Oligomers comprising polymerized high Tg monomers

Abstract

The present invention relates to oligomers comprising polymerized high Tg monomer units, polymerized low Tg monomer units, polymerized chromophore monomer units, and optionally at least one polymerized additional monomer unit. The invention also relates to an ultraviolet curable composition comprising the oligomer, and a coating formed from the cured ultraviolet curable composition.

Description

Technical Field

[0001] The present invention relates to an oligomer. The oligomer comprises a polymerized high T g Monomer unit, polymerized low T g monomer units, polymerized chromophore monomer units and optionally at least one polymerized additional monomer unit. The present invention also relates to the use of the curable composition as a coating and to a method of coating a substrate. Background Art

[0002] Oligomers having acrylic polymerized monomers and chromophores can generally be crosslinked by irradiation with ultraviolet light (UV light), but there are certain disadvantages during processing. For example, oligomers having a T of equal to or greater than 0°C g Oligomers of ethylene oxide can be difficult to fully crosslink, which can weaken coatings and adhesives derived therefrom. Such difficulties limit their applications due to performance requirements.

[0003] With a T equal to or greater than 0°C g The oligomers can be processed to form high T g coatings and adhesives, with a T of less than 0°C g The oligomers formed by low T g Compared with coatings and adhesives, the high T g Coatings and adhesives offer many advantages, such as improved hardness. However, developing such oligomers that achieve desired properties, such as sufficient crosslinking upon curing, can be challenging. Therefore, it is desirable to have a T of equal to or greater than 0°C. g And maintain highly cross-linked oligomers during curing.

[0004] Embodiments of the oligomers disclosed herein overcome the disadvantages of having a T equal to or greater than 0°C. g The disadvantages associated with known oligomers. Summary of the invention

[0005] The first aspect disclosed herein is an oligomer comprising, based on the total weight of the oligomer: 1 wt % to 95 wt % of a polymerized high T g Monomer units, 0.1 wt % to 98.9 wt % of polymerized low T g monomer units, 0.1 wt % to 40 wt % of polymerized chromophore monomer units, and 0 to 20 wt % of at least one polymerized additional monomer unit; wherein: the high T g The monomer unit has a Fox equation average glass transition temperature (T) equal to or greater than 25°C. g ) of a (meth)acrylate monomer; the low T g The monomer unit has a Fox equation average T of less than 25°C. gThe monovalent (meth) acrylate monomer of the high T g Fox equation average T of monomer unit g Lower than the T g Fox equation average T of monomer unit g The chromophore monomer unit is a (meth)acrylate monomer having a pendent Norrish II type chromophore; the oligomer has a weight average molecular weight of at least 10,000 grams per mole (g / mol); and the oligomer has a T of equal to or greater than 0°C. g .

[0006] Another aspect disclosed herein is a curable composition comprising the oligomer and a reactive diluent.

[0007] Another aspect disclosed herein is a coating formed by curing a UV curable composition.

[0008] Another aspect disclosed herein is a method of preparing the curable composition of the present invention, wherein the method comprises the steps of:

[0009] - preparing the oligomer according to the invention dissolved in a non-reactive solvent;

[0010] - adding a reactive diluent to obtain a diluted curable composition;

[0011] - removing at least part of the non-reactive solvent from the diluted curable composition to obtain the curable composition.

[0012] Another aspect disclosed herein is a method of curing a curable composition of the present invention or prepared by the method of the present invention, wherein the method comprises curing a curable composition comprising an oligomer and a reactive diluent by irradiating the curable composition with a light source having a wavelength and / or intensity capable of activating polymerized chromophore monomer units of the oligomer and causing crosslinking of the oligomer and / or the reactive diluent.

[0013] This Summary is provided to introduce some concepts that are further described in the Detailed Description. This Summary is not intended to identify key or essential features of the claimed subject matter, nor is it intended to be used as an aid in limiting the scope of the claimed subject matter.

[0014] Additional features and advantages of the embodiments will be described in the following detailed description. Additional features and advantages of the embodiments will be apparent to those skilled in the art in part from the description or recognized by practicing the embodiments (including the following detailed description, drawings and claims). BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 A graph of gel content for cured comparative examples and examples according to one or more embodiments described herein;

[0016] Figure 2 A graph of gel content for cured comparative examples and examples according to one or more embodiments described herein;

[0017] Figure 3 A graph of gel content for cured comparative examples and examples according to one or more embodiments described herein;

[0018] Figure 4 A graph of gel content for cured comparative examples and examples according to one or more embodiments described herein;

[0019] Figure 5 A graph of gel content for cured comparative examples and examples according to one or more embodiments described herein;

[0020] Figure 6 is a graph of curing speeds of comparative examples and examples according to one or more embodiments described herein;

[0021] Figure 7 is a graph of curing speeds of comparative examples and examples according to one or more embodiments described herein;

[0022] Reference will now be made in greater detail to various embodiments, examples of which are illustrated in the accompanying drawings. DETAILED DESCRIPTION

[0023] definition

[0024] As used herein, the term "comprising" may mean "including one or more".

[0025] Unless otherwise stated, weight percentages in compounds or compositions are expressed relative to the weight of the compound, respectively composition.

[0026] The term "substituted" as used herein means that at least one hydrogen atom (-H) bonded to a carbon atom or heteroatom of a corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., R S The term "full substitution" means that each hydrogen atom (-H) bonded to a carbon atom or heteroatom of the corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., R SThe term "polysubstituted" means that at least two but less than all hydrogen atoms bonded to carbon atoms or heteroatoms of the corresponding unsubstituted compound or functional group are replaced by substituents. Unless otherwise defined or limited in a particular context, substituents are generally referred to as R S The substituents of can be any chemical moiety, typically but not necessarily limited to chemical moieties having 1 to 50, or 1 to 40, or 1 to 30, or 1 to 20, or 1 to 10 total atoms. The substituent R S Examples of include, but are not limited to, hydrocarbon, heterohydrocarbon, aryl, heteroaryl, alkyl, cycloalkyl, heteroatom, carbonyl, hydroxyl, ester, ether, amine, amide, or halide, as defined herein or as generally understood, wherein any substituent itself may be substituted or unsubstituted. In some embodiments, the substituent R S Can be selected from (C1-C 30 ) hydrocarbon group, (C1-C 30 ) heteroalkyl, (C6-C 30 )aryl or (C6-C 30 ) heteroaryl.

[0027] The term "hydrocarbyl" refers to a monovalent hydrocarbon, wherein each hydrocarbon is aromatic or non-aromatic, saturated or unsaturated, straight chain or branched, cyclic (having three or more carbons, and including monocyclic and polycyclic, fused and non-fused polycyclic and bicyclic) or acyclic, and is substituted by one or more R S In the present disclosure, the hydrocarbon group may be an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, or an unsubstituted or substituted aryl group. The hydrocarbon group may not contain any heteroatoms selected from O, N or S. 30 ) The hydrocarbon group is a hydrocarbon group having 1 to 30 carbon atoms.

[0028] The term "heteroalkyl" refers to an alkyl group with one or more heteroatoms independently selected from O, N or S. 30 ) The heteroalkyl group is a heteroalkyl group having 1 to 30 carbon atoms.

[0029] The term "aryl" refers to an optionally substituted polyunsaturated aromatic group. The aryl group may contain a single ring (i.e., phenyl) or more than one ring, wherein at least one ring is aromatic. When the aryl group contains more than one ring, the rings may be fused, connected by covalent bonds (e.g., biphenyl). The aromatic ring may optionally contain one to two additional fused rings (i.e., cycloalkyl, heterocycloalkyl, or heteroaryl). Examples include phenyl, naphthyl, biphenyl, phenanthryl, and benzanthryl (naphthacenyl).

[0030] The term "alkyl" refers to a group of the formula -C n H 2n+1A monovalent saturated non-cyclic hydrocarbon radical of alkyl, wherein n is 1 to 20. The alkyl group may be linear or branched. Examples of the alkyl group 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, and the like.

[0031] The term "cycloalkyl" refers to a monovalent saturated alicyclic hydrocarbon group containing a ring. Examples of cycloalkyl groups include cyclopentyl, cyclohexyl and isobornyl, any of which may be substituted or unsubstituted.

[0032] The term "heterocycloalkyl" refers to a cycloalkyl group having at least one ring atom as a heteroatom selected from O, N or S.

[0033] The term "halogen" refers to an atom selected from Cl, Br, F and I.

[0034] The term "alkoxy" refers to a group of the formula -O-alkyl, wherein alkyl is as defined above.

[0035] The term "aryloxy" refers to a group of the formula -O-aryl wherein aryl is as defined above.

[0036] The term "thioalkyl" refers to a group of the formula -S-alkyl, wherein alkyl is as defined above.

[0037] The term "thioaryl" refers to a group of the formula -S-aryl wherein aryl is as defined above.

[0038] The term "alkenyl" refers to a monovalent non-cyclic hydrocarbon group containing at least one C=C double bond. The alkenyl group may be straight-chain or branched.

[0039] The term "alkynyl" refers to a monovalent non-cyclic hydrocarbon group containing at least one C≡C triple bond. Alkynyl groups may be straight-chain or branched.

[0040] The term "aralkyl" refers to an aryl group substituted with an alkyl group. An example of an aralkyl group is tolyl.

[0041] The term "alkaryl" refers to an alkyl group substituted with an aryl group. An example of an alkaryl group is benzyl (-CH2-phenyl).

[0042] The term "heteroaryl" refers to an aryl group having at least one ring atom which is a heteroatom.

[0043] The term "alkylamino" refers to an alkyl group substituted with at least one amino group.

[0044] The term "alkylthiol" refers to an alkyl group substituted with at least one thiol group.

[0045] The term "hydroxyalkyl" refers to an alkyl group substituted with at least one hydroxy group.

[0046] The term "haloalkyl" refers to an alkyl group substituted with at least one halogen.

[0047] The term "alkylene" or "alkanediyl" refers to a linker derived from a group consisting of m H 2m+2 The alkane of the linker is prepared by removing one hydrogen atom at each point of attachment of the linker. The alkylene group can be divalent, trivalent, tetravalent or have an even higher valence.

[0048] The term "alkoxylated" refers to compounds, groups or linkers that contain one or more oxyalkylene moieties, in particular one or more oxyalkylene moieties selected from oxyethylene (-O-CH2-CH2-), oxypropylene (-O-CH2-CH(CH3)- or -O-CH(CH3)-CH2-), oxybutylene (-O-CH2-CH2-CH2-CH2-) and mixtures thereof. For example, the alkoxylated compound, group or linker may contain 1 to 30 oxyalkylene moieties.

[0049] The term "(meth)acrylate" refers to acrylate or methacrylate. The term "acrylate" refers to an acryloyloxy group (-OC(=O)-CH=CH2). The term "methacrylate" refers to a methacryloyloxy group (-OC(=O)-C(CH3)=CH2).

[0050] The term (meth)acrylate monomer refers to a monomer carrying a (meth)acrylate group.

[0051] As used herein, the "monomer" has a number average molecular weight of less than 1,000 g / mol, preferably 100 to 950 g / mol.

[0052] As used herein, the "oligomer" has a number average molecular weight equal to or greater than 1,000 g / mol, preferably 1,050 to 60,000 g / mol, more preferably 10,000 to 50,000 g / mol.

[0053] The term "glass transition temperature" or "T g ” refers to the temperature at which a material transitions from a glassy state to a rubbery state. In this case, the term “glassy” means that the material is hard and brittle, while the term “rubbery” means that the material is elastic and flexible. For polymeric materials, T g is the critical temperature that distinguishes its glass and rubber behavior. g At temperatures below 100 °C, large-scale molecular motion is severely restricted because the material is essentially frozen. On the other hand, if a polymer-based material is heated above its T gAt temperatures below 300 °C, molecular motion on the scale of its repeating unit occurs, allowing it to be soft or rubbery.

[0054] The monomer T referred to in this article is g Both refer to the T of the homopolymer formed by the monomer g . Common monomer T g The values ​​are well known in the literature. If not reported in the literature, the glass transition temperature value can be determined as the inflection temperature (T i The glass transition temperatures of the oligomers described herein and in the examples below are calculated using the Fox equation based on the mass fraction of each individual monomer in a polymeric material or oligomer containing more than one discrete monomer type and T g Value calculated.

[0055] The terms "mass fraction" and "weight fraction" are used interchangeably herein and should be considered equivalent for purposes of the examples or embodiments herein.

[0056] The “Fox equation” refers to equation (1):

[0057] 1 / T g,mix ≈∑ i ω i / T g,i Equation (1)

[0058] Among them, T g,mix is the glass transition temperature of a mixture of i chemically unrelated components (such as two or more different monomers of an oligomer or polymer), T g,i is the glass transition temperature of the ith component, and ω i is the mass fraction of the ith component based on the total mass of the oligomer or polymer. Hereinafter, the value T for multiple unrelated monomers in the oligomer or polymer is g,mix The Fox equation average T of multiple unrelated monomers is called g ”.

[0059] For two components A and B of each type of monomer, the Fox equation simplifies to equation (2):

[0060] 1 / T g,mix ≈ω A / T g,A +ω B / T g,B Equation (2)

[0061] The term "high T g "Monomer unit" means a monomer unit which, when homopolymerized, produces a monomer having a T of equal to or greater than 25°C. g In the following oligomer embodiment: only one high T g The monomer units are present in oligomers, and the high T g T of monomer unit g Is this a high T g T of the homopolymer of the monomer unit g In an embodiment of the oligomers wherein two or more types of different high T g The monomer units exist in oligomers, and the high T g T of monomer unit g Commonly referred to as high T g Fox equation average T of monomer unit combination g , where for equation (1), the individual mass fraction ω i is the individual high T in the oligomer g The mass fraction of monomer units based on all high T present in the oligomer g Monomer units (i.e., having a T equal to or greater than 25°C g The total mass of the monomer units) is used as the basis for the calculation, rather than the total mass of the entire oligomer.

[0062] The term "Fox equation average (value)" may be used herein even for a single monomer that is not part of a mixture of two or more monomers. It should be readily understood that the Fox equation average T for a single monomer is g Equal to the T of a single monomer g (as defined herein), since in such case the term mass fraction term ω is equal to 1.

[0063] The term "low T g "Monomer unit" means a monomer unit which, when homopolymerized, produces a monomer having a T of less than 25°C. g In the following oligomer embodiment: only one low T g The monomer units are present in oligomers, the low T g T of monomer unit g Is this a low T g T of the homopolymer of the monomer unit g In an embodiment of the oligomers wherein two or more types of different low T g The monomer units exist in oligomers, and the low T g T of monomer unit g Commonly referred to as low Tg Fox equation average T of monomer unit combination g , where for equation (1), the individual mass fraction ω i It is the individual low T in the oligomer g The mass fraction of the monomer unit, based on all low T present in the oligomer g Monomer units (i.e., having a T of less than 25°C g The total mass of the monomer units) is used as the basis for the calculation, rather than the total mass of the entire oligomer.

[0064] The term "photoinitiator" may be considered to be any type of substance which, when exposed to radiation (eg, actinic radiation), forms a substance that initiates reaction and curing of polymeric organic materials present in the curable composition.

[0065] The term "chromophore" as used herein refers to a Norrish type II light absorbing molecule that enters an excited state upon absorption of light. From this excited state, the molecule can interact or react with other molecules to produce reactive radical species.

[0066] When used to describe certain chemical groups containing carbon atoms, it has the form "A 1 -A 4 " refers to the 1 To A 4 Every A in the range including 1 and 4 x For example, a group of the form "A 1 -A 4 " refers to A 1 , A 2 , A 3 and A 4 . With the form "Z 1 -Z 4 " refers to the expression from Z 1 To Z 4 Every Z in the range including 1 and 4 x For example, a group of the form "Z 1 -Z 4 " refers to Z 1 , Z 2 , Z 3 and Z 4 .

[0067] The term "independently selected from" is used herein to refer to substituents such as Z 1 , Z 2 , Z 3 and Z 4 , which may be the same or different (e.g., Z 1 , Z 2 , Z3 and Z 4 All can be -CH3; or Z 1 and Z 2 Can be -CH3 and Z 3 and Z 4 The chemical names associated with substituents are intended to convey chemical structures that are recognized in the art to correspond to the chemical structures of the chemical names. Therefore, the chemical names are intended to supplement and illustrate, rather than exclude, structural definitions known to those skilled in the art.

[0068] When used to describe certain chemical groups containing carbon atoms, the group having the form "(C x -C y )" means that the unsubstituted form of the chemical group has from x to y carbon atoms, including x and y. For example, (C1-C 20 ) Hydrocarbyl is a hydrocarbon group having 1 to 20 carbon atoms in unsubstituted form. In some embodiments and general structures, certain chemical groups may be substituted by one or more substituents such as R S Replace. Use "(C x -C y )" brackets define the chemical group R S The substituted version may contain more than y carbon atoms, depending on any group R S For example, "being exactly one group R S Substituted (C1-C 20 ) alkyl, wherein R S is phenyl (-C6H5)" may contain 7 to 27 carbon atoms. Therefore, generally when brackets "(C x -C y )" is replaced by one or more carbon-containing substituents R S When substituted, the minimum and maximum total number of carbon atoms in the chemical group is determined by adding all the substituents R containing carbon atoms. S The number of carbon atoms is determined by the combined sum of both x and y.

[0069] The term "-H" refers to a hydrogen atom covalently bonded to an atom other than hydrogen. "Hydrogen" and "-H" are interchangeable and have the same meaning unless expressly stated otherwise.

[0070] The term "(C1-C 30 )hydrocarbyl refers to a monovalent hydrocarbon of 1 to 30 carbon atoms, wherein each monovalent hydrocarbon is aromatic or non-aromatic, saturated or unsaturated, straight chain or branched, cyclic (having three or more carbon atoms, and including monocyclic and polycyclic, fused and non-fused polycyclic and bicyclic) or acyclic, and is substituted by one or more R S In the present disclosure, (C1-C30 The hydrocarbon group may be unsubstituted or substituted (C1-C 30 )alkyl, (C3-C 30 )cycloalkyl or (C6-C 30 )aryl.

[0071] The term "(C2-C 30 )alkyl" refers to an alkyl group which is unsubstituted or substituted with one or more R S Substituted saturated straight or branched monovalent hydrocarbons of 2 to 30 carbon atoms. 30 Examples of alkyl groups are unsubstituted (C2-C 20 ) alkyl; unsubstituted (C6-C 25 )alkyl; unsubstituted (C4-C8)alkyl; 1-butyl; 2-butyl; 2-methylpropyl; 1,1-dimethylethyl; 1-pentyl; 1-hexyl; 1-heptyl; 1-nonyl; and 1-decyl. Substituted (C2-C 30 Examples of alkyl groups are substituted (C2-C 20 ) alkyl, substituted (C2-C 10 )alkyl.

[0072] The term "(C6-C 40 ) aryl" refers to an unsubstituted or (substituted by one or more R S ) substituted monocyclic, bicyclic or tricyclic aromatic monovalent hydrocarbons of 6 to 40 carbon atoms, wherein at least 6 to 14 carbon atoms are aromatic ring carbon atoms. Monocyclic aromatic monovalent hydrocarbons include one aromatic ring; bicyclic aromatic monovalent hydrocarbons have two rings; and tricyclic aromatic monovalent hydrocarbons have three rings. When bicyclic or tricyclic aromatic monovalent hydrocarbons are present, at least one ring of the monovalent hydrocarbon is aromatic. The other one or more rings of the aromatic monovalent hydrocarbon may independently be fused or non-fused and be aromatic or non-aromatic. Unsubstituted (C6-C 40 Examples of aryl groups include: unsubstituted (C6-C 20 ) aryl, unsubstituted (C6-C 18 )aryl; 2-(C1-C5)alkyl-phenyl; phenyl; fluorenyl; tetrahydrofluorenyl; indanyl; tetrahydroindanyl; tetrahydroindanyl; indenyl; dihydroindenyl; naphthyl; tetrahydronaphthyl; and phenanthrene. Substituted (C6-C 40 Examples of aryl groups include: substituted (C1-C 20 ) aryl; and substituted (C6-C 18 )aryl.

[0073] The term "(C6-C 12 ") cycloalkyl" refers to an unsubstituted or substituted saturated cyclic monovalent hydrocarbon of 6 to 12 carbon atoms. Other cycloalkyl groups (e.g., (C x -C y)cycloalkyl) is defined in a similar manner as having x to y carbon atoms and being unsubstituted or substituted by one or more R S Substituted. Unsubstituted (C6-C 12 Examples of cycloalkyl groups are unsubstituted (C6-C8)cycloalkyl, unsubstituted (C6-C 10 )cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl. 12 Examples of cycloalkyl groups are substituted (C6-C8)cycloalkyl, substituted (C6-C 10 )cycloalkyl, isobornyl and 3,3,5-trimethylcyclohexyl.

[0074] The term "heteroatom" refers to an atom other than hydrogen or carbon. Examples of heteroatoms include O, S, N, Si. The term "heterohydrocarbon" refers to a molecule or molecular framework in which one or more carbon atoms of a hydrocarbon are replaced by a heteroatom. The term "(C1-C 30 )heteroalkyl" refers to a monovalent heteroalkyl of 1 to 30 carbon atoms, and the term "(C1-C 30 "Heteroalkylene" refers to a divalent heteroalkyl group of 1 to 30 carbon atoms. (C1-C 30 )heteroalkyl or (C1-C 30 ) The heteroalkylene has one or more heteroatoms. The valence or point of attachment of the heteroalkylene may be on a carbon atom or a heteroatom. The two valences of the heteroalkylene may be on a single carbon atom or a single heteroatom. In addition, one of the two valences or points of attachment of the diradical (diradical) may be on a carbon atom and the other valence may be on a different carbon atom; one of the two valences or points of attachment may be on a carbon atom and the other may be on a heteroatom; or one of the two valences or points of attachment may be on a heteroatom and the other valence or point of attachment may be on a different heteroatom. Each (C1-C 30 ) heteroalkyl and (C1-C 30 The heteroalkylene group may be unsubstituted or substituted, aromatic or non-aromatic, saturated or unsaturated, linear or branched, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic) or acyclic.

[0075] The term "saturated" means lacking carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen, carbon-phosphorus, and carbon-silicon double bonds. S When substituted, the substituent R S One or more double bonds and / or triple bonds may or may not be present. The term "unsaturated" means containing one or more carbon-carbon double bonds, carbon-carbon triple bonds or (in a group containing heteroatoms) one or more carbon-nitrogen, carbon-phosphorus or carbon-silicon double bonds, excluding the substituent R SAny double bonds present in the (hetero)aromatic ring (if any) or any double bonds present in the (hetero)aromatic ring (if any).

[0076] The term "linker" refers to a multivalent group. A linker can connect at least two parts of a compound together, in particular, connect 2 to 16 parts of a compound together. For example, a linker that connects two parts of a compound together is called a divalent linker, and a linker that connects three parts of a compound together is called a trivalent linker.

[0077] Oligomer

[0078] The oligomers of the present invention include at least one polymerized chromophore monomer unit, as defined herein. The oligomers herein also include at least one polymerized high T g Monomer units and at least one polymerized low T g The oligomers herein optionally include at least one polymerized additional monomer unit, as defined herein. The oligomers herein may not include any polymerized high T g Monomer unit, polymerized low T g The polymerized monomer units are other than the monomer units, polymerized chromophore monomer units, and optionally polymerized additional monomer units. g Monomer unit, polymerized low T g The total weight of the monomer units, polymerized chromophore monomer units and polymerized additional monomer units may comprise at least 97%, particularly at least 98%, more particularly at least 99%, still more particularly 100% of the total weight of the oligomer.

[0079] In an embodiment, the oligomer comprises from 1 wt % to 95 wt % of a polymerized high T g Monomer units, 0.1 wt % to 98.9 wt % of polymerized low T g monomer units, 0.1 wt % to 40 wt % polymerized chromophore monomer units, and 0 to 20 wt % polymerized additional monomer units.

[0080] In an embodiment, the oligomer has formula (I):

[0081]

[0082] in:

[0083] - Each A 1 Independently (C1-C 30 )alkyl or (C1-C 30 ) heteroalkyl, preferably (C1-C 30 ) hydrocarbon group, more preferably at least part of A 1 The moiety is selected from isobutyl, tert-butyl or cyclic (C1-C30 ) alkyl;

[0084] - Each A 2 Independently (C2-C 30 )alkyl or (C2-C 30 ) heteroalkyl, preferably (C4-C 30 ) alkyl;

[0085] - Each A 3 is independently a monovalent residue comprising a Norrish type II chromophore, preferably a monovalent residue comprising benzophenone;

[0086] - Each A 4 Independently (C1-C 30 )alkyl or (C1-C 30 ) heteroalkyl, preferably with a -(C1-C 30 ) Heteroalkyl: acidic group, nitrogen-containing group, hydroxyl group, epoxy group, carbonyl group, acetoacetoxy group, acetoacetamide group, 1,1-dimethyl-3-oxobutyl (diacetone) group, thiol group, silane group, ether bond, ester bond and combinations thereof;

[0087] -Z 1 , Z 2 , Z 3 and Z 4 are independently -H or -CH3;

[0088] -m is the high T of the aggregate g Weight fraction of monomer units;

[0089] -n is the low T of the aggregate g Weight fraction of monomer units;

[0090] - p is the weight fraction of polymerized chromophore monomer units;

[0091] -q is the weight fraction of at least one additional monomer unit polymerized, and is optionally zero; and

[0092] -m+n+p+q equals 1.

[0093] In one example, in the oligomer according to formula (I), m may be 0.01 to 0.95; n may be 0.001 to 0.989, p may be 0.001 to 0.4, and q may be 0 to 0.2.

[0094] In some embodiments, q is 0, whereby polymerized additional monomer units are not present in the oligomer.

[0095] For A 1 , A 2 , A 3 , A4 , Z 1 , Z 2 , Z 3 , Z 4 Further preferred expressions for m, n, p and q are defined below for the respective monomer units.

[0096] High T g Monomer unit

[0097] In an embodiment, the oligomer comprises a polymerized high T g monomer units, which can increase the T of the oligomers formed therefrom g . High T g The monomer unit is different from the low T g monomer units, chromophore monomer units and additional monomer units. Therefore, low T g The monomer unit may not contain any of the following groups:

[0098] - chromophore moiety;

[0099] - Functional groups as defined below for the additional monomer units in addition to the ether bonds.

[0100] Polymerized high T g The monomer units may be the same or a combination of multiple types of unrelated monomer units such as two types of unrelated monomer units, three types of unrelated monomer units, four types of unrelated monomer units, or more than four types of unrelated monomer units. g The monomer unit has a glass transition temperature (T) equal to or greater than 25°C. g ) or Fox equation average T g As defined herein, the T of a monomer as referred to herein is g refers to the T of the homopolymer formed by the monomer g In the following embodiments: wherein the oligomer comprises two or more different high T g A combination of monomer units such as methyl (meth)acrylate and isobornyl (meth)acrylate, T g It refers to high T g Fox equation average T of monomer unit g , as defined above in this document. In an embodiment, the high T g Fox equation average T of monomer unit g Greater than 25°C, such as equal to or greater than 30°C, equal to or greater than 35°C, equal to or greater than 40°C, equal to or greater than 45°C, equal to or greater than 50°C, equal to or greater than 55°C, equal to or greater than 60°C, equal to or greater than 65°C, equal to or greater than 70°C, equal to or greater than 75°C, or even equal to or greater than 80°C. In an embodiment, the high T gThe monomer units may have the following T g : 25℃ to 200℃, 25℃ to 150℃, 25℃ to 130℃, 30℃ to 200℃, 30℃ to 150℃, 30℃ to 130℃, 35℃ to 200℃, 35℃ to 150℃, 35℃ to 130℃, 40℃ to 200℃, 40℃ to 150℃, 40℃ to 130℃, 45℃ to 200℃, 45℃ to 150℃, 45℃ to 130℃, 50℃ to 200℃, 50℃ to 150℃, 50℃ to 130℃ , 55°C to 200°C, 55°C to 150°C, 55°C to 130°C, 60°C to 200°C, 60°C to 150°C, 60°C to 130°C, 65°C to 200°C, 65°C to 150°C, 65°C to 130°C, 70°C to 200°C, 70°C to 150°C, 70°C to 130°C, 75°C to 200°C, 75°C to 150°C, or even 75°C to 130°C, or any and all sub-ranges formed by any of these endpoints.

[0101] High T g Fox equation average T of monomer unit g Greater than low T g Fox equation average T of monomer unit g In an embodiment, high T g Fox equation average T of monomer unit g T g Fox equation average T of monomer unit g At least 20°C higher. In an embodiment, the high T g Fox equation average T of monomer unit g With low T g Fox equation average T of monomer unit g The difference between the temperature and the humidity is greater than 20°C, such as greater than 25°C, greater than 30°C, greater than 35°C, greater than 40°C, greater than 45°C, greater than 50°C, greater than 55°C, greater than 60°C, greater than 65°C, greater than 70°C, greater than 75°C, greater than 80°C, greater than 85°C, greater than 90°C, greater than 95°C, greater than 100°C, greater than 105°C, greater than 110°C, greater than 115°C or greater than 120°C. In an embodiment, the high T g Fox equation average T of monomer unit g and low T g Fox equation average T of monomer unit g The difference between is 20°C to 200°C. As a non-limiting example, high T g Fox equation average T of monomer unit g and low T g Fox equation average T of monomer unit gThe difference between the above values ​​may be 20°C to 200°C, 20°C to 150°C, 20°C to 120°C, 20°C to 100°C, 20°C to 90°C, 20°C to 80°C, 20°C to 70°C, 20°C to 60°C, 20°C to 50°C, 20°C to 40°C, 20°C to 30°C, 30°C to 200°C, 30°C to 150°C, 30°C to 120°C, 3 0℃ to 100℃, 30℃ to 90℃, 30℃ to 80℃, 30℃ to 70℃, 30℃ to 60℃, 30℃ to 50℃, 30℃ to 40℃, 40℃ to 200℃, 40℃ to 150℃, 40℃ to 120℃, 40℃ to 100℃, 40℃ to 90℃, 40℃ to 80℃, 40℃ to 70℃, 40℃ to 60℃, 40℃ to ℃ and 50 ℃, 50 ℃ and 20 ℃, 50 ℃ and 150 ℃, 50 ℃ and 120 ℃, 50 ℃ and 100 ℃, 50 ℃ and 90 ℃, 50 ℃ and 80 ℃, 50 ℃ and 70 ℃, 50 ℃ and 60 ℃, 60 ℃ and 200 ℃, 60 ℃ and 150 ℃, 60 ℃ and 120 ℃, 60 ℃ and 100 ℃, 60 ℃ and 90 ℃, 60 ℃ and 80 ℃, 60 ℃ and 70 ℃, 70 ℃ and 200 ℃, 70 ℃ and 150 ℃, 70 ℃ and 120 ℃, 70 ℃ and 100 ℃, 70 ℃ and 90 ℃, 70 ℃ and 80 ℃, 80 ℃ and 200 ℃, 80 ℃ and 150 ℃, 80 ℃ and 120 ℃, 80 ℃ and 100 ℃, or 80 ℃ and 90 ℃, or any and all subranges formed by any of these endpoints.

[0102] High T g The monomer units consist of one or more (meth)acrylate monomers, preferably one or more monofunctional (meth)acrylate monomers.

[0103] In an embodiment, the high T g The monomer units are monovalent. In other embodiments, the high T g The monomer units may be multivalent, wherein a single monomer unit contains two or more active sites that participate in crosslinking during curing. Examples of monovalent monomer units may include ethyl methacrylate and tert-butyl acrylate. Examples of multivalent monomer units may include divalent monomer units, such as dicyclopentadienyl diacrylate.

[0104] In an embodiment, each high T g The monomer units (before polymerisation to form the backbone of the oligomer) may independently be according to formula (II):

[0105]

[0106] in:

[0107] -A 1 is (C1-C 30 )alkyl or (C1-C30 ) heteroalkyl, preferably (C1-C 30 ) a hydrocarbon group; and

[0108] -Z 1 It is -H or -CH3.

[0109] For example, in an embodiment, A 1 is selected from methyl, ethyl, isopropyl, isobutyl, tert-butyl, substituted or unsubstituted (C6-C 12 ) cycloalkyl, or a combination thereof. In an embodiment, A 1 Selected from methyl, tert-butyl, isobornyl, cyclohexyl, or 3,3,5-trimethylcyclohexyl, or a combination thereof.

[0110] Preferably, at least part of the high T g The monomer units are according to formula (I), wherein Z 1 is -H or -CH3 and A 1 isobutyl, tert-butyl, substituted or unsubstituted (C6-C 12 )cycloalkyl, substituted or unsubstituted (C6-C 12 ) aryl, or a combination thereof. More preferably, A 1 is selected from isobutyl, tert-butyl, isobornyl, cyclohexyl, 3,3,5-trimethylcyclohexyl, tert-butylcyclohexyl, benzyl, adamantyl, dicyclopentanyl, tricyclodecyl, -CH2-tricyclodecyl, phenyl, -CH2-CH2-phenyl, or -CH2-CH2-O-phenyl.

[0111] When A 1 When Z is isobutyl or cyclohexyl, 1 For CH3.

[0112] The above embodiment also applies to A in the oligomer of formula (I). 1 Accordingly, A in the oligomer of formula (I) 1 At least a portion of the moieties may be selected from isobutyl, tert-butyl, substituted or unsubstituted (C6-C 12 )cycloalkyl, substituted or unsubstituted (C6-C 12 ) aryl, or a combination thereof. Preferably, A in the oligomer of formula (I) 1At least a portion of the moieties are selected from isobutyl, tert-butyl, isobornyl, cyclohexyl, 3,3,5-trimethylcyclohexyl, tert-butylcyclohexyl, benzyl, adamantyl, dicyclopentyl, tricyclodecyl, -CH2-tricyclodecyl, phenyl, -CH2-CH2-phenyl, or -CH2-CH2-O-phenyl.

[0113] The high T in the oligomers of this paper g Examples of the monomer units include, but are not limited to, monomer units such as 2-phenylethyl methacrylate, 3,3,5-trimethylcyclohexyl acrylate, tert-butyl acrylate, octadecyl methacrylate, octadecyl acrylate, propyl methacrylate, benzyl methacrylate, isobutyl methacrylate, ethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 2,2,2-trifluoroethyl methacrylate, isopropyl methacrylate, isobornyl acrylate, methyl methacrylate, isobornyl methacrylate, phenyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, 4-tert-butylcyclohexyl acrylate, 4-tert-butylcyclohexyl methacrylate, 3,3,5-trimethylcyclohexyl acrylate, 3,3,5-trimethylcyclohexyl methacrylate, substituted or unsubstituted (meth)acrylic acid (C6-C 12 )cycloalkyl ester, adamantyl (meth)acrylate, dicyclopentyl (meth)acrylate, tricyclodecanemethanol mono(meth)acrylate, 2-phenoxyethyl methacrylate, or a combination thereof.

[0114] Preferably, the high T g The monomer unit includes a sterically hindered (meth)acrylate, such as isobutyl methacrylate, tert-butyl (meth)acrylate or a cyclic (meth)acrylate. Examples of suitable cyclic (meth)acrylates include phenyl methacrylate, 2-phenylethyl methacrylate, 2-phenoxyethyl methacrylate, isobornyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, cyclohexyl methacrylate, benzyl methacrylate, adamantyl (meth)acrylate, dicyclopentyl (meth)acrylate, tricyclodecane methanol mono (meth)acrylate, and combinations thereof.

[0115] The sterically hindered (meth)acrylates may optionally be combined with non-sterically hindered (meth)acrylates such as methyl methacrylate.

[0116] High T in oligomers g The weight fraction of the monomer units will vary depending on the desired properties of the oligomer (such as T g , molecular weight and gel content after curing).

[0117] As described herein, m of formula (I) is the polymerized high T in the oligomer. g In further embodiments, m is greater than or equal to 0.01, such as greater than or equal to 0.05, greater than or equal to 0.1, greater than or equal to 0.15, greater than or equal to 0.2, greater than or equal to 0.25, greater than or equal to 0.30, greater than or equal to 0.35, greater than or equal to 0.40, greater than or equal to 0.45, greater than or equal to 0.50, greater than or equal to 0.55, or greater than or equal to 0.60. In an embodiment, m is 0.10 to 0.95, 0.10 to 0.95, 0.10 to 0.90, 0.10 to 0.85, 0.10 to 0.80, 0.10 to 0.75, 0.10 to 0.70, 0.10 to 0.60, 0.10 to 0.50, 0.10 to 0.40, 0.10 to 0.30, 0.10 to 0.20, 0.20 to 0.9 5. 0.20 to 0.90, 0.20 to 0.85, 0.20 to 0.80, 0.20 to 0.70, 0.20 to 0.60, 0.20 to 0.50, 0.20 to 0.40, 0.20 to 0.30, 0.30 to 0.95, 0.30 to 0.90, 0.30 to 0.85, 0.30 to 0.80, 0.30 to 0.70, 0.30 to 0 .60, 0.30 to 0.50, 0.30 to 0.40, 0.40 to 0.95, 0.40 to 0.90, 0.40 to 0.85, 0.40 to 0.80, 0.40 to 0.70, 0.40 to 0.60, 0.40 to 0.50, 0.50 to 0.95, 0.50 to 0.90, 0.50 to 0.85, 0.50 to 0.95, 0.5 From 0 to 0.90, 0.50 to 0.85, 0.50 to 0.80, 0.50 to 0.70, 0.50 to 0.60, 0.60 to 0.95, 0.60 to 0.90, 0.60 to 0.85, 0.60 to 0.80, 0.60 to 0.70, 0.70 to 0.95, 0.70 to 0.90, 0.70 to 0.85, or 0.70 to 0.80.

[0118] In a preferred embodiment, m is from 0.20 to 0.90, in particular from 0.25 to 0.85, more in particular from 0.30 to 0.80, even more in particular from 0.35 to 0.75, still more in particular from 0.40 to 0.75.

[0119] It is understood that when an oligomer includes more than one unrelated type of polymerized high T g Monomer units, high T in oligomers g The weight fraction m of monomer units is equal to the high T of each unrelated type of polymerization in the oligomer gThe sum of the individual weight fractions of the monomer units.

[0120] Low T g Monomer unit

[0121] In an embodiment, the oligomer comprises a polymerized low T g Monomer unit. Low T g Monomer units are different from high T g monomer units, chromophore monomer units and additional monomer units. Therefore, low T g The monomer unit may not contain any of the following groups:

[0122] - chromophore moiety;

[0123] - a functional group as defined below for the additional monomeric unit.

[0124] Polymerized Low T g The monomer units may be the same or a combination of multiple types of unrelated monomer units such as two types of unrelated monomer units, three types of unrelated monomer units, four types of unrelated monomer units, or more than four types of unrelated monomer units. g The monomer unit may have a glass transition temperature (T g ) or less than 25℃ Fox equation average T g As defined herein, the T of a monomer as referred to herein is g refers to the T of the homopolymer formed by the monomer g In the following embodiments: wherein the oligomer comprises two or more different low T g Monomer unit, T g Refers to low T g Fox equation average T of monomer unit g , as previously defined herein. In an embodiment, the low T g The monomer units have a Fox equation average T of less than 25°C, such as less than 20°C, less than 15°C, less than 10°C, less than 5°C, less than 0°C, less than -5°C, less than -10°C, less than -15°C, less than -20°C or less than -30°C. g In an embodiment, the low T g The monomer units have a Fox equation average T of -150°C to 24°C, such as preferably -80°C to 0°C, and most preferably -60°C to -10°C. g .

[0125] Low T g The monomer units consist of one or more (meth)acrylate monomers, preferably one or more monofunctional (meth)acrylate monomers.

[0126] In an embodiment, the low Tg The monomer unit may be monovalent. In an embodiment, the low T g The monomer unit may include (meth)acrylate monomers, including acrylate monomers and methacrylate monomers. Examples of acrylate monomers include sec-butyl acrylate monomers and n-butyl acrylate monomers. Examples of methacrylate monomers include butyl methacrylate monomers and amyl methacrylate monomers.

[0127] In an embodiment, each low T g The monomer units (before polymerizing into the backbone of the oligomer) may independently be according to formula (III):

[0128]

[0129] in:

[0130] -A 2 is (C2-C 30 )alkyl or (C2-C 30 ) heteroalkyl, preferably (C4-C 30 ) a hydrocarbon group; and

[0131] -Z 2 It is -H or -CH3.

[0132] In an embodiment, A 2 Straight or branched chain (C2-C 30 ) alkyl, preferably linear or branched (C4-C 30 ) alkyl. In an embodiment, A 2 Selected from n-butyl, isobutyl, hexyl, 2-ethylhexyl, isooctyl, isodecyl, tridecyl, lauryl or a combination thereof.

[0133] When A 2 When Z is isobutyl or cyclohexyl, 2 Then it is H.

[0134] The above embodiment also applies to A in the oligomer of formula (I). 2 .

[0135] Low T of oligomers gFurther examples of monomer units include, but are not limited to, monomer units selected from the group consisting of n-butyl (meth)acrylate, isobutyl acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, isodecyl (meth)acrylate, tridecyl (meth)acrylate, lauryl (meth)acrylate, nonyl acrylate, decyl (meth)acrylate, octyl (meth)acrylate, propyl acrylate, isobutyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, ethyl acrylate, sec-butyl acrylate, dodecyl acrylate, tetradecyl (meth)acrylate, isopropyl acrylate, amyl (meth)acrylate, benzyl acrylate, cyclohexyl acrylate, hexadecyl (meth)acrylate, 2-methylbutyl acrylate, 2-octyl acrylate, or combinations thereof.

[0136] Preferably, the oligomer has a low T g The monomer unit is n-butyl acrylate.

[0137] Low T in oligomers g The weight fraction of the monomer units will vary depending on the desired properties of the oligomer (such as T g , molecular weight and gel content after curing).

[0138] As described herein, n of formula (I) is the number of oligomers in the polymerization reaction. gIn an embodiment, n is greater than or equal to 0.001, such as greater than or equal to 0.02, greater than or equal to 0.05, greater than or equal to 0.10, greater than or equal to 0.15, greater than or equal to 0.20, greater than or equal to 0.25, greater than or equal to 0.30, greater than or equal to 0.35, greater than or equal to 0.40, greater than or equal to 0.45, greater than or equal to 0.50, greater than or equal to 0.55, greater than or equal to 0.60, greater than or equal to 0.65, greater than or equal to 0.70, greater than or equal to 0.75, or greater than or equal to 0.80.In embodiments, n is 0.001 to 0.989, 0.001 to 0.90, 0.001 to 0.80, 0.001 to 0.70, 0.001 to 0.60, 0.001 to 0.50, 0.001 to 0.40, 0.001 to 0.30, 0.001 to 0.20, 0.001 to 0.10, 0.001 to 0.05, 0.01 to 0.989, 0.01 to 0.90, 0.01 to 0.80, 0.01 to 0.70, 0.01 to 0.60, 0.01 to 0.50, 0.01 to 0.4 0, 0.01 to 0.30, 0.01 to 0.20, 0.01 to 0.10, 0.01 to 0.05, 0.05 to 0.989, 0.05 to 0.90, 0.05 to 0.80, 0.05 to 0.70, 0.05 to 0.60, 0.05 to 0.50, 0.05 to 0.40, 0.05 to 0.30, 0.05 to 0.20, 0.05 to 0.10, 0.10 to 0.989, 0.10 to 0.90, 0.10 to 0.80, 0.10 to 0.70, 0.10 to 0.60, 0.10 to 0. 50, 0.10 to 0.40, 0.10 to 0.30, 0.10 to 0.20, 0.20 to 0.989, 0.20 to 0.90, 0.20 to 0.80, 0.20 to 0.70, 0.20 to 0.60, 0.20 to 0.50, 0.20 to 0.40, 0.20 to 0.30, 0.30 to 0.989, 0.30 to 0.90, 0.30 to 0.80, 0.30 to 0.70, 0.30 to 0.60, 0.30 to 0.50, 0.30 to 0.40, 0.40 to 0.989, 0.30 to 0.90, From 0.90, 0.40 to 0.80, 0.40 to 0.70, 0.40 to 0.60, 0.40 to 0.50, 0.50 to 0.989, 0.50 to 0.90, 0.50 to 0.80, 0.50 to 0.70, 0.50 to 0.60, 0.60 to 0.989, 0.60 to 0.90, 0.60 to 0.80, 0.60 to 0.70, 0.70 to 0.989, 0.70 to 0.90, 0.70 to 0.80, 0.80 to 0.989, 0.80 to 0.90, or 0.90 to 0.989.

[0139] In a preferred embodiment, n is from 0.10 to 0.80, in particular from 0.15 to 0.75, more in particular from 0.20 to 0.70, even more in particular from 0.25 to 0.65, still more in particular from 0.25 to 0.60.

[0140] It is understood that when an oligomer comprises more than one unrelated type of polymerized low T g Monomer unit, low T in the oligomer gThe weight fraction n of monomer units is equal to the low T of each unrelated type of polymerization in the oligomer g The sum of the individual weight fractions of the monomer units.

[0141] Low T g Monomer unit and high T g The weight ratio of the monomer units can be varied depending on the desired properties of the oligomer such as T g and the gel content after curing. In an embodiment, the low T in the oligomer g Monomer unit and high T g The weight ratio of the monomer units can be 10:1 to 1:9, 5:1 to 1:9, 2:1 to 1:9, 1:1 to 1:9, 10:1 to 1:5, 5:1 to 1:5, 2:1 to 1:5, 1:1 to 1:5, 10:1 to 1:5, or any and all subranges formed by any of these endpoints.

[0142] Chromophore monomer unit

[0143] In addition to at least one polymerized high T g Monomer units and at least one polymerized low T g In addition to the monomer unit, the oligomer further comprises at least one polymerized chromophore monomer unit. The chromophore monomer unit is different from the high T g Monomer unit, low T g Monomer units and additional monomer units.

[0144] The polymerized chromophore monomer units can act as photoinitiators and initiate the curing of the oligomer upon irradiation.A photoinitiator is generally a moiety that, upon absorption of light, generates reactive species (ions or free radicals) and initiates one or several chemical reactions or transformations.

[0145] The photoinitiator may include a free radical photoinitiator. The photoinitiator may be selected so that it is susceptible to activation by photons of wavelengths associated with the actinic radiation (e.g., ultraviolet radiation, visible light) intended for curing the curable composition. The Norrish II type (i.e., non-cleavable) photoinitiator portion does not decompose upon excitation, thereby providing a smaller possibility of leaching small molecules from the matrix composition. For reference, see, for example, A. Gilbert, J. Baggott: "Essentials of Molecular Photochemistry", Blackwell, London, 1991). The excited non-cleavable photoinitiator does not decompose into free radicals upon excitation, but rather extracts hydrogen atoms from organic molecules, or more efficiently extracts electrons from electron donors (such as amines or thiols). Electron transfer generates free radical anions on the photoinitiator and free radical cations on the electron donor. Subsequently, protons are transferred from the free radical cations to the free radical anions to generate two uncharged free radicals; wherein the free radicals on the electron donor are sufficiently reactive to abstract hydrogen atoms from most substrates.

[0146] The photoinitiator may be a chromophore. Benzophenone and related ketones (such as thioxanthone, Antonone, anthraquinone, fluorenone, dibenzosuberone, benzil and phenylcoumarin ketone) are examples of Norrish type II chromophores. Most amines with a C—H bond alpha to the nitrogen atom and many thiols are electron donors. Some titanocenes are Norrish type II chromophores within the scope of the chromophore monomers herein.

[0147] In an embodiment, the polymerized chromophore monomer unit is a (meth)acrylate monomer having a Norrish Type II chromophore attached. That is, the Norrish Type II chromophore is not located at the terminal end of the monomer.

[0148] Any of the above-mentioned Norrish II-type chromophores may be the attached part of the chromophore monomer unit of the oligomer. In an embodiment, the Norrish II-type chromophore is selected from benzophenone, thioxanthone or titanocene. In a specific example, the Norrish II-type chromophore is benzophenone.

[0149] In embodiments, each chromophore monomer unit (before polymerizing into the backbone of the oligomer) may independently be according to formula (IV):

[0150]

[0151] in

[0152] A 3is a monovalent residue containing a Norrish type II chromophore, particularly A 3 is X or -LX;

[0153] L is (C1-C 10 ) heterohydrocarbylene linker;

[0154] X is a monovalent residue of a Norrish type II chromophore, preferably a monovalent residue of benzophenone;

[0155] Z 3 It is -H or -CH3.

[0156] In an embodiment, A of formula (IV) 3 is X or -LX, where L is (C1-C 10 ) heteroalkylene linker, and X is a monovalent residue of a Norrish type II chromophore. As used in the present disclosure, the term "residue" shall refer to a product of a reactant, such as a portion of a monomer remaining from a polymer, such as a portion of a Norrish type II chromophore. In other embodiments, A 3 is a monovalent residue of a Norrish type II chromophore. In an embodiment, X may be a monovalent residue of any of the above-mentioned Norrish type II chromophores. In an embodiment, A 3 is a monovalent residue of benzophenone. In an embodiment, A 3 Having formula (IVa):

[0157]

[0158] In an embodiment, A of formula (IV) 3 is a residue comprising a monovalent group comprising a moiety selected from thioxanthone, anthraquinone or camphorquinone. 3 is a residue comprising a monovalent group comprising thioxanthone.

[0159] In particular, A of formula (IV) 3 It may have the following formula (IVb) or (IVc):

[0160]

[0161] Wherein, in formula (IVb) and formula (IVc):

[0162] L 1 is an alkylene group;

[0163] L 2 is a divalent linker comprising at least 2 carbon atoms;

[0164] R 1 and R 2 are each independently selected from -H, halogen, alkyl, cycloalkyl, heterocycloalkyl, alkoxy, aryloxy, sulfanyl, sulfaryl, alkenyl, alkynyl, aryl, aralkyl, alkaryl, heteroaryl, -C(=O)R a 、-NR b R c , alkylamino, alkylthiol, halogenated alkyl, -NO2, -CN, -C(=O)OR d 、-C(=O)NR b R c ;

[0165] R a is selected from optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, and optionally substituted aryl; and

[0166] R b , R c and R d are independently selected from -H, alkyl and aryl.

[0167] In particular, in formula (IVb) and formula (IVc), R 1 and R 2 is independently -H, halogen, alkyl or alkoxy. More particularly, R 1 and R 2 is independently H or alkyl. Even more particularly, R 1 and R 2 is independently H or methyl. Still more particularly, R 1 and R 2 All are -H.

[0168] In formula (IVb) and formula (IVc), L 1 In particular, each L 1 L may independently be a linear or branched alkylene group having 1 to 6, 1 to 4 or 1 to 2 carbon atoms. More particularly, L 1 is -CH2- or -CH(CH3)-. Even more particularly, L 1 It is -CH2-.

[0169] In formula (IVb) and formula (IVc), L 2 is a divalent linker containing at least 2 carbon atoms. 2 It can be an aromatic, aliphatic or alicyclic hydrocarbon linker, a polyether linker, a polyester linker, a polycarbonate linker, a polycaprolactone linker, a polyurethane (polyurethane) linker, a polyorganosiloxane linker, a polybutadiene linker, and combinations thereof. In particular, L 2It may be selected from aromatic, aliphatic or cycloaliphatic hydrocarbon linkers, polyether linkers, polyester linkers and combinations thereof.

[0170] In formula (IVb) and formula (IVc), L 2 It may be -CH2-CH(OH)-CH2-, or a residue of a diol. As used herein, the term "residue of a diol" refers to a linker obtained by removing two OH groups from a diol. Examples of suitable diols include 1,3-propylene glycol, 1,3- or 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 3,3-dimethyl-1,5-pentanediol, neopentyl glycol, 2,4-diethyl-1,5-pentanediol, cyclohexanediol, cyclohexane-1,4-dimethanol, norbornene dimethanol, norbornane dimethanol, tricyclodecane diols, tricyclodecane dimethanol, bisphenol A, B, F or S, hydrogenated bisphenol A, B, F or S, di-, tri- or tetraethylene glycol, di-, tri- or tetrapropylene glycol, di-, tri- or tetrabutylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly(ethylene glycol-co-propylene glycol), dianhydrohexitols (i.e., isosorbide, isomannide, isoidide), polybutadiene polyols, polyester polyols, polyether polyols, polyorganosiloxane polyols, polycarbonate polyols and their alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives and derivatives obtained by ring-opening polymerization of ε-caprolactone initiated with one of the above polyols.

[0171] In formula (IVb) and formula (IVc), L 2 It may be -CH2-CH(OH)-CH2- or a divalent linker selected from one of formulas (A)-(E):

[0172] -(CR 22 R' 22 ) a -(A)

[0173] -[(CR 23 R' 23 ) b -O] c -(CR 23 R' 23 ) b -(B)

[0174] -[(CR 24 R' 24 ) d -O] e -(CR 25 R'25 ) f -[O-(CR 26 R' 26 ) d’ ] e’ -(C)

[0175] -[(CR 27 R' 27 ) g -C(=O)O] h -(CR 28 R' 28 ) i -or-(CR 28 R' 28 ) i -[(CR 27 R' 27 ) g -C(=O)O] h -(D)

[0176] -[(CR 29 R' 29 ) j -OC(=O)-(CR 30 R' 30 ) k -C(=O)-O] l -(CR 29 R' 29 ) j -(E)

[0177] in

[0178] R 22 , R' 22 , R 25 , R' 25 , R 29 , R' 29 , R 30 and R' 30 are independently H or alkyl;

[0179] R 23 , R' 23 , R 24 , R' 24 , R 26 , R' 26 , R 27 , R' 27 , R 28 and R' 28 are independently H or methyl;

[0180] a is 2 to 20;

[0181] b, d and d' are independently 2 to 4;

[0182] c is 1 to 20;

[0183] e and e' are independently 0 to 20, provided that at least one of q and q' is not 0;

[0184] f is 2 to 20;

[0185] g is 3 to 12;

[0186] h is 1 to 20;

[0187] i is 2 to 8;

[0188] j is 2 to 20;

[0189] k is 2 to 30;

[0190] l is 1 to 20.

[0191] In particular, in Formula (IVb) and Formula (IVc), L 2 may be -CH2-CH(OH)-CH2- or a divalent linker selected from alkylene groups such as 1,3-propanediyl, 1,3- or 1,4-butanediyl, 1,5-pentanediyl, 1,6-hexanediyl, 1,8-octanediyl, 1,9-nonanediyl, 1,10-decanediyl, 1,12-decanediyl, 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 (especially ethoxylated and / or propoxylated) derivatives of the abovementioned alkylene groups; esterified (especially by ring-opening polymerization of lactones such as ε-caprolactone) derivatives of the abovementioned alkylene groups; residues of di-, tri-, tetra- or polyoxyalkylene groups having no OH groups, such as di-, tri- or tetraethylene glycol, di-, tri- or tetrapropylene glycol, di-, tri- or tetrabutylene glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, poly(ethylene glycol-co-propylene glycol).

[0192] In one embodiment, A of formula (IV) 3 According to one of the following formulae (IVd) or (IVe):

[0193]

[0194] Wherein h is 1 to 20.

[0195] Other suitable linker groups may be used, including other linker groups that do not contain a carbonyl group.

[0196] The above A of formula (IV) 3All the above embodiments also apply to A in the oligomer of formula (I) 3 .

[0197] The weight fraction of the polymerized chromophore monomer units in the oligomer can vary based on factors known in the art such as the desired curing time. As described herein, p of formula (I) is the weight fraction of the polymerized chromophore monomers. In an embodiment, p is greater than or equal to 0.001, such as greater than or equal to 0.005 or greater than or equal to 0.01. In an embodiment, p is 0.001 to 0.40, 0.001 to 0.30, 0.001 to 0.20, 0.001 to 0.10, 0.001 to 0.05, 0.001 to 0.03, 0.005 to 0.40, 0.005 to 0.30, 0.005 to 0.20, 0.005 to 0.10, 0.005 to 0.05, 0.005 to 0.03 or 0.005 to 0.02.

[0198] In a preferred embodiment, p is from 0.005 to 0.30, in particular from 0.005 to 0.20, more in particular from 0.005 to 0.15, even more in particular from 0.005 to 0.10, still more in particular from 0.01 to 0.10.

[0199] It is understood that when the oligomer includes more than one unrelated type of polymerized chromophore monomeric unit, the weight fraction p of the polymerized chromophore monomeric unit in the oligomer is equal to the sum of the individual weight fractions of each unrelated type of polymerized chromophore monomeric unit. Further, it is understood that even though the chromophore monomeric unit may be based only on T g Characterized by high T g Single or low T g Monomers, but any monomer containing an attached chromophore is not considered a high T for purposes of calculating the weight fractions m and n of formula (I). g Single or low T g monomer.

[0200] Additional monomer units

[0201] The oligomers disclosed herein optionally include at least one polymerized additional monomer unit. The additional monomer unit is different from the high T g Monomer unit, low T g Monomer units and chromophore monomer units.

[0202] The additional monomer units may contain functional groups selected from the following: polymerizable groups other than (meth)acrylate groups (i.e., vinyl groups, allyl groups, conjugated diene groups, alkenyl groups), acidic groups (i.e., carboxylic acid groups, phosphonic acid (-P(=O)(OH)2) groups, phosphonate (-P(=O)(OR)2) groups, sulfonic acid (-S(=O)2OH) groups, sulfonate (-S(=O)2OR) groups, phosphate (-OP(=O)(OR)2) groups, wherein each R is independently a counterion, a hydrogen atom or an optionally substituted hydrocarbon group), nitrogen-containing groups (i.e., amino groups, cyano groups or heterocycles having one or more nitrogen ring atoms), hydroxyl groups, epoxy groups, carbonyl groups, acetoacetoxy groups, acetoacetamide groups, 1,1-dimethyl-3-oxobutyl (diacetone) groups, thiol groups, silane groups, ether bonds, ester bonds (not contained in (meth)acrylate groups) and combinations thereof.

[0203] Preferably, the additional monomer unit comprises a functional group selected from an acidic group and a nitrogen-containing group. More preferably, the additional monomer unit comprises a functional group selected from a carboxylic acid group, a tertiary amine group or a heterocycle having one or more nitrogen ring atoms.

[0204] It should be emphasized that (meth)acrylic acid corresponds to an additional monomer. Therefore, the amount by weight of polymerized (meth)acrylic acid units (if present) should be included in the total amount of polymerized additional monomer units, rather than the polymerized high T g The total amount of monomer units.

[0205] Additional monomer units may include g Monomer unit, low T g In an embodiment, the additional monomer units may include other unsaturated monomer units (except the (meth) acrylic monomer units), such as vinyl amide, vinyl ether, vinyl ester, vinyl oxazolidinone, (meth) acrylamide and combinations thereof. In an embodiment, the additional monomer units may include other monomer units polymerized in oligomers, such as styrene derivatives and maleimide.

[0206] In an embodiment, the additional monomer unit may include epoxy, ether, ester, acid or ketone functional groups that are not polymerized in the oligomer. For example, the additional monomer unit may include caprolactone extended acrylate (SR495B, Sartomer), cyclic trimethylolpropane formal acrylate (SR531, Sartomer), propoxylated tetrahydrofurfuryl acrylate (SR611, Sartomer), β-carboxyethyl acrylate, glycidyl methacrylate, or 2-(2-ethoxyethoxy)ethyl acrylate (SR256), neopentyl monomethacrylate, tetrahydrofurfuryl (meth)acrylate, phenoxyethyl acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-cyanobutyl acrylate, 4-cyanobutyl acrylate, 2-cyanoethyl acrylate, cyanomethyl acrylate, and combinations thereof.

[0207] In embodiments, the additional monomer units may be or may include monomers that synergize with the polymerized chromophore monomer units and / or reduce oxygen inhibition. Oxygen inhibition may limit surface cure and, thereby, the properties of the resulting cured product.

[0208] Common synergist functional groups that can act as synergists for Type II photoinitiators can include acidic groups, heterocycles having one or more nitrogen ring atoms, tertiary amine functional groups, alkyleneoxy functional groups (i.e., one or more oxyalkylene units), thiol groups, or other readily abstractable sources of hydrogen. Typical additional monomer units containing synergist functional groups are exemplified by monomers such as (meth)acrylic acid, dimethylaminoethyl acrylate (DMAEA), dimethylaminoethyl methacrylate (DMAEMA), diethylaminoethyl acrylate (DEAEA), diethylaminoethyl methacrylate (DEAEMA), N-vinyl pyrrolidone (NVP), N-vinyl caprolactam (VCAP), acryloyl morpholine (ACMO), dimethylacrylamide (DMAC), poly(ethylene oxide) mono(meth)acrylate, hydroxyethylethylene urea (meth)acrylate (HEEU(M)A), reaction products of cyclic anhydrides and hydroxyl functional (meth)acrylates, and combinations thereof.

[0209] In embodiments, the additional monomer units may include an amine synergist. Some examples of amine synergists include tertiary amines. When the monomer containing the amine synergist is combined with the Norrish II type chromophore of the polymerized chromophore monomer unit and included in the oligomer, the tertiary amine provides an active hydrogen donor site for the excited triplet state of the chromophore, thereby generating a reactive alkylamino radical that can subsequently initiate polymerization. The tertiary amine can also convert the non-reactive peroxy species formed by the reaction between oxygen and the free radicals into reactive alkylamino radicals, thereby reducing the effect of oxygen on curing.

[0210] Examples of amine synergists that can be used as components of additional monomers for polymerization include low molecular weight tertiary amines (i.e., tertiary amines with a molecular weight less than 200 g / mol), such as triethanolamine, N-methyldiethanolamine. Other types of amine synergists are aminobenzoates, polymerizable aminobenzoates, polymeric aminobenzoates and mixtures thereof. Examples of aminobenzoates include 4-(dimethylamino)ethyl benzoate (EDB), 4-(dimethylamino)benzoic acid amyl ester, 4-(dimethylamino)benzoic acid 2-ethylhexyl ester and 4-(dimethylamino)benzoic acid 2-butoxyethyl ester (BEDB).

[0211] In an embodiment, the additional monomer unit is a (meth)acrylate monomer having a pendant amine functional group.

[0212] Any of the above synergists or amine-based synergists may be pendant residues in additional monomer units of the oligomers herein.

[0213] In an embodiment, each additional monomer unit (before polymerizing into the backbone of the oligomer) may independently be according to formula (V):

[0214]

[0215] in:

[0216] -A 4 is (C1-C 30 )alkyl or (C1-C 30 ) heteroalkyl, preferably (C1-C 30 ) Heteroalkyl: acidic group, nitrogen-containing group, hydroxyl group, epoxy group, carbonyl group, acetoacetoxy group, acetoacetamide group, 1,1-dimethyl-3-oxobutyl (diacetone) group, thiol group, silane group, ether bond, ester bond and combinations thereof;

[0217] -Z 4 It is -H or -CH3.

[0218] A 4 Can contain any monovalent residue of the above-mentioned synergists. In an embodiment, Z 4 is -H or -CH3 and A 4 Yes –C(=O)-OR 4 , where R 4 is selected from H, dimethylaminomethyl, dimethylaminoethyl, morpholinyl, dimethylamino, -CH2-CH2-imidazolidinone or a combination thereof. 4 For -H and A 4 Contains a heterocyclic ring with one or more nitrogen ring atoms, such as A 4 It can correspond to one of the following formulas:

[0219]

[0220] The above embodiment also applies to A in the oligomer of formula (I). 4 and Z 4 . The weight fraction of the additional monomer units polymerized in the oligomer may vary according to factors known in the art such as the desired cure time and the desired degree of cure. As described herein, q of formula (I) is the weight fraction of the additional monomers polymerized. In an embodiment, q is 0. In other embodiments, q is greater than or equal to 0.001, such as greater than or equal to 0.005, or greater than or equal to 0.01. In an embodiment, q is 0.001 to 0.20, 0.001 to 0.10, 0.001 to 0.05, 0.001 to 0.03, 0.005 to 0.20, 0.005 to 0.10, 0.005 to 0.05, 0.005 to 0.03, or 0.005 to 0.02.

[0221] Preferably, q is from 0 to 0.10.

[0222] Properties of oligomers

[0223] The oligomers described herein can be obtained by different monomer units (i.e., high T g Monomer unit, low T gThe oligomer can be obtained by polymerization of different monomer units dissolved in a non-reactive solvent in the presence of an initiator. The solution polymerization can be carried out at a temperature of at least 50° C., preferably at least 60° C. Examples of suitable non-reactive solvents include toluene, heptane, ethyl acetate, methyl ethyl ketone (MEK), isopropanol, and combinations thereof. The initiator can be a thermal initiator. 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, lauroyl peroxide; peracids such as peracetic acid and perbenzoic acid; redox initiators in which a reducing agent such as ferrous compounds promotes the decomposition of the peroxide; and other free radical generating materials such as azo initiators (i.e., compounds containing nitrogen-nitrogen double bonds), such as 2,2'-azobisisobutyronitrile, 4,4'-azobis(4-cyanovaleric acid), or 2,2'-azobis(2-methylbutyronitrile); and combinations thereof. The initiator may be added in an amount such that the total monomer:initiator weight ratio is from 100:1 to 1000:1. Solution polymerization typically provides a mixture of oligomers dissolved in a non-reactive solvent. The non-reactive solvent can be eliminated by heating. Reactive diluents can be added before eliminating the non-reactive solvent to form a curable composition as described in detail below. At the end of solution polymerization (i.e. before introducing reactive diluents), the mixture can have a solid content of 25% by weight to 70% by weight, preferably 30% by weight to 50% by weight, based on the total weight of the mixture. The mixture can have a monomer residual amount of less than 2% by weight, particularly less than 1% by weight, more particularly less than 0.5% by weight, based on the total weight of the mixture. Experimental conditions well known to those skilled in the art can be used to adjust the experimental parameters of solution polymerization (i.e. solid content, reaction temperature, reaction time and total monomer: initiator ratio) to produce relatively low molecular weight oligomers.

[0224] Preferably, the oligomers are not obtained by telomerization, i.e. in the presence of telogenic compounds (i.e. compounds with at least one cleavable bond selected from CH, SH, PH, Si-H or CX, wherein X=Cl, Br or I), such as tetrabromomethane (CBr4), bromotrichloromethane (CBrCl3), dibromodichloromethane (CBr2Cl2), mercaptans, hydrogen disulfide.

[0225] In an embodiment, the oligomer may have a weight average molecular weight of at least 10,000 grams per mole (g / mol). In an embodiment, the oligomer may have a weight average molecular weight of 10,000 g / mol to 600,000 g / mol. In an embodiment, the oligomer may have a weight average molecular weight equal to or greater than 10,000 g / mol, equal to or greater than 25,000 g / mol, or even equal to or greater than 50,000 g / mol. In an embodiment, the oligomer may have a weight average molecular weight equal to or less than 600,000 g / mol, equal to or less than 500,000 g / mol, equal to or less than 400,000 g / mol, equal to or less than 300,000 g / mol, equal to or less than 200,000 g / mol, or even equal to or less than 100,000 g / mol. In an embodiment, the oligomer may have a molecular weight of 10,000 g / mol to 600,000 g / mol, 10,000 g / mol to 500,000 g / mol, 10,000 g / mol to 400,000 g / mol, 10,000 g / mol to 300,000 g / mol, 10,000 g / mol to 200,000 g / mol, 10,000 g / mol to 100,000 g / mol, 25,000 g / mol to 600,000 g / mol, 25,000 g / mol to 500,000 g / mol, 25,000 g / mol to 400,000 g / mol, 25,000 g / mol to 300,000 g / mol, 10,000 g / mol to 200,000 g / mol, 10,000 g / mol to 100,000 g / mol, g / mol to 300,000 g / mol, 25,000 g / mol to 200,000 g / mol, 25,000 g / mol to 100,000 g / mol, 50,000 g / mol to 600,000 g / mol, 50,000 g / mol to 500,000 g / mol, 50,000 g / mol to 400,000 g / mol, 50,000 g / mol to 300,000 g / mol, 50,000 g / mol to 200,000 g / mol, or even 50,000 g / mol to 100,000 g / mol, or any and all subranges formed from any of these endpoints.

[0226] In a preferred embodiment, the oligomer may have a weight average molecular weight of 10,000 g / mol to 100,000 g / mol, particularly 10,000 g / mol to 90,000 g / mol, particularly 11,000 g / mol to 80,000 g / mol, more particularly 12,000 g / mol to 75,000 g / mol, even more particularly 15,000 g / mol to 70,000 g / mol, still more particularly 15,000 g / mol to 65,000 g / mol.

[0227] Unless explicitly stated otherwise, the number average molecular weight and weight average molecular weight reported herein were determined using size exclusion chromatography (SEC) using a poly(methyl methacrylate) reference standard and tetrahydrofuran as the solvent.

[0228] In an embodiment, the oligomer may have a T of 0°C or greater, such as 5°C or greater, 10°C or greater, 15°C or greater, 20°C or greater, 25°C or greater, 30°C or greater, 35°C or greater, 40°C or greater, 45°C or greater, or 50°C or greater. g In an embodiment, the oligomer may have a T of 0°C to 100°C, such as 0°C to 90°C, 0°C to 80°C, 0°C to 70°C, 0°C to 60°C, 0°C to 50°C, 10°C to 100°C, 10°C to 90°C, 10°C to 80°C, 10°C to 70°C, 10°C to 60°C, 10°C to 50°C, 20°C to 100°C, 20°C to 90°C, 20°C to 80°C, 20°C to 70°C, 20°C to 60°C, or 20°C to 50°C. g .

[0229] Preferably, the oligomer has a T of 20°C to 100°C, more particularly 30 to 100°C. g .

[0230] In embodiments, the oligomer may have a gel content of at least 10%, as measured by the method disclosed herein, "Method A - Gel Content". For example, the oligomer may have a gel content of at least 10%, at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, at least 55%, or even at least 60%. In this context, the gel content is measured based on the pure oligomer (i.e., without other compounds, such as diluents).

[0231] In a preferred embodiment, the oligomer may have formula (V):

[0232]

[0233] in:

[0234] - Each A 1a are independently selected from isobutyl, tert-butyl or cyclic (C1-C 30 ) alkyl;

[0235] - Each A 1b independently selected from the group consisting of isobutyl, tert-butyl or cyclic (C1-C 30 )Other than hydrocarbon groups (C1-C 30 ) alkyl;

[0236] - Each A 2 Independently (C2-C 30 )alkyl or (C2-C 30 ) heteroalkyl;

[0237] - Each A 3 is independently a monovalent residue comprising a Norrish type II chromophore, preferably a monovalent residue comprising benzophenone;

[0238] - Each A 4 Independently (C1-C 30 )alkyl or (C1-C 30 ) heteroalkyl, preferably with a -(C1-C 30 ) Heteroalkyl: acidic group, nitrogen-containing group, hydroxyl group, epoxy group, carbonyl group, acetoacetoxy group, acetoacetamide group, 1,1-dimethyl-3-oxobutyl (diacetone) group, thiol group, silane group, ether bond, ester bond and combinations thereof;

[0239] -Z 1 , Z 2 , Z 3 and Z 4 are independently -H or -CH3;

[0240] - m1 is from 0.01 to 0.95, in particular from 0.20 to 0.90, more in particular from 0.25 to 0.85, even more in particular from 0.30 to 0.80, still more in particular from 0.35 to 0.75, still more in particular from 0.40 to 0.75;

[0241] - m2 is from 0 to 0.94, in particular from 0 to 0.90, more in particular from 0 to 0.80, even more in particular from 0 to 0.70, still more in particular from 0 to 0.60, still more in particular from 0 to 0.50;

[0242] - n is from 0.001 to 0.989, in particular from 0.10 to 0.80, more in particular from 0.15 to 0.75, even more in particular from 0.20 to 0.70, still more in particular from 0.25 to 0.65, still more in particular from 0.25 to 0.60;

[0243] - p is from 0.001 to 0.40, in particular from 0.005 to 0.30, more in particular from 0.005 to 0.20, even more in particular from 0.005 to 0.15; still more in particular from 0.005 to 0.10, still more in particular from 0.01 to 0.10;

[0244] - q is from 0 to 0.20, in particular from 0 to 0.10; and

[0245] -m1+m2+n+p+q is equal to 1;

[0246] - m1+m2 is from 0.01 to 0.95, in particular from 0.20 to 0.90, more in particular from 0.25 to 0.85, even more in particular from 0.30 to 0.80, still more in particular from 0.35 to 0.75, still more in particular from 0.40 to 0.75.

[0247] As a non-limiting example, the oligomer may have formula (V):

[0248]

[0249] wherein m is 0.2 to 0.8, n is 0.1 to 0.8, and p is 0.001 to 0.2.

[0250] In an embodiment, Z of formula (V) 1 , Z 2 and Z 3 is independently -H or -CH3. For example, in an embodiment, Z 1 is -CH3 and Z 2 and Z 3 Both are -H.

[0251] Curable composition

[0252] In embodiments, a curable composition, preferably a UV curable composition, may include at least one of the oligomers described herein. In embodiments, the UV curable composition may not include any additional photoinitiator other than the polymerized chromophore monomer units of the oligomer. That is, in embodiments, the oligomer may be cured upon irradiation without any additional photoinitiator. In other embodiments, the curable composition may further include one or more photoinitiators in addition to the polymerized chromophore monomer units of the oligomer. In preferred embodiments, the curable composition may be substantially free of photoinitiators other than the oligomers of the present invention. In particular, the curable composition may include less than 0.1%, particularly less than 0.05%, more particularly less than 0.001%, and even more particularly 0% by weight of photoinitiators other than the oligomers of the present invention.

[0253] Preferably, the curable composition does not contain a g More preferably, the curable composition does not contain a (meth)acrylic copolymer other than the oligomer of the present invention.

[0254] In an embodiment, the curable composition may include one or more (meth)acrylate monomers or oligomers, diluents, (meth)acrylate oligomers, fillers, photoinitiators, slip agents, thickeners, slip agents, hindered amine light stabilizers, ultraviolet absorbing monomers or other auxiliary additives. In an embodiment, at least one (meth)acrylate oligomer is included in the curable composition and is selected from at least one of urethane acrylates and urethane methacrylates, and at least one (meth)acrylate monomer is included and is selected from at least one of 2-hydroxyethyl methacrylate and isobornyl methacrylate.

[0255] In a preferred embodiment, the curable composition comprises an oligomer according to the present invention and a reactive diluent. The reactive diluent may be used together with the non-reactive solvent used to prepare the oligomer or completely replace the non-reactive solvent.

[0256] In an embodiment, the reactive diluent may have a viscosity of 3000 cP or less, as measured at 25° C. using a Spindle SC-27 by a Brookfield DV-III viscometer, such as 2750 cP or less, 2500 cP or less, 2250 cP or less, 2000 cP or less, 1750 cP or less, 1500 cP or less, or even 1250 cP or less. In an embodiment, the reactive diluent may have a viscosity of 5 cP or more, as measured at 25° C. using a Spindle SC-27 by a Brookfield DV-III viscometer, such as 25 cP or more, 50 cP or more, 100 cP or more, 250 cP or more, 500 cP or more, 750 cP or more, or even 1000 cP or more.In embodiments, the reactive diluent may have a molecular weight of 25 cP to 3000 cP, 25 cP to 2750 cP, 25 cP to 2500 cP, 25 cP to 2250 cP, 25 cP to 2000 cP, 25 cP to 1750 cP, 25 cP to 1500 cP, 25 cP to 1250 cP, 25 cP to 3000 cP, 25 cP to 2750 cP, 25 cP to 2500 cP, 25 cP to 2250 cP, 25 cP to 2000 cP, 25 cP to 1750 cP, 25 cP to 1500 cP, 25 cP to 1250 cP, 50 cP to 3000 cP. , 50cP to 2750cP, 50cP to 2500cP, 50cP to 2250cP, 50cP to 2000cP, 50cP to 1750cP, 50cP to 1500cP, 50cP to 1250cP, 100cP to 3000cP, 100cP to 2750cP, 100cP to 2500cP, 100cP to 2250cP, 100cP to 2000cP, 100cP to 1750cP, 100cP to 1500cP, 100cP to 1250cP, 250cP to 3000cP, 250cP to 2750cP, 250cP 250cP to 2500cP, 250cP to 2250cP, 250cP to 2000cP, 250cP to 1750cP, 250cP to 1500cP, 250cP to 1250cP, 500cP to 3000cP, 500cP to 2750cP, 500cP to 2500cP, 500cP to 2250cP, 500cP to 2000cP, 500cP to 1750cP, 500cP to 1500cP, 500cP to 1250cP, 750cP to 3000cP, 750cP to 2750cP, 750cP to 2500cP, 750cP to cP to 2250 cP, 750 cP to 2000 cP, 750 cP to 1750 cP, 750 cP to 1500 cP, 750 cP to 1250 cP, 1000 cP to 3000 cP, 1000 cP to 2750 cP, 1000 cP to 2500 cP, 1000 cP to 2250 cP, 1000 cP to 2000 cP, 1000 cP to 1750 cP, 1000 cP to 1500 cP, or even 1000 cP to 1250 cP, or any and all sub-ranges formed by any of these endpoints, as measured by a Brookfield DV-III viscometer using a Spindle SC-27 at 25°C.

[0257] The reactive diluent may include at least one radically polymerizable diluent. The reactive diluent may include a mixture of radically polymerizable diluents. When the reactive diluent includes a mixture of radically polymerizable diluents, the embodiments related to viscosity apply to the mixture of radically polymerizable diluents.

[0258] As used herein, a free radical polymerizable diluent is a compound having at least one polymerizable carbon-carbon double bond and preferably having a suitable viscosity as defined above. A polymerizable carbon-carbon double bond can participate in free radical polymerization, wherein at least one of the carbon atoms of the double bond is covalently bound to another atom (particularly a carbon atom) in a second molecule. In particular, a reactive diluent may include at least one free radical polymerizable diluent selected from the group consisting of (meth) acrylates, vinyl ethers, vinyl amides, vinyl oxazolidinones, and combinations thereof. These diluents may be monofunctional (i.e., with a single polymerizable carbon-carbon double bond) or multifunctional (i.e., with at least two polymerizable carbon-carbon double bonds). These diluents may be selected to provide the target final properties of the cured formulation, as long as they provide sufficient viscosity reduction of oligomers while producing sufficient properties when the curable composition is cured.

[0259] The reactive diluent may include a monofunctional (meth)acrylate (i.e., a monomer with a single (meth)acrylate group). Examples of suitable monofunctional (meth)acrylates include mono(meth)acrylates of aliphatic alcohols (wherein the aliphatic alcohol may be linear, branched, or alicyclic and may be a monohydric alcohol, a dihydric alcohol, or a polyhydric alcohol, provided that only one hydroxyl group is esterified with (meth)acrylic acid); mono(meth)acrylates of aromatic alcohols (e.g., phenols, including alkylated phenols); mono(meth)acrylates of alkylaryl alcohols (e.g., benzyl alcohol); mono(meth)acrylates of oligomeric and polymeric diols (such as diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol, and polypropylene glycol); ) 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, a dihydric alcohol or a polyhydric alcohol, provided that only one hydroxyl group of the alkoxylated aliphatic alcohol is esterified with (meth)acrylic acid); mono(meth)acrylates of alkoxylated (e.g. ethoxylated and / or propoxylated) aromatic alcohols (such as alkoxylated phenols); caprolactone mono(meth)acrylate; and the like.The following compounds are specific examples of mono(meth)acrylate functional monomers suitable for use: methyl(meth)acrylate; ethyl(meth)acrylate; n-propyl(meth)acrylate; n-butyl(meth)acrylate; isobutyl(meth)acrylate; n-hexyl(meth)acrylate; 2-ethylhexyl(meth)acrylate; n-octyl(meth)acrylate; isooctyl(meth)acrylate; n-decyl(meth)acrylate; n-dodecyl(meth)acrylate; tridecyl(meth)acrylate; tetradecyl(meth)acrylate; hexadecyl(meth)acrylate; 2-hydroxyethyl(meth)acrylate; 2- and 3-hydroxypropyl(meth)acrylate; 2-methoxyethyl(meth)acrylate; 2-ethoxyethyl(meth)acrylate; 2- and 3-ethoxypropyl(meth)acrylate; tetrahydrofurfuryl(meth)acrylate; alkoxylated tetrahydrofurfuryl(meth)acrylate; 2-(2-ethyl)-(meth)acrylate 2-Hexoxyethoxy)ethyl ester; cyclohexyl (meth)acrylate; glycidyl (meth)acrylate; isodecyl (meth)acrylate; lauryl (meth)acrylate; 2-phenoxyethyl (meth)acrylate; alkoxylated phenol (meth)acrylate; alkoxylated nonylphenol (meth)acrylate; cyclic trimethylolpropane formal (meth)acrylate; isobornyl (meth)acrylate; tricyclodecane methanol (meth)acrylate; tert-butyl cyclohexanol (meth)acrylate Acid; trimethylcyclohexanol (meth)acrylate; diethylene glycol monomethyl ether (meth)acrylate; diethylene glycol monoethyl ether (meth)acrylate; diethylene glycol monobutyl ether (meth)acrylate; triethylene glycol monoethyl ether (meth)acrylate; ethoxylated lauryl (meth)acrylate; methoxy polyethylene glycol (meth)acrylate; hydroxyethyl butyl carbamate (meth)acrylate; 3-(2-hydroxyalkyl) oxazolidinone (meth)acrylate; and combinations thereof.

[0260] The reactive diluent may include a monofunctional (meth)acrylate with one or more of the following groups: a ring or ring system (i.e., one or more rings selected from aromatic rings and / or (hetero)cycloaliphatic rings, which may be fused and / or bridged), a C7-C20 hydrocarbon chain (i.e., a straight or branched chain carrying only carbon and hydrogen atoms, wherein the number of carbon atoms in the chain is from 7 to 20), one or more oxyalkylene units (such as oxyethylene, oxypropylene and / or oxybutylene units), one or more ring-opened ester units derived from lactones (such as ε-caprolactone), and combinations thereof. Examples of such monofunctional (meth)acrylates are isobornyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, phenol (meth)acrylate, nonylphenol (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate; lauryl (meth)acrylate; tridecyl (meth)acrylate, stearyl (meth)acrylate, (poly)caprolactone mono(meth)acrylate, di-, tri-, tetra- or polyethylene glycol mono(meth)acrylate, di-, tri-, tetra- or polyethylene glycol monomethyl ether (meth)acrylate, di-, tri-, tetra- or polyethylene glycol monoethyl ether (meth)acrylate, and alkoxylated (i.e. ethoxylated and / or propoxylated) derivatives thereof, and combinations thereof.

[0261] The reactive diluent may include a T g Monofunctional (meth)acrylate monomers: above 25° C., preferably above 30° C., more preferably above 35° C., even more preferably above 40° C., more preferably also above 45° C., more preferably also above 50° C. Examples of such monomers include 2-phenylethyl methacrylate, neopentyl methacrylate, 3,3,5-trimethylcyclohexyl acrylate, tert-butyl acrylate, octadecyl methacrylate, octadecyl acrylate, glycidyl methacrylate, propyl methacrylate, tetrahydrofurfuryl methacrylate, benzyl methacrylate, isobutyl methacrylate, glycidyl methacrylate, ethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 2-hydroxypropyl methacrylate, 2,2,2-trifluoroethyl methacrylate, methacrylate 2-Hydroxyethyl ester, isopropyl methacrylate, isobornyl acrylate, methyl methacrylate, butyl cyanoacrylate, isobornyl methacrylate, phenyl methacrylate, 2-cyanobutyl acrylate, tert-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 4-tert-butylcyclohexyl acrylate, 4-tert-butylcyclohexyl methacrylate, ethyl cyanoacrylate, methyl cyanoacrylate, 3,3,5-trimethylcyclohexyl acrylate, 3,3,5-trimethylcyclohexyl methacrylate, substituted or unsubstituted (meth)acrylic acid (C6-C12 )cycloalkyl ester, adamantyl (meth)acrylate, dicyclopentyl (meth)acrylate, tricyclodecanemethanol mono(meth)acrylate, 2-phenoxyethyl methacrylate, or a combination thereof.

[0262] The reactive diluent may include a multifunctional (meth)acrylate (i.e., a monomer with at least two (meth)acrylate groups), such as 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. meth)acrylate; polytetramethylene glycol di(meth)acrylate; 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 Neopentyl glycol di(meth)acrylate; 2-methyl-2,4-pentanediol di(meth)acrylate; polybutadiene di(meth)acrylate; cyclohexane-1,4-dimethanol di(meth)acrylate; tricyclodecane dimethanol di(meth)acrylate; metal di(meth)acrylate; modified metal di(meth)acrylate; glyceryl di(meth)acrylate; glyceryl tri(meth)acrylate; trimethylolethane tri(meth)acrylate; trimethylolethane di(meth)acrylate; trimethylolpropane tri(meth)acrylate; trimethylolpropane di(meth)acrylate acrylates; pentaerythritol di(meth)acrylate; pentaerythritol tri(meth)acrylate; pentaerythritol tetra(meth)acrylate, di(trimethylolpropane) diacrylate; di(trimethylolpropane) triacrylate; di(trimethylolpropane) tetraacrylate, sorbitol penta(meth)acrylate; di(pentaerythritol) tetraacrylate; di(pentaerythritol) pentaacrylate; di(pentaerythritol) hexa(meth)acrylate; tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate; and alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives thereof; and combinations thereof.

[0263] Reactive diluents may include vinyl ethers such as dodecyl vinyl ether, hydroxybutyl vinyl ether, cyclohexane dimethylol divinyl ether, and DVE-3 (triethylene glycol divinyl ether), and combinations thereof.

[0264] The reactive diluent may include vinyl amides such as N-vinyl pyrrolidone (NVP), N-vinyl caprolactam (V-CAP), and combinations thereof.

[0265] The reactive diluent may include a vinyl oxazolidinone, such as vinyl methyl oxazolidinone (VMOX).

[0266] In a preferred embodiment, the reactive diluent preferably includes a monofunctional (meth)acrylate, a multifunctional (meth)acrylate, or a mixture of a monofunctional (meth)acrylate and a multifunctional (meth)acrylate.

[0267] The amount of reactive diluent in the curable composition can vary according to the desired viscosity. In an embodiment, the curable composition may include 20% to 80% by weight of reactive diluent based on the weight of the curable composition. In an embodiment, the curable composition may include 20% to 80% by weight of reactive diluent based on the weight of the curable composition. In an embodiment, the curable composition may include 20% or more by weight, 25% or more by weight, 30% or more by weight, 35% or more by weight, or even 40% by weight of reactive diluent based on the weight of the curable composition. In an embodiment, the curable composition may include 80% or less by weight, 75% or less by weight, 70% or less by weight, 65% or less by weight, or even 60% by weight of reactive diluent based on the weight of the curable composition. In embodiments, the amount by weight of the reactive diluent in the curable composition may be 20% to 80%, 20% to 75%, 20% to 70%, 20% to 75%, 20% to 60%, 25% to 80%, 20% to 75%, 25% to 70%, 25% to 75%, 25% to 60%, 30% to 80%, 30% to 75%, 30% to 70%, 30% to 75%, 30% to 60%, 35% to 80%, 35% to 75%, 35% to 70%, 35% to 75%, 35% to 60%, 40% to 80%, 40% to 75%, 40% to 70%, 40% to 75%, or even 40% to 60%, or any and all subranges formed by any of these endpoints, based on the total weight of the curable composition.

[0268] In a preferred embodiment, the curable composition may comprise at least 5 wt%, at least 10 wt%, at least 15 wt%, at least 20 wt%, at least 30 wt%, at least 40 wt%, or at least 50 wt% of a monofunctional (meth) acrylate monomer as defined above, based on the total weight of the curable composition. Alternatively, the curable composition may comprise less than 5 wt%, less than 4 wt%, less than 3 wt%, less than 2 wt%, less than 1 wt%, or even 0 wt% of a monofunctional (meth) acrylate monomer as defined above, based on the total weight of the curable composition.

[0269] In a preferred embodiment, the curable composition may comprise at least 5 wt%, at least 10 wt%, at least 15 wt%, at least 20 wt%, at least 30 wt%, at least 40 wt%, or at least 50 wt% of a multifunctional (meth) acrylate monomer as defined above, based on the total weight of the curable composition. Alternatively, the curable composition may comprise less than 5 wt%, less than 4 wt%, less than 3 wt%, less than 2 wt%, less than 1 wt%, or even 0 wt% of a multifunctional (meth) acrylate monomer as defined above, based on the total weight of the curable composition.

[0270] In an embodiment, the weight ratio of the oligomer to the reactive diluent in the curable composition may be 4:1 to 1:4, such as 3:1 to 1:4, 2:1 to 1:4, 1:1 to 1:4, 3:1 to 1:3, 2:1 to 1:3, 1:1 to 1:3, 3:1 to 1:2, 2:1 to 1:2, 1:1 to 1:2, 3:1 to 1:1, or even 2:1 to 1:1, or any and all subranges formed by any of these endpoints.

[0271] In a preferred embodiment, the curable composition comprises an oligomer according to the present invention and a (meth)acrylate functionalized oligomer.

[0272] The (meth)acrylate functionalized oligomer may 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.

[0273] The (meth)acrylate functionalized oligomer may have 1 to 18 (meth)acrylate groups, specifically 2 to 6 (meth)acrylate groups, more specifically 2 to 6 acrylate groups.

[0274] The (meth)acrylate functionalized oligomer may have a number average molecular weight equal to or greater than 600 g / mol, specifically 800 to 15,000 g / mol, more specifically 1,000 to 5,000 g / mol.

[0275] In particular, the curable composition may comprise a (meth)acrylate functionalized oligomer selected from epoxy (meth)acrylates, polyester (meth)acrylates, polyether (meth)acrylates, urethane (meth)acrylates, (meth)acrylated poly (meth)acrylates, and mixtures thereof.

[0276] Non-limiting examples of epoxy (meth)acrylates are reaction products of epoxides such as glycidyl ethers, glycidyl esters, alicyclic epoxides or epoxides obtained by epoxidation of mono- and / or polyunsaturated compounds and (meth)acrylating agents such as (meth)acrylic acid, (meth)acrylic anhydride, (meth)acryloyl chloride or combinations thereof. The epoxide may be an epoxide EPOX selected from the following: 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 novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3 ,4-Epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 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'-methylcyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di(3,4-epoxycyclohexane) 1,2- or 1,3-propylene glycol 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, 1,10-decanediol diglycidyl ether, 1,12-dodecanediol diglycidyl ether, 2-methyl-1,3-propanediol diglycidyl ether diglycidyl ether of 2,2-diethyl-1,3-propanediol, diglycidyl ether of 3-methyl-1,5-pentanediol, diglycidyl ether of 3,3-dimethyl-1,5-pentanediol, diglycidyl ether of 2,4-diethyl-1,5-pentanediol, diglycidyl ether of 3,3-butylethyl-1,5-pentanediol, diglycidyl ether of di-, tri- or tetra-(ethylene glycol) diglycidyl ether, di-, tri- or tetra-(1,2-propylene glycol) diglycidyl ether, di-, tri- or tetra-(1,3-propylene glycol) diglycidyl ether, di-, tri- or tetra-(1,4-butylene glycol) diglycidyl ether, poly(ethylene glycol) diglycidyl ether, poly(propylene glycol) diglycidyl ether, poly(trimethylene glycol) diglycidyl ether, poly(tetramethylene glycol) diglycidyl ether, poly(ethylene glycol-co-propylene glycol) diglycidyl ether, glycerol triglycidyl ether, polyglycerol polyglycidyl ether, trimethylolmethane triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, di( trimethylolpropane) tetraglycidyl ether, pentaerythritol tetraglycidyl ether, diglycidyl cyclohexane dicarboxylate, cyclohexane diglycidyl ether, cyclohexane-1,4-dimethanol diglycidyl ether, tricyclodecane dimethanol diglycidyl ether, isosorbide diglycidyl ether, catechol diglycidyl ether, resorcinol diglycidyl ether, cardol diglycidyl ether, phloroglucinol triglycidyl ether, pyrogallol (py triglycidyl ether of 1,2-dihydroxyphenyl)methane, triglycidyl ether of 1,2-dihydroxyphenyl) ...

[0277] A non-limiting example of polyester (meth) acrylate is the reaction product of a hydroxyl-terminated polyester polyol and a (meth) acrylate agent (such as (meth) acrylic acid, (meth) acrylic anhydride, (meth) acryloyl chloride or a combination thereof). The reaction process may be carried out so that a significant concentration of residual hydroxyl groups is retained in the polyester (meth) acrylate, or may be carried out so that all or substantially all of the hydroxyl groups of the polyester polyol are (meth) acrylated. The polyester polyol may be made by a polycondensation reaction of a polyhydroxyl functional component (particularly a diol) and a polycarboxylic acid functional compound (particularly a dicarboxylic acid or anhydride). To prepare the polyester (meth) acrylate, the hydroxyl groups of the polyester polyol are subsequently partially or completely esterified by reaction with a (meth) acrylate agent. The polyester (meth) acrylate may also be synthesized by reacting a hydroxyl-containing (meth) acrylate (such as a hydroxyalkyl (meth) acrylate (e.g., hydroxyethyl acrylate)) with a poly (poly) carboxylic acid. The polyhydroxy-functional and polycarboxylic acid-functional components may each have a linear, branched, alicyclic, or aromatic structure, and may be used alone or as a mixture.

[0278] Non-limiting examples of polyether (meth) acrylates are condensation products of polyether alcohols as polyether polyols with (meth) acrylate agents (e.g., (meth) acrylic acid, (meth) acrylic anhydride, (meth) acryloyl chloride or combinations thereof). Suitable polyether alcohols may be straight or branched substances containing ether bonds and terminal hydroxyl groups. Polyether alcohols may be prepared by ring-opening polymerization of epoxides and other oxygen-containing heterocyclic compounds (e.g., ethylene oxide, 1,2-propylene oxide, butylene oxide, tetrahydrofuran and combinations thereof) with initiator molecules. Suitable initiator molecules include water, hydroxyl functional materials, polyester polyols and amines. Polyether alcohols may also be obtained by condensation of diols such as glycols.

[0279] The non-limiting examples of carbamate (meth) acrylate are the condensation reaction products of at least one polyisocyanate (e.g., diisocyanate, triisocyanate), at least one polyol (such as polyether polyol or polyester polyol) and hydroxyl-functional (meth) acrylate (such as 2-hydroxyethyl (meth) acrylate or 3-hydroxypropyl (meth) acrylate) to provide terminal (meth) acrylate groups. For example, carbamate (meth) acrylate may contain two, three, four or more (meth) acrylate groups per molecule. The order of addition of the components for preparing carbamate (meth) acrylate is well known in the art. For example, hydroxyl-functional (meth) acrylate may first react with polyisocyanate to obtain isocyanate-functional (meth) acrylate, which is then reacted with polyol. In yet another embodiment, polyisocyanate may first react with polyol to obtain isocyanate-functional polyol, which is then reacted with hydroxyl-functional (meth) acrylate. Alternatively, all components may be combined and reacted simultaneously.

[0280] A non-limiting example of a (meth)acrylated poly(meth)acrylate is a material having an oligomeric (meth)acrylic backbone functionalized with one or more (meth)acrylate groups (which may be at the end of the oligomer or attached to the acrylic backbone). The (meth)acrylic backbone may be a homopolymer, a random copolymer or a block copolymer comprising repeating units of a (meth)acrylic monomer. The (meth)acrylic monomer may be any monomeric (meth)acrylate such as a C1-C6 alkyl (meth)acrylate and a functionalized (meth)acrylate such as a (meth)acrylate with hydroxyl, carboxylic acid and / or epoxy groups. (Meth)acrylated poly(meth)acrylates can be prepared using any procedure known in the art, such as by oligomerizing (meth)acrylic monomers, at least a portion of which are functionalized with hydroxyl, carboxylic acid and / or epoxy groups (e.g., hydroxyalkyl (meth)acrylates, (meth)acrylic acid, glycidyl (meth)acrylate) to obtain functionalized poly(meth)acrylates, which are subsequently reacted with one or more (meth)acrylate-containing reactants to introduce the desired (meth)acrylate functional groups.

[0281] The curable composition may comprise 0 to 80 wt %, in particular 5 to 75 wt %, more in particular 10 to 70 wt %, even more in particular 15 to 60 wt %, still more in particular 20 to 50 wt % of (meth)acrylate functional oligomer, based on the total weight of the curable composition. In particular, the curable composition may comprise 0 to 50 wt %, 1 to 45 wt %, 5 to 40 wt %, 10 to 35 wt % or 15 to 30 wt % of (meth)acrylate functional oligomer, based on the total weight of the polymerizable components.

[0282] In an embodiment, the curable composition may have a glass transition temperature T of about 20° C. or more when cured, or about 30° C. or less when cured. g In an embodiment, the curable composition may be liquid at a temperature of 25°C ± 2°C. In an embodiment, the curable composition may have a viscosity of 50,000 cP or less, such as 45,000 cP or less, 40,000 cP or less, 35,000 cP or less, 30,000 cP or less, 25,000 cP or less, 20,000 cP or less, 15,000 cP or less, 12,500 cP or less, or even 10,000 cP or less, measured at 60°C by a Brookfield DV-III viscometer using a Spindle SC-27. Such viscosity characteristics facilitate the spreading of the composition on a substrate to form a film.

[0283] In a preferred embodiment, the curable composition may have a viscosity of 50,000 cP or less, such as 45,000 cP or less, 40,000 cP or less, 35,000 cP or less, 30,000 cP or less, 25,000 cP or less, 20,000 cP or less, 15,000 cP or less, 12,500 cP or less, or even 10,000 cP or less, as measured at 25° C. by a Brookfield DV-III viscometer using a Spindle SC-27.

[0284] In embodiments, the curable composition may include less than 1 wt % of a solvent and less than 1 wt % of water, or be free of solvent and free of water. In embodiments, a film or coating may be formed by curing the curable composition.

[0285] Method for preparing and curing curable composition

[0286] The present invention also relates to a method for preparing a curable composition according to the present invention. The method for preparing a curable composition comprises the following steps:

[0287] - preparing the oligomer according to the invention dissolved in a non-reactive solvent;

[0288] - adding a reactive diluent to obtain a diluted curable composition;

[0289] - removing at least part of the non-reactive solvent from the diluted curable composition to obtain the curable composition according to the present invention.

[0290] The oligomer dissolved in the non-reactive solvent can be prepared by solution polymerization as described above. The oligomer, the non-reactive solvent and the reactive diluent can be as defined above. The non-reactive solvent can be at least partially removed by heating, for example, at a temperature of 40° C. or higher, particularly 50° C. or higher, more particularly 60° C. or higher. The amount of non-reactive solvent after the removal step can be less than 1%, less than 0.5% or even 0%, based on the weight of the non-reactive solvent based on the weight of the curable composition.

[0291] The present invention also relates to a method of curing a curable composition according to the present invention.The method of curing a curable composition comprises curing the curable composition.

[0292] The curing step may be carried out at ambient temperature (ie 10-30°C).

[0293] The curing step can be carried out by irradiating the composition with a light source having a wavelength and / or intensity capable of activating the polymerized chromophore monomer units of the oligomer of the present invention and causing crosslinking of the oligomer and / or the reactive diluent. The curing step can be carried out in the absence of a photoinitiator other than the oligomer of the present invention. In other words, the curable composition can contain less than 0.1 wt %, particularly less than 0.05 wt %, more particularly less than 0.001 wt %, even more particularly 0 wt % of a photoinitiator other than the oligomer of the present invention, based on the weight of the curable composition.

[0294] The method of curing the curable composition of the present invention may not involve a pre-curing step, in particular a step of curing at least part of the reactive diluent before cross-linking the oligomer of the present invention, for example by irradiating the curable composition with a light source having a long wavelength and / or low intensity in the presence of a photoinitiator other than the oligomer of the present invention. As used herein, a light source having a long wavelength and / or low intensity is a light source that is unable to activate the polymerized chromophore monomer units of the oligomer of the present invention and cause the oligomer and / or the reactive diluent to crosslink. An example of a light source having a long wavelength and / or low intensity is a black light (as opposed to a mercury vapor lamp capable of activating a chromophore comprising a benzophenone moiety or an LED-UV lamp capable of activating a chromophore comprising a thioxanthone moiety). Preferably, the method of curing the curable composition of the present invention comprises a curing step in which at least part of the reactive diluent and at least part of the oligomer of the present invention are cured simultaneously. Without being bound by theory, such a curing method is believed to enable at least part of the reactive diluent to be grafted onto at least part of the oligomer of the present invention.

[0295] coating

[0296] In an embodiment, a coating can be formed by curing a curable composition. The process for preparing a cured coating according to an embodiment includes curing the curable composition. In particular, the curable composition can be cured by exposing the composition to radiation (such as visible radiation, UV radiation, LED radiation, laser radiation, electron beam radiation, peroxide, accelerator and heat). More particularly, the curable composition can be fully cured by exposing the composition to ultraviolet (UV) radiation. The ultraviolet curable composition can be advantageously cured by exposing the composition to an LED light source.

[0297] Before curing, the UV curable composition can be applied to the substrate surface in any known conventional manner, for example by spraying, spraying, knife coating, roller coating, casting, drum coating, dipping and the like, and combinations thereof. Indirect application using a transfer process can also be employed.

[0298] The substrate on which the UV curable composition is applied and cured can be any type of substrate. When used as an adhesive, the polymerizable composition can be placed between two substrates and then cured, whereby the cured composition bonds the substrates together to provide an adhered product. The UV curable composition according to the present disclosure can also be shaped or cured in a bulk manner (for example, the UV curable composition can be cast (cast, casting) into a suitable mold and then cured).

[0299] Multiple layers of a UV-curable composition according to the present disclosure may be applied to a substrate surface; the multiple layers may be cured simultaneously (e.g., by exposure to a single dose of radiation), or each layer may be cured sequentially prior to applying additional layers of the UV-curable composition.

[0300] In embodiments, the coating may have a gel content of 30% to 99% as measured by the method disclosed herein, "Method A - Gel Content." For example, the coating may have a gel content of 30% to 95%, 40% to 80%, 50% to 70%, or any and all subranges formed by any of these endpoints.

[0301] Without intending to be bound by a particular theory, it is believed that the high T g Monomer unit, polymerized low T g The oligomer of monomer units, polymerized chromophore monomer units, and optionally at least one polymerized additional monomer unit can be cured to form a coating having a high gel content and thus a high degree of crosslinking. In addition, it is believed that having a T equal to or greater than 0°C g The oligomer can be cured to form a polymer having a T of equal to or greater than 0°C. g It is believed that, as disclosed herein, the high T g单体 The oligomers described herein may undergo a greater degree of hydrogen abstraction and crosslinking during curing, which may increase the strength of coatings formed from the oligomers described herein.

[0302] Example

[0303] The following examples will further illustrate various embodiments disclosed herein. The examples are illustrative in nature and should not be construed as limiting the embodiments disclosed herein.

[0304] Material

[0305] The following materials were used in the examples:

[0306] [Table 1]

[0307]

[0308] Preparation

[0309] Table 2 shows the components (in weight percent) used to form the oligomers and certain properties of Comparative Examples C1 to C26 and Examples E1 to E21

[0310] Oligomers are obtained by solution polymerization of the monomers shown in Table 2 using the amount of MEK shown in Table 2 as solvent. Solvent and monomer are added to 60mL vials. Vazo52 initiator solution in solvent is prepared in a separate vial and then added to the monomer solution (total monomer: initiator weight ratio is 400: 1). The vial is then placed in a water bath at 65°C and gently shaken for 11 hours. Experimental conditions well known to those skilled in the art can be used to adjust solvent type, solid content, reaction temperature, reaction time and initiator: monomer ratio to produce oligomers of various molecular weights. Monomers between 100: 1 and 1000: 1: Vazo52 ratios are typically used to produce relatively low molecular weight oligomers, as described and used in the following examples.

[0311] The formulations for evaluating cure speed according to Method B below were prepared by adding the components listed in Table 2 to The SR355 in a polypropylene cup is used Mix with a DAC 400.2VAC high speed stirrer at 1500 Rpm for two minutes until homogeneous.

[0312] [Table 2]

[0313]

[0314]

[0315]

[0316]

[0317] method

[0318] The following methods are used in the application:

[0319] Molecular weight

[0320] The number average molecular weight (Mn) and weight average molecular weight (Mw) of the oligomers were determined using size exclusion chromatography (SEC) using a poly(methyl methacrylate) reference standard and tetrahydrofuran as solvent using the following conditions:

[0321] - Column: Agilent PLgel 5 micron 100A, 250 x 4.6 mm; Agilent PLgel 3 micron MiniMix E, 250 x 4.6 mm; Agilent PLgel 5 micron MiniMix D, 250 x 4.6 mm,

[0322] -Detector: Refractive index detector.

[0323] -Solvent flow rate: 0.45μL / min

[0324] - Temperature: 40℃

[0325] -Sample injection volume: 25 μL

[0326] Method A - Gel Content

[0327] The gel content of pure oligomers is measured by curing 3MIL wet coatings using an H bulb (small Fusion LC6, 15fpm, three times). The draw-down thickness depends on the final MEK percentage in the oligomer. For example, if the embodiment is provided with 60% monomer and 40% MEK, or 50% monomer and 50% MEK, the embodiment with 40% MEK is drawn from a thickness of 5MIL, and the embodiment with 50% MEK is drawn from a thickness of 6MIL, so that after evaporation of MEK, the film thickness is 3MIL. After the draw-down, the glass sheet is placed in an oven at 60°C for 1 hour to remove the solvent. The sample is cured in air or nitrogen. After curing, the sample is removed from the glass sheet and placed in a solution of MEK for 24 hours. The gel content is provided as a percentage of the remaining weight relative to the initial weight of the sample after the sample is soaked in MEK for 24 hours, as provided by the following formula.

[0328]

[0329] Reference now Figure 1 , the environment, i.e., air (shown in gray bars) or nitrogen (shown in black bars), has minimal effect on the gel content. Example E1, an oligomer comprising 54.5 wt % BA, 44.5 wt % MMA, and 1 wt % BENZO, has a gel content of less than 5 wt % when cured in air and nitrogen. On the other hand, Comparative Example C7, an oligomer comprising 69.5 wt % BA, 26.5 wt % MMA, and 1 wt % BENZO, has a gel content of 67 wt % (air) and 79 wt % (nitrogen). Figure 1 As shown in Table 1, with MMA (high T g The increase of monomer units, the decrease of gel content, T g Therefore, the high T gLow T of monomer units and polymers g The amount of monomer units can be tailored to achieve the desired amount of cross-linking and T as indicated by gel content. g Both.

[0330] Reference now Figure 2 and 3 , use alternative high T g The monomer unit IBOMA replaces MMA, when the predicted T g When normalized, both in air ( Figure 2 ) or in nitrogen ( Figure 3 ) cure, all exhibited an increase in gel content. For example, Example E2, an oligomer comprising 38.5 wt % BA, 60.4 wt % MMA, and 1 wt % BENZO, had a predicted T of 25 °C. g and 5 wt% gel content (air and nitrogen). Example E4, an oligomer comprising 38.5 wt% BA, 50.4 wt% IBOMA and 1 wt% BENZO, has a predicted T of 24°C. g and a gel content of 40 wt % (air) and 51 wt % (nitrogen). Figure 2 , Figure 3 As shown in Table 1, some high T of oligomers can be customized. g The choice of monomer units and the high T of polymerization g Low T of monomer units and polymers g The amount of monomer units to achieve the desired amount of cross-linking as indicated by gel content and higher T g both.

[0331] Reference now Figure 4 and 5 , use alternative high T g Monomer units such as SR506A and tBMA replace MMA, when the predicted T g When normalized, both in air ( Figure 4 ) or in nitrogen ( Figure 5 ) cure, both exhibited an increase in gel content. Further, replacing IBOMA with other alicyclic moieties such as SR421A and SR218 resulted in T values ​​of 25°C and 50°C, respectively. g While not wishing to be bound by theory, unlike copolymers containing MMA, incorporation of the cycloaliphatic moiety may allow adjacent acrylic copolymer chains to initiate hydrogen abstraction more quickly and efficiently due to the availability of tertiary protons on the cycloaliphatic ring. Further, the size of the cycloaliphatic interpolymer and the availability of a large number of sites for hydrogen abstraction may provide more available protons to adjacent chains with less steric hindrance than with small aliphatic interpolymers such as MMA.

[0332] like Figure 2-5 As shown in Table 1, the high T g monomer units to achieve the desired amount of cross-linking at a given copolymer ratio, as indicated by gel content.

[0333] Method B - Photo Differential Scanning Calorimetry (PhotoDSC)

[0334] The sample was combined with SR355 at an initial weight ratio of oligomer:SR355 and placed in a Tzero tray and the residual solvent was flashed off in an oven. The initial weight ratio of oligomer:SR355 was chosen so as to achieve a 1:1 weight ratio of oligomer:SR355 after flashing off the solvent. The sample was exposed to broad spectrum UV light (100 mW / cm 2 ) for two minutes.

[0335] Reference now Figure 6 , record the time taken to reach the peak maximum ( Figure 6 During the cure, the heat flow under each curve (shown as gray bars) was measured. Figure 6 As shown by the black bars in Figure 6 As shown in Figure 2, as the amount of MMA increases, the curing speed increases. Therefore, the high T g Low T of monomer units and polymers g The amount of monomer units can be tailored to achieve the desired cure speed. Figure 6 All examples in induced cross-linking with SR355.

[0336] Reference now Figure 7 The time taken to reach the peak maximum was recorded to determine the curing speed of each oligomer. Figure 7 As shown, all examples have similar curing speeds. g As the T increases, the curing speed tends to slow down. g Low T of monomer units and polymers g The amount of monomer units can be tailored to adjust the oligomer T g and achieve the desired curing speed.

[0337] A UV curable coating (layer) composition was prepared by adding enough oligomer to ditrimethylolpropane tetraacrylate (SR355) so that after evaporation of the MEK the resulting composition had a 1:1 weight ratio of oligomer to SR355. A DAC 400.2VAC high speed mixer was used at 1500 rpm for 2 minutes to mix the UV curable coating composition until homogeneous.

[0338] Gel content is measured by curing a 4 mil wet coating of a UV curable coating composition on a glass sheet. After pull down, the glass sheet is placed in an oven at 60°C for 1 hour to remove the solvent. The samples are cured in air or nitrogen. For air: After drying in the oven, the samples are cured using a small Fusion LC6 microwave bulb at 15 feet per minute, three times. For nitrogen: After drying in the oven, the samples are placed in a nitrogen chamber and a nitrogen flow is applied for five minutes. A nitrogen chamber with a quartz window is passed under the Fusion LC6 microwave bulb at 15 feet per minute, three times. After curing, the sample is removed from the glass sheet and placed in a solution of MEK for 24 hours. The gel content is provided as a percentage of the remaining weight of the sample after soaking in MEK for 24 hours relative to the initial weight of the sample, as provided in the following formula.

[0339]

[0340] The gel content of the UV-curable coating composition containing oligomer E5 and SR355 was 59.1% ± 1.4% in air and 57.7% ± 0.6% in nitrogen. The gel content of the UV-curable coating composition containing oligomer E12 and SR355 was 64.1% ± 1.2% in air and 60.9% ± 5.4% in nitrogen.

[0341] aspect

[0342] Further aspects of the invention are provided by the subject matter of the following clauses:

[0343] Item 1. An oligomer comprising, based on the total weight of the oligomer: 1 wt % to 95 wt % of a polymerized high T g Monomer units, 0.1 wt % to 98.9 wt % of polymerized low T g monomer units, 0.1 wt % to 40 wt % of polymerized chromophore monomer units, and 0 to 20 wt % of at least one polymerized additional monomer unit; wherein: the high T g The monomer unit has a Fox equation average glass transition temperature (T) equal to or greater than 25°C. g ) of a (meth)acrylate monomer, the low T g The monomer unit has a Fox equation average T of less than 25°C. g The monovalent (meth)acrylate monomer of the high T g Fox equation average T of monomer unit g Lower than the T g Fox equation average T of monomer unit gThe oligomer has a T of at least 0°C, the chromophore monomer unit is a (meth)acrylate monomer having a Norrish II type chromophore attached, the oligomer has a weight average molecular weight of at least 10,000 grams per mole (g / mol), and the oligomer has a T of equal to or greater than 0°C. g .

[0344] Clause 2. The oligomer of any preceding clause, wherein the oligomer is according to formula (I):

[0345]

[0346] - Each A 1 Independently (C1-C 30 )alkyl or (C1-C 30 ) heteroalkyl, preferably (C1-C 30 ) hydrocarbon group, more preferably at least part of A 1 The moiety is selected from isobutyl, tert-butyl or cyclic (C1-C 30 ) alkyl;

[0347] - Each A 2 Independently (C2-C 30 )alkyl or (C2-C 30 ) heteroalkyl, preferably (C4-C 30 ) alkyl;

[0348] - Each A 3 is independently a monovalent residue comprising a Norrish type II chromophore, preferably a monovalent residue comprising benzophenone;

[0349] - Each A 4 Independently (C1-C 30 )alkyl or (C1-C 30 ) heteroalkyl, preferably with a -(C1-C 30 ) Heteroalkyl: acidic group, nitrogen-containing group, hydroxyl group, epoxy group, carbonyl group, acetoacetoxy group, acetoacetamide group, 1,1-dimethyl-3-oxobutyl (diacetone) group, thiol group, silane group, ether bond, ester bond and combinations thereof;

[0350] -Z 1 , Z 2 , Z 3 and Z 4 are independently -H or -CH3;

[0351] -m is the high T of the aggregate g The weight fraction of the monomer units, in particular m, is from 0.01 to 0.95;

[0352] -n is the low T of the aggregate gThe weight fraction of the monomer units, in particular n, is from 0.001 to 0.989;

[0353] - p is the weight fraction of polymerized chromophore monomer units, in particular p is from 0.001 to 0.4;

[0354] - q is the weight fraction of at least one polymerized additional monomer unit and is optionally zero, in particular q is from 0 to 0.20; and

[0355] -m+n+p+q equals 1.

[0356] Item 3. The oligomer of any of the preceding items, wherein at least part of A 1 The moiety is selected from isobutyl, tert-butyl, substituted or unsubstituted (C6-C 12 )cycloalkyl, substituted or unsubstituted (C6-C 12 ) aryl, or a combination thereof, A 2 Is a straight chain or branched chain (C4-C 30 ) alkyl or a combination thereof, and A 3 is X or -LX, where L is (C1-C 10 ) a heteroalkylene linker, and X is a monovalent residue of a Norrish type II chromophore.

[0357] Item 4. The oligomer of any of the preceding items, wherein at least part of A 1 The moiety is selected from isobutyl, tert-butyl, isobornyl, cyclohexyl, 3,3,5-trimethylcyclohexyl, tert-butylcyclohexyl, benzyl, adamantyl, dicyclopentyl, tricyclodecyl, -CH2-tricyclodecyl, phenyl, -CH2-CH2-phenyl, or -CH2-CH2-O-phenyl, or a combination thereof, A 2 is selected from n-butyl, isobutyl, hexyl, 2-ethylhexyl, isooctyl, isodecyl, tridecyl, lauryl, or a combination thereof, and A 3 It is a monovalent residue of a Norrish type II chromophore.

[0358] Item 5. The oligomer of any preceding item, wherein the Norrish type II chromophore is selected from benzophenone, thioxanthone or titanocene.

[0359] Clause 6. The oligomer of any preceding clause, wherein A 3 -LX, where L is (C1-C 10 ) is a heteroalkylene linker, and X is a monovalent group of benzophenone.

[0360] Clause 7. The oligomer of any preceding clause, wherein at least part of A 1The moiety is selected from isobutyl, tert-butyl, isobornyl, cyclohexyl, 3,3,5-trimethylcyclohexyl, tert-butylcyclohexyl, benzyl, adamantyl, dicyclopentyl, tricyclodecyl, -CH2-tricyclodecyl, phenyl, -CH2-CH2-phenyl, or -CH2-CH2-O-phenyl, A 2 is n-butyl, and A 3 It is the monovalent residue of benzophenone.

[0361] Clause 8. The oligomer of any preceding clause, wherein A 3 Having the formula (IVa) disclosed below:

[0362]

[0363] Item 9. The oligomer of any preceding item, wherein q is from 0.001 to 0.20, preferably from 0.001 to 0.10, and the additional monomer unit comprises a functional group selected from the following: an acidic group, a heterocyclic ring having one or more nitrogen ring atoms, a tertiary amine functional group, an alkyleneoxy functional group or a thiol group, preferably, the additional monomer unit is selected from (meth)acrylic acid, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, N-vinyl pyrrolidone, N-vinyl caprolactam, acryloyloxymorpholine, dimethylacrylamide, poly(ethylene oxide) mono(meth)acrylate, hydroxyethylethylene urea (meth)acrylate, the reaction product of a cyclic anhydride and a hydroxy-functional (meth)acrylate, and combinations thereof

[0364] Clause 10. The oligomer of any preceding clause, wherein the oligomer has formula (V):

[0366]

[0367] in:

[0368] - Each A 1a are independently selected from isobutyl, tert-butyl or cyclic (C1-C 30 ) alkyl;

[0369] - Each A 1b independently selected from the group consisting of isobutyl, tert-butyl or cyclic (C1-C 30 )Other than hydrocarbon groups (C1-C 30 ) alkyl;

[0370] - Each A 2 Independently (C2-C 30 )alkyl or (C2-C 30 ) heteroalkyl;

[0371] - Each A 3 is independently a monovalent residue comprising a Norrish type II chromophore, preferably a monovalent residue comprising benzophenone;

[0372] - Each A 4 Independently (C1-C 30 )alkyl or (C1-C 30 ) heteroalkyl, preferably with a -(C1-C 30 ) Heteroalkyl: acidic group, nitrogen-containing group, hydroxyl group, epoxy group, carbonyl group, acetoacetoxy group, acetoacetamide group, 1,1-dimethyl-3-oxobutyl (diacetone) group, thiol group, silane group, ether bond, ester bond and combinations thereof;

[0373] -Z 1 , Z 2 , Z 3 and Z 4 are independently -H or -CH3;

[0374] - m1 is from 0.01 to 0.95, in particular from 0.20 to 0.90, more in particular from 0.25 to 0.85, even more in particular from 0.30 to 0.80, still more in particular from 0.35 to 0.75, still more in particular from 0.40 to 0.75;

[0375] - m2 is from 0 to 0.94, in particular from 0 to 0.90, more in particular from 0 to 0.80, even more in particular from 0 to 0.70, still more in particular from 0 to 0.60, still more in particular from 0 to 0.50;

[0376] - n is from 0.001 to 0.989, in particular from 0.10 to 0.80, more in particular from 0.15 to 0.75, even more in particular from 0.20 to 0.70, still more in particular from 0.25 to 0.65, still more in particular from 0.25 to 0.60;

[0377] - p is from 0.001 to 0.40, in particular from 0.005 to 0.30, more in particular from 0.005 to 0.20, even more in particular from 0.005 to 0.15; still more in particular from 0.005 to 0.10, still more in particular from 0.01 to 0.10;

[0378] - q is from 0 to 0.20, in particular from 0 to 0.10; and

[0379] -m1+m2+n+p+q is equal to 1;

[0380] - m1+m2 is from 0.01 to 0.95, in particular from 0.20 to 0.90, more in particular from 0.25 to 0.85, even more in particular from 0.30 to 0.80, still more in particular from 0.35 to 0.75, still more in particular from 0.40 to 0.75.

[0381] Clause 11. The oligomer of any preceding clause, according to formula (V) as described below:

[0382]

[0383] wherein: m is 0.2 to 0.8, n is 0.1 to 0.8, and p is 0.001 to 0.2; Z of formula (V) 1 , Z 2 and Z 3 is independently -H or -CH3; and wherein the oligomer has a weight average molecular weight of at least 20,000 g / mol.

[0384] Clause 12. The oligomer of any preceding clause, wherein Z 1 is H or -CH3, Z 2 and Z 3 is -H, and Z 4 is -H (if q is greater than 0).

[0385] Clause 13. The oligomer of any preceding clause, wherein the oligomer has a T g It is 0°C to 100°C, particularly 20°C to 100°C, more particularly 30 to 100°C.

[0386] Clause 14. The oligomer of any preceding clause, wherein the additional monomer unit is a (meth)acrylate monomer.

[0387] Clause 15. The oligomer of any preceding clause, wherein the additional monomer unit is a (meth)acrylate monomer having a pendant amine functionality.

[0388] Clause 16. The oligomer of any preceding clause, wherein q is from 0.001 to 0.20, preferably from 0.001 to 0.10, and the additional monomer unit is selected from dimethylaminomethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, morpholinyl (meth)acrylate, dimethylamino (methacrylate), or a combination thereof.

[0389] Clause 17. The oligomer of any preceding clause, wherein: m is from 0.40 to 0.90, n is from 0.10 to 0.60, and p is from 0.005 to 0.03.

[0390] Clause 18. The oligomer of any preceding clause, wherein: m is from 0.70 to 0.90, n is from 0.10 to 0.30, and p is from 0.005 to 0.03.

[0391] Clause 19. The oligomer of any preceding clause, wherein: m is from 0.40 to 0.60, n is from 0.40 to 0.60, and p is from 0.005 to 0.03.

[0392] Clause 20. The oligomer of any preceding clause, wherein the oligomer has a gel content of at least 10% when cured.

[0393] Clause 21. The oligomer of any preceding clause, wherein the oligomer has a gel content of at least 20% when cured.

[0394] Item 22. A curable composition comprising an oligomer according to any preceding item and one or more of the following compounds: (meth)acrylate monomers, diluents, (meth)acrylate oligomers, fillers, photoinitiators, lubricants, thickeners, lubricants, hindered amine light stabilizers, UV absorbing monomers or other auxiliary additives.

[0395] Item 23. The curable composition of Item 22, wherein the curable composition comprises a reactive diluent.

[0396] Clause 24. The curable composition of Clause 23, wherein the reactive diluent comprises a polyol having a T greater than 25°C. g The monofunctional (meth)acrylate monomer is selected from the group consisting of 2-phenylethyl methacrylate, neopentyl methacrylate, 3,3,5-trimethylcyclohexyl acrylate, tert-butyl acrylate, octadecyl methacrylate, octadecyl acrylate, glycidyl methacrylate, propyl methacrylate, tetrahydrofurfuryl methacrylate, benzyl methacrylate, isobutyl methacrylate, glycidyl methacrylate, ethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 2-hydroxypropyl methacrylate, 2,2,2- trifluoroethyl ester, 2-hydroxyethyl methacrylate, isopropyl methacrylate, isobornyl acrylate, methyl methacrylate, butyl cyanoacrylate, isobornyl methacrylate, phenyl methacrylate, 2-cyanobutyl acrylate, tert-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 4-tert-butylcyclohexyl acrylate, 4-tert-butylcyclohexyl methacrylate, ethyl cyanoacrylate, methyl cyanoacrylate, 3,3,5-trimethylcyclohexyl acrylate, 3,3,5-trimethylcyclohexyl methacrylate, substituted or unsubstituted (meth)acrylic acid (C6-C 12)cycloalkyl ester, adamantyl (meth)acrylate, dicyclopentyl (meth)acrylate, tricyclodecanemethanol mono(meth)acrylate, 2-phenoxyethyl methacrylate, or a combination thereof.

[0397] Item 25. The curable composition of Item 23 or 24, wherein the reactive diluent comprises a multifunctional (meth)acrylate, in particular a multifunctional (meth)acrylate selected from the group consisting of 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. meth)acrylate; polypropylene glycol di(meth)acrylate; polytetramethylene glycol di(meth)acrylate; 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 Alkanediol di(meth)acrylate; Neopentyl glycol di(meth)acrylate; 2-methyl-2,4-pentanediol di(meth)acrylate; Polybutadiene di(meth)acrylate; Cyclohexane-1,4-dimethanol di(meth)acrylate; Tricyclodecane dimethanol di(meth)acrylate; Metal di(meth)acrylate; Modified metal di(meth)acrylate; Glyceryl di(meth)acrylate; Glyceryl tri(meth)acrylate; Trimethylolethane tri(meth)acrylate; Trimethylolethane di(meth)acrylate; Trimethylolpropane tri(meth)acrylate; Trimethylolpropane di(meth)acrylate; pentaerythritol di(meth)acrylate; pentaerythritol tri(meth)acrylate; pentaerythritol tetra(meth)acrylate, di(trimethylolpropane) diacrylate; di(trimethylolpropane) triacrylate; di(trimethylolpropane) tetraacrylate, sorbitol penta(meth)acrylate; di(pentaerythritol) tetraacrylate; di(pentaerythritol) pentaacrylate; di(pentaerythritol) hexa(meth)acrylate; tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate; and alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives thereof; and combinations thereof.

[0398] Item 26. The curable composition of any one of items 23-25, wherein the curable composition is substantially free of photoinitiators other than the oligomers of any one of items 1 to 21, in particular, the curable composition comprises less than 0.1 wt. %, in particular less than 0.05 wt. %, more in particular less than 0.001 wt. %, even more in particular 0 wt. % of photoinitiators other than the oligomers according to any one of items 1 to 21.

[0399] Item 27. A coating formed by curing the UV curable composition of any of Items 22 to 26.

[0400] Item 28. The coating of Item 27, wherein the coating has a gel content of at least 30%.

[0401] Item 29. The coating of Item 27 or 28, wherein the coating has a gel content of at least 50%.

[0402] Clause 30. The coating of any one of Clauses 27 to 29, wherein the coating has a gel content of at least 70%.

[0403] Clause 31. A method of preparing the curable composition of any one of Clauses 23 to 26, wherein the method comprises the following steps:

[0404] - preparing an oligomer as defined in any one of clauses 1 to 21 dissolved in a non-reactive solvent;

[0405] - adding a reactive diluent to obtain a diluted curable composition;

[0406] - removing at least part of the non-reactive solvent from the diluted curable composition to obtain the curable composition according to the present invention.

[0407] Item 32. A method of curing a curable composition of any one of Items 23 to 26 or prepared by a method according to Item 31, wherein the method comprises curing the curable composition by irradiating the curable composition with a light source having a wavelength and / or intensity capable of activating polymerized chromophore monomer units of the oligomer and causing crosslinking of the oligomer and / or the reactive diluent.

[0408] It will be apparent to those skilled in the art that various modifications and variations may be made without departing from the scope disclosed herein. Since those skilled in the art may conceive of modifications, combinations, sub-combinations and variations of the disclosed embodiments, which incorporate the spirit and substance disclosed herein, the scope disclosed herein should be interpreted as including all contents within the scope of the appended claims and their equivalents.

[0409] For the purpose of defining the present technology, the transitional phrase "consisting of" may be introduced into a claim as a closed preamble term to limit the scope of the claim to the listed components or steps and any naturally occurring impurities. For the purpose of defining the present technology, the transitional phrase "consisting essentially of" may be introduced into a claim to limit the scope of one or more claims to the listed elements, components, materials, or method steps and any unlisted elements, components, materials, or method steps that do not materially affect the novel characteristics of the claimed subject matter.

[0410] As used in the specification and the appended claims, the singular forms "a, an," "a, an," and "the" include plural references unless the context clearly indicates otherwise. The verb "comprise" and its conjugated forms should be interpreted as referring to elements, components, or steps in a non-exclusive manner. The referenced elements, components, or steps may be present, used, or combined with other elements, components, or steps that are not explicitly referenced.

[0411] It should be understood that any two values ​​assigned to a property may constitute a range for that property, and the present disclosure contemplates all combinations of ranges formed by all said values ​​for a given property. The subject matter disclosed herein has been described in detail by specific embodiments. It should be understood that any detailed description of a component or feature of an embodiment does not necessarily mean that the component or feature is essential to a particular embodiment or any other embodiment.

Claims

1. An oligomer comprising, based on the total weight of the oligomer: 1 wt % to 95 wt % of the polymerized high T g Monomer unit; 0.1 wt% to 98.9 wt% of polymerized low T g Monomer unit; 0.1 wt % to 40 wt % polymerized chromophore monomer units; and 0 to 20 weight percent of at least one polymerized additional monomeric unit; in: The high T g The monomer unit has a Fox equation average glass transition temperature (T) equal to or greater than 25°C. g ) (meth)acrylate monomer; The low T g The monomer unit has a Fox equation average T of less than 25°C. g A monovalent (meth)acrylate monomer; The high T g Fox equation average T of monomer unit g Lower than the T g Fox equation average T of monomer unit g At least 20℃ higher. The chromophore monomer unit is a (meth)acrylate monomer having an attached Norrish II type chromophore; The oligomer has a weight average molecular weight of at least 10,000 grams per mole (g / mol); and The oligomer has a T equal to or greater than 0°C g .

2. The oligomer according to claim 1, which is according to formula (I): - Each A 1 Independently (C1-C 30 )alkyl or (C1-C 30 ) heteroalkyl, preferably (C1-C 30 ) hydrocarbon group, more preferably at least part of A 1 The moiety is selected from isobutyl, tert-butyl or cyclic (C1-C 30 ) alkyl; - Each A 2 Independently (C2-C 30 )alkyl or (C2-C 30 ) heteroalkyl, preferably (C4-C 30 ) alkyl; - Each A 3 is independently a monovalent residue comprising a Norrish type II chromophore, preferably a monovalent residue comprising benzophenone; - Each A 4 Independently (C1-C 30 )alkyl or (C1-C 30 ) heteroalkyl, preferably with a -(C1-C 30 ) Heteroalkyl: acidic group, nitrogen-containing group, hydroxyl group, epoxy group, carbonyl group, acetoacetoxy group, acetoacetamide group, 1,1-dimethyl-3-oxobutyl (diacetone) group, thiol group, silane group, ether bond, ester bond and combinations thereof; -Z 1 , Z 2 , Z 3 and Z 4 are independently -H or -CH3; -m is the high T of the aggregate g Weight fraction of monomer units; -n is the low T of the aggregate g Weight fraction of monomer units; - p is the weight fraction of polymerized chromophore monomer units; -q is the weight fraction of at least one additional monomer unit polymerized, and is optionally zero; and -m+n+p+q equals 1.

3. The oligomer according to claim 2, wherein: At least part of A 1 The moiety is selected from isobutyl, tert-butyl, substituted or unsubstituted (C6-C 12 )cycloalkyl, substituted or unsubstituted (C6-C 12 ) aryl, or a combination thereof; A 2 Straight or branched chain (C2-C 30 )alkyl or a combination thereof; and A 3 is X or -LX, where L is (C1-C 10 ) a heteroalkylene linker, and X is a monovalent residue of a Norrish type II chromophore.

4. The oligomer according to claim 2, wherein: At least part of A 1 The moiety is selected from isobutyl, tert-butyl, isobornyl, cyclohexyl, 3,3,5-trimethylcyclohexyl, tert-butylcyclohexyl, benzyl, adamantyl, dicyclopentyl, tricyclodecyl, -CH2-tricyclodecyl, phenyl, -CH2-CH2-phenyl, or -CH2-CH2-O-phenyl; A 2 is selected from n-butyl, isobutyl, hexyl, 2-ethylhexyl, isooctyl, isodecyl, tridecyl, lauryl, or a combination thereof; and A 3 It is a monovalent residue of a Norrish type II chromophore.

5. The oligomer according to any one of claims 1 to 4, wherein the Norrish type II chromophore is selected from benzophenone, thioxanthone or titanocene.

6. The oligomer according to any one of claims 2 to 5, wherein A 3 It is the monovalent residue of benzophenone.

7. The oligomer according to any one of claims 2 to 6, wherein: At least part of A 1 The moiety is selected from isobutyl, tert-butyl, isobornyl, cyclohexyl, 3,3,5-trimethylcyclohexyl, tert-butylcyclohexyl, benzyl, adamantyl, dicyclopentyl, tricyclodecyl, -CH2-tricyclodecyl, phenyl, -CH2-CH2-phenyl, or -CH2-CH2-O-phenyl A 2 is n-butyl; and A 3 It is the monovalent residue of benzophenone.

8. The oligomer according to any one of claims 2 to 7, wherein A 3 Having formula (IVa):

9. The oligomer according to any one of claims 2 to 8, wherein: q is from 0.001 to 0.20, preferably from 0.001 to 0.10; and The additional monomer unit comprises a functional group selected from the following: an acidic group, a heterocycle having one or more nitrogen ring atoms, a tertiary amine functional group, or a thiol group. Preferably, the additional monomer unit is selected from (meth)acrylic acid, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, N-vinyl pyrrolidone, N-vinyl caprolactam, acryloyloxymorpholine, dimethylacrylamide, poly(ethylene oxide) mono(meth)acrylate, hydroxyethylethylene urea(meth)acrylate, the reaction product of a cyclic anhydride and a hydroxy-functional (meth)acrylate, and combinations thereof.

10. The oligomer according to any one of claims 2 to 9, wherein the oligomer is according to formula (V): in: - Each A 1a are independently selected from isobutyl, tert-butyl or cyclic (C1-C 30 ) alkyl; - Each A 1b independently selected from the group consisting of isobutyl, tert-butyl or cyclic (C1-C 30 )Other than hydrocarbon groups (C1-C 30 ) alkyl; - Each A 2 Independently (C2-C 30 )alkyl or (C2-C 30 ) heteroalkyl; - Each A 3 is independently a monovalent residue comprising a Norrish type II chromophore, preferably a monovalent residue comprising benzophenone; - Each A 4 Independently (C1-C 30 )alkyl or (C1-C 30 ) heteroalkyl, preferably with a -(C1-C 30 ) Heteroalkyl: acidic group, nitrogen-containing group, hydroxyl group, epoxy group, carbonyl group, acetoacetoxy group, acetoacetamide group, 1,1-dimethyl-3-oxobutyl (diacetone) group, thiol group, silane group, ether bond, ester bond and combinations thereof; -Z 1 , Z 2 , Z 3 and Z 4 are independently -H or -CH3; - m1 is from 0.01 to 0.95, in particular from 0.20 to 0.90, more in particular from 0.25 to 0.85, even more in particular from 0.30 to 0.80, still more in particular from 0.35 to 0.75, still more in particular from 0.40 to 0.75; - m2 is from 0 to 0.94, in particular from 0 to 0.90, more in particular from 0 to 0.80, even more in particular from 0 to 0.70, still more in particular from 0 to 0.60, still more in particular from 0 to 0.50; - n is from 0.001 to 0.989, in particular from 0.10 to 0.80, more in particular from 0.15 to 0.75, even more in particular from 0.20 to 0.70, still more in particular from 0.25 to 0.65, still more in particular from 0.25 to 0.60; - p is from 0.001 to 0.40, in particular from 0.005 to 0.30, more in particular from 0.005 to 0.20, even more in particular from 0.005 to 0.15; still more in particular from 0.005 to 0.10, still more in particular from 0.01 to 0.10; - q is from 0 to 0.20, in particular from 0 to 0.10; and -m1+m2+n+p+q is equal to 1; - m1+m2 is from 0.01 to 0.95, in particular from 0.20 to 0.90, more in particular from 0.25 to 0.85, even more in particular from 0.30 to 0.80, still more in particular from 0.35 to 0.75, still more in particular from 0.40 to 0.

75.

11. The oligomer according to any one of claims 2 to 10, according to formula (VI): in: m is 0.2 to 0.8; n is 0.1 to 0.8; and p is 0.001 to 0.2; in: The oligomer has a weight average molecular weight of at least 20,000 g / mol.

12. The oligomer according to any one of claims 2 to 11, wherein: Z 1 is -CH3; Z 2 and Z 3 is -H; and If q is greater than 0, then Z 4 is -H.

13. The oligomer according to any one of claims 1 to 12, wherein the T of the oligomer is g It is 0°C to 100°C, particularly 20°C to 100°C, more particularly 30 to 100°C.

14. A curable composition comprising the oligomer according to any one of claims 1 to 13 and a reactive diluent.

15. The curable composition according to claim 14, wherein the reactive diluent comprises a polyol having a T greater than 25°C. g The monofunctional (meth)acrylate monomer is selected from the group consisting of 2-phenylethyl methacrylate, neopentyl methacrylate, 3,3,5-trimethylcyclohexyl acrylate, tert-butyl acrylate, octadecyl methacrylate, octadecyl acrylate, glycidyl methacrylate, propyl methacrylate, tetrahydrofurfuryl methacrylate, benzyl methacrylate, isobutyl methacrylate, glycidyl methacrylate, ethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 2-hydroxypropyl methacrylate, 2,2,2- trifluoroethyl ester, 2-hydroxyethyl methacrylate, isopropyl methacrylate, isobornyl acrylate, methyl methacrylate, butyl cyanoacrylate, isobornyl methacrylate, phenyl methacrylate, 2-cyanobutyl acrylate, tert-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 4-tert-butylcyclohexyl acrylate, 4-tert-butylcyclohexyl methacrylate, ethyl cyanoacrylate, methyl cyanoacrylate, 3,3,5-trimethylcyclohexyl acrylate, 3,3,5-trimethylcyclohexyl methacrylate, substituted or unsubstituted (meth)acrylic acid (C6-C 12 )cycloalkyl ester, adamantyl (meth)acrylate, dicyclopentyl (meth)acrylate, tricyclodecanemethanol mono(meth)acrylate, 2-phenoxyethyl methacrylate, or a combination thereof.

16. The curable composition according to claim 14 or 15, wherein the reactive diluent comprises a multifunctional (meth)acrylate, in particular a multifunctional (meth)acrylate selected from the group consisting of 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. di(meth)acrylate of 1,5-pentanediol; di(meth)acrylate of 1,6-hexanediol; di(meth)acrylate of 1,8-octanediol; di(meth)acrylate of 1,9-nonanediol; di(meth)acrylate of 1,10-nonanediol; di(meth)acrylate of 1,12- Dodecanediol di(meth)acrylate; neopentyl glycol di(meth)acrylate; 2-methyl-2,4-pentanediol di(meth)acrylate; polybutadiene di(meth)acrylate; cyclohexane-1,4-dimethanol di(meth)acrylate; tricyclodecane dimethanol di(meth)acrylate; metal di(meth)acrylate; modified metal di(meth)acrylate; glyceryl di(meth)acrylate; glyceryl tri(meth)acrylate; trimethylolethane tri(meth)acrylate; trimethylolethane di(meth)acrylate; trimethylolpropane tri(meth)acrylate; trimethylolpropane di(meth)acrylate; pentaerythritol di(meth)acrylate; pentaerythritol tri(meth)acrylate; pentaerythritol tetra(meth)acrylate, di(trimethylolpropane) diacrylate; di(trimethylolpropane) triacrylate; di(trimethylolpropane) tetraacrylate, sorbitol penta(meth)acrylate; di(pentaerythritol) tetraacrylate; di(pentaerythritol) pentaacrylate; di(pentaerythritol) hexa(meth)acrylate; tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate; and alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives thereof; and combinations thereof.

17. A curable composition according to any one of claims 14 to 16, wherein the curable composition is substantially free of photoinitiators other than the oligomers according to any one of clauses 1 to 21, in particular, the curable composition comprises less than 0.1 wt.%, in particular less than 0.05 wt.%, more in particular less than 0.001 wt.%, even more in particular 0 wt.% of photoinitiators other than the oligomers according to any one of clauses 1 to 21.

18. A coating formed by curing the ultraviolet curable composition according to any one of claims 14 to 17.

19. The coating of claim 18, wherein the coating has a gel content of at least 30%.

20. A method for preparing a curable composition according to any one of claims 14 to 17, wherein the method comprises the following steps: - preparing an oligomer as defined in any one of claims 1 to 13 dissolved in a non-reactive solvent; - adding a reactive diluent to obtain a diluted curable composition; - removing at least part of the non-reactive solvent from the diluted curable composition to obtain the curable composition.

21. A method of curing a curable composition according to any one of claims 14 to 17 or prepared by the method according to claim 20, wherein the method comprises curing the curable composition by irradiating the curable composition with a light source having a wavelength and / or intensity capable of activating polymerized chromophore monomer units of an oligomer and causing crosslinking of the oligomer and / or the reactive diluent.

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