EP2313463A2

EP2313463A2 - Epoxide/(meth)acrylate composition

Info

Publication number: EP2313463A2
Application number: EP09780749A
Authority: EP
Inventors: Markus Haufe; Andreas Kramer
Original assignee: Sika Technology AG
Current assignee: Sika Technology AG
Priority date: 2008-07-17
Filing date: 2009-07-17
Publication date: 2011-04-27
Also published as: US20130079437A1; WO2010007148A3; WO2010007148A2; US8318870B2; US20120022183A1

Abstract

The invention relates to a composition comprising at least one radically polymerisable monomer M; at least one radical former, at least one epoxide resin A comprising an average of more than one epoxide group per molecule, and at least one compound of formula (I). Such compositions are suitable as adhesives, sealants or coatings. Shortly after the application thereof, they have a high initial strength and, after further hardening at room temperature, they reach a high level of final strength.

Description

EPOXID (METH) ACRYLATE COMPOSITION

Technical area

The invention relates to the field of polymerizable compositions based on epoxy resins and free-radically polymerizable monomers.

State of the art

Both the use of (meth) acrylate compositions and of epoxy resins is widespread in the adhesive, sealing and coating technology. Here, (meth) acrylate compositions are distinguished, above all, by a high initial strength and generally rapid curing, epoxy resins, above all by a high final strength.

To exploit the advantages of both technologies, hybrid systems with (meth) acrylates and epoxides are produced. Such hybrid systems are described, for example, in EP 1 431 365 A1 and EP 0 160 621 A1. The disadvantage of these compositions is that the curing of the epoxy resin, an elevated temperature in the range of about 120 to 150 ⁰ C is necessary and that they are therefore unsuitable for heat-sensitive substrates. Another reason against the use of thermosetting compositions arises for example in applications in which the composition is applied over a large area and where the substrate provided with the composition due to its dimensions not readily uniform and over the entire surface at the same time, for example in an oven, can be heated so that the composition could harden. For example, this is the case with large-surface coatings, in particular also with floor coverings. Non-uniform heating and the associated non-uniform curing of thermosetting compositions in such a case can lead to stresses within the cured composition.

Likewise unsuitable are heat-curing compositions from the prior art for the bonding of substrates with different coefficients of thermal expansion, since these after cooling on the curing of the adhesive have different contractions, which can lead to unfavorable stresses in the adhesive bond. For such applications, the compositions according to the invention are particularly suitable. The heretofore known curing agents for epoxy resins, in particular aliphatic amines, which enable curing of the epoxy resin even at room temperature, are not suitable for use in a hybrid system with (meth) acrylates and epoxides since they inhibit the free-radical polymerization reaction of the (meth) acrylate monomers and thus no optimal initial strength is achieved.

Presentation of the invention

The object of the present invention is therefore to provide a composition which has a high initial strength shortly after its application and, after further curing at room temperature, attains a high final strength.

Surprisingly, it has now been found that compositions according to claim 1 solve this problem.

By the use of specific compounds as hardeners for the epoxy resin, which is in no way obvious to the person skilled in the art, the free-radical polymerization reaction can be used immediately after the application of the composition and can proceed without inhibition, so that a high initial strength is achieved. At the same time, this specific compound allows the epoxy resin to cure completely without additional energy being supplied to the system in any way, ie in particular that no additional heat has to be added to the composition for curing and / or postcuring.

Further aspects of the invention are the subject of further independent claims. Particularly preferred embodiments of the invention are the subject of the dependent claims. Ways to carry out the invention

The present invention relates in a first aspect to a composition comprising a) at least one free-radically polymerizable monomer M; b) at least one radical generator; c) at least one epoxy resin A, which has on average more than one epoxide group per molecule; and d) at least one compound of the formula (I).

In this case, the radical R ^{1 is} a hydrocarbon radical having 1 to 6 C atoms, in particular an ethyl or a methyl group.

The radicals R ^3, R ^4, R ^5, R ^6, R ⁷ and R ⁸ are each independently a hydrogen atom or a hydrocarbon radical having 1 to 6 carbon atoms, particularly an ethyl or a methyl group. The radicals R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are preferably a hydrogen atom.

The radicals R ² and R ⁹ independently of one another each represent a hydrogen atom or a hydrocarbon radical having 1 to 6 C atoms, in particular an ethyl or a methyl group, or a radical of the formula (II)

wherein the radical R ^{10 is} a hydrogen atom or a methyl group. Preferably, the radicals R ² and / or R ^{9 is} a radical of the formula (II).

Substance names beginning with "poly", such as, for example, polyisocyanate, polyurethane, polyester or polyol, refer in the present case Document Substances that formally contain two or more of the functional groups occurring in their name per molecule.

The term "polymer" in the present document comprises, on the one hand, a collective of chemically uniform, but different in terms of degree of polymerization, molecular weight and chain length macromolecules, which was prepared by a polyreaction (polymerization, polyaddition, polycondensation) Derivatives of such a collective of macromolecules from polyreactions, ie compounds which have been obtained by reactions, such as additions or substitutions, of functional groups on predetermined macromolecules and which may be chemically uniform or chemically non-uniform Prepolymers, that is to say reactive oligomeric pre-adducts whose functional groups are involved in the synthesis of macromolecules The term "polymeric polyol" in the present document comprises any polymer according to the preceding definition which has more than one hydroxyl group e has. Accordingly, the term "polymeric diol" includes any polymer having exactly two hydroxyl groups.

The term "polyurethane polymer" encompasses all polymers which are prepared by the so-called diisocyanate-polyaddition process, including those polymers which are almost or completely free of urethane groups.Examples of polyurethane polymers are polyether polyurethanes, polyester polyurethanes, Polyether polyureas, polyureas, polyester-polyureas, polyisocyanurates and polycarbodiimides The term "solid epoxy resin" is well known to the person skilled in the epoxy art and is used in contrast to "liquid epoxy resin." The glass transition temperature T _{9 of} the solid epoxy resins is above room temperature of 23 ^° C., ie it can be reduced to free-flowing particles at room temperature. In this document, the term "bifunctional" refers to

Monomers or in general to molecules which have two different types of chemically reactive functional groups. For example, a bifunctional monomer to both a radical polymerizable group and a group reactive with epoxy resins.

In contrast, the term "difunctional" refers to molecules having two identical chemically reactive functional groups or two functional groups of the same type, for example, one difunctional molecule has two hydroxyl groups.

The term "diphenol" in the present document refers to mononuclear, polynuclear and fused aromatics and heteroaromatics which have two phenolic hydroxyl groups. "Molecular weight" as used herein means always the number average molecular weight M _n .

Suitable free-radically polymerizable monomers M are, in particular, vinyl esters, (meth) acrylic esters, acrylamides or styrene. For example, suitable radically polymerizable monomers

M is selected from the group consisting of vinyl acetate, methyl (meth) acrylate, ethyl (meth) acrylate, n- and i-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl ( meth) acrylate, cyclohexyl (meth) acrylate, 3-tetrahydrofuryl (meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2- Hydroxyethyl (meth) acrylate, 2- and 3-hydroxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, butyl diglycol (meth) acrylate, isotridecyl (meth) acrylate, Lauryl (meth) acrylate, stearyl (meth) acrylate, phenoxyethyl (meth) acrylate, dicyclopentadienyloxyethyl (meth) acrylate, dihydrodicyclopentadienyl (meth) acrylate and ethoxylated nonylphenol (meth) acrylate.

Preferably, the radically polymerizable monomer M is a

Methacrylate, in particular selected from the group consisting of methyl methacrylate (MMA), tetrahydrofurfuryl methacrylate (THFMA), cyclohexyl methacrylate (CHMA), isobornyl methacrylate (IBMA) and trimethylcyclohexyl methacrylate (TMCHMA). Furthermore, suitable free-radically polymerizable monomers M are crosslinking monomers such as, for example, allyl (meth) acrylate or crosslinking difunctional (meth) acrylates, for example oligomeric or polymeric compounds of the formula (III).

The rest R ¹⁰ has already been described above. Of the

Index n represents a value of 2 to 5. Furthermore, Z is a polyol after removal of n hydroxyl groups and Y is O or NR ', where R' is a hydrocarbon radical or a hydrogen atom, preferably a hydrogen atom. The compound of the formula (III) is in particular selected from

A group consisting of ethylene glycol di (meth) acrylate, 1,3- and 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethoxylated and propoxylated neopentyl glycol di (meth) acrylate, propoxylated glyceryl tri (meth) acrylate , Trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, modified pentaerythritol tri (meth) acrylate, propoxylated ethoxylated pentaerythritol tetra (meth) acrylate, dithmethylolpropane tetra (meth) acrylate and dipentaerythritol penta (meth) acrylate ,

In particular, n in the compound of formula (III) is a value of 2 and Z is a polymeric polyol after removal of two OH groups. In particular, this polymeric polyol is a polyalkylene polyol, a polyoxyalkylene polyol or a polyurethane polyol; a polyhydroxy functional ethylene-propylene-diene, ethylene-butylene-diene or ethylene-propylene-diene copolymer; a polyhydroxy-functional copolymer of dienes such as 1,3-butadiene or diene mixtures and vinyl monomers such as styrene, acrylonitrile or isobutylene; a polyhydroxy-functional polybutadiene polyol; a polyhydroxy-functional acrylonitrile / butadiene copolymer; or a polysiloxane polyol.

For example, such difunctional (meth) acrylates are selected from the group consisting of polyethylene glycol di (meth) acrylate such as Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate; Polypropylene glycol di (meth) acrylate such as dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate; and tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate. Also suitable is Z a diphenol, in particular an alkoxylated

Diphenol, after removal of two OH groups, preferably ethoxylated bisphenol A. For example, such a difunctional (meth) acrylate under the trade name Sartomer ^® SR 348 commercially available from Sartomer Company, Inc., USA. Also suitable as free-radically polymerizable monomers M are difunctional (meth) acrylates such as epoxy (meth) acrylates, in particular epoxy (meth) acrylates, which are obtainable from the reaction of bisphenol A diglycidyl ether with (meth) acrylic acid. For example, such a difunctional (meth) acrylate under the trade name Sartomer CN ^® 104 commercially available from Sartomer Company, Inc., USA.

Suitable polyhydroxy-terminated acrylonitrile / butadiene copolymers are typically selected from carboxyl-terminated acrylonitrile / butadiene copolymers.

Copolymers, which, for example, under the name Hypro ^® (formerly Hycar ^®) CTBN from Emerald Performance Materials, LLC, are commercially available US and epoxides or amino alcohols.

Such suitable radically polymerizable monomers M of Formula (III) are for example commercially available from Kraton Polymers, USA, or performance under the trade names Hypro ^® VTB and Hypro ^® VTBNX from the company Emerald Performance Materials, LLC, USA.

The radically polymerizable monomer M of the formula (III) is, in particular, a polyurethane (meth) acrylate. Such compounds are typically, in a manner known to those skilled in the art, prepared from the reaction of at least one polyisocyanate, in particular a diisocyanate, and a (meth) acrylic acid, a (meth) acrylamide or a (meth) acrylic acid ester, which Has hydroxyl group. Optionally, the diisocyanate prior to reaction with (meth) - acrylic acid, a (meth) acrylamide or a (meth) acrylic acid ester which has a hydroxyl group, with at least one polyol P, in particular a diol, are reacted in a method known in the art to a polyurethane polymer having isocyanate groups. Hydroxyalkyl (meth) acrylate, such as hydroxypropyl acrylate (HPA), hydroxypropyl methacrylate (HPMA), hydroxybutyl acrylate (HBA) or hydroxybutyl methacrylate (HBMA), preferably hydroxyethyl acrylate (HEA) or hydroxyethyl methacrylate (HEMA), are particularly suitable for the reaction with the isocyanate groups of the polyisocyanate. , or a monohydroxypoly (meth) acrylate of a polyol, preferably of glycerol or trimethylolpropane.

Polyurethane (meth) acrylates can also be prepared by esterification of a hydroxyl-containing polyurethane polymer with (meth) acrylic acid.

Furthermore, polyurethane (meth) acrylates can be prepared by the reaction of a (meth) acrylic acid ester having at least one isocyanate group, with a hydroxyl-containing polyurethane polymer or with a polyol, as described for example in the present document. As the (meth) acrylic ester having at least one isocyanate group, for example, 2-isocyanatoethyl methacrylate is suitable.

In principle, all diisocyanates are suitable as diisocyanates. For example, mention may be made of 1,6-hexamethylene diisocyanate (HDI), 2-methylpentamethylene-1,5-diisocyanate, 2,2,4- and 2,4,4-trimethyl-1,6-hexamethylene diisocyanate (TMDI), 1,1-dodecamethylene diisocyanate, lysine and lysine ester diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, 1-isocyanato-SSδ-trimethyl-δ-isocyanatomethylcyclohexane (= isophorone diisocyanate or IPDI) , Perhydro-2,4'-diphenylmethane diisocyanate and perhydro-4,4'-diphenylmethane diisocyanate, 1,4-diisocyanato-2,2,6-trimethylcyclohexane (TMCDI), 1, 3 and 1, 4-bis ( isocyanatomethyl) -cyclohexane, m- and p-xylylene diisocyanate (m- and p-XDI), m- and p-tetramethyl-1,3-xylylene diisocyanate, m- and p-tetramethyl-1,4-xylylene diisocyanate, bis- (1-isocyanato-1-methylethyl) -naphthalene, 2,4- and 2,6-toluene diisocyanate (TDI), 4,4'-, 2,4'- and 2,2'-diphenylmethanedi isocyanate (MDI), 1, 3- and 1, 4-phenylene diisocyanate, 2,3,5,6-tetramethyl-1,4-diisocyanatobenzene, naphthalene-1,5-diisocyanate (NDI), 3,3'-dimethyl- 4,4'-diisocyanatodiphenyl (TODI); Oligomers and polymers of the aforementioned isocyanates, as well as any mixtures of the aforementioned isocyanates.

Preferred polyols P are polyoxyalkylene polyols, also called "polyether polyols", polyester polyols, polycarbonate polyols and mixtures thereof The most preferred polyols are diols, in particular polyoxyethylene diols, polyoxypropylene diols or polyoxybutylene diols.

Polyether polyols, also called polyoxyalkylene polyols or oligoetherols, are particularly suitable which are polymerization products of ethylene oxide, 1, 2-propylene oxide, 1, 2- or 2,3-butylene oxide, oxetane, tetrahydrofuran or mixtures thereof, optionally polymerized with the aid a starter molecule having two or more active hydrogen atoms, such as, for example, water, ammonia or compounds having several OH or NH groups, such as, for example, 1,2-ethanediol, 1,2- and 1,3-propanediol, neopentyl glycol, diethylene glycol, ethylene glycol, the isomeric dipropylene glycols and tripropylene glycols, the isomeric butanediols, pentanediols, hexanediols, heptanediols, octanediols, nonanediols, decanediols, undecanediols, 1,3- and 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, 1,1,1-trimethylol- ethane, 1, 1, 1-trimethylolpropane, glycerol, aniline, and mixtures of the compounds mentioned. Both polyoxyalkylene polyols having a low degree of unsaturation (measured according to ASTM D-2849-69 and expressed in milliequivalents of unsaturation per gram of polyol (mEq / g)) prepared, for example, by means of so-called double metal cyanide complex catalysts (DMC Catalysts), as well as polyoxyalkylene polyols having a higher degree of unsaturation, prepared for example with the aid of anionic catalysts such as NaOH, KOH, CsOH or alkali metal alkoxides.

Particularly suitable are polyoxyethylene polyols and polyoxypropylene polyols, in particular polyoxyethylene diols, polyoxypropylene diols, polyoxyethylene triols and polyoxypropylene triols. Polyoxyalkylenediols or polyoxyalkylenetriols having a degree of unsaturation lower than 0.02 meq / g and having a degree of unsaturation are particularly suitable

Molecular weight in the range of 1000 to 30O00 g / mol, as well as polyoxyethylene diols, polyoxyethylene triols, polyoxypropylene diols and Polyoxypropylen- triols having a molecular weight of 400 to 8'0OO g / mol.

Also particularly suitable are so-called ethylene oxide terminated ("EO" endcapped) polyoxypropylene polyols, the latter being specific polyoxypropylene polyoxyethylene polyols obtained, for example, by pure polyoxypropylene polyols, especially polyoxypropylene diols and triols, upon completion of the polypropoxylation reaction alkoxylated with ethylene oxide and thereby having primary hydroxyl groups .Preferred in this case are polyoxypropylenepolyoxyethylenediols and polyoxypropylenepolyoxyethylenetriols.

Also suitable are styrene-acrylonitrile grafted polyether polyols, such as are commercially available for example under the trade name Lupranol ^® by the company Elastogran GmbH, Germany.

Particularly suitable polyester polyols are polyesters which carry at least two hydroxyl groups and are prepared by known processes, in particular the polycondensation of hydroxycarboxylic acids or the polycondensation of aliphatic and / or aromatic polycarboxylic acids with dihydric or polyhydric alcohols.

Particularly suitable are polyester polyols which are prepared from dihydric to trihydric alcohols, for example 1,2-ethanediol, diethylene glycol, 1,2-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6. Hexanediol, neopentyl glycol, glycerol, 1,1,1-thymethylolpropane or mixtures of the abovementioned alcohols with organic dicarboxylic acids or their anhydrides or esters such as succinic acid, glutaric acid, adipic acid, trimethyladipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, dimer fatty acid, Phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, dimethyl terephthalate, hexahydrophthalic acid, trimellitic acid and trimellitic acid. anhydride or mixtures of the aforementioned acids, and polyester polyols from lactones such as ε-caprolactone.

Particularly suitable are polyester diols, in particular those which are prepared from adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, dimer fatty acid, phthalic acid, isophthalic acid and terephthalic acid as dicarboxylic acid or from lactones such as ε-caprolactone and from ethylene glycol, diethylene glycol, neopentyl glycol, 1, 4 Butanediol, 1, 6-hexanediol, dimer fatty acid diol and 1, 4-cyclohexanedimethanol as a dihydric alcohol.

Suitable polycarbonate polyols are, in particular, those which are obtainable by reacting, for example, the abovementioned alcohols used for the synthesis of the polyester polyols with dialkyl carbonates, such as dimethyl carbonate, diaryl carbonates, such as diphenyl carbonate or phosgene. Particularly suitable are polycarbonate diols, especially amorphous polycarbonate diols.

Further suitable polyols are poly (meth) acrylate polyols.

Also suitable are polyhydroxy-functional fats and oils, for example natural fats and oils, in particular castor oil, or so-called oleochemical polyols obtained by chemical modification of natural fats and oils, which are prepared, for example, by epoxidation of unsaturated oils and subsequent ring opening with carboxylic acids or

Alcohols obtained epoxy polyesters or Epoxypolyether, or obtained by hydroformylation and hydrogenation of unsaturated oils polyols.

Furthermore, these are polyols, which from natural fats and oils by

Degradation processes such as alcoholysis or ozonolysis and subsequent chemical linkage, for example by transesterification or

Dimerization, the degradation products or derivatives thereof obtained. Suitable degradation products of natural fats and oils are in particular fatty acids and fatty alcohols and fatty acid esters, in particular the methyl esters (FAME), which, for example, by Hydroformylation and hydrogenation can be derivatized to Hydroxyfettsäureestem.

Likewise suitable are also polyhydrocarbon polyols, also called oligohydrocarbonols, for example polyhydroxy-functional ethylene-propylene, ethylene-butylene or ethylene-propylene-diene copolymers, as are produced, for example, by Kraton Polymers, USA, or polyhydroxy-functional copolymers of dienes, such as 1, 3-butadiene or diene mixtures and vinyl monomers such as styrene, acrylonitrile or isobutylene, or polyhydroxy-functional polybutadiene, for example those which are prepared by copolymerization of 1, 3-butadiene and allyl alcohol or by oxidation of polybutadiene and may also be hydrogenated.

Also suitable are polyhydroxy-functional acrylonitrile / butadiene

Copolymers, such as, for example, from epoxides or aminoalcohols and carboxyl-terminated acrylonitrile / butadiene copolymers (commercially available under the name Hypro ^® CTBN from the company Emerald Performance

Materials, LLC, USA).

These stated polyols preferably have an average molecular weight of from 250 to 30 000 g / mol, in particular from 10 000 to 30 000 g / mol, and an average OH functionality in the range from 1.6 to 3.

In addition to these mentioned polyols, small amounts of low molecular weight di- or polyhydric alcohols such as 1, 2-ethanediol, 1, 2- and 1, 3-propanediol, neopentyl glycol, diethylene glycol, triethylene glycol, the isomeric dipropylene glycols and tripropylene glycols, the isomeric Butanediols, pentanediols, hexanediols, heptanediols, octanediols, nonanediols, decanediols, undecanediols, 1, 3- and 1, 4-cyclohexanedimethanol, hydrogenated bisphenol A, dimeric fatty alcohols, 1,1,1-trimethylolethane, 1,1,1-tri- methylolpropane, glycerol, pentaerythritol, sugar alcohols such as XyNt, sorbitol or mannitol, sugars such as sucrose, other higher-value alcohols, low-molecular alkoxylation products of the aforementioned di- and polyhydric alcohols. hole, as well as mixtures of the aforementioned alcohols in the preparation of the isocyanate group-containing polyurethane polymer are used.

For example, suitable polyols P are described in Sections [0029] to [0039] of US 2006/0122352 A1, the entire disclosure of which is hereby incorporated by reference.

In particular, the free-radically polymerizable monomer M of the formula (III) is liquid at room temperature, which also includes viscous and highly viscous elastomers.

Of course, it is possible and may even be advantageous to use mixtures of the previously described radically polymerizable monomers M.

The proportion of free-radically polymerizable monomer M is preferably 10 to 90 wt .-%, in particular 25 to 75 wt .-%, preferably 30 to 65 wt .-%, of the total composition.

Furthermore, the composition comprises at least one free radical generator.

The radical generator is in particular a peroxide, a hydroperoxide or a perester. Most preferably, the free radical generator is dibenzoyl peroxide.

Typically, the composition further comprises at least one catalyst for radical formation. This catalyst is especially a tertiary amine, a transition metal salt or a transition metal complex. For example, such suitable tertäre amines, aromatic amines, in particular selected from the group consisting of N, N-dimethylaniline, N, N-diethylaniline, N, N-bis (hydroxyalkyl) aniline such as N ₁ N-bis (2-hydroxyethyl) aniline, N, N-alkylhydroxyalkylaniline such as N-ethyl-N-hydroxyethylaniline, N, N-dimethyl-p-toluidine, N, N-diethyl-p-toluidine, N-methyl-N-hydroxyethyl-p-toluidine, N, N- Bis (2-hydroxyethyl) -p-toluidine and alkoxylated N, N-bis (hydroxyethyl) -p-toluidines, N-ethoxylated p-toluidine, N, N-bis (2-hydroxyethyl) -xylidine, N-alkylmorpholine, and mixtures thereof. Transition metal salts and transition metal complexes are, for example, salts and complexes of cobalt, nickel, copper, manganese or vanadium. Other preferred catalysts for radical formation are described, for example, in Sections [0041] - [0054] of US 2002/0007027 A1, the entire disclosure of which is hereby incorporated by reference.

The catalyst for the radical formation is usually used in an amount of 0.01 to 2.5 wt .-%, in particular from 0.1 to 2 wt .-%, based on the composition.

For example, molecules which under the influence of heat or of electromagnetic radiation form radicals which then lead to the polymerization of the composition can also be used as radical formers. Typically these are thermally activatable free radical generators and photoinitiators.

Suitable thermally activatable radical formers are those which are still sufficiently stable at room temperature but already form radicals at a slightly elevated temperature.

Photoinitiators are free-radical formers which form radicals under the influence of electromagnetic radiation. Particularly suitable is a photoinitiator which forms free radicals upon irradiation with an electromagnetic radiation of the wavelength of 230 nm to 400 nm and is liquid at room temperature. For example, such photoinitiators are selected from the group consisting of α-hydroxy ketones, phenylglyoxylates, monoacylphosphines, diacylphosphines, phosphine oxides and mixtures thereof.

Furthermore, the composition comprises at least one epoxy resin

A, which has on average more than one epoxide group per molecule. Epoxy resins A are preferably epoxy resins of the formula (IV).

In this case, the radical R ^{11 is} a hydrogen atom or a methyl group.

The index p stands for a value of 0 to 12, in particular for a value of 0 to 1, preferably for a value of 0 to 0.2. Typically, epoxy resin A is available from the reaction of

Epichlorohydrin and / or 2-Methylepichlorhydrin with a diphenol of the formula HO - X - OH. The radical X is independently of one another in each case a divalent radical of a diphenol after removal of the two hydroxyl groups. Diphenols are particularly suitable as diphenols, which are selected from the group consisting of 1, 2, 1, 3, and 1, 4-dihydroxybenzene, 1, 3-dihydroxytoluene, 3,5-dihydroxybenzoates, 2,2-bis ( 4-hydroxyphenyl) propane (= bisphenol A), bis (4-hydroxyphenyl) methane (= bisphenol F), bis (4-hydroxyphenyl) sulfone (= bisphenol S), naphthororcinol, dihydroxynaphthalene, dihydroxyanthraquinone, dihydroxybiphenyl, 3,3 Bis (p-hydroxyphenyl) phthalides, 5,5-bis (4-hydroxyphenyl) hexahydro-4,7-methanoindane, phenolphthalein, fluorescein, 4,4 '- [bis (hydroxyphenyl) -1,3-phenylenebis - (1-methylethylidene)] (= bisphenol M), 4,4 '- [bis (hydroxyphenyl) -1,4-phenylenebis (i-methylethylidene)] (= bisphenol P), 2,2'- Diallyl-bisphenol-A, diphenols and dicresols prepared by reacting phenols or cresols with diisopropylidenbenzene and all isomers of the aforementioned compounds.

Furthermore, suitable epoxy resins A are also obtainable from the reaction of epichlorohydrin and / or 2-methylepichlorohydrin with an aminophenol of the formula H ₂ N - X - OH or with a dianiline of the formula H ₂ N - X - NH ₂ , where the radical X is already previously described. Examples of such epoxy resins are N, N, O-triglycidyl-p-aminophenol, N, N ₁ O-thglycidyl-m-aminophenol, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane and N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylpropane. Further preferably, the radical X is bisphenol A or bisphenol F after removal of the two hydroxyl groups.

The epoxy resin A is preferably an epoxide

Liquid resin. In a further embodiment, the composition also contains at least one solid epoxy resin in addition to the liquid epoxy resin. in the

Epoxy solid resin is the index p for values of> 1, in particular for values of> 1.5.

Preferred liquid epoxy resins are available commercially for example under the trade names Araldite ^® GY 250, Araldite ^® PY 304 or Araldite ^® GY 282 from Huntsman International LLC, USA, or DER ^® 331 or DER ^® 330 from The Dow Chemical Company, USA, or under the trade name Epikote ^® 828 or Epikote ^® 862 from Hexion Specialty Chemicals Inc, USA.

Preferred solid epoxy resins are available commercially for example under the trade names Araldite ^® GT 7071 or Araldite ^® GT 7004 from Huntsman International, LLC, United States. Other suitable solid epoxy resins are, for example, commercially available from The Dow Chemical Company, USA, or from Hexion Specialty Chemicals Ine, USA.

Also suitable as epoxy resins A, for example, aliphatic polyepoxides of the formulas (V) or (VI).

) Here r stands for a value from 1 to 9, in particular from 3 to 5. In addition, u stands for a value from 0 to 10 and t for a value from 0 to 10, with the proviso that the sum of u and t ≥ 1 is. The radical R ¹¹ has already been described above. Finally, a represents the structural element derived from ethylene oxide, and b represents the structural element derived from propylene oxide, wherein building blocks a and b may be block-like, alternating or random. Thus, formula (VI) is (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether and (poly) ethylene glycol / propylene glycol diglycidyl ether Particularly suitable aliphatic or cycloaliphatic diglycidyl ethers are ethylene glycol diglycidyl ether, butanediol diglycidyl ether or hexanediol diglycidyl ether.

The proportion of epoxy resin A is preferably 5 to 40 wt .-%, in particular 8 to 30 wt .-%, preferably 15 to 25 wt .-%, of the total composition.

Furthermore, the composition comprises at least one compound of the formula (I) as described above. Such compounds can be prepared, for example, by double alkoxylation of alkylamines or by simple alkoxylation of N-alkylalkanolamines. For example, N-methyldiethanolamine is available from the reaction of methylamine with ethylene oxide.

Suitable compounds of the formula (I), in addition to N-methyldiethanolamine, are, for example, also N-methyldipropanolamine, N-methyldiisopropanolamine, N-butyldiethanolamine and the like.

The composition of the invention may further comprise at least one bifunctional monomer L which is reactive with both the free-radically polymerizable monomer M and the epoxy resin A.

Such bifunctional monomers L are, for example, selected from the group consisting of glycidyl (meth) acrylate, α, β-unsaturated Carboxylic acids such as (meth) acrylic acid, α, ß-unsaturated dicarboxylic acids, 2- (meth) acrylamido-2-methylpropanesulfonic acid, maleic anhydride, partially hydrogenated phthalic anhydride and (meth) acrylates of the formula (VII).

In this case, the radical R ^{12 is} either a hydrogen atom or a methyl group. The subscript m stands for a value from 1 to 15, in particular from 1 to 5, preferably from 1 to 3. The index q stands for a value of 1 to 3 and the index s for a value of 3 minus q. In particular, such (meth) acrylates of the formula (VII) are 2-hydroxyethyl (meth) acrylate-phosphoric acid partial esters. Preference is given to bifunctional monomers which in at

Room temperature relative to the epoxy resin A are reactive. Most preferably, the bifunctional monomer L is glycidyl (meth) acrylate.

The proportion of bifunctional monomer L is preferably 1 to 30 wt .-%, in particular 5 to 20 wt .-%, preferably 7 to 15 wt .-%, of the total composition.

The composition may furthermore additionally contain at least one adhesion promoter, in particular a (meth) acrylic acid, a metal (meth) acrylate or a (meth) acrylate of the formula (VII), as described above.

Preferred metal (meth) acrylates are metal (meth) acrylates of

Calcium, magnesium or zinc, which have a hydroxyl group and / or (meth) - acrylic acid or (meth) acrylate as a ligand or anion. Particularly preferred metal (meth) acrylates are zinc di (meth) acrylate, calcium di (meth) acrylate, Zn (OH) (meth) acrylate and magnesium di (meth) acrylate. Preferred (meth) acrylates of the formula (VII) are 2-methacryloyloxyethyl phosphate, bis (2-methacryloyloxyethyl) phosphate and tris (2-methacryloyl-oxyethyl) phosphate and mixtures thereof.

Further suitable adhesion promoters are silanes, in particular organofunctional silanes. Particularly suitable are (meth) acryloxyalkyltrialkoxysilanes such as 3-methacryloxypropyltrimethoxysilane, glycidyloxyalkyl trialkoxysilanes such as 3-glycidoxypropyltrimethoxysilane, and the like. For example, such suitable silanes under the trade name Dynasylan ^® MEMO from Evonik Degussa GmbH, Germany, or under the trade name Silquest ^® A-187, Momentive Performance Materials Inc., USA, are commercially available.

The proportion of the optional adhesion promoter to the total composition is preferably 0.01 to 12 wt .-%, in particular 0.5 to 8 wt .-%.

Furthermore, the composition may additionally contain at least one core-shell polymer. Core-shell polymers consist of an elastic core polymer (core) and a rigid shell polymer (shell). Particularly suitable core-shell polymers consist of a rigid shell of a rigid thermoplastic polymer grafted onto a core of crosslinked elastic acrylate or butadiene polymer.

Particularly suitable core-shell polymers are those which swell in the free-radically polymerizable monomer M, but do not dissolve therein.

Preferred core-shell polymers are the so-called MBS polymers commercially for example under the trade name Clearstrength ^® from Arkema Inc., USA, or Paraloid ^® from Rohm and Haas, USA, is. The core-shell polymers are preferably used in an amount of from 0.01 to 30% by weight, in particular from 10 to 20% by weight, based on the total composition. The composition may further contain additional solid or liquid toughening agents. A "toughener" is here and hereinafter understood to mean an addition to a polymer matrix which, even at low additions of from 0.1 to 15% by weight, in particular from 0.5 to 8% by weight, based on the total weight of the composition Increases the toughness and thus is able to absorb higher bending, tensile, impact or impact stress before the matrix penetrates or breaks.

In addition to the core-shell polymers described above, suitable solid tougheners are, for example, organic ion-exchanged layer minerals, as known to the person skilled in the art under the terms organoclay or nanoclay; Polymers or block copolymers, in particular the monomers styrene, butadiene, isoprene, chloroprene, acrylonitrile and methyl methacrylate, and chlorosulfonated polyethylene; and amorphous silica.

As liquid toughness are particularly suitable liquid rubbers as commercially available under the trade name Hypro ^® CTBN ETBN or VTBN are performance from the company Emerald Performance Materials, LLC, USA, and epoxidharzmodifizierte liquid rubbers of the type Hypro ^® CTBN.

Furthermore, the composition may additionally contain at least one filler. Particularly suitable are natural, ground or precipitated calcium carbonates (chalks), which are optionally coated with fatty acids, in particular stearates, montmorillonites, bentonites, barium sulfate (BaSO ₄ , also called barite or barite), calcined kaolins, quartz powder, aluminum oxides, Aluminum hydroxides, silicic acids, in particular fumed silicas, modified castor oil derivatives and polymer powder or polymer fibers. Preferred are calcium carbonates, most preferred are coated calcium carbonates.

The filler is usually used in an amount of 0.01 to 30 wt .-%, in particular from 10 to 30 wt .-%, preferably 15 to 20 wt .-%, based on the total composition. Furthermore, the composition may additionally have at least one reactive diluent G having epoxide groups. These reactive diluents G are in particular glycidyl ethers of monofunctional saturated or unsaturated, branched or unbranched, cyclic or open-chain alcohols having 4 to 30 C atoms, for example butanol glycidyl ether, hexanol glycidyl ether, 2-ethylhexanol glycidyl ether, allyl glycidyl ether, tetrahydrofurfuryl and furfuryl glycidyl ether , Trimethoxysilyl glycidyl ether and the like. Also suitable are glycidyl ethers of difunctional saturated or unsaturated, branched or unbranched, cyclic or open-chain alcohols having 2 to 30 carbon atoms, for example ethylene glycol, butanediol, hexanediol, octanediol, Cyclohexandimethanoldigylcidylether, Neopentylglycoldiglycidylether and the like. Also suitable are glycidyl ethers of trifunctional or polyfunctional, saturated or unsaturated, branched or unbranched, cyclic or open-chain alcohols such as epoxidized castor oil, epoxidized trimethylolpropane, epoxidized pentaerythrol or polyglycidyl ethers of aliphatic polyols such as sorbitol, glycerol, trimethylolpropane and the like. Also suitable are glycidyl ethers of phenolic and aniline compounds such as phenyl glycidyl ether, cresyl glycidyl ether, p-tert-butylphenyl glycidyl ether, nonylphenol glycidyl ether, 3-n-pentadecenyl glycidyl ether (from cashew nut shell oil), N, N-diglycidyl aniline and the like.

Further suitable reactive diluents G are epoxidized amines such as N, N-diglycidylcyclohexylamine and the like; epoxidized mono- or dicarboxylic acids such as glycidyl neodecanoate, glycidyl methacrylate, glycidyl benzoate, diglycidyl phthalate, tetra- and hexahydrophthalate, diglycidyl esters of dimer fatty acids, and the like; and epoxidized di- or trifunctional, low to high molecular weight polyether polyols such as polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether and the like.

Particularly preferred are hexanediol diglycidyl ethers, cresyl glycidyl ethers, p-tert-butylphenyl glycidyl ethers, polypropylene glycol diglycidyl ethers and polyethylene glycol diglycidyl ethers. Advantageously, the proportion of reactive diluent G comprising epoxide groups is from 0.5 to 20% by weight, preferably from 1 to 8% by weight, based on the total weight of the composition.

The composition may, if appropriate, additionally

Contain ingredients. Such additional constituents are, in particular, toughening modifiers, dyes, pigments, inhibitors, UV and heat stabilizers, metal oxides, antistatic agents, flame retardants, biocides, plasticizers, waxes, leveling agents, adhesion promoters, thixotropic agents, spacers and other common raw materials and additives known to the person skilled in the art.

The composition is preferably a two-component composition, wherein two components K1 and K2 are stored separately from each other until application. Typically, the first component K1 comprises the free-radically polymerizable monomer M, the compound of the formula (I) and the optionally present bifunctional monomer L. The second component K2 contains in particular the free radical generator and the epoxy resin A.

Furthermore, in a two-component composition, other constituents, especially those which would interfere with the storage stability of the composition by reaction with each other, can be stored separately. Component K1 in the described two-component compositions preferably contains the constituents radically polymerizable monomers M, compounds of the formula (I), catalysts for radical formation, bifunctional monomers L, adhesion promoters and fillers and component K2 the constituents epoxy resin A, free-radical formers and fillers. The volume ratio when mixing K1 to K2 is in particular in the range from 1: 1 to 10: 1.

In certain cases, it may be advantageous to color the two components K1 and K2 differently. This can be done in the mix the components check the mixing quality and mixing errors can be detected early. Likewise, this measure can qualitatively check whether the intended mixing ratio has been observed.

Such a two-component composition is typically stored in a package having two separate chambers. The component K1 is in this case in one chamber and the component K2 is present in the other chamber of the package. Suitable packages are, for example, double cartridges, such as twin or coaxial cartridges, or multi-chamber tubular bags with adapters. Preferably, the mixing of the two components K1 and K2 takes place with the aid of a static mixer, which can be placed on the package with two chambers.

Such suitable packages are described, for example, in US 2006/0155045 A1, WO 2007/096355 A1 and in US 2003/0051610 A1, the entire disclosure of which is hereby incorporated by reference.

In a large-scale plant, the two components K1 and K2 are typically stored separately in barrels or hobbocks and, during application, for example, by means of gear pumps, pressed out and mixed. The composition can be applied to a substrate by hand or in an automated process by means of robots.

The composition of the invention is cured on the one hand by a radical polymerization reaction of the free-radically polymehsierbaren monomers M and optionally further radically polymerizable constituents in the composition, on the other hand by a homopolymerization reaction of the epoxy resin A under the influence of the compound of formula (I).

The process, in particular the speed, of the two reactions leading to the curing of the composition can be adjusted by the choice of the constituents used. Typically, it runs the curing of the composition in two stages. In a first step, the radical polymerization reaction takes place, whereby the composition obtains a high initial strength even at an early stage. In a second step, the slower homopolymerization of the epoxy resin proceeds. As a result, the composition further hardens and obtains its high final strength.

Most preferably, the compound of the formula (I) present in the composition is a bifunctional monomer, that is to say R ² and / or R ^{9 are} a radical of the formula (II), with respect both to the free-radically polymerizable monomer Monomer M as well as with respect to the epoxy resin A is reactive.

The composition is curable in particular at room temperature, that is at a temperature in the range of 23 ⁰ C. Of course, the skilled artisan will appreciate that the composition may also be cured at elevated temperatures, however, the

Curing at room temperature preferred.

Furthermore, the invention relates to the use of a composition, as described above, as an adhesive, sealant or as a coating. In particular, the composition according to the invention is suitable for bonding, sealing or coating substrates in which no thermosetting adhesives, sealants and coatings can be used due to the nature of the material and / or the process. This may be due, for example, to the fact that substrates to be bonded, sealed or coated may be exposed when exposed to elevated temperatures which are often necessary for curing epoxy resin-containing compositions as described in the prior art. Such substrates are, for example, plastics such as polyethylene, polypropylene, polyvinyl chloride and polymethyl (meth) acrylate and coated substrates. The substrate on the surface of which the composition is applied may have been previously treated with suitable pretreatment agents or cleaners. Such pretreatments include, in particular, physical and / or chemical cleaning methods, for example grinding, sandblasting, brushing or the like, or treatment with cleaners or solvents, or flame treatment or plasma treatment, in particular air plasma treatment at atmospheric pressure.

It is particularly suitable pretreatment or cleaning the substrates with Sika ^® Cleaner P or Sika ^® ADPrep which are commercially available from Sika Switzerland AG.

The composition of the invention is used in particular in a method of bonding two substrates S1 and S2 comprising the steps of i) applying a composition according to the preceding

Description on a substrate S1; ii) contacting the applied composition with a second

Substrate S2 within open time; or i ') applying a composition according to the preceding

Description on a substrate S1; ii ') applying a composition according to the preceding

Description on a substrate S2; iii ') joining the two compositionally applied substrates S1 and S2 within the open time.

In this case, the second substrate S2 consists of the same or a different material as the substrate S1. In the case of a two-component composition, before step i), or i ') and ii'), at least partial mixing of the two components takes place.

Also possible is a method of bonding two substrates S1 and S2 comprising the steps i ") applying a component K1 according to the preceding

Description on a substrate S1; ii ") applying a component K2 according to the preceding

Description on a substrate S2; iii ") joining the two coated with one component K1 or K2 substrates S1 and S2.

In such a method, the two components K1 and K2 mix during the joining of the substrates. This method is particularly suitable for gluing over very thin adhesive layers.

In particular, the composition according to the invention is also used in a method of sealing or coating a substrate S1 comprising the steps i '") applying a composition as described above to a substrate S1; ii'") curing the composition.

In the case of a two-component composition, before step i "'), at least partial mixing of the two components takes place.

Furthermore, the present invention comprises a cured

A composition obtainable from a previously described composition by a curing process. In particular, the composition is a two-component composition such that the cured composition is obtainable by at least partial mixing of the two components K1 and K2. Most preferably, the curing process proceeds at room temperature.

The invention also includes articles which have been bonded, sealed or coated by a previously described method. These articles are preferably a building, in particular a building construction or civil engineering, or an industrial good or a consumer good, in particular a window, a household machine, a tool or a means of transport, in particular a vehicle at sea or on land, preferably an automobile, a bus, a truck, a train or a ship. Such articles are preferably also add-on parts of industrial goods or means of transport, in particular also module parts which are used on the production line as modules and in particular are glued or glued on. In particular, these prefabricated attachments are used in transport construction. For example, such attachments are cabs of trucks or locomotives or sunroofs of automobiles. Preferably, these articles are windows and doors, as used in buildings.

Further, the invention encompasses the use of a compound of formula (I), as previously described, as a curing agent for compositions comprising both at least one epoxy resin and at least one free radically polymerizable monomer. Most preferably, the radicals R ² and / or R ⁹ in the compound of the formula (I) are radicals of the formula (II). Thus, the compound of the formula (I) is a bifunctional compound or a bifunctional monomer which serves as a curing agent for the epoxy resin and can be incorporated as a radical polymerizable monomer in the polymer matrix and in particular also incorporated. Particularly preferred is the compound of formula (I) for this purpose, because it initiates or favors the homopolymerization of the epoxy resin, but does not affect the radical polymerization reaction.

Examples

In the following, exemplary embodiments are listed which are intended to explain the described invention in more detail. Of course, the invention is not limited to these described embodiments.

Preparation of 2-hydroxypropyl-3 - ((2-hydroxyethyl) (methyl) amino) propyl methacrylate MV

In a 250 ml three-necked flask equipped with magnetic stir bar, thermometer and reflux condenser, 10.0 g (133.1 mmol) of 2- (methylamino) ethanol and 85 g Weighed in tetrahydrofurfuryl methacrylate. At room temperature, 19.5 g (137.1 mmol) of glycidyl methacrylate were slowly added dropwise with constant stirring. A slight exotherm was observed, but the temperature never exceeded 70 ^° C. After stirring for 6 hours at 70 ^° C., only slight traces of 2- (methylamino) ethanol could be detected by means of a gas chromatograph. This approximately 25% product solution in tetrahydrofurfuryl methacrylate was filled into a glass bottle and used without further work-up in the model formulations.

Preparation of the compositions

The following compositions were prepared: As component K1, the constituents listed in Tables 1 in the proportions by weight were mixed together in a dissolver at a maximum temperature of 80 ^° C. and stirred until a macroscopically homogeneous paste was obtained.

As component K2, the constituents listed in Tables 1 were mixed together in the proportions by weight stated in a dissolver.

The produced components K1 and K2 were introduced into the separate chambers of coaxial cartridges and mixed during application by means of static mixer.

Description of the test methods

The tensile strength, elongation at break and the elastic modulus were determined according to DIN EN 53504 (pulling speed: 200 mm / min) aushärteten of films with a layer thickness of 2 mm, which under standard conditions (23 ± 1 ⁰ C, 50 ± 5% relative humidity). The samples were tested directly and continuously after their preparation.

The elastic modulus is given in the range of 0.5 to 1% elongation.

Table 1 Compositions 1 to 3 and the reference examples Ref1 to Ref3 in parts by weight and the results; a catalyst for radical formation (toluidine-based tertiary amine); b 40% by weight in plasticizer; c The measurements were carried out after 3 hours; k.A .: not specified; In the example Ref3 no hardening occurred.

Claims

claims

A composition comprising a) at least one free-radically polymerizable monomer M; b) at least one radical generator; c) at least one epoxy resin A, which has on average more than one epoxide group per molecule; and d) at least one compound of the formula (I)

wherein the radical R is a hydrocarbon radical having 1 to 6 C atoms, in particular an ethyl or a methyl group; the radicals R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom or a hydrocarbon radical having 1 to 6 C atoms, in particular an ethyl or a methyl group, preferably a Hydrogen atom; the radicals R ² and R ⁹ independently of one another each represent a hydrogen atom or a hydrocarbon radical having 1 to 6 C atoms, in particular an ethyl or a methyl group, or a radical of the formula (II),

wherein the radical R ^{10 is} a hydrogen atom or a methyl group.

2. A composition according to claim 1, characterized in that the radicals R ² and / or R ^{9 is} a radical of the formula (II).

3. Composition according to one of the preceding claims, characterized in that the free-radically polymerizable monomer M is a methacrylate, in particular selected from the group consisting of methyl methacrylate (MMA), tetrahydrofurfuryl methacrylate (THFMA), cyclohexyl methacrylate (CHMA), isobornyl methacrylate (IBMA) and trimethylcyclohexyl methacrylate (TMCHMA).

4. A composition according to any one of the preceding claims, characterized in that the proportion of free-radically polymerizable monomer M M 10 to 90 wt .-%, in particular 25 to 75 wt .-%, preferably 30 to 65 wt .-%, of the total composition is.

5. Composition according to one of the preceding claims, characterized in that the radical generator is a peroxide, a hydroperoxide or a perester, most preferably dibenzoyl peroxide.

6. Composition according to one of the preceding claims, characterized in that the composition additionally comprises at least one tertiary amine or a transition metal salt or a

Transition metal complex contains as a catalyst for radical formation.

7. Composition according to one of the preceding claims, characterized in that the epoxy resin A is obtainable from the reaction of epichlorohydrin and / or 2-Methylepichlorhydrin with a diphenol, which is in particular selected from the group consisting of 1, 4-dihydroxybenzene, 1, 3-Dihydroxybenzene, 1, 2-dihydroxybenzene, 1, 3-dihydroxytoluene, 3,5-dihydroxybenzoates, 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), bis (4-hydroxyphenyl) methane (= Bisphenol F), bis (4-hydroxyphenyl) sulfone (= bisphenol S), naphtho resorcinol, dihydroxynaphthalene, dihydroxyanthraquinone, dihydroxybiphenyl, 3,3-bis (p-hydroxyphenyl) phthalide, 5,5-bis (4 -hydroxyphenyl) - hexahydro-4,7-methanoindane, phenolphthalein, fluorescein, 4,4 '- [bis- (hydroxyphenyl) -1,3-phenylenebis- (1-methylethylidene)] (= bisphenol M), 4,4 '- [bis (hydroxyphenyl) -1,4-phenylenebis- (1-methylethylidene)] (= bisphenol Phenoi P), 2,2'-diallyl-bisphenol-A, diphenols and dicresols prepared by reacting phenols or cresols with diisopropylidenbenzene and all isomers of the aforementioned compounds.

8. A composition according to any one of the preceding claims, characterized in that the proportion of the epoxy resin A 5 to 40 wt .-%, in particular 8 to 30 wt .-%, preferably 15 to 25 wt .-%, of the total composition.

9. Composition according to one of the preceding claims, characterized in that the composition further comprises at least one bifunctional monomer L which is reactive both with respect to the free-radically polymerizable monomer M and with respect to the epoxy resin A.

10. The composition according to claim 9, characterized in that the bifunctional monomer L is glycidyl (meth) acrylate.

11. A composition according to any one of the preceding claims, characterized in that the composition is two-component, wherein the first component K1 comprises the radically polymerizable monomer M, the compound of formula (I) and the optionally present bifunctional monomer L; and the second component K2 comprises the radical generator and the epoxy resin A.

12. A composition according to any one of the preceding claims, characterized in that the composition is curable at room temperature.

13. Use of a composition according to any one of claims 1 to 12 as an adhesive or sealant or as a coating, in particular for bonding or sealing or coating of substrates in which material-related and / or process-related no thermosetting adhesives, sealants and coatings can be used.

Use of a compound of formula (I) as described in a composition according to any one of claims 1 to 12 as a curing agent for compositions comprising both at least one epoxy resin and at least one free radically polymerizable monomer.

15. Use according to claim 14, characterized in that the compound of formula (I) wherein R ² and / or R ⁹ corresponds to a radical of the formula (II), as radically polymerizable monomer in the

Polymer matrix is installed.