to 700 g / eq, for example, 120 to 320 g / eq. And generally, biepoxides having an epoxy equivalent of less than 500 g / eq or even less than 400 g / eq are preferred: this is primarily from a cost perspective, as lower molecular weight epoxy resins require more limited processing during purification in their production.

[0088] Examples of types or groups of polyepoxide compounds that can be polymerized in this invention include: glycidyl ethers of polyols and polyphenols; glycidyl esters of polycarboxylic acids; and epoxidized polyene-bonded unsaturated hydrocarbons, esters, ethers, and amides.

[0089] Suitable diglycidyl ether compounds can be aromatic, aliphatic, or alicyclic in nature, and therefore can be derived from diphenols and diols. Available types of such diglycidyl ethers include: diglycidyl ethers of aliphatic and alicyclic diols such as 1,2-ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,12-dodecanediol, cyclopentanediol, and cyclohexanediol; bisphenol A-based diglycidyl ethers; bisphenol F-based diglycidyl ethers; diglycidyl ethers based on polyalkylene glycols, particularly polypropylene glycol diglycidyl ethers; and diglycidyl ethers based on polycarbonate diols.

[0090] Other exemplary polyepoxide compounds include, but are not limited to: glycerol polyglycidyl ether; trimethylolpropane polyglycidyl ether; pentaerythritol polyglycidyl ether; diglycerol polyglycidyl ether; polyglycerol polyglycidyl ether; and sorbitol polyglycidyl ether.

[0091] The glycidyl esters of the polycarboxylic acids used in this invention are derived from polycarboxylic acids containing at least two carboxylic acid groups and free from other groups that react with epoxy groups. The polycarboxylic acids can be aliphatic, alicyclic, aromatic, and 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: oxalic acid; sebacic acid; adipic acid; succinic acid; pimelic acid; octanoic acid; glutaric acid; dimer and trimer acids of unsaturated fatty acids, such as dimer and trimer acids of linseed fatty acids; phthalic acid; isophthalic acid; terephthalic acid; trimellitic acid; pyromellitic acid; phenylene diacetic acid; chlorobenzene; hexahydrophthalic acid, especially hexahydrophthalic acid (1,2-cyclohexanedicarboxylic acid); biphenyl phthalic acid; naphthalene dicarboxylic acid; polyacid-terminated esters of dicarboxylic acids and aliphatic polyols; polymers and copolymers of (meth)acrylic acid; and crotonic acid.

[0092] Other suitable diepoxides that may be mentioned include: diunsaturated fatty acids C1-C 18 Diepoxides of alkyl esters; butadiene diepoxides; polybutadiene diglycidyl ether; vinylcyclohexene diepoxides; and limonene diepoxides.

[0093] Examples of highly preferred polyepoxide compounds 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 DFER TM 354; Bisphenol A / F epoxy resin blends, such as DER TM 353; Aliphatic glycidyl ethers, such as DER TM 736; Polypropylene glycol diglycidyl ether, such as DER TM 732; Solid bisphenol A epoxy resin, such as DER TM 661 and DER TM 664UE; a solution of bisphenol A solid epoxy resin, such as DER. TM 671-X75; epoxy phenolic varnish resin, such as DEN TM 438; Brominated epoxy resins, such as DER TM 542; Castor oil triglycidyl ether, for example, ERISYS TM GE-35H; polyglycerol-3-polyglycidyl ether, such as ERISYS TM GE-38; sorbitol glycidyl ether, such as ERISYS TM GE-60; and bis(2,3-epoxypropyl)cyclohexane-1,2-dicarboxylic acid ester, such as the commercially available Lapox Arch-11.

[0094] For completeness, this invention aims to cover the use of polymers containing epoxy functional groups, wherein said polymers have both epoxy and (meth)acrylate functional groups. Such multifunctional epoxy (meth)acrylate compounds are typically obtained by adding (meth)acrylic acid to the epoxy groups present in the multifunctional epoxy compound. For example, a resin having both types of functional groups is described in U.S. Patent No. 4,751,138 (Tumey et al.). A commercial example is polymer HCT-1, a partially acrylated bisphenol A epoxy resin (CAS No. 55127-80-5).

[0095] While not representing a preferred embodiment, the present invention does not exclude the inclusion of curable compositions comprising one or more cyclic monomers selected from the group consisting of: oxetanes; cyclic carbonates; cyclic anhydrides; and lactones. The disclosures of the following cited documents may be instructive for disclosing suitable cyclic carbonate functional compounds: U.S. Patent No. 3,535,342; U.S. Patent No. 4,835,289; U.S. Patent No. 4,892,954; British Patent No. GB-A-1485,925; and EP-A-0 119,840. However, such cyclic comonomers should constitute less than 20% by weight of the total weight of the epoxy compound, preferably less than 10% by weight or less than 5% by weight.

[0096] b) Organoboron compounds

[0097] The compositions of the present invention comprise b) at least one organoboron compound as defined below. More specifically, the compositions of the present invention comprise 0.5-30% by weight, preferably 1-25% by weight, of b) at least one organoboron compound as defined below. For example, the compositions of the present invention comprise 5 to 20% by weight or 5 to 15% by weight of said at least one organoboron compound, based on their weight.

[0098] The at least one organoboron compound is selected from tetrasubstituted borates of monovalent tertiary amine cations. The tetrasubstituted borate anion can be represented by general formula (II):

[0099]

[0100] Where R 6 R 7 R 8 and R 9 Independently selected from C1-C6 alkyl, C6-C 18 Aryl and C7-C 24 Alkyl aryl. Although the monovalent cation can be a tetraalkylammonium ion, it is preferred that the cation is a heterocyclic moiety – which can be monocyclic, bicyclic or polycyclic – wherein the charged nitrogen atom is part of a heteroalicyclic or heteroaromatic ring system.

[0101] Examples of heterocyclic tertiary amines from which monovalent cations can be derived include: pyridines, such as methylpyridine, isoquinoline, quinoline (1-benzopyridine), N,N-dimethyl-4-aminopyridine, bipyridine, and 2,6-dimethylpyridine; imidazoles; pyrazoles, such as pyrazole and 1,4-dimethylpyrazole; morpholines, such as 4-(2-hydroxyethyl)morpholine, N-ethylmorpholine, N-methylmorpholine, and 2,2′-dimorpholine diethyl ether; piperazines, such as 1-(2-hydroxyethyl)piperazine and N,N-dimethylpiperazine; piperidines, such as N-(2-hydroxyethyl)piperidine, N-ethylpiperidine, N-propylpiperidine, N-butylpiperidine, N-hexylpiperidine, N-cyclohexylpiperidine, and N-octylpiperidine; pyrrolidines, such as N-butylpyrrolidine and N-octylpyrrolidine; and cycloamidines. Other exemplary heterocyclic amines include hexamethylenetetramine, hexamethylenetetramine, and hexapropyltetramine. However, preferred cycloamidinium and imidazodium cations may be mentioned.

[0102] In the first embodiment, the organoboron compound of this portion of the composition is represented by the following general formula (III):

[0103]

[0104] Among them, R 1 R 2 R 3 R 4 and R 5 Independently selected from hydrogen, C1-C 18 Alkyl, C6-C 18 Aryl, C3-C 18 cycloalkyl, C2-C 20 alkenyl, -C(O)R q -C(O)OH, -CN, and -NO2;

[0105] R q It is a C1-C6 alkyl group; and

[0106] R 6 R 7 R 8 and R 9 Independently selected from C1-C6 alkyl, C6-C 18 Aryl and C7-C 24 Alkyl aryl.

[0107] Preferably, R 1 R 2 R 3 R 4 and R 5 Independently selected from hydrogen, C1-C 12 Alkyl, C6-C 18 Aryl, C3-C 12Cycloalkyl, C2-C6 alkenyl, CO2H, -CN, and -NO2. As an alternative or supplement to the preferred statement regarding the imidazole moiety, the R in the borate moiety... 6 R 7 R 8 and R 9 At least three of them are the same. More preferably, R 6 R 7 R 8 and R 9 All are identical and selected from C1-C6 alkyl and phenyl groups. Tetraphenylborate anions are particularly preferred.

[0108] Exemplary compounds of formula (III) that can be used alone or in combination include, but are not limited to: tetraphenylborate imidazole; tetraphenylborate methylimidazole; 2-ethyl-4-methylimidazole tetraphenylborate; 2-ethyl-1,4-dimethylimidazole tetraphenylborate; 1-cyanoethyl-2-ethyl-4-methylimidazole tetraphenylborate; 1-cyanoethyl-2-undecylimidazole tetraphenylborate; 1-cyanoethyl-2-phenylimidazole tetraphenylborate; 1-vinyl-2-methylimidazole tetraphenylborate; 1-vinyl-2,4-dimethylimidazole tetraphenylborate; 1-β-hydroxy-ethyl-2-methylimidazole tetraphenylborate; 1-allyl-2-methylimidazole tetraphenylborate; 1-allyl-2-phenylimidazole tetraphenylborate; and 1-allyl-2-undecylimidazole tetraphenylborate. Particularly preferred are imidazole tetraphenylborate, methylimidazolium tetraphenylborate, 2-ethyl-4-methylimidazolium tetraphenylborate and 2-ethyl-1,4-dimethylimidazolium tetraphenylborate.

[0109] While not intended to limit the synthetic method of compounds of formula (III), exemplary preparation procedures include reactions i) and ii) as follows:

[0110] i) Imidazole salts of formula (IV)

[0111]

[0112] Where R 1 To R 5 As defined above, and X n- To counteract anions; and

[0113] ii) Tetrasubstituted borates of formula (V)

[0114]

[0115] Where R 6 To R 9 As defined above, and M + It is an alkali metal cation.

[0116] Preferably, Xn- It is an anion of chloride, bromide, iodide, sulfate, nitrate, or acetate. Independently or otherwise, M + Li is preferred + Na + or K + .

[0117] The above reactions can typically be carried out in polar protic solvents, such as water, acetic acid, methanol, ethanol, n-propanol, and n-butanol. Furthermore, the reaction temperature can typically range from 10°C to 100°C, for example, from 20°C to 80°C.

[0118] For completeness, the imidazole salt of formula (IV) can be prepared by reacting an imidazole provided below with at least one acid selected from the group consisting of: inorganic acids, such as hydrochloric acid, sulfuric acid, and nitric acid; organic acids, such as acetic acid, oxalic acid, and succinic acid; and acidic aromatic nitro compounds, such as picric acid and picric acid; and quaternizing agents, such as alkyl halides, aryl halides, or aralkyl halides.

[0119]

[0120] The synthesis of imidazole salts (IV) according to this reaction can generally be carried out in polar protic solvents such as water, acetic acid, methanol, ethanol, n-propanol, and n-butanol. Furthermore, the reaction temperature can typically range from 10°C to 100°C, for example, from 20°C to 80°C.

[0121] In a second embodiment of this part of the composition, the organoboron compound is represented by the following general formula (VI):

[0122]

[0123] Where: R 10 Selected from H, C1-C6 alkyl, C6-C 18 Aryl, C7-C 24 Aryl alkyl, C3-C 18 cycloalkyl and C2-C 20 alkenyl;

[0124] R 6 R 7 R 8 and R 9 Independently selected from C1-C6 alkyl, C6-C 18 Aryl and C7-C 24 Alkyl aryl; and

[0125] n is an integer from 1 to 3, for example, 1 or 2.

[0126] Preferably, R 10 Selected from H, C1-C6 alkyl, C3-C 12Cycloalkyl, phenyl, naphthyl or C7-C 12 Aryl alkyl group. More preferably, R 10 Selected from H, C1-C6 alkyl, C3-C 12 Cycloalkyl, phenyl, naphthyl, benzyl, or tolyl. As an alternative or supplement to the preferred statement regarding the bicyclic moiety, the R in the borate moiety... 6 R 7 R 8 and R 9 At least three of them are the same. More preferably, R 6 R 7 R 8 and R 9 All are identical and selected from C1-C6 alkyl and phenyl groups. Tetraphenylborate anions are particularly preferred.

[0127] Examples of compounds according to formula (VI) above include: 8-benzyl-1,8-diazabicyclo[5.4.0]undec-7-ene tetraphenylboronic acid; 1,8-diazabicyclo[5.4.0]undec-7-ene tetraphenylboronic acid; and 1,5-diazabicyclo[4.3.0]non-5-ene tetraphenylboronic acid.

[0128] c) Methacrylamide monomer

[0129] The compositions of the present invention comprise c) at least one (meth)acrylamide monomer. More specifically, the compositions of the present invention, based on their weight, comprise 10 to 50% by weight, preferably 15 to 45% by weight, of the at least one (meth)acrylamide monomer described in c). For example, the compositions of the present invention, based on their weight, comprise 15 to 40% by weight or 25% to 40% by weight of the at least one acrylamide monomer described in c).

[0130] The (meth)acrylamide monomer is monofunctional and conforms to the following general formula (VII):

[0131]

[0132] Among them, R a For H or Me;

[0133] G is selected from -NH2, -NHR b and -N(R) b (R) c );

[0134] R b and R c Independently selected from C1-C 18 Alkyl, C1-C 18 Hydroxyalkyl, C1-C 18 Alkylalkoxy, C6-C 18Aryl and –(CH2) n –N(R d (R) e );

[0135] n is an integer from 1 to 4; and

[0136] R d and R e Independently selected from H and C1-C6 alkyl groups;

[0137] In an embodiment of the (meth)acrylamide monomer according to formula (VII):

[0138] R a For H or Me;

[0139] G is selected from -NH2, -NHR b and -N(R) b (R) c );

[0140] R b and R c Independently selected from C1-C 12 Alkyl, C1-C 12 Hydroxyalkyl, C1-C 12 Alkylalkoxy and –(CH2)n–NR d R e ;

[0141] n is an integer from 2 to 4; and

[0142] R d and R e It is independently selected from C1-C4 alkyl groups.

[0143] Examples of suitable (meth)acrylamide monomers according to formula (VII) include, but are not limited to: (meth)acrylamide; N-methyl (meth)acrylamide; N,N-dimethyl (meth)acrylamide; N-ethyl (meth)acrylamide; N,N-diethyl (meth)acrylamide; N-isopropyl (meth)acrylamide; N-n-butyl (meth)acrylamide; N-tert-butyl (meth)acrylamide; N,N-di-n-butyl (meth)acrylamide; N-octyl (meth)acrylamide; N-dodecyl (meth)acrylamide; N-octadecyl (meth)acrylamide; N-phenyl (meth)acrylamide; N,N-dimethylaminoethyl (meth)acrylamide; N-(2-methoxyethyl)(meth)acrylamide; N-(2-ethoxyethyl)(meth)acrylamide; N-(2-hydroxyethyl)(meth)acrylamide; and N-(2-hydroxypropyl)(meth)acrylamide.

[0144] While not representing a preferred embodiment, the present invention does not preclude curable compositions further comprising one or more polyfunctional (meth)acrylamide compounds. However, in the curable composition, based on the total weight of c) monofunctional (meth)acrylamide monomers, such polyfunctional (meth)acrylamide monomers should account for less than 20% by weight, preferably less than 10% by weight or less than 5% by weight.

[0145] An exemplary multifunctional (meth)acrylamide compound can be represented by the following formula (VIII):

[0146]

[0147] Where: R is H or Me;

[0148] L is –O-, C2-C4 alkylene, or a divalent linking group formed by combining these.

[0149] Examples of divalent linking groups mentioned later include, but are not limited to: -OCH2CH2-, -OCH2CH2CH2-, -OCH2CH2CH2CH2-, -CH2OCH2-, -CH2OCH2CH2- and -CH2OCH2CH2CH2-.

[0150] d) Free radical photoinitiators

[0151] The compositions of the present invention include d) at least one free radical photoinitiator compound, which initiates polymerization or hardening of the composition upon irradiation with photochemical radiation. It has been determined that the compositions of the present invention can be cationically polymerizable or free radicalally polymerizable: although the epoxy groups are cationically active, the inventors have chosen a free radical polymerization mechanism based on the presence of free radical-active unsaturated groups in the composition.

[0152] Generally, radical photoinitiators are classified into radical photoinitiators that form radicals through cleavage (referred to as "Norrish Type I") and radical photoinitiators that form radicals through dehydrogenation (referred to as "Norrish Type II"). Norrish Type II photoinitiators require a hydrogen donor to act as the radical source: since initiation is based on a bimolecular reaction, Norrish Type II photoinitiators are typically slower than Norrish Type I photoinitiators, which form radicals based on a unimolecular reaction. On the other hand, Norrish Type II photoinitiators exhibit better light absorption in the near-ultraviolet spectral region. Although active hydrogen is indeed present in the compositions according to the invention, those skilled in the art should be able to select a suitable radical photoinitiator based on the photochemical radiation employed during curing and the sensitivity of the photoinitiator at that wavelength.

[0153] According to one embodiment of the invention, the composition comprises d) at least one free radical photoinitiator selected from the group consisting of: benzoylphosphine oxide; aryl ketones; benzophenone; hydroxylated ketones; 1-hydroxyphenyl ketones; ketals; and metallocenes. For completeness, combinations of two or more of these photoinitiators are not excluded in this invention.

[0154] According to a preferred embodiment of the present invention, the composition comprises d) at least one free radical photoinitiator selected from the group consisting of: benzoin dimethyl ether; 1-hydroxycyclohexylphenyl ketone; benzophenone; 4-chlorobenzophenone; 4-methylbenzophenone; 4-phenylbenzophenone; 4,4'-bis(diethylamino)benzophenone; 4,4'-bis(N,N'-dimethylamino)benzophenone (Michler ketone); isopropylthioxanthone; 2-hydroxy-2-methylphenylpropanone (Daracur 1173); 2-methyl-4-(methylthio)-2-morpholinophenylacetone; methyl benzoylcarboxylate; methyl 2-benzoylbenzoate; 2-ethylhexyl 4-(dimethylamino)benzoate; ethyl 4-(N,N-dimethylamino)benzoate; phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide; diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide; and ethyl phenyl(2,4,6-trimethylbenzoyl)phosphite. Again, of course, combinations of two or more of these photoinitiators are not excluded in this invention.

[0155] The amount of photoinitiator d) in the composition, based on the weight of the composition, should be 0.05 to 10.0% by weight, for example, 0.1 to 5.0% by weight or 0.1 to 2.5% by weight.

[0156] The purpose of irradiating a curable composition is to generate an active substance from a photoinitiator (d) that initiates the curing reaction. Once this substance is generated, the curing chemistry follows the same thermodynamic rules as any chemical reaction: the reaction rate can be accelerated by heating. The use of heat treatment to enhance the photochemical radiation curing of monomers is well known in the art.

[0157] The use of photoinitiator d) and the photoalkali and acid generators mentioned below can produce residual compounds from photochemical reactions in the final cured product. These residues can be detected using conventional analytical techniques, such as infrared, ultraviolet, and NMR spectroscopy; gas chromatography or liquid chromatography; and mass spectrometry. Therefore, the present invention may comprise a cured matrix (co)polymer and detectable amounts of residues from the free radical photoinitiator and photoalkali / acid generators. These residues are present in small amounts and generally do not interfere with the desired physicochemical properties of the final cured product.

[0158] Those skilled in the art will understand that photosensitizers can be incorporated into the composition to improve the efficiency of photoinitiator d) in utilizing the energy transferred. The term "photosensitizer" is used according to its standard meaning to indicate any substance that increases the rate of photoinitiated polymerization or alters the wavelength at which polymerization occurs. Based on the weight of the at least one free radical photoinitiator described in d), the amount of photosensitizer should be from 0 to 25% by weight.

[0159] e1) Optional (meth)acrylate monomers

[0160] In some embodiments, the composition may further comprise, based on its weight, up to 15% by weight of e1) at least one (meth)acrylate monomer represented by formula M:

[0161] H2C=CQCO2R 1 (M)

[0162] Wherein: Q is hydrogen, halogen, or C1-C4 alkyl; and

[0163] R 1 Selected from C1-C 30 Alkyl, C3-C 30 cycloalkyl, C2-C 20 alkenyl, C2-C 12 alkynyl group, C6-C 18 Aryl, C7-C 18 Alkyl and C7-C 18 Aryl group.

[0164] The composition may contain, for example, 0 to 10 wt% or 0 to 5 wt% of at least one (meth)acrylate monomer represented by formula M. Ideally, the monomer (M) is characterized by R 1 Selected from C1-C 18 Alkyl and C3-C 18 Cycloalkyl. This preferred statement is expressly intended to include R therein. 1 It is an embodiment of C1-C6 hydroxyalkyl.

[0165] Exemplary (meth)acrylate monomers according to formula (M) that can be used alone or in combination include, but are not limited to: methyl (meth)acrylate; ethyl (meth)acrylate; butyl (meth)acrylate; hexyl (meth)acrylate; 2-ethylhexyl (meth)acrylate; dodecyl (meth)acrylate; lauryl (meth)acrylate; cyclohexyl (meth)acrylate; isobornyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate (HEMA); 2-hydroxypropyl (meth)acrylate; ethylene glycol monomethyl ether (meth)acrylate; ethylene glycol monoethyl ether (meth)acrylate; ethylene glycol monododecyl ether (meth)acrylate; diethylene glycol monomethyl ether (meth)acrylate; trifluoroethyl (meth)acrylate; perfluorooctyl (meth)acrylate; benzyl (meth)acrylate; phenoxyethyl (meth)acrylate; phenoxydiethylene glycol (meth)acrylate; phenoxypropyl (meth)acrylate; and phenoxydipropylene glycol (meth)acrylate. e2) Optional (meth)acrylate functionalized oligomers

[0166] Independent of or in addition to the (meth)acrylate monomer (M) described above, the compositions of the present invention may further comprise up to 10 wt% of e2) at least one (meth)acrylate-functionalized oligomer, which does not have epoxy groups. The compositions may comprise, for example, 0 to 10 wt% or 0 to 5 wt% of e2) the at least one (meth)acrylate-functionalized oligomer. The oligomer may have one or more acrylate and / or methacrylate groups attached to the oligomer backbone, the (meth)acrylate functional groups being at terminal positions on the oligomer and / or distributed along the oligomer backbone.

[0167] Preferably, e2) the at least one (meth)acrylate functionalized oligomer: i) has two or more (meth)acrylate functional groups per molecule; and / or ii) has a weight-average molecular weight (Mw) of 300 to 1000 Daltons.

[0168] Examples of such oligomers that can be used alone or in combination include, but are not limited to: (meth)acrylate-functionalized urethane oligomers, such as (meth)acrylate-functionalized polyester urethanes and (meth)acrylate-functionalized polyether urethanes; (meth)acrylate-functionalized polybutadiene; (meth)acrylate polyol (meth)acrylates; polyester (meth)acrylate oligomers; polyamide (meth)acrylate oligomers; and polyether (meth)acrylate oligomers. Such (meth)acrylate-functionalized oligomers and methods for their preparation are particularly disclosed in the following: U.S. Patent Nos. 4,574,138; 4,439,600; 4,380,613; 4,309,526; 4,295,909; 4,018,851; 3,676,398; 3,770,602; 4,072,529; 4,511,732; 3,700,643; 4,133,723; 4,188,455; 4,206,025; and 5,002,976.

[0169] In some embodiments, component e2) may include at least one (meth)acrylate corresponding to formula (O) or be composed of it:

[0170]

[0171] Where: R 4 It can be selected from hydrogen, C1-C4 alkyl, and

[0172]

[0173] R 5 It can be selected from hydrogen, halogens, and C1-C4 alkyl groups;

[0174] R 6 It can be selected from hydrogen, hydroxyl, and

[0175]

[0176] m is an integer ≥ 1, preferably 1 to 8;

[0177] v is 0 or 1; and

[0178] n is an integer, and n≥3, preferably 3 to 30.

[0179] Among polyether (meth)acrylates of this type O, poly(ethylene glycol) di(meth)acrylates having the following structure may be specifically mentioned:

[0180]

[0181] Wherein: n≥3, preferably 3 to 30, more preferably 3 to 20.

[0182] Therefore, specific examples include, but are not limited to: PEG 200DMA (n≈4); PEG 400DMA (n≈9); PEG600DMA (n≈14); and PEG 800DMA (n≈19), wherein the specified number (e.g., 400) represents the weight-average molecular weight of the diol portion of the molecule.

[0183] f) Additives and auxiliary ingredients

[0184] The compositions obtained in this invention typically further comprise additives and auxiliaries that can impart improved properties to these compositions. For example, additives and auxiliaries may impart one or more of the following properties: improved elastic properties; improved resilience; longer processing time; faster curing time; and lower residual tack. Such additives and auxiliaries include catalysts, plasticizers, coupling agents, adhesion promoters, stabilizers (including UV stabilizers), antioxidants, secondary tougheners, fillers, reactive diluents, desiccants, fungicides, flame retardants, rheology modifiers, colored pigments or color pastes, and / or optionally, within a very small range, non-reactive diluents.

[0185] Suitable catalysts are substances that promote the (homogeneous) polymerization of epoxy compounds. Without limiting the catalysts used in this invention, suitable catalysts may be mentioned as follows: i) acids or compounds that can be hydrolyzed into acids, particularly 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) sulfonates; d) inorganic acids, such as phosphoric acid; e) Lewis acid compounds, such as BF3 amine complexes, SbF6 thionium salts, and diaromatic iron complexes; f) Bronsted acid compounds, such as pentafluoroantimony acid complexes; and e) mixtures of the above acids and esters; ii) phenols, particularly bisphenols; iii) phenolic resins; iv) Mannich bases; and v) phosphites, such as diphenyl phosphites and triphenyl phosphites.

[0186] In one embodiment, the amine catalyst used to cure the epoxy resin-based composition can be a photoalkali generator: said photoalkali generator releases amines upon exposure to UV radiation of a typical wavelength of 320–420 nm. There are no particular limitations on the photoalkali generator, as long as it generates amines directly or indirectly under light irradiation. However, suitable photoalkali generators that may be mentioned include: benzyl carbamate; benzoyl carbamate; O-carbamoyl hydroxylamine; O-carbamoyl oxime; aromatic sulfonamides; α-lactams; N-(2-allylvinyl)amides; aryl azides; N-arylformamides; and 4-(o-nitrophenyl)dihydropyridine.

[0187] For completeness, the preparation of photoalkali-generating compounds is known in the art, and guiding references include U.S. Patent No. 5,650,261 (Winkel).

[0188] In an alternative embodiment, the acid catalyst may be selected from a photoacid generator (PAG): upon irradiation with light energy, the ionic photoacid generator undergoes a cleavage reaction and releases one or more Lewis acid or Bronsted acid molecules, which catalyze ring-opening and introduce epoxy side groups to form crosslinks. Useful photoacid generators are thermally stable, do not undergo thermally induced reactions with the formed copolymer, and are readily soluble or dispersed in the curable composition.

[0189] Exemplary cations that can be used as the cationic portion of the ionic PAG of the present invention include organic onium cations, such as those described in U.S. Patent 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 include onium salts centered on aliphatic or aromatic Group IVA and VIIA (CAS version), preferably onium salts centered on I, S, P, Se, N, and C, such as those selected from sulfonium oxide, iodoonium salts, sulfonium salts, selenium salts, pyridinium salts, carboonium salts, and phosphonium salts.

[0190] As is known in the art, the properties of counter anions in ionic photoacid generators (PAGs) can affect the rate and extent of cationic addition polymerization of epoxy groups. For illustrative purposes, the reactivity order of commonly used nucleophilic anions is SbF6 > AsF6 > PF6 > BF4. The influence of anions on reactivity is attributed to three main factors that should be compensated for by those skilled in the art in this invention: (1) the acidity of the protons or Lewis acids produced; (2) the degree of ion-pair separation in the growing cationic chain; and (3) the sensitivity of the anion to defluorination and subsequent chain termination.

[0191] It will be apparent to those skilled in the art that the presence of a combination of photoalkali-generating agents and photoacid-generating agents with at least one free radical photoinitiator described in d) is not excluded in this invention. However, overall, the amount of photoinitiator in the composition, based on the weight of the composition, should be less than 12% by weight, preferably less than 10% by weight.

[0192] The "plasticizer" used for the purposes of this invention is a substance that reduces the viscosity of a composition and thus benefits its processability. In this document, based on the total weight of the composition, the plasticizer may comprise up to 10% by weight or up to 5% by weight, and is preferably selected from the group consisting of: polydimethylsiloxane (PDMS); diurethane; monofunctional linear or branched C4-C... 16 Ethers of 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 with OH groups or epoxidized fatty acids; glycolates; benzoates; phosphate esters; sulfonates; trimellitates; polyether plasticizers, such as terminally capped polyethylene glycol or polypropylene glycol; polystyrene; hydrocarbon plasticizers; chlorinated paraffins; and mixtures thereof. It should be noted that phthalates can be used as plasticizers in principle, but they are not preferred due to their potential toxicological hazards.

[0193] In some embodiments, the composition, based on its weight, comprises up to 5% by weight of at least one epoxy silane coupling agent, which can be used to enhance the adhesion of the cured composition to a designated surface. The hydrolyzable groups of the coupling agent can react with the surface to remove unwanted hydroxyl groups; its epoxy groups react with the film-forming polymer to chemically bond the polymer to the surface. Preferably, the coupling agent has 1 to 3 hydrolyzable functional groups and at least one epoxy group.

[0194] Examples of suitable epoxy silane coupling agents include, but are not limited to: glycidyloxy polymethylene trimekoxy silanes, such as 3-glycidyloxy-1-propyl-trimethoxy silane; (meth)acryloyloxy polymethylene trimekoxy silanes, such as 3-methacryloyloxy-1-propyltrimethoxy silane; γ-methacryloyloxypropyltrimethoxy silane (A-174, purchased from GE Silicones); γ-glycidyloxypropyltrimethoxy silane (A-187, purchased from Momentive Performance Materials, Inc.); α-glycidyloxypropylmethyldiethoxy silane (A-2287, purchased from Momentive Performance Materials, Inc.); vinyl-tris(2-methoxyethoxy)silane (A-172, purchased from Momentive Performance Materials, Inc.); and α-chloropropyltrimethoxy silane (KBM-703, purchased from Shin-Etsu Chemical Co., Ltd.).

[0195] The term "stabilizer" used for the purposes of this invention should be understood as an antioxidant, UV stabilizer, or hydrolytic stabilizer. In this document, a stabilizer may comprise up to 10% by weight or up to 5% by weight of the total weight of the composition. Standard commercial examples of stabilizers suitable for use herein include: sterically hindered phenols; thioethers; benzotriazoles; benzophenone; benzoate esters; cyanoacrylates; acrylates; amines of the hindered amine light stabilizer (HALS) type; phosphorus; sulfur; and mixtures thereof.

[0196] As described above, the compositions according to the invention may additionally contain fillers. Suitable fillers include, for example, chalk, lime powder, precipitated and / or pyrolytic silica, zeolite, bentonite, magnesium carbonate, diatomaceous earth, alumina, clay, talc, titanium dioxide, iron oxide, zinc oxide, sand, quartz, flint, mica, glass powder, and other ground minerals. Organic fillers may also be used, particularly carbon black, graphite, wood fiber, wood flour, sawdust, cellulose, cotton, pulp, cotton, sawdust, chopped straw, chaff, ground walnut shells, and other chopped fibers. Short fibers, such as glass fiber, glass filament, polyacrylonitrile, carbon fiber, Kevlar fiber, or polyethylene fiber, may also be added. Aluminum powder is also suitable as a filler.

[0197] Pyrolysis and / or precipitation of silica advantageously have 10 to 90 m 2 / g BET surface area. When used, they do not cause any additional increase in viscosity of the compositions according to the invention, but do help to enhance the cured composition.

[0198] Similarly, it is conceivable to use materials with a larger surface area, advantageously 100 to 250 m². 2 / g, especially 110 to 170m 2 / g of pyrolytic and / or precipitated silica as filler: Due to its large BET surface area, silica can be used in a smaller weight proportion to enhance the curing composition.

[0199] Hollow spheres with mineral or plastic shells are also suitable as fillers. These can be, for example, trade names like Glass. Hollow glass spheres for sale. Plastic-based hollow spheres can also be used, for example... or They are described in EP 0520426 B1: They are made of inorganic or organic matter and each has a diameter of 1 mm or less, preferably 500 μm or less.

[0200] Fillers that impart thixotropic properties to a composition are preferred for many applications: such fillers are also described as rheology modifiers, such as hydrogenated castor oil, fatty acid amides, or swellable plastics such as PVC.

[0201] The total amount of filler present in the compositions of the present invention is based on the total weight of the composition, preferably 0 to 40% by weight, more preferably 0 to 20% by weight. The desired viscosity of the liquid curable composition will generally determine the total amount of filler added: in the present invention, ideally the liquid curable composition has a viscosity of 200 to 150,000 mPas, preferably 200 to 50,000 mPas or even 200 to 10,000 mPas.

[0202] Examples of suitable pigments are titanium dioxide, iron oxide, or carbon black.

[0203] To further extend shelf life, it is generally recommended to use a desiccant to further stabilize the moisture penetration of the compositions of the present invention. Sometimes it is also necessary to reduce the viscosity of the coating, adhesive, or sealant compositions according to the present invention for specific applications by using a reactive diluent. The total amount of reactive diluent is typically up to 15% by weight, preferably 1 to 5% by weight, based on the total weight of the composition.

[0204] The presence of a non-reactive diluent is not excluded in the compositions of the present invention, if it can effectively adjust the viscosity of the composition. For example, but only for illustrative purposes, the composition may comprise 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 (from Exxon); alkylphenols, such as tert-butylphenol, nonylphenol, dodecylphenol and 8,11,14-pentadecanterenephenol; stylated phenols; bisphenols; aromatic hydrocarbon resins, especially those containing phenolic groups, such as ethoxylated or propoxylated phenols; adipates; sebacic acid esters; phthalates; benzoates; organophosphates or sulfonates; and sulfonamides.

[0205] In addition to the above, it is preferred that the non-reactive diluent accounts for less than 10% by weight of the total weight of the composition, particularly less than 5% by weight or less than 2% by weight.

[0206] Exemplary embodiments of one-component (1K) compositions

[0207] In an exemplary embodiment of the invention, the liquid single-component (1K) composition comprises, by weight:

[0208] 30 to 70% by weight of a) at least one epoxy resin;

[0209] 5 to 15% by weight of b) at least one organoboron compound selected from cycloamidinium tetrasubstituted borate and imidazolium tetrasubstituted borate;

[0210] 25 to 40% by weight of c) at least one (meth)acrylamide monomer of formula (VII):

[0211]

[0212] Among them, R a For H or Me;

[0213] G is selected from -NH2, -NHR b and -N(R) b (R) c );

[0214] R b and R c Independently selected from C1-C 12 Alkyl, C1-C 12 Hydroxyalkyl, C1-C 12 Alkylalkoxy and –(CH2) n –NR d R e ;

[0215] n is an integer from 2 to 4; and

[0216] R d and R e Independently selected from C1-C4 alkyl groups; and

[0217] d) 0.1 to 2.5% by weight of at least one free radical photoinitiator.

[0218] Methods and Applications

[0219] To form the composition, the above-mentioned components are brought together and mixed. As is known in the art, to form a one-component (1K) curable composition, the components of the composition are brought together and mixed uniformly under conditions that inhibit or prevent the reaction of reactive components: as will be readily understood by those skilled in the art, this may include mixing conditions that limit or prevent exposure to moisture, heat, or radiation, or limit or prevent the activation of potential catalysts. Therefore, it is generally preferred that the curing agent components are mixed in predetermined amounts under anhydrous conditions, not by hand, but by a machine such as a static or dynamic stirrer, without deliberate heating or light exposure.

[0220] According to the most extensive aspect of the invention, the above composition is applied to a substrate and then cured in situ. Pretreatment of the relevant surface to remove foreign matter is generally recommended before application of the composition; if applicable, this step promotes subsequent adhesion of the composition to the surface. Such treatment is known in the art and can be carried out in one or more steps, for example, by using one or more of the following: etching with an acid suitable for the substrate and optionally an oxidizing agent; ultrasonic treatment; plasma treatment, including chemical plasma treatment, corona treatment, atmospheric pressure plasma treatment, and flame plasma treatment; immersion in an aqueous alkaline degreasing bath; treatment with an aqueous cleaning emulsion; treatment with a cleaning solvent such as carbon tetrachloride or trichloroethylene; and rinsing with water, preferably deionized water or softened water. In those cases using an aqueous alkaline degreasing bath, any residual degreasing agent on the surface is ideally removed by rinsing the substrate surface with deionized water or softened water.

[0221] In some embodiments, adhesion of the coating composition of the present invention to a preferably pretreated substrate can be promoted by applying a primer to it. While those skilled in the art can select a suitable primer, guidance for selecting a primer includes, but is not limited to, U.S. Patent Nos. 3,671,483, 4,681,636, 4,749,741, 4,147,685, and 6,231,990.

[0222] The composition is then applied to a preferably pretreated, optionally primed, surface of the substrate using conventional application methods, such as: brushing; roller coating using, for example, a 4-roller coating apparatus for solvent-free compositions or a 2-roller coating apparatus for solvent-containing compositions; doctor 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 to apply the composition to a wet film thickness of 10 to 500 μm. Applying thinner layers within this range is more economical and reduces the likelihood of thick cured areas that may require sanding for coating applications. However, careful control is necessary when applying thinner coatings or layers to avoid the formation of discontinuous cured films.

[0223] Typically, the energy source used to initiate the curing of the applied composition emits at least one of ultraviolet radiation, infrared (IR) radiation, visible light, X-rays, gamma rays, or an electron beam. After application, when irradiated with commercial curing equipment, radiation-curable coating compositions can typically be activated in less than 5 minutes, and usually in 1 to 60 seconds, for example, in 3 to 12 seconds.

[0224] Irradiating ultraviolet light should typically have a wavelength of 150 to 600 nm, preferably 200 to 450 nm. Available ultraviolet light sources include, for example, ultra-high pressure mercury lamps, high pressure mercury lamps, medium pressure mercury lamps, low-intensity fluorescent lamps, metal halide lamps, microwave-powered lamps, xenon lamps, UV-LED lamps, and laser beam sources such as excimer lasers and argon ion lasers.

[0225] When using an electron beam to cure the applied coating, the standard parameters of the operating device can be: accelerating voltage: 0.1 keV to 100 keV; vacuum: 10 to 10 -3 Pa; current: 0.0001 to 1 ampere; and power: 0.1 watt to 1 kilowatt.

[0226] The amount of radiation required to ideally cure a single coating composition, thus fixing the coating, will depend on several factors, including the angle of exposure and the thickness of the coating. However, broadly speaking, it ranges from 5 to 5000 mJ / cm². 2The curing dosage can be considered to be typically 50 to 500 mJ / cm³. 2 For example, 50 to 400 mJ / cm 2 The curing dosage can be considered highly effective.

[0227] The purpose of irradiation is to generate an active substance from the photoinitiator d) that initiates the curing reaction. Once this substance is generated, curing chemistry follows the same thermodynamic rules as any chemical reaction: the reaction rate can be accelerated by heating or slowed down by lower temperatures.

[0228] Complete curing of the applied curable composition should generally occur at a temperature of 100°C to 200°C, preferably 100°C to 170°C, and especially 120°C to 160°C. The suitable temperature depends on the specific compound present and the desired curing rate, and in individual cases can be determined by a person skilled in the art using simple preliminary tests (if necessary). Where applicable, conventional means, including microwave induction, can be used to raise the temperature of the curable composition above the mixing and / or application temperature.

[0229] The curable compositions according to the invention can be used for: varnishes; inks; adhesives for fibers and / or particles; glass coatings; coatings and bonding of mineral building materials such as lime and / or cement-bonded plaster, gypsum-containing surfaces, fiber cement building materials and concrete; coatings, sealing or bonding of wood and wood-based materials such as cardboard, fiberboard and paper; coatings or bonding of metal surfaces; coatings of pavements containing asphalt and tar; coatings, sealing or bonding of various plastic surfaces; and coatings of leather and textiles.

[0230] In a particularly preferred embodiment, the composition of the invention is applied to a structural substrate to produce an adhesive, highly abrasion-resistant coating or bond. The bonding operation can typically be performed at temperatures below 200°C, and effective abrasion resistance is achieved upon curing. Furthermore, when bonded to the surface of a mechanical structure or to a floor or pavement, the coating composition provides strong and reliable adhesion, offers thermal stability and corrosion protection to the surface, and prevents the surface from coming into contact with compounds detrimental to the operation or efficiency of the particular structure.

[0231] The following examples are used to illustrate the invention and are not intended to limit the scope of the invention in any way.

[0232] Example

[0233] The following compounds and materials were used in the examples:

[0234] JER TM 828: Bisphenol A liquid epoxy resin, formed by the polycondensation of bisphenol A and epichlorohydrin, purchased from Mitsubishi Chemical.

[0235] 2-Ethyl-4-methylimidazolium tetraphenylborate: purchased from Fuji Film Wako Chemical (CAS No. 53831-70-2)

[0236] N,N-Dimethylacrylamide: purchased from Sigma Aldrich (CAS No. 2680-03-7)

[0237] Daracure 1173: 2-hydroxy-2-methyl-1-phenyl-prop-1-one (CAS No. 7473-98-5), liquid photoinitiator, purchased from BASF.

[0238] HCT-1: Partially acrylated bisphenol A epoxy resin (CAS No. 55127-80-5).

[0239] The mixture forms the formulations described in Table 1 below.

[0240] Table 1

[0241]

[0242] Each formulation was a clear, colorless liquid that showed no significant increase in viscosity after 28 days of storage at room temperature. Formulation 1 had an initial viscosity of 330 mPas at 25°C upon formation. Formulation 2 had an initial viscosity of 2400 mPas at 25°C upon formation. Both formulations were found to cure independently under UV irradiation and thermosetting conditions.

[0243] In specific tests, each formulation was exposed to 100 mW / cm² from a high-pressure mercury lamp. 2 The product is cured by irradiating it with ultraviolet light at a high intensity for 1 second and then heating it at 150°C for 60 minutes. The resulting cured product is a transparent amber-colored solid.

[0244] In view of the foregoing description and embodiments, it will be apparent to those skilled in the art that modifications may be made thereto without departing from the scope of the claims.

Claims

1. A liquid one-component composition, wherein, based on the weight of the composition, the composition comprises: 10 to 90% by weight of a) at least one epoxy resin; 0.5 to 30% by weight of b) at least one organoboron compound selected from a tetrasubstituted borate of a monovalent tertiary amine cation; c) at least one (meth)acrylamide monomer of formula (VII) 10 to 50% by weight: (VII) wherein R is H or Me; and a is H or Me; G is selected from -NH2, -NHR b and -N(R) b (R) c ); R b and R c Independently selected from C1-C 18 Alkyl, C1-C 18 Hydroxyalkyl, C1-C 18 Alkylalkoxy, C6-C 18 Aryl and –(CH2) n –N(R d (R) e ); n is an integer from 1 to 4; and R d and R e Independently selected from H and C1-C6 alkyl groups; d) at least one free radical photoinitiator, ranging from 0.05 to 10% by weight; (Meth)acrylate monomers or (meth)acrylate-functionalized oligomers may be present; as well as, Any available additives.

2. The composition of claim 1, wherein, based on the weight of the composition, the composition comprises: 20 to 80% by weight of a) at least one epoxy resin; 1 to 25% by weight of b) at least one organoboron compound selected from a tetrasubstituted borate of a monovalent tertiary amine cation; c) at least one (meth)acrylamide monomer, ranging from 15 to 45% by weight; and d) 0.1 to 5% by weight of at least one free radical photoinitiator.

3. The composition according to claim 1 or 2, wherein component a) comprises at least one epoxy resin selected from: glycidyl ethers of polyols and polyphenols; glycidyl esters of polycarboxylic acids; and epoxidized polyene-bonded unsaturated hydrocarbons, esters, ethers and amides.

4. The composition according to claim 1 or 2, wherein component a) comprises an epoxy-functionalized polymer having both epoxy and (meth)acrylate functional groups.

5. The composition according to claim 1 or 2, wherein component b) comprises cycloamidinium tetrasubstituted borate and / or imidazodium tetrasubstituted borate.

6. The composition according to claim 5, wherein component b) comprises a compound represented by the following general formula (III): Equation (III) in, R 1 R 2 R 3 R 4 and R 5 Independently selected from hydrogen, C1-C 18 Alkyl, C6-C 18 Aryl, C3-C 18 cycloalkyl, C2-C 20 alkenyl, -C(O)R q -C(O)OH, -CN, and -NO2; R q It is a C1-C6 alkyl group; and R 6 R 7 R 8 and R 9 Independently selected from C1-C6 alkyl, C6-C 18 Aryl and C7-C 24 Alkyl aryl.

7. The composition according to claim 6, wherein R 1 R 2 R 3 R 4 and R 5 Independently selected from hydrogen, C1-C 12 Alkyl, C6-C 18 Aryl, C3-C 12 Cycloalkyl, C2-C6 alkenyl, CO2H, -CN and -NO2.

8. The composition according to claim 5, wherein component b) comprises a compound represented by the following general formula (VI): (WE) in: R 10 Selected from H, C1-C6 alkyl, C6-C 18 Aryl, C7-C 24 Aryl alkyl, C3-C 18 cycloalkyl and C2-C 20 alkenyl; R 6 R 7 R 8 and R 9 Independently selected from C1-C6 alkyl, C6-C 18 Aryl and C7-C 24 Alkyl aryl; and n is an integer from 1 to 3.

9. The composition according to any one of claims 6 to 8, wherein R 6 R 7 R 8 and R 9 All are identical and selected from C1-C6 alkyl and phenyl groups.

10. The composition according to claim 8, wherein R 10 Selected from H, C1-C6 alkyl, C3-C 12 Cycloalkyl, phenyl, naphthyl, benzyl or tolyl.

11. The composition according to claim 5, wherein component b) comprises at least one salt selected from the group consisting of: imidazole tetraphenylborate; methylimidazolium tetraphenylborate; 2-ethyl-4-methylimidazolium tetraphenylborate; 2-ethyl-1,4-dimethylimidazolium tetraphenylborate; 8-benzyl-1,8-diazabicyclo[5.4.0]undecyl-7-ene tetraphenylborate; 1,8-diazabicyclo[5.4.0]undecyl-7-ene tetraphenylborate; and 1,5-diazabicyclo[4.3.0]nonyl-5-ene tetraphenylborate.

12. The composition according to claim 1 or 2, wherein component c) comprises at least one (meth)acrylamide monomer of formula (VII): (VII) in, R a For H or Me; G is selected from -NH2, -NHR b and -N(R) b (R) c ); R b and R c Independently selected from C1-C 12 Alkyl, C1-C 12 Hydroxyalkyl, C1-C 12 Alkylalkoxy and –(CH2) n –NR d R e ; n is an integer from 2 to 4; and R d and R e It is independently selected from C1-C4 alkyl groups.

13. The composition according to claim 1 or 2, wherein component c) comprises at least one (meth)acrylamide monomer selected from the group consisting of: (meth)acrylamide; N-methyl (meth)acrylamide; N,N-dimethyl (meth)acrylamide; N-ethyl (meth)acrylamide; N,N-diethyl (meth)acrylamide; N-isopropyl (meth)acrylamide; N-n-butyl (meth)acrylamide; N-tert-butyl (meth)acrylamide; N,N-di-n-butyl (meth)acrylamide; N-octyl (meth)acrylamide; N-dodecyl (meth)acrylamide; N-octadecyl (meth)acrylamide; N-phenyl (meth)acrylamide; N,N-dimethylaminoethyl (meth)acrylamide; N-(2-methoxyethyl)(meth)acrylamide; N-(2-ethoxyethyl)(meth)acrylamide; N-(2-hydroxyethyl)(meth)acrylamide; and N-(2-hydroxypropyl)(meth)acrylamide.

14. The composition according to claim 1 or 2, wherein component d) comprises at least one free radical photoinitiator selected from the group consisting of: benzoin dimethyl ether; 1-hydroxycyclohexylphenyl ketone; benzophenone; 4-chlorobenzophenone; 4-methylbenzophenone; 4-phenylbenzophenone; 4,4'-bis(diethylamino)benzophenone; 4,4'-bis(N,N'-dimethylamino)benzophenone; isopropylthioxanthone; 2-hydroxy-2-methyl Acetone; 2-methyl-4-(methylthio)-2-morpholinoacetone; methyl benzoylcarboxylate; methyl 2-benzoylbenzoate; 2-ethylhexyl 4-(dimethylamino)benzoate; ethyl 4-(N,N-dimethylamino)benzoate; phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide; diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide; and ethyl phenyl(2,4,6-trimethylbenzoyl)phosphine oxide.

15. The composition according to claim 2, wherein, based on the weight of the composition, the composition comprises 30 to 70% by weight of a) at least one epoxy resin.

16. The composition according to claim 2, wherein, based on the weight of the composition, the composition comprises 5 to 15% by weight of b) at least one organoboron compound selected from a tetrasubstituted borate of a monovalent tertiary amine cation.

17. The composition according to claim 2, wherein, based on the weight of the composition, the composition comprises 25 to 40% by weight of c) at least one (meth)acrylamide monomer.

18. The composition according to claim 2, wherein, based on the weight of the composition, the composition comprises 0.1 to 2.5% by weight of d) at least one free radical photoinitiator.

19. A cured product obtained from any one of the liquid one-component compositions according to claims 1 to 18.

20. Use of the cured product according to claim 19 as a coating, sealant or adhesive.

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