Oxathiolanone group-containing polymers

Abstract

A (meth)acrylate polymer A obtainable by a free-radical polymerization process of a monomer 5 M1 of formula (I), wherein R1 is H or methyl, X is C1-C4-alkylene, and optionally at least one monoethylenically unsaturated monomer M2, wherein the amount of the monomer M1 of formula (I) is at least 8 wt%, based on the total weight of all monomers. The (meth)acrylate polymer is suitable as part of a curable composition 0 for various applications, especially for producing an adhesive, a sealant, a coating, a 3D printed object, a shaped article, a chemical anchor or a dental material.

Description

[0001] Oxathiolanone group-containing polymers

[0002] Description

[0003] The present invention relates to an oxathiolanone group-containing (meth)acrylate polymer, a process of preparing and the use thereof. Further, the invention relates to a curable composition, preferably a curable two-component composition, comprising the (meth)acrylate polymer, to the use thereof and to an article obtainable by polymerizing the curable composition.

[0004] Background of the invention

[0005] JP 2007-178903 A discloses that 5-(methacryloyloxy)methyl-1 ,3-oxathiolane-2-one of formula may be used as a comonomer for radical polymerization. Especially, a positive radiation sensitive resin composition for producing a plated shaped article, for example, a bump for integrated circuit element is described. The composition contains a cross-linked polymer, obtained by polymerizing p-isopropenylphenol, isobornylacrylate, benzylacrylate, t-butylacrylate, 1 ,6-hexanedioldiacrylate and 5-(methacryloyloxy)methyl-1 ,3-oxathiolane-2-one at 70 to 100°C. The S-containing unit is described to have improved adhesion property after cyan gold plating.

[0006] JP 2007-320999 A discloses a radiation sensitive resin composition containing a methacrylate copolymer of 50 mol% of a monomer of formula (IV) and 50 mol% of a monomer of formula (V) which is used for forming resist patterns.

[0007] JP 2004-323702 A discloses a resin comprising copolymers of a monomer of formula (V) and isobornylmethacrylate or a copolymer of monomer of formula (VI) and isobornylmethacrylate. Said copolymers are described having glass transition temperatures above 120°C for optical applications. JP 2005-36084 A discloses a thiourethane-containing mold releasing agent obtained by curing a copolymer formed from a monomer of formula (IV) and stearyl methacrylate and 1 ,6- hexamethylene diamine as a reactive compound. The mold releasing agent is described as having good heat-resisting property, solvent resistance and rub-off property.

[0008] WO 2020 / 043517 A1 discloses a polymer obtainable by an addition reaction of a compound of formula (la) with amines, for example, with tris(2-aminoethyl)amine at 30°C within 4 minutes.

[0009] In order to introduce urethane groups in the side chain of a (meth)acrylate polymer isocyanato- alkyl-(meth)acrylate, for example isocyanatoethyl-acrylate, may be used as monomer. However, these monomers are usually sensitive to air and moisture which requires specific handling. Said polymers are only capable of crosslinking once by curing with amines.

[0010] Thus, there is a need for (meth)acrylate polymers having S-containing units capable of crosslinking to form isocyanate-free polymers with urethane groups having tailor-made properties for various applications.

[0011] Therefore, it is an object of the present invention to provide a S-containing (meth)acrylate polymer as an intermediate for a polymer having urethane groups avoiding the use of isocyanates, for example, to provide polymers having, for example, a high cross-linking density.

[0012] Further, it is an object of the present invention to provide a process for preparing a S-containing (meth)acrylate polymer as an intermediate for a polymer having urethane groups avoiding the use of isocyanates.

[0013] Further, it is an object of the present invention to provide a S-containing (meth)acrylate polymer as an intermediate to be used in a system offering a combination of desirable properties, like good adhesion, flexibility, sufficient hardness, high refractive index and / or low shrinkage.

[0014] Summary of the invention

[0015] It has now been found that a (meth)acrylate polymer may be obtained as an intermediate having the opportunity to cross-link via a polymer having urethane and thiol groups to an isocyanate-free polymer having urethane groups and thioether and / or disulfide groups.

[0016] Accordingly, in a first aspect the invention relates to a (meth)acrylate polymer A, obtainable by a free-radical polymerization process of an oxathiolanone group-containing monomer M1 of formula

[0017] (I), wherein

[0018] R1is H or methyl, X is Ci-C4-alkylene, and optionally at least one monoethylenically unsaturated monomer M2, wherein the amount of the monomer M1 of formula (I) is at least 8 wt%, based on the total weight of the monomers.

[0019] In a further aspect, the invention relates to a process for preparing a (meth)acrylate polymer A, as defined in any aspect herein, the process comprising polymerizing a monomer M1 of formula (I), as defined in any aspect herein, and optionally at least one monoethylenically unsaturated monomer M2, as defined in any aspect herein.

[0020] In a further aspect, the invention relates to a curable composition containing a) a (meth)acrylate polymer A, as defined in any aspect herein, b) a compound B having at least one amino group, selected from a primary amino group, a secondary amino group and any combination thereof, said primary or secondary amino group may be present in a masked, latently reactive form, and c) optionally a compound C having at least one functional group reactive towards a SH group.

[0021] In a further aspect, the invention relates to the use of a (meth)acrylate polymer A, as defined in any aspect herein, as an intermediate for preparing an adhesive, a sealant, a coating, a 3D printing ink, a shaped article, a chemical anchor, a dental material or a repair system thereof.

[0022] In a further aspect, the invention relates to the use of a curable composition, as defined in any aspect herein, for preparing an adhesive, a sealant, a coating, a 3D printing ink, a shaped article, a chemical anchor, a dental material or a repair system thereof.

[0023] In a further aspect, the invention relates to an article, selected from an adhesive, a sealant, a coating, a 3D printing ink, a shaped article, a chemical anchor and a dental material, wherein the article is obtainable by applying the curable composition, as defined in any aspect herein, to a substrate and polymerizing the curable composition.

[0024] Detailed description of the invention

[0025] The terms “alkyl”, “alkylene”, “alkoxy”, “cycloalkyl”, “cycloalkylene”, “aryl”, “halogen” are known in the art and generally have the following meaning, if said groups are not further specified in specific embodiments mentioned below:

[0026] Alkyl, e.g., Ci-C25-alkyl, C3-C2o-alkyl, Ci-C20-alkyl, Ci-Ci8-alkyl, Ci-Ci2-alkyl, C-i-C-io-alkyl, Ci-C8- alkyl, or Ci-C4-alkyl, may be within the given limits of carbon atoms linear or branched, where possible. Examples are methyl (Me), ethyl (Et), n-propyl, isopropyl, n-butyl, 1 -methylpropyl, 2- methylpropyl, t-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, 1 -methylhexyl, n- heptyl, 1 ,1 ,3,3-tetramethylbutyl, 1 -methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, n-nonyl, n- decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n- octadecyl, n-eicosyl, n-heneicosyl, n-docosyl, n-tetracosyl, n-pentacosyl and constitutional isomers of the aforementioned n-alkyl radicals. Alkylene, e.g., Ci-C25-alkylene, Ci-Ci8-alkylene, Ci-C4-alkylene, C2-C4-alkylene, C2-C5-alkylene or C2-C3-alkylene, may be derived from linear or branched alkyl, if possible, by abstracting a H atom from any terminal carbon atom of the alkyl.

[0027] Alkoxy, e.g., Ci-Ci2-alkoxy, is alkyl-O.

[0028] Alkylthio, e.g., Ci-Ci2-alkylthio, is alkyl-S.

[0029] Cycloalkyl, e.g., C3-Ci8-cycloalkyl, C3-Ci2-cycloalkyl, C5-Ci4-cycloalkyl, C5-C6-cycloalkyl, includes cycloalkyl groups and bicyclic groups, which may be unsubstituted or substituted with alkyl groups. Examples are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl, cyclohexadecyl or 1 ,4-cyclohexylene-cyclohexyl. Bicyclic alkyl may be isobornyl (= 1 ,7,7-trimethyl- bicyclo[2.2.1]heptyl) or norbornyl (= bicyclo[2.2.1]heptyl). Cyclohexyl and cyclopentyl are preferred, more preferred is cyclohexyl.

[0030] Cycloalkylene, e.g., C5-C7-cycloalkylene, includes cycloalkylene groups, which may be unsubstituted or substituted with alkyl groups, preferably unsubstituted. Examples are 1 ,2- cyclopentylene, 1 ,3-cyclopentylene, 1 ,2-cyclohexylene, 1 ,4-cyclohexylene or 1 ,2- cycloheptylene.

[0031] Aryl, e.g., C6-Ci8-aryl, or C6-Ci2-aryl, may be within the given limits of carbon atoms phenyl, fluorenyl, biphenylyl, terphenylyl or naphthyl, which may have a fused ring, such as in indanyl. Preferred examples are phenyl, 1-naphthyl, 2-naphthyl, 3- or 4-biphenylyl. Each aryl may be unsubstituted or substituted one or more times.

[0032] Halogen (Hal) denotes I, Br, Cl, or F, preferably Cl on alkyl and Cl or Br on aryl.

[0033] The substituent «Ci2 / Ci4» means a substituent derived from Ci2 / Ci4fatty alcohol.

[0034] The term “substituted” means “substituted one or more times with”, that is 1 to 3 times, where possible, preferably 1 or 2 times, more preferably 1 . If a substituent occurs more than once in a group, it may be different in each occurrence.

[0035] The term "(meth)acryloyl" or similar terms, as used herein, encompasses acryloyl, methacryloyl and mixtures thereof.

[0036] The term “(meth)acrylate polymer”, as used herein, means a polymer containing at least one unit derived from a monomer of formula (I) and optionally one or more (meth)acrylic comonomers.

[0037] The term “oxathiolanone group”, as used herein, means a 1 ,3-oxathiolane-2-one group. The term “ethylenically unsaturated group”, as used herein, means a non-aromatic ethylenically unsaturated group.

[0038] The term “(mono)ethylenically unsaturated monomer”, as used herein, means a non-aromatic monoethylenically unsaturated monomer, wherein the C=C double bond is susceptible to radical polymerization.

[0039] The quantity for monomers of a polymer is based, unless otherwise explicitly stated, on 100 weight parts of all of the monomers.

[0040] The term “based on the total weight of the monomers”, as used herein with respect to the (meth)acrylate polymer A, means all of the monomers used to form the (meth)acrylate polymer A (monomers M including M1 , optionally M2 and optionally further monomers).

[0041] Unless otherwise stated, molecular weights of polymers refer herein to the weight-average molecular weight, measured by gel-permeation chromatography using a polystyrene standard.

[0042] The term “any combination thereof’, as used herein, means two or more combinations thereof, either different kinds of one constituent or one group, i.e., different subgroups, or different kinds of a list of constituents or groups.

[0043] As used herein, the indefinite article “a” comprises the singular but also the plural, i.e., an indefinite article in respect to a component of a composition means that the component is a single compound or a plurality of compounds. If not stated otherwise, the indefinite article “a” and the expression “at least one” are used synonymously.

[0044] The invention relates also to a (meth)acrylate polymer A containing a unit derived from an oxathiolanone group-containing monomer M1 of formula

[0045] (I), wherein

[0046] R1is H or methyl,

[0047] X is Ci-C4-alkylene, and optionally at least one unit derived from a monoethylenically unsaturated monomer M2, wherein the amount of the monomer M1 of formula (I) is at least 8 wt%, based on the total weight of the monomers.

[0048] Preferred is an oxathiolanone group-containing monomer M1 of formula

[0049] (I), wherein

[0050] R1is H or methyl, especially methyl; and

[0051] X is Ci-C4-alkyl.

[0052] Further preferred is a monomer M1 of formula (I), wherein X is methylene or ethylene, especially methylene.

[0053] Accordingly, in a preferred aspect, the invention relates to a (meth)acrylate polymer, obtainable by a free-radical polymerization process of a monomer M1 of formula

[0054] (I), wherein

[0055] R1is methyl,

[0056] X is methylene or ethylene, and optionally at least one monoethylenically unsaturated monomer M2, wherein the amount of the monomer M1 of formula (I) is at least 8 wt%, based on the total weight of the monomers.

[0057] More preferred is an oxathiolanone group-containing monomer M1 of formula (la)

[0058] (la).

[0059] The (meth)acrylate polymer A may be a homopolymer containing only a unit derived from the monomer MI of formula (I).

[0060] Alternatively, the meth(acrylate) polymer A may contain at least one further unit derived from a monomer M2, which is different from the monomer M1 of formula (I). The monomer M2 preferably does not contain an oxathiolanone group.

[0061] Preferably, the meth(acrylate) polymer contains at least one further unit derived from an ethylenically unsaturated monomer M2, which is a monoethylenically unsaturated monomer. The monoethylenically unsaturated monomer M2 may be an ethylenically unsaturated carboxylic acid or salt thereof, an ethylenically unsaturated carboxylic anhydride, an ethylenically unsaturated amide, an ethylenically unsaturated nitrile, an ethylenically unsaturated carboxylic ester or any combination thereof.

[0062] Examples of an ethylenically unsaturated carboxylic acid include (meth)acrylic acid and salts thereof.

[0063] Examples of an ethylenically unsaturated carboxylic anhydride include unsaturated acid anhydrides such as itaconic anhydride, maleic anhydride, 2,3-dimethyl maleic anhydride, and 2- chloromaleic anhydride.

[0064] Examples of an ethylenically unsaturated amide include (meth)acrylamide, N-substituted (meth)acrylamides, e.g. N-methylol(meth)acrylamide, N-ethyl(meth)acrylamide, N- hexyl(meth)acrylamide, N-cyclohexyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, N- phenyl(meth)acrylamide, N-benzyl(meth)acrylamide, N-ethyl-N-phenyl(meth)acrylamide, N-(4- hydroxyphenyl)(meth)acrylamide, N-isobutoxymethyl (meth)acrylamide and diacetone (meth)acrylamide.

[0065] Examples of an ethylenically unsaturated nitrile include (meth)acrylonitrile.

[0066] Examples of an ethylenically unsaturated carboxylic ester include (meth)acrylic esters such as: alkylesters or cycloalkylesters, e.g., methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl-, pentyl, hexyl, cyclohexyl, 2-ethylhexyl, octyl, or isobornyl ester; hydroxyalkyl esters, e.g., 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl, 4- hydroxybutyl, 3,4-dihydroxybutyl or glycerol ester; haloalkylesters, e.g., 2-chloroethyl; aminoalkylesters, e.g., N,N’-dimethylaminoethyl, N,N’-dimethylaminopropyl or N,N’-dimethyl- aminobutyl; poly-C2-C4-alkylene oxide-containing esters, e.g., Ci-Ci0-alkyl-poly-C2-C4-alkyleneoxide (meth)acrylate or poly-C2-C4-alkyleneoxide (meth)acrylate; epoxyalkyl esters, e.g., glycidyl, 2-glycidyloxyethyl, 2,3-epoxybutyl, 3,4-epoxy butyl, 2,3- epoxycyclohexyl, or 10, 11 -epoxyundecyl ester; aryl-containing esters, e.g., phenyl, benzyl-, o-, m- or p-hydroxyphenyl ester; maleic acid esters; itaconic acid esters; methylene succinic acid esters; butenolides and pentenolides, e.g., 2(5H)-furanone.

[0067] Accordingly, in a preferred aspect, the invention relates to a (meth)acrylate polymer A, obtainable by a free-radical polymerization process of a monomer M1 of formula

[0068] (I), wherein R1is H or methyl,

[0069] X is Ci-C4-alkylene, and at least one monoethylenically unsaturated monomer M2, wherein the amount of the monomer M1 of formula (I) is at least 8 wt%, based on the total weight of the monomers, and the at least one monoethylenically unsaturated monomer M2 is selected from the group consisting of an ethylenically unsaturated carboxylic acid or salt thereof, an ethylenically unsaturated carboxylic anhydride, an ethylenically unsaturated amide, an ethylenically unsaturated nitrile, an ethylenically unsaturated carboxylic ester and any combination thereof.

[0070] The at least one monoethylenically unsaturated Monomer M2 is preferably an ethylenically unsaturated carboxylic ester.

[0071] Preferably, the ethylenically unsaturated monomer M2 is a (meth)acrylic ester of formula (II), wherein

[0072] R2is H or CH3;

[0073] R3is Ci-C25-alkyl; Ci-Ci8-alkyl substituted with COOH, halogen, Ci-Ci2-alkoxy, Ci-Ci2-alkylthio, OH, N(Ci-C4-alkyl)2, C6-Ci8-aryl, C6-Ci8-aryloxy, C3-Ci8-cycloalkyl or epoxy; C3-Ci8-cycloalkyl;

[0074] C6-Ci8-aryl; C6-Ci8-aryl substituted with OH, COOH, Ci-Ci2-alkyl, Ci-Ci2-alkoxy or Ci-Ci2- alkylthio; or a group of formula -(Z-Y)n- R4(III),

[0075] R4is H or Ci-C-io-alkyl;

[0076] Z is at each occurrence C2-C4-alkylene;

[0077] Y is O or S; and n is a real number in the range of > 2 to < 30.

[0078] Accordingly, in a preferred aspect, the invention relates to a (meth)acrylate polymer A, obtainable by a free-radical polymerization process of a monomer M1 of formula

[0079] (I), wherein

[0080] R1is H or methyl,

[0081] X is Ci-C4-alkylene, and at least one monoethylenically unsaturated monomer M2, wherein the amount of the monomer M1 of formula (I) is at least 8 wt%, based on the total weight of the monomers, and the at least one monoethylemcally unsaturated monomer M2 is a (meth)acryhc ester of formula ,

[0082] R2is H or CH3;

[0083] R3is Ci-C25-alkyl; Ci-Ci8-alkyl substituted with COOH, halogen, Ci-Ci2-alkoxy, Ci-Ci2-alkylthio, OH, N(Ci-C4-alkyl)2, C6-Ci8-aryl, C6-Ci8-aryloxy, C3-Ci8-cycloalkyl or epoxy; C3-Ci8-cycloalkyl; C6-Ci8-aryl; C6-Ci8-aryl substituted with OH, COOH, Ci-Ci2-alkyl, Ci-Ci2-alkoxy or Ci-Ci2- alkylthio; or a group of formula -(Z-Y)n- R4(III),

[0084] R4is H or Ci-C-io-alkyl;

[0085] Z is at each occurrence C2-C4-alkylene;

[0086] Y is O or S; and n is a real number in the range of > 2 to < 30.

[0087] The group R3is preferably C3-C20-alkyl; Ci-Ci8-alkyl substituted with COOH, halogen, Ci-C4- alkoxy, Ci-C4-alkylthio, OH, N(Ci-C4-alkyl)2, C6-Ci2-aryl, C6-Ci2-aryloxy, C3-C9-cycloalkyl or epoxy; C6-Ci2-aryl; C6-Ci2-aryl substituted with OH, COOH, Ci-C4-alkyl, Ci-C4-alkoxy or Ci-C4- alkylthio; or a group of formula -(Z-Y)n- R4(III),

[0088] R4is H or Ci-C8-alkyl;

[0089] Z is at each occurrence C2-C4-alkylene;

[0090] Y is O or S; and n is a real number in the range of > 2 to < 30.

[0091] More preferred is a group of formula -(Z-Y)n- R4(III), wherein

[0092] R4is H or Ci-C8-alkyl;

[0093] Z is at each occurrence C2-C3-alkylene;

[0094] Y is O; and n is a real number in the range of > 2 to < 30, especially > 2 to < 20.

[0095] The group of formula -(Z-Y)n- (VII) may be an ethylene oxide group (EO) or a propylene group (PO) or a combination thereof, wherein

[0096] EO is CH2-CH2-O-, and

[0097] PO is CH(CH3)-CH2-O- or CH2-CH(CH3)-O-.

[0098] Accordingly, a group of formula -(Z-Y)n- R4(III) is more preferred, wherein R4is H or Ci-C8-alkyl;

[0099] (Z-Y) is EO or PO or a combination thereof;

[0100] EC is CH2-CH2-O-,

[0101] PO is CH(CH3)-CH2-O- or CH2-CH(CH3)-O-; and n is a real number in the range of > 2 to < 30. A suitable group of formula (VII) is a group of formula -(EO)n- (Vila), a group of formula -(PO)n- (VI I b) or a group of formula (EO)P- (PO)q(Vile), wherein n is a real number in the range of > 2 to < 30, p is a real number in the range of > 1 to < 29, q is a real number in the range of > 1 to < 20, whereby the concatenations of p and q are distributed to form a random or block polymeric structure, and with the proviso that n = p + q.

[0102] Especially preferred is a group of formula (VII) selected from a group of formula

[0103] -(EO)n - (Vila), or a group of formula -(EO)P- (PO)q- (Vile), wherein n is a real number in the range of > 2 to < 20, p is a real number in the range of > 1 to < 19, q is a real number in the range of > 1 to < 10, whereby the concatenations of p and q are distributed to form a random or block polymeric structure, and with the proviso that n = p + q.

[0104] A preferred group R3is C3-C2o-alkyl; Ci-Ci8-alkyl substituted with Ci-C4-alkoxy, Ci-C4-alkylthio, OH or N(Ci-C4-alkyl)2, phenyl, phenoxy, C3-Ci2-cycloalkyl or epoxy; C3-Ci2-cycloalkyl; phenyl; or phenyl substituted with OH, Ci-C4-alkyl, Ci-C4-alkoxy or Ci-C4-alkylthio.

[0105] Accordingly, in a preferred aspect, the invention relates to a (meth)acrylate polymer, obtainable by a free-radical polymerization process of a monomer M1 of formula

[0106] (I), wherein

[0107] R1is H or methyl,

[0108] X is Ci-C4-alkylene, and at least one monoethylenically unsaturated monomer M2, wherein the amount of the monomer M1 of formula (I) is at least 8 wt%, based on the total weight of the monomers, the at least one monoethylenically unsaturated monomer M2 is a (meth)acrylate monomer of formula (II), wherein R3is preferably C3-C2o-alkyl; Ci-Ci8-alkyl substituted with Ci-C4-alkoxy, Ci-C4-alkylthio, OH or N(Ci-C4-alkyl)2, phenyl, phenoxy, C3-Ci2-cycloalkyl or epoxy; C3-Ci2-cycloalkyl; phenyl; or phenyl substituted with OH, Ci-C4-alkyl, Ci-C4-alkoxy or Ci-C4-alkylthio; a group of formula -(Z-Y)n- R4(III),

[0109] R4is H or Ci-C8-alkyl;

[0110] Z is at each occurrence C2-C3-alkylene;

[0111] Y is O; and n is a real number in the range of > 2 to < 30, especially > 2 to < 20.

[0112] The group Z may be ethylene and / or propylene.

[0113] Accordingly, R3is preferably C3-C20-alkyl; Ci-Ci8-alkyl substituted with Ci-C4-alkoxy, Ci-C4- alkylthio, OH or N(Ci-C4-alkyl)2, phenyl, phenoxy, C3-C6-cycloalkyl or epoxy; C3-Ci2-cycloalkyl; phenyl; or phenyl substituted with OH, Ci-C4-alkyl, Ci-C4-alkoxy or Ci-C4-alkylthio; a group of formula -(Z-Y)n- R4(III),

[0114] R4is H or Ci-C8-alkyl;

[0115] (Z-Y) is EO or PO or a combination thereof;

[0116] EO is CH2-CH2-O-, and

[0117] PO is CH(CH3)-CH2-O- or CH2-CH(CH3)-O-, and n is a real number in the range of > 2 to < 30.

[0118] More preferably, R3is C3-C20-alkyl; Ci-Ci8-alkyl substituted with Ci-C4-alkoxy, Ci-C4-alkylthio, OH or N(Ci-C4-alkyl)2, phenyl, phenoxy, C3-Ci2-cycloalkyl or epoxy; C3-Ci2-cycloalkyl; phenyl; or phenyl substituted with OH, Ci-C4-alkyl, Ci-C4-alkoxy or Ci-C4-alkylthio; a group of formula -(Z-Y)n- R4(III),

[0119] R4is H or Ci-C8-alkyl; the group of formula -(Z-Y)n- (VII) is a group of formula -(EO)n- (Vila), or a group of formula - (EO)P- (PO)q- (Vile), wherein

[0120] EO is CH2-CH2-O-, and

[0121] PO is CH(CH3)-CH2-O- or CH2-CH(CH3)-O-, n is a real number in the range of > 2 to < 20, p is a real number in the range of > 1 to < 19, q is a real number in the range of > 1 to < 10, whereby the concatenations of p and q are distributed to form a random or block polymeric structure, and with the proviso that n = p + q.

[0122] Suitable examples include n-butyl(meth)acrylate, isobutyl(meth)acrylate, n-pentyl(meth)acrylate, neopentyl(meth)acrylate, n-hexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, n- octyl(meth)acrylate, isooctyl(meth)acrylate, isobornyl(meth)acrylate, n-hexadecyl(meth)acrylate, n-heptadecyl(meth)acrylate, n-octadecyl(meth)acrylate, phenoxyethyl(meth)acrylate, glycidyl (meth)acrylate, methoxy-polyethylene glycol mono(meth)acrylate, methoxypolypropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polyethylene glycol-propylene glycol)-(meth)acrylate, the sequence of the ethylene oxide and propylene oxide units being blockwise or random, and methoxy-poly(ethylene glycol-propylene glycol)-(meth)acrylate, the sequence of the ethylene oxide and propylene oxide units being blockwise or random.

[0123] It is understood that a (meth)acrylate polymer A may contain an epoxy group-containing (meth)acrylate as monomer M2, for example, glycidyl (meth)acrylate, usually in a mixture with one or more monomers M2, which are different to an epoxy-group containing monomer M2. The epoxy group may react as a functional group towards a SH group, i.e., the (meth)acrylate polymer A may react as a possible compound C.

[0124] Therefore, a preferred (meth)acrylate polymer A is obtainable, wherein the at least one monomer M2 is a mixture comprising glycidyl (meth)acrylate in an amount of up to 10 wt%, based on the total weight of the monomers M, preferably 1 to 5 wt%. Such mixture may be of advantage to adjust the zero-shear viscosity of the (meth)acrylate polymer A.

[0125] The meth(acrylate polymer) A preferably comprises 8 to 50 wt% of a unit derived from monomer M1 , more preferably 8 to 45 wt%, based on the total weight of all monomers.

[0126] Accordingly, in a preferred aspect, the invention relates to a (meth)acrylate polymer A, obtainable by a free-radical polymerization process of a monomer M1 of formula (I), especially (la) and at least one monoethylenically unsaturated monomer M2, wherein the amount of the monomer M1 of formula (I) is of from 8 to 50 wt%, based on the total weight of the monomers.

[0127] The (meth)acrylate polymer A preferably comprises 0 to 92 wt% of a unit derived from the monomer M2, more preferably 45 to 92 wt%, especially 50 to 92 wt%.

[0128] The (meth)acrylate polymer A may contain in a minor amount units derived from a further monomer other than monomers M1 and M2, for example, a vinyl monomer like a vinyl ester, a vinyl ether, a vinyl aromatic compound or a vinyl halide.

[0129] The (meth)acrylate polymer A is preferably derived from monomer M1 and at least one monomer M2 in an amount of more than 95 wt%, based on the total weight of all of the monomers used to form the (meth)acrylate polymer A (monomers M), more preferably 98 wt%, most preferably, the poly(meth)acrylate polymer A consists of units derived from monomers M1 and M2.

[0130] Accordingly, a (meth)acrylate polymer A is preferred, wherein the amount of the monomer M1 and the at least one monoethylenically unsaturated monomer M2 is at least 98 wt%, preferably 98-100 wt%, based on the total weight of the monomers M.

[0131] The (meth)acrylate polymer A preferably has a number-average molecular weight in the range of from 800 to 30,000 g / mol, especially in the range of from 1000 to 20,000. The weight-average molecular weight of the poly(meth)acrylate polymer is preferably in the range of from 1200 to 50,000 g / mol, especially in the range of from 1500 to 40,000. The molecular weights can be measured by gel permeation chromatography with polystyrene as standard.

[0132] Accordingly, in a preferred aspect, the invention relates to a (meth)acrylate polymer A, obtainable by a free-radical polymerization process of a monomer M1 of formula (I), especially (la) and optionally at least one monoethylenically unsaturated monomer M2, wherein the (meth)acrylate polymer A has a number-average molecular weight Mnof from 800 to 30,000 g / mol.

[0133] The (meth)acrylate polymer A preferably has a zero-shear viscosity at 23°C of < 7000 Pa s, more preferably < 6500 Pa s, especially measured under oscillatory shear at a shear amplitude of 10%, in particular, at angular frequency ramp log 100-0.1 s1, measuring gap 0.5 mm, evaluation according to Carreau-Gahleitner I, and piston diameter 25 mm (using an Anton Paar MCR 100 rheometer in plate / plate geometry).

[0134] Accordingly, in a preferred aspect, the invention relates to a (meth)acrylate polymer A, obtainable by a free-radical polymerization process of a monomer M1 of formula (I), especially (la) and optionally at least one monoethylenically unsaturated monomer M2, wherein the (meth)acrylate polymer A has a zero-shear viscosity at 23°C of < 7000 Pa s.

[0135] The polymerization of the monomers M, including the monomer M1 of formula (I), optionally at least one monomer M2 and optionally further monomers, to obtain the (meth)acrylate polymer A may be conducted by customary methods of a free-radical polymerization process, for example, by solution polymerization, precipitation polymerization or emulsion polymerization, preferably by solution polymerization.

[0136] The process for preparing the (meth)acrylate polymer A is usually conducted in a non-aqueous medium as polymerization medium. In other words, the polymerization is conducted in a medium which does not comprise any water or comprises water in only a small amount in the manner of a solution or precipitation polymerization. Based on the total weight of the mixture to be polymerized, the amount of water is preferably < 2 wt%, more preferably < 1 wt%, most preferably < 0.5 wt%.

[0137] The non-aqueous medium is usually an organic solvent, generally with a boiling point of at least 50°C, preferably of at least 75°C, more preferably of from 80 to 220°C, most preferably 80 to 200°C.

[0138] Suitable solvents include aprotic solvents or protic solvents as well as any mixture of an aprotic and protic solvent.

[0139] Examples of aprotic solvents include aromatic hydrocarbons like toluene, xylenes, o-xylene or chlorobenzene; aliphatic hydrocarbons like cyclohexane, n-heptane or 1 ,2-dichloroethane; ketones like cyclohexanone, acetone, butanone or methyl amyl ketone; ethers like dioxane, monoglyme, 2-methyl-tetrahydrofuran or anisole; esters like ethyl acetate, propyl acetate, n- butyl acetate, methyl butyrate, ethyl butyrate, propyl butyrate, methyl propionate, ethyl propionate, propyl propionate, cyclohexyl acetate, 1-methoxy-2-propyl acetate, 2-methoxyethyl acetate, y-butyrolactone or y- or b-valerolactone; amides like N,N-dimethylformamide, N,N- dimethylacetamide, N-methylpyrrolidone or N-ethylpyrrolidone; sulfoxides like dimethyl sulfoxide; or mixtures of two or more of these aprotic solvents.

[0140] Examples of protic solvents include alcohols like n-propanol, 2-propanol, n-butanol, 2-butanol, isobutanol, t-butanol, n-pentanol, 2-pentanol, benzyl alcohol, 1-methoxy-2-propanol or 1- methoxy-2-methyl-2-propanol; or mixtures of two or more of these protic solvents.

[0141] Preferred solvents are aromatic hydrocarbons like xylenes or o-xylol; alkyl esters like ethyl acetate, n-butyl acetate or 1-methoxy-2-propylacetate; alcohols like 2-propanol, 2-butanol, 2- pentanol or 1-methoxy-2-propanol; ketones like cyclohexanone or butanone; and any mixture of two or more thereof.

[0142] Preferably, the organic solvent will be such that the amount of monomers to be polymerized, based on the total amount of the monomers plus solvent, is in the range from 10 to 90 wt%, especially in the range from 20 to 80 wt%.

[0143] In connection with the instant process of polymerization a free-radical initiator may be used. These may, in principle, be a peroxo-type initiator, an azo-type initiator or a redox initiator system. Suitable for this purpose are usually all customary initiators that are known for (meth)acrylates.

[0144] Examples of a peroxo-type initiator include t-amyl peroxybenzoate, dibenzoyl peroxide, 2,2- bis(t-butylperoxy)butane, 1 ,1-bis(t-butylperoxy)-cyclohexane, 2,5-bis(t-butylperoxy)-2,5- dimethylhexane, 1 ,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, t-butyl hydroperoxide, t-butyl peracetate, t-butyl-peroxypivalate, t-amyl-peroxypivalate, t-butylperoxide, t-butyl peroxybenzoate, t-butylperoxy isopropyl carbonate, cumene hydroperoxide, cyclohexanone peroxide, dicumyl peroxide, lauroyl peroxide, 2,4-pentanedione peroxide, peracetic acid and potassium persulfate.

[0145] Examples of an azo-type initiator include 2,2’-azobisisobutyronitrile (AIBN), 1 ,1 ’-azobis(cyclo- hexanecarbonitrile), 2,2’-azobis(2-methylbutyronitrile), 2-t-butylazo-2-cyanopropane and dimethyl-2,2’-azobis(2-methylpropionate).

[0146] Examples of a redox initiator system are combinations of an oxidizing compound and a reducing compound. Examples of an oxidizing compound include the peroxo-type initiators listed above. Examples of a reducing compound include sulfur compounds with a low oxidation state such as alkali metal sulfites, for example potassium and / or sodium sulfite, alkali metal hydrogensulfites, for example potassium and / or sodium hydrogensulfite, alkali metal metabisulfites, for example potassium and / or sodium metabisulfite, formaldehyde sulfoxylates, for example potassium and / or sodium formaldehyde sulfoxylate, alkali metal salts, specifically potassium and / or sodium salts of aliphatic sulfinic acids and alkali metal hydrogensulfides, for example potassium and / or sodium hydrogensulfide, salts of polyvalent metals, such as iron(ll) sulfate, iron(ll) ammonium sulfate, iron(ll) phosphate, ene diols such as dihydroxymaleic acid, benzoin and / or ascorbic acid, and reducing saccharides such as sorbose, glucose, fructose and / or dihydroxyacetone. A suitable example of a redox initiator system includes the combination of t-butyl hydroperoxide ascorbic acid. The weight ratio of oxidizing compound to the reducing compound is preferably 50:1 to 0.05:1.

[0147] A preferred initiator is a peroxo-type initiator.

[0148] The amount of the free-radical initiator to be used may vary depending on the polymerization conditions, the type of radical initiator and / or the type of monomers. The free-radical initiator may be used in a catalytically effective amount, for example, in an amount of from 0.01 to 20 wt%, based on the total weight of the monomers, preferably from 0.01 to 15 wt%, more preferably from 0.1 to 12 wt%.

[0149] Preferably, the polymerization reaction is performed in an inert atmosphere, for example, under nitrogen or argon atmosphere.

[0150] Customary polymerization techniques may be employed. The polymerization may be performed by initially charging the majority, i.e., at least 60 wt%, especially at least 80 wt% or the total amount of the monomer(s) to be polymerized in the polymerization vessel or by feeding the majority of the monomers to be polymerized, for example at least 60 wt%, particularly at least 80 wt% and especially at least 90 wt%, to the polymerization vessel in the course of the polymerization reaction. The monomers, if more than one monomer is used, are usually fed as a monomer mixture.

[0151] The free-radical initiator may be initially charged in the polymerization vessel or added in the course of the polymerization reaction. The procedure may also be conducted by adding a small amount of monomer(s), for example 0.1 to 20 wt%, based on the total amount of monomers to be polymerized, optionally together with a portion of the initiator, for example, 0.1 to 10 wt%, based on the total amount of initiator, in the polymerization vessel, to start the polymerization, for example, by heating the polymerization mixture, and then to add the remainder of the monomers and the remainder of polymerization initiator over the course of the polymerization.

[0152] Typically, the monomers are dissolved in the solvent as well as the free-radical initiator. Part of the solvent is also usually charged in the polymerization vessel.

[0153] The polymerization temperatures typically employed for the polymerization are, depending on the initiator system selected, in the range of from 50 to 180°C, preferably from 80 to 150°C and especially from 80 to 130°C. The polymerization pressure is of minor importance and may be in the region of standard pressure or slightly reduced pressure, for example > 800 mbar (absolute), or elevated pressure, for example up to 10 bar, though higher or lower pressures may likewise be employed. The polymerization time does preferably not exceed 12 hours and is frequently in the range from 1 to 10 hours.

[0154] After the polymerization has ended, the polymerization mixture can be worked up in a customary manner. In case of a precipitation polymerization, the polymer can, for example, be filtered off. Volatile components, for example solvents, can also be removed by distillation measures. In case of a solution polymerization, it is also possible to precipitate the polymer obtained, for example by adding an organic solvent in which the polymer is insoluble.

[0155] Optionally, the polymerization may also be followed by a solvent exchange, for example in order to convert the polymer from a solution to a dispersion. Optionally, the polymer obtained is be subjected to devolatilization, in order to remove further volatile constituents. Any method of purifying the polymer known in the art may be used.

[0156] In a further aspect, the invention relates to a process for preparing a (meth)acrylate polymer, the process comprising polymerizing a monomer M1 of formula

[0157] (I), as defined in any aspect herein, and optionally at least one monoethylenically unsaturated monomer M2, as defined in any aspect herein, in the presence of a free-radical initiator.

[0158] Preferred is a process for preparing a (meth)acrylate polymer, wherein the step of polymerizing is conducted at a temperature of at least 75°C, preferably of from 80 to 150°C, in the presence of an organic solvent, the amount of free-radical initiator is of from 0.01 to 15 wt%, based on the total weight of the monomers, the amount of the monomer M1 of formula (I) is of from 8 to 50 wt%, based on the total weight of the total weight of all of the monomers, and preferably the obtained (meth)acrylate polymer A has a zero-shear viscosity at 23°C of < 7000 Pa s.

[0159] The (meth)acrylate polymer A may be used for a variety of applications. Typically, the (meth)acrylate polymer A is a constituent or a component of a curable composition containing further a compound B having at least one amino group selected from a primary amino group, a secondary amino group or any combination thereof, wherein the at least one amino group may be present in a masked, latently reactive form.

[0160] Accordingly, in a further aspect, the invention relates to a curable composition containing a) a (meth)acrylate polymer A, as defined in any aspect herein, b) a compound B having at least one amino group, selected from a primary amino group, a secondary amino group and any combination thereof, said primary or secondary amino group may be present in a masked, latently reactive form, and c) optionally a compound C having at least one functional group reactive towards a SH group.

[0161] A curable composition is generally understood as meaning a composition that comprises at least two polyfunctional constituents that react with one another with bond formation, thereby forming a polymer network. Accordingly, a curable composition preferably comprises, in addition to at least one (meth)acrylate polymer A, at least one compound B having at least 2 functional groups, especially at least two amino groups selected from a primary amino group, a secondary amino group and any combination thereof, or at least one compound C having at least two functional groups reactive towards a SH group.

[0162] A curable composition is preferred, with the proviso that at least one compound of the compounds B and C is polyfunctional.

[0163] Accordingly, in a preferred aspect, the invention relates to a curable composition, with the proviso that

[0164] - the compound B is polyfunctional, in case the compound C is not present, or

[0165] - at least one compound of the compounds B and C is polyfunctional, in case the compound C is present.

[0166] The curable composition may be a curable one-component composition or a curable two- component composition.

[0167] A polyfunctional compound B may have two or more amino groups selected from a primary amino group, a secondary amino group and any combination thereof. Also, a polyfunctional compound B may have at least one amino group selected from a primary amino group, a secondary amino group and a combination thereof, and at least one ethylenically unsaturated group, a CEC bond-containing group or a silicon-functional group.

[0168] A polyfunctional compound C may have two or more functional groups reactive towards a SH group. Also, a polyfunctional compound C may have at least one functional group reactive towards a SH group and a silicon-functional group or an oxathiolanone group.

[0169] Preferably, the curable composition is a two-component composition, wherein the first component contains the (meth)acrylate polymer A and the optional compound C, and the second component contains the compound B.

[0170] Accordingly, in a preferred aspect, the invention relates to a curable composition, which is a curable two-component composition containing

[0171] (1) a first component containing a) the (meth)acrylate polymer A, and c) optionally the compound C having at least two functional groups reactive towards a SH group, and

[0172] (2) a second component containing b) the compound B having at least one amino group, selected from a primary amino group, a secondary amino group and any combination thereof, said primary or secondary amino group may be present in a masked, latently reactive form.

[0173] The (meth)acrylate polymer A may be used alone or as a mixture of two or more (meth)acrylate polymers A. The (meth)acrylate polymers A may vary in kind or ratio of the monomer(s) M2. Preferably, the curable composition contains only one kind of (meth)acrylate polymer A.

[0174] The (meth)acrylate polymer A may be used with a further compound A1 having one or two oxathiolanone groups, which are liquid at room temperature, for example, at a temperature of from 15 to 40°C and 1 bar, preferably at a temperature of from 20 to 30°C and 1 bar. Also possible is a mixture of compounds A1 , for example a solid compound A1 dissolved in a liquid compound A1 , wherein said mixture is liquid at room temperature, for example, at a temperature of from 15 to 40°C and 1 bar, preferably at a temperature of from 20 to 30°C and 1 bar.

[0175] The compound A1 does generally not contain a further functional group reactive towards a SH group.

[0176] The compound A1 may be of formula

[0177] (VIII), wherein

[0178] R5is H, Ci-Cis-alkyl; Ci-Ci8-alkyl substituted with halogen or interrupted with O; or phenyl; or of formula

[0179] (IX), wherein

[0180] W is Ci-Cis-alkylene; Ci-C25-alkylene interrupted with O, S, COO, Cs-Cz-cycloalkylene and / or phenylene.

[0181] Suitable examples are compounds A1 of formulae

[0182] A mixture of a (meth)acrylate polymer A with a compound A1 may be of advantage, for example, a (meth)acrylate polymer A may be used for immediate strength without reducing the pot life of the two-component adhesive composition too much, plus a compound A1 which may be slower for final curing, may modulate the properties of the final two-component adhesive composition or may be of advantage for processing the curable composition, e.g., for lowering the zero-shear viscosity of the mixture with the (meth)acrylate polymer A. Compounds A1 may be obtainable by a process, as described in WO 2019 / 034469 A1 , WO 2019 / 034470 A1 or WO 2019 / 034473 A1. The process usually comprises the following steps: a) a compound having one, two or more epoxy groups is used as starting material, b) said compound is reacted with phosgene or an alkyl chloroformate to form an adduct, and c) said adduct is reacted with an anionic sulfur-containing compound to form a compound that contains one, two or more oxathiolanone groups.

[0183] Further processes for preparing alkylene monothiocarbonates are described, for example, in US 3072676, US 3201416, US 3517029 and US 3349100 and US 2828318.

[0184] The compound A1 may be present in an amount of up to 30 wt%, based on the total weight of the (meth)acrylate polymer A, preferably from up to 20 wt%.

[0185] The curable composition comprises at least one compound B, also called curing compound B. The compound B has at least one amino group selected from a primary amino group, a secondary amino group and any combination thereof, wherein the amino group may be present in a masked, latently reactive form.

[0186] The compound B may be a monoamine or a polyamine.

[0187] Generally, the compound B does not comprise any oxathiolanone group.

[0188] The compound B may comprise further functional groups than a primary and / or a secondary amino group. The compound B may comprise, for example, a tertiary amino group, an ether group, a carboxylic ester group, a silicon-functional group or an ethylenically unsaturated group. Preferably, compound B does not comprise any further functional group other than a tertiary amino group, an ether group, a carboxylic ester group, a silicon-functional group or an ethylenically unsaturated group.

[0189] Preferably, the compound B is a compound having at least two primary amino groups, two secondary amino groups and any combination thereof, more preferably a compound having at least two primary amino groups.

[0190] The compound B is preferably a compound having at least one amino group selected from an aliphatic primary amino group, a cycloaliphatic primary amino group, an aliphatic secondary amino group, a cycloaliphatic secondary amino group and any combination thereof, preferably selected from an aliphatic primary group, a cycloaliphatic primary group and any combination thereof.

[0191] The compound B may be a low molecular-weight substance, i.e., one having a molecular weight below 500 g / mol, or an oligomeric or polymeric substance that has a molecular weight above 500 g / mol, preferably a low-molecular-weight compound having a molecular weight below 500 g / mol. Depending on the application, for example, for good adhesion or sealing properties or generally for good polymer flexibility, it is preferable that the compound B and / or the optional compound C each contain at least one flexible spacer group. A flexible spacer group is a linear or branched linking group that has a molecular weight of at least 200 g / mol. The spacer group may be situated between two functional groups in the curing agent B. The spacer group is preferably selected from an alkylene group, a polyether group, a polycarbonate group, a polyester group, and a poly(meth)acrylate group. Examples of spacer groups are linear or branched alkylene groups having at least 15 carbon atoms; polyether groups of the general formula (Z1-O)m-, wherein Z1is C2-C5-alkylene and m is a number chosen such that the molecular weight of (Z1- O)m- is at least 200 g / mol; polycarbonate groups; polyester groups; and poly(meth)acrylate groups. A preferred spacer group is a polyether group.

[0192] The compounds B include, for example, aliphatic and cycloaliphatic monoamines and polyamines, aromatic and araliphatic monoamines and polyamines, and also polymeric amines, for example polyethyleneimines, polyvinylamine, aminoplasts and polyamidoamines.

[0193] The compound B having one amino group is, for example, a monoalkylamine with a primary amino group or a dialkylamine with a secondary amino group.

[0194] Examples of a compound B having one amino group, selected from a primary amino or secondary amino group, are:

[0195] - monoalkylamines such as Ci-C2o-alkylamines, di(Ci-C20-)alkylamines, (dimethyl amino)propylamine, 3-(diethyl amino)propyl amine or 2-(diethylamino) ethylamine;

[0196] - cycloalkyl amines such as C3-Ci2-cycloalkyl amines;

[0197] - cyclic monoamines such as piperidine;

[0198] - etheramines such as 2-methoxyethylamine or 3-methoxypropylamine;

[0199] - di- or polyether amines such as di- or polyglycol amine or polyoxypropylene amine.

[0200] Preferred compounds B have an average of at least two primary or secondary amino groups or any combination thereof per molecule, e.g., two, three or four primary or secondary amino groups or any combination thereof per molecule. They may additionally contain one or more tertiary amino groups.

[0201] Examples of suitable polyamines are

[0202] - aliphatic polyamines such as ethylenediamine, propane-1 , 2-diamine, propane-1 , 3-diamine, pentamethylenediamine, 2-methyl-1 ,5-pentamethylenediamine, hexamethylenediamine, octamethylenediamine, 1 ,10-diaminodecane, 1 ,12-diaminododecane, diethylenetriamine (DETA), triethylenetetramine (TETA), dimethyl-diethylenetriamine (DMDETA), tetraethylenepentamine, 2,2-dimethyl-1 ,3-propanediamine, trimethylhexamethylenediamine, 1- (3-aminopropyl)-3-aminopropane, 1 ,3-bis(3-aminopropyl)propane, 4-ethyl-4-methylamino-1- octylamine, 1 ,2-dimethylethylenediamine (DMEDA), polyethyleneimine or polyvinylamine;

[0203] - cycloaliphatic diamines such as 1 ,2-diaminocyclohexane, 1 ,2-, 1 ,3-, 1 ,4-bis(aminomethyl)- cyclohexane, 1-methyl-2,4-diaminocyclohexane, N-cyclohexylpropylene-1 , 3-diamine, 4-(2- aminopropan-2-yl)-1-methylcyclohexan-1 -amine, isophoronediamine, 4,4'- diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 3, 3', 5,5'- tetramethyl-4,4'-diaminodicyclohexylmethane, 4,8-diamino-tricyclo[5.2.1 .0]decane, norbornanediamine, menthanediamine or menthenediamine;

[0204] - aromatic diamines such as tolylenediamine, xylylenediamine, in particular meta- xylylenediamine (MXDA), bis(4-aminophenyl)methane (MDA or methylenedianiline) or bis(4- aminophenyl)sulfone (also known as DADS, DDS or dapsone);

[0205] - cyclic polyamines such as piperazine or N-aminoethylpiperazine;

[0206] - etheramines such as diaminodiglycol;

[0207] - polyetheramines, in particular difunctional and trifunctional primary polyetheramines based on polypropylene glycol, polyethylene glycol, polybutylene oxide, poly(butane-1 ,4-diol), polytetrahydrofuran (polyTHF) or polypentylene oxide, e.g. 4,7,10-trioxatridecane-1 ,3-diamine, 4,7,10-trioxatridecane-1 ,13-diamine, 1 ,8-diamino-3,6-dioxaoctane (XTJ-504, Huntsman), 1 ,10- diamino-4,7-dioxadecane (XTJ-590, Huntsman), 1 ,12-diamino-4,9-dioxadodecane (BASF), 1 ,3-diamino-4,7,10-trioxatridecane (BASF), primary polyetheramines based on polypropylene glycol and having an average molar mass of 230, such as Polyetheramine D 230 (BASF) or Jeffamine® D 230 (Huntsman), difunctional, primary polyetheramines based on polypropylene glycol and having an average molar mass of 400, such as Polyetheramine D 400 (BASF) or Jeffamine XTJ 582 (Huntsman), difunctional, primary polyetheramines based on polypropylene glycol and having an average molar mass of 2000, such as Polyetheramine D 2000 (BASF), Jeffamine D 2000 or Jeffamine XTJ 578 (Huntsman), difunctional, primary polyetheramines based on propylene oxide having an average molar mass of 4000, such as Polyetheramine D 4000 (BASF), trifunctional, primary polyetheramines prepared by reacting propylene oxide with trimethylolpropane followed by amination of the terminal OH groups and having an average molar mass of 403, such as Polyetheramine T 403 (BASF) or Jeffamine T 403 (Huntsman), trifunctional, primary polyetheramines prepared by reacting propylene oxide with glycerol followed by amination of the terminal OH groups and having an average molar mass of 5000, such as Polyetheramine T 5000 (BASF) or Jeffamine T 5000 (Huntsman), aliphatic polyetheramines formed from a polyethylene glycol grafted with propylene oxide and having an average molar mass of 600, such as Jeffamine ED-600 or Jeffamine XTJ-501 (Huntsman), aliphatic polyetheramines formed from a polyethylene glycol grafted with propylene oxide and having an average molar mass of 900, such as Jeffamine ED-900 (Huntsman), aliphatic polyetheramines formed from a polyethylene glycol grafted with propylene oxide and having an average molar mass of 2000, such as Jeffamine ED-2003 (Huntsman), difunctional, primary polyetheramines prepared by amination of a diethylene glycol grafted with propylene oxide and having an average molar mass of 220, such as Jeffamine HK-511 (Huntsman), aliphatic polyetheramines based on a copolymer formed from poly(tetramethylene ether glycol) and polypropylene glycol and having an average molar mass of 1000, such as Jeffamine XTJ- 542 (Huntsman), aliphatic polyetheramines based on a copolymer formed from poly(tetramethylene ether glycol) and polypropylene glycol and having an average molar mass of 1900, such as Jeffamine XTJ-548 (Huntsman), aliphatic polyetheramines based on a copolymer formed from poly(tetramethylene ether glycol) and polypropylene glycol and having an average molar mass of 1400, such as Jeffamine XTJ-559 (Huntsman), polyethertriamines based on an at least trihydric alcohol grafted with butylene oxide and having an average molar mass of 400, such as Jeffamine XTJ-566 (Huntsman), aliphatic polyetheramines prepared by amination of alcohols grafted with butylene oxide and having an average molar mass of 219, such as Jeffamine XTJ-568 (Huntsman), polyetheramines based on pentaerythritol and propylene oxide and having an average molar mass of 600, such as Jeffamine XTJ-616 (Huntsman), polyetheramines based on triethylene glycol and having an average molar mass of 148, e.g. Jeffamine EDR-148 (Huntsman), difunctional, primary polyetheramines prepared by amination of an ethylene glycol grafted with propylene oxide and having an average molar mass of 176, such as Jeffamine EDR-176 (Huntsman), and polyetheramines prepared by amination of polytetrahydrofuran (polyTHF) and having an average molar mass of 250, e.g. PolyTHF-Amine 350 (BASF) and mixtures of said amines;

[0208] - polyamidoamines (amidopolyamines) obtainable by reacting dimeric fatty acids (e.g., linoleic acid dimer) with low-molecular-weight polyamines such as diethylenetriamine, 1-(3- aminopropyl)-3-aminopropane or triethylenetetramine or other diamines such as the aliphatic or cycloaliphatic diamines mentioned herein-before;

[0209] - adducts obtainable by reacting polyamines, in particular diamines, with a substoichiometric amount of epoxy resin or reactive diluent;

[0210] - urethane groups-containing adducts obtainable by reacting compounds with oxathiolanone groups and compounds with primary or secondary amino groups, wherein the amino groups are in stoichiometric excess compared to the oxathiolanone groups, thus giving a urethane groups-comprising adduct which still has primary or secondary amino groups, but essentially no oxathiolanone groups

[0211] - phenalkamines, such as those known from epoxide chemistry;

[0212] - Mannich bases, for example those prepared through condensation of polyamines, preferably diethylenetriamine, triethylenetetramine, isophoronediamine, 2,2,4- and 2,4,4- trimethylhexamethylenediamine, 1 ,3- and 1 ,4-bis(aminomethyl)cyclohexane with aldehydes, preferably formaldehyde, and monohydric or polyhydric phenols having at least one aldehydereactive ring position, e.g. the various cresols and xylenols, p-t-butylphenol, resorcinol, 4,4'- dihydroxydiphenylmethane, 4,4'-dihydroxy-2,2-diphenylpropane, but preferably phenol;

[0213] - amino acids, for example lysine or ornithine.

[0214] Preferred is a curable composition, wherein the compound B is a compound having at least two amino groups selected from a primary amino group, a secondary amino group and any combination thereof.

[0215] The primary and secondary amino groups are especially aliphatic or cycloaliphatic amino groups.

[0216] Also preferred is a curable composition, wherein the compound B is a compound having at least one primary amino group, preferably at least two primary amino groups.

[0217] Accordingly, in a preferred aspect, the invention relates to a curable composition containing a) a (meth)acrylate polymer A, as defined in any aspect herein, b) a compound B having at least one primary amino group, preferably at least two primary amino groups, and c) optionally a compound C having at least two functional groups reactive towards a SH group.

[0218] Also preferred is a curable two-component composition containing

[0219] (1) a first component containing a) a (meth)acrylate polymer A, as defined in any aspect herein, and c) optionally a compound C having at least two functional groups reactive towards a SH group, and

[0220] (2) a second component containing b) a compound B having at least one primary amino group, preferably at least two primary amino groups.

[0221] Preferred compounds B are

[0222] - aliphatic polyamines, in particular 2, 2-dimethylpropylenediamine,

[0223] - cycloaliphatic diamines, in particular 1 ,3-bis(aminomethyl))cyclohexane, isophoronediamine, N-cyclohexylpropylene-1 ,3-diamine and 4,4'-diaminodicyclohexylmethane (Dicykan);

[0224] - etheramines, in particular diaminodiglycol;

[0225] - difunctional or trifunctional primary polyetheramines based on polyethylene glycol or poly-THF;

[0226] - polyamines in which there is high mobility and low steric hindrance about the amino group, for example, a,w-diamino-n-alkanes, in which the alkyl chain may be interrupted by oxygen atoms (for example 4,9-dioxadodecane-1 ,12-diamine or 4,7,10-trioxatridecane-1 ,13-diamine, PolyTHF-Amine 350 (BASF)) or polyethyleneimine (for example Lupasol® FG).

[0227] Preference is also given to a curable composition having the longest possible open time, for example, in adhesive or sealant compositions, which are obtained by using a compound B in which the amino group(s) are present in a masked, latently reactive form, for example in the form of oxazolidines, aldimines, ketimines or enamines. Removal of the protecting groups usually occurs under the conditions of the reaction, for example, it may be triggered by either temperature, light, pH or the presence of water / humidity.

[0228] A mixture of different compounds B may also be used, for example a small amount of a rapid curing compound B that establishes immediate strength without reducing the pot life of the product to be cured too much, plus a slow curing compound B for final curing. A suitable example may be a mixture of a compound B having at least one primary amino group with low steric hindrance and a compound B having at least one primary amino group with higher steric hindrance.

[0229] Dependent on the final application, various mixtures of the above-mentioned compounds B may be used, in particular a compound having two primary amino groups, selected from an aliphatic amino group or a cycloaliphatic amino group, in admixture with, for example, above-mentioned polyetheramines.

[0230] The compound B may comprise further functional groups than a primary and / or a secondary amino group, preferably a group which may additionally contribute to cross-linking, for example a silicon-functional group or a polymerizable ethylenically unsaturated group. The compound B may comprise or may be a compound B1 that, in addition to the at least one amino group selected from a primary amino group, a secondary amino group and any combination thereof, still has at least one functional group reactive towards a SH group, selected from an ethylenically unsaturated group or CEC bond-containing group. Molecular weights and number of amino groups, including ethylenically unsaturated groups, are preferably as described for compound B. The compound B1 preferably has one, two or three primary or secondary amino groups, particularly preferably at least one or precisely one primary amino group. The compound B1 preferably has one, two or three ethylenically unsaturated groups or a CEC bond-containing group, more preferably one ethylenically unsaturated group, most preferably a vinyl or allyl group.

[0231] The compound B1 preferably contains no other functional groups aside from an ethylenically unsaturated group, a CEC bond-containing group, a primary or secondary amino group, a hydroxy group, a carboxylic ester group or an ether group. The compound B1 is particularly preferably a compound having only one primary amino group and only one ethylenically unsaturated group, especially a compound having only one primary amino group and only one ethylenically unsaturated group, selected from a vinyl group and an allyl group.

[0232] Examples of a suitable compound B1 include an aminoalkyl vinyl ether having 1 to 10 carbon atoms in the alkyl group (e.g., 3-aminopropyl vinyl ether), allylamine and diallylamine.

[0233] A suitable example of a compound B1 with a CEC bond-containing group is propargyl amine.

[0234] The compound B may comprise or may be a compound B2 that, in addition to the at least one amino group selected from a primary amino group, a secondary amino group and any combinations thereof, still has at least one silicon-functional group. The compound B2 preferably has one, two or three primary or secondary amino groups, particularly preferably at least one or precisely one primary amino group. The compound B2 preferably has one, two or three silicon-functional groups, more preferably one silicon-functional group.

[0235] The silicon-functional group is preferably of formula

[0236] -SiR1sR2sR3s(X), wherein at least one of the groups R1sto R3sis Ci-C4-alkoxy and the remaining groups R1sto R3sare independently of one another hydrogen, Ci-C4-alkyl, vinyl or Ci-C4-alkylene-vinyl; preferably two or three of the groups R1sto R3sare Ci-C4-alkoxy and the remaining group of R1sto R3sis hydrogen, Ci-C4-alkyl, vinyl or Ci-C4-alkylene-vinyl, more preferably two or three of the groups R-IS R3SareCi-C2-alkoxy and the remaining group of R1sto R3sis Ci-C2-alkyl, vinyl or allyl, especially Ci-C2-alkyl. The compound B2 preferably contains no other functional groups aside from the silicon-functional group, primary or secondary amine groups, and ether groups.

[0237] The compound B2 is particularly preferably a compound having only one primary amino group and only one silicon-functional group or a compound having one primary amino group, one secondary amino group and one silicon-functional group. Examples of suitable compounds B2 are 3-aminopropyldimethoxymethylsilane, 3-aminopropyl- diethoxymethylsilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane or [3-(2- aminoethylamino)-propyl]-trimethoxysilane.

[0238] Preferably, a compound B with one primary amino group is

[0239] - a monoalkyl amine such as Ci-C2o-alkylamine;

[0240] - a cycloalkyl amine such as C3-Ci2-cycloalkyl amine;

[0241] - an etheramine such as 2-methoxyethylamine or 3-methoxypropylamine;

[0242] - a di- or polyether amine such as di- or polyglycol amine or polyoxypropylene amine;

[0243] - a compound B1 having one primary amino group and one vinyl or allyl group such as 3- aminopropyl vinyl ether or allyl amine; or

[0244] - a compound B2 having one primary amino group and one silicon-functional group such as 3- aminopropyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, 3- aminopropyltrimethoxysilane or 3-aminopropyltriethoxysilane.

[0245] A preferred mixture of compounds B is a mixture of a compound B having at least two amino groups, selected from a primary amino group, a secondary amino group and a combination thereof, and a compound B having one amino group selected from a primary amino group, a secondary amino group and any combination thereof.

[0246] A more preferred mixture of compounds B is a mixture of a compound B having at least two amino groups, selected from a primary amino group, and a compound B having one amino group selected from a primary amine group.

[0247] Also preferred is a mixture of a compound B having at least two or more primary amino groups and a compound B2 having one primary amino group and one silicon-functional group.

[0248] In case of a mixture of a compound B having at least two amino groups, preferably a primary amino group, and a compound B having one amino group, preferably a primary amino group, including a compound B1 or a compound B2, the compound having only one amino group may be present in an amount of up to 30 wt%, based on the total weight of the compounds B, preferably up to 20 wt%.

[0249] In case a compound C is not present, compound B is preferably polyfunctional.

[0250] The compound B or a polyfunctional compound B may have two or more amino groups selected from a primary amino group, a secondary amino group and any combination thereof. Also, the compound B or a polyfunctional compound B may have at least one, especially one, amino group selected from a primary amino group, a secondary amino group and a combination thereof, and at least one, especially one, ethylenically unsaturated group, a CEC bondcontaining group or a silicon-functional group.

[0251] Preferably, a polyfunctional compound B may have - two or more amino groups selected from a primary amino group, a secondary amino group and any combination thereof, especially two or three primary amino groups;

[0252] - one amino group, selected from a primary amino group and a secondary amino group, and one or two ethylenically unsaturated groups; especially one primary amino group and one vinyl group or allyl group;

[0253] - one or two amino groups, selected from a primary amino group, a secondary amino group and a combination thereof, and one silicon-functional group of formula (X); especially one primary amino group and one silicon-functional group of formula (X) or one primary amino group and / or one secondary amino group and one silicon-functional group of formula (X).

[0254] Therefore, a curable composition is preferred, with the proviso that the compound B is polyfunctional, in case the first component does not comprise a compound C.

[0255] Especially preferred is a curable composition, wherein a polyfunctional compound B having at least two, especially two or three, primary amino groups is present.

[0256] Accordingly, a curable composition is more preferred, with the proviso that compound B is polyfunctional, when the first component does not comprise a compound C, wherein a polyfunctional compound B comprises a compound having two or more amino groups selected from a primary amino group, a secondary amino group and any combination thereof.

[0257] The curable composition may optionally comprise at least one compound C that has at least one functional group reactive towards a SH group. A curable composition is preferred, wherein compound C is present.

[0258] In a preferred aspect, the invention relates to a curable composition containing a) a (meth)acrylate polymer A, as defined in any aspect herein, b) a compound B having at least one primary amino group and / or a secondary amino group, said primary or secondary amino group may be present in a masked, latently reactive form, and c) a compound C having at least one functional group reactive towards a SH group.

[0259] Preferably, with the proviso that at least one of the compounds B and C is polyfunctional.

[0260] Preferably, the reaction of the functional group reactive towards a SH group with a SH group may be an addition reaction. A less preferred reaction is a condensation reaction, for example a reaction with a carbonyl group, or a nucleophilic substitution reaction, for example with an organic halide like an organic chloride.

[0261] A compound C undergoing an addition reaction may have at least one functional group reactive towards a group SH selected from an ethylenically unsaturated group, a CEC bond-containing group, an epoxy group and any combination thereof.

[0262] Preferably, the compound C has at least one functional group reactive towards a SH group selected from an ethylenically unsaturated group, an epoxy group and any combination thereof. A particular preferred ethylenically unsaturated group is a (meth)acryloyl group, an allyl group or a vinyl group, especially a (meth)acryloyl group.

[0263] The compound C may have a molecular weight of up to 500,000 g / mol. In the case of polymers, this is the weight-average molecular weight, measured by gel-permeation chromatography using a polystyrene standard. The compound C preferably has a molecular weight of up to 1000 g / mol, particularly preferably from 60 g / mol to 500 g / mol.

[0264] It is possible for a compound C to have, for example, up to 1000, in particular up to 500, preferably up to 100, functional groups reactive towards a SH group. The compound C particularly preferably has two or three functional groups reactive towards a SH group.

[0265] A CEC bond-containing group may react twice with SH groups. An SH group may first add to a CEC bond, converting the CEC bond into a C=C bond. The C=C bond formed may react with a further SH group. A C=C bond-containing group is therefore equivalent to two ethylenically unsaturated groups reactive towards a SH group.

[0266] Examples of a compound C containing a CEC bond-containing group are alkynes such as acetylene or propyne, propargyl alcohol, ethers of propargyl alcohol, esters of propargyl alcohol or amides of propargylamine.

[0267] Preferably, the compound C does not comprise a primary amino group or a secondary amino group.

[0268] The compound C may have one functional group reactive towards a SH group or two or more functional groups reactive towards a SH group, preferably one, 2 or 3 functional groups reactive towards a SH group, more preferably 2 or 3 functional groups towards a SH group.

[0269] Preferred functional groups towards a SH group, which is an ethylenically unsaturated group may be following groups:

[0270] A vinyl group CH2=CH-; a vinylene group -CH=CH-; an acryloyl group CH2=CH-C(=O)-; a methacryloyl group CH2=C(CH3)-C(=O)-; an acryloyloxy group CH2=CH-C(=O)-O-; a methacryloyloxy group CH2=C(CH3)-C(=O)-O; an acrylamido group CH2=CH-C(=O)-N; a cyanoacryl group CH2=C(CN)-C(=O)-O; a methylenemalonato group CH2=C[C(=O)-O]2; a vinylene-1 ,3-dicarbonyl group CH2=C[C(=O)-]2; a 1 ,4-dicarboxyalkylene group -OC(=O)-CH =CH-C(=O)O-]; an allyl group CH2=CH-CH2-, in particular an allyl ether group CH2=CH-CH2-O-; a maleimido group or a crotonyl group.

[0271] Examples of a preferred compound C having one ethylenically unsaturated group include an acryloyl compound, a methacryloyl compound, a vinyl ester, for example vinyl acetate, a vinyl ether, or a vinyl lactam, for example N-vinylpyrrolidone. A particularly preferred compound C having one ethylenically unsaturated group is a (meth)acryloyl compound and a vinyl ether. Examples of a (meth)acryloyl compound are (meth)acrylic esters, in particular alkyl or hydroxyalkyl (meth)acrylates, like glycerol- mono(meth)acrylate, or (meth)acrylonitrile. Vinyl ethers are, for example, vinyl alkyl ethers. Alkyl groups preferably have 1 to 20, particularly preferably 1 to 8, carbon atoms. Especially preferred examples of a compound C having one ethylenically unsaturated group include Ci-C8-alkyl or hydroxy-Ci-C8-alkyl (meth)acrylates, especially methacrylates, for example, glycerol- mono(meth)acrylate.

[0272] An especially preferred compound C is a compound having at least two (meth)acryloyl groups, a compound having at least two vinyl groups, an olefin having at least two C=C bonds, a polyester substituted with two or more ethylenically unsaturated groups, a cyanurate substituted with two or more ethylenically unsaturated groups or an isocyanurate substituted with two or more ethylenically unsaturated groups.

[0273] Preferred compounds C having at least two ethylenically unsaturated groups are:

[0274] - Olefins having two or more C=C bonds are, for example, butadiene, cyclooctadiene, cyclododecatriene, isoprene, limonene, divinylcyclohexane, trivinylcyclohexane, polybutadiene or polyisoprene;

[0275] - (Meth)acrylic esters of polyfunctional alcohols or of alkoxylated, especially ethoxylated or propoxylated, polyfunctional alcohols; examples of polyfunctional alcohols are bifunctional alcohols, such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1 ,4-butanediol, 1 ,5-pentanediol, 1 ,6-hexanediol, neopentyl glycol, 1 ,7-heptanediol, 1 ,8-octanediol, 1 ,9-nonanediol, 1 ,10-decandiol, alkoxylated phenols, such as ethoxylated or propoxylated bisphenols, 1 ,2- or 1 ,4-cyclohexanedimethanol, isosorbide, tricyclodecanedimethanol, 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol; trifunctional and higher functional alcohols are, for example, glycerol, trimethylolpropane, butanetriol, trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol and the corresponding alkoxylated, especially ethoxylated and / or propoxylated alcohols;

[0276] - (Meth)acrylic esters of polyesterols; suitable polyesterols are, for example, ones that can be prepared by esterifying polycarboxylic acids, preferably dicarboxylic acids, with polyols, preferably with diols; preferred dicarboxylic acids are succinic acid, glutaric acid, adipic acid, sebacic acid, and orthophthalic acid and the isomers and hydrogenation products thereof, and also the esterifiable or transesterifiable derivatives of said acids, for example the anhydrides and alkyl esters thereof; also suitable as dicarboxylic acids are maleic acid, fumaric acid, and tetrahydrophthalic acid or their anhydrides; preferred polyols are ethylene glycol, 1 ,2- and 1 ,3- propylene glycol, butane-1 ,4-diol, hexane-1 ,6-diol, neopentyl glycol, cyclohexanedimethanol, and polyglycols of ethylene glycol and / or propylene glycol;

[0277] - Epoxy (meth)acrylates, for example, those that can be prepared by reacting epoxidized olefins or poly-, mono- or diglycidyl ethers such as bisphenol A diglycidyl ether with (meth)acrylic acid;

[0278] - Urethane (meth)acrylates, such as the reaction products of hydroxyalkyl (meth)acrylates with poly- or diisocyanates;

[0279] - Unsaturated polyesters, in particular those containing C=C bonds from maleic acid, itaconic acid or fumaric acid units; - Compounds having at least two vinyl or allyl groups, for example divinyl ethers such as diethylene glycol divinyl ether or triethylene glycol divinyl ether or divinyl sulfone; also suitable as compounds C having two or more ethylenically unsaturated groups are diallylorthophthalate, triallyl-isocyanurate or triallyl-cyanurate.

[0280] A compound C having at least two ethylenically unsaturated groups is more preferably a (meth)acrylic ester of a polyfunctional alcohol, a compound having a vinyl ether group or an unsaturated polyester.

[0281] Most preferred, a compound C having at least two ethylenically unsaturated groups include a (meth)acrylic ester, especially a methacrylic ester, of a polyfunctional alcohol or of an alkoxylated polyfunctional alcohol, for example, 1 , 1 ,1 -trimethylolpropane tri(meth)acrylate, ethoxylated 1 , 1 ,1 -trimethylolpropane tri(meth)acrylate, a C2-C8-alkanediol di(meth)acrylate, isosorbide di(meth)acrylate, and tricyclodecanedimethanol-di(meth)acrylate.

[0282] Preferred compounds C having at least two ethylenically unsaturated groups are in particular polyfunctional (meth)acrylic esters available under the names Laromer® (BASF), Sartomer® (Arkema) or Miramer® (Miwon).

[0283] In a preferred embodiment, the compound C does not comprise other functional groups than a functional group reactive towards a SH group, a carboxylic ester group or an ether group.

[0284] Any mixture of one or more compounds C having at least one ethylenically unsaturated groups may also be used.

[0285] Preferred is a mixture of a compound C having at least two ethylenically unsaturated groups with a compound C having one ethylenically unsaturated group, wherein the amount of a compound C having one ethylenically unsaturated group may be in the range of up to 20 wt%, based on the total weight of compound C having at least two ethylenically unsaturated groups.

[0286] Also suitable as a compound C are those having at least one epoxy group, for example compounds obtainable by reacting compounds having at least one alcohol group with epichlorohydrin.

[0287] Compounds C having one epoxy group are, for example, epichlorohydrin or derivatives thereof in which the chloride of the epichlorohydrin is replaced by a hydroxy group (glycidol), by an ether group (glycidyl ether), by an ester group (glycidyl ester) or by an amino group (glycidyl amine).

[0288] Compounds C having at least two epoxy groups, are, for example, compounds obtainable by reacting compounds having at least two alcohol group with epichlorohydrin.

[0289] Examples of compound C having at least two epoxy groups are - diglycidyl ethers of bisphenol A or of bisphenol F or of bisphenol S, the diglycidyl ethers of hydrogenated bisphenol A or of hydrogenated bisphenol F, and diglycidyl ethers of aliphatic diols, for example diglycidyl ethers of polyalkoxylene diols;

[0290] - oligoglycidyl ethers of oligoalcohols;

[0291] - epoxy resins obtainable by using compounds having at least two alcohol groups in excess with respect to epichlorohydrin; in epoxy resins of this kind, the degree of polymerization of the compound having at least two alcohol groups is preferably 2 to 25, in particular 2 to 10;

[0292] - epoxidized fatty acids, epoxidized fatty acid esters, and epoxidized fatty alcohols that in each case have at least two epoxy groups;

[0293] - tetraglycidyl methylenedianiline (TGMDA), triglycidyl p-aminophenol, and triglycidyl isocyanurate;

[0294] - compounds obtainable by polymerization or copolymerization of glycidyl vinyl ether or of glycidyl (meth)acrylate, wherein a copolymer of glycidyl (meth)acrylate is different from a (meth)acrylate polymer A and usually do not have an oxathiolanone group.

[0295] Any mixture of one or more compounds C having at least one epoxy groups may also be used.

[0296] Preferred is a mixture of a compound C having at least two epoxy groups with a compound C having one epoxy group, wherein the amount of a compound C having one epoxy group may be in the range of up to 20 wt%, based on the total weight of compound C having at least two epoxy groups.

[0297] Preference is also given to using a mixture of at least one compound C having at least one ethylenically unsaturated group and at least one compound C having at least one epoxy group.

[0298] Preference is also given to using a mixture of at least one compound C having at least two ethylenically unsaturated groups and at least one compound C having at least two epoxy groups. Especially preferred is a mixture of trimethylolpropane trimethacrylate and trimethylolpropane triglycidylether.

[0299] A compound C may have different functional groups reactive towards a SH group, for example at least two different ethylenically unsaturated groups, or one ethylenically unsaturated group and one epoxy group. Suitable examples of such a compound C are vinyl (meth)acrylate, allyl (meth)acrylate, glycidyl (meth)acrylate or allyl glycidyl ether or polymeric compounds comprising different functional groups, wherein the polymeric compounds usually do not have an oxathiolanone group.

[0300] The compound C may comprise or may be a compound C1 that, in addition to the at least one functional group reactive towards a SH group, still has at least one silicon-functional group. The compound C1 preferably has one, two or three functional groups reactive towards a SH group, particularly preferably at least one or precisely one functional group reactive towards a SH group. The compound C1 has preferably one, two or three silicon-functional groups, more preferably one silicon-functional group. The functional group reactive towards a SH group may be an ethylenically unsaturated group, especially a (meth)acryloyl group, or an epoxy group. Preferred compounds C1 with a silicon-functional group comprise one or two functional groups, that react with a group -SH, selected from a (meth)acryloyl group, and one alkoxysilane group -SiR1sR2sR3s,

[0301] The silicon-functional group is preferably of formula

[0302] -SiR1sR2sR3s(X), wherein at least one of the groups R1sto R3sis Ci-C4-alkoxy and the remaining groups R1sto R3sare independently of one another hydrogen, Ci-C4-alkyl, vinyl or Ci-C4-alkylene-vinyl; preferably two or three of the groups R1sto R3sare Ci-C4-alkoxy and the remaining group of R1sto R3sis hydrogen, Ci-C4-alkyl, vinyl or Ci-C4-alkylene-vinyl, more preferably two or three of the groups R-IS R3SareCi-C2-alkoxy and the remaining group of R1sto R3sis Ci-C2-alkyl, vinyl or allyl, especially Ci-C2-alkyl. The compound C1 preferably contains no other functional groups aside from the silicon-functional group, and a functional group reactive towards a SH group.

[0303] The compound C1 is particularly preferably a compound having only one functional group reactive towards a SH group, which is a meth(acryloyl) group, and only one silicon-functional group.

[0304] Examples of a compound C1 with a silicon-functional group are 3-trimethoxysilylpropyl methacrylate, 3-(dimethoxymethylsilyl)propyl methacrylate, trimethoxysilylpropyl acrylate or 3- (dimethoxymethylsilyl)propyl acrylate, preferably trimethoxysilylpropyl methacrylate or 3- (dimethoxymethylsilyl)propyl methacrylate.

[0305] The compound C may comprise or may be a compound C2 that, in addition to the at least one functional group reactive towards a SH group, still has one oxathiolanone group. The compound C2 preferably has one functional group reactive towards a SH group and one oxathiolanone group. The functional group reactive towards a SH group may be an ethylenically unsaturated group, especially a (meth)acryloyl group, in particular a methacryloyl group.

[0306] A preferred compound C2 is a monomer M1 of formula (I), more preferably a monomer M1 of formula (la).

[0307] Any mixture of two or more compounds C may be used.

[0308] In case of a mixture of a compound C having at least two functional groups reactive towards a SH group and a compound C having one functional group reactive towards a SH group, including a compound C1 or a compound C2, the compound having only one functional amino group may be present in an amount of up to 30 wt%, based on the total weight of the compounds C, preferably up to 20 wt%.

[0309] A polyfunctional compound C may have two or more functional groups reactive towards a SH group. Also, a polyfunctional compound C may have at least one, preferably one, functional group reactive towards a group SH and a silicon-functional group or an oxathiolanone group. Preferably, a polyfunctional compound C may have

[0310] - two or more functional groups reactive towards a SH group, especially two or three functional groups reactive towards a SH group, selected from a (meth)acryloyl group, an epoxy group and a combination thereof;

[0311] - one functional group reactive towards a SH group and one silicon-functional group of formula (X), especially meth(acryloyl) group and one silicon-functional group of formula (X); or

[0312] - one functional group reactive towards a SH group and one oxathiolanone group, especially a meth(acryloyl) group and one oxathiolanone group.

[0313] Preferred is a curable composition, containing a) a (meth)acrylate polymer A, as defined in any aspect herein, b) a compound B having at least one amino group, selected from a primary amino group, a secondary amino group and any combination thereof, said primary or secondary amino group may be present in a masked, latently reactive form, and c) optionally a compound C having at least one functional group reactive towards a SH group, with the proviso that at least one of the compounds B and C is polyfunctional, wherein a polyfunctional compound B comprises a compound having two or more amino groups selected from a primary amino group, a secondary amino group and any combination thereof, or a compound having at least one amino group selected from a primary amino group, a secondary amino group and any combination thereof, and having at least one group, selected from an ethylenically unsaturated group, a CEC bond-containing group and a silicon-functional group; and a polyfunctional compound C comprises a compound having at least two functional groups reactive towards a SH group, or a compound having at least one functional group reactive towards a group SH and a silicon- functional group or an oxathiolanone group.

[0314] More preferred is a curable composition, wherein the polyfunctional compound B comprises a compound having two or three primary amino groups; or a compound having one primary amino group and having one vinyl group or allyl group; or a compound having one primary amino group and one silicon-functional group of formula (X); and the polyfunctional compound C comprises a compound having two or three functional groups reactive towards a SH group, selected from a (meth)acryloyl group or an epoxy group; or a compound having one (meth)acryloyl group and one silicon-functional group of formula (X); or a compound having one (meth)acryloyl group and one oxathiolanone group.

[0315] A curable composition, especially a curable two-component composition, is preferred, wherein compound C is present. Accordingly, in a preferred aspect, the invention relates to a curable composition, wherein the compound C is a compound having at least two functional groups reactive towards a SH group, selected from an ethylenically unsaturated group, an epoxy group and any combination thereof, preferably selected from a (meth)acryloyl group, an epoxy group and any combination thereof.

[0316] Further preferred is a curable two-component composition, wherein the compound C is a compound having at least two functional groups reactive towards a SH group, selected from an ethylenically unsaturated group, an epoxy group and any combination thereof, preferably selected from a (meth)acryloyl group, an epoxy group and any combination thereof.

[0317] Preferred is a curable composition containing a) a (meth)acrylate polymer A, as defined in any aspect herein, b) a compound B having at least one primary amine group, and c) a compound C having at least two functional groups reactive towards a SH group, selected from an ethylenically unsaturated group or an epoxy group, preferably selected from a (meth)acryloyl group or an epoxy group.

[0318] Further preferred is a curable composition containing a) a (meth)acrylate polymer A, as defined in any aspect herein, b) a compound B having at least two primary amine groups, and c) a compound C having at least two functional groups reactive towards a SH group, selected from an ethylenically unsaturated group or an epoxy group, preferably selected from a (meth)acryloyl group or an epoxy group.

[0319] Further preferred is a curable two-component composition containing

[0320] (1) a first component containing a) a (meth)acrylate polymer A, as defined in any aspect herein, and c) a compound C having at least two functional groups reactive toward a SH group, selected from an ethylenically unsaturated group or an epoxy group, preferably selected from a (meth)acryloyl group or an epoxy group; and

[0321] (2) a second component containing b) a compound B having at least one primary amino group.

[0322] Further preferred is a curable two-component composition containing

[0323] (1) a first component containing a) a (meth)acrylate polymer A, as defined in any aspect herein, and c) a compound C having at least two functional groups reactive toward a SH group, selected from an ethylenically unsaturated group or an epoxy group, preferably selected from a (meth)acryloyl group or an epoxy group; and

[0324] (2) a second component containing b) a compound B having at least two primary amino groups.

[0325] Within the process of curing the curable composition, the oxathiolanone group of the (meth)acrylate polymer A typically reacts with a compound B to form a mercaptourethane group resulting in the formation of a (meth)acrylate polymer having urethane groups and -SH groups. Generally, primary amines react more rapidly than secondary amines, and aliphatic amines react more rapidly than aromatic amines. It is understood that a reaction with a secondary amine results in a N-substituted urethane group (a carbamate group).

[0326] The principles of the reaction of a compound with an oxathiolanone group (corresponding to (meth)acrylate polymer A), a compound B and optionally a compound C as well as details of the parameters of the reaction are described in WO 2019 / 034470 A1 and WO 2019 / 034473 A1.

[0327] Without or with sub-stoichiometric addition of a compound C, the -SH groups may oxidize and may form disulfide bridges. Such oxidation may occur at room temperature in the presence of oxygen. Such reaction may also occur in case SH groups remain after the reaction of compound C. Disulfide bridges may improve mechanical properties of the polymer obtained.

[0328] In case a compound C is present, the SH-groups react with the reactive groups of the compound C to obtain a cross-linked polymer. The obtained (meth)acrylate polymer comprises as structural element a urethane group N(C=O)O with a sulfur atom bonded via an ethylene group to the oxygen of the urethane group. In case of a reaction with a compound B having a secondary amino group a substituted urethane group (carbamate group) is formed. This structural unit may be represented by the following general formula

[0329] (XI).

[0330] Within the curable composition of (meth)acrylate polymer A, compound B and optional compound C, it is preferable to avoid a large excess of the (meth)acrylate polymer A, respectively the amount of the monomer M 1 , compound B or compound C. The (meth)acrylate polymer A, compound B and compound C are generally used in an amount that deviates not more than 50% from the equimolar amounts corresponding to the stoichiometry of the reaction, preferably not more than 20%.

[0331] The number of functional groups, to be cured, in (meth)acrylate polymer A, compound B, optional compound C and optional compounds like compound A1 , compound B1 , compound B2, compound C1 and compound C2, is preferably such that this results in the formation of cross-linked polymers.

[0332] The curable composition, especially the curable two-component composition, preferably comprises compound B in an amount such that the amount of primary and / or secondary amino groups in compound B is of from 50 to 150 mol%, preferably from 80 to 120 mol%, based on one mole of oxathiolanone groups present in the curable composition, with the proviso that only the amount of primary amino groups is considered in case of the compound B has primary and secondary amino groups.

[0333] The amount of secondary amino groups is considered in case the compound B does not have primary amino groups.

[0334] The term “one mole of oxathiolanone groups present in the curable composition” means all oxathiolanone groups present in the (meth)acrylate polymer A, the optional compound A1 and the optional compound C2.

[0335] The curable composition, especially the curable two-component composition, preferably comprises compound C in an amount such that the amount of functional groups reactive towards a SH group of compound C is of from 0 to 120 mol%, more preferably from 50 to 120 mol%, most preferably from 90 to 110 mol%, based on one mole of oxathiolanone groups present in the curable composition.

[0336] The reaction between (meth)acrylate polymer A, compound B and compound C may be carried out in one step or two steps.

[0337] A one-step reaction means that all compounds are reacted simultaneously. The result of the one-step reaction depends on the nature of compound C, as reactive group(s) of compound C may also react with the amino group(s) of compound B thus reducing the availability amino groups for the ring-opening reaction of the oxathiolanone group.

[0338] A one-step reaction is preferably carried out with a compound C having at least one methacryloyl group as ethylenically unsaturated group or a compound C having at least one other ethylenically unsaturated group which is a non-activated double bond, such as a vinyl ether or an olefin. The addition of -SH to said non-activated double bond is preferably achieved via radical reaction which may be thermally catalyzed and / or photoinitiated.

[0339] In a two-step reaction, the oxathiolanone groups undergo the ring opening reaction with the amino group(s) of the compound B separately in a first step, followed by the reaction of the formed -SH groups of the obtained polymer having urethane groups with the reactive group(s) of compound C.

[0340] Preferably, a compound C with at least one epoxy group as functional group is reacted with (meth)acrylate polymer A and compound B following the two-step reaction by first reacting (meth)acrylate polymer A with compound B and then reacting the SH-group and urethane group containing polymer with compound C.

[0341] In case of a one-step reaction the curable composition may be obtainable by mixing a) a (meth)acrylate polymer A, as defined in any aspect herein, b) a compound B having at least one amino group, selected from a primary amine group, a secondary amine group and any combination thereof, said primary or secondary amino group may be present in a masked, latently reactive form, and c) optionally a compound C having at least one functional group reactive towards a SH group.

[0342] In case of a two-step reaction a curable composition may be obtainable by mixing the reaction product of a) a (meth)acrylate polymer A, as defined in any aspect herein, and b) a compound B having at least one amino group, selected from a primary amine group, a secondary amine group and amino group, wherein the at least one functional group may be present in a masked, latently reactive form, with c) a compound C having at least one functional group reactive towards a SH group.

[0343] A curable one-component composition may be obtained by blending the (meth)acrylate polymer A, the compound B and the optional compound C in a suitable mixer. Once the one-component curable composition is formulated, it is packaged in a suitable container.

[0344] Preferably for storage prior to use the curable composition may be a curable two-component coating composition, wherein the (meth)acrylate polymer A and the compound B may be held in separate components that are mixed only shortly before use. If present, compound C is already mixed with (meth)acrylate polymer A.

[0345] The curable composition may be cured thermally by heating the mixture of the (meth)acrylate polymer A and compound B to a temperature above the mixing temperature. Curing may also take place at relatively low temperatures. The curable composition is typically cured at temperatures within a range of from -10°C to 150°C, preferably within a range of from O to 100°C, and in particular within a range of from 10 to 70°C, especially from 10 to 50°C. Curing at temperatures of 20-30°C is particularly advantageous. Which temperature is suitably applied depends on the particular compound B and on the desired curing rate and may be established in the individual case by those skilled in the art, for example on the basis of simple preliminary tests. In the lower temperature range (5 to approx. 35°C), which corresponds to the generally prevailing ambient temperature, it is of course sufficient to mix the (meth)acrylate polymer A and compound B. Alternatively, curing is preferably microwave-induced.

[0346] In case of solvents are present in the curable composition, curing at a higher temperature is usually needed, dependent on the solvent.

[0347] The curing of the curable composition is preferably carried out at temperatures of < 70°C, preferably of < 50°C, more preferably < 30°C, especially without heating.

[0348] In addition to the constituents A, B and optionally C, the curable composition, especially the curable two-component composition, may comprise additives customary for this purpose. The choice of suitable conventional additives for the curable composition generally depends on the particular intended use and can be determined in the individual case by those skilled in the art.

[0349] Examples of suitable additives include catalysts, initiators, inhibitors, antioxidants, UV absorbers / light stabilizers, metal deactivators, antistatic agents, reinforcers, fillers, antifogging agents, biocides, plasticizers, lubricants, emulsifiers, colorants, pigments, rheological agents, adhesion regulators, optical brighteners, flame retardants, antidrip agents, nucleating agents, wetting agents, thickeners, protective colloids, defoamers, tackifiers and mixtures of two or more thereof.

[0350] Further, solvents may be present, usually to dissolve or reduce the viscosity. The curable composition may comprise a solvent, for example, for dissolving a (meth)acrylate polymer A, which is solid at room temperature. If present, a solvent is present in the first component of the curable composition.

[0351] If present, the solvents should be non-aqueous. Suitable examples include tetrahydrofuran, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, methyl ethyl ketone, acetone, heptane, toluene, trichloroethane, ethyl acetate, butyl acetate, t-butyl acetate and acetonitrile. Mixtures of said solvents may also be used. Solvents may be present in an amount of from 0 to 30 wt%, preferably 0 to 15 wt%, based on the total weight of the curable composition.

[0352] The curable composition, especially the curable two-component composition, is preferably solvent-free. Solvent-free means that it contains less than 5 wt% of organic solvent or water, more preferably less than 2 wt% or none at all.

[0353] The curable composition may comprise at least one catalyst. The curable composition preferably comprises at least one catalyst.

[0354] The curable composition may comprise

[0355] - at least one catalyst for catalyzing the reaction of the oxathiolanone groups, present in the curable composition, mainly of (meth)acrylate polymer A and optionally of a compound A1 and a compound C2, with the primary and / or secondary amino groups, present in the curable composition, mainly in compound B including compound B1 and compound B2, and / or

[0356] - at least one catalyst or initiator for catalyzing or initiating the reaction of SH groups with one another, and / or

[0357] - at least one catalyst or initiator for catalyzing the reaction of SH groups with the functional groups that are reactive therewith, for example, with an ethylenically unsaturated group or a CEC group-containing group; and / or

[0358] - at least one catalyst for the reaction of the silicon-functional groups.

[0359] Preferred is a curable composition, which comprises at least one catalyst for catalyzing the reaction of the oxathiolanone groups with primary and / or secondary amino groups. In one embodiment, no catalyst is needed, particularly in the case of compound B that has amino groups as functional groups, i.e., the content of catalysts in the composition is then less than 0.01 wt%. A catalyst is preferably used when the compound B having primary and / or secondary amino groups having a higher steric hindrance, for example, polyetheramines based on polypropylene glycol.

[0360] Suitable catalysts for catalyzing the reaction of the oxathiolanone groups with the primary and / or secondary amino groups are, for example, basic catalysts, preferably organic amines and organic phosphines. Preferred organic amines are amidines such as 1 ,8- diazabicyclo[5.4.0]undec-7-ene (DBU), 1 ,5-diazabicyclo[4.3.0]non-5-ene (DBN), guanidines such as 1 ,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) or 7-methyl-1 ,5,7-triazabicyclo[4.4.0]dec-ene (mTBD), pyridines such as pyridine, and tertiary amines such as tri-Ci-C6-alkylamines, in particular triethylamine. Preferred organic phosphines are trialkylphosphines and triarylphosphines, for example tri-n-butylphosphine and triphenylphosphine.

[0361] Preferably, the curable composition comprises a basic catalyst, selected from an organic amine, an organic phosphine and any combination thereof, especially from an organic amine selected from an amidine, a guanidine, a pyridine and a tertiary amine.

[0362] More preferably, the curable composition comprises a basic catalyst, selected from an organic amine, an organic phosphine and any combination thereof, especially from an organic amine selected from an amidine, a guanidine, a pyridine, and a tri-Ci-C6-alkylamines, wherein the basic catalyst is present in an amount of from 0.01 to about 10 wt%, based on the total weight of the compound B, preferably 0.01 to 5 wt%.

[0363] Especially, the curable, two-component composition comprises a basic catalyst, selected from an organic amine, an organic phosphine and any combination thereof, especially from an organic amine selected from an amidine, a guanidine, a pyridine, and a tri-Ci-C6-alkylamines, in the second component, wherein the basic catalyst is present in an amount of from 0.01 to about 10 wt%, based on the total weight of the compound B, preferably from 0.01 to 5 wt%.

[0364] Suitable catalysts or initiators for catalyzing or initiating the reaction of SH groups with one another are, for example, metal oxides, like MnO2. If present, the catalyst or initiator for catalyzing or initiating the reaction of SH groups with one another is generally used in an amount of from 0.01 to about 10 wt%, based on the total weight of the (meth)acrylate polymer A, preferably from 0.01 to 5 wt%.

[0365] Suitable catalysts or initiators for catalyzing or initiating the reaction of a SH group with an ethylenically unsaturated group or a CEC bond-containing group are compounds that form free radicals, e.g., azo initiators such as AIBN, organic peroxide compounds, redox pairs (H2O2, t- butyl peroxide, ascorbic acid) and also photoinitiators and oxygen itself. In the case of an activated double bond (so-called Michael systems), the reaction of the double bond can take place nucleophilically and can therefore be catalyzed, e.g., by tertiary amines, guanidines, pyridines, phosphines, etc.. In the case of a non-activated double bond, the reaction of the double bond may take place in a free-radical process and may be initiated thermally with a radical initiator or photochemically with a photoinitiator.

[0366] If present, the catalyst or initiator for catalyzing or initiating the reaction of a SH group with an ethylenically unsaturated group or a CEC bond-containing group is generally used in an amount of from 0.01 to about 10 wt%, based on the total weight of the compound C, preferably from 0.01 to 5 wt%.

[0367] In case of a compound B2 and / or a compound C1 having a silicon-functional group, a silanol condensation catalyst may be present, for example, organotin compounds, fluorine compounds or titanates. If present, such catalyst is generally used in an amount of from 0.01 to about 10 wt%, based on the total weight of curable composition, preferably from 0.01 to 5 wt%.

[0368] The various kinds of catalysts may also be used in the form of any mixture.

[0369] The catalysts may be added either in the first or second component of the curable composition. For example, organic bases may preferably be added to the second component. Radicalforming catalysts may preferably be added to the first component.

[0370] The additives may be added to the first and / or second component of the curable composition, for example, to obtain similar zero-shear viscosities of both components.

[0371] The curable composition, especially the curable two-component composition, is preferably free from an isocyanate-containing compound, i.e., it preferably does not comprise any isocyanate compound as compound A ((meth)acrylate polymer A), compound B and optional compound C.

[0372] The first component and the second component of the curable two-component composition are preferably liquid at the time of mixing at 23°C and preferably have a zero-shear viscosity < 1000 Pa s, preferably < 800 Pa s more preferably < 500 Pa s, especially < 300 Pa s.

[0373] After the components have been mixed, the two-component composition is usually in a curable, not yet cured, state, meaning that the oxathiolanone groups, present in the curable composition, and the primary and / or secondary amino groups, present in the curable composition, are both present and have not yet reacted with one another. The curable two-component composition is preferably liquid. Curing is demonstrated, for example, by an increase in zero-shear viscosity.

[0374] The instant (meth)acrylate polymer A having an oxathiolanone group in the side chain is suitable as an intermediate polymer to provide cross-linked polymers for a variety of applications, for example, for preparing an adhesive, a sealant, a coating, a 3D printed object, a shaped article, a chemical anchor, a dental material or a repair system for any of said applications. The curable composition, preferably the two-component composition, may be applied to any substrate in a usual manner, as known in the art for the various applications, for example, by joining I bonding, sealing, coating, 3-D printing, casting I molding or inserting. The substrate may be any surface, for example, a gap, a 3-dimensional template, like a molding, or a hole. The substrate may be of any kind of material, usually dependent on the application of the curable composition.

[0375] The curable composition for a coating may be applied by usual means, such as knife coating, roller coating or spraying to any substrate. Any substrate may be coated, for example, wood, fabric, metal surfaces, mineral surfaces, like concrete, or polymeric surfaces, especially synthetic polymer surfaces. The curable composition may be used as single coating, as part of a multi-layer system, or as a powder coating. Generally, the curable composition may be applied to a substrate and cured to form a coating having a thickness of from 0.01 to 10 mm.

[0376] The curable composition may be used for any kind of coating including a render. A render is a coating for interior or exterior walls, generally applied in a plurality of layers and with a larger layer thickness (several mm). The render is generally applied for smoothing or providing a more attractive appearance, and, in the case of exterior application, for protecting the surface from moisture.

[0377] The coating may be decorative or protective, for example in the field of construction or any other industry. An example of a protective coating may be an industrial coating, which may usually be used in interior or exterior applications.

[0378] A variety of substrates may be sealed or bonded using the instant curable composition, for example in the field of construction, e.g., for grouting tiles, or any other industry. The substrates to be bonded or sealed may be the same or different from one another. Examples of substrates include metal, wood, glass, plastic shaped bodies, plastic films, paper and paperboard.

[0379] Preferred substrates are metal, wood, glass, plastic shaped bodies or plastic films, especially metal and wood.

[0380] The adhesive compositions, preferably the two-component adhesive composition, may be suitably used as a laminating or as a structural adhesive. Preferred bonding processes are composite film lamination, glossy film lamination, and the lamination of shaped bodies, as used particularly in furniture lamination or in the lamination of automotive interior parts, and the use as structural adhesive. Details for bonding processes are usually known to one skilled in the art.

[0381] The preferred two component adhesive may be used in a bonding process being a lamination process for producing a laminated article, selected from a glossy film, a composite film and a laminated shaped body, wherein a) a first substrate in the form of a first film is provided, b) a second substrate is provided, selected from a paper, a second film that may be the same or different from the first film, and a shaped body, c) a curable two-component composition, as described in any aspect herein, and d) the curable two-component composition is, after mixing the components, applied onto the first substrate and / or onto the second substrate, optionally being allowed to dry, and the first substrate is laminated onto the second substrate, wherein the lamination is optionally carried out under thermal activation.

[0382] The first film is preferably selected from plastic films, for example, thermoplastic films, which may be metallized, and metal films, like aluminum films. The lamination takes place preferably under pressure and / or at elevated temperature, in particular by thermal activation. Optionally, the film may be surface-treated before coating with the two-component composition, for example, a corona treatment to boost adhesion. Alternatively or in addition, it is optionally also possible to use primers or tie coats between the film substrate and adhesive layer and / or shaped body substrate. Further, functional layers may be present externally or internally, i.e., between film substrate and adhesive layer.

[0383] The amount of the two-component adhesive composition applied is preferably 0.5 to 1000 g / m2, dependent on the kind of bonding process. Bonding preferably takes place under pressure.

[0384] A shaped article may be any article which may be produced by casting or molding the curable composition onto a substrate, especially a 3-dimensional template, like a molding.

[0385] A chemical anchor may be any material for use in the chemical fastening technology, wherein the curable plugging composition may be inserted in a hole, for example, a drill-hole, to fasten anchoring elements such as screws, anchor rods, tie bars, rock bolts, etc..

[0386] The curable composition may also be suitably used as a 3D printing ink to prepare a 3-D printed object. The ink may be cured following dispensing and / or depositing the ink onto the substrate. The curable composition may be formulated as a single ink, corresponding to a one-component curable composition, or a dual ink system, corresponding to a two-component curable composition, as described herein-before. A single ink may be useful for a stereolithography (SLA) printing system, where the constituents are combined under conditions that are not sufficient for substantial reaction between the (meth)acrylate polymer A and the compound B to occur prior to printing. A dual ink system may be useful for an ink-jet or so-called multi-jet modeling (MJM) system. Details on various 3D printing systems are, for example, described in S.C. Ligon et al, Chem. Rev. 2017, 117, 10212-10290.

[0387] The process of printing a 3D object may comprise selectively jetting or otherwise depositing layers of an ink in a fluid state onto a substrate, for example, in a layer-by-layer manner according to an image of the 3D article in a computer readable format or to preselected computer aided design (CAD). Curing may be carried out in a layer-by-layer manner during the printing process or in a post-processing step after completion of printing of all layers.

[0388] The curable composition may also be suitably used for dental applications, i.e., as a dental material, especially as a dental cement, a dental filling material or a bonding for dental filling material. The curable composition is used, in particular, by applying it to a substrate of artificial or natural teeth material to be treated and curing it.

[0389] Accordingly, in a further aspect, the invention relates to the use of a (meth)acrylate polymer A, as defined in any aspect herein, as an intermediate for preparing an adhesive, a sealant, a coating, a 3D printed object, a shaped article, a chemical anchor, a dental material or any repair system thereof.

[0390] The instant (meth)acrylate polymer A may be preferably used as part of a curable composition to form cross-linked polymers.

[0391] Upon polymerizing the curable composition an article, selected from an adhesive, a sealant, a coating, a 3D printed object, a shaped article, a chemical anchor and a dental material, may be obtained.

[0392] Accordingly, in a further aspect, the invention relates to the use of a curable composition, as defined in any aspect herein, for preparing an adhesive, a sealant, a coating, a 3D printed object, a shaped article, a chemical anchor, a dental material or any repair system thereof.

[0393] In a further aspect, the invention relates to an article, selected from an adhesive, a sealant, a coating, a 3D printed object, a shaped article, a chemical anchor or a dental material, obtainable by applying the curable composition, as defined in any aspect herein, to a substrate and hardening the curable composition.

[0394] The (meth)acrylate polymer A of the invention is advantageous in that the polymer may function as intermediate to form isocyanate-free urethane groups. Thus, reduced toxicity may be achieved at least in part by the exclusion of isocyanates and / or isocyanate degradation or reaction products.

[0395] The viscosity and molecular weight of the (meth)acrylate polymer A may be adjusted by appropriately selecting polymerization conditions such as optional monomer(s) M2, the polymerization temperature, the organic solvent, and the kind and concentration of the radical initiator, especially the organic solvent.

[0396] The (meth)acrylate polymer A is preferably a flowable or viscous polymer, which flowability may be significantly increased using suitable reactive diluents as compound C. The molecular weights of the (meth)acrylate polymers are such that they may be desirably cured with compounds B and optionally compound C without a solvent, and especially at room temperature within a suitable period of time.

[0397] Compared to compounds having only one, two or three oxathiolanone groups, the (meth)acrylate polymer A has a lower vapor pressure, and less volatile organic content, which is desirable in preparing and processing a curable composition. Combined with the advantages of the class of poly(meth)acrylate a suitable (meth)acrylate polymer A could be achieved with varying amount of oxathiolanone groups leading to a high cross-linking density when processing with polyfunctional amines B and compounds C.

[0398] The (meth)acrylate polymer may be reacted with amines to form urethane thiols that in a subsequent further reaction, e.g., with double bonds or with epoxides, may cure further through the formation of polythioethers or disulfides, thus allowing the formulation of curable compositions, especially two-component curable compositions, for example, applicable as adhesive, sealant or coating compositions.

[0399] The instant curable compositions allow for materials having good adhesion strength, especially on metals or wood, and elasticity upon curing as well as good flexibility, sufficient hardness and low shrinkage. The cured materials are usually transparent and having a high refractive index, thus suitable for optical materials.

[0400] Further, the instant curable compositions allow for significant load bearing strength within the first 30 minutes, i.e., they reach handling strength within a curing time of < 20 min, thus offering a system with a sufficient long open time combined with fast setting times.

[0401] The two-component adhesive composition is able to develop high bonding strengths within a short space of time and with organic amine catalysts in particular, even at room temperature.

[0402] The definitions and preferences given for the process mentioned herein-before apply in any combination as well as in any combination for the other aspects of the invention.

[0403] The present invention will now be explained in more detail with reference to the following examples. These examples should not be construed as limited. Unless otherwise stated, “%” is always % by weight (wt%).

[0404] Examples

[0405] The parameters were determined as follows:

[0406] Zero-shear viscosity:

[0407] The zero-shear viscosity is the threshold value of the viscosity function at infinitely low shear rates. It is measured using an Anton Paar MCR 100 rheometer (US 200 evaluation software) in plate / plate geometry. The samples are measured under oscillatory shear at a low shear amplitude of 10%. Temperature 23°C (or as stated), angular frequency ramp log 100-0.1 s1, measuring gap 0.5 mm, evaluation according to Carreau-Gahleitner I, piston diameter 25 mm.

[0408] Molecular weight: Gel permeation chromatography (GPC), THF as mobile phase, polystyrene standard

[0409] Glass transition temperature (Tn): DSC Q2000 V24.10 (TA Instruments) About 8 mg of a sample were heated up to 150°C and then cooled down to -70°C, followed by measuring the heat flow during a heating rate of 20 K / min until reaching 150°C.

[0410] Cross-cut test (in analogy to DIN EN ISO 2409:2013)

[0411] Cross-cuts with 1 mm spacing were made with the Multi Cross Cutter Model 295. A pressuresensitive adhesive tape (Tesa film) was glued to the cross-hatch pattern on the coated panel and pulled off after pressing down on the coating. The cross-cut area was then examined with a microscope (STEM I SR I Zeiss) to determine the classification 0 to 5.

[0412] 1 none of the squares of the lattice is detached

[0413] 5 any degree of flaking that cannot even be classified by classification 4

[0414] Erichsen cupping (in analogy to DIN EN ISO 1520:2006)

[0415] The coated plates were stored in a hood before testing. The test was carried out with the lacquer and paint testing machine “Erichsen Model 202» at 20-26°C and 60-70% relative humidity. The middle of the coated plate was clamped between the sheet holder and the ball shaped die and formed with a ball punch at a specified speed until a crack becomes visible in the coating of the plate. The distance travelled by the ball in mm until the crack becomes visible is then recorded as the Erichsen’s value.

[0416] Adhesion strength determined with weights

[0417] In order to prepare a test specimen a curable system was applied on a square area (2.5 x 2.5 cm, roughened with sandpaper) on the edges of 2 steel specimens (stainless steel test specimens, material no. 1.4301 , 100 x 25 x 2 mm). The coated area was then fixed with 2 clamps, and the clamps were removed before testing.

[0418] The test specimens were hung on a rod by means of a hook and a weight was attached to the lower end of the test specimen. The measurement was started on the first test specimen (curing time 5 min) with 1 kg weight. If this weight was hold for 2 min the weight was increased to 2 kg (8 kg, 10 kg and 11 kg maximum) until the test specimens either broke or slipped away from each other. Target was 2 min with each weight.

[0419] Tensile lap-shear strength I (in analogy to DIN EN 1465:2009)

[0420] The test specimens, prepared as described for adhesion strength determined with weights, were analysed using a TA.XTplus Texture Analyser (Stable Micro Systems).

[0421] Micro Shore A hardness (in analogy to DIN EN ISO 868:2003)

[0422] The test was carried out with the durometer Digi Test II (Bareiss) using a head M Shore A (type DTM IIA). The amount, as specified in the Examples (ca. 3 g) of the curable system was weighed in a lid made of tinplate blank, suitable for cans 0 45 mm, to obtain a sample thickness of ca. 1 mm. The M Shore A hardness was measured hourly for the first 24 hours and then once daily for 6 days at 20-26°C and 60-70% relative humidity.

[0423] Dynamic-mechanical thermal analysis (DMTA) Anton Paar MCR 100 rheometer (plate / plate geometry with disposable plates, in oscillatory shear (amplitude between 2% and 0.5%, depending on hardness).

[0424] The mixed material was placed between the plates and cured for 12 hours at 23°C, detecting the crossover point of storage modulus and loss modulus. Then the cured material was annealed for 1 hour at 100°C in 2°C / min to check for further conversion and then cooled to 23°C, resulting in the final modulus. After that the system was heated to 100°C the change of storage modulus, loss modulus and loss factor (tanb) was observed.

[0425] Lap shear test II

[0426] Standard test specimen (Rocholl GmbH): stainless steel (SS), aluminum (ALU), polypropylene in 10 cm x 2.5 cm x 0.2 cm or beechwood in 8 x 4 x 0.5 cm geometry.

[0427] After placing the reacting mixture as fast as possible onto the test specimen, the parts were clamped together (with an overlap of 2.5 cm x 2.5 cm, for beechwood 2 cm x 4 cm) and stored at room temperature for 2 days. The application amount was 0.2 g / (2.54 cm)2. Then a tensile test was performed with a Zwick tensile tester at 100 mm / min speed. Optionally, further test specimen were placed in a closed twist-off glass containing a water soaked sponge and placed in an oven at 70°C for one week. After one week, the test specimen were re-dried at room temperature before the tensile test was performed again.

[0428] Synthesis Example 1 5-(methacryloyloxy)methyl-1 ,3-oxathiolane-2-one of formula (la) was prepared according to Example 8 of WO 2019 / 034469 A1.

[0429] Synthesis Example 2

[0430] Trimethylolpropane-(3.2 EO)-trimethacylate was prepared by alkoxylation of trimethylolpropane, followed by reaction with methacrylic acid, using standard procedures.

[0431] Synthesis Example 3

[0432] Isosorbide-dimethacrylate was obtained by conversion of isosorbide with methacryloyl anhydride, using standard procedures.

[0433] Example 1

[0434] Feed A t-butylperoctoate 98% (1 .25 g)

[0435] 2-butanol (1.0 g)

[0436] Feed B monomer of formula (la) (8.75 g) n-butyl acrylate (8.75 g) ethylhexyl acrylate (8.75 g) xylene, technical grade (35.0 g) A 200 ml reactor was equipped with a thermometer, nitrogen purge line, oil bath with temperature control, mechanical stirring device and raw material feed pumps. 24 g of 2-butanol were added to the reactor, intertized by a nitrogen stream for 30 min under continuous stirring and subsequently heated to 99°C internal temperature. As soon as a temperature of >98°C was reached the initiator feed A and the monomer feed B were started. Within the feeding time of 300 min the internal temperature, nitrogen stream and stirring were kept constant. Afterwards the mixture was allowed to further react at 100°C for 180 min, followed by vacuum distillation at 120°C oil temperature and maximum vacuum of 15 mbar. The product was obtained as clear, colorless viscous liquid.

[0437] Zero-shear viscosity (23°C) [Pa s] 268

[0438] Zero-shear viscosity (30°C) [Pa s] 83.8

[0439] Molecular weight Mn[g / mol] 2356

[0440] Molecular weight Mw[g / mol] 4237

[0441] PDI 1.80

[0442] Example 2

[0443] Feed A t-butylperoctoate 98% (1 .25 g) 2-butanol (1.0 g)

[0444] Feed B monomer of formula (la) (8.75 g) n-butyl acrylate (8.75 g) n-heptadecyl acrylate (8.75 g) xylene (35.0 g)

[0445] A 200 ml reactor was equipped with a thermometer, nitrogen purge line, oil bath with temperature control, mechanical stirring device and raw material feed pumps. 24 g of 2-butanol were added to the reactor, intertized by a nitrogen stream for 30 min under continuous stirring and subsequently heated to 99°C internal temperature. As soon as a temperature of >98°C was reached the initiator feed A and the monomer feed B were started. Within the feeding time of 300 min the internal temperature, nitrogen stream and stirring were kept constant. Afterwards the mixture was allowed to further react at 100°C for 180 min, followed by vacuum distillation at 120°C oil temperature and maximum vacuum of 15 mbar. The product was obtained as clear, colorless viscous liquid.

[0446] Zero-shear viscosity (23°C) [Pa s] 284

[0447] Zero-shear viscosity (30°C) [Pa s] 118

[0448] Molecular weight Mn[g / mol] 2625

[0449] Molecular weight Mw[g / mol] 4432

[0450] PDI 1.96

[0451] Example 3

[0452] Feed A t-butylperoctoate 98% (1 .25 g)

[0453] 2-butanol (1.0 g)

[0454] Feed B monomer of formula (la) (8.75 g) n-butyl acrylate (8.75 g) Bisomer PEM 63P HD (8.75 g) xylene (35.0 g)

[0455] A 200 ml reactor was equipped with a thermometer, nitrogen purge line, oil bath with temperature control, mechanical stirring device and raw material feed pumps. 24 g of 2-butanol were added to the reactor, intertized by a nitrogen stream for 30 min under continuous stirring and subsequently heated to 99°C internal temperature. As soon as a temperature of >98°C was reached the initiator feed A and the monomer feed B were started. Within the feeding time of 300 min the internal temperature, nitrogen stream and stirring were kept constant. Afterwards the mixture was allowed to further react at 100°C for 180 min, followed by vacuum distillation at 120°C oil temperature and maximum vacuum of 15 mbar. The product was obtained as clear, colorless viscous liquid.

[0456] Zero-shear viscosity (23°C) [Pa s] 297

[0457] Zero-shear viscosity (30°C) [Pa s] 113

[0458] Molecular weight Mn[g / mol] 3527

[0459] Molecular weight Mw[g / mol] 6602

[0460] PDI 1.85

[0461] Example 4

[0462] Feed A t-butylperoctoate 98% (1 .25 g)

[0463] 2-butanol (1.0 g)

[0464] Feed B monomer of formula (la) (8.75 g) n-butyl acrylate (8.75 g)

[0465] Bisomer MPEG350-MA (8.75 g) xylene (35.0 g)

[0466] A 200 ml reactor was equipped with a thermometer, nitrogen purge line, oil bath with temperature control, mechanical stirring device and raw material feed pumps. 24 g of 2-butanol were added to the reactor, intertized by a nitrogen stream for 30 min under continuous stirring and subsequently heated to 99°C internal temperature. As soon as a temperature of >98°C was reached the initiator feed A and the monomer feed B were started. Within the feeding time of 300 min the internal temperature, nitrogen stream and stirring were kept constant. Afterwards the mixture was allowed to further react at 100°C for 180 min, followed by vacuum distillation at 120°C oil temperature and maximum vacuum of 15 mbar. The product was obtained as clear, colorless viscous liquid.

[0467] Zero-shear viscosity (23°C) [Pa s] 118

[0468] Zero-shear viscosity (30°C) [Pa s] 59

[0469] Molecular weight Mn[g / mol] 3249

[0470] Molecular weight Mw[g / mol] 5794

[0471] PDI 1.78 Example 5

[0472] Feed A t-butylperoctoate 98% (1 .25 g)

[0473] 2-butanol (1.0 g)

[0474] Feed B monomer of formula (la) (8.75 g) n-butyl acrylate (8.75 g)

[0475] Bisomer MPEG550-MA (8.75 g) xylene (35.0 g)

[0476] A 200 ml reactor was equipped with a thermometer, nitrogen purge line, oil bath with temperature control, mechanical stirring device and raw material feed pumps. 24 g of 2-butanol were added to the reactor, intertized by a nitrogen stream for 30 min under continuous stirring and subsequently heated to 99°C internal temperature. As soon as a temperature of >98°C was reached the initiator feed A and the monomer feed B were started. Within the feeding time of 300 min the internal temperature, nitrogen stream and stirring were kept constant. Afterwards the mixture was allowed to further react at 100°C for 180 min, followed by vacuum distillation at 120°C oil temperature and maximum vacuum of 15 mbar. The product was obtained as clear, colorless viscous liquid.

[0477] Zero-shear viscosity (23°C) [Pa s] 86.4

[0478] Zero-shear viscosity (30°C) [Pa s] 40.5

[0479] Molecular weight Mn[g / mol] 3174

[0480] Molecular weight Mw[g / mol] 5697

[0481] PDI 1.79

[0482] Example 6

[0483] Feed A t-butylperoctoate 98% (1 .88 g)

[0484] 2-butanol (1.0 g)

[0485] Feed B monomer of formula (la) (8.75 g) n-butyl acrylate (16.25 g) xylene (35.0 g)

[0486] A 200 ml reactor was equipped with a thermometer, nitrogen purge line, oil bath with temperature control, mechanical stirring device and raw material feed pumps. 24 g of 2-butanol were added to the reactor, intertized by a nitrogen stream for 30 min under continuous stirring and subsequently heated to 99°C internal temperature. As soon as a temperature of >98°C was reached the initiator feed A and the monomer feed B were started. Within the feeding time of 300 min the internal temperature, nitrogen stream and stirring were kept constant. Afterwards the mixture was allowed to further react at 100°C for 180 min, followed by vacuum distillation at 120°C oil temperature and maximum vacuum of 15 mbar. The product was obtained as clear, colorless viscous liquid.

[0487] Zero-shear viscosity (23°C) [Pa s] 659

[0488] Zero-shear viscosity (30°C) [Pa s] 236 Molecular weight Mn[g / mol] 1790 Molecular weight Mw[g / mol] 3681

[0489] Polydispersity 2.06

[0490] Example 7

[0491] Feed A t-butylperoctoate 98% (2.39 g) 2-butanol (1.0 g)

[0492] Feed B monomer of formula (la) (8.75 g) n-butyl acrylate (16.25 g) xylene (35.0 g)

[0493] The procedure of Example 6 was repeated except that 2.39 g of t-butylperoctoate are used in feed A instead of 1 .88 g. The product was obtained as clear, colorless viscous liquid.

[0494] Zero-shear viscosity (23°C) [Pa s] 122

[0495] Zero-shear viscosity (30°C) [Pa s] 54

[0496] Molecular weight Mn[g / mol] 1525

[0497] Molecular weight Mw[g / mol] 3245

[0498] Polydispersity 2.13

[0499] Example 8

[0500] Feed A t-butylperoctoate 98% (1 .25 g) 2-butanol (1.0 g)

[0501] Feed B monomer of formula (la) (8.75 g) n-butyl acrylate (16.25 g) xylene (35.0 g)

[0502] The procedure of Example 6 was repeated except that 1 .25 g of t-butylperoctoate are used in feed A instead of 1 .88 g. The product was obtained as clear, colorless viscous liquid.

[0503] Zero-shear viscosity (23°C) [Pa s] 1453

[0504] Zero-shear viscosity (23°C) [Pa s] 500

[0505] Molecular weight Mn2056 g / mol

[0506] Molecular weight Mw5222 g / mol

[0507] Polydispersity 2.54

[0508] Feed A: n-butylacrylate (100.68 g, 0.786 mol) monomer of formula (la) (33.56 g) o-xylene (67.12 g)

[0509] Feed B: t-butylperoxypivalate (3.58 g) o-xylene (29.53 g)

[0510] Feed C: t-butylperoxypivalate (0.54 g) o-xylene (20.14 g) Under semi-batch process conditions, 201.36 g of o-xylene were heated in a reactor under nitrogen atmosphere to 120°C (internal temperature). During heating at 100°C, 5 wt% of the mixture of feed A were added under stirring, and at 117°C 5 wt% of the mixture of feed B were added. After 3 min at 120°C the remaining amounts of feed A and feed B were added simultaneously within 3 hours. 15 min after finishing feed A and feed B, the mixture of feed C was added within 30 min. After cooling to about 30°C the solution was transferred to a distillation apparatus to remove the solvent under vacuum. The product was obtained as clear, colorless viscous liquid.

[0511] Zero-shear viscosity (23°C) [Pa s] 416

[0512] Zero-shear viscosity (30°C) [Pa s] 192

[0513] Molecular weight Mn[g / mol] 2270

[0514] Molecular weight Mw[g / mol] 5370

[0515] Polydispersity 2.4

[0516] Glass transition temperature Tg[°C] -32

[0517] Example 10 Monomers: n-butylacrylate (160 g) monomer of formula (la) (18 g)

[0518] Feed A: t-butylperoxypivalate (4.80 g) o-xylene (39.60 g)

[0519] Feed B: t-butylperoxypivalate (0.72 g) o-xylene (27.00 g)

[0520] Under batch process conditions, 360.00 g of o-xylene and the monomers were heated in a reactor under nitrogen atmosphere to 120°C (internal temperature). After reaching > 119°C feed A was added within 3 hours. 15 min after finishing feed A, the mixture of feed B was added within 30 min. After cooling to about 30°C the solution was transferred to a distillation apparatus to remove the solvent under vacuum. The product was obtained as clear, colorless viscous liquid.

[0521] Zero-shear viscosity (23°C) [Pa s] 373

[0522] Zero-shear viscosity (30°C) [Pa s] 211

[0523] Molecular weight Mn(GPC) [g / mol] 4860

[0524] Molecular weight Mw(GPC) [g / mol] 23800

[0525] Polydispersity 4.9

[0526] Glass transition temperature Tg[°C] -42

[0527] Example 11

[0528] Feed A: 2-ethyl-hexylacrylate (65 g) monomer of formula (la) (35 g) o-xylene (50 g)

[0529] Feed B: t-butylperoxypivalate (2.67 g) o-xylene (22 g) Feed C: t-butylperoxypivalate (0.4 g) o-xylene (15 g)

[0530] Under semi-batch process conditions, 150 g of o-xylene were heated in a reactor under nitrogen atmosphere to 120°C internal temperature. During heating at 100°C, 5 wt% of the mixture of feed A were added under stirring, and at 117°C 5 wt% of the mixture of feed B were added. After 3 min at 120°C the remaining amounts of feed A and feed B were added simultaneously within 3 hours. After 15 min, the mixture of feed C was added within 30 min. After cooling to about 30°C the solution was transferred to a distillation apparatus and the solvent distilled off under vacuum. The product was obtained as clear, colorless viscous liquid.

[0531] Zero-shear viscosity (23°C) [Pa s] 1496

[0532] Molecular weight Mn[g / mol] 2579

[0533] Molecular weight Mw[g / mol] 4527

[0534] Polydispersity 1 .76

[0535] Example 12

[0536] Feed A: n-butylacrylate (117 g) monomer of formula (la) (63 g) o-xylene (19 g)

[0537] Feed B: t-butylperoxypivalate (4.8 g) o-xylene (39.6 g)

[0538] Feed C: t-butylperoxypivalate (0.72 g,) o-xylene (27 g)

[0539] Under semi-batch process conditions, 270 g of o-xylene were heated in a reactor under nitrogen atmosphere to 120°C internal temperature. During heating at 100°C, 5 wt% of the mixture of feed A were added under stirring, and at 117°C 5 wt% of the mixture of feed B were added. After 3 min at 120°C the remaining amounts of feed A and feed B were added simultaneously within 3 hours. After 15 min, the mixture of feed C was added within 30 min. After cooling to about 30°C the solution was transferred to a distillation apparatus and the solvent distilled off under vacuum. The product was obtained as clear, colorless viscous liquid.

[0540] Zero-shear viscosity (23°C) [Pa s] 6296

[0541] Molecular weight Mn[g / mol] 3413

[0542] Molecular weight Mw[g / mol] 7317

[0543] Polydispersity 2.14

[0544] Example 13

[0545] A composition of the copolymer obtained in Example 6 and trimethylolpropane-(3.2 EO)- trimethacrylate, obtained in Synthesis Example 2, was obtained by mixing to a homogenous mixture.

[0546] 85 wt% copolymer obtained in Example 6

[0547] 15 wt% trimethylolpropane-(3.2 EO)-trimethacrylate Zero-shear viscosity (23°C) [Pa s] 51.7

[0548] Zero-shear viscosity (30°C) [Pa s] 23

[0549] Example 14

[0550] A composition of the copolymer obtained in Example 6 and the reactive diluents isosorbidemethacrylate, obtained in Synthesis Example 3, and isobornyl-methacrylate was obtained by mixing to a homogenous mixture.

[0551] 78 wt% copolymer obtained in Example 6

[0552] 15 wt% isosorbide-dimethacrylate

[0553] 7 wt% isobornyl-methacrylate

[0554] Zero-shear viscosity (23°C) [Pa s] 26.0

[0555] Zero-shear viscosity (30°C) [Pa s] 11 .6

[0556] Example 15

[0557] 5.64 g copolymer obtained in Example 6

[0558] 1 .09 g trimethylolpropane trimethacrylate (TMPTMA)

[0559] 0.71 g triethylenetetramine (TETA)

[0560] 0.04 g 1 ,8-diazabicyclo[5.4.0]undec-7-ene (DBU)

[0561] The copolymer obtained in Example 6 was heated to 60°C, followed by adding TMPTMA under mixing at 2350 rpm for 20 min (without further heating) and forming a homogenous liquid mixture. A cooled mixture of TETA and DBU (4°C) was added and mixed for 60 sec with 2000 rpm. 2.89 g of the resulting mixture were added in a tinplate lid and cured at room temperature (20-26°C) and 60-70% relative humidity in a hood. After 4 hours it was possible to measure M Shore A hardness.

[0562] Example 16

[0563] 5.78 g copolymer obtained in Example 6

[0564] 1.13 g TMPTMA

[0565] 0.73 g triethylenetetramine

[0566] The copolymer obtained in Example 6 was heated to 60°C, followed by adding TMPTMA under mixing at 2350 rpm for 20 min (without further heating) and forming a homogenous liquid mixture. 0.73 g of TETA were added and mixed for 30 sec at 2000 rpm. 2.97 g of the resulting mixture were added in tinplate lid and cured at room temperature (20-26°C) and 60-70% relative humidity in a hood. After 30 min it was possible to measure M Shore A.

[0567] Example 17 copolymer obtained in Example 6

[0568] Epilox P13-30 (triglycidether of trimethylolpropane, epoxy eq. 140-160; Leuna Harze)

[0569] TETA / DBU (weight ratio 95 : 5) 11 .56 g of the copolymer obtained in Example 6 were heated to 60°C, followed by adding 2.02 g of Epilox P13-30 under mixing for 20 min at 2350 rpm (without further heating) to form a homogenous liquid mixture. To 3.83 g of this mixture 0.43 g of TETA / DBU were added and mixed for 20 sec at 2350 rpm. 2.86 g of the resulting mixture were added in a tinplate lid and cured at room temperature (20-26°C) and 60-70% relative humidity in a hood. After 50 min it was possible to measure M Shore A.

[0570] Example 18 copolymer obtained in Example 6

[0571] Epilox P13-30

[0572] TETA

[0573] 11 .56 g of the copolymer obtained in Example 6 were heated to 60°C, followed by adding 2.02 g of Epilox P13-30 under mixing for 20 min at 2350 rpm (without further heating) to form a homogenous liquid mixture. To 3.93 g of this mixture 0.41 g of TETA were added and mixed for 20 sec at 2350 rpm. 2.77 g of the resulting mixture were added in a tinplate lid and cured at room temperature (20-26°C) and 60-70% relative humidity in a hood. After 70 min it was possible to measure M Shore A.

[0574] The results of the final M Shore A hardness of the fully cured samples are listed in Table 1.

[0575] Table 1

[0576] Example 19 copolymer obtained in Example 6

[0577] Epilox P13-30

[0578] TETA / DBU (weight ratio 95 : 5)

[0579] A mixture of 11 .21 g copolymer obtained in Example 6 and 1 .96 g of Epilox P13-30 were mixed at 2350 rpm at 60°C for ca. 1 hour to form a homogenous liquid mixture. To 3.78 g of the resulting warm mixture, 0.43 g of a mixture of TETA and DBU was added at 2350 rpm for 20 sec (without further heating). The resulting warm mixture was applied with a 200 pm bar coater to a stainless steel test panel (Gardobond 26S / 6800 / OC). The mixture was cured at room temperature (20-26°C) and 60-70% relative humidity in a hood for 3 days, to obtain a coating with a layer thickness of about 80 pm.

[0580] Example 20 copolymer obtained in Example 6 trimethylolpropane trimethacrylate (TMPTMA) triethylenetetramine (TETA)

[0581] A mixture of 11 .58 g of the copolymer obtained in Example 6 and 2.25 g of TMPTMA were mixed at 50°C for ca. 1 hour at 2350 rpm to form a homogenous liquid mixture. To 2 g of the resulting warm mixture 0.30 g of TETA were added and mixed for 20-30 sec at 2350 rpm (without further heating). The resulting warm mixture was applied with a 200 pm bar coater to a stainless steel test panel (Gardobond 26S / 6800 / OC). The mixture was cured at room temperature (20-26°C) and 60-70% relative humidity in a hood for 3 days to obtain a coating with a layer thickness of about 80 pm.

[0582] Example 21

[0583] 11 .35 g copolymer obtained in Example 6

[0584] 2.22 g trimethylolpropane trimethacrylate (TMPTMA)

[0585] 1 .44 g TETA

[0586] 0.07 g DBU

[0587] A mixture of the copolymer obtained in Example 6 and TMPTMA was mixed at 50-55°C for ca. 1 hour at 2350 rpm to form a homogenous liquid mixture. 4 smaller batches of the resulting warm mixture were made. A corresponding amount of a TETA / DBU mixture was added to one batch under mixing for 20-30 sec at 2350 rpm (without further heating). The resulting warm mixture was applied with a 200 pm bar coater to a stainless steel test panel (Gardobond 26S / 6800 / OC). The mixture was cured at room temperature (20-26°C) and 60-70% relative humidity in a hood for 3 days to obtain a coating with a layer thickness of about 80 pm.

[0588] For testing the coated test panels were further cured at 50°C for 1 hour and at 100°C for 15 min. The results of the coated test panels of Examples 19 to 21 are listed in Table 2.

[0589] Table 2

[0590] Example 22

[0591] 5.78 g copolymer obtained in Example 6

[0592] 1.13 g trimethylolpropane trimethacrylate (TMPTMA)

[0593] 0.77 g TETA I DBU (weight ratio 95 : 5)

[0594] The copolymer obtained in Example 6 was heated to 60°C, followed by adding TMPTMA under mixing at 2350 rpm for 30 min (without further heating) to form a homogenous liquid mixture. A cooled mixture of TETA and DBU (4°C) was added and mixed for 30 sec with 2000 rpm. The resulting mixture was applied on a square area (2.5 x 2.5 cm, roughened with sandpaper) on the edges of 2 steel specimens (stainless steel test specimens, material no. 1 .4301 , 100 x 25 x 2 mm). The coated area was then fixed with 2 clamps, and the clamps were removed before testing.

[0595] Several test specimens were prepared and tested one after the other at subsequent intervals. The test specimens which held the weights for 2 min were also measured in analogy to DIN EN 1465. The results for the determination of adhesion strength by weights (2ndcol.) and the tensile lap-shear strength I in analogy to DIN EN 1465 (3rdcol.) are listed in Table 3.

[0596] Table 3

[0597] The results show that the curable system builds up significant load bearing strength within a curing time of 30 min as well as handling strength within 15 min offering significant open times (a value for handling strength or fixture strength is usually quoted as between 0.1-0.3 N / mm2).

[0598] General procedure for Examples 23 to 29

[0599] 2 to 3 g of the copolymer obtained in Examples 9, 10, 11 or 12 were mixed with the for crosslinking necessary amount of polyfunctional olefin. Then, the stoichiometrically needed amount of polyfunctional amine was added and mixed carefully. If a catalyst like DBU was used, it was mixed in as last compound. The mixture was then a) placed between the disposable plates in a rheometer and the storage modulus and loss modulus measured according to the above-described procedure “Dynamic-mechanical thermal analysis (DMTA)”, or b) placed on test specimen according to test procedure “lap shear test II”.

[0600] Example 23

[0601] 2 g copolymer obtained in Example 12

[0602] 0.356 g trimethylolpropane-trimethacrylate (TMPTMA)

[0603] 0.478 g Jeffamine T-403 Polyetheramine (trifunctional primary amine having an average molecular weight of ~440, based on oxypropylene units; Huntsman)

[0604] Gel point detected via crossover of moduli after curing of 12 hours at 23°C + 1 hour at 100°C

[0605] Example 24

[0606] 2 g copolymer obtained in Example 12 0.356 g trimethylolpropane-trimethacrylate (TMPTMA)

[0607] 0.478 g Jeffamine T-403 Polyetheramine

[0608] 0.06 ml 1 ,8-diazabicyclo(5.4.0)undec-7-ene (DBU)

[0609] Gel point detected via crossover of moduli already after curing of 3 hours at 23°C

[0610] Example 25

[0611] 3 g copolymer obtained in Example 10

[0612] 0.38 g Bisphenol A-glycerolate dimethacrylate

[0613] 0.105 g 1 ,3-bis(aminomethyl)cyclohexane

[0614] Curing at room temperature (12 hours) and annealing at 100°C; followed by DMTA with heating to 100°C;

[0615] Gel point detected via crossover of moduli after 12 hours at 23°C + 1 hour at 100°C;

[0616] Cross-linking detected via temperature independent storage modulus, maximum of loss factor <23°C as indication of glass transition temperature Tg.

[0617] Example 26

[0618] 3 g copolymer obtained in Example 9

[0619] 0.951 g Bisphenol A-glycerolate dimethacrylate

[0620] 0.246 g 1 ,3-bis(aminomethyl)cyclohexane

[0621] Curing at room temperature (12 hours) and annealing at 100°C; followed by DMTA with heating to 100°C

[0622] Gel point detected via crossover of moduli after 12 hours at 23°C + 1 hour at 100°C;

[0623] Cross-linking detected via temperature independent storage modulus, maximum of loss factor between 30 and 35°C as indication of Tg.

[0624] Example 27

[0625] 3 g copolymer obtained in Example 12

[0626] 1 .33 g Bisphenol A-glycerolate dimethacrylate

[0627] 0.37 g 1 ,3-bis(aminomethyl)cyclohexane

[0628] Curing at room temperature and annealing at 100°C; followed by DMTA with heating to 100°C Gel point detected via crossover of moduli after 10 hours at 23°C;

[0629] Cross-linking detected via temperature independent storage modulus, maximum of loss factor between 45 and 50°C as indication of Tg.

[0630] Mixed and cured according to test procedure “lap shear test II”. The results are listed in Table 4.

[0631] Example 28

[0632] 3 g copolymer obtained in Example 11

[0633] 1 .33 g Bisphenol A-glycerolate dimethacrylate

[0634] 0.37 g 1 ,3-bis(aminomethyl)cyclohexane Mixed and cured according to test procedure “lap shear test II”. The results are listed in Table 4.

[0635] Example 29

[0636] 2 g copolymer obtained in Example 12

[0637] 0.388 g TMPTMA

[0638] 0.245 g 1 ,3-bis(aminomethyl)cyclohexane

[0639] Mixed and cured according to test procedure “lap shear test II”. The result is listed in Table 4.

[0640] Table 4 n.d. = not determined

[0641] The compositions of Examples 27 and 28 were also analysed in analogy to the lap-shear test II after 7 days at 23°C (adhesive layer thickness of 500 pm). The results are listed in Table 5.

[0642] Table 5

Claims

Claims1. A (meth)acrylate polymer A, obtainable by a free-radical polymerization process of a monomer M1 of formula(I), whereinR1is H or methyl,X is Ci-C4-alkylene, and optionally at least one monoethylenically unsaturated monomer M2, wherein the amount of the monomer M1 of formula (I) is at least 8 wt%, based on the total weight of the monomers.

2. The (meth)acrylate polymer A according to claim 1 , wherein the at least one monoethylenically unsaturated monomer M2 is selected from an ethylenically unsaturated carboxylic acid or salt thereof, an ethylenically unsaturated carboxylic anhydride, an ethylenically unsaturated amide, an ethylenically unsaturated nitrile, an ethylenically unsaturated carboxylic ester and any combination thereof.

3. The (meth)acrylate polymer A according to claim 1 or 2, wherein the at least one monoethylenically unsaturated monomer M2 is a (meth)acrylic ester of formula (II)(II), whereinR2is H or CH3;R3is Ci-C25-alkyl; Ci-Ci8-alkyl substituted with COOH, halogen, Ci-Ci2-alkoxy, Ci-Ci2-alkylthio, OH, N(Ci-C4-alkyl)2, C6-Ci8-aryl, C6-Ci8-aryloxy, C3-Ci8-cycloalkyl or epoxy; C3-Ci8-cycloalkyl;C6-Ci8-aryl; or C6-Ci8-aryl substituted with OH, COOH, Ci-Ci2-alkyl, Ci-Ci2-alkoxy or C1-C12- alkylthio; a group of formula -(Z-Y)n- R4(III),R4is H or Ci-C-io-alkyl;Z is C2-C4-alkylene;Y is O or S; and n is a real number in the range of > 2 to < 30.

4. The (meth)acrylate polymer A according to claim 3, whereinR3is C3-C2o-alkyl; Ci-Ci8-alkyl substituted with Ci-C4-alkoxy, Ci-C4-alkylthio, OH or N(CI-C4)2, phenyl, phenoxy, C3-C6-cycloalkyl or epoxy; C3-Ci2-cycloalkyl; phenyl; or phenyl substituted with OH, Ci-C4-alkyl, Ci-C4-alkoxy or Ci-C4-alkylthio; a group of formula -(Z-Y)n- R4(III),R4is H or Ci-C8-alkyl;Z is C2-C3-alkylene;Y is O; and n is a real number in the range of > 2 to < 30, especially > 2 to < 20.

5. The (meth)acrylate polymer A according to any one of the preceding claims, whereinX is methylene or ethylene, andR1is methyl.

6. The (meth)acrylate polymer A according to any one of the preceding claims, wherein the amount of the monomer M1 of formula (I) is of from 8 to 50 wt%, based on the total weight of the monomers.

7. The (meth)acrylate polymer A according to any one of the preceding claims, wherein the (meth)acrylate polymer A has a number-average molecular weight Mnof from 800 to 30,000 g / mol.

8. A process for preparing a (meth)acrylate polymer A, as defined in any one of claims 1 to 7, the process comprising polymerizing a monomer M1 of formula(I), as defined in claim 1 or 5, and optionally at least one monoethylenically unsaturated monomer M2, as defined in any one of claims 1 to 4, in the presence of a free-radical initiator.

9. A curable composition containing a) a (meth)acrylate polymer A, as defined in any one of claims 1 to 7, b) a compound B having at least one amino group, selected from a primary amino group, a secondary amino group and any combination thereof, said primary or secondary amino group may be present in a masked, latently reactive form, and c) optionally a compound C having at least one functional group reactive towards a SH group.

10. The curable composition according to claim 9, with the proviso that- the compound B is polyfunctional, in case the compound C is not present, or- at least one compound of the compounds B and C is polyfunctional, in case the compound C is present.11 . The curable composition according to claim 9 or 10, which is a curable two-component composition, containing(1) a first component containing a) the (meth)acrylate polymer A, and c) optionally the compound C having at least two functional groups reactive towards a SH group, and(2) a second component containing b) the compound B having at least one amino group, selected from a primary amino group, a secondary amino group and any combination thereof, said primary or secondary amino group may be present in a masked, latently reactive form.

12. The curable composition according to claim 9, 10 or 11 , wherein the compound B is a compound having at least one primary amino group, preferably at least two primary amino groups.

13. The curable composition according to any one of the claims 9 to 12, wherein the compound C is a compound having at least two functional groups reactive towards a SH group, selected from an ethylenically unsaturated group, an epoxy group and any combination thereof, preferably selected from a (meth)acryloyl group, an epoxy group and any combination thereof.

14. The use of a (meth)acrylate polymer A, as defined in any one of claims 1 to 7, as an intermediate for preparing an adhesive, a sealant, a coating, a 3D printed object, a shaped article, a chemical anchor, a dental material or a repair system thereof.

15. The use of a curable composition, as defined in any one of claims 9 to 13, for preparing an adhesive, a sealant, a coating, a 3D printed object, a shaped article, a chemical anchor, a dental material or a repair system thereof.

16. An article selected from an adhesive, a sealant, a coating, a 3D printed object, a shaped article, a chemical anchor and a dental material, wherein the article is obtainable by applying the curable composition, as defined in any of claims 9 to 13, to a substrate and hardening the curable composition.

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