Dual curable oligomers

Abstract

The invention relates to dual curable oligomers comprising a segment a) comprising at least one ethylenic unsaturation, a segment b) comprising at least one epoxy group and a segment c) comprising at least one urethane bond, the segments a) and b) being connected to each other by means of the segment c). The invention also relates to curable compositions comprising such dual curable oligomers and their use as adhesives, inks, printing masks, coloring systems, 3D printing resins, sealants, coatings and other potential applications.

Description

Technical Field

[0001] This invention relates to dual-curable oligomers comprising at least one segment containing an unsaturated group and at least one segment containing an epoxy group, wherein the two segments are linked by a urethane bond. The invention also relates to curable compositions comprising such dual-curable oligomers and their use as adhesives, inks, printing masks, coloring systems, 3D printing resins, sealants, coatings, and other potential applications. Background Technology

[0002] Dual-curing systems are valuable for producing materials that undergo rapid photocuring, allowing for pre-fixing of material size and shape, reducing the risk of migration of uncured components, and preventing flow out of selected areas.

[0003] One type of dual-curable system described in the prior art is based on a combination of two different resins: epoxy resin and acrylate resin. Notably, CN 1159625 C (LIANZHI SCIENCE AND TECHNOLOGY Co., Ltd.) discloses a formulation containing epoxy resin and acrylate resin as a mixture to achieve dual-curable properties. However, besides the lack of uniformity in the cured macrostructure, these systems are unsatisfactory due to the poor interface between the photocured acrylate resin and the thermocured epoxy resin.

[0004] Other systems are based on the use of bifunctional components containing epoxy and acrylate functional groups. EP 3548541 B1 (3M Innovative Properties Company) describes a bifunctional monomer containing epoxy and alkenyl groups, which provides a pathway for the formation of thiol-epoxy and thiol-alkene polymers. This monomer can be prepared by alkylation of a polyol (or polyamine) with an α-halo-ω-olefin such as an allyl halide to provide an alkenyl group, and by alkylation of a glycidyl compound to provide an epoxy group. Alternatively, the alkenyl group can be provided by reacting a polyol with a compound having an isocyanate group and a terminal alkenyl group, and by reacting the remaining hydroxyl group of the polyol with an isocyanate compound having an epoxy group. This document provides a method for preparing a multifunctional photocurable monomer. However, it is based on non-commercially available components, which reduces its practical and industrial feasibility.

[0005] US 3,873,638 (Minnesota Mining and Manufacturing Company) describes a thermosetting adhesive. According to some embodiments, the adhesive is based on a dual-curing system containing both unsaturated groups and epoxy groups. This dual-curing system is prepared by reacting methacrylic acid and bisphenol A diglycidyl ether (containing two epoxy functional groups) in a controlled molar ratio in the presence of a combination of triphenylantimony and triphenylphosphine (TPP) as catalysts. However, the presence of residual TPP in the formulation due to premature curing leads to shelf-life stability issues. This negatively impacts the storage of dual-curing resins because the residual TPP acts as an effective catalyst, resulting in undesirable gelation and even crosslinking during processing, packaging, and transportation.

[0006] One object of this invention is to provide a dual-curable oligomer that can be effectively cured upon exposure to radiation and / or heat, and exhibits improved performance in terms of shelf-life stability. Another object of this invention is to provide a method for preparing such a dual-curable oligomer based on commercially and industrially available components. Yet another object of this invention is to provide a curable composition that, upon curing, exhibits mechanical properties highly suitable for withstanding environmental stresses such as high temperatures and vibrations. Summary of the Invention

[0007] In a first aspect, the present invention provides a dual-curable oligomer comprising:

[0008] a) A segment containing at least one olefinic unsaturation;

[0009] b) A segment containing at least one epoxy group;

[0010] c) A segment containing at least one carbamate bond;

[0011] Links a) and b) are connected to each other via link c).

[0012] Chain segment a) may have a structure of formula (A1) or (A2):

[0013] (A1) (A2)

[0014] in:

[0015] - a is at least 1;

[0016] - Each R1 is independently H or CH3;

[0017] - Each R2 is independently selected from the direct connection key, -C(=O)-O-、 -C(=O)-NH-, -O- and -CH2-O-, Indicates the connection point with a carbon-carbon double bond;

[0018] - R3 is the (a+1) valence join part; and

[0019] - symbol This indicates the connection point with link segment c).

[0020] Chain segment b) can have the structure of formula (B1):

[0021] (B1)

[0022] in:

[0023] - b is at least 1;

[0024] - R4 is the (b+1) valence connection part;

[0025] - Each R5 is independently selected from direct bond, -O-CH2-# and -C(=O)-O-CH2-#, with -O-CH2-# being preferred;

[0026] - The symbol # indicates the junction point with the epoxide ring; and

[0027] - The symbol § indicates the connection point with chain segment c).

[0028] Chain segment c) can have the structure of formula (C1):

[0029] (C1)

[0030] in:

[0031] - c is 0 or 1;

[0032] - U corresponds to equation (U1) or (U2):

[0033] (U1)

[0034] (U2)

[0035] in:

[0036] - Each R7 is an independent residue of diisocyanate;

[0037] - Each R7' is independently a triisocyanate residue;

[0038] - Each R8 is an independent residue of a diol;

[0039] - Each d is an independent integer from 0 to 10;

[0040] - symbol Indicates the connection point with link segment a);

[0041] The symbol § indicates the connection point with chain segment b).

[0042] In a second aspect, the present invention provides a method for preparing the dual-curable oligomers described herein, comprising the following steps:

[0043] - To react the olefinically unsaturated monoisocyanate component with the epoxy monohydric alcohol component; or

[0044] - React the olefinically unsaturated monohydric alcohol component, the polyisocyanate component, the epoxy monohydric alcohol component, and the optional diol component.

[0045] In a third aspect, the present invention provides a curable composition comprising at least one of the dual-curable oligomers described herein.

[0046] In a fourth aspect, the present invention provides the use of the curable compositions of the present invention as adhesives, inks, masks for printing, coloring systems, 3D printing resins, sealants or coatings.

[0047] In a fifth aspect, the present invention provides a method for preparing a cured composition, comprising curing the curable composition of the present invention, for example by exposing the curable composition to UV / EB radiation and heat.

[0048] In a sixth aspect, the present invention relates to cured compositions obtained by curing the curable compositions of the present invention. Detailed Implementation

[0049] In this application:

[0050] The expression "included between ... and ... (...to ... or between ... and ...)" should be understood to include the endpoints;

[0051] - Any description, even one relating to a particular embodiment, applies to other embodiments of the invention and may be interchanged with them;

[0052] - Where an element or component is referred to as being included in and / or selected from the list of enumerated elements or components, it should be understood that, in the relevant embodiments explicitly considered herein, the element or component may also be any one of the individually enumerated elements or components, or may be a group consisting of any two or more of the explicitly listed elements or components; any element or component listed in the list of elements or components may be omitted from the list; and

[0053] - Any description of a range of numbers by endpoints in this document includes all numbers contained within the range, as well as the endpoints and equivalents of the range.

[0054] definition

[0055] As used herein, the term "residue" refers to an atomic group remaining in the product after the removal of functional groups that have reacted with another compound to form a linker. For example, the residue of a diol having the structure HO-R8-OH will be understood as R8.

[0056] As used herein, the term "C1-C6" refers to the number of carbon atoms contained in a particular group or linking moiety. For example, C1-C6 alkyl groups are alkyl groups containing 1 to 6 carbon atoms.

[0057] As used herein, the term "aliphatic compound, group, or linking part" refers to a non-aromatic compound, group, or linking part. The term aliphatic compound, group, or linking part encompasses compounds, groups, or linking parts containing a non-aromatic ring (i.e., an alicyclic ring). It can be straight-chain or branched, saturated or unsaturated, cyclic or acyclic. It can be substituted with one or more groups, such as those selected from alkyl, hydroxyl, halogen (Br, Cl, I), isocyanate, carbonyl (=O), amine, carboxylic acid, -C(=O)-OR', -C(=O)-OC(=O)-R', each R' being independently a C1-C6 alkyl group. It can contain one or more bonds selected from ethers, esters, amides, carbamates, ureas, carbonates, organosiloxanes, and mixtures thereof.

[0058] As used herein, the term "aromatic compound, group, or linking moiety" refers to a compound, group, or linking moiety containing at least one aromatic ring (i.e., a ring that obeys Hückel's aromaticity rule, such as a phenyl ring), particularly one, two, or three, preferably one or two aromatic rings. Aliphatic compound, group, or linking moiety (i.e., containing both aromatic and non-aromatic portions) is included in the term "aromatic compound, group, or linking moiety." It may be substituted by one or more groups as defined in the term "aliphatic compound, group, or linking moiety." It may contain one or more bonds as defined in the term "aliphatic compound, group, or linking moiety."

[0059] As used in this article, the term "acyclic compound, group or linking part" refers to a compound, group or linking part that does not contain any rings.

[0060] As used herein, the term "cyclic compound, group or linking part" refers to a compound, group or linking part that contains at least one aromatic or non-aromatic ring.

[0061] As used herein, the term "saturated compound, group or linking part" refers to a compound, group or linking part that does not contain any carbon-carbon double or triple bonds.

[0062] As used herein, the term "unsaturated compound, group or linking part" refers to a compound, group or linking part that contains one or more carbon-carbon double or triple bonds, particularly one or more carbon-carbon double bonds.

[0063] As used herein, the term "hydrocarbon group or linking part" refers to a group or linking part that contains carbon and hydrogen atoms. Unless otherwise stated, a hydrocarbon linking part may not contain atoms other than carbon and hydrogen.

[0064] As used herein, the term "linking moiety" refers to a polyvalent group containing at least one carbon atom and / or at least one heteroatom such as O, N, or S. A linking moiety can connect at least two parts of a compound together, particularly two to six parts. For example, a linking moiety connecting two parts of a compound is called a divalent linking moiety, a linking moiety connecting three parts of a compound is called a trivalent linking moiety, and so on.

[0065] As used in this article, the term "polyether linking portion" refers to a linking portion containing one or more ether bonds.

[0066] As used in this article, the term "polyester linking portion" refers to a linking portion containing one or more ester bonds.

[0067] As used in this article, the term "polycarbonate linking portion" refers to a linking portion containing one or more carbonate bonds.

[0068] As used herein, the term "polyorganosiloxane linker" refers to a linker containing one or more organosiloxane bonds.

[0069] As used herein, the term "polycaprolactone linking portion" refers to a linking portion comprising one or more units derived from the open ring of ε-caprolactone, i.e., one or more units of the formula -O-(C=O)-(CH2)5-. A polycaprolactone linking portion is a specific example of a polyester linking portion.

[0070] As used herein, the term "polydiene linking portion" refers to the linking portion derived from the polymerization of polydienes such as butadiene or isoprene. Polydiene linking portions also include fully or partially hydrogenated polydiene linking portions obtained through hydrogenation of the polydiene linking portion.

[0071] As used herein, the term "isocyanurate linker" refers to the linker containing the isocyanurate portion, i.e., the portion according to the following formula:

[0072] .

[0073] As used herein, the term "(hetero)alkyl" refers to a hydrocarbon group consisting of hydrogen and carbon, which may be saturated or unsaturated, such as (hetero)alkyl, (hetero)alkenyl, (hetero)ynyl, (hetero)aryl, or (hetero)cyclic, optionally containing one or more heteroatoms, such as O, N, and S. (Hetero)alkyl groups may contain functional groups such as urethanes, esters, and amides. These functional groups may be in or at the end of the chain. (Hetero)alkyl groups may contain 1 to 100 carbon atoms, 1 to 50 carbon atoms, 1 to 30 carbon atoms, or 1 to 20 carbon atoms.

[0074] The term "alkyl" as used in this article refers to the formula -C n H 2n+1 The alkyl group is a monovalent saturated acyclic hydrocarbon group, where n is 1 to 100. The alkyl group can be straight-chain or branched. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, 2-methylbutyl, 2,2-dimethylpropyl, n-hexyl, 2-methylpentyl, 2,2-dimethylbutyl, n-heptyl, 2-ethylhexyl, etc.

[0075] As used herein, the term "heteroatom-containing alkyl" refers to an alkyl group containing one or more heteroatoms independently selected from O, N, or S. For example, they may include functional groups such as urethanes, esters, amides, ethers, thioethers, and alkylamines. Heteroatoms may be oxidized to form moieties such as, but not limited to, -C(O)-, -S(O)-, and -S(O)2-. The heteroatom moiety may substitute hydrogen atoms in the alkyl group to form hydroxyl, mercapto, or amino groups. Alternatively, the heteroatom moiety may be a linking atom or inserted between two carbon atoms.

[0076] As used herein, the term "cycloalkyl" refers to a monovalent saturated hydrocarbon group having one to three rings, including monocycloalkyl, bicycloalkyl, and tricycloalkyl groups, having three to twenty carbons capable of forming rings, preferably three to ten carbons. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclododecyl, and isobornyl.

[0077] As used herein, the term "heterocyclic alkyl" refers to a cycloalkyl group having at least one cyclic atom selected as a heteroatom from O, N, or S.

[0078] As used herein, the term "alkenyl" refers to a monovalent acyclic hydrocarbon group containing at least one carbon-carbon double bond. Alkenyl groups can be straight-chain or branched. Examples of alkenyl groups include vinyl, propenyl, butenyl, and 2-methylbutenyl.

[0079] As used herein, the term "alkynyl" refers to a monovalent acyclic hydrocarbon group containing at least one carbon-carbon triple bond. Alynyl groups can be straight-chain or branched. Examples of alkynyl groups include ethynyl, propynyl, butynyl, and 3-methylbutynyl.

[0080] As used herein, the term "aryl" refers to an aromatic ring system having any suitable number of carbocyclic atoms and any suitable number of rings with optional substitutions. Aryl groups may also include saturated straight-chain, branched aliphatic hydrocarbon groups. Aryl groups may include any suitable number of carbocyclic atoms, such as C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, or C16, as well as C6-8, C6-12, or C6-20. Aryl groups may contain a single ring (i.e., phenyl) or more than one ring, wherein at least one ring is aromatic. Aryl groups may be monocyclic, fused to form bicyclic (e.g., benzocyclohexyl) or tricyclic groups, or linked by bonds to form biaryl groups. Examples include phenyl, benzyl, naphthyl, biphenyl, phenanthrene, and tetraphenyl. The araliphatic groups used in this article typically comprise at least one aromatic moiety (e.g., one, two, or three aromatic rings, optionally substituted) and at least one non-aromatic moiety (e.g., a C1-20 heteroalkyl group or a C1-20 heteroolefin group).

[0081] As used in this article, "heteroaryl" refers to an aryl group having at least one ring atom selected as a heteroatom of O, N, or S.

[0082] As used herein, the term "aralkyl" refers to an aryl group that has been substituted with an alkyl group. An example of an aralkyl group is tolyl.

[0083] As used herein, the term "alkylaryl" refers to an alkyl group that has been substituted with an aryl group. An example of an alkylaryl group is benzyl (-CH2-phenyl).

[0084] As used in this article, the term "halogen" refers to an atom selected from Cl, Br, F, and I.

[0085] As used in this article, the term "alkoxy" refers to a group of the formula -O-alkyl, where the alkyl group is as defined above.

[0086] As used in this article, the term "aryloxy group" refers to a group of the formula -O-aryl, where the aryl group is as defined above.

[0087] As used in this article, the term "thioalkyl" refers to a group of the formula -S-alkyl, wherein the alkyl group is as defined above.

[0088] As used in this article, the term "thioaryl" refers to a group of the formula -S-aryl, where the aryl group is as defined above.

[0089] As used in this article, the term "araneoxy" refers to a group of the formula -O-aranealkyl, wherein the aranealkyl group is as defined above.

[0090] As used in this article, the term "alkylaryloxy" refers to a group of the formula -O-alkylaryl, where the alkylaryl group is as defined above.

[0091] As used in this article, "alkylene" refers to a compound derived from C64 by removing one hydrogen atom from each connection point of the connecting portion. m H 2m+2 The alkylene moiety is a polyvalently linked portion of an alkane, where m is 1 to 100. The alkylene moiety can be divalent, trivalent, tetravalent, or have even higher valences.

[0092] As used herein, the term "heteroatom-containing alkylene" refers to an alkylene containing one or more heteroatoms independently selected from O, N, or S. For example, they may include functional groups such as urethanes, esters, amides, ethers, thioethers, and alkylamines. Heteroatoms may be oxidized to form moieties such as, but not limited to, -C(O)-, -S(O)-, and -S(O)2-. The heteroatom moiety may substitute hydrogen atoms in the alkyl group to form hydroxyl, mercapto, or amino groups. Alternatively, the heteroatom moiety may be a linking atom or inserted between two carbon atoms.

[0093] As used herein, the term "oxoalkylene" refers to a group of the formula -O-alkylene-.

[0094] As used in this article, the term "alkoxylated alkylene" refers to the formula -(alkylene-O)n 39 -alkylene-(O-alkylene)n 40 The group, where n 39 and n 40 Independently 0 to 100, provided that n is n 39 and n 40 At least one of them is not 0.

[0095] As used herein, the term "cycloalkylene" refers to a polyvalently linked portion containing a non-aromatic ring. Examples of cycloalkylenes include cyclopentylene, cyclohexylene, and cyclohexyldimethylene (i.e., -CH2-Cy-CH2, where Cy is cyclohexylene).

[0096] As used herein, the term "heterocyclic alkyl" refers to a multivalent linker of a non-aromatic ring having at least one ring atom selected as a heteroatom of O, N, or S.

[0097] As used in this article, the term "subarylene" refers to a multivalently connected portion containing at least one aromatic ring.

[0098] As used herein, the term "hybrid aryl" refers to a multivalent linker of an aromatic ring having at least one ring atom selected as a heteroatom of O, N, or S.

[0099] As used in this article, the term "alkylamino" refers to an alkyl group that is substituted with at least one amino group.

[0100] As used in this article, the term "alkyl mercapto" refers to an alkyl group that is substituted with at least one mercapto group.

[0101] As used in this article, the term "hydroxyalkyl" refers to an alkyl group that is substituted with at least one hydroxyl group.

[0102] As used in this article, the term "halogenated alkyl" refers to an alkyl group that has been substituted with at least one halogen.

[0103] As used in this article, the term "perfluoroalkyl" refers to an alkyl group in which all hydrogen atoms are replaced by fluorine atoms.

[0104] As used herein, the term "polyol" refers to a compound containing at least two hydroxyl groups.

[0105] As used in this article, the term "residue of a polyol" refers to the portion obtained by removing the hydroxyl groups of the polyol.

[0106] Alkyl, alkenyl, alkynyl, cycloalkyl, and aryl groups can be substituted or unsubstituted. For example, they can be substituted by one or more groups selected from halogen, hydroxyl, amino, alkylamino, amide, acyl, nitro, cyano, sulfonyl, sulfonic acid, and alkoxy groups.

[0107] As used herein, the term "alkoxy" refers to a cyclic or acyclic alkyl group having carbon atoms linked by oxygen bridges. Therefore, "alkoxy" includes the definitions of alkyl and cycloalkyl groups.

[0108] The term "hydroxyl group" used in this article refers to -OH.

[0109] The term "NCO group" as used in this article refers to -N=C=O.

[0110] A capped NCO group refers to a portion that can generate an NCO group in situ, for example, through heating. A capped NCO group can correspond to -NH-C(O)-R, where the R group (sometimes called the capping group) is a (hetero)hydrocarbon group.

[0111] As used herein, the term "amino" refers to the part -NRR'-, where each R and R' group is H or an alkyl group. For example, an amino group can be -NH2.

[0112] The term "carboxyl group" used in this article refers to -COOH.

[0113] As used in this article, the term "acyl" refers to the -C(O)R moiety, where R is an alkyl group.

[0114] The term "direct link" used in this article refers to a covalent bond.

[0115] The term "ester bond" as used in this article refers to the -C(=O)-O- or -OC(=O)- bond.

[0116] The term "ether bond" used in this article refers to the -O- bond.

[0117] The term "organosiloxane bond" used in this article refers to -Si(R) c1 )2-O- bond, where R c1 It is an organic group, especially an organic group selected from alkyl, alkoxy and aryl groups.

[0118] The term "carbonate bond" used in this article refers to the -OC(=O)-O- bond.

[0119] The term "carbamate bond or urethane" as used in this article refers to the -NH-C(=O)-O- or -OC(=O)-NH- bond.

[0120] As used in this article, the term "polyisocyanate" refers to a compound containing at least two isocyanate groups.

[0121] As used herein, the term "optionally substituted compound, group or linking part" refers to a compound, group or linking part that is optionally substituted with one or more groups selected from halogen, alkyl, heteroatom-containing alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, alkoxy, aryloxy, aralkyl, alkylaryl, arylalkoxy, alkylaryloxy, haloalkyl, -OH, -SH, hydroxyalkyl, thioalkyl, thioaryl, alkyl mercapto, amino, alkylamino, isocyanate, nitrile, oxo(=O), -C(=O)-R', -OC(=O)-R', -C(=O)-OR', -C(=O)-N(R')2, -NR'-C(=O)-R', -C(=O)-OC(=O)-R' and -SO2-N(R')2, where each R' is independently H or an optionally substituted group selected from alkyl, aryl and alkylaryl.

[0122] Dual-curable oligomers

[0123] This invention relates to a dual-curable oligomer. A dual-curable oligomer is an oligomer capable of curing via two different curing mechanisms, such as free radical polymerization and cationic polymerization. This oligomer contains at least two portions with different curing mechanisms in its main chain, such as a portion cured by free radical polymerization and a portion cured by cationic polymerization.

[0124] The dual-curable oligomers of the present invention comprise: a) a segment containing at least one olefinic unsaturation; b) a segment containing at least one epoxy group; and c) a segment containing at least one urethane bond; wherein segments a) and b) are linked to each other via segment c). Based on these functionalities, the dual-curable oligomers of the present invention can be considered as olefinic unsaturated epoxy-urethane oligomers, particularly (meth)acrylated epoxy-urethane oligomers.

[0125] More specifically, the dual-curable oligomers of the present invention contain the following functional groups in the same molecule:

[0126] - At least one olefinic unsaturation, i.e. at least one polymerizable carbon-carbon double bond, especially at least one carbon-carbon double bond capable of participating in free radical polymerization, wherein at least one carbon atom of the double bond becomes covalently bonded to another atom, especially a carbon atom, in the second molecule;

[0127] - At least one epoxy group capable of participating in cationic polymerization, wherein at least one carbon atom of the epoxide ring becomes covalently bonded to another atom in a third molecule, particularly a nitrogen or oxygen atom; and

[0128] At least one urethane bond, i.e. at least one -NH-C(=O)-O- bond.

[0129] When exposed to photochemical radiation (e.g., UV, near-UV, visible light, infrared, near-infrared and / or electron beam radiation) and / or heat, the dual-curable oligomers of the present invention can be effectively cured, optionally in the presence of a free radical initiator and / or a cationic initiator.

[0130] This polymerization or curing reaction can lead to the incorporation of the dual-curable oligomer of the present invention into the polymer matrix or polymer chain.

[0131] When exposed to radiation and / or heat, the dual-curable oligomers of the present invention can be effectively cured and exhibit improved performance in terms of shelf-life stability. Cured compositions obtained from curable compositions incorporating such oligomers possess mechanical properties well-suited for withstanding environmental stresses, such as high temperatures and vibrations.

[0132] Chain segment a)

[0133] The dual-curable oligomer of the present invention comprises a segment containing at least one olefinic unsaturation, also referred to as segment a). Segment a) is connected to segment c). Segment a) is different from segments b) and c). Therefore, segment a) may not contain any epoxy group unsaturation, and segment a) may not contain any urethane bonds. The dual-curable oligomer of the present invention may comprise more than one segment a). In this case, each segment a) is connected to segment c).

[0134] At least one olefinic unsaturation (i.e., carbon-carbon double bond) in segment a) may be present as part of an α,β-unsaturated carbonyl moiety, such as an α,β-unsaturated ester moiety, like an acrylate functional group (-OC(O)-CH=CH2) or a methacrylate functional group (-OC(O)-C(CH3)=CH2); or an α,β-unsaturated amide moiety, such as an acrylamide functional group (-NH-C(O)-CH=CH2) or a methacrylamide functional group (-NH-C(O)-C(CH3)=CH2). The carbon-carbon double bond may also exist in segment a) in the form of vinyl (-CH=CH2), vinyl ether (-O-CH=CH2), allyl (-CH2-CH=CH2), or allyl ether (-O-CH2-CH=CH2).

[0135] Specifically, segment a) may contain at least one (meth)acrylate group, such as 1, 2, 3, 4, 5, or 6 (meth)acrylate groups. As used herein, the term (meth)acrylate group refers indiscriminately to either an acrylate functional group or a methacrylate functional group. Segment a) may contain a mixture of acrylate and methacrylate functional groups.

[0136] In particular, segment a) can have the structure of formula (A1):

[0137] (A1)

[0138] in:

[0139] -a must be at least 1;

[0140] - Each R1 is independently H or CH3;

[0141] - Each R2 is independently selected from the direct connection key, -C(=O)-O-、 -C(=O)-NH-, -O- and -CH2-O-, Indicates the connection point with a carbon-carbon double bond;

[0142] -R3 is the (a+1) valence join part; and

[0143] -symbol This indicates the connection point with link segment c).

[0144] More specifically, segment a) can have the structure of formula (A2):

[0145] (A2)

[0146] Where a, R1, R3 and symbols As defined above. In such an embodiment, the dual-curable oligomer comprises at least one acrylate functional group (-OC(O)-CH=CH2) and / or at least one methacrylate functional group (-OC(O)-C(CH3)=CH2).

[0147] In the chain segment of formula (A1) or (A2), a is at least 1. In other words, a ≥ 1. In particular, a can be equal to 1, 2, 3, 4, 5 or 6, preferably 1, 2 or 3. A can be an integer or a decimal, because the doubly curable oligomer can be a mixture of oligomers with different proportions of a.

[0148] In the chain segment of formula (A1) or (A2), R3 is an (a+1) valence linker. In particular, R3 can be an (a+1) valence linker selected from aliphatic, aromatic or arylaliphatic hydrocarbon linkers, polyether linkers, polyester linkers, polycarbonate linkers, polyorganosiloxane linkers, polydiene linkers, isocyanurate linkers, and combinations thereof.

[0149] More specifically, R3 can be an (a+1) valence linker selected from alkylene, alkoxylated alkylene, polycaprolactone linker and combinations thereof.

[0150] In one implementation, R3 can be a bivalent linker selected from one of the following formulas (1) to (5):

[0151] -(CR 22 R 22 ) m - (1)

[0152] -[(CR 23 R' 23 ) n -O] o -(CR 23 R' 23 ) n - (2)

[0153] -[(CR 24 R' 24 ) p -O] q -(CR 25 R' 25 ) r -[O-(CR 26 R' 26 ) p’ ] q’ - (3)

[0154] -[(CR 27 R' 27 ) s-C(=O)O] t -(CR 28 R' 28 ) u - (4)

[0155] -[(CR 29 R' 29 ) v -OC(=O)-(CR 30 R' 30 ) w -C(=O)-O] x -(CR 29 R' 29 ) v - (5)

[0156] in:

[0157] R 22 、R' 22 R 25 、R' 25 R 29 、R' 29 R 30 and R' 30 Independently H or alkyl;

[0158] R 23 、R' 23 R 24 、R' 24 R 26 、R' 26 R 27 、R' 27 R 28 and R' 28 Independently, it is either H or methyl;

[0159] m ranges from 2 to 50;

[0160] n, p, and p' are independently 2 to 4;

[0161] o ranges from 1 to 20;

[0162] q and q' are independently between 0 and 20, provided that at least one of q and q' is not 0;

[0163] r is between 2 and 20;

[0164] s is 3 to 12;

[0165] t ranges from 1 to 20;

[0166] u ranges from 2 to 8;

[0167] v ranges from 2 to 20;

[0168] w ranges from 2 to 30;

[0169] x is between 1 and 20;

[0170] symbol This indicates the connection point with the (meth)acrylate group.

[0171] Specifically, R3 can be a divalent moiety selected from the following: alkylene, such as 1,2-ethylene, 1,2- or 1,3-propylene, 1,2-, 1,3- or 1,4-butylene, 1,5-pentaneene, 1,6-hexaneene, 1,8-octaneene, 1,9-nonaneene, 1,10-decaneene, 1,12-dodecylene, 1,18-octadecylene, 2-methyl-1,3-propanediyl, 2,2-diethyl-1,3-propanediyl, 3-methyl-1,5-pentanediyl, 3,3-dimethyl... 1,5-pentanediyl, 2,2-dimethyl-1,3-propanediyl, 2,4-diethyl-1,5-pentanediyl; alkoxylated derivatives of the above alkylene groups; esterified derivatives of the above alkylene groups; residues of di-, tri-, tetra- or polyoxyalkylene groups (excluding OH groups), such as residues of di-, tri- or tetraethylene glycol, di-, tri- or tetrapropylene glycol, di-, tri- or tetrabutanediol, polyethylene glycol, polypropylene glycol, polybutanediol, poly(ethylene glycol-co-propylene glycol); and residues of polyester polyols (excluding OH groups).

[0172] In another embodiment, R3 may be a trivalent connection portion according to one of the following formulas (11), (12), (13), (19) and (20), or a tetravalent connection portion according to one of the following formulas (14) and (15):

[0173] (11) (12) (13)

[0174] (14) (15)

[0175] (19) (20)

[0176] Where: each R h 、R' h R i and R' i Independently H or alkyl; and

[0177] R k 、R' k and R'' k Independently alkylene.

[0178] In a preferred embodiment, segment a) corresponds to one of the following structures (A3) to (A5):

[0179] (A3) (A4)

[0180] (A5)

[0181] Among the symbols This indicates the connection point with link segment c).

[0182] In the present invention, the total amount of chain segment a) in the dual-curable oligomer can account for 5 to 60% by weight of the total weight of the dual-curable oligomer, particularly 10 to 50% by weight, and even more particularly 15 to 40% by weight.

[0183] Chain segment b)

[0184] The dual-curable oligomer of the present invention comprises a segment containing at least one epoxy group, also referred to as segment b). Segment b) is connected to segment c). Segment b) is different from segments a) and c). Therefore, segment b) may not contain any olefinic unsaturation, and segment b) may not contain any urethane bonds. The dual-curable oligomer of the present invention may comprise a single segment b).

[0185] The epoxy group of segment b) may be selected from glycidyl ether group, glycidyl ester group, and epoxy group that is not part of glycidyl ether group or glycidyl ester group. Segment b) may contain a mixture of glycidyl ether group and glycidyl ester group.

[0186] As used herein, the term "glycidyl ether group" refers to the group of formula (21):

[0187] (twenty one).

[0188] As used herein, the term "glycidyl ester group" refers to the group of formula (22):

[0189] (twenty two).

[0190] In particular, segment b) can have the structure of formula (B1):

[0191] (B1)

[0192] in:

[0193] b is at least 1;

[0194] R4 is the (b+1) valence connection part;

[0195] Each R5 is independently selected from direct bond, -O-CH2-# and -C(=O)-O-CH2-#, with -O-CH2-# being preferred;

[0196] The symbol # indicates the connection point with the epoxide ring;

[0197] The symbol § indicates the connection point with chain segment c).

[0198] In equation (B1), b is at least 1. In particular, b can be 1, 2, 3 or 4, more particularly b is 2 or 3, and even more particularly b is 2.

[0199] In formula (B1), R4 is a (b+1) valence linking portion. Specifically, R4 can be a (b+1) valence linking portion selected from alkylene, heteroatom-containing alkylene, cycloalkylene, heterocycloalkylene, aryl, heteroaryl, and combinations thereof. More specifically, R4 can be a (b+1) valence linking portion selected from alkylene, heteroatom-containing alkylene, cycloalkylene, aryl, and combinations thereof.

[0200] In formula (B1), each R5 is independently selected from a straight bond, -O-CH2-#, and -C(=O)-O-CH2-#. When R5 is -O-CH2-#, segment b) contains a glycidyl ether group. When R5 is -C(=O)-O-CH2-#, segment b) contains a glycidyl ester group. When R5 is a straight bond, segment b) contains an epoxy group that is not part of a glycidyl ether group or a glycidyl ester group. In particular, each R5 can be -O-CH2-#.

[0201] More specifically, segment b) may have the structure of formula (B2), (B3), (B4), or (B5):

[0202] (B2) (B3)

[0203] (B4) (B5)

[0204] in:

[0205] - R5, b, and the symbol § are defined above;

[0206] - Ar is the (b+1) valence aromatic linkage part;

[0207] - Al is the (b+1) valence aliphatic linkage;

[0208] - Ar It is the divalent aromatic linkage; and

[0209] - Al It is a divalent aliphatic linker.

[0210] In formula (B2), Ar is the aromatic linking moiety. In particular, Ar may contain at least one arylene moiety, more particularly at least one optionally substituted phenylene moiety, and even more particularly the phenylene moiety optionally substituted by one or more groups selected from alkyl, cycloalkyl, aryl, and halogen atoms.

[0211] For example, Ar can correspond to one of the following formulas (6) to (15):

[0212] (6) (7) (8)

[0213] (9) (10) (11)

[0214] (12) (13) (14) (15)

[0215] in:

[0216] Each Ph is independently a divalent phenylene with optional substitution, preferably a divalent phenylene with optional substitution by one or more groups selected from alkyl, cycloalkyl, aryl and halogen atoms;

[0217] Each Ph The trivalent phenylene is independently substituted, preferably a trivalent phenylene that is optionally substituted by one or more groups selected from alkyl, cycloalkyl, aryl and halogen atoms;

[0218] Each Alk is independently a divalent alkylene or a heteroatom-containing alkylene;

[0219] Each Alk Independently a trivalent alkylene group or an alkylene group containing heteroatoms;

[0220] L is selected from direct-connected bonds, -O-, -S-, -SO-, -SO2-, -C(=O)-, C(=CCl2)-, Alk, -CR'1R'2-, -C(=O)-O-Alk-OC(=O)-, -CR'3R'4-Ph-CR'5R'6- and their combinations;

[0221] in:

[0222] Alk and Ph are defined as above;

[0223] R'1 and R'2 are independently selected from H, alkyl, cycloalkyl, aryl, haloalkyl and perfluoroalkyl, or R'1 and R'2 can form a ring with the carbon atom to which they are attached;

[0224] R'3, R'4, R'5, and R'6 are independently selected from H, alkyl, cycloalkyl, aryl, haloalkyl, and perfluoroalkyl.

[0225] In particular, Ar can be represented by one of the following equations (16) to (21):

[0226] in:

[0227] L is as defined above;

[0228] R e 、R' e and R'' e Independently selected from H, alkyl, cycloalkyl, aryl, alkylaryl, aralkyl, alkoxy, -C(=O)O-alkyl and halogen atoms;

[0229] R f It is H or methyl;

[0230] Each a' and c' is independently 0 or 1;

[0231] b' is 1 or 2.

[0232] In particular, Ar can be represented by one of equations (16) or (17) as defined above, preferably by equation (16).

[0233] More specifically, Ar can correspond to the optionally substituted aromatic polyol Ar OH The residues (excluding OH groups) of the aromatic polyol may optionally be substituted with one or more groups selected from alkyl, cycloalkyl, aryl, and halogen atoms. For example, Ar may be an optionally substituted aromatic polyol containing 1 to 3, preferably 1 or 2, aromatic rings. OH The residues. In particular, Ar can be selected from optionally substituted aromatic diols, such as catechol, resorcinol, cardiotonic phenol, (hydroxymethyl)phenol, benzyl alcohol, bisphenols (e.g., bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol C2, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, bisphenol Z, dinitrobisphenol A or tetrabromobisphenol A) or biphenyl diols; optionally substituted aromatic triols, such as phloroglucinol, pyroglucinol, tris(hydroxyphenyl)methane or tris(hydroxyphenyl)ethane; condensation products of optionally substituted aromatic alcohols and formaldehyde (also known as phenolic varnishes); alkoxylated derivatives of the above polyols; and esterified derivatives of the above polyols.

[0234] In formula (B3), Al is an aliphatic linking moiety. In particular, Al can be an aliphatic linking moiety selected from alkylene, heteroatom-containing alkylene, cycloalkylene, heterocycloalkylene, and combinations thereof.

[0235] For example, Al can be represented by one of the following equations (22) to (29):

[0236] in

[0237] -L is defined above for the connector Ar;

[0238] - Each Cy is independently a optionally substituted divalent cycloalkyl or heteroalkylene group, preferably a divalent cycloalkyl or heteroalkylene group optionally substituted by one or more groups selected from alkyl, cycloalkyl, aryl and halogen atoms;

[0239] - Each Cy Independently, it is an optionally substituted trivalent cycloalkyl or heterocyclic alkyl group, preferably a trivalent cycloalkyl or heterocyclic alkyl group optionally substituted by one or more groups selected from alkyl, cycloalkyl, aryl and halogen atoms;

[0240] - Each Alk is independently a divalent alkylene or a heteroatom-containing alkylene;

[0241] - Each Alk Independently a trivalent alkylene group or an alkylene group containing heteroatoms;

[0242] - Each Alk It is independently a tetravalent alkylene or an alkylene containing heteroatoms.

[0243] Specifically, Al can be represented by one of equations (30) to (41):

[0244] in

[0245] L is defined above for the connecting part Ar;

[0246] R' e As defined in equation (17) above;

[0247] Each R g 、R' g R h R i and R' i Independently H or alkyl;

[0248] Each R j Independently, it can be H, alkyl, cycloalkyl, aryl, alkylaryl, aralkyl, alkoxy, -C(=O)O-alkyl, or a halogen atom;

[0249] R k 、R' k and R'' k Independently alkylene;

[0250] d' is 1 to 12;

[0251] Each e' and f' is independently 0 or 1.

[0252] More specifically, Al may correspond to a residue (excluding an OH group) of an optionally substituted aliphatic polyol. The aliphatic polyol may optionally be substituted with one or more groups selected from alkyl, cycloalkyl, and halogen atoms. For example, Al may be an optionally substituted aliphatic polyol selected from optionally substituted aliphatic diols. OH The residues, wherein the optionally substituted aliphatic diols are such as ethylene glycol, 1,2- or 1,3-propanediol, di-, tri- or tetra-(1,2-propanediol), di-, tri- or tetra-(1,3-propanediol), 1,2-, 1,3- or 1,4-butanediol, di-, tri- or tetra-(1,4-butanediol), 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol 1,10-Decanediol, 1,12-Dodecanediol, 2-Methyl-1,3-propanediol, Neopentyl glycol, 2,2-Diethyl-1,3-propanediol, 2-Methyl-2-ethyl-1,3-propanediol, 3-Methyl-1,5-pentanediol, 3,3-Dimethyl-1,5-pentanediol, 2,4-Diethyl-1,5-pentanediol, 3-Butyl-3-ethyl-1,5-pentanediol, 2,2,4- Trimethyl-1,5-pentanediol, cyclohexanediol, cyclohexane-1,4-diethanol, norbornanediethanol, tricyclodecanediol, tricyclodecanediethanol, hydrogenated bicyclodecanediethanol, hydrogenated bisphenols (e.g., hydrogenated bisphenol A, hydrogenated bisphenol AP, hydrogenated bisphenol AF, hydrogenated bisphenol B, hydrogenated bisphenol BP, hydrogenated bisphenol C, hydrogenated bisphenol C2, hydrogenated bisphenol F, hydrogenated bisphenol G, hydrogenated bisphenol M, hydrogenated bisphenol S, hydrogenated bisphenol P, hydrogenated bisphenol PH, hydrogenated bisphenol TMC, hydrogenated bisphenol Z, hydrogenated dinitrobisphenol A, or hydrogenated tetrabromobisphenol A), dihydrohexitols (i.e., isosorbide, isomannitol, iso-idyl alcohol), or hydrogenated dimer fatty acids (i.e., diols obtained by dimerizing one or more unsaturated fatty acids such as oleic acid or linoleic acid and then hydrogenating the resulting product to convert the carboxylic acid group to a hydroxyl group, such as Pripol® from Croda). 2033); optionally substituted triols, such as trimethylolmethane, trimethylolethane, trimethylolpropane, glycerol, hydroxylated vegetable oils or tri(2-hydroxyalkyl)isocyanurate; optionally substituted tetraols, such as di(trimethylolpropane) or pentaerythritol; alkoxylated derivatives of the above polyols; and esterified derivatives of the above polyols (e.g., derivatives obtained by ring-opening polymerization of ε-caprolactone initiated with one of the above polyols).

[0253] In equation (B4), Ar It is the aramid bivalent connective. Specifically, Ar... It may contain at least one arylene moiety, more particularly at least one optionally substituted phenylene moiety, and even more particularly at least one phenylene moiety optionally substituted by one or more groups selected from alkyl, cycloalkyl, aryl and halogen atoms.

[0254] For example, Ar This can correspond to one of the equations (6) to (9) defined above. Specifically, Ar It can be represented by one of the above-defined equations (16) or (17), preferably by equation (16).

[0255] More specifically, Ar This can correspond to the residues (excluding OH groups) of an optionally substituted aromatic diol. The aromatic diol may optionally be substituted with one or more groups selected from alkyl, cycloalkyl, aryl, and halogen atoms. For example, Ar... It can be residues of an optionally substituted aromatic diol containing one to three, preferably one or two, aromatic rings, such as Ar as shown above. OH The defined substituted aromatic diols.

[0256] In equation (B5), Al It is the aliphatic divalent linkage. Specifically, Al It can be an aliphatic divalent linkage selected from alkylene, heteroatom-containing alkylene, cycloalkylene, heterocycloalkylene, and combinations thereof.

[0257] For example, Al It can be represented by one of the equations (22) to (26) as defined above. In particular, Al It can be represented by the formulas (1), (2), (3), (4), (5), (30), (31), (36), (37), (38) or (41) as defined above.

[0258] More specifically, Al This can correspond to the residues of an optionally substituted aliphatic diol (excluding the OH group). The aliphatic diol can optionally be substituted with one or more groups selected from alkyl, cycloalkyl, and halogen atoms. For example, Al... These can be residues of an optionally substituted aliphatic diol, such as Al as shown above. OH The defined optional substituted aliphatic diols.

[0259] In a preferred embodiment, segment b) has the structure of formula (B4) as defined above, and Ar It is represented by the following formula (16):

[0260] (16)

[0261] in:

[0262] - Each R e Independently selected from H, alkyl, cycloalkyl, aryl, alkylaryl, aralkyl, alkoxy, -C(=O)O-alkyl and halogen atoms, preferably selected from H and alkyl;

[0263] - Each a' is independently 0 or 1, preferably 0.

[0264] In a preferred embodiment, segment b) corresponds to formula (B6) or (B7), preferably (B6):

[0265] (B6)

[0266] (B7)

[0267] in:

[0268] -t-Bu is tert-butyl;

[0269] -R1 is H or methyl;

[0270] - The symbol § indicates the connection point with link segment c).

[0271] In a particularly preferred embodiment, segment b) corresponds to equation (B6).

[0272] In the present invention, the total amount of chain segment b) in the dual-curable oligomer can account for 20 to 90% by weight of the total weight of the dual-curable oligomer, particularly 30 to 85% by weight, and even more particularly 40 to 80% by weight.

[0273] Chain segment c)

[0274] The dual-curable oligomer of the present invention comprises a segment containing at least one urethane bond, also referred to as segment c). Segment c) is connected to segments a) and b). Therefore, segment c) is located between segments a) and b). Segment c) is different from segments a) and b). Therefore, segment c) may not contain any olefinic unsaturation, and segment c) may not contain any epoxy groups. The dual-curable oligomer of the present invention may comprise a single segment c).

[0275] In particular, segment c) can have the structure of formula (C1):

[0276] (C1)

[0277] in:

[0278] -c is 0 or 1;

[0279] -U corresponds to equation (U1) or (U2):

[0280] (U1)

[0281] (U2)

[0282] in:

[0283] - Each R7 is an independent residue of diisocyanate;

[0284] - Each R7' is independently a triisocyanate residue;

[0285] - Each R8 is an independent residue of a diol;

[0286] - Each d is independently 0 or an integer from 1 to 10;

[0287] -symbol Indicates the connection point with link segment a);

[0288] - The symbol § indicates the connection point with link segment b).

[0289] In formula (U1), each R7 is independently a diisocyanate residue (without an NCO group). Specifically, each R7 may be independently selected from one of formulas (42) to (51):

[0290] in:

[0291] - Each Alk' is independently a straight-chain or branched alkylene, particularly methylene, 1,2-ethylene, 1,2- or 1,3-propylene, 1,2-, 1,3- or 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 2,2,4- or 2,4,4-trimethylhexylene, 1,8-octylene, 1,9-nonylene, 1,10-decylene, 1,12-dodecylene, 1,18-octadecylene;

[0292] - Each Ar' is independently an optionally substituted arylene, particularly an optionally substituted arylene selected from phenylene, tolyne, biphenylene, naphthylene, anthracene, and more particularly an arylene optionally substituted by one or more groups selected from alkyl, cycloalkyl, aryl, and halogen atoms.

[0293] - Each Cy' is independently an optionally substituted cycloalkylene, particularly an optionally substituted cyclohexylene, and even more particularly a cycloalkylene optionally substituted with one or more groups selected from alkyl, cycloalkyl, aryl and halogen atoms.

[0294] In formula (U2), each R7' can independently correspond to a triisocyanate residue (excluding the -NCO group). Specifically, each R7' can independently be selected from one of formulas (52) to (58):

[0295]

[0296] in

[0297] - Each Alk'' is independently a straight-chain or branched alkylene group, particularly methylene, methanetriyl, undecane-1,6,11-triyl;

[0298] - Each Ar'' is independently an optionally substituted arylene, particularly an optionally substituted arylene selected from phenylene, tolyne and biphenylene, and more particularly an arylene optionally substituted by one or more groups selected from alkyl, cycloalkyl, aryl and halogen atoms;

[0299] - Each R7 is independently defined as above for formula (U1), in particular 1,6-hexamethylene.

[0300] In a preferred embodiment, U can be selected from:

[0301] - A portion of equation (U1), wherein each R7 is independently selected from one of equations (42), (44), (46), (49), or (50) as defined above:

[0302] in

[0303] Each Alk' is independently a straight-chain or branched alkylene, particularly methylene, 1,2-ethylene, 1,2- or 1,3-propylene, 1,2-, 1,3- or 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 2,2,4- or 2,4,4-trimethylhexylene, 1,8-octylene, 1,9-nonylene, 1,10-decylene, 1,12-dodecylene, 1,18-octadecylene;

[0304] Each Cy' is independently an optionally substituted cycloalkylene group, particularly an optionally substituted cyclohexylene group, and even more particularly a cycloalkylene group optionally substituted by one or more groups selected from alkyl, cycloalkyl, aryl and halogen atoms;

[0305] -(U2) portion, wherein R7 corresponds to formula (57) as defined above, wherein each R7 is independently a straight-chain or branched alkylene, particularly 1,6-hexene;

[0306] And their mixtures.

[0307] In formulas (U1) and (U2), each R8 is independently a residue of a diol (without an OH group). In particular, each R8 may independently correspond to a divalent linker selected from one of formulas (1) to (5) as defined above for R3.

[0308] More specifically, each R8 can be an independent residue of a polymeric diol or a non-polymeric diol.

[0309] As used herein, the term "polymeric glycol" refers to a polymer having two isocyanate-reactive hydroxyl groups per molecule. As used herein, the term "non-polymeric glycol" refers to a non-polymeric compound having two isocyanate-reactive hydroxyl groups per molecule. In the context of this invention, the term "polymer" refers to a compound containing five or more repeating units per molecule, and the term "non-polymeric compound" refers to a compound containing at most four repeating units per molecule (and therefore both monomeric and oligomeric compounds containing 2 to 4 repeating units per molecule). For example, ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol are examples of non-polymeric glycols, while polyethylene glycol containing five or more oxoalkylene repeating units is an example of a polymeric glycol.

[0310] The molecular weight of the residues in a polymeric glycol can be varied as needed or desired to achieve specific properties in a dual-curable oligomer. The number-average molecular weight of the residues in the polymeric glycol can be at least 300, at least 350, or at least 400 g / mol. The number-average molecular weight of the residues in a polymeric glycol can be less than 5000, less than 4500, or less than 4000 g / mol. For example, the number-average molecular weight of a polymeric glycol can be from 300 to 5000 g / mol, 350 to 4500 g / mol, or 400 to 4000 g / mol.

[0311] The polymeric part of a polymeric polyol may contain multiple repeating units, such as oxoalkylene units, ester units, carbonate units, acrylic units, alkylene units, or combinations thereof.

[0312] In one embodiment, each R8 may independently be a residue of a polymeric diol selected from residues of polyether diols, polyester diols, polycarbonate diols, polyorganosiloxane diols (e.g., residues of polydimethylsiloxane diol), or residues of polydiened diols including fully or partially hydrogenated polydiened diols (e.g., residues of polybutadiene diol).

[0313] Specifically, each R8 may independently be a residue of a polyether glycol or a polyester glycol. More specifically, each R8 may independently be a residue of a polyether glycol selected from polyethylene glycol, poly(1,2-propanediol), poly(1,3-propanediol), poly(1,4-butanediol), and combinations thereof, or a residue of a polyester glycol selected from poly(caprolactone), poly(lactide), poly(alkylene glycol adipate), and poly(alkylene glycol succinate).

[0314] In another embodiment, each R8 may be independently a residue selected from nonpolymerized polyols that are nonpolymerized aliphatic diols and nonpolymerized aromatic diols.

[0315] Suitable examples of non-polymerized aliphatic diols include Al, as mentioned above. OH Defined.

[0316] In the present invention, the total amount of chain segment c) in the dual-curable oligomer can account for 3 to 60% by weight of the total weight of the dual-curable oligomer, particularly 4 to 40% by weight, and even more particularly 5 to 20% by weight.

[0317] Structure of dual-curable oligomers

[0318] The dual-curable oligomer of the present invention may have the structure of formula (I):

[0319] (I)

[0320] Where a, b, c, R1, R2, R3, R4, R5 and U are as defined above.

[0321] Preferably, each R2 is -C(=O)-O-, and the dual-curable oligomer of the present invention has the structure of formula (II):

[0322] (II)

[0323] Where a, b, c, R1, R3, R4, R5 and U are as defined above.

[0324] In one embodiment, c is 0, and the dual-curable oligomer has the structure of formula (III):

[0325] (III)

[0326] Where a, b, R1, R3, R4 and R5 are defined as above.

[0327] In particular, the dual-curable oligomers may have structures of formula (IIIa), (IIIb), (IIIc), or (IIId):

[0328] (IIIa)

[0329] (IIIb)

[0330] (IIIc)

[0331] (IIId)

[0332] Where a, b, R1, R3, R5, Ar, Al, Ar And Al As defined above.

[0333] More specifically, dual-curable oligomers can have a structure of formula (IIIe):

[0334] (IIIe)

[0335] Where a, R1, R3, and t-Bu are defined as above.

[0336] In another embodiment, c is 1, U is according to formula (U1) or (U2), and the dual-curable oligomer of the present invention has the structure of formula (IV) or (V):

[0337] (IV)

[0338] (V)

[0339] Where a, b, d, R1, R3, R4, R5, R7 and R8 are defined as above.

[0340] In particular, dual-curable oligomers may have structures of formula (IVa), (IVb), (IVc), or (IVd):

[0341]

[0342] in:

[0343] Where a, b, d, R1, R3, R5, R7, R8, Ar, Al, Ar And Al As defined above.

[0344] More specifically, dual-curable oligomers can have a structure of formula (IVe):

[0345]

[0346] in:

[0347] Where a, d, R1, R3, R7, R8 and t-Bu are as defined above.

[0348] Segments a), b), and c), and groups R1 to R8 are defined below in conjunction with a method for preparing such oligomers, particularly with respect to the raw materials used in preparing such oligomers. All elements described in conjunction with these raw materials apply to the dual-curable oligomers of the present invention.

[0349] Method for preparing dual-curable oligomers

[0350] The method for preparing the dual-curable oligomer of the present invention comprises the following steps:

[0351] - To react the olefinically unsaturated monoisocyanate component with the epoxy monohydric alcohol component; or

[0352] - React the olefinically unsaturated monohydric alcohol component, the polyisocyanate component, the epoxy monohydric alcohol component, and the optional diol component.

[0353] The olefinically unsaturated monoisocyanate component comprises at least one compound having at least one degree of olefinic unsaturation and a single NCO group or a terminal NCO group. The epoxy monohydric alcohol component comprises at least one compound having at least one epoxy group and a single hydroxyl group, preferably a single secondary hydroxyl group. The olefinically unsaturated monohydric alcohol component comprises at least one compound having at least one degree of olefinic unsaturation and a single OH group. The polyisocyanate component comprises at least one compound having at least two NCO groups or terminal NCO groups. The diol component comprises at least one compound having two hydroxyl groups.

[0354] In one embodiment, the method may include the step of reacting an olefinically unsaturated monoisocyanate component comprising at least one compound having the structure of formula (A) with an epoxy monohydric alcohol component comprising at least one compound having the structure of formula (B):

[0355]

[0356] in:

[0357] a, b, R1, R2, R3, R4, and R5 are defined as in the above description of chain segments a) and b);

[0358] X1 is an NCO group or a capped NCO group;

[0359] X2 is a hydroxyl group, preferably a secondary hydroxyl group.

[0360] This method provides dual-curable oligomers having structures as defined above (III), particularly structures as defined above (IIIa), (IIIb), (IIIc) or (IIId), and even more particularly structures as defined above (IIIe).

[0361] The amounts of (A) and (B) can vary depending on the desired properties of the curable composition. For example, the equimolar ratio range of [OH groups of (B)] / [NCO groups of (A)] can be 1 / 2 to 2 / 1, or 1 / 1.5 to 1.5 / 1, or 1 / 1.1 to 1.1 / 1, or 1.05 / 1 to 1.05 / 1, or about 1 / 1.

[0362] In another embodiment, the method may include the step of reacting an olefinically unsaturated monohydric alcohol component comprising at least one compound having a structure of formula (D), a polyisocyanate component comprising at least one compound having a structure of formula (E1) or (E2), an epoxy monohydric alcohol component comprising at least one compound having a structure of formula (B), and optionally a diol component comprising at least one compound having a structure of formula (F):

[0363]

[0364] in:

[0365] -a, b, R1, R2, R3, R4, R5, R7, R7' and R8 are defined above for chain segments a), b) and c);

[0366] - Each X3 is an NCO group or a capped NCO group;

[0367] -X2 is a hydroxyl group, preferably a secondary hydroxyl group.

[0368] This method provides dual-curable oligomers having structures as defined above (IV) or (V), particularly structures as defined above (IVa), (IVb), (IVc) or (IVd), and even more particularly structures as defined above (IVe).

[0369] The amounts of (D), (E1), (E2), (F), and (B) can vary depending on the desired properties of the curable composition. For example, the equimolar ratio range [OH groups of (D) + OH groups of (B) + OH groups of (F)] / [NCO groups of (E1) or (E2)] can be 1 / 2 to 2 / 1, or 1 / 1.5 to 1.5 / 1, or 1 / 1.1 to 1.1 / 1, or 1.05 / 1 to 1.05 / 1, or about 1 / 1.

[0370] The method may include mixing all reactants and components substantially simultaneously in a "one-step" manner, with or without the addition of other ingredients and optional additives, or adding reactants stepwise. The reaction may be carried out in bulk or in solution, with or without the addition of a carbamate catalyst that promotes the reaction of isocyanates with alcohols.

[0371] The reaction can be carried out in an organic solvent, but preferably in the presence of less than 5% by weight of the solvent, or even more preferably in the absence of an organic solvent, for example by melt extrusion at temperatures from 60°C to 250°C, or for example, from 65°C to 200°C or from 70°C to 150°C. When such a solvent is used, it is typically used in an amount of less than 5% by weight based on the total weight of the components involved in the reaction. For example, the amount of solvent used is less than 4% by weight, less than 3% by weight, less than 2% by weight, less than 1% by weight, and less than 0.5% by weight. When the reactants are in solid form (e.g., powder form), the solvent can be used, for example, at the beginning of the reaction to promote homogeneous mixing of the components. The solvent can be equivalently referred to herein as a diluent. If a solvent is used, a low-viscosity / high-boiling-point liquid is preferred. The solvent may preferably contain epoxy functional groups and / or allyl / vinyl / acrylate groups.

[0372] Epoxy Monohydric Alcohol Components

[0373] The epoxy monohydric alcohol component comprises or is composed of at least one epoxy monohydric alcohol. The epoxy monohydric alcohol component may comprise or be composed of a mixture of epoxy monohydric alcohols.

[0374] An epoxy monohydric alcohol is a compound having at least one epoxy group and a single hydroxyl group, preferably a single secondary hydroxyl group. An epoxy monohydric alcohol may contain 1, 2, 3, or 4 epoxy groups, particularly 2 or 3 epoxy groups, and more particularly 2 epoxy groups. Each epoxy group may be independently selected from glycidyl ether groups, glycidyl ester groups, and epoxy groups that are not part of a glycidyl ether group or a glycidyl ester group. An epoxy monohydric alcohol may contain a mixture of glycidyl ether groups and glycidyl ester groups.

[0375] In particular, the epoxy monohydric alcohol component may contain at least one compound having the structure of formula (B):

[0376] (B)

[0377] in:

[0378] -b, R4, and R5 are defined as above for chain segment b);

[0379] -X2 is a hydroxyl group, preferably a secondary hydroxyl group.

[0380] All preferred embodiments of R4, R5 and b described above for segment b) are also applicable to compounds of formula (B).

[0381] In particular, the epoxy monohydric alcohol component may comprise at least one compound having the structure of formula (B2a), (B3a), (B4a), or (B5a):

[0382]

[0383] in:

[0384] -R5, X2, and b are defined as above;

[0385] -Ar, Al, Ar And Al As defined above for chain segment b) of equations (B2), (B3), (B4), or (B5).

[0386] The above refers to Ar, Al, and Ar as described in segment b). And Al All preferred embodiments are equally applicable to compounds of formulas (B2a), (B3a), (B4a), and (B5a).

[0387] More specifically, the epoxy monohydric alcohol component may contain at least one compound selected from: glycidyl, ethylene glycol monoglycidyl ether, 1,2- or 1,3-propanediol monoglycidyl ether, 1,2-, 1,3- or 1,4-butanediol monoglycidyl ether, 1,5-pentanediol monoglycidyl ether, 1,6-hexanediol monoglycidyl ether, 1,8-octanediol monoglycidyl ether, 1,9-nonanediol monoglycidyl ether, 1,10-decanediol monoglycidyl ether, 1,12-dodecane. Glyceryl ether monoglycidyl ether, 2-methyl-1,3-propanediol monoglycidyl ether, neopentyl glycol monoglycidyl ether, 2,2-diethyl-1,3-propanediol monoglycidyl ether, 3-methyl-1,5-pentanediol monoglycidyl ether, 3,3-dimethyl-1,5-pentanediol monoglycidyl ether, 2,4-diethyl-1,5-pentanediol monoglycidyl ether, 3,3-butylethyl-1,5-pentanediol monoglycidyl ether, glycerol diglycidyl ether, diglycerol triglycidyl ether, tri- Hydroxymethylmethane diglycidyl ether, trimethylolethane diglycidyl ether, trimethylpropane diglycidyl ester, di(trimethylolpropane)triglycidyl ether, pentaerythritol triglycidyl ether, cyclohexanedicarboxylic acid monoglycidyl ester, 1,2-, 1,3- or 1,4-cyclohexane monoglycidyl ether, cyclohexane-1,2, 1,3 or 1,4-diethanol monoglycidyl ether, tricyclodecanediethanol monoglycidyl ether, isosorbide monoglycidyl ether, catechol monoglycidyl ether, isophthalic acid... Phenolic monoglycidyl ether, cardiac phenolic monoglycidyl ether, phloroglucinol diglycidyl ether, pyroglucinol diglycidyl ether, tris(hydroxyphenyl)methane diglycidyl ether, tris(hydroxyphenyl)ethane diglycidyl ether, epoxidized diglyceride, isocyanuric acid diglycidyl ether, bisphenol monoglycidyl ether (wherein bisphenol is as defined above), hydrogenated bisphenol monoglycidyl ether, tert-butylcatechol dimer diglycidyl ether of formula (B6a), bisphenol dimer diglycidyl ether of formula (B7a), and combinations thereof.

[0388] (B6a)

[0389] (B7a)

[0390] Among them, t-Bu and R l As defined above in equations (B6) and (B7).

[0391] Preferably, the epoxy monohydric alcohol component comprises a compound according to formula (B6a). This product is available from DIC Corporation as EPICLON® HP-820.

[0392] olefinic unsaturated monoisocyanate components

[0393] The olefinically unsaturated monoisocyanate component comprises or consists of at least one olefinically unsaturated monoisocyanate. The olefinically unsaturated monoisocyanate component may comprise or consist of a mixture of olefinically unsaturated monoisocyanates.

[0394] An olefinically unsaturated monoisocyanate is a compound having at least one olefinically unsaturated degree and a single NCO group or a capped NCO group. An olefinically unsaturated monoisocyanate may contain at least one olefinically unsaturated degree, which is part of a functional group selected from acrylate functional groups, methacrylate functional groups, acrylamide functional groups, methacrylamide functional groups, vinyl groups, vinyl ether groups, allyl groups, and allyl ether groups.

[0395] Specifically, olefinically unsaturated monoisocyanates may contain at least one (meth)acrylate group, such as 1, 2, 3, 4, 5, or 6 (meth)acrylate groups. Olefinically unsaturated monoisocyanates may contain a mixture of acrylate functional groups and methacrylate functional groups.

[0396] The olefinic unsaturated monoisocyanate component may contain at least one compound having the structure of formula (A):

[0397] (A)

[0398] in:

[0399] -a, R1, R2, and R3 are defined as in chain segment a) above.

[0400] -X1 is an NCO group or a capped NCO group.

[0401] In particular, the olefinically unsaturated monoisocyanate component may contain at least one compound having the structure of formula (A2a):

[0402] (A2a)

[0403] in:

[0404] -a, R1, and R3 are defined as in the above for chain segment a);

[0405] -X1 is an NCO group or a capped NCO group.

[0406] In such an embodiment, the olefinic unsaturated monoisocyanate component comprises at least one compound having at least one acrylate functional group and / or at least one methacrylate functional group.

[0407] All preferred embodiments of a, R1, R2 and R3 described above for segment a) are also applicable to compounds of formula (A) and (A2a).

[0408] In formula (A) or (A2a), X1 is an NCO group or a capped NCO group. The chemical structure of the capped NCO group typically affects the effective temperature for oligomer production, as well as the volatile content and properties of the resin. It also typically affects the curing rate of the resin. In particular, the capped NCO group can be partially -NH-C(O)-OR 10 Or -NH-C(O)-N(R'10)2, where R 10 R'10 and R'10 are each independently (hetero)hydrocarbon groups, or two R' 10 The groups can form a ring with the nitrogen atom to which they are attached, such as optionally substituted pyrazoles.

[0409] In particular, the R in the capped NCO group 10 It includes one or more of the following parts: phenol, nonylphenol, methyl ethyl ketoxime (-N=C(Me)Et), hydroxyl, ε-caprolactam, amide, imidazole and / or pyrazole.

[0410] Preferably, the olefinic unsaturated monoisocyanate component comprises at least one compound selected from ethyl 2-isocyanate methacrylate (MOI), ethyl 2-isocyanate acrylate (AOI, AOI-VM), ethyl 2-(O-[1'-methylpropyleneamino]carboxyamino) methacrylate (MOI-BM), ethyl 2-[(3,5-dimethylpyrazolyl)carboxyamino] methacrylate (MOI-BP), 1,1-(bisacryloyloxymethyl)ethyl isocyanate (BEI), 2-[2-(methacryloyloxy)ethoxy]ethyl isocyanate (MOI-EG), and mixtures thereof.

[0411] olefinic unsaturated monohydric alcohol components

[0412] The olefinically unsaturated monohydric alcohol component comprises or consists of at least one olefinically unsaturated monohydric alcohol. The olefinically unsaturated monohydric alcohol component may comprise or consist of a mixture of olefinically unsaturated monohydric alcohols.

[0413] An olefinically unsaturated monohydric alcohol is a compound having at least one olefinically unsaturated degree and a single OH group. An olefinically unsaturated monohydric alcohol may contain at least one olefinically unsaturated degree, which is part of a functional group selected from acrylate functional groups, methacrylate functional groups, acrylamide functional groups, methacrylamide functional groups, vinyl groups, vinyl ether groups, allyl groups, and allyl ether groups.

[0414] Specifically, olefinically unsaturated monohydric alcohols may contain at least one (meth)acrylate group, such as 1, 2, 3, 4, 5, or 6 (meth)acrylate groups. olefinically unsaturated monoisocyanates may contain a mixture of acrylate functional groups and methacrylate functional groups.

[0415] The olefinic unsaturated monohydric alcohol component may contain at least one compound having the structure of formula (D):

[0416] (D)

[0417] Where a, R1, R2 and R3 are defined as in the above description of chain segment a).

[0418] In particular, the olefinic unsaturated monohydric alcohol component may contain at least one compound having the structure of formula (D1a):

[0419] (D1a)

[0420] in:

[0421] -a, R1, and R3 are defined as in the above for chain segment a).

[0422] In such an embodiment, the olefinic unsaturated monohydric alcohol comprises at least one acrylate functional group and / or at least one methacrylate functional group.

[0423] All preferred embodiments of a, R1, R2 and R3 described above for segment a) are also applicable to compounds of formula (D) and (D1a).

[0424] Preferably, the olefinically unsaturated monohydric alcohol component comprises at least one compound selected from: hydroxyalkyl methacrylates (e.g., 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, neopentyl glycol mono(meth)acrylate or 1,6-hexanediol mono(meth)acrylate), 2-hydroxy-3-phenoxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, tris(2-hydroxyethyl)isocyanurate di(meth)acrylate, di-, tri-, tetra- or polyethylene glycol mono(meth)acrylate, di-, tri-, tetra- or poly(1,2-propanediol) mono(meth)acrylate, di-, tri-, tetra- or poly(1,3-propanediol) mono(meth)acrylate, di-, tri-, tetra- or poly(1,3-propanediol) Mono(meth)acrylates, di-, tri-, tetra- or poly(1,4-butanediol) mono(meth)acrylates, glycerol di(meth)acrylates, 2-hydroxy-1-acryloyloxy-3-(meth)acryloyloxypropane, trimethylolpropane di(meth)acrylates, di(trimethylolpropane)tri(meth)acrylates, trimethylolethane di(meth)acrylates, pentaerythritol tri(meth)acrylates, dipentaerythritol penta(meth)acrylates, and their alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives and their (poly)caprolactone derivatives obtained by ring-opening polymerization of ε-caprolactone initiated with one of the above-mentioned hydroxyl-functionalized (meth)acrylate compounds (i.e., (poly)caprolactone (meth)acrylates, such as (poly)caprolactone 2-hydroxyethyl (meth)acrylates according to the following formula): CH2=CR 11 -C(=O)-O-CH2-CH2-[O-(C=O)-(CH2)5] t -OH, where R 11 It is H or methyl, t is 1-20), and combinations thereof.

[0425] In a preferred embodiment, the olefinic unsaturated monohydric alcohol component comprises pentaerythritol triacrylate.

[0426] Polyisocyanate components

[0427] The polyisocyanate component comprises or is composed of at least one polyisocyanate. The polyisocyanate component may comprise or be composed of a mixture of polyisocyanates.

[0428] Polyisocyanates are compounds containing at least two NCO groups or terminal NCO groups. Terminal NCO groups can be defined as olefinic unsaturated monoisocyanates as described above.

[0429] The polyisocyanate component may contain polyisocyanates with 2 or 3 NCO groups, preferably 2 NCO groups.

[0430] In particular, the polyisocyanate component may comprise a diisocyanate having the structure of formula (E1) and / or a triisocyanate having the structure of formula (E3):

[0431] (E1)

[0432] Compound (E2)

[0433] in:

[0434] -R7 and R7' are defined as in link segment c) above.

[0435] -X3 is an NCO group or a capped NCO group.

[0436] All preferred embodiments of R7 and R7' described above for segment c) are equally applicable to compounds of formulas (E1) and (E2).

[0437] Suitable examples of the diisocyanates according to formula (E1) include 2,4- and 2,6-toluene diisocyanate (TDI), isophorone diisocyanate (IPDI - corresponding to 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate), methylene diisocyanate, ethylene diisocyanate, 1,2- or 1,3-propylene diisocyanate, 1,2-, 1,3 or 1,4-butylene diisocyanate, 1,5-pentamethylene diisocyanate (PDI), 1,6-hexamethylene diisocyanate (HDI), 2,2,4- and 2,4,4-trimethylhexamethylene diisocyanate (TMDI), 1,10-decamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, 1,18-octadecamethylene diisocyanate, 2,2’-, 2,4’- and 4,4’-diphenylmethane diisocyanate (MDI), 2,2’-, 2,4’- and 4,4’-dicyclohexylmethane diisocyanate (H12MDI), benzidine diisocyanate, 3,3’-dimethyl-4,4’-biphenyl diisocyanate, dianisidine diisocyanate, 3,3’-dimethyl-4,4’-diphenylmethane diisocyanate, 1,3- and 1,4-phenylene diisocyanate, 1,4- and 1,5-naphthylene diisocyanate (NDI), 1,4- and 9,10-anthrylene diisocyanate, 1,3- and 1,4-cyclohexane diisocyanate, 1-methyl-2,4-diisocyanatocyclohexane, 1-methyl-2,6-diisocyanatocyclohexane, 1,3 and 1,4-bis(isocyanatomethyl)cyclohexane, m-tetramethylxylylene diisocyanate, m-xylylene diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-ethoxy-1,3-phenylene diisocyanate, 5,6-dimethyl-1,3-phenylene diisocyanate, 2,4’- or 4,4’-diisocyanate diphenyl ether, lysine diisocyanate, dimer acid diisocyanate, dimers of the foregoing diisocyanates (especially uretdione or urethane dimers), and polyurea or polyurethane prepolymers functionalized with isocyanate functional groups, and combinations thereof.

[0438] Suitable examples of the triisocyanates according to formula (E2) include 1,6,11-undecane triisocyanate, triphenylmethane triisocyanate, 2,4,6-toluene triisocyanate, 2,4,4’-triisocyanate diphenyl ether, trimers of the diisocyanates detailed above for formula (E1) (especially isocyanurate or biuret trimers), polymeric derivatives of the diisocyanates detailed above for formula (E1), and combinations thereof.

[0439] As used herein, the isocyanurate trimer of a diisocyanate of the formula O=C=N-R7-N=C=O corresponds to the following formula:

[0440]

[0441] R7 is defined as above.

[0442] As used in this article, the biuret trimer of the diisocyanate of formula O=C=N-R7-N=C=O corresponds to the following formula:

[0443]

[0444] R7 is defined as above.

[0445] Preferably, the polyisocyanate component comprises a diisocyanate, more preferably isophorone diisocyanate.

[0446] Optional diol components

[0447] The optional diol component comprises or consists of at least one diol. The diol component may comprise a mixture of diols or a composition thereof.

[0448] The diol contains two OH groups.

[0449] In particular, the diol component may contain a diol having the structure of formula (F):

[0450] (F)

[0451] R8 is defined as in link segment c) above.

[0452] All preferred embodiments of R8 described above for segment c) are also applicable to compounds of formula (F).

[0453] In particular, the diol component may contain at least one polymeric diol or at least one non-polymeric diol.

[0454] The diol component may contain at least one polymeric diol. Alternatively, the diol component may be substantially free of polymeric diols.

[0455] The molecular weight of the polyglycol can be varied as needed or desired to achieve specific properties in a dual-curable oligomer. The number-average molecular weight of the polyglycol can be at least 330 g / mol, at least 350 g / mol, or at least 400 g / mol. The number-average molecular weight of the polyglycol can also be less than 5000, less than 4500, or less than 4000 g / mol. For example, the number-average molecular weight of the polyglycol can be from 330 to 5000 g / mol, 350 to 4500 g / mol, or 400 to 4000 g / mol.

[0456] The polymer portion of a polydiol can contain a variety of repeating units, such as oxyalkylene units, ester units, carbonate units, acrylic units, alkylene units, etc., or combinations thereof.

[0457] In particular, the diol component may contain at least one polymeric diol selected from polyether diols, polyester diols, polycarbonate diols, polyorganosiloxane diols (e.g., polydimethylsiloxane diols), and polydienediols including fully or partially hydrogenated polydienediols (e.g., polybutadiene diols).

[0458] More specifically, the diol component may contain at least one polyether diol or at least one polyester diol.

[0459] More specifically, the diol component may include at least one polyether diol selected from polyethylene glycol, poly(1,2-propanediol), poly(1,3-propanediol) and poly(1,4-butanediol), or at least one polyester diol selected from poly(caprolactone), poly(lactide), poly(alkylene glycol adipate) and poly(alkylene glycol succinate).

[0460] The diol component may contain at least one non-polymerized diol. Alternatively, the diol component may be substantially free of non-polymerized diols.

[0461] In particular, the diol component may contain at least one non-polymeric aliphatic diol.

[0462] More specifically, the diol component may contain at least one of the following: Al (as described above) OH The defined non-polymerized aliphatic diol.

[0463] catalyst

[0464] The method for preparing dual-curable oligomers can be carried out in the presence of at least one catalyst.

[0465] Any catalyst known in the art for catalyzing the reaction of isocyanates with hydroxyl groups may be used herein. Such catalysts include organic and inorganic acid salts of bismuth, lead, tin, iron, antimony, uranium, cadmium, cobalt, thorium, aluminum, mercury, zinc, nickel, cerium, molybdenum, vanadium, copper, manganese, and zirconium, as well as organometallic derivatives, and phosphine and organic tertiary amines.

[0466] Representative organotin catalysts include stannous octoate, stannous oleate, dibutyltin dioctanoate, and dibutyltin dilaurate.

[0467] Suitable non-tin catalysts include, for example, one or more non-tin catalysts selected from the following: bismuth carboxylate complexes (such as bismuth octanoate or bismuth neodecanoate); zirconium acetylacetone complexes; hafnium acetylacetone complexes; titanium acetylacetone complexes; zirconium β-diketone imine complexes; hafnium β-diketone imine complexes; titanium β-diketone imine complexes; zirconium amidoyl complexes; hafnium amidoyl complexes; titanium amidoyl complexes; zinc carboxylate complexes; tertiary amines; imidazoles; N-heterocyclic carbenes; tetraalkylammonium (pseudo)halides; phosphine; and combinations thereof.

[0468] In some embodiments, the amount of catalyst used varies from 0.01 wt% to 2.0 wt%, for example from 0.02 wt% to 1.0 wt% or from 0.3 wt% to 0.8 wt%, based on the total weight of the reactants (i.e., isocyanates and alcohols).

[0469] stabilizer

[0470] The method for preparing dual-curable oligomers can be carried out in the presence of at least one stabilizer (e.g., an antioxidant, a light-blocking / absorbing agent, or a polymerization inhibitor). Alternatively, the method may not require the presence of a stabilizer.

[0471] Stabilizers can be used during the preparation of curable compositions to prevent undesirable reactions from occurring during the processing of the olefinically unsaturated components of the curable composition. Stabilizers can be compounds or substances that delay or prevent the reaction or curing of polymerizable functional groups present in the composition in the absence of radiation. However, it is advantageous to select the amount and type of stabilizer that allows the composition to remain curable upon exposure to radiation (i.e., the stabilizer does not prevent radiation curing of the composition). Stabilizers can in particular be free radical stabilizers (i.e., stabilizers that function by inhibiting free radical reactions).

[0472] Any stabilizers known in the art related to (meth)acrylate functionalized compounds may be used in this invention. Quinone indicates a particularly preferred type of inhibitor, which may be used in the context of this invention. As used herein, the term "quinone" includes quinones and hydroquinones, as well as their ethers, such as monoalkyl ethers, monoaryl ethers, monoarylalkyl ethers, and bis(hydroxyalkyl) ethers of hydroquinone. Hydroquinone monomethyl ether is an example of a suitable inhibitor that may be used. Other inhibitors known in the art include hydroquinone (HQ), 4-tert-butylcatechol (TBC), 3,5-di-tert-butyl-4-hydroxytoluene (BHT), phenothiazine (PTZ), pyrogallol, phosphite compounds, triphenylantimony, and tin(II) salts.

[0473] The concentration of the stabilizer used in the method of the present invention depends on the specific inhibitor or combination of inhibitors selected, the desired degree of inhibition, and the sensitivity of the components in the curable composition to degradation in the absence of inhibitors. In some embodiments of the invention, the reaction mixture during each stage of the method for preparing the curable composition contains at least some stabilizer, for example, at least 10 ppm, at least 100 ppm, or at least 1000 ppm. Based on the total weight of the components in the reaction, the total amount of stabilizer used during the reaction can be less than 5% by weight, less than 4% by weight, less than 3% by weight, or less than 2% by weight.

[0474] Curable Composition

[0475] The curable compositions of the present invention comprise at least one dual-curable oligomer as described herein.

[0476] Based on the total weight of the curable composition, the compositions of the present invention may contain 5% to 99.9% by weight of one or more dual-curable oligomers, such as 10% to 99.5% by weight, 20% to 99% by weight, 30% to 98% by weight, 50% to 97% by weight, or 60% to 95% by weight.

[0477] The composition may contain several different oligomers, such as two or more. In some embodiments, the composition comprises a mixture of oligomers with different segments a). In such embodiments, the composition may comprise a mixture of oligomers wherein a first oligomer (O1) such that segment a) comprises an α,β-unsaturated ester moiety, such as an acrylate functional group (-OC(O)-CH=CH2) or a methacrylate functional group (-OC(O)-C(CH3)=CH2), and a second oligomer (O2) such that segment a) comprises a vinyl group (-CH=CH2), a vinyl ether group (-O-CH=CH2), an allyl group (-CH2-CH=CH2), or an allyl ether group (-O-CH2-CH=CH2). The molar ratio O1:O2 may vary between 10:1 and 1:10, for example between 5:1 and 1:5, between 3:1 and 1:3, or between 2:1 and 1:2.

[0478] The curable compositions described in this article exhibit improved performance in terms of shelf-life stability.

[0479] The curable composition of the present invention may further comprise one or more of the following:

[0480] a. A polymerizable component comprising one or more olefinically unsaturated compounds and / or one or more cationically polymerizable compounds, in addition to the dual-curable oligomer;

[0481] b. Inhibitors;

[0482] c. Initiator, which is selected from free radical initiators, cationic initiators, and combinations thereof;

[0483] d. Epoxy crosslinking agent;

[0484] e. Additives selected from antioxidants, ultraviolet absorbers, light stabilizers, foam inhibitors, flow agents or leveling agents, colorants, pigments, dispersants (wetting agents), sliding additives, fillers, thixotropic agents, matting agents, waxes, and any additives and combinations thereof that are conventionally used in coatings, sealants, adhesives, inks or molding compositions.

[0485] polymerizable components

[0486] The curable composition of the present invention may contain polymerizable components.

[0487] The polymerizable component comprises or consists of one or more olefinically unsaturated compounds and / or one or more cationically polymerizable compounds.

[0488] The polymerizable component differs from the dual-curable oligomer of this invention.

[0489] The polymerizable component may contain one or more olefinically unsaturated compounds. In particular, the polymerizable component may contain one or more olefinically unsaturated compounds selected from (meth)acrylate-functionalized monomers, (meth)acrylate-functionalized oligomers, and mixtures thereof. In particular, the polymerizable component may contain one or more (meth)acrylate-functionalized monomers.

[0490] As used herein, the term "(meth)acrylate-functionalized monomer" refers to a monomer containing a (meth)acrylate group, particularly an acrylate group. The term "(meth)acrylate-functionalized oligomer" refers to an oligomer containing a (meth)acrylate group, particularly an acrylate group.

[0491] The polymerizable component may contain at least one (meth)acrylate-functionalized monomer. The polymerizable component may contain a mixture of (meth)acrylate-functionalized monomers.

[0492] The molecular weight of (meth)acrylate-functionalized monomers can be less than 600 g / mol, particularly 100 to 550 g / mol, and even more particularly 200 to 500 g / mol.

[0493] (Meth)acrylate functionalized monomers may have 1 to 6 (meth)acrylate groups, particularly 1 to 3 (meth)acrylate groups.

[0494] The polymerizable component may comprise a mixture of monomers functionalized with (meth)acrylates of different functionalities. For example, the polymerizable component may comprise a mixture of monomers functionalized with (meth)acrylates containing a single acrylate or methacrylate group per molecule (referred to herein as "mono(meth)acrylate functionalized compounds") and monomers functionalized with (meth)acrylates containing two or more, preferably two or three acrylate and / or methacrylate groups per molecule (referred to herein as "poly(meth)acrylate functionalized compounds").

[0495] In particular, the polymerizable component may contain mono(meth)acrylate-functionalized monomers. Mono(meth)acrylate-functionalized monomers can advantageously serve as reactive diluents and reduce the viscosity of the composition.

[0496] Examples of suitable mono(meth)acrylate functionalized monomers include, but are not limited to, mono(meth)acrylates of aliphatic alcohols (wherein the aliphatic alcohol may be linear, branched, or alicyclic, and may be a monohydric, dihydric, or polyhydric alcohol, provided that only one hydroxyl group is (meth)acrylated); mono(meth)acrylates of aromatic alcohols (such as phenols, including alkylated phenols); mono(meth)acrylates of alkylaryl alcohols (such as benzyl alcohol); and mono(meth)acrylates of oligomeric glycols and polymeric glycols (such as diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol, and polypropylene glycol). (Meth)acrylates; mono(meth)acrylates of monoalkyl ethers of glycols and oligomeric glycols; mono(meth)acrylates of alkoxylated (e.g., ethoxylated and / or propoxylated) aliphatic alcohols (wherein the aliphatic alcohol may be linear, branched or alicyclic, and may be a monohydric alcohol, dihydric alcohol or polyhydric alcohol, provided that only one hydroxyl group of the alkoxylated aliphatic alcohol is (meth)acrylated); mono(meth)acrylates of alkoxylated (e.g., ethoxylated and / or propoxylated) aromatic alcohols (such as alkoxylated phenols); caprolactone mono(meth)acrylates; etc.

[0497] The following compounds are specific examples of monomers suitable for mono(meth)acrylate functionalization in component B): methyl methacrylate; ethyl methacrylate; n-propyl methacrylate; n-butyl methacrylate; isobutyl methacrylate; n-hexyl methacrylate; 2-ethylhexyl methacrylate; n-octyl methacrylate; isooctyl methacrylate; n-decyl methacrylate; n-dodecyl methacrylate; tridecyl methacrylate; tetradecyl methacrylate; hexadecyl methacrylate; 2-hydroxyethyl methacrylate; 2-hydroxypropyl methacrylate and 3-hydroxypropyl methacrylate; 2-methoxyethyl methacrylate; 2-ethoxyethyl methacrylate; 2-ethoxypropyl methacrylate and 3-ethoxypropyl methacrylate; tetrahydrofurfuryl methacrylate; alkoxylated tetrahydrofurfuryl methacrylate; (methyl) 2-(2-ethoxyethoxy)ethyl acrylate; cyclohexyl (meth)acrylate; glycidyl (meth)acrylate; isodecanyl (meth)acrylate; lauryl (meth)acrylate; 2-phenoxyethyl (meth)acrylate; alkoxylated phenol (meth)acrylate; alkoxylated nonylphenol (meth)acrylate; cyclic trimethylolpropane acetal (meth)acrylate; isobornyl (meth)acrylate; tricyclodecane methanol (meth)acrylate; tert-butylcyclohexanol (meth)acrylate Acrylates; trimethylcyclohexanol (meth)acrylates; diethylene glycol monomethyl ether (meth)acrylates; diethylene glycol monoethyl ether (meth)acrylates; diethylene glycol monobutyl ether (meth)acrylates; triethylene glycol monoethyl ether (meth)acrylates; ethoxylated lauryl acrylate; methoxylated polyethylene glycol (meth)acrylates; hydroxyethyl-butylcarbamate (meth)acrylates; 3-(2-hydroxyalkyl)azolidinone (meth)acrylates; and combinations thereof.

[0498] The polymerizable component may contain poly(meth)acrylate-functionalized monomers.

[0499] Poly(meth)acrylate functionalized monomers may have 2 to 6 (meth)acrylate groups, especially 2 to 6 acrylate groups.

[0500] Examples of suitable poly(meth)acrylate functionalized monomers include acrylates and methacrylates of polyols. Examples of suitable polyols, as mentioned above, are Ar... OH And Al OH The listed polyols can be fully or partially esterified (using (meth)acrylic acid, (meth)acrylic anhydride, (meth)acryloyl chloride, etc.), provided that they contain at least two (meth)acrylate functional groups per molecule.

[0501] Exemplary poly(meth)acrylate functionalized monomers may include bisphenol A di(meth)acrylate; hydrogenated bisphenol A di(meth)acrylate; ethylene glycol di(meth)acrylate; diethylene glycol di(meth)acrylate; triethylene glycol di(meth)acrylate; tetraethylene glycol di(meth)acrylate; polyethylene glycol di(meth)acrylate; propylene glycol di(meth)acrylate; dipropylene glycol di(meth)acrylate; tripropylene glycol di(meth)acrylate; tetrapropylene glycol di(meth)acrylate; polypropylene glycol di(meth)acrylate; polytetramethylene glycol di(meth)acrylate; and polytetramethylene glycol di(meth)acrylate. (Meth)acrylates; 1,2-Butanediol di(meth)acrylate; 2,3-Butanediol di(meth)acrylate; 1,3-Butanediol di(meth)acrylate; 1,4-Butanediol di(meth)acrylate; 1,5-Pentanediol di(meth)acrylate; 1,6-Hexanediol di(meth)acrylate; 1,8-Octanediol di(meth)acrylate; 1,9-Nonanediol di(meth)acrylate; 1,10-Nonanediol di(meth)acrylate; 1,12-Dodecanediol di(meth)acrylate; Neopentylenediol di(meth)acrylate ; 2-Methyl-2,4-pentanediol di(meth)acrylate; polybutadiene di(meth)acrylate; cyclohexane-1,4-diethanol di(meth)acrylate; tricyclodecanediethanol di(meth)acrylate; metal di(meth)acrylate; modified metal di(meth)acrylate; glyceryl di(meth)acrylate; tri(meth)acrylate; trimethylolethane tri(meth)acrylate; trimethylolethane di(meth)acrylate; trimethylolpropane tri(meth)acrylate; trimethylolpropane di(meth)acrylate; pentaerythritol di( Methacrylates; pentaerythritol tri(meth)acrylates; pentaerythritol tetra(meth)acrylates, di(trimethylolpropane)diacrylates; di(trimethylolpropane)triacrylates; di(trimethylolpropane)tetraacrylates, sorbitol penta(meth)acrylates; di(pentaerythritol)tetraacrylates; di(pentaerythritol)pentaacrylates; di(pentaerythritol)hexa(meth)acrylates; tri(2-hydroxyethyl)isocyanurate tri(meth)acrylates; and their alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives; and combinations thereof.

[0502] In a preferred embodiment, the polymerizable component comprises at least one poly(meth)acrylate-functionalized monomer selected from glycerol tri(meth)acrylate; diglycerol tetra(meth)acrylate, triglycerol penta(meth)acrylate, tetraglycerol hexa(meth)acrylate, trimethylolethane tri(meth)acrylate; trimethylolpropane tri(meth)acrylate; pentaerythritol tetra(meth)acrylate, di(trimethylolpropane) tetraacrylate, sorbitol penta(meth)acrylate; di(pentaerythritol) hexa(meth)acrylate; tri(2-hydroxyethyl) isocyanurate tri(meth)acrylate, and their alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives, and combinations thereof.

[0503] Based on the total weight of the polymerizable component, the polymerizable component may contain 0 to 100% by weight, particularly 5 to 90% by weight, more particularly 10 to 80% by weight, even more particularly 15 to 75% by weight, and more particularly 20 to 70% by weight of (meth)acrylate-functionalized monomers. Specifically, based on the total weight of the polymerizable component, the polymerizable component may contain 50 to 100% by weight, or 55 to 99.5% by weight, or 60 to 99% by weight, or 65 to 98.5% by weight, or 70 to 98% by weight of (meth)acrylate-functionalized monomers.

[0504] The polymerizable component may contain (meth)acrylate-functionalized oligomers. The polymerizable component may contain a mixture of (meth)acrylate-functionalized oligomers.

[0505] (Meth)acrylate-functionalized oligomers can be selected to enhance properties such as flexibility, strength, and / or modulus of the cured polymer prepared by curing the curable composition of the present invention.

[0506] (Meth)acrylate-functionalized oligomers may have 1 to 18 (meth)acrylate groups, particularly 2 to 6 (meth)acrylate groups, and even more particularly 2 to 6 acrylate groups.

[0507] (Meth)acrylate-functionalized oligomers can have a number average molecular weight equal to or greater than 600 g / mol, particularly 800 to 15,000 g / mol, and even more particularly 1,000 to 5,000 g / mol.

[0508] In particular, the polymerizable component may include (meth)acrylate-functionalized oligomers selected from epoxy (meth)acrylates, polyester (meth)acrylates, polyether (meth)acrylates, urethane (meth)acrylates, (meth)acrylated poly(meth)acrylates, and mixtures thereof.

[0509] Non-limiting examples of epoxy (meth)acrylates are reaction products of epoxides (e.g., glycidyl ethers, glycidyl esters, alicyclic epoxides, or epoxides obtained by epoxidation of monounsaturated and / or polyunsaturated compounds) with (meth)acrylate esterifying agents (e.g., (meth)acrylic acid, (meth)acrylic anhydride, (meth)acryloyl chloride, or combinations thereof). The epoxide can be selected from the following epoxides (EPOX): 1,2,3,4-diepoxybutane; 1,2,4,5-diepoxypentane; 1,2,5,6-diepoxyhexane; 1,2,7,8-diepoxyoctane; 1,2,9,10-diepoxydecane; bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, epoxy phenolic varnish resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether 3,4-Epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-1,4-dioxane, bis(3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene oxide, 4-vinylepoxycyclohexane, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3',4'-epoxy-6'-methylcyclohexane carboxylate, methylene bis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di(3,4- Epoxycyclohexylmethyl ether, ethylene bis(3,4-epoxycyclohexane carboxylate), ethylene glycol diglycidyl ether, 1,2- or 1,3-propanediol diglycidyl ether, 1,2-, 1,3- or 1,4-butanediol diglycidyl ether, 1,5-pentanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,7-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,9-nonanediol diglycidyl ether and 1,10-decanediol diglycidyl ether, 1,12-dodecanediol diglycidyl ether, 2-methyl-1,3-propanediol diglycidyl ether Glyceryl ether, neopentyl glycol diglycidyl ether, 2,2-diethyl-1,3-propanediol diglycidyl ether, 3-methyl-1,5-pentanediol diglycidyl ether, 3,3-dimethyl-1,5-pentanediol diglycidyl ether, 2,4-diethyl-1,5-pentanediol diglycidyl ether, 3,3-butylethyl-1,5-pentanediol diglycidyl ether, di-, tri- or tetra-(ethylene glycol) diglycidyl ester, di-, tri- or tetra-(1,2-propanediol) diglycidyl ether, di-, tri- or tetra-(1,3-propanediol) diglycidyl ether, di-, tri- or tetra-(1,2 ...4-Butanediol) diglycidyl ether, poly(ethylene glycol) diglycidyl ether, poly(propylene glycol) diglycidyl ether, poly(trimethylene) diglycidyl ether, poly(tetramethylene) diglycidyl ether, poly(ethylene glycol-co-propylene glycol) diglycidyl ether, glycerol triglycidyl ether, polyglycerol polyglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolpropane triglycidyl ether, di( Hydroxyphenylmethane tetraglycidyl ether, pentaerythritol tetraglycidyl ether, diglycidylcyclohexane dicarboxylic acid ester, cyclohexane diglycidyl ether, cyclohexane-1,4-diethanol diglycidyl ether, tricyclodecane diethanol diglycidyl ether, isosorbide diglycidyl ether, catechol diglycidyl ester, resorcinol diglycidyl ester, cardiac phenol diglycidyl ester, phloroglucinol triglycidyl ester Glyceryl ether dicarboxylic acid, pyrogallol triglycidyl ether, tris(hydroxyphenyl)methane triglycidyl ether, tris(hydroxyphenyl)ethane triglycidyl ether, diglycidyl phthalate, diglycidyl terephthalate, diglycidyl isophthalate, polyglycidyl ethers of polyether polyols obtained by adding one or more epoxides to aliphatic polyols (such as ethylene glycol, propylene glycol, polypropylene glycol, and glycerol), diglycidyl ethers of aliphatic long-chain (C6-C22) dicarboxylic acids, monoglycidyl ethers of aliphatic higher alcohols, the following monoglycidyl ethers: phenol, cresol, butylphenol, or polyether alcohols obtained by adding epoxides to these compounds, glycidyl ethers of higher fatty acids, epoxidized vegetable oils (such as epoxidized soybean oil and epoxidized linseed oil), epoxidized butyl stearic acid, epoxidized octyl stearic acid, epoxidized polybutadiene, triglycidyl isocyanurate, etc. ,

[0510] Non-limiting examples of polyester (meth)acrylates are the reaction products of hydroxyl-terminated polyester polyols with esterifying agents for (meth)acrylate (e.g., (meth)acrylic acid, (meth)acrylic anhydride, (meth)acryloyl chloride, or combinations thereof). The reaction process can be carried out such that a significant concentration of residual hydroxyl groups is retained in the polyester (meth)acrylate, or the reaction process can be carried out such that all or substantially all of the hydroxyl groups of the polyester polyol have been esterified with (meth)acrylate. Polyester polyols can be prepared by polycondensation of a polyhydroxy functional component (particularly a diol) and a polycarboxylic acid functional compound (particularly a dicarboxylic acid or anhydride). To prepare polyester (meth)acrylates, the hydroxyl groups of the polyester polyol are then partially or completely esterified by reaction with a esterifying agent for (meth)acrylate. Polyester (meth)acrylates can also be synthesized by reacting a hydroxyl-containing (meth)acrylate, such as a hydroxyalkyl (meth)acrylate (e.g., hydroxyethyl acrylate), with a polycarboxylic acid. The polyhydroxy and polycarboxylic acid functional components can each have straight-chain, branched, alicyclic, or aromatic structures, and can be used alone or as a mixture.

[0511] Non-limiting examples of polyether (meth)acrylates are the products of condensation reactions of polyether alcohols (which are polyether polyols) with (meth)acrylate esterifying agents (e.g., (meth)acrylic acid, (meth)acrylic anhydride, (meth)acryloyl chloride, or combinations thereof). Suitable polyether alcohols can be straight-chain or branched substances containing ether bonds and terminal hydroxyl groups. Polyether alcohols can be prepared by ring-opening polymerization of epoxides and other oxygen-containing heterocyclic compounds (e.g., ethylene oxide, 1,2-epoxypropane, epoxide, tetrahydrofuran, or combinations thereof) with initiator molecules. Suitable initiator molecules include water, hydroxyl-functionalized materials, polyester polyols, and amines. Polyether alcohols can also be obtained by the condensation of glycols such as ethylene glycol.

[0512] Non-limiting examples of urethane (meth)acrylates are condensation reaction products of at least one polyisocyanate (e.g., diisocyanate, triisocyanate), at least one polyol (e.g., polyether polyol or polyester polyol), and a (meth)acrylate (e.g., 2-hydroxyethyl (meth)acrylate or 3-hydroxypropyl (meth)acrylate) providing hydroxyl-functionalized terminal (meth)acrylate groups. For example, each molecule of urethane (meth)acrylate may contain two, three, four, or more (meth)acrylate groups. The order of addition of the components in preparing urethane (meth)acrylates is well known in the art. For example, a hydroxyl-functionalized (meth)acrylate may first react with a polyisocyanate to obtain an isocyanate-functionalized (meth)acrylate, and then react it with a polyol. In yet another embodiment, the polyisocyanate may first react with a polyol to obtain an isocyanate-functionalized polyol, and then react it with a hydroxyl-functionalized (meth)acrylate. Alternatively, all components may be combined and reacted simultaneously.

[0513] Non-limiting examples of (meth)acrylated poly(meth)acrylates are substances having an oligomeric (meth)acrylate backbone functionalized with one or more (meth)acrylate groups (which may be terminal or side-attached to the acrylic backbone of the oligomer). The (meth)acrylate backbone may be a homopolymer, random copolymer, or block copolymer comprising repeating units of (meth)acrylate monomers. The (meth)acrylate monomers may be any monomeric (meth)acrylate, such as C1-C6 alkyl (meth)acrylates, and functionalized (meth)acrylates, such as (meth)acrylates with hydroxyl, carboxylic acid, and / or epoxy groups. (Meth)acrylate-esterified poly(meth)acrylates can be prepared using any procedure known in the art, for example by functionalizing at least a portion of an oligomeric (meth)acrylate monomer with hydroxyl, carboxylic acid, and / or epoxy groups (e.g., hydroxyalkyl (meth)acrylate, (meth)acrylic acid, glycidyl (meth)acrylate) to obtain a functionalized poly(meth)acrylate, which is then reacted with one or more (meth)acrylate-containing reactants to introduce the desired (meth)acrylate functional groups.

[0514] Based on the total weight of the polymerizable component, the polymerizable component may contain 0 to 100% by weight, particularly 10 to 95% by weight, more particularly 20 to 90% by weight, even more particularly 25 to 85% by weight, and even more particularly 30 to 80% by weight of (meth)acrylate-functionalized oligomers. Specifically, based on the total weight of the polymerizable component, the polymerizable component may contain 0 to 50% by weight, 0.1 to 45% by weight, 0.2 to 40% by weight, 0.3 to 35% by weight, or 0.4 to 30% by weight of (meth)acrylate-functionalized oligomers.

[0515] The polymerizable component may contain one or more olefinically unsaturated compounds other than (meth)acrylate-functionalized monomers or oligomers. Examples of such olefinically unsaturated compounds include:

[0516] - Polyvinyl and / or polyallyl monomers (especially divinylbenzene, 1,4-butanediol divinyl ether, tri(ethylene glycol) divinyl ether, diallyl ether, glyceryl diallyl ether, glyceryl triallyl ether, trimethylolpropane diallyl ether, trimethylolpropane triallyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, diallyl phthalate, triallyl isocyanurate, 2,4,6-trienylpropoxy-1,3,5-triazine, glyoxal bis(diallyl acetal) and mixtures thereof);

[0517] Vinyl esters of carboxylic acids (especially vinyl acetate, vinyl propionate, vinyl hexanoate, 2-ethylhexanoate, vinyl octanoate, vinyl nonanoate, vinyl laurate, vinyl stearate, vinyl tert-carbonates and mixtures thereof);

[0518] - Vinyl ethers (especially vinyl methyl ether, vinyl ethyl ether, vinyl n-butyl ether, vinyl isobutyl ether and mixtures thereof, ethylene glycol divinyl ether, triethylene glycol divinyl ether and trimethylolpropane trivinyl ether);

[0519] - Alicyclic vinyl monomers (especially vinylcyclohexane);

[0520] -Olefins (especially ethylene, propylene, 1-butene, isobutene, diisobutene, 1-nonene, 1-decene and mixtures thereof);

[0521] - Conjugated dienes (especially butadiene, isoprene, pentadiene, chloride dienes and mixtures thereof);

[0522] -Vinyl aromatic monomers (especially styrene, α-methylstyrene, tert-butylstyrene, o-, m- and p-methylstyrene, o-, m- and p-ethylstyrene, o-methyl-p-isopropylstyrene, p-chlorostyrene, p-bromostyrene, o-, p-dichlorostyrene, o-, p-dibromostyrene, o-, m- and p-methoxystyrene, optionally substituted indene, optionally substituted vinylnaphthalene, acenaphthene, diphenylethylene, vinylanthracene and mixtures thereof);

[0523] Mono- or dicarboxylic acid monomers, cyclic anhydride monomers and their salts (especially 3-butenoic acid, crotonic acid, vinylacetic acid, fumaric acid, maleic acid, maleic anhydride, tetrahydrophthalic acid, tetrahydrophthalic anhydride, itaconic acid, mesocarboxylic acid, citraconic acid, pentenoic acid, mucoconic acid and mixtures thereof);

[0524] -Unsaturated polymers such as polybutadiene;

[0525] -and their alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives;

[0526] And their mixtures.

[0527] The polymerizable component may contain one or more cationically polymerizable compounds.

[0528] The term "cationically polymerizable compound" refers to a compound containing polymerizable functional groups that can be polymerized via a cationic mechanism, such as heterocyclic groups or carbon-carbon double bonds substituted with electron-donating groups. In the cationic polymerization mechanism, a cationic initiator forms a Brønsted acid or Lewis acid, which binds to a cationically polymerizable compound, then becomes reactive and causes chain growth through reaction with another cationically polymerizable compound.

[0529] The cationicly polymerizable compound may be selected from epoxides, oxetanes, oxetanes, cyclic acetals, cyclic lactones, thiohexacyclopropanes, thiohexacyclobutanes, spiroacetic acid esters, their derivatives and mixtures thereof, and is preferably selected from epoxides, oxetanes and mixtures thereof.

[0530] Based on the total weight of the polymerizable component, the polymerizable component may contain 0 to 100% by weight, particularly 5 to 90% by weight, more particularly 10 to 80% by weight, even more particularly 15 to 75% by weight, and more particularly 20 to 70% by weight of a cationicly polymerizable compound. Specifically, based on the total weight of the polymerizable component, the polymerizable component may contain 0 to 50% by weight, 0.1 to 40% by weight, 0.2 to 30% by weight, or 0.3 to 20% by weight of a cationicly polymerizable compound.

[0531] In a preferred embodiment, the polymerizable component comprises an epoxide.

[0532] Exemplary epoxides suitable for use include monoepoxides, diepoxides, and polyepoxides (compounds containing three or more epoxy groups per molecule).

[0533] In one embodiment, the epoxide may have two or three glycidyl ether groups. The epoxide may be an aromatic epoxide or an aliphatic epoxide.

[0534] Aromatic epoxides can be aromatic glycidyl ethers. As used herein, the term "aromatic glycidyl ether" refers to a compound comprising at least two glycidyl ether groups linked together by an aromatic linking moiety. Such a compound can be represented by formula (G):

[0535] (G)

[0536] in:

[0537] -Ar is defined as in chain segment b) above;

[0538] -a is at least 2, preferably 2 to 10, and more preferably 2 to 6.

[0539] Aliphatic epoxides can be aliphatic glycidyl ethers. As used herein, the term "aliphatic glycidyl ether" refers to a compound comprising at least two glycidyl ether groups linked together by an aliphatic linking moiety. Such compounds can be represented by formula (H):

[0540] (H)

[0541] in

[0542] -Al is defined as in link segment b) above;

[0543] -d is at least 2, preferably 2 to 10, and more preferably 2 to 6.

[0544] In another embodiment, the epoxide may be an alicyclic epoxide, i.e., a compound having an epoxide ring fused with a cyclohexyl ring.

[0545] In another embodiment, the epoxide may be an epoxidized vegetable oil. As used herein, the term "epoxidized vegetable oil" refers to an unsaturated vegetable oil in which at least a portion of the carbon-carbon double bonds have been converted to an epoxide.

[0546] Specific examples of suitable epoxides are listed above in the section on EPOXes that can be used in polymerizable components.

[0547] The polymerizable component may include oxobutane compounds.

[0548] Suitable exemplary oxetanes include oxetane itself and its substituted derivatives, provided that the substituents do not interfere with the desired reaction / polymerization / curing of the oxetane. Substituents can be, for example, alkyl, hydroxyalkyl, halogen, haloalkyl, aryl, aralkyl, etc. Oxetanes can be monooxetanes (compounds containing a single oxetane ring), dioxetanes (compounds containing two oxetane rings), trioxetanes (compounds containing three oxetane rings), or oxetane compounds containing four or more oxetane rings. Suitable examples of oxetanes include, but are not limited to, oxetane, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis[(3-ethyl-3-oxetane-butylmethoxy)methyl]benzene, 3-ethyl-3-phenoxymethyloxetane, 3-ethyl-3-{[(3-ethyloxetane-3-yl)methoxy]methyl}oxetane, 3,3-bis(chloromethyloxetane), 3-ethyl-3-[(phenylmethoxy)methyl]oxetane, 4,4'-bis(3-ethyl-3-oxetane-butyl)methoxymethyl]biphenyl, and 3,3-bis(iodomethyl)oxetane. Butane, 3,3-bis(methoxymethyl)oxetane, 3,3-bis(phenoxymethyl)oxetane, 3-methyl-3-chloromethyloxetane, 3,3-bis(acetoxymethyl)oxetane, 3,3-bis(fluoromethyl)oxetane, 3,3-bis(bromomethyl)oxetane, 3b3-dimethyloxetane, 3-ethyl-3-[[(2-ethylhexyl)oxy]methyl]oxetane, bis[(3-ethyloxetane-3-yl)methoxy](dimethyl)silane, trimethylolpropane tri(3-ethyl-3-oxetane-butylmethyl) ether, and combinations thereof.

[0549] Examples of compounds that can be used having two or more oxetane rings include 3,7-bis(3-oxetane)-5-oxononane, 3,3'-(1,3-(2-methylene)propanediylbis(oxymethylene))bis(3-ethyloxetane), 1,4-bis[(3-ethyl-3-oxetanemethoxy)methyl]benzene, 1,2-bis[(3-ethyl-3-oxetanemethoxy)methyl]ethane, 1,3- bis[(3-ethyl-3-oxetanebutylmethoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxetanebutylmethyl) ether, dicyclopentenyl bis(3-ethyl-3-oxetanebutylmethyl) ether, triethylene glycol bis(3-ethyl-3-oxetanebutylmethyl) ether, tetraethylene glycol bis(3-ethyl-3-oxetanebutylmethyl) ether, tricyclodecanediyldimethylene(3-ethyl-3-oxetanebutylmethyl) ether, trimethylolpropane tri(3- Ethyl-3-oxetane(methyl) ether, 1,4-bis(3-ethyl-3-oxetane(methyl)methoxy)butane, 1,6-bis(3-ethyl-3-oxetane(methyl)methoxy)hexane, pentaerythritol tris(3-ethyl-3-oxetane(methyl) ether, pentaerythritol tetra(3-ethyl-3-oxetane(methyl) ether, caprolactone-modified dipentaerythritol penta(3-ethyl-3-oxetane(methyl) ether, bis(trimethylolpropane)tetra(3-ethyl- 3-Oxetrazolylbutyric methyl) ether, EO-modified bisphenol A bis(3-ethyl-3-oxetrazolylbutyric methyl) ether, PO-modified bisphenol A bis(3-ethyl-3-oxetrazolylbutyric methyl) ether, EO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetrazolylbutyric methyl) ether, PO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetrazolylbutyric methyl) ether, EO-modified bisphenol F (3-ethyl-3-oxetrazolylbutyric methyl) ether, and combinations thereof.

[0550] Other examples of suitable oxetanes are described in the following patent documents, the disclosures of which are incorporated herein by reference in their entirety for all purposes: U.S. Patent Publication No. 2010 / 0222512 A1, U.S. Patent No. 3,835,003, U.S. Patent No. 5,750,590, U.S. Patent No. 5,674,922, U.S. Patent No. 5,981,616, U.S. Patent No. 6,469,108, U.S. Patent No. 6,015,914, and U.S. Patent No. 8,377,623. Suitable oxetanes are available from commercial sources, such as those sold by Toagosei Corporation under the trade names OXT-221, OXT-121, OXT-101, OXT-212, OXT-211, CHOX, OX-SC, and PNOX-1009.

[0551] Inhibitors

[0552] In some embodiments, the curable composition of the present invention comprises at least one dual-curable oligomer as described herein and at least one inhibitor. According to these embodiments, the composition may contain 10 ppm to 5% by weight of one or more inhibitors, for example 20 ppm to 4% by weight, 50 ppm to 3% by weight, 100 ppm to 1% by weight, or 120 ppm to 0.1% by weight, based on the total weight of the curable composition.

[0553] Inhibitors can be introduced into curable compositions to provide sufficient storage stability and shelf life. As mentioned above, inhibitors can generally delay or prevent the reaction or curing of polymerizable functional groups present in the composition, especially in the absence of radiation.

[0554] As described above, any inhibitors known in the art related to olefinically unsaturated compounds can be used in the compositions of the present invention.

[0555] Initiator

[0556] The curable composition may contain an initiator selected from free radical initiators, cationic initiators, and combinations thereof. The curable composition may contain a mixture of free radical initiators and cationic initiators.

[0557] Initiators are generally classified into two categories, depending on their mode of action: free radical initiators and cationic initiators.

[0558] Free radical initiators encompass both photoinitiators and thermal initiators.

[0559] Photoinitiators are compounds that generate free radicals when exposed to light of appropriate wavelength and / or intensity. Photoinitiators can employ two distinct modes of action and are classified as Norrish type I and Norrish type II photoinitiators based on their mode of action. As used herein, the term "activity" in relation to Norrish type I and Norrish type II activity is intended to refer to Norrish photoinitiation and similar reactions. For example, within the scope of this invention, a photoinitiator having Norrish type I activity would be one characterized by, upon exposure to light, undergoing a cleavage reaction to form two free radical segments. For initiators having Norrish type II activity, exposure to light induces the extraction of atoms (e.g., hydrogen) to generate free radicals.

[0560] Thermal initiators are compounds that can generate free radicals when exposed to heat and / or in the presence of a reducing agent.

[0561] Cationic initiators are typically salts, such as iodonium and sulfonium salts. When these salts are activated (i.e., by irradiation with photochemical radiation such as light), they undergo homolytic bond breaking to form free radicals, which react with proton donors to produce Brønsted or Lewis acids. The resulting acids then initiate polymerization.

[0562] The curable composition may contain a free radical initiator, which is a photoinitiator, particularly a photoinitiator with Norrish type I activity and / or Norrish type II activity, and more particularly a free radical initiator with Norrish type I activity.

[0563] Non-limiting types of photoinitiators suitable for the curable compositions of the present invention include, for example, benzoin, benzoin ether, acetophenone, α-hydroxyacetophenone, benzyl, benzyl ketal, anthraquinone, phosphine oxide, acylphosphine oxide, α-hydroxy ketone, phenylglyoxylate, α-amino ketone, benzophenone, thioxanthone, xanthones, acridine derivatives, phenazine derivatives, quinoxaline derivatives, triazine compounds, benzoylcarbamate, aromatic oximes, metallocenes, acylsilyl or acylgermanyl compounds, camphorquinone, polymeric derivatives thereof, and mixtures thereof.

[0564] Examples of suitable photoinitiators include, but are not limited to, 2-methylanthraquinone, 2-ethylanthraquinone, 2-chloroanthraquinone, 2-benzylanthraquinone, 2-tert-butylanthraquinone, 1,2-benzo-9,10-anthraquinone, benzyl, benzoin, benzoin ether, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, α-methylbenzoin, α-phenylbenzoin, michidone, acetophenone such as 2,2-dialkoxybenzophenone and 1-hydroxyphenyl ketone, benzophenone, 4,4'-bis-(diethylamino)benzophenone, acetophenone, 2,2-diethoxyacetophenone, diethoxyacetophenone, 2-isopropylthioxanthone, thioxanthone, diethylthioxanthone, 1,5-acetylnaphthalene, benzoinone, α-hydroxy ketone, 2,4,6 -Trimethylbenzoyl diphenylphosphine oxide, benzyl dimethyl ketal, 2,2-dimethoxy-1,2-diphenyl ethyl ketone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinoacetone-1, 2-hydroxy-2-methyl-1-phenyl-propanone, oligo-α-hydroxy ketone, benzoylphosphine oxide, phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl (2,4,6-trimethylbenzoyl)phenylphosphine sulfate, anisolein, anthraquinone, anthraquinone-2-sulfonic acid, sodium salt monohydrate, (benzene)tricarbonylchromium, benzoyl, benzoin isobutyl ether, benzophenone / 1-hydroxycyclohexylphenyl ketone, 50 / 50 blend, 3,3',4,4'- Benzophenone tetracarboxylic acid dianhydride, 4-benzoylbiphenyl, 2-benzyl-2-(dimethylamino)-4'-morpholinobenzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dimethylamino)benzophenone, camphorquinone, 2-chlorothiazol-9-one, dibenzocycloheptenone, 4,4'-dihydroxybenzophenone, 2,2-dimethoxy-2-phenylacetophenone, 4-(dimethylamino)benzophenone, 4,4'-dimethylbenzoin, 2,5-dimethylbenzophenone, 3,4-dimethylbenzophenone, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide / 2-hydroxy-2-methylacetophenone, 50 / 50 blend, 4'-ethoxyacetophenone, 2 4,6-Trimethylbenzoyl diphenylphosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, ferrocene, 3'-hydroxyacetophenone, 4'-hydroxyacetophenone, 3-hydroxybenzophenone, 4-hydroxybenzophenone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methylphenylacetone, 2-methylbenzophenone, 3-methylbenzophenone, methylbenzoylcarbamate, 2-methyl-4'-(methylthio)-2-morpholinophenylacetone, phenanthrenequinone, 4'-phenoxyacetophenone, (cumene)cyclopentadienyl iron(ii) hexafluorophosphate, 9,10-diethoxy and 9,10-dibutoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, thioxanthone-9-one and combinations thereof.

[0565] Specifically, the photoinitiator may include photoinitiators selected from benzophenones such as SpeedCure photoinitiators, such as SpeedCure® BP (benzophenone), SpeedCure® 7005 (polymerized benzophenone), SpeedCure® 7006 (polymerized benzophenone), SpeedCure® EMK (4,4'-bis(diethylamino)benzophenone), or SpeedCure® BMS (4-benzoyl-4'-methyldiphenyl sulfide); thioxanthones, such as SpeedCure® 7010 (polymerized thioxanthone), SpeedCure® ITX (isopropylthioxanthone), Speed... Cure® DETX (2,4-diethylthioxanthone) or SpeedCure® CPTX (1-chloro-4-propoxythioxanthone); α-hydroxyacetophenone; acylphosphine oxides such as SpeedCure® BPO (phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide), SpeedCure® TPO (2,4,6-trimethylbenzoyl diphenylphosphine oxide), or SpeedCure® TPO-L ((2,4,6-trimethylbenzoyl)phenylphosphine ethyl ester); phenyl glyoxylates, such as SpeedCure® MBF (methylbenzoyl carbamate); and mixtures thereof.

[0566] The curable composition may contain a free radical initiator as a thermal initiator.

[0567] Thermal initiators are well known in the art and include, for example, peroxides (i.e., compounds containing oxygen-oxygen single bonds), especially inorganic persulfate compounds such as ammonium persulfate, potassium persulfate, and sodium persulfate; hydrogen peroxide; organic peroxides such as cumene hydroperoxide, tert-butyl hydroperoxide, acetyl peroxide, benzoyl peroxide, and lauroyl peroxide; peracids such as peracetic acid and perbenzoic acid; redox initiators wherein reducing agents such as ferrous compounds promote the decomposition of peroxides; and other materials that generate free radicals, such as azo initiators (i.e., compounds containing nitrogen-nitrogen double bonds), such as 2,2'-azobisisobutyronitrile, 4,4'-azobis(4-cyanopentanoic acid), or 2,2'-azobis(2-methylbutyronitrile); and combinations thereof.

[0568] The curable composition may contain a cationic photoinitiator.

[0569] In particular, the cationic photoinitiator may be selected from onium salts of anions with weak nucleophilicity, such as halonium salts or sulfonium salts (e.g., triarylsulfonium salts, such as triarylsulfonium hexafluoroantimonate); sulfonium oxide salts; diazonium salts; metallocene salts; and mixtures thereof.

[0570] Haloon salts are of particular interest. Haloon salts are ionic compounds containing haloon cations (i.e., positively charged halogen atoms). The haloon cations can be represented using the general structure RX. + -R' indicates that X is a halogen, preferably iodine, and R and R' are any groups, preferably aryl. Haloium cations can have cyclic or open-chain molecular structures. Haloium cations containing fluorine, chlorine, bromine, and iodine atoms are called fluoronium, chloroonium, bromonium, and iodonium, respectively. The counter ion of the salt can be any type of anion, such as Cl-. - ,Br - I - fluoroalkyl-SO3 - arylSO3 - SbF6 - SbF5OH - AsF6 - PF6 - BF4 - Or B(C6F5)4 - .

[0571] The cationic initiator can be an iodonium salt. Preferred iodonium salts include diaryliodonium salts, such as diphenyliodonium chloride, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, bis(4-methylphenyl)iodonium tetrafluoroborate; phenyl-4-methylphenyliodonium tetrafluoroborate; bis(4-heptylphenyl)iodonium tetrafluoroborate; bis(3-nitrophenyl)iodonium hexafluorophosphate; bis(4-chlorophenyl)iodonium hexafluorophosphate; bis(naphthyl)iodonium tetrafluoroborate; bis(4-trifluoromethylphenyl)iodonium tetrafluoroborate; bis(4-methylphenyl)iodonium hexafluorophosphate; diphenyliodonium hexafluoroarsenate; bis(4-phenoxyphenyl)iodonium tetrafluorophosphate. Borate; phenyl-2-thienyl iodonium hexafluorophosphate; 3,5-dimethylpyrazolyl-4-phenyliodonium hexafluorophosphate; 2,2'-diphenyliodonium tetrafluoroborate; di(2,4-dichlorophenyl)iodonium hexafluorophosphate; di(4-bromophenyl)iodonium hexafluorophosphate; di(4-methoxyphenyl)iodonium hexafluorophosphate; di(3-carboxyphenyl)iodonium hexafluorophosphate; di(3-methoxycarbonylphenyl)iodonium hexafluorophosphate; di(3-methoxysulfonylphenyl)iodonium hexafluorophosphate; di(4-acetamidophenyl)iodonium hexafluorophosphate; di(2-benzothienyl)iodonium hexafluorophosphate; and diphenyliodonium hexafluoroantimonylate. Particularly preferred iodonium salts are diaryliodonium hexafluorophosphate, diaryliodonium hexafluoroantimonate, 4-octyloxyphenylphenyliodonium hexafluoroantimonate, 4-(2-hydroxytetradecyloxyphenyl)phenyliodonium hexafluoroantimonate, and 4-(1-methylethyl)phenyl-4-methylphenyliodonium tetra(pentafluorophenyl)borate.

[0572] The cationic initiator can be a sulfonium salt. Preferred sulfonium salts include Cyracure® UVI-6974 and UVI-6976 (which is a mixture of S,S,S,S'-tetraphenylthiobis(4,1-phenylene)disulfonium difluoroantimonate and diphenyl(4-phenylthiophenyl)sulfonium hexafluoroantimonate), Cyracure® UVI-6970, UVI-6960, UVI-6990 ((DOW Corp.), CD1010, CD-1011, CD-1012 (Sartomer Corp.), Adekaoptomer SP150, SP-151, SP-170, SP-171 (AsahiDenka Kogyo Co., Ltd.), Irgacure® 261, CI-2481, CI-2624, CI-2639, CI2064 (Nippon Soda). Co, Ltd.) and DTS-102, DTS-103, NAT-103, NDS-103, TPS-103, MDS-103, MPI-103, BBI-103 (Midori Chemical Co, Ltd.).The most preferred are UVI-6974, CD-1010, UVI-6976, Adekaoptomer SP-170, SP-171, CD-1012, MPI-103, and KI78 (sulfonium hexafluoroantimonate from Asahi Denka), a mixture of S,S,S,S'-tetraphenylthiobis(4,1-phenylene)disulfonium dihexafluoroantimonate and diphenyl(4-phenylthiophenyl)sulfonium hexafluoroantimonate, 4-[4-(3-chlorobenzoyl)phenylthio]phenylbis(4-fluorophenyl)sulfonium hexafluoroantimonate, 4-[4-(3-chlorobenzoyl)phenylthio]phenylbis(4-fluorophenyl)sulfonium tetra(pentafluorophenyl)borate, 4-[4-(3-chlorobenzoyl)phenylthio]phenylbis(4-fluorophenyl)sulfonium tetra(pentafluorophenyl)borate, and 4-[4-(3-chlorobenzoyl)phenylthio]phenylbis(4-fluorophenyl) Sulfonium tetra(3,5-difluoro-4-methoxyphenyl)borate, 4-[4-(3-chlorobenzoyl)phenylthio]phenylbis(4-fluorophenyl)sulfonium tetra(2,3,5,6-tetrafluoro-4-methoxyphenyl)borate, tris(4-(4-acetylphenyl)phenylthio)sulfonium tetra(pentafluorophenyl)borate (from BASF's Irgacure® PAG290), tris(4-(4-acetylphenyl)mercaptophenyl)sulfonium tri[(trifluoromethyl)sulfonyl]methyl compound (from BASF) Irgacure® GSID 26-1), tris(4-(4-acetylphenyl)mercaptophenyl)sulfonium hexafluorophosphate (Irgacure® 270 from BASF), and HS-1 from San-Apro Ltd, bis[4-diphenylsulfoniumphenyl]sulfide bis(4-fluorophenyl)sulfonium antimonate; thiophenoxyphenyl sulfonium hexafluoroantimonate (available from Chitec as Chivacure 1176), 4-[4-(2-chlorobenzoyl)phenylthio]phenyl bis(4-fluorophenyl)sulfonium hexafluoroantimonate (available from Adeka as SP-172), SP-300 from Adeka, and those with anion (PF). 6-m (C n F 2n+1 ) m ) - Aromatic sulfonium salts, where m is an integer from 1 to 5 and n is an integer from 1 to 4 (available as CPI-200K or CPI-200S, which are monovalent sulfonium salts from San-Apro Ltd., TK-1 available from San-Apro Ltd., or HS-1 available from San-Apro Ltd.).

[0573] The amount of initiator can vary appropriately depending on factors such as the selected initiator, the amount and type of polymerizable material present in the curable composition, the radiation source used, and the radiation conditions. However, based on the total weight of the curable composition, the total amount of initiator can typically be 0 to 10% by weight, particularly 0.1 to 9% by weight, more particularly 0.5 to 8% by weight, and even more particularly 1 to 6% by weight. For example, based on the total weight of the curable composition, the total amount of initiator can be 0 to 5% by weight, 0.02 to 3% by weight, 0.05 to 2% by weight, 0.1 to 1.5% by weight, or 0.2 to 1% by weight. In another example, based on the total weight of the curable composition, the amount of photoinitiator, different from that in b), can be 1 to 5% by weight, 1.5 to 5% by weight, 2 to 5% by weight, 2.5 to 5% by weight, or 3 to 5% by weight.

[0574] Epoxy crosslinking agent

[0575] The curable composition may contain an epoxy crosslinking agent.

[0576] Epoxy crosslinking agents are components that react with the epoxy functional groups of dual-curable oligomers to produce a three-dimensional crosslinked system. When a curable composition contains an epoxy crosslinking agent, the composition is preferably a two-component composition (or a 2K composition), wherein the dual-curable oligomer remains separate from the epoxy crosslinking agent during storage, and the end user mixes the two components shortly before use.

[0577] Epoxy crosslinking agents can be compounds containing one or more functional groups selected from amines, carboxylic acids, acid anhydrides, or thiols. Specific examples of epoxy crosslinking agents that can be used in the compositions of the present invention are formaldehyde crosslinking agents and polyamine crosslinking agents. Formaldehyde crosslinking agents include phenol-formaldehyde, resorcinol-formaldehyde, catechol-formaldehyde, hydroquinone-formaldehyde, cresol-formaldehyde, phloroglucinol-formaldehyde, pyroglucinol-formaldehyde, melamine-formaldehyde, urea-formaldehyde, and blends or derivatives thereof. Polyamine crosslinking agents include aliphatic or alicyclic polyamines, such as ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), polyoxypropylene diamine, polyoxypropylene triamine, isophorone diamine, menthane diamine, bis(4-amino-3-methyldicyclohexyl)methane, etc.

[0578] Additives (e.g., fillers, elastomers)

[0579] The curable compositions of the present invention may optionally contain one or more additives selected from the following: antioxidants, ultraviolet absorbers, light stabilizers, foam inhibitors, flow agents or leveling agents, colorants, pigments, dispersants (wetting agents), sliding additives, fillers, elastomers, thixotropic agents, matting agents, waxes, any additives conventionally used in coatings, sealants, adhesives, inks or molding compositions, and combinations thereof.

[0580] In some embodiments, the curable composition of the present invention comprises one or more fillers. Examples of fillers include glass particles, quartz, graphite powder, carbon black, and alumina powder.

[0581] In some embodiments, the curable composition of the present invention comprises one or more elastomers. Examples of elastomers include RTV rubber and silicone rubber.

[0582] In some embodiments, the curable compositions of the present invention are solvent-free. Notably, in such embodiments, they do not contain organic solvents.

[0583] According to some embodiments, the viscosity of the curable composition at 25°C ranges from 100 mPa·s to 500,000 mPa·s, for example, from 1,000 mPa·s to 300,000 mPa·s. Viscosities less than 100 mPa·s may not be suitable for the applications of this invention because they exhibit insufficient adhesion. Viscosities greater than 500,000 mPa·s may also be unsuitable because applying the composition to a substrate surface may be difficult. The viscosity of the composition can be measured on a rotational viscometer.

[0584] End-use applications

[0585] The curable compositions of the present invention can be used as adhesives, inks, printing masks, coloring systems, 3D printing resins, sealants, coatings and other potential applications.

[0586] The cured compositions prepared from the curable compositions described herein can be used, for example, for laminated or adhesive articles (where a first component of the article is laminated or adhered to a second component by means of the cured composition), three-dimensional articles (where the three-dimensional article may consist substantially of or be composed of the cured composition), coated articles (where a substrate is coated with one or more layers of the cured composition), or printed articles (where graphics, etc., are embossed onto a substrate (e.g., a paper, plastic, or metal substrate) using the cured composition).

[0587] The cured compositions are particularly useful as adhesives for electrical or electronic components (including microelectronic components), adhesives for gyroscopes, solder masks for printed circuit boards (PCBs), integrated circuit (IC) packaging, liquid crystal fast sealing, optical / display device assembly, and water-based dual-curable coatings.

[0588] The curable compositions described herein are particularly suitable for use as UV / EB curable resins, i.e., compositions intended for use as adhesives for electrical or electronic components in navigation systems and devices for measuring orientation, such as gyroscopes. During operation, these components and articles may be subjected to environmental stresses, which can adversely affect their properties and impair their function. Temperature and vibration are examples of such environmental factors that can cause components to lose their function during use. Due to their inherent properties, the curable compositions of the present invention are particularly suitable for providing a uniform temperature environment and minimizing the effects of vibration on articles and components.

[0589] Method for preparing cured compositions

[0590] The method for preparing the cured composition of the present invention includes curing the curable composition as described herein. The cured composition exhibits mechanical properties highly suitable for withstanding environmental stresses such as high temperatures and vibrations.

[0591] Curing can be accelerated or promoted by providing energy to the composition, for example by exposing the composition to a radiation source, such as visible or UV light, infrared radiation, and / or electron beam radiation, and / or by heating the composition. The cured composition is a reaction product obtained by curing the curable composition described herein.

[0592] In some embodiments, methods for preparing a cured composition include exposing the curable composition to ultraviolet (UV) radiation, electron beam (EB) radiation, and / or heat.

[0593] The curable compositions of the present invention are particularly suitable for curing using LEDs (light-emitting diodes) (e.g., UV LED curing), using radiation from a UV LED device, and heating (e.g., a temperature range of 30 to 200°C).

[0594] Specifically, thermosetting can be carried out in a temperature range of 60°C to 200°C. The choice of temperature for thermosetting can notably depend on the type of curing agent that can be used in the composition to be cured. In some embodiments, thermosetting is carried out in a temperature range of 50°C to 100°C, for example, in a temperature range of 60°C to 95°C. In some other embodiments, thermosetting is carried out in a temperature range of 100°C to 150°C, for example, in a temperature range of 110°C to 145°C. In still other embodiments, thermosetting is carried out in a temperature range of 150°C to 200°C, for example, in a temperature range of 155°C to 195°C.

[0595] In particular, the curable compositions of the present invention are ideal for applications requiring rapid curing.

[0596] In some preferred embodiments, the method for preparing the cured composition comprises exposing the curable composition to UV / EB radiation and heat. The oligomers of the present invention exhibit particularly unique properties, polymerizing not only under UV radiation when combined with a photoinitiator or treated with a high-energy electron beam, but also under heat. This makes the oligomers of the present invention best suited for applications requiring rapid curing.

[0597] In some embodiments, the method for preparing the cured composition according to the invention comprises two successive steps:

[0598] - Involves a step of activating one of the two segments of a dual-cured oligomer in response to a first curing source; and

[0599] - This involves steps that activate another segment of the dual-cured oligomer in response to a second curing source.

[0600] In such embodiments, the first curing source is preferably a radiation source, such as visible or UV light, infrared radiation, and / or electron beam radiation, to activate segments with unsaturation, wherein an effective amount of radiation (i.e., radiation of sufficient intensity and duration) is applied to induce at least partial curing of the composition. The second curing source is preferably a heat source to activate the epoxy segments of the dual-cured oligomer. In these embodiments, the first curing step can be performed to set / stabilize the shape of the cured composition, while the second curing step can enhance the mechanical properties of the composition.

[0601] The composition of the present invention can be applied to a substrate surface and then cured by exposure to a first curing source (e.g., a dose of radiation) followed by exposure to a second curing source (e.g., heat); or the composition of the present invention can be applied to a substrate surface and cured by exposure to a first curing source (e.g., a dose of radiation) followed by exposure to a second curing source (e.g., heat).

[0602] Multilayer compositions can also be applied to a substrate surface; multiple layers can be cured simultaneously, or each layer can be cured sequentially before additional layers of the composition are applied.

[0603] In some embodiments, the method for preparing the cured composition according to the invention comprises the following sequential steps:

[0604] - Apply the curable composition to the surface of a substrate;

[0605] - The composition is cured by exposing the surface to an effective amount of radiation (e.g., electron beam radiation, UV radiation, visible light) for a duration sufficient to cause at least partial curing (e.g., at least 50% or at least 60% curing) of the composition; and

[0606] - The composition is cured by heating the surface for a time sufficient to complete the curing process of step b).

[0607] In these implementations, step b) can be performed simultaneously with step a).

[0608] Aspects of the present invention

[0609] The present invention can be based on the following aspects.

[0610] Aspect 1. Dually curable oligomers, comprising:

[0611] a) A segment containing at least one olefinic unsaturation;

[0612] b) A segment containing at least one epoxy group;

[0613] c) A segment containing at least one carbamate bond;

[0614] Links a) and b) are connected to each other via link c).

[0615] Aspect 2. The oligomer of aspect 1, wherein segment a) has a structure of formula (A1) or (A2):

[0616] (A1) (A2)

[0617] in:

[0618] -a must be at least 1;

[0619] - Each R1 is independently H or CH3;

[0620] - Each R2 is independently selected from the direct connection key, -C(=O)-O-、 -C(=O)-NH-, -O- and -CH2-O-, Indicates the connection point with a carbon-carbon double bond;

[0621] -R3 is the (a+1) valence join part; and

[0622] -symbol This indicates the connection point with link segment c).

[0623] Aspect 3. The oligomer of aspect 1 or 2, wherein in the segment of formula (A1) or (A2), a equals 1, 2, 3, 4, 5 or 6; preferably 1, 2 or 3.

[0624] Aspect 4. Oligomers of any one of Aspects 1-3, wherein R3 is an (a+1) valence linker in a segment of formula (A1) or (A2).

[0625] Aspect 5. An oligomer of any one of Aspects 1-4, wherein R3 is an (a+1) valence linker selected from aliphatic, aromatic or aryl-aliphatic hydrocarbon linkers, polyether linkers, polyester linkers, polycarbonate linkers, polyorganosiloxane linkers, polydiene linkers, isocyanurate linkers, and combinations thereof.

[0626] Aspect 6. An oligomer of any one of Aspects 1-5, wherein R3 is an (a+1) valence linker selected from alkylene, alkoxylated alkylene, polycaprolactone linker and combinations thereof.

[0627] Aspect 7. Oligomers of any one of Aspects 1-6, wherein R3 is a divalent linker of any one of the following formulas (1) to (5):

[0628] -(CR 22 R 22 ) m - (1)

[0629] -[(CR 23 R' 23 ) n -O] o -(CR 23 R' 23 ) n - (2)

[0630] -[(CR 24 R' 24 ) p -O] q -(CR 25 R' 25 ) r -[O-(CR 26 R' 26 ) p’ ] q’ - (3)

[0631] -[(CR 27 R' 27 ) s -C(=O)O] t -(CR 28 R' 28 ) u - (4)

[0632] -[(CR 29 R' 29 ) v -OC(=O)-(CR 30 R' 30 ) w -C(=O)-O] x-(CR 29 R' 29 ) v - (5)

[0633] in:

[0634] R 22 、R' 22 R 25 、R' 25 R 29 、R' 29 R 30 and R' 30 Independently H or alkyl;

[0635] R 23 、R' 23 R 24 、R' 24 R 26 、R' 26 R 27 、R' 27 R 28 and R' 28 Independently, it is either H or methyl;

[0636] m ranges from 2 to 50;

[0637] n, p, and p' are independently 2 to 4;

[0638] o ranges from 1 to 20;

[0639] q and q' are independently between 0 and 20, provided that at least one of q and q' is not 0;

[0640] r is between 2 and 20;

[0641] s is 3 to 12;

[0642] t ranges from 1 to 20;

[0643] u ranges from 2 to 8;

[0644] v ranges from 2 to 20;

[0645] w ranges from 2 to 30;

[0646] x is between 1 and 20;

[0647] symbol This indicates the connection point with the (meth)acrylate group.

[0648] Aspect 8. An oligomer of any one of Aspects 1-7, wherein R3 is a divalent moiety selected from: alkylene, such as 1,2-ethylene, 1,2- or 1,3-propylene, 1,2-, 1,3- or 1,4-butylene, 1,5-pentaneene, 1,6-hexaneene, 1,8-octaneene, 1,9-nonaneene, 1,10-decaneene, 1,12-dodecylene, 1,18-octadecylene, 2-methyl-1,3-propanediyl, 2,2-diethyl-1,3-propanediyl, 3-methyl-1,5-pentanediyl 3,3-Dimethyl-1,5-pentanediyl, 2,2-dimethyl-1,3-propanediyl, 2,4-diethyl-1,5-pentanediyl; alkoxylated derivatives of the above alkylene groups; esterified derivatives of the above alkylene groups; residues of di-, tri-, tetra- or polyoxyalkylene groups (excluding OH groups), such as residues of di-, tri- or tetraethylene glycol, di-, tri- or tetrapropylene glycol, di-, tri- or tetrabutanediol, polyethylene glycol, polypropylene glycol, polybutanediol, poly(ethylene glycol-co-propylene glycol); and residues of polyester polyols (excluding OH groups).

[0649] Aspect 9. Oligomers of any one of Aspects 1-6, wherein R3 is a trivalent linker according to any one of Equations (11), (12), (13), (19) and (20), or a tetravalent linker according to any one of Equations (14) and (15):

[0650]

[0651] in:

[0652] Each R h 、R' h R i and R' i Independently H or alkyl; and

[0653] R k 、R' k and R'' k Independently alkylene.

[0654] Aspect 10. An oligomer of any one of Aspects 1-6, wherein R3 has any one of formulas (A3) to (A5):

[0655] (A3) (A4)

[0656] (A5)

[0657] Among the symbols This indicates the connection point with link segment c).

[0658] Aspect 11. An oligomer of any one of Aspects 1-10, wherein the total amount of segment a) in the dual-curable oligomer of the present invention accounts for 5 to 60% by weight of the total weight of the dual-curable oligomer, particularly 10 to 50% by weight, and even more particularly 15 to 40% by weight.

[0659] Aspect 12. An oligomer of any one of Aspects 1-11, wherein segment b) is selected from glycidyl ether groups, glycidyl ester groups and epoxy groups that are not part of glycidyl ether groups or glycidyl ester groups.

[0660] Aspect 13. An oligomer of any one of Aspects 1-12, wherein segment b) has the structure of formula (B1):

[0661] (B1)

[0662] in:

[0663] -b must be at least 1;

[0664] -R4 is the (b+1) valence join part;

[0665] - Each R5 is independently selected from direct bond, -O-CH2-# and -C(=O)-O-CH2-#, with -O-CH2-# being preferred;

[0666] - The symbol # indicates the junction point with the epoxide ring; and

[0667] - The symbol § indicates the connection point with link segment c).

[0668] Aspect 14. The oligomer of aspect 13, wherein b equals 1, 2, 3, or 4; preferably 2 or 3; even more preferably, b is 2.

[0669] Aspect 15. Oligomers of aspect 13 or 14, wherein R4 is a (b+1) valence linker.

[0670] Aspect 16. An oligomer of any one of Aspects 13-15, wherein R4 may be selected from alkylene, heteroatom-containing alkylene, cycloalkylene, heterocycloalkylene, aryl, heteroaryl and combinations thereof, preferably selected from (b+1) valence linkages of alkylene, heteroatom-containing alkylene, cycloalkylene, aryl and combinations thereof.

[0671] Aspect 17. An oligomer of any one of Aspects 13-16, wherein each R5 is independently selected from straight bonds, -O-CH2-# and -C(=O)-O-CH2-#.

[0672] Aspect 18. An oligomer of any one of Aspects 1-17, wherein segment b) has the structure of any one of formulas (B2), (B3), (B4) and (B5):

[0673] (B2) (B3)

[0674] (B4) (B5)

[0675] in:

[0676] - R5, b, and the symbol § are defined above;

[0677] - Ar is the (b+1) valence aromatic linkage part;

[0678] - Al is the (b+1) valence aliphatic linkage;

[0679] - Ar It is the divalent aromatic linkage; and

[0680] - Al It is a divalent aliphatic linker.

[0681] Aspect 19. The oligomer of aspect 18, wherein, in formula (B2), Ar is an aromatic linking moiety comprising at least one arylene moiety, more particularly at least one optionally substituted phenylene moiety, and even more particularly a phenylene moiety optionally substituted by one or more groups selected from alkyl, cycloalkyl, aryl and halogen atoms.

[0682] Aspect 20. Oligomers of aspect 18 or 19, wherein, in formula (B2), Ar has one of formulas (6) to (15):

[0683] (6) (7) (8)

[0684] (9) (10) (11)

[0685] (12) (13) (14) (15)

[0686] in:

[0687] - Each Ph is independently an optionally substituted divalent phenylene, preferably a divalent phenylene that is optionally substituted by one or more groups selected from alkyl, cycloalkyl, aryl and halogen atoms;

[0688] -per Ph The trivalent phenylene is independently substituted, preferably a trivalent phenylene that is optionally substituted by one or more groups selected from alkyl, cycloalkyl, aryl and halogen atoms;

[0689] - Each Alk is independently a divalent alkylene or a heteroatom-containing alkylene;

[0690] - Each Alk Independently a trivalent alkylene group or an alkylene group containing heteroatoms;

[0691] -L is selected from direct-connected keys, -O-, -S-, -SO-, -SO2-, -C(=O)-, C(=CCl2)-, Alk, -CR'1R'2-, -C(=O)-O-Alk-OC(=O)-, -CR'3R'4-Ph-CR'5R'6- and their combinations;

[0692] in:

[0693] -Alk and Ph are defined as above;

[0694] - R'1 and R'2 are independently selected from H, alkyl, cycloalkyl, aryl, haloalkyl and perfluoroalkyl, or R'1 and R'2 can form a ring with the carbon atom to which they are attached;

[0695] -R'3, R'4, R'5 and R'6 are independently selected from H, alkyl, cycloalkyl, aryl, haloalkyl and perfluoroalkyl.

[0696] Aspect 21. An oligomer of any one of Aspects 18-20, wherein, in formula (B2), Ar has one of formulas (16) to (21), preferably formula (16):

[0697]

[0698] in:

[0699] -L is defined above;

[0700] -R e 、R' e and R'' e Independently selected from H, alkyl, cycloalkyl, aryl, alkylaryl, aralkyl, alkoxy, -C(=O)O-alkyl and halogen atoms;

[0701] -R f It is H or methyl;

[0702] - Each a' and c' is independently 0 or 1;

[0703] -b' is 1 or 2.

[0704] Aspect 22. The oligomer according to aspect 18, wherein in formula (B3), Al is an aliphatic linking moiety selected from alkylene, heteroatom-containing alkylene, cycloalkylene, heterocycloalkylene, and combinations thereof.

[0705] Aspect 23. Oligomers of any one of Aspects 18 or 22, wherein, in formula (B3), Al is represented by one of formulas (22) to (29):

[0706] in

[0707] -L is defined above for the connector Ar;

[0708] - Each Cy is independently a optionally substituted divalent cycloalkyl or heteroalkylene group, preferably a divalent cycloalkyl or heteroalkylene group optionally substituted by one or more groups selected from alkyl, cycloalkyl, aryl and halogen atoms;

[0709] - Each Cy Independently, it is an optionally substituted trivalent cycloalkyl or heterocyclic alkyl group, preferably a trivalent cycloalkyl or heterocyclic alkyl group optionally substituted by one or more groups selected from alkyl, cycloalkyl, aryl and halogen atoms;

[0710] - Each Alk is independently a divalent alkylene or a heteroatom-containing alkylene;

[0711] - Each Alk Independently a trivalent alkylene group or an alkylene group containing heteroatoms;

[0712] - Each Alk It is independently a tetravalent alkylene or an alkylene containing heteroatoms.

[0713] Aspect 24. Oligomers of any one of Aspects 18 or 22, wherein, in formula (B3), Al is represented by one of formulas (30) to (41):

[0714]

[0715] in

[0716] -L is defined above for the connector Ar;

[0717] -R' e As defined in equation (17) above;

[0718] - Each R g 、R' g R h R i and R' i Independently H or alkyl;

[0719] - Each R j Independently, it can be H, alkyl, cycloalkyl, aryl, alkylaryl, aralkyl, alkoxy, -C(=O)O-alkyl, or a halogen atom;

[0720] -R k 、R' k and R'' k Independently alkylene;

[0721] -d' is 1 to 12;

[0722] - Each e' and f' is independently 0 or 1.

[0723] Oligomers of aspect 25 and aspect 18, wherein, in formula (B4), Ar It is an aromatic divalent linkage that includes at least one arylene moiety, more particularly at least one optionally substituted phenylene moiety, and even more particularly at least one phenylene moiety optionally substituted by one or more groups selected from alkyl, cycloalkyl, aryl and halogen atoms.

[0724] Aspect 26. The oligomer according to any one of Aspects 18 or 25, wherein, in formula (B4), Ar Corresponding to one of the above-defined equations (6) to (9), (16) or (17), equation (16) is preferred.

[0725] Oligomers of aspect 27 and aspect 18, wherein in formula (B4), Al It is an aliphatic divalent linkage selected from alkylene, heteroatom-containing alkylene, cycloalkylene, heterocycloalkylene, and combinations thereof.

[0726] Aspect 28. Oligomers of aspects 18 or 27, wherein, in formula (B4), Al It is represented by one of the formulas (1), (2), (3), (4), (5), (22)-(26), (30), (31), (36), (37), (38) or (41) as defined above.

[0727] Aspect 29. An oligomer of any one of Aspects 1-28, wherein segment b) has a structure of formula (B6) or (B7), preferably (B6):

[0728] (B6)

[0729] (B7)

[0730] in:

[0731] -t-Bu is tert-butyl;

[0732] -R1 is H or methyl;

[0733] - The symbol § indicates the connection point with link segment c).

[0734] Aspect 30. An oligomer of any one of aspects 1-29, wherein the total amount of chain segment b) in the dual-curable oligomer of the present invention accounts for 20 to 90% by weight, particularly 30 to 85% by weight, and even more particularly 40 to 80% by weight of the total weight of the dual-curable oligomer.

[0735] Aspect 31. An oligomer of any one of Aspects 1-30, wherein segment c) has the structure of formula (C1):

[0736] (C1)

[0737] in:

[0738] -c is 0 or 1;

[0739] -U corresponds to equation (U1) or (U2):

[0740] (U1)

[0741] (U2)

[0742] in:

[0743] - Each R7 is an independent residue of diisocyanate;

[0744] - Each R7' is independently a triisocyanate residue;

[0745] - Each R8 is an independent residue of a diol;

[0746] - Each d is independently 0 or an integer from 1 to 10;

[0747] -symbol Indicates the connection point with link segment a);

[0748] - The symbol § indicates the connection point with link segment b).

[0749] Aspect 32. Oligomers of aspect 31, wherein, in formula (U1), each R7 is independently selected from one of formulas (42) to (51):

[0750] in:

[0751] - Each Alk' is independently a straight-chain or branched alkylene, particularly methylene, 1,2-ethylene, 1,2- or 1,3-propylene, 1,2-, 1,3- or 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 2,2,4- or 2,4,4-trimethylhexylene, 1,8-octylene, 1,9-nonylene, 1,10-decylene, 1,12-dodecylene, 1,18-octadecylene;

[0752] - Each Ar' is independently an optionally substituted arylene, particularly an optionally substituted arylene selected from phenylene, tolyne, biphenylene, naphthylene, anthracene, and more particularly an arylene optionally substituted by one or more groups selected from alkyl, cycloalkyl, aryl, and halogen atoms.

[0753] - Each Cy' is independently an optionally substituted cycloalkylene, particularly an optionally substituted cyclohexylene, and even more particularly a cycloalkylene optionally substituted with one or more groups selected from alkyl, cycloalkyl, aryl and halogen atoms.

[0754] Aspect 33. Oligomers of aspect 31, wherein, in formula (U2), each R7' is independently selected from one of formulas (52) to (58):

[0755]

[0756] in

[0757] - Each Alk'' is independently a straight-chain or branched alkylene group, particularly methylene, methanetriyl, undecane-1,6,11-triyl;

[0758] - Each Ar'' is independently an optionally substituted arylene, particularly an optionally substituted arylene selected from phenylene, tolyne and biphenylene, and more particularly an arylene optionally substituted by one or more groups selected from alkyl, cycloalkyl, aryl and halogen atoms;

[0759] - Each R7 is independently defined as above for formula (U1), in particular 1,6-hexamethylene.

[0760] Oligomers of aspect 34 and aspect 31, wherein U is selected from:

[0761] - A portion of equation (U1), wherein each R7 is independently selected from one of equations (42), (44), (46), (49), or (50) as defined above:

[0762] in

[0763] Each Alk' is independently a straight-chain or branched alkylene, particularly methylene, 1,2-ethylene, 1,2- or 1,3-propylene, 1,2-, 1,3- or 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 2,2,4- or 2,4,4-trimethylhexylene, 1,8-octylene, 1,9-nonylene, 1,10-decylene, 1,12-dodecylene, 1,18-octadecylene;

[0764] Each Cy' is independently an optionally substituted cycloalkylene group, particularly an optionally substituted cyclohexylene group, and even more particularly a cycloalkylene group optionally substituted by one or more groups selected from alkyl, cycloalkyl, aryl and halogen atoms;

[0765] - part of formula (U2), wherein R7 corresponds to formula (57) as defined above, wherein each R7 is independently a straight-chain or branched alkylene, particularly 1,6-hexene;

[0766] And their mixtures.

[0767] Aspect 35. Oligomers of aspect 31, wherein each R8 independently corresponds to a divalent linker selected from one of formulas (1) to (5) as defined above for R3.

[0768] Aspect 36. An oligomer of any one of Aspects 1-35, wherein the total amount of segment c) in the dual-curable oligomer accounts for 3 to 60% by weight of the total weight of the dual-curable oligomer, particularly 4 to 40% by weight, and even more particularly 5 to 20% by weight.

[0769] Aspect 37. Oligomers of any one of Aspects 1-36, having the structure of formulas (I)-(III):

[0770] (I)

[0771] (II)

[0772] (III)

[0773] Where a, b, c, R1, R2, R3, R4, R5 and U are as defined above.

[0774] Aspect 38. An oligomer of any one of Aspects 1-37, having a structure of formula (IIIa), (IIIb), (IIIc) or (IIId):

[0775] (IIIa)

[0776] (IIIb)

[0777] (IIIc)

[0778] (IIId)

[0779] Where a, b, R1, R3, R5, Ar, Al, Ar And Al As defined above.

[0780] Aspect 39. An oligomer of any one of Aspects 1-38, having the structure of formula (IIIe):

[0781] (IIIe)

[0782] Where a, R1, R3, and t-Bu are defined as above.

[0783] Aspect 40. An oligomer of any one of Aspects 1-37, having a structure of formula (IV) or (V):

[0784] (IV)

[0785] (V)

[0786] Where a, b, d, R1, R3, R4, R5, R7 and R8 are defined as above.

[0787] Aspect 41. An oligomer of any one of Aspects 1-37, having a structure of formula (IVa), (IVb), (IVc) or (IVd):

[0788]

[0789] in:

[0790] Where a, b, d, R1, R3, R5, R7, R8, Ar, Al, Ar And Al As defined above.

[0791] Aspect 42. The oligomer of any one of Aspects 1-37, having a dual-curable oligomer structure of formula (IVe):

[0792] in:

[0793] Where a, d, R1, R3, R7, R8 and t-Bu are as defined above.

[0794] Aspect 43. A method for preparing a dual-curable oligomer of any one of aspects 1-42, comprising the step of reacting an olefinically unsaturated monoisocyanate component and an epoxy monohydric alcohol component.

[0795] Aspect 44. A method for preparing a dual-curable oligomer of any one of aspects 1-42, comprising the step of reacting an olefinically unsaturated monohydric alcohol component, a polyisocyanate component, an epoxy monohydric alcohol component, and optionally a diol component.

[0796] Aspect 45. The method of aspect 43 or 44, wherein:

[0797] - The olefinic unsaturated monoisocyanate component comprises at least one compound having at least one olefinic unsaturation and a single NCO group or a capped NCO group;

[0798] - The epoxy monohydric alcohol component comprises at least one compound having at least one epoxy group and a single hydroxyl group, preferably a single secondary hydroxyl group;

[0799] - An olefinically unsaturated monohydric alcohol component comprises at least one compound having at least one olefinically unsaturated degree and a single OH group;

[0800] - The polyisocyanate component contains at least one compound having at least two NCO groups or NCO groups capped; and / or

[0801] - The diol component contains at least one compound having two hydroxyl groups.

[0802] Aspect 46. The method of aspect 43 includes the step of reacting an olefinically unsaturated monoisocyanate component comprising at least one compound having the structure of formula (A) with an epoxy monohydric alcohol component comprising at least one compound having the structure of formula (B):

[0803] (A) (B)

[0804] in:

[0805] - a, b, R1, R2, R3, R4 and R5 are as defined by chain segments a) and b);

[0806] - X1 is an NCO group or a capped NCO group;

[0807] - X2 is a hydroxyl group, preferably a secondary hydroxyl group.

[0808] Aspect 47. The method of aspect 46, wherein the amounts of (a) and (B) are such that the equimolar ratio of [OH group of (B)] / [NCO group of (A)] ranges from 1 / 2 to 2 / 1, or 1 / 1.5 to 1.5 / 1, or 1 / 1.1 to 1.1 / 1, or 1.05 / 1 to 1.05 / 1, or about 1 / 1.

[0809] Aspect 48. The method of aspect 44, comprising the step of reacting an olefinically unsaturated monohydric alcohol component comprising at least one compound having the structure of formula (D), a polyisocyanate component comprising at least one compound having the structure of formula (E1) or (E2), an epoxy monohydric alcohol component comprising at least one compound having the structure of formula (B), and optionally a diol component comprising at least one compound having the structure of formula (F):

[0810] (D) (E1) (E2)

[0811] (F) (B)

[0812] in:

[0813] - a, b, R1, R2, R3, R4, R5, R7, R7' and R8 are as defined by chain segments a), b) and c);

[0814] - Each X3 is an NCO group or a capped NCO group independently;

[0815] - X2 is a hydroxyl group, preferably a secondary hydroxyl group.

[0816] Aspect 49. The method of aspect 48, wherein the amounts of (D), (E1), (E2), (F) and (B) are such that the equimolar ratio [OH group of (D) + OH group of (B) + OH group of (F)] / [NCO group of (E1) or (E2)] ranges from 1 / 2 to 2 / 1, or 1 / 1.5 to 1.5 / 1, or 1 / 1.1 to 1.1 / 1 or 1.05 / 1 to 1.05 / 1, or about 1 / 1.

[0817] Methods of any of the aspects 50 and 43-49, including mixing all reactants and components substantially simultaneously in a “one-step” process.

[0818] Aspect 51. The method of any one of Aspects 43-49, comprising the stepwise addition of reactants with or without the addition of other ingredients and optional additives.

[0819] Aspect 52. The method according to any one of Aspects 43-51, wherein the method is carried out, for example by melt extrusion, at a temperature of 60°C to 250°C, such as 65°C to 200°C or 70°C to 150°C, in the presence of a solvent in an amount of less than 5% by weight, or even preferably in the absence of an organic solvent.

[0820] Aspect 53. The method of any one of Aspects 43, 45-46, wherein the epoxy monohydric alcohol component comprises at least one compound having the structure of formula (B2a), (B3a), (B4a) or (B5a):

[0821]

[0822] in:

[0823] -R5, X2, and b are defined as above;

[0824] -Ar, Al, Ar And Al As defined above for chain segment b) of equations (B2), (B3), (B4), or (B5).

[0825] Aspect 54. The method of any one of Aspects 43, 45-46, and 53, wherein the olefinic unsaturated monoisocyanate component comprises at least one compound selected from: ethyl 2-isocyanate methacrylate (MOI), ethyl 2-isocyanate acrylate (AOI, AOI-VM), ethyl 2-(O-[1'-methylpropyleneamino]carboxyamino) methacrylate (MOI-BM), ethyl 2-[(3,5-dimethylpyrazolyl)carboxyamino] methacrylate (MOI-BP), 1,1-(bisacryloyloxymethyl)ethyl isocyanate (BEI), 2-[2-(methacryloyloxy)ethoxy]ethyl isocyanate (MOI-EG), and mixtures thereof.

[0826] Aspect 55. The method of aspect 44 or 45, wherein the olefinic unsaturated monohydric alcohol component comprises at least one compound having the structure of formula (D1a):

[0827] (D1a)

[0828] in:

[0829] A, R1, and R3 are as defined above for chain segment a).

[0830] Aspect 56. The method of any one of Aspects 44-45 and 55, wherein the olefinically unsaturated monohydric alcohol component comprises at least one compound selected from: hydroxyalkyl (meth)acrylates (e.g., 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, neopentyl glycol mono(meth)acrylate or 1,6-hexanediol mono(meth)acrylate), 2-hydroxy-3-phenoxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, tris(2-hydroxyethyl)isocyanurate di(meth)acrylate, di-, tri-, tetra- or polyethylene glycol mono(meth)acrylate, di-, tri-, tetra- or poly(1,2-propanediol) mono(meth)acrylate, di-, tri-, tetra- Or poly(1,3-propanediol) mono(meth)acrylate, di-, tri-, tetra- or poly(1,4-butanediol) mono(meth)acrylate, glycerol di(meth)acrylate, 2-hydroxy-1-acryloyloxy-3-(meth)acryloyloxypropane, trimethylolpropane di(meth)acrylate, di(trimethylolpropane)tri(meth)acrylate, trimethylolethane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and their alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives and their (poly)caprolactone derivatives obtained by ring-opening polymerization of ε-caprolactone initiated with one of the above-mentioned hydroxyl-functionalized (meth)acrylate compounds (i.e., (poly)caprolactone (meth)acrylate, such as (poly)caprolactone 2-hydroxyethyl (meth)acrylate according to the following formula): CH2=CR 11 -C(=O)-O-CH2-CH2-[O-(C=O)-(CH2)5] t -OH, where R 11 It is H or methyl, t is 1-20), and combinations thereof.

[0831] Aspect 57. The method of any one of Aspects 44-45, 55 and 56, wherein the polyisocyanate component comprises a diisocyanate having the structure of formula (E1) and / or a triisocyanate having the structure of formula (E3):

[0832] (E1)

[0833] Compound (E2)

[0834] in:

[0835] -R7 and R7' are defined as in link segment c) above.

[0836] -X3 is an NCO group or a capped NCO group.

[0837] Aspect 58. The method of aspect 57, wherein the diisocyanate (E1) is selected from 2,4- and 2,6-toluene diisocyanate (TDI), isophorone diisocyanate (IPDI - corresponding to 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate), methylene diisocyanate, ethylene diisocyanate, 1,2- or 1,3-propylidene diisocyanate, 1,2-, 1,3- or 1,4-butylidene diisocyanate, 1,5-pentamethylene diisocyanate (PDI), 1,6-hexamethylene diisocyanate Acetate (HDI), 2,2,4- and 2,4,4-trimethylhexamethylene diisocyanate (TMDI), 1,10-decylene diisocyanate, 1,12-dodecylene diisocyanate, 1,18-octadecylene diisocyanate, 2,2'-, 2,4'- and 4,4'-diphenylmethane diisocyanate (MDI), 2,2'-, 2,4'- and 4,4'-dicyclohexylmethane diisocyanate (H12MDI), benzidine diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate Isocyanates, bianisidine diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 1,3- and 1,4-phenylene diisocyanate, 1,4- and 1,5-naphthylene diisocyanate (NDI), 1,4- and 9,10-anthraylene diisocyanate, 1,3- and 1,4-cyclohexane diisocyanate, 1-methyl-2,4-diisocyanate cyclohexane, 1-methyl-2,6-diisocyanate cyclohexane, 1,3- and 1,4-bis(isocyanate methyl)cyclohexane, m-tetramethyl Xylene diisocyanate, m-xylene diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-ethoxy-1,3-phenylene diisocyanate, 5,6-dimethyl-1,3-phenylene diisocyanate, 2,4'- or 4,4'-diisocyanate diphenyl ether, lysine diisocyanate, dimer acid diisocyanate, dimers of the aforementioned diisocyanates (especially urea diketone or urethane dimers), and polyurea or polyurethane prepolymers functionalized with isocyanate functional groups, and combinations thereof.

[0838] Aspect 59. The method of aspect 57, wherein the triisocyanate (E2) is selected from 1,6,11-undecane triisocyanate, triphenylmethane triisocyanate, 2,4,6-toluene triisocyanate, diphenyl ether of 2,4,4'-triisocyanate, trimers of the diisocyanates detailed in formula (E1) above (especially isocyanurate or biuret trimers), polymeric derivatives of the diisocyanates detailed in formula (E1) above, and combinations thereof.

[0839] 60. The method of any one of aspects 44-45, 55-56 and 58, wherein the diisocyanate is isophorone diisocyanate.

[0840] Aspect 61. The method of any one of Aspects 48-53 and 55-60, wherein the diol component comprises a variety of repeating units, such as oxoalkylene units, ester units, carbonate units, acrylic units, alkylene units, etc., or combinations thereof.

[0841] 62. The method of any one of aspects 43-61, wherein the method is carried out in the presence of at least one catalyst.

[0842] Aspect 63. The method of aspect 62, wherein the catalyst is selected from the following: organic and inorganic acid salts of bismuth, lead, tin, iron, antimony, uranium, cadmium, cobalt, thorium, aluminum, mercury, zinc, nickel, cerium, molybdenum, vanadium, copper, manganese and zirconium, as well as organometallic derivatives, and phosphine and organic tertiary amines.

[0843] Aspect 64. The method of any one of Aspects 43-63, wherein the method is carried out in the presence of at least one stabilizer such as an antioxidant, a light blocker / absorber or a polymerization inhibitor.

[0844] Aspect 65. A curable composition comprising at least one dual-curable oligomer according to any one of aspects 1-42.

[0845] Aspect 66. Aspect 65 of curable compositions comprising 5% to 99.9% by weight of one or more dual-curable oligomers, such as 10% to 99.5% by weight, 20% to 99% by weight, 30% to 98% by weight, 50% to 97% by weight, or 60% to 95% by weight, based on the total weight of the curable composition.

[0846] A curable composition of aspect 67. or aspect 65 or 66, further comprising one or more of the following:

[0847] a. A polymerizable component comprising one or more olefinically unsaturated compounds and / or one or more cationically polymerizable compounds, in addition to the dual-curable oligomer;

[0848] b. Inhibitors;

[0849] c. Initiator, which is selected from free radical initiators, cationic initiators, and combinations thereof;

[0850] d. Epoxy crosslinking agent;

[0851] e. Additives selected from antioxidants, ultraviolet absorbers, light stabilizers, foam inhibitors, flow agents or leveling agents, colorants, pigments, dispersants (wetting agents), sliding additives, fillers, thixotropic agents, matting agents, waxes, and any additives and combinations thereof that are conventionally used in coatings, sealants, adhesives, inks or molding compositions.

[0852] Aspect 68. A curable composition of aspect 67, wherein the polymerizable component comprises one or more olefinically unsaturated compounds selected from (meth)acrylate-functionalized monomers, (meth)acrylate-functionalized oligomers, and mixtures thereof.

[0853] Aspect 69. Aspect 67 or 68 of a curable composition comprising 10 ppm to 5 wt%, 20 ppm to 4 wt%, 50 ppm to 3 wt%, 100 ppm to 1 wt%, or 120 ppm to 0.1 wt% of one or more inhibitors, based on the total weight of the curable composition.

[0854] 70. A curable composition of any one of aspects 67-69, comprising an initiator selected from free radical initiators, cationic initiators, and combinations thereof.

[0855] Aspect 71. A curable composition of any one of Aspects 67-70, wherein the epoxy crosslinking agent is a compound comprising one or more functional groups selected from amines, carboxylic acids, acid anhydrides or thiols.

[0856] Use of any curable composition of any one of aspects 65-71 as an adhesive, ink, mask for printing, coloring system, 3D printing resin, sealant or coating.

[0857] Aspect 73. Method of using the curable composition of any one of Aspects 65-71 as an adhesive, ink, mask for printing, coloring system, 3D printing resin, sealant or coating.

[0858] The use of the curable composition according to any one of aspects 74, 65-71 as a UV / EB curable resin, particularly as an adhesive for electrical or electronic components in navigation systems and devices for measuring orientation, such as gyroscopes.

[0859] Aspect 75. A method of using the curable composition of any one of Aspects 65-71 as a UV / EB curable resin, particularly as an adhesive for electrical or electronic components in navigation systems and in devices for measuring orientation, such as gyroscopes.

[0860] Aspect 76. A method for preparing a cured composition, the method comprising curing the curable composition described in any one of aspects 65-71.

[0861] Aspect 77. The method of aspect 76 includes exposing a curable composition to UV / EB radiation and heat.

[0862] Aspect 78. A cured composition obtained by curing any one of the curable compositions of aspects 65-71.

[0863] Although the invention has been described in detail with reference to illustration and examples for ease of understanding, those skilled in the art will understand that certain changes and modifications can be made within the scope of the appended claims. Furthermore, each reference provided herein is incorporated herein by reference in its entirety as if it were incorporated individually by reference. In the event of any conflict between this application and the references provided herein, this application shall prevail.

[0864] Example

[0865] The following examples illustrate the present invention but are not intended to limit it.

[0866] raw material

[0867]

[0868] Table 1

[0869] Methods for measuring the properties of dual-curable oligomers

[0870] Viscosity

[0871] The viscosity of the oligomers was measured using a Brookfield RVDV-II+Pro instrument at 60°C with a #28 rotor and a rotational speed of 20 rpm. Additionally, the viscosity of the oligomers was measured using a Brookfield RVDV-II+Pro instrument at 25°C with a #28 rotor and a rotational speed of 10 rpm.

[0872] Epoxy Equivalent (EEW)

[0873] EEW is measured according to ASTM D1763-1981.

[0874] Refractive index

[0875] The refractive index of the oligomers was measured at 25°C using an RX-7000α from ATAGO.

[0876] Tensile strength, modulus, elongation at break

[0877] These mechanical properties are measured according to ASTM D638.

[0878] Synthesis of oligomers

[0879] Comparison of oligomers (reference)

[0880] Bisphenol A epoxy resin (77 g) and Me-HQ (0.14 g) were added to a four-necked round-bottom flask and stirred. Dry air was injected into the flask, and then the flask was heated to 80°C. TPP (0.36 g) was added to the flask. AA (22 g) was introduced into the flask simultaneously with TPP at a constant rate for 240 minutes. The flask was heated to 110°C and maintained at this temperature for 60 minutes after the initial addition of AA until an acid value below 1 mg KOH / g and an epoxy value below 60 mg KOH / g were achieved. The obtained comparative epoxy acrylate oligomer has the following structure:

[0881]

[0882] Viscosity (60℃): Approximately 2390 mPa·s

[0883] EEW: 1020 g / equivalent

[0884] Oligomer A (Invention)

[0885] Add EPICLON® HP-820 (310 g), BHT (0.80 g), and DBTDL (0.3 g) to a four-necked round-bottom flask and stir. Inject dry air into the flask. Add AOI-VM (99 g) to the flask, and then heat the flask to 80°C. After starting to add AOI-VM, maintain the temperature at 80°C for 60 minutes. Oligomer A has the following structure:

[0886]

[0887] Viscosity (25°C): Approximately 7,000 mPa·s

[0888] EEW: 295 g / equivalent

[0889] Oligomer B (Invention)

[0890] Add EPICLON® HP-820 (310 g), BHT (0.80 g), and DBTDL (0.3 g) to a four-necked round-bottom flask and stir. Inject dry air into the flask. Add Karenz BEI (168 g) to the flask and heat the flask to 80°C. After starting the addition of Karenz BEI, maintain the temperature at 80°C for 60 minutes. Oligomer B has the following structure:

[0891]

[0892] Viscosity (60°C): Approximately 16,000 mPa·s

[0893] EEW: 305 g / equivalent

[0894] Oligomer C (Invention)

[0895] IPDI (74 g), BHT (0.80 g), and DBTDL (0.3 g) were added to a four-necked round-bottom flask and stirred. Dry air was injected into the flask. SR444D NS (173 g) was added to the flask, and the mixture was stirred continuously for 30 minutes. Then EPICLON® HP-820 (212 g) was added to the flask. The flask was then slowly heated to 80°C. After the addition of EPICLON® HP-820 was started, the temperature was maintained at 80°C for 60 minutes. Oligomer C has the following structure:

[0896]

[0897] Viscosity (25°C): Approximately 3,800 mPa·s

[0898] EEW: 488 g / equivalent

[0899] Oligomer D (contrast)

[0900] Add E-42 (400.00 g), BHT (0.80 g), and DBTDL (0.32 g) to a four-necked round-bottom flask and stir. Inject dry air into the flask and heat the mixture to 50°C. Add AOI-VM (21.74 g) to the flask, and then heat the flask to 80°C. After starting to add AOI-VM, maintain the temperature at 80°C for 60 minutes. Oligomer D has the following structure:

[0901]

[0902] Viscosity (60°C): Approximately 3,425 mPa·s

[0903] EEW: 262 g / equivalent

[0904] The viscosity, refractive index, and EEW measurement results for the example oligomers are summarized in Table 2 below.

[0905]

[0906] Table 2

[0907] Tests performed on compositions containing oligomers (comparative and in this invention)

[0908] Storage stability

[0909] Storage stability was tested by placing the oligomers under test alone or mixed with ADH (as a curing agent) at 65°C for 48 hours (thermal test) and measuring their viscosity (cps@60°C).

[0910] The results are listed in Table 3 below.

[0911]

[0912] Table 3

[0913] After being stored at 65°C for 48 hours, neither the reference nor oligomer C showed significant viscosity changes when not mixed with ADH.

[0914] However, when the reference oligomer (comparative) was mixed with 20% by weight of ADH, the composition gelled after 48 hours at 65°C. In contrast, oligomer C (of the present invention) exhibited a smaller viscosity change (+ / -10%), which makes it more performant for a longer pot life and ideal for power-consuming, coating, sealing, and packaging processes, especially those processes that require viscosity stability during processing based on their valuable dispensing or patterned dimensional control requirements.

[0915] Mechanical properties

[0916] Mechanical property tests were performed on compositions containing the oligomer to be tested mixed with SR506, a photoinitiator, and / or a curing agent, as detailed in Tables 4, 5, and 6 below.

[0917] UV + thermosetting test: Mix 80 wt% of the oligomer with 20 wt% of SR506. Add 3 wt% of TPO and 1 wt% of 2E4MZ to the mixture (based on the total weight of oligomer + SR506).

[0918]

[0919] Table 4

[0920] UV curing test: Mix 80% by weight of the oligomer with 20% by weight of SR506. Add 3% by weight of TPO (based on the total weight of oligomer + SR506) to the mixture.

[0921]

[0922] Table 5

[0923] Test for thermosetting: Mix 80% by weight of the oligomer with 20% by weight of SR506. Add 1% by weight of 2E4MZ to the mixture (based on the total weight of oligomer + SR506).

[0924]

[0925] Table 6

[0926] As mentioned above, oligomer C exhibits both photoreactivity and thermal reactivity, making it ideal for dual-curing applications. In particular, the combination of olefinic unsaturation and epoxy groups provides synergistic properties to oligomer C or any oligomer incorporating this combination of functional groups. Measurements of its mechanical properties confirm that oligomer C is a flexible, rather than a rigid, material, due to the presence of flexible segments within its structure. Oligomer C not only exhibits excellent photoreactivity upon exposure to UV and / or thermal curing but also demonstrates excellent storage stability. It is well-suited for one-pot formulations when mixed with a curing agent.

Claims

1. A dual-curable oligomer comprising: a) A segment containing at least one olefinic unsaturation; b) A segment containing at least one epoxy group; c) A segment containing at least one carbamate bond; Links a) and b) are connected to each other via link c).

2. The oligomer according to claim 1, wherein segment a) has a structure of formula (A1) or (A2): (A1) (A2) in: - a is at least 1; - Each R1 is independently H or CH3; - Each R2 is independently selected from the direct connection key, -C(=O)-O-、 -C(=O)-NH-, -O- and -CH2-O-, Indicates the connection point with a carbon-carbon double bond; - R3 is the (a+1) valence connection part; and - symbol This indicates the connection point with link segment c).

3. The oligomer according to claim 1 or 2, wherein segment b) has the structure of formula (B1): (B1) in: - b is at least 1; - R4 is the (b+1) valence connection part; - Each R5 is independently selected from direct bond, -O-CH2-# and -C(=O)-O-CH2-#, with -O-CH2-# being preferred; - The symbol # indicates the junction point with the epoxide ring; and - The symbol § indicates the connection point with chain segment c).

4. The oligomer according to any one of claims 1 to 3, wherein segment b) has a structure of any one of formula (B2), (B3), (B4) or (B5): (B2) (B3) (B4) (B5) in: - R5, b and symbol § are as defined in claim 3; - Ar is the (b+1) valence aromatic linkage part; - Al is the (b+1) valence aliphatic linkage; - Ar It is the divalent aromatic linkage; and - Al It is a divalent aliphatic linker.

5. The oligomer according to any one of claims 1 to 4, wherein segment b) has the structure of formula (B4), and Ar It is represented by the following formula (16): (16) in: - Each R e Independently selected from H, alkyl, cycloalkyl, aryl, alkylaryl, aralkyl, alkoxy, -C(=O)O-alkyl and halogen atoms, preferably selected from H and alkyl; - Each a' is independently 0 or 1, preferably 0.

6. The oligomer according to any one of claims 1 to 5, wherein segment c) has the structure of formula (C1): (C1) in: - c is 0 or 1; - U corresponds to equation (U1) or (U2): (U1) (U2) in: - Each R7 is an independent residue of diisocyanate; - Each R7' is independently a triisocyanate residue; - Each R8 is an independent residue of a diol; - Each d is an independent integer from 0 to 10; - symbol Indicates the connection point with link segment a); - The symbol § indicates the connection point with chain segment b).

7. The oligomer according to any one of claims 1 to 6, wherein it has a structure of any one of formula (I), (II) or (III): (I) (II) (III) Wherein a, b, c, R1, R2, R3, R4, R5 and U are as defined in any one of claims 2 to 6.

8. The oligomer according to claim 7, wherein it has a structure of any one of formula (IIIa), (IIIb), (IIIc) or (IIId): (IIIa) (IIIb) (IIIc) (IIId) Where a, b, R1, R3, R5, Ar, Al, Ar And Al As defined in any one of claims 2 to 6.

9. The oligomer according to claim 8, wherein it has the structure of formula (IIIc), and Ar It is represented by the following formula (16): (16) in: - Each R e Independently selected from H, alkyl, cycloalkyl, aryl, alkylaryl, aralkyl, alkoxy, -C(=O)O-alkyl and halogen atoms, preferably selected from H and alkyl; - Each a' is independently 0 or 1, preferably 0.

10. The oligomer according to claim 7, wherein the oligomer has a structure of formula (IV) or (V): (IV) (V) Wherein a, b, d, R1, R3, R4, R5, R7 and R8 are as defined in any one of claims 2 to 6.

11. The oligomer according to claim 10, wherein it has a structure of any one of formula (IVa), (IVb), (IVc) or (IVd): (IVa) (IVb) (IVc) (IVd) in: Where a, b, d, R1, R3, R5, R7, R8, Ar, Al, Ar And Al As defined in any one of claims 2 to 6.

12. The oligomer according to claim 11, wherein it has the structure of formula (IVc), and Ar It is represented by the following formula (16): (16) in: - Each R e Independently selected from H, alkyl, cycloalkyl, aryl, alkylaryl, aralkyl, alkoxy, -C(=O)O-alkyl and halogen atoms, preferably selected from H and alkyl; - Each a' is independently 0 or 1, preferably 0.

13. The oligomer according to claim 10, wherein the oligomer has a structure of formula (IVe): (IVe) in: Wherein a, d, R1, R3, R7, and R8 are as defined in any one of claims 2 to 6, and t-Bu is tert-butyl.

14. A method for preparing a dual-curable oligomer according to any one of claims 1 to 13, comprising the following steps: - To react the olefinically unsaturated monoisocyanate component with the epoxy monohydric alcohol component; or - Reacts the olefinic unsaturated monohydric alcohol component, the polyisocyanate component, the epoxy monohydric alcohol component, and optionally the diol component.

15. The method of claim 14, further comprising the step of reacting an olefinically unsaturated monoisocyanate component comprising at least one compound having the structure of formula (A) with an epoxy monohydric alcohol component comprising at least one compound having the structure of formula (B): (A) (B) in: - a, b, R1, R2, R3, R4 and R5 as defined in any one of claims 2 to 6; - X1 is an NCO group or a capped NCO group; - X2 is a hydroxyl group, preferably a secondary hydroxyl group.

16. The method of claim 14, further comprising the step of reacting an olefinically unsaturated monohydric alcohol component comprising at least one compound having the structure of formula (D), a polyisocyanate component comprising at least one compound having the structure of formula (E1) or (E2), an epoxy monohydric alcohol component comprising at least one compound having the structure of formula (B), and optionally a diol component comprising at least one compound having the structure of formula (F): (D) (E1) (E2) (F) (B) in: - a, b, R1, R2, R3, R4, R5, R7, R7' and R8 as defined in any one of claims 2 to 6; - Each X3 is an NCO group or a capped NCO group independently; - X2 is a hydroxyl group, preferably a secondary hydroxyl group.

17. A curable composition comprising at least one dual-curable oligomer according to any one of claims 1 to 13.

18. Use of the curable composition according to claim 17 as an adhesive, ink, mask for printing, coloring system, 3D printing resin, sealant or coating.

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