Oligomers containing overlapping high-Tg monomers

Abstract

The present invention relates to an oligomer comprising polymerized high-T g monomer units, 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 an ultraviolet curable composition comprising the oligomer, and a coating formed from the curing of the ultraviolet curable composition.

Description

Technical Field

[0001] The present invention relates to oligomers. The oligomers include polymerized high-T g monomer units, 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 oligomers as coatings for curable compositions and to methods of coating substrates.

Background Art

[0002] Oligomers having acrylic polymer monomers and chromophores can generally be crosslinked by irradiation with ultraviolet (UV) light, but have certain drawbacks during processing. For example, oligomers having a T g of 0 °C or higher can be difficult to crosslink sufficiently, and the resulting coatings and adhesives may be weak. Such difficulties limit their use due to performance requirements.

[0003] Oligomers having a T g of 0 °C or higher can provide advantages such as improved hardness over low-T g coatings and adhesives formed from oligomers having a T g of less than 0 °C and can be processed to form high-T g coatings and adhesives. However, it can be difficult to develop oligomers that achieve desired properties such as sufficient crosslinkability during curing. Accordingly, there is a need for oligomers having a T g of 0 °C or higher while maintaining high crosslinkability during curing.

[0004] Embodiments of the oligomers disclosed herein overcome the drawbacks associated with known oligomers having a T g of 0 °C or higher.

Summary of the Invention

[0005] The first aspect disclosed herein is, based on the total weight of the oligomer, 1 wt% to 95 wt% of 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; the high-T g monomer units are (meth)acrylate monomers having a Fox equation average glass transition temperature (T g ) of 25 °C or higher; the low-T g monomer units are monovalent (meth)acrylate monomers having a Fox equation average T g of less than 25 °C; the Fox equation average T g of the high-T g monomer units is at least 20 °C higher than the Fox equation average T g of the low-T g monomer units; the chromophore monomer units are (meth)acrylate monomers having a pendant-type Nolish 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 g of 0 °C or higher.

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

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

[0008] Another aspect disclosed herein is a method for preparing a curable composition of the present invention, comprising: - a step of preparing by dissolving the oligomer according to the present invention in a non-reactive solvent; - a step of adding a reactive diluent to obtain a diluted curable composition; - a step of removing at least a part of the non-reactive solvent from the diluted curable composition to obtain a curable composition including.

[0009] Another aspect disclosed herein is a method of curing a curable composition of the present invention or a curable composition prepared by the method of the present invention, the method comprising irradiating a curable composition comprising an oligomer and a reactive diluent with a light source having a wavelength and / or intensity capable of activating the polymerized chromophore monomer units of the oligomer and causing crosslinking of the oligomer and / or the reactive diluent to effect curing.

[0010] This summary is provided to introduce a selected concept that will be 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.

[0011] Additional features and advantages of the described embodiments will be set forth in the detailed description which follows. The additional features and advantages of the described embodiments will be, in part, readily apparent to those of ordinary skill in the art from the description or, alternatively, will be recognized by practicing the described embodiments, which include the detailed description, the drawings and the claims. BRIEF DESCRIPTION OF THE DRAWINGS

[0012]

Figure 1

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Figure 7

[0013] Reference is now made in more detail to various embodiments, some of which are illustrated in the accompanying drawings. DETAILED DESCRIPTION OF THE INVENTION

[0014] [Definitions] As used herein, the term "comprises a" may mean "comprises one or more".

[0015] Unless otherwise specified, weight percentages in compounds or compositions are expressed relative to the respective weights of the compounds or compositions.

[0016] As used herein, the term "substituted" means that at least one hydrogen atom (-H) bonded to a carbon or heteroatom of the corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., R S ). The term "over-substituted" means that every hydrogen atom (H) bonded to a carbon or heteroatom of the corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., R S ). The term "multi-substituted" means that at least two (but not all) hydrogen atoms bonded to a carbon or heteroatom of the corresponding unsubstituted compound or functional group are replaced by substituents. Unless otherwise defined or limited in a particular context, substituents in general, or substituents referred to as R S can be any chemical moiety, typically a chemical moiety having from 1 to 50, or from 1 to 40, or from 1 to 30, or from 1 to 20, or from 1 to 10 total atoms, but is not necessarily limited thereto. Substituent R SExamples include, but are not limited to, hydrocarbyl, heterohydrocarbyl, aryl, heteroaryl, alkyl, cycloalkyl, heteroatom, carbonyl, hydroxy, ester, ether, amine, amide, or halide according to each definition herein or its generally understood meaning, and any of these substituents may be either substituted or unsubstituted themselves. In some embodiments, substituent R S is selected from (C1-C 30 ) hydrocarbyl, (C1-C 30 ) heterohydrocarbyl, (C6-C 30 ) aryl, or (C6-C 30 ) heteroaryl.

[0017] The term "hydrocarbyl" means a monovalent hydrocarbon in which each hydrocarbon is aromatic or non-aromatic, saturated or unsaturated, straight-chain or branched-chain, cyclic (having three or more carbons, including monocyclic and polycyclic, fused and non-fused polycyclic, and bicyclic) or acyclic, and is either substituted by one or more R S or unsubstituted. In this disclosure, hydrocarbyl can be unsubstituted or substituted alkyl, unsubstituted or substituted cycloalkyl, or unsubstituted or substituted aryl. Hydrocarbyl may not contain any heteroatoms selected from O, N, or S. (C1-C 30 ) hydrocarbyl is a hydrocarbyl having from 1 to 30 carbon atoms.

[0018] The term "heterohydrocarbyl" means a hydrocarbyl having one or more heteroatoms independently selected from O, N, or S. (C1-C 30 ) heterohydrocarbyl is a heterohydrocarbyl having from 1 to 30 carbon atoms.

[0019] The term "aryl" means an optionally substituted polyunsaturated aromatic group. Aryl can be monocyclic (i.e., phenyl) or can contain more than one ring where at least one ring is aromatic. When aryl contains more than one ring, the rings can be fused together via covalent bonds (e.g., biphenyl). The aromatic ring can optionally contain one or two additional fused rings (i.e., cycloalkyl, heterocycloalkyl, or heteroaryl). Examples include phenyl, naphthyl, biphenyl, phenanthrenyl, and naphthacenyl.

[0020] The term "alkyl" means a monovalent saturated acyclic hydrocarbon group of the formula -C n H 2n+1 (where n is from 1 to 20). Alkyl can be linear or branched. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, 2-methylbutyl, 2,2-dimethylpropyl, n-hexyl, 2-methylpentyl, 2,2-dimethylbutyl, n-heptyl, 2-ethylhexyl, and the like.

[0021] The term "cycloalkyl" means a monovalent saturated alicyclic hydrocarbon group containing a ring. Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, and isobornyl, any of which can be substituted or unsubstituted.

[0022] The term "heterocycloalkyl" means a cycloalkyl having at least one ring atom that is a heteroatom selected from O, N, or S.

[0023] The term "halogen" means an atom selected from Cl, Br, F, and I.

[0024] The term "alkoxy" means a group of the formula -O-alkyl, where alkyl is as defined above.

[0025] The term "aryloxy" means a group of the formula -O-aryl, where aryl is as defined above.

[0026] The term "thioalkyl" means a group of the formula -S-alkyl, where alkyl is as defined above.

[0027] The term "thioaryl" means a group of the formula -S-aryl, where aryl is as defined above.

[0028] The term "alkenyl" means a monovalent acyclic hydrocarbon group containing at least one C=C double bond. Alkenyl can be straight-chain or branched.

[0029] The term "alkynyl" means a monovalent acyclic hydrocarbon group containing at least one C≡C triple bond. Alkynyl can be straight-chain or branched.

[0030] The term "aralkyl" means aryl substituted with an alkyl group. An example of an aralkyl group is tolyl.

[0031] The term "alkaryl" means alkyl substituted with an aryl group. An example of an alkaryl group is benzyl (-CH2-phenyl).

[0032] The term "heteroaryl" means aryl having at least one ring atom that is a heteroatom.

[0033] The term "alkylamino" means alkyl substituted with at least one amino group.

[0034] The term "alkylthiol" means alkyl substituted with at least one thiol group.

[0035] The term "hydroxyalkyl" means alkyl substituted with at least one hydroxy group.

[0036] The term "haloalkyl" means an alkyl substituted with at least one halogen.

[0037] The term "alkylene" or "alkanediyl" means a linker derived by removing one hydrogen atom from each point of attachment of the linker from an alkane of the formula C m H 2m+2 An alkylene can be divalent, trivalent, tetravalent or can have an even higher valence.

[0038] The term "alkoxylation" means a compound, group or linker containing one or more oxyalkylene moieties, in particular one or more oxyalkylenes 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, an alkoxylated compound, group or linker can contain from 1 to 30 oxyalkylene moieties.

[0039] The term "(meth)acrylate" means acrylate or methacrylate. The term "acrylate" means an acryloyloxy group (-O-C(=O)-CH=CH2). The term "methacrylate" means a methacryloyloxy group (-O-C(=O)-C(CH3)=CH2).

[0040] The term "(meth)acrylate monomer" means a monomer having a (meth)acrylate group.

[0041] As used herein, a "monomer" has a number average molecular weight of less than 1000 g / mol, preferably from 100 to 950 g / mol.

[0042] As used herein, an "oligomer" has a number average molecular weight of 1000 g / mol or more, preferably from 1050 to 60000 g / mol, more preferably from 10000 to 50000 g / mol.

[0043] The term "glass transition temperature" or "T g " refers to the temperature at which a material changes from a glassy state to a rubbery state. In this context, the term "glassy" means that the material is hard and brittle, and the term "rubbery" means that the material is elastic and flexible. In the case of a polymeric material, T g is the critical temperature that separates glassy behavior from rubbery behavior. When a polymeric material is at a temperature below its T g , the material is essentially frozen, and large-scale molecular motion is significantly restricted. On the other hand, when a polymeric material is at a temperature above its T g , molecular motion occurs on the scale of its repeating units, and it becomes flexible or rubbery.

[0044] All references herein to the T g of a monomer refer to the T g of the homopolymer formed from that monomer. The T g values of common monomers are well known from the literature. If not reported in the literature, the glass transition temperature value can be determined as the inflection temperature (T i ) in accordance with ASTM E1356-08, "Standard Test Method for Assignment of the Glass Transition Temperature by Differential Scanning Calorimetry". The glass transition temperatures of the oligomers described herein and referred to in the following examples are calculated using the Fox equation based on the mass fraction and T g values of each individual monomer of the polymeric material containing the oligomer or multiple separate types of monomers.

[0045] The terms "mass fraction" and "weight fraction" are used interchangeably herein and are considered equivalent to each other with respect to the embodiments or examples herein.

[0046] The "Fox equation" refers to Equation (1): TIFF2025523911000001.tif10170Here, T g,mixis the glass transition temperature of a mixture of i chemically distinct components, such as two or more separate monomers of an oligomer or polymer, and T g,i is the glass transition temperature of the i-th component, and ω i is the mass fraction of the i-th component based on the total mass of the oligomer or polymer. Hereinafter, the value of T g,mix for a plurality of separate monomers in the oligomer or polymer is referred to as the "Fox equation average T g ".

[0047] In the case of a two-component system of each type of monomer A and B, the Fox equation is simplified to equation (2): TIFF2025523911000002.tif11170

[0048] The term "high T g monomer unit" refers to a monomer that, when homopolymerized, produces a homopolymer having a T g of 25 °C or higher. In an embodiment of an oligomer in which only one type of high T g monomer unit is present, the T g of the high T g monomer unit is the T g of the homopolymer of one type of high T g monomer unit. In an embodiment of an oligomer in which two or more distinct high T g monomer units are present, the T g of the high T g monomer units of the oligomer is such that in equation (1), the individual mass fractions ω i are not based on the total mass of the entire oligomer, but rather on the total mass of all high T g monomer units (i.e., monomer units having a T g of 25 °C or higher) present in the oligomer, and are the mass fractions of each individual high T g monomer unit in the oligomer. The Fox equation average T g of the combination of high T g monomer units is collectively referred to as such.

[0049] The term "Fox average" may also be used here with respect to a single monomer that is not part of a mixture of two or more monomers. The Fox average T for a single monomer g is equal to the T of the single monomer itself as defined here, since the mass fraction term ω in such a situation is equal to 1. g It should be readily understood to be equal.

[0050] The term "low T g monomer unit" refers to a monomer that, when homopolymerized, produces a homopolymer having a T of less than 25 °C. g In an embodiment of an oligomer in which only one type of low T g monomer unit is present, the T of the low T g monomer unit g is the T of the homopolymer of one type of low T g monomer unit. g In an embodiment of an oligomer in which two or more distinct low T g monomer units are present, the T of the low T g monomer units of the oligomer g is the Fox average T of the combination of low T i monomer units, where in equation (1), the individual mass fractions ω g are not based on the total mass of the entire oligomer, but rather on the total mass of all low T g monomer units (i.e., monomer units having a T of less than 25 °C) present in the oligomer, and are the mass fractions of each individual low T g monomer unit in the oligomer. g Collectively refers to the Fox average T g of the combination of low T monomer units.

[0051] The term "photoinitiator" can be considered to be any type of substance that, when exposed to radiation (e.g., actinic radiation), forms species that initiate the reaction and curing of the polymerizable organic substances present in the curable composition.

[0052] The term "chromophore" as used herein refers to a Nolish II type light-absorbing molecule that becomes excited upon absorbing light. From this excited state, the molecule can interact or react with other molecules to generate reactive radical species.

[0053] When used to describe a predetermined carbon atom-containing chemical group, the expression of the form "A 1 -A 4 " refers to each A 1 from A 4 to A x within the range. For example, the expression of the form "A 1 -A 4 " refers to A 1 , A 2 , A 3 , and A 4 . The expression of the form "Z 1 -Z 4 " refers to each Z 1 from Z 4 to Z x within the range. For example, the expression of the form "Z 1 -Z 4 " refers to Z 1 , Z 2 , Z 3 , and Z 4 .

[0054] The term "independently selected" as used herein is used to indicate that substituents, such as Z 1 , Z 2 , Z 3 , and Z 4 may be the same or different (e.g., Z 1 , Z 2 , Z 3 , and Z 4 may all be -CH3, or Z 1 and Z 2 are -CH3, and Z 3 and Z 4(e.g., may be -H). Chemical names associated with substituents are intended to convey a chemical structure that is recognized in the art as corresponding to the structure of the chemical name. Thus, the chemical names are intended to supplement and illustrate, rather than preclude, structural definitions known to those of skill in the art.

[0055] When used to describe certain carbon atom-containing chemical groups, "(C x -C y A parenthetical expression of the form "(C1-C2)" means that the unsubstituted form of the chemical group contains x and y, and has from x carbon atoms to y carbon atoms. For example, (C1-C2) 20 ) Hydrocarbyl is a hydrocarbyl group having 1 to 20 carbon atoms in its unsubstituted form. In some embodiments and general structures, a given chemical group is R S The parenthesized "(C x -C y ) for chemical groups defined using S The substituted version can be represented by any group R S Depending on the identity of R, the compound may contain more than y carbon atoms. For example, "exactly one group R S (C1-C 20 ) alkyl (where R S A phenyl group (-C6H5) can contain from 7 to 27 carbon atoms. x -C y ) is a chemical group defined using one or more carbon atom-containing substituents R S If the chemical group is substituted with any of the carbon atom-containing substituents R, the minimum and maximum total number of carbon atoms in the chemical group shall be S The number of carbon atoms in the 1 to 4 carbon atoms is determined by adding the combined total of the numbers of carbon atoms in the 1 to 4 ...

[0056] The term "-H" means a hydrogen atom covalently bonded to a non-hydrogen atom. "Hydrogen" and "-H" are interchangeable and have the same meaning unless expressly specified.

[0057] "(C1-C30 ) The term "hydrocarbyl" means a monovalent hydrocarbon of 1 to 30 carbon atoms, each monovalent hydrocarbon being aromatic or non-aromatic, saturated or unsaturated, straight-chain or branched-chain, cyclic (having 3 or more carbon atoms, including monocyclic and polycyclic, fused and non-fused polycyclic, and bicyclic) or acyclic, and being unsubstituted or substituted with one or more R S groups. In this disclosure, (C1-C 30 ) hydrocarbyl can be unsubstituted or substituted (C1-C 30 ) alkyl, (C3-C 30 ) cycloalkyl, or (C6-C 30 ) aryl.

[0058] The term "(C2-C 30 ) alkyl" means a saturated straight-chain or branched-chain monovalent hydrocarbon of 2 to 30 carbon atoms, unsubstituted or substituted with one or more R S groups. Examples of unsubstituted (C2-C 30 ) alkyl 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. Examples of substituted (C2-C 30 ) alkyl are substituted (C2-C 20 ) alkyl, substituted (C2-C 10 ) alkyl.

[0059] The term "(C6-C 40 ) aryl" means an unsubstituted or (one or more R Smeans a monocyclic, bicyclic, or tricyclic aromatic monovalent hydrocarbon substituted with). A monocyclic aromatic monovalent hydrocarbon contains one aromatic ring; a bicyclic aromatic monovalent hydrocarbon has two rings; a tricyclic aromatic monovalent hydrocarbon has three rings. When a bicyclic or tricyclic aromatic monovalent hydrocarbon is present, at least one of the rings of the monovalent hydrocarbon is aromatic. The other rings of the aromatic monovalent hydrocarbon are independently fused or unfused and may be aromatic or non-aromatic. Unsubstituted (C6-C 40 ) Examples of aryl include unsubstituted (C6-C 20 ) aryl, unsubstituted (C6-C 18 ) aryl; 2-(C1-C5)alkyl-phenyl; phenyl; fluorenyl; tetrahydrofluorenyl; idacenyl; hexahydracenyl; hexahydroindacenyl; indenyl; dihydroindenyl; naphthyl; tetrahydronaphthyl; and phenanthrene. Examples of substituted (C6-C 40 ) aryl include substituted (C1-C 20 ) aryl; and substituted (C6-C 18 ) aryl.

[0060] The term “(C6-C 12 ) cycloalkyl” means a saturated cyclic monovalent hydrocarbon having 6 to 12 carbon atoms, which is unsubstituted or substituted. Other cycloalkyl groups (e.g., (C x -C y ) cycloalkyl) are similarly defined as having x to y carbon atoms and being unsubstituted or substituted with one or more R S . Examples of unsubstituted (C6-C 12 ) cycloalkyl are unsubstituted (C6-C8) cycloalkyl, unsubstituted (C6-C 10 ) cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. Examples of substituted (C6-C 12 ) cycloalkyl are substituted (C6-C8) cycloalkyl, substituted (C6-C 10 ) cycloalkyl, isobornyl, and 3,3,5-trimethylcyclohexyl.

[0061] The term "heteroatom" refers to an atom other than hydrogen or carbon. Examples of heteroatoms include O, S, N, and Si. The term "heterohydrocarbon" refers to a molecule or molecular framework in which one or more carbon atoms of a hydrocarbon have been replaced by heteroatoms. The term "(C1-C 30 )heterohydrocarbyl" means a monovalent heterohydrocarbon having from 1 to 30 carbon atoms, and the term "(C1-C 30 )heterohydrocarbylene" means a divalent heterohydrocarbon having from 1 to 30 carbon atoms. The (C1-C 30 )heterohydrocarbyl or (C1-C 30 )heterohydrocarbylene heterohydrocarbons have one or more heteroatoms. The valence or point of attachment of a heterohydrocarbyl can be on a carbon atom or a heteroatom. The two valences of a heterohydrocarbylene can be on a single carbon atom or a single heteroatom. In addition, one of the two valences or points of attachment of a diradical can be on a carbon atom and the other on a different carbon atom; one of the two valences or points of attachment can be on a carbon atom and the other on a heteroatom; or one of the two valences or points of attachment can be on a heteroatom and the other valence or point of attachment can be on a different heteroatom. Each (C1-C 30 )heterohydrocarbyl and (C1-C 30 )heterohydrocarbylene can be unsubstituted or substituted, aromatic or non-aromatic, saturated or unsaturated, straight-chain or branched-chain, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic), or acyclic.

[0062] The term "saturated" means lacking carbon-carbon double bonds, carbon-carbon triple bonds, and (in the case of heteroatom-containing groups) carbon-nitrogen, carbon-phosphorus, and carbon-silicon double bonds. When a saturated chemical group is substituted with one or more substituents R S , one or more double bonds and / or triple bonds are in the substituents R Smay optionally be present or absent. The term "unsaturated" means containing one or more carbon-carbon double bonds, carbon-carbon triple bonds, or (in the case of heteroatom-containing groups) one or more carbon-nitrogen, carbon-phosphorus, or carbon-silicon double bonds, and even if present, double bonds that may be present in substituent R S or, even if present, double bonds that may be present in the (hetero)aromatic ring are not included.

[0063] The term "linker" means a polyvalent group. A linker can link together at least two moieties of a compound, particularly from 2 to 16 moieties of a compound. For example, a linker that links two moieties of a compound is called a divalent linker, and a linker that links three moieties of a compound is called a trivalent linker.

[0064] [Oligomer] The oligomers of the present invention contain at least one polymerized chromophore monomer unit as defined herein. The oligomers herein contain at least one polymerized high T g monomer unit and at least one polymerized low T g monomer unit. The oligomers herein optionally contain at least one polymerized additional monomer unit as defined herein. The oligomers herein may not contain polymerized monomer units other than polymerized high T g monomer units, polymerized low T g monomer units, polymerized chromophore monomer units, and optionally polymerized additional monomer units. The total weight of the polymerized high T g monomer units, polymerized low T g monomer units, polymerized chromophore monomer units, and polymerized additional monomer units can account for at least 97%, particularly at least 98%, more particularly at least 99%, and even more particularly 100% of the total weight of the oligomer.

[0065] In an embodiment, the oligomer contains, based on the total weight of the oligomer, from 1% to 95% by weight of polymerized high T g monomer units and from 0.1% to 98.9% by weight of polymerized low Tg It contains monomer units, 0.1% to 40% by weight of polymerized chromophore monomer units, and 0 to 20% by weight of polymerized additional monomer units.

[0066] In an embodiment, the oligomer has the formula (I): TIFF2025523911000003.tif56170(In the above formula, - Each A 1 is independently a (C1-C 30 ) hydrocarbyl or a (C1-C 30 ) heterohydrocarbyl, preferably a (C1-C 30 ) hydrocarbyl, and more preferably at least a part of the A 1 moiety is selected from isobutyl, tert-butyl or cyclic (C1-C 30 ) hydrocarbyl; - Each A 2 is independently a (C2-C 30 ) hydrocarbyl or a (C2-C 30 ) heterohydrocarbyl, preferably a (C4-C 30 ) hydrocarbyl; - Each A 3 is independently a monovalent residue containing a Norrish type II chromophore, preferably a monovalent residue containing benzophenone; - Each A 4 is independently a (C1-C 30 ) hydrocarbyl or a (C1-C 30 ) heterohydrocarbyl, preferably a -(C1-C 30 ) heterohydrocarbyl having a functional group selected from acidic groups, nitrogen-containing groups, 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, and combinations thereof; - Z 1 、Z 2 、Z 3 、and Z 4 are independently -H or -CH3; - m is the polymerized high T gis the weight fraction of the monomer unit; - n is the polymerized low T g is the weight fraction of the monomer unit; - p is the weight fraction of the polymerized chromophore monomer unit; - q is the weight fraction of at least one polymerized additional monomer unit and is optionally 0; and - m + n + p + q equals 1) has.

[0067] In one example, in the oligomer of formula (I), m can be from 0.01 to 0.95; n can be from 0.001 to 0.989, p can be from 0.001 to 0.4, and q can be from 0 to 0.2.

[0068] In some embodiments, q is 0, and thus no polymerized additional monomer units are present in the oligomer.

[0069] A 1 、A 2 、A 3 、A 4 、Z 1 、Z 2 、Z 3 、Z 4 For further preferred descriptions of m, n, p, and q, they are defined below for each corresponding monomer unit.

[0070] [High T g monomer unit] In an embodiment, the oligomer contains polymerized high T g monomer units, whereby the T g of the oligomer formed therefrom can be increased. The high T g monomer units are different from the low T g monomer units, chromophore monomer units, and additional monomer units. Thus, the high T g monomer units may not contain any of the following groups: - a chromophore moiety; - a functional group defined below for additional monomer units other than an ether bond.

[0071] Overlapped high T g The monomer units can be the same or a combination of multiple types of different monomer units, such as, for example, two different monomer units, three different monomer units, four different monomer units, or more than four different monomer units. In an embodiment, high T g The monomer unit has a glass transition temperature (T g ) or Fox formula average T g as defined herein. As used herein, the reference to T g for a monomer refers to the T g of the homopolymer formed from that monomer. In an embodiment where the oligomer contains two or more distinct high T g monomer units, such as a combination of methyl (meth) acrylate and isobornyl (meth) acrylate, T g refers to the Fox formula average T g of the high T g monomer units as described above herein. In an embodiment, the Fox formula average T g of the high T g monomer units is 25°C or higher, such as 30°C or higher, 35°C or higher, 40°C or higher, 45°C or higher, 50°C or higher, 55°C or higher, 60°C or higher, 65°C or higher, 70°C or higher, 75°C or higher, or 80°C or higher. In an embodiment, high T gThe monomer unit has a T formed from any and all partial ranges formed from 25°C to 200°C, 25°C to 150°C, 25°C to 130°C, 30°C to 200°C, 30°C to 150°C, 30°C to 130°C, 35°C to 200°C, 35°C to 150°C, 35°C to 130°C, 40°C to 200°C, 40°C to 150°C, 40°C to 130°C, 45°C to 200°C, 45°C to 150°C, 45°C to 130°C, 50°C to 200°C, 50°C to 150°C, 50°C to 130°C, 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 of these endpoints. g It may have.

[0072] High T g The Fox formula average T of the monomer unit g is higher than the low T g The Fox formula average T of the monomer unit g In an embodiment, the high T g The Fox formula average T of the monomer unit g is higher than the low T g The Fox formula average T of the monomer unit g by at least 20°C. In an embodiment, the high T g The Fox formula average T of the monomer unit g and the low T g The Fox formula average T of the monomer unit g The difference between them is more than 20°C, for example, more than 25°C, more than 30°C, more than 35°C, more than 40°C, more than 45°C, more than 50°C, more than 55°C, more than 60°C, more than 65°C, more than 70°C, more than 75°C, more than 80°C, more than 85°C, more than 90°C, more than 95°C, more than 100°C, more than 105°C, more than 110°C, more than 115°C, or more than 120°C. In an embodiment, the high T g The Fox formula average T of the monomer unit g and the low T g The Fox formula average T of the monomer unit g The difference between them is from 20°C to 200°C. As a non-limiting example, the high T g The Fox formula average T of the monomer unitg and low T g The Fox formula average T of the monomer unit g The difference from can be any and all partial ranges formed from 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, 30°C to 100°C, 30°C to 90°C, 30°C to 80°C, 30°C to 70°C, 30°C to 60°C, 30°C to 50°C, 30°C to 40°C, 40°C to 200°C, 40°C to 150°C, 40°C to 120°C, 40°C to 100°C, 40°C to 90°C, 40°C to 80°C, 40°C to 70°C, 40°C to 60°C, 40°C to 50°C, 50°C to 200°C, 50°C to 150°C, 50°C to 120°C, 50°C to 100°C, 50°C to 90°C, 50°C to 80°C, 50°C to 70°C, 50°C to 60°C, 60°C to 200°C, 60°C to 150°C, 60°C to 120°C, 60°C to 100°C, 60°C to 90°C, 60°C to 80°C, 60°C to 70°C, 70°C to 200°C, 70°C to 150°C, 70°C to 120°C, 70°C to 100°C, 70°C to 90°C, 70°C to 80°C, 80°C to 200°C, 80°C to 150°C, 80°C to 120°C, 80°C to 100°C, or 80°C to 90°C, or any of these endpoints.

[0073] high T g The monomer unit consists of one or more (meth)acrylate monomers, preferably one or more monofunctional (meth)acrylate monomers.

[0074] In an embodiment, high T g The monomer unit is monovalent. In other embodiments, high T g The monomer unit may be polyvalent, in which case the individual monomer units contain two or more active sites involved in crosslinking during curing. Examples of monovalent monomer units can include ethyl methacrylate and tert-butyl acrylate. Examples of polyvalent monomer units can include divalent monomer units such as dicyclopentadienyl diacrylate.

[0075] In an embodiment, high T g Each of the monomer units (before being polymerized to form the backbone of the oligomer) is independently of the formula (II): TIFF2025523911000004.tif45170(wherein - A 1 is (C1-C 30 ) hydrocarbyl or (C1-C 30 ) heterohydrocarbyl, preferably (C1-C 30 ) hydrocarbyl; and - Z 1 is -H or -CH3) can conform to.

[0076] 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 is selected from methyl, tert-butyl, isobornyl, cyclohexyl, or 3,3,5-trimethylcyclohexyl, or a combination thereof.

[0077] Preferably, at least a portion of the high T g monomer units conform to formula (I), where Z 1 is -H or -CH3, and A 1 is isobutyl, tert-butyl, substituted or unsubstituted (C6-C 12 ) cycloalkyl optionally bonded to an alkylene moiety, substituted or unsubstituted (C6-C 12 ) aryl optionally bonded to an alkylene or oxyalkylene moiety, or a combination thereof. More preferably, A 1is 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.

[0078] A 1 When A is isobutyl or cyclohexyl, Z 1 is CH3.

[0079] The above embodiment is similarly applicable to A in the oligomer of formula (I). Accordingly, at least a part of at least a part of the A 1 moiety in the oligomer of formula (I) can be selected from isobutyl, tert-butyl, substituted or unsubstituted (C6-C 1 ) cycloalkyl optionally bonded to an alkylene moiety, substituted or unsubstituted (C6-C 12 ) aryl optionally bonded to an alkylene or oxyalkylene moiety, or a combination thereof. Preferably, at least a part of the A 12 moiety in the oligomer of formula (I) 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. 1 Here, the high T in the oligomer

[0080] g ​Examples of monomer units include, but are not limited to, 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 (C6-C 12 ) cycloalkyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentanyl (meth)acrylate, tricyclodecanemethanol mono(meth)acrylate, 2-phenoxyethyl methacrylate, or a combination thereof, and the like.

[0081] Preferably, the high T of the oligomer g The monomer units include sterically hindered (meth)acrylates such as isobutyl methacrylate, tert-butyl (meth)acrylate or 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, dicyclopentanyl (meth)acrylate, tricyclodecanemethanol mono(meth)acrylate, and combinations thereof.

[0082] The (meth)acrylate with steric hindrance may be optionally combined with a (meth)acrylate without steric hindrance such as methyl methacrylate.

[0083] The weight fraction of the polymerized high-T in the oligomer g of the monomer units varies according to the desired properties of the oligomer, such as g T, molecular weight, gel content after curing, etc.

[0084] As described herein, m in formula (I) is the polymerized high-T in the oligomer gIt is the weight fraction of the monomer unit. In a further embodiment, m is 0.01 or more, for example 0.05 or more, 0.1 or more, 0.15 or more, 0.2 or more, 0.25 or more, 0.30 or more, 0.35 or more, 0.40 or more, 0.45 or more, 0.50 or more, 0.55 or more, or 0.60 or more. In an embodiment, m is from 0.10 to 0.95, from 0.10 to 0.95, from 0.10 to 0.90, from 0.10 to 0.85, from 0.10 to 0.80, from 0.10 to 0.75, from 0.10 to 0.70, from 0.10 to 0.60, from 0.10 to 0.50, from 0.10 to 0.40, from 0.10 to 0.30, from 0.10 to 0.20, from 0.20 to 0.95, from 0.20 to 0.90, from 0.20 to 0.85, from 0.20 to 0.80, from 0.20 to 0.70, from 0.20 to 0.60, from 0.20 to 0.50, from 0.20 to 0.40, from 0.20 to 0.30, from 0.30 to 0.95, from 0.30 to 0.90, from 0.30 to 0.85, from 0.30 to 0.80, from 0.30 to 0.70, from 0.30 to 0.60, from 0.30 to 0.50, from 0.30 to 0.40, from 0.40 to 0.95, from 0.40 to 0.90, from 0.40 to 0.85, from 0.40 to 0.80, from 0.40 to 0.70, from 0.40 to 0.60, from 0.40 to 0.50, from 0.50 to 0.95, from 0.50 to 0.90, from 0.50 to 0.85, from 0.50 to 0.95, from 0.50 to 0.90, from 0.50 to 0.85, from 0.50 to 0.80, from 0.50 to 0.70, from 0.50 to 0.60, from 0.60 to 0.95, from 0.60 to 0.90, from 0.60 to 0.85, from 0.60 to 0.80, from 0.60 to 0.70, from 0.70 to 0.95, from 0.70 to 0.90, from 0.70 to 0.85, or from 0.70 to 0.80.

[0085] In a preferred embodiment, m is from 0.20 to 0.90, particularly from 0.25 to 0.85, more particularly from 0.30 to 0.80, even more particularly from 0.35 to 0.75, and still more particularly from 0.40 to 0.75.

[0086] When the oligomer contains more than one separate type of polymerized high T g Monomer units, the polymerized high T in the oligomer gThe weight fraction m of the monomer unit is equal to the sum of the individual weight fractions of all the different types of polymerized high T g monomer units in the oligomer and should be understood as such.

[0087] [low T g monomer unit] In an embodiment, the oligomer contains polymerized low T g monomer units. The low T g monomer units are distinguished from the high T g monomer units, chromophore monomer units, and additional monomer units. Thus, the low T g monomer units may not contain any of the following groups: - A chromophore moiety; - A functional group as defined below for the additional monomer units.

[0088] The polymerized low T g monomer units can be the same or a combination of multiple types of different monomer units such as two different monomer units, three different monomer units, four different monomer units, or more than four different monomer units. In an embodiment, the low T g monomer units can have a glass transition temperature (T g ) below 25 °C or a Fox equation average T g below 25 °C. When defined herein, the reference to T g of the monomer here refers to the T g of the homopolymer formed from that monomer. In an embodiment where the oligomer contains two or more different low T g monomer units, T g refers to the Fox equation average T g of the low T g monomer units as previously defined herein. In an embodiment, the low T g monomer units have a Fox equation average T g below 25 °C, for example below 20 °C, 15 °C, 10 °C, 5 °C, 0 °C, -5 °C, -10 °C, -15 °C, -20 °C, or -30 °C. In an embodiment, the low T gThe monomer unit has a Fox formula average T from -150°C to 24°C, for example preferably from -80°C to 0°C, most preferably from -60°C to -10°C. g It has.

[0089] Low T g The monomer unit consists of one or more (meth)acrylate monomers, preferably one or more monofunctional (meth)acrylate monomers.

[0090] In an embodiment, the low T g The monomer unit can 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 monomer and n-butyl acrylate monomer. Examples of methacrylate monomers include butyl methacrylate monomer and pentyl methacrylate monomer.

[0091] In an embodiment, the low T g Each of the monomer units (before being polymerized into the backbone of the oligomer) independently has the formula (III): TIFF2025523911000005.tif46170 (wherein, - A 2 is (C2-C 30 ) hydrocarbyl or (C2-C 30 ) heterohydrocarbyl, preferably (C4-C 30 ) hydrocarbyl; and - Z 2 is -H or -CH3) can follow.

[0092] In an embodiment, A 2 is linear or branched (C2-C 30 ) alkyl, preferably linear or branched (C4-C 30 ) alkyl. In an embodiment, A 2is selected from n-butyl, isobutyl, hexyl, 2-ethylhexyl, isooctyl, isodecyl, tridecyl, lauryl, or a combination thereof.

[0093] A 2 When is isobutyl or cyclohexyl, Z 2 is H.

[0094] The above embodiments also apply to A of the oligomer of formula (I) 2 similarly.

[0095] Low T of the oligomer g Further examples of monomer units include, but are not limited to, 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, pentyl (meth)acrylate, benzyl acrylate, cyclohexyl acrylate, hexadecyl (meth)acrylate, 2-methylbutyl acrylate, 2-octyl acrylate, or a combination thereof.

[0096] Preferably, the low T g monomer unit of the oligomer is n-butyl acrylate.

[0097] The polymerized low T g weight fraction of the monomer unit in the oligomer varies depending on the desired properties of the oligomer, such as T g , molecular weight, and gel content after curing.

[0098] As described herein, n in formula (I) is the number of polymerized low T in the oligomer gIt is the weight fraction of the monomer unit. In an embodiment, n is 0.001 or more, for example, 0.02 or more, 0.05 or more, 0.10 or more, 0.15 or more, 0.20 or more, 0.25 or more, 0.30 or more, 0.35 or more, 0.40 or more, 0.45 or more, 0.50 or more, 0.55 or more, 0.60 or more, 0.65 or more, 0.70 or more, 0.75 or more, or 0.80 or more.In an embodiment, n is from 0.001 to 0.989, from 0.001 to 0.90, from 0.001 to 0.80, from 0.001 to 0.70, from 0.001 to 0.60, from 0.001 to 0.50, from 0.001 to 0.40, from 0.001 to 0.30, from 0.001 to 0.20, from 0.001 to 0.10, from 0.001 to 0.05, from 0.01 to 0.989, from 0.01 to 0.90, from 0.01 to 0.80, from 0.01 to 0.70, from 0.01 to 0.60, from 0.01 to 0.50, from 0.01 to 0.40, from 0.01 to 0.30, from 0.01 to 0.20, from 0.01 to 0.10, from 0.01 to 0.05, from 0.05 to 0.989, from 0.05 to 0.90, from 0.05 to 0.80, from 0.05 to 0.70, from 0.05 to 0.60, from 0.05 to 0.50, from 0.05 to 0.40, from 0.05 to 0.30, from 0.05 to 0.20, from 0.05 to 0.10, from 0.10 to 0.989, from 0.10 to 0.90, from 0.10 to 0.80, from 0.10 to 0.70, from 0.10 to 0.60, from 0.10 to 0.50, from 0.10 to 0.40, from 0.10 to 0.30, from 0.10 to 0.20, from 0.20 to 0.989, from 0.20 to 0.90, from 0.20 to 0.80, from 0.20 to 0.70, from 0.20 to 0.60, from 0.20 to 0.50, from 0.20 to 0.40, from 0.20 to 0.30, from 0.30 to 0.989, from 0.30 to 0.90, from 0.30 to 0.80, from 0.30 to 0.70, from 0.30 to 0.60, from 0.30 to 0.50, from 0.30 to 0.40, from 0.40 to 0.989, from 0.40 to 0.90, from 0.40 to 0.80, from 0.40 to 0.70, from 0.40 to 0.60, from 0.40 to 0.50, from 0.50 to 0.989, from 0.50 to 0.90, from 0.50 to 0.80, from 0.50 to 0.70, from 0.50 to 0.60, from 0.60 to 0.989, from 0.60 to 0.90, from 0.60 to 0.80, from 0.60 to 0.70, from 0.70 to 0.989, from 0.70 to 0.90, from 0.70 to 0.80, from 0.80 to 0.989, from 0.80 to 0.90, or from 0.90 to 0.989.

[0099] In a preferred embodiment, n is from 0.10 to 0.80, particularly from 0.15 to 0.75, more particularly from 0.20 to 0.70, even more particularly from 0.25 to 0.65, and still more particularly from 0.25 to 0.60.

[0100] When the oligomer contains more than one separate type of polymerized low T g monomer units, the weight fraction n of the polymerized low T g monomer units in the oligomer is understood to be equal to the sum of the individual weight fractions of all separate types of polymerized low T g monomer units in the oligomer.

[0101] low T g monomer units and high T g The weight ratio of monomer units can be adjusted according to the desired properties of the oligomer, such as T g and the gel content after curing. In an embodiment, the weight ratio of low T g monomer units to high T g monomer units in the oligomer can be from 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 partial ranges formed from any of these endpoints.

[0102] [Chromophore monomer unit] At least one polymerized high T g monomer units and at least one polymerized low T g In addition to monomer units, the oligomer further comprises at least one polymerized chromophore monomer unit. The chromophore monomer unit is distinct from the high T g monomer units, low T g monomer units and additional monomer units.

[0103] Overlapping chromophore monomer units can act as photoinitiators and induce the curing of oligomers by radiation. A photoinitiator is generally a moiety that generates reactive species (ions or radicals) upon absorption of light and initiates one or several chemical reactions or transformations.

[0104] Photoinitiators can include free radical photoinitiators. The photoinitiator can be selected to be susceptible to activation by photons of wavelengths associated with actinic radiation (e.g., ultraviolet light, visible light) intended to cure the curable composition. Since Norrish type II (i.e., non-cleaving) photoinitiator moieties do not decompose upon excitation, the possibility of small molecules leaching out from the matrix composition is reduced. For reference, see, for example, A. Gilbert, J. Baggott: “Essentials of Molecular Photochemistry”, Blackwell, London, 1991. The excited non-cleaving photoinitiator does not decompose into radicals upon excitation, but abstracts a hydrogen atom from an organic molecule or, more efficiently, an electron from an electron donor (such as an amine or a thiol). By electron transfer, a radical anion is generated on the photoinitiator and a radical cation is generated on the electron donor. Subsequently, proton transfer from the radical cation to the radical anion generates two uncharged radicals; of these, the radical on the electron donor is sufficiently reactive to abstract a hydrogen atom from most substrates.

[0105] The photoinitiator can be a chromophore. Benzophenone and related ketones, such as thioxanthone, xanthone, anthraquinone, fluorenone, dibenzosuberone, benzyl, and phenylketocoumarin are examples of Norrish type II chromophores. Most amines having a C-H bond at the α-position of the nitrogen atom and many thiols are electron donors. Some titanocenes are Norrish type II chromophores within the scope of the chromophore monomers here.

[0106] In an embodiment, the polymerized chromophore monomer unit is a (meth)acrylate ester monomer having a pendant Norrish type II chromophore. That is, the Norrish type II chromophore is not located at the end of the monomer.

[0107] Any of the above Norrish type II chromophores can be a pendant part of the chromophore monomer unit of the oligomer. In an embodiment, the Norrish type II chromophore is selected from benzophenone, thioxanthone, or titanocene. In a specific example, the Norrish type II chromophore is benzophenone.

[0108] In an embodiment, each of the chromophore monomer units (before being polymerized into the backbone of the oligomer) independently has the formula (IV): TIFF2025523911000006.tif42170(In the above formula, A 3 is a monovalent residue containing a Norrish type II chromophore, and in particular A 3 is X or -L-X; L is a (C1-C 10 ) heterohydrocarbylene linker; X is a monovalent residue of a Norrish type II chromophore, preferably a monovalent residue of benzophenone; Z 3 is -H or -CH3) can follow.

[0109] In an embodiment, A in formula (IV) 3 is X or -L-X, where L is a (C1-C 10 ) heterohydrocarbylene linker and X is a monovalent residue of a Norrish type II chromophore. As used in this disclosure, the term "residue" is meant to mean the product of a reactant such as a portion remaining from a monomer in a polymer such as a part 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 can be a monovalent residue of any one of the above Norrish type II chromophores. In an embodiment, A 3is a monovalent residue of benzophenone. In an embodiment, A 3 is of formula (IVa): has TIFF2025523911000007.tif48170.

[0110] In an embodiment, A of formula (IV) 3 is a residue containing a monovalent radical containing a moiety selected from thioxanthone, anthraquinone, or camphorquinone. According to one or more embodiments, A 3 is a residue containing a monovalent radical containing thioxanthone.

[0111] In particular, A of formula (IV) 3 is of the following formula (IVb) or (IVc): TIFF2025523911000008.tif100170 (wherein, in formula (IVb) and formula (IVc), L 1 is alkylene; L 2 is a divalent linker containing at least 2 carbon atoms; each R 1 and R 2 is independently selected from -H, halogen, alkyl, cycloalkyl, heterocycloalkyl, alkoxy, aryloxy, thioalkyl, thioaryl, alkenyl, alkynyl, aryl, aralkyl, alkaryl, heteroaryl, -C(=O)R a , -NR b R c alkylamino, alkylthiol, haloalkyl, -NO2, -CN, -C(=O)OR d -C(=O)NR b R c ; R a is selected from optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted heterocycloalkyl and optionally substituted aryl; and R b R c and R d are independently selected from -H, alkyl and aryl) may have.

[0112] In particular, in formula (IVb) and formula (IVc), R 1 and R 2 are independently -H, halogen, alkyl or alkoxy. More specifically, R 1 and R 2 are independently H or alkyl. Even more specifically, R 1 and R 2 are independently H or methyl. Even more specifically still, R 1 and R 2 are all -H.

[0113] In formula (IVb) and formula (IVc), L 1 is alkylene. In particular, each L 1 can independently be a straight-chain or branched alkylene having 1 to 6, 1 to 4, or 1 to 2 carbon atoms. More specifically, L 1 is -CH2- or -CH(CH3)-. Even more specifically, L 1 is -CH2-.

[0114] In formula (IVb) and formula (IVc), L 2 is a divalent linker containing at least 2 carbon atoms. L 2 can be an aromatic, aliphatic or alicyclic hydrocarbon linker, a polyether linker, a polyester linker, a polycarbonate linker, a polycaprolactone linker, a polyurethane linker, a polyorganosiloxane linker, a polybutadiene linker, and combinations thereof. In particular, L 2 can be selected from an aromatic, aliphatic or alicyclic hydrocarbon linker, a polyether linker, a polyester linker, and combinations thereof.

[0115] In formula (IVb) and formula (IVc), L 2can be -CH2-CH(OH)-CH2- or a residue of a diol. As used herein, the term "residue of a diol" means 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-butylene glycol, 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, norbornenedimethanol, norbornanedimethanol, tricyclodecanediol, tricyclodecanedimethanol, 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), dianhydrohexitol (i.e., isosorbide, isomannide, isoidide), polybutadiene polyol, polyester polyol, polyether polyol, polyorganosiloxane polyol, polycarbonate polyol, 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 aforementioned polyols are included.

[0116] In Formulas (IVb) and (IVc), L 2 can be -CH 2- CH(OH)-CH2- or a divalent linker selected from one of Formulas (A)-(E): TIFF2025523911000009.tif62170 (In the above formula, R 22, R ’22 , R 25 , R ’25 , R 29 , R ’29 , R 30 and R ’30 are independently H or alkyl; 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; a is from 2 to 20; b, d, and d' are independently from 2 to 4; c is from 1 to 20; e and e' are independently from 0 to 20, provided that at least one of q and q' is not 0; f is from 2 to 20; g is from 3 to 12; h is from 1 to 20; i is from 2 to 8; j is from 2 to 20; k is from 2 to 30; l is from 1 to 20)

[0117] In particular, in formula (IVb) and formula (IVc), L 2 is -CH 2-It is CH(OH)-CH2-, or an alkylene 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; an alkoxylation (especially ethoxylation and / or propoxylation) derivative of the aforementioned alkylene; an esterification derivative of the aforementioned alkylene (especially by ring-opening polymerization of lactones such as ε-caprolactone); a divalent linker selected from residues of 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) and other OH group-free di-, tri-, tetra- or polyoxyalkenes.

[0118] In one embodiment, A of formula (IV) 3 is of the following formula (IVd) or (IVe): TIFF2025523911000010.tif79170 (wherein h is from 1 to 20) and follows one of them.

[0119] Other suitable linker groups can also be used, including those that do not contain a carbonyl group.

[0120] A of formula (IV) 3 All of the embodiments described above for A 3 also apply equally to A of the oligomer of formula (I).

[0121] The weight fraction of the polymerized chromophore monomer units in the oligomer can be varied based on factors known in the art, such as the desired curing time among other factors. As described herein, p in formula (I) is the weight fraction of the polymerized chromophore monomers. In embodiments, p is 0.001 or greater, such as 0.005 or greater, or 0.01 or greater. In embodiments, p is from 0.001 to 0.40, from 0.001 to 0.30, from 0.001 to 0.20, from 0.001 to 0.10, from 0.001 to 0.05, from 0.001 to 0.03, from 0.005 to 0.40, from 0.005 to 0.30, from 0.005 to 0.20, from 0.005 to 0.10, from 0.005 to 0.05, from 0.005 to 0.03, or from 0.005 to 0.02.

[0122] In preferred embodiments, p is from 0.005 to 0.30, particularly from 0.005 to 0.20, more particularly from 0.005 to 0.15; even more particularly from 0.005 to 0.10, still more particularly from 0.01 to 0.10.

[0123] It should be understood that when the oligomer contains more than one distinct type of polymerized chromophore monomer unit, the weight fraction p of the polymerized chromophore monomer units in the oligomer is equal to the sum of the individual weight fractions of all the distinct types of polymerized chromophore monomer units. Further, any monomer containing a pendant chromophore, even if it can be characterized as a high T g monomer or a low T g monomer based only on T g is considered neither a high T g monomer nor a low T g monomer with respect to the calculation of the weight fractions m and n in formula (I).

[0124] [Additional monomer unit] The oligomers disclosed herein optionally contain at least one polymerized additional monomer unit. The additional monomer units are different from high T g monomer units, low T g monomer units, and chromophore monomer units.

[0125] The additional monomer unit may contain a functional group selected from polymerizable groups other than (meth)acrylate groups (i.e., vinyl group, allyl group, conjugated diene group, alkenyl group), acidic groups (i.e., carboxylic acid group, phosphonic acid (-P(=O)(OH)2) group, phosphonate (-P(=O)(OR)2) group, sulfonic acid (-S(=O)2OH) group, sulfonate (-S(=O)2OR) group, phosphoric acid (-O-P(=O)(OR)2) group (in this formula, each R is independently a counter ion, hydrogen atom, or optionally substituted hydrocarbyl)), nitrogen-containing groups (i.e., amino group, cyano group, or a heterocyclic ring having one or more nitrogen ring atoms), 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 (not included in the (meth)acrylate group), and combinations thereof.

[0126] Preferably, the additional monomer unit contains a functional group selected from acidic groups and nitrogen-containing groups. More preferably, the additional monomer unit contains a functional group selected from a carboxylic acid group, a tertiary amine group, or a heterocyclic ring having one or more nitrogen ring atoms.

[0127] It should be emphasized that (meth)acrylic acid corresponds to the additional monomer. Therefore, the amount by weight of the polymerized (meth)acrylic acid unit, if present, should be considered in the total amount of the polymerized additional monomer units, and the polymerized high T g The total amount of monomer units should not be considered.

[0128] The additional monomer unit includes high T g Monomer units, low T gIt may include monomer units and monomer units copolymerizable with chromophore monomer units. In embodiments, the additional monomer units may include other unsaturated monomer units (other than (meth)acrylic monomer units) such as vinylamides, vinyl ethers, vinyl esters, vinyl oxazolidinones, (meth)acrylamides, and combinations thereof. In embodiments, the additional monomer units may include other monomer units polymerized within the oligomer such as styrene derivatives and maleimides.

[0129] In embodiments, the additional monomer units may include epoxy, ether, ester, acid, or ketone functional groups that are not polymerized within the oligomer. For example, the additional monomer units may include caprolactone-extended acrylate (SR495B, Sartomer), cyclic trimethylolpropane formal acrylate (SR531, Sartomer), propoxylated tetrahydrofurfuryl acrylate (SR611, Sartomer), beta-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.

[0130] In embodiments, the additional monomer units may be, or may include, monomers that act synergistically with the polymerized chromophore monomer units and / or reduce oxygen inhibition. Oxygen inhibition may limit surface curing and thus the performance of the resulting cured product.

[0131] Common synergistic functional groups that function as synergists for type II photoinitiators can include acidic groups, heterocycles containing one or more nitrogen ring atoms, tertiary amine functional groups, alkyleneoxy functional groups (i.e., one or more oxyalkylene units), mercaptan groups, or other sources of easily abstractable hydrogen. Typical additional monomer units containing synergistic functional groups include monomers such as (meth)acrylic acid, dimethylaminoethyl acrylate (DMAEA), dimethylaminoethyl methacrylate (DMAEMA), diethylaminoethyl acrylate (DEAEA), diethylaminoethyl methacrylate (DEAEMA), N-vinylpyrrolidone (NVP), N-vinylcaprolactam (VCAP), acryloxymorpholine (ACMO), dimethylacrylamide (DMAC), poly(ethylene oxide) mono(meth)acrylate, hydroxyethyl ethyleneurea (meth)acrylate (HEEU(M)A), reaction products of cyclic anhydrides and hydroxy-functional (meth)acrylates, and combinations thereof.

[0132] In embodiments, the additional monomer unit can include an amine synergist. Some examples of amine synergists include tertiary amines. When an amine synergist-containing monomer is included in an oligomer in combination with the photoactive chromophore monomer units of the polymerized chromophore, the tertiary amine provides an active hydrogen donating site to the excited triplet state of the chromophore, resulting in the generation of a reactive alkylamino radical that can then initiate polymerization. Tertiary amines can also convert non-reactive peroxy species formed by the reaction of oxygen and free radicals into reactive alkylamino radicals, thus reducing the effect of oxygen on curing.

[0133] Examples of amine synergists that can be components of the overlapping additional monomers include low molecular weight tertiary amines such as triethanolamine and N-methyldiethanolamine (i.e., tertiary amines having a molecular weight of less than 200 g / mol). Other types of amine synergists are aminobenzoates, polymerizable aminobenzoates, polymeric aminobenzoates, and mixtures thereof. Examples of aminobenzoates include ethyl 4-(dimethylamino)benzoate (EDB), pentyl 4-(dimethylamino)benzoate, 2-ethylhexyl 4-(dimethylamino)benzoate, and 2-butoxyethyl 4-(dimethylamino)benzoate (BEDB).

[0134] In an embodiment, the additional monomer unit is a (meth)acrylate monomer having a pendant amine functional group.

[0135] Any of the above synergists or amine-based synergists can be pendant residues in the additional monomer units of the oligomers herein.

[0136] In an embodiment, each of the additional monomer units (before polymerization into the oligomer backbone) is independently of formula (V): TIFF2025523911000011.tif43170(wherein - A 4 is a (C1-C 30 ) hydrocarbyl or (C1-C 30 ) heterohydrocarbyl, preferably a (C1-C 30 ) heterohydrocarbyl having a functional group selected from acidic groups, nitrogen-containing groups, hydroxyl groups, epoxy groups, carbonyl groups, acetoacetoxy groups, acetoacetamide groups, 1,1-dimethyl-3-oxobutyl (diacetone) groups, thiol groups, silane groups, ether linkages, ester linkages, and combinations thereof - Z 4 is -H or -CH3) and can follow.

[0137] A 4may include a monovalent residue of any one of the synergists discussed above. In an embodiment, Z 4 is -H or -CH3, and A 4 is -C(=O)-O-R 4 where R 4 is selected from H, dimethylaminomethyl, dimethylaminoethyl, morpholino, dimethylamino, -CH2-CH2-imidazolidinone, or combinations thereof. In an embodiment, Z 4 is -H, and A 4 includes a heterocycle having one or more nitrogen ring atoms. For example, A 4 may correspond to one of the following formulas: TIFF2025523911000012.tif28170

[0138] The above embodiments are equally applicable to A 4 and Z 4 in the oligomers of formula (I). The weight fraction of the polymerized additional monomer units in the oligomer can vary depending on factors well known in the art, such as the desired curing time and the desired degree of cure. As described herein, q in formula (I) is the weight fraction of the polymerized additional monomer. In an embodiment, q is 0. In other embodiments, q is 0.001 or more, for example 0.005 or more, or 0.01 or more. In an embodiment, q is from 0.001 to 0.20, from 0.001 to 0.10, from 0.001 to 0.05, from 0.001 to 0.03, from 0.005 to 0.20, from 0.005 to 0.10, from 0.005 to 0.05, from 0.005 to 0.03, or from 0.005 to 0.02.

[0139] Preferably, q is from 0 to 0.10.

[0140] [Properties of the Oligomer] The oligomers described herein have different monomer units (i.e., high T g monomer units, low T gIt can be formed by the polymerization of monomer units, chromophore monomer units, and optionally at least one additional monomer unit). General methods known in the art include, but are not limited to, solution polymerization. Thus, the oligomer can be obtained by polymerizing different monomer units dissolved in a non-reactive solvent in the presence of an initiator. 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 an oxygen-oxygen single bond), particularly inorganic persulfate compounds such as ammonium persulfate, potassium persulfate, and sodium persulfate; hydrogen peroxide; organic peroxides such as cumene hydroperoxide, t-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 a ferrous compound promotes the decomposition of the peroxide; and azo initiators (i.e., compounds containing a nitrogen-nitrogen double bond), such as other free radical generating substances such as 2,2'-azobisisobutyronitrile, 4,4'-azobis(4-cyanovaleric acid) or 2,2'-azobis(2-methylbutyronitrile), and combinations thereof. The initiator can be added in an amount such that the total monomer:initiator weight ratio is from 100:1 to 1000:1. In solution polymerization, typically a mixture of oligomers dissolved in a non-reactive solvent is obtained. The non-reactive solvent can be removed by heating. A reactive diluent can be added before removing the non-reactive solvent to form a curable composition as detailed below. The mixture at the end of solution polymerization (i.e., before the introduction of the reactive diluent) can have a solids content by weight of from 25% to 70%, preferably from 30% to 50%, based on the total weight of the mixture. The mixture can have a residual monomer 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.Using experimental conditions well known to those skilled in the art, the experimental parameters of solution polymerization (i.e., solids content, reaction temperature, reaction time, and total monomer:initiator ratio) can be adjusted to produce relatively low molecular weight oligomers.

[0141] Preferably, the oligomers are not obtained by telomerization, i.e., in the presence of a telogen compound such as carbon tetrabromide (CBr4), bromotrichloromethane (CBrCl3), dibromodichloromethane (CBr2Cl2), mercaptan, hydrogen sulfide, etc. (i.e., a compound having at least one cleavable bond selected from C-H, S-H, P-H, Si-H or C-X where X = Cl, Br or I).

[0142] In an embodiment, the oligomer can have a weight average molecular weight of at least 10,000 grams per mole (g / mol). In an embodiment, the oligomer can have a weight average molecular weight from 10,000 g / mol to 600,000 g / mol. In an embodiment, the oligomer can have a weight average molecular weight of 10,000 g / mol or more, 25,000 g / mol or more, or even 50,000 g / mol or more. In an embodiment, the oligomer can have a weight average molecular weight of 600,000 g / mol or less, 500,000 g / mol or less, 400,000 g / mol or less, 300,000 g / mol or less, 200,000 g / mol or less, or even 100,000 g / mol or less. In an embodiment, the oligomer can have a weight average molecular weight from 10,000 g / mol to 600,000 g / mol, from 10,000 g / mol to 500,000 g / mol, from 10,000 g / mol to 400,000 g / mol, from 10,000 g / mol to 300,000 g / mol, from 10,000 g / mol to 200,000 g / mol, from 10,000 g / mol to 100,000 g / mol, from 25,000 g / mol to 600,000 g / mol, from 25,000 g / mol to 500,000 g / mol, from 25,000 g / mol to 400,000 g / mol, from 25,000 g / mol to 300,000 g / mol, from 25,000 g / mol to 200,000 g / mol, from 25,000 g / mol to 100,000 g / mol, from 50,000 g / mol to 600,000 g / mol, from 50,000 g / mol to 500,000 g / mol, from 50,000 g / mol to 400,000 g / mol, from 50,000 g / mol to 300,000 g / mol, from 50,000 g / mol to 200,000 g / mol, or even from 50,000 g / mol to 100,000 g / mol, or can have a weight average molecular weight of all partial ranges formed from any of these endpoints.

[0143] In a preferred embodiment, the oligomer can have a weight average molecular weight of from 10,000 g / mol to 100,000 g / mol, particularly from 10,000 g / mol to 90,000 g / mol, particularly from 11,000 g / mol to 80,000 g / mol, more particularly from 12,000 g / mol to 75,000 g / mol, even more particularly from 15,000 g / mol to 70,000 g / mol, and still more particularly from 15,000 g / mol to 65,000 g / mol.

[0144] The number average molecular weight and weight average molecular weight reported herein are quantified using size exclusion chromatography (SEC) with poly(methyl methacrylate) reference standards and tetrahydrofuran as the solvent, unless otherwise specified.

[0145] In an embodiment, the oligomer can have a T of 0 °C or higher, such as 5 °C or higher, 10 °C or higher, 15 °C or higher, 20 °C or higher, 25 °C or higher, 30 °C or higher, 35 °C or higher, 40 °C or higher, 45 °C or higher, or 50 °C or higher. g In an embodiment, the oligomer can have a T of from 0 °C to 100 °C, such as from 0 °C to 90 °C, from 0 °C to 80 °C, from 0 °C to 70 °C, from 0 °C to 60 °C, from 0 °C to 50 °C, from 10 °C to 100 °C, from 10 °C to 90 °C, from 10 °C to 80 °C, from 10 °C to 70 °C, from 10 °C to 60 °C, from 10 °C to 50 °C, from 20 °C to 100 °C, from 20 °C to 90 °C, from 20 °C to 80 °C, from 20 °C to 70 °C, from 20 °C to 60 °C, or from 20 °C to 50 °C. g In an embodiment, the oligomer can have a T of from 0 °C to 100 °C, such as from 0 °C to 90 °C, from 0 °C to 80 °C, from 0 °C to 70 °C, from 0 °C to 60 °C, from 0 °C to 50 °C, from 10 °C to 100 °C, from 10 °C to 90 °C, from 10 °C to 80 °C, from 10 °C to 70 °C, from 10 °C to 60 °C, from 10 °C to 50 °C, from 20 °C to 100 °C, from 20 °C to 90 °C, from 20 °C to 80 °C, from 20 °C to 70 °C, from 20 °C to 60 °C, or from 20 °C to 50 °C.

[0146] Preferably, the oligomer has a T of from 20 °C to 100 °C, more particularly from 30 °C to 100 °C. g In an embodiment, the oligomer has a T of from 20 °C to 100 °C, more particularly from 30 °C to 100 °C.

[0147] In an embodiment, the oligomer can have a gel content of at least 10% when measured by the method "Method A - Gel Content" disclosed herein. For example, the oligomer can 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 case, the gel content is measured based on the neat oligomer (i.e., without other compounds such as diluents).

[0148] In a preferred embodiment, the oligomer has the formula (V): TIFF2025523911000013.tif52170(wherein - each A 1a is independently selected from isobutyl, tert-butyl or cyclic (C1-C 30 ) hydrocarbyl; - each A 1b is independently selected from (C1-C 30 ) hydrocarbyl other than isobutyl, tert-butyl or cyclic (C1-C 30 ) hydrocarbyl; - each A 2 is independently (C2-C 30 ) hydrocarbyl or (C2-C 30 ) heterohydrocarbyl; - each A 3 is independently a monovalent residue containing a Norrish type II chromophore, preferably a monovalent residue containing benzophenone; - each A 4 is independently (C1-C 30 ) hydrocarbyl or (C1-C 30 ) heterohydrocarbyl, preferably a functional group selected from acidic groups, nitrogen-containing groups, 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, and combinations thereof - (C1-C 30 ) heterohydrocarbyl; - Z 1 、Z 2 、Z 3 、and Z 4 is independently -H or -CH3; - m1 is from 0.01 to 0.95, particularly from 0.20 to 0.90, more particularly from 0.25 to 0.85, even more particularly from 0.30 to 0.80, still more particularly from 0.35 to 0.75, and yet more particularly from 0.40 to 0.75; - m2 is from 0 to 0.94, particularly from 0 to 0.90, more particularly from 0 to 0.80, even more particularly from 0 to 0.70, still more particularly from 0 to 0.60, and yet more particularly from 0 to 0.50; - n is from 0.001 to 0.989, particularly from 0.10 to 0.80, more particularly from 0.15 to 0.75, even more particularly from 0.20 to 0.70, still more particularly from 0.25 to 0.65, and yet more particularly from 0.25 to 0.60; - p is from 0.001 to 0.40, particularly from 0.005 to 0.30, more particularly from 0.005 to 0.20, even more particularly from 0.005 to 0.15; still more particularly from 0.005 to 0.10, and yet more particularly from 0.01 to 0.10; - q is from 0 to 0.20, particularly from 0 to 0.10; and - m1 + m2 + n + p + q equals 1; - m1 + m2 is from 0.01 to 0.95, particularly from 0.20 to 0.90, more particularly from 0.25 to 0.85, even more particularly from 0.30 to 0.80, still more particularly from 0.35 to 0.75, and yet more particularly from 0.40 to 0.75) may have.

[0149] As a non - limiting example, the oligomer may have the formula (V): TIFF2025523911000014.tif115170(wherein m is from 0.2 to 0.8, n is from 0.1 to 0.8, and p is from 0.001 to 0.2).

[0150] In an embodiment, Z of formula (V) 1 Z 2 and Z 3 are each independently -H or -CH3. For example, in an embodiment, Z 1 is -CH3, and both Z 2 and Z 3 are -H. may have.

[0151] [Curable Composition] In an embodiment, a curable composition, preferably an ultraviolet curable composition, may include at least one of the oligomers described herein. In an embodiment, the ultraviolet curable composition may not include any additional photoinitiators other than the polymerized chromophore monomer units of the oligomer. That is, in an embodiment, the oligomer can be cured upon irradiation without an additional photoinitiator. In other embodiments, the curable composition may include one or more photoinitiators in addition to the polymerized chromophore monomer units of the oligomer. In a preferred embodiment, the curable composition may substantially not include photoinitiators other than the oligomers of the present invention. In particular, the curable composition may include less than 0.1% by weight, particularly less than 0.05% by weight, more particularly less than 0.001% by weight, and even more particularly 0% of photoinitiators other than the oligomers of the present invention.

[0152] Preferably, the curable composition does not include a (meth)acrylic copolymer having a T g below 0°C. More preferably, the curable composition does not include a (meth)acrylic copolymer other than the oligomers of the present invention.

[0153] In an embodiment, the curable composition may include one or more (meth)acrylate monomers or oligomers, a diluent, a (meth)acrylate oligomer, a filler, a photoinitiator, a slip agent, a thickener, a slip agent, a hindered amine light stabilizer, an ultraviolet absorbing monomer, or other auxiliary additives. In an embodiment, at least one (meth)acrylate oligomer is included in the curable composition, selected from at least one of urethane acrylate and urethane methacrylate, and at least one (meth)acrylate monomer is included, selected from at least one of 2-hydroxyethyl methacrylate and isobornyl methacrylate.

[0154] In a preferred embodiment, the curable composition includes an oligomer according to the present invention and a reactive diluent. The reactive diluent can be used together with a non-reactive solvent used in the preparation of the oligomer or can be completely replaced.

[0155] In an embodiment, the reactive diluent may have a viscosity of 3000 cP or less, 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 or less when measured with a Brookfield DV-III viscometer using spindle SC-27 at 25°C. In an embodiment, the reactive diluent may have a viscosity of 5 cP or more, 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 when measured with a Brookfield DV-III viscometer using spindle SC-27 at 25°C.In an embodiment, the reactive diluent may have a viscosity of from 25 cP to 3000 cP, from 25 cP to 2750 cP, from 25 cP to 2500 cP, from 25 cP to 2250 cP, from 25 cP to 2000 cP, from 25 cP to 1750 cP, from 25 cP to 1500 cP, from 25 cP to 1250 cP, from 25 cP to 3000 cP, from 25 cP to 2750 cP, from 25 cP to 2500 cP, from 25 cP to 2250 cP, from 25 cP to 2000 cP, from 25 cP to 1750 cP, from 25 cP to 1500 cP, from 25 cP to 1250 cP, from 50 cP to 3000 cP, from 50 cP to 2750 cP, from 50 cP to 2500 cP, from 50 cP to 2250 cP, from 50 cP to 2000 cP, from 50 cP to 1750 cP, from 50 cP to 1500 cP, from 50 cP to 1250 cP, from 100 cP to 3000 cP, from 100 cP to 2750 cP, from 100 cP to 2500 cP, from 100 cP to 2250 cP, from 100 cP to 2000 cP, from 100 cP to 1750 cP, from 100 cP to 1500 cP, from 100 cP to 1250 cP, from 250 cP to 3000 cP, from 250 cP to 2750 cP, from 250 cP to 2500 cP, from 250 cP to 2250 cP, from 250 cP to 2000 cP, from 250 cP to 1750 cP, from 250 cP to 1500 cP, from 250 cP to 1250 cP, from 500 cP to 3000 cP, from 500 cP to 2750 cP, from 500 cP to 2500 cP, from 500 cP to 2250 cP, from 500 cP to 2000 cP, from 500 cP to 1750 cP, from 500 cP to 1500 cP, from 500 cP to 1250 cP, from 750 cP to 3000 cP, from 750 cP to 2750 cP, from 750 cP to 2500 cP, from 750 cP to 2250 cP, from 750 cP to 2000 cP, from 750 cP to 1750 cP, from 750 cP to 1500 cP, from 750 cP to 1250 cP, from 1000 cP to 3000 cP, from 1000 cP to 2750 cP, from 1000 cP to 2500 cP, from 1000 cP to 2250 cP, from 1000 cP to 2000 cP, from 1000 cP to 1750 cP, from 1000 cP to 1500 cP, or further from 1000 cP to 1250 cP, or any and all partial ranges formed from any of these endpoints.

[0156] 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 viscosity-related embodiments apply to the mixture of radically polymerizable diluents.

[0157] As used herein, a radically polymerizable diluent is a compound having at least one polymerizable carbon-carbon double bond and preferably having an appropriate viscosity as defined above. The polymerizable carbon-carbon double bond can participate in free radical polymerization in which at least one of the carbon atoms of the double bond covalently bonds with another atom, particularly a carbon atom, within a second molecule. In particular, the reactive diluent may include at least one radically polymerizable diluent selected from (meth)acrylates, vinyl ethers, vinyl amides, vinyl oxazolidinones, and combinations thereof. These diluents can be monofunctional (i.e., having a single polymerizable carbon-carbon double bond) or polyfunctional (i.e., having at least two polymerizable carbon-carbon double bonds). These diluents can be selected to provide the targeted final properties of the cured formulation as long as they result in an appropriate reduction in the viscosity of the oligomer while creating appropriate properties when the curable composition cures.

[0158] Reactive diluents can include monofunctional (meth)acrylates (i.e., monomers having a single (meth)acrylate group). Examples of suitable monofunctional (meth)acrylates include mono(meth)acrylate esters of aliphatic alcohols (where the aliphatic alcohol can be straight-chain, branched, or cycloaliphatic and can be a monoalcohol, dialcohol, or polyalcohol, provided that only one hydroxyl group is esterified with (meth)acrylic acid); mono(meth)acrylate esters of aromatic alcohols (such as phenols including alkylated phenols); mono(meth)acrylate esters of alkylaryl alcohols (such as benzyl alcohol); mono(meth)acrylate esters of oligomers and polymeric glycols (such as diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol, and polypropylene glycol); mono(meth)acrylate esters of monoalkyl ethers of glycols and oligoglycols; mono(meth)acrylate esters of alkoxylated (e.g., ethoxylated and / or propoxylated) aliphatic alcohols (where the aliphatic alcohol can be straight-chain, branched, or cycloaliphatic and can be a monoalcohol, dialcohol, or polyalcohol, provided that only one hydroxyl group of the alkoxylated aliphatic alcohol is esterified with (meth)acrylic acid); mono(meth)acrylate esters of alkoxylated (e.g., ethoxylated and / or propoxylated) aromatic alcohols (such as alkoxylated phenols); caprolactone mono(meth)acrylate, and the like are included.The following compounds are specific examples of mono(meth)acrylate-functionalized 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-ethoxyethoxy)ethyl (meth)acrylate; 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; tricyclodecanemethanol (meth)acrylate; tert-butylcyclohexanol (meth)acrylate; 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; methoxypolyethylene glycol (meth)acrylate; hydroxyl ethyl-butyl urethane (meth)acrylate; 3-(2-hydroxyalkyl)oxazolidinone (meth)acrylate; and combinations thereof.

[0159] The reactive diluent may include a monofunctional (meth)acrylate having one or more of the following groups: a ring or ring system (i.e., one or more rings selected from an aromatic ring and / or a (hetero)alicyclic ring, which may be condensed and / or crosslinked), a C7-C20 hydrocarbon chain (i.e., a straight or branched chain having only carbon and hydrogen atoms, and 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 ester units derived from the ring opening of a lactone (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 their alkoxylated (i.e., ethoxylated and / or propoxylated) derivatives, and combinations thereof.

[0160] The reactive diluent has a T higher than 25 °C, preferably higher than 30 °C, more preferably higher than 35 °C, even more preferably higher than 40 °C, still more preferably higher than 45 °C, and yet more preferably higher than 50 °C gIt may contain a monofunctional (meth)acrylate monomer having. 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, 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 (C6-C 12 ) cycloalkyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentanyl (meth)acrylate, tricyclodecanemethanol mono(meth)acrylate, 2-phenoxyethyl methacrylate, or a combination thereof.

[0161] Reactive diluents are polyfunctional (meth)acrylates (i.e., monomers having 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; 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-decanediol 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; 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 their alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives; and combinations thereof may be included.;

[0162] The reactive diluent may include vinyl ethers such as dodecyl vinyl ether, hydroxybutyl vinyl ether, cyclohexanedimethanol divinyl ether, and DVE-3 (triethylene glycol divinyl ether) and combinations thereof.

[0163] The reactive diluent may include vinyl amides such as N-vinyl pyrrolidone (NVP), N-vinyl caprolactam (V-CAP) and combinations thereof.

[0164] The reactive diluent may include vinyl oxazolidinones such as vinyl methyl oxazolidinone (VMOX).

[0165] In a preferred embodiment, the reactive diluent preferably includes a monofunctional (meth)acrylate, a polyfunctional (meth)acrylate, or a mixture of a monofunctional (meth)acrylate and a polyfunctional (meth)acrylate.

[0166] The amount of the reactive diluent in the curable composition varies according to the desired viscosity. In an embodiment, the curable composition may contain 20% to 80% by weight of the reactive diluent based on the weight of the curable composition. In an embodiment, the curable composition may contain 20% or more, 25% or more, 30% or more, 35% or more, or 40% or more by weight of the reactive diluent based on the weight of the curable composition. In an embodiment, the curable composition may contain 80% or less, 75% or less, 70% or less, 65% or less, or even 60% or less by weight of the reactive diluent based on the weight of the curable composition. In an embodiment, 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 40% to 60%, or any and all partial ranges formed from any of these endpoints, based on the total weight of the curable composition.

[0167] In a preferred embodiment, the curable composition may contain at least 5%, at least 10%, at least 15%, at least 20%, at least 30%, at least 40%, or at least 50% by weight of the monofunctional (meth)acrylate monomer as defined above, based on the total weight of the curable composition. Alternatively, the curable composition may contain less than 5%, less than 4%, less than 3%, less than 2%, less than 1%, or even 0% by weight of the monofunctional (meth)acrylate monomer as defined above, based on the total weight of the curable composition.

[0168] In a preferred embodiment, the curable composition may contain at least 5%, at least 10%, at least 15%, at least 20%, at least 30%, at least 40%, or at least 50% by weight of the polyfunctional (meth)acrylate monomer as defined above, based on the total weight of the curable composition. Alternatively, the curable composition may contain less than 5%, less than 4%, less than 3%, less than 2%, less than 1%, or even 0% by weight of the polyfunctional (meth)acrylate monomer as defined above, based on the total weight of the curable composition.

[0169] In an embodiment, the weight ratio of the oligomer to the reactive diluent in the curable composition can be from 4:1 to 1:4, such as from 3:1 to 1:4, from 2:1 to 1:4, from 1:1 to 1:4, from 3:1 to 1:3, from 2:1 to 1:3, from 1:1 to 1:3, from 3:1 to 1:2, from 2:1 to 1:2, from 1:1 to 1:2, from 3:1 to 1:1, or even from 2:1 to 1:1, or any and all partial ranges formed from any of these endpoints.

[0170] In a preferred embodiment, the curable composition contains the oligomer according to the present invention and a (meth)acrylate-functionalized oligomer.

[0171] In order to enhance the properties of the cured polymer prepared by curing the curable composition of the present invention, especially flexibility, strength and / or modulus of elasticity, a (meth)acrylate-functionalized oligomer can be selected.

[0172] The (meth)acrylate-functionalized oligomer can have 1 to 18 (meth)acrylate groups, especially 2 to 6 (meth)acrylate groups, more specifically 2 to 6 acrylate groups.

[0173] The (meth)acrylate-functionalized oligomer can have a number average molecular weight of 600 g / mol or more, especially from 800 to 15000 g / mol, more specifically from 1000 to 5000 g / mol.

[0174] In particular, the curable composition may include a (meth)acrylate-functionalized oligomer selected from the group consisting of epoxy (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, urethane (meth)acrylate, (meth)acrylated poly(meth)acrylate, and mixtures thereof.

[0175] 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-unsaturated and / or poly-unsaturated compounds) and (meth)acrylating agents (such as (meth)acrylic acid, (meth)acrylic anhydride, (meth)acryloyl chloride, or combinations thereof). The epoxides are epoxides EPOX selected from 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, di(3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylenebis(3,4-epoxycyclohexanecarboxylate), ethylene glycol diglycidyl ether, 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, neopentyl glycol diglycidyl ether, 2,2 - diethyl - 1,3 - propanediol diglycidyl ether, 3 - methyl - 1,5 - pentanediol diglycidyl ether, 3,3 - dimethyl - 1,5 - pentanediol diglycidyl ether, 2,4 - diethyl - 1,5 - pentanediol diglycidyl ether, 3,3 - butylethyl - 1,5 - pentanediol diglycidyl ether, di -, tri - or tetra(ethylene glycol) diglycidyl 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 cyclohexanedicarboxylate, cyclohexane diglycidyl ether, cyclohexane - 1,Polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as 4-dimethylol diglycidyl ether, tricyclodecane dimethanol diglycidyl ether, isosorbide diglycidyl ether, pyrocatechol diglycidyl ether, resorcinol diglycidyl ether, cardol diglycidyl ether, phloroglucinol triglycidyl ether, pyrogallol triglycidyl ether, tris(hydroxyphenyl)methane triglycidyl ether, tris(hydroxyphenyl)ethane triglycidyl ether, diglycidyl phthalate, diglycidyl terephthalate, diglycidyl isophthalate, ethylene glycol, propylene glycol, glycerol, etc., diglycidyl esters of aliphatic long-chain (C6-C22) dibasic acids, monoglycidyl ethers of aliphatic higher alcohols, monoglycidyl ethers of phenol, cresol, butylphenol, or polyether alcohols obtained by adding alkylene oxides to these compounds, glycidyl esters of higher fatty acids, epoxidized vegetable oils (epoxidized soybean oil, epoxidized linseed oil, etc.), epoxybutyl stearate, epoxyoctyl stearate, epoxidized polybutadiene, triglycidyl isocyanurate, etc. may be used.,

[0176] Non-limiting examples of polyester (meth)acrylates are reaction products of hydroxyl-terminated polyester polyols with (meth)acrylation agents such as (meth)acrylic acid, (meth)acrylic anhydride, (meth)acryloyl chloride, or combinations thereof. The reaction process may be carried out such that a significant concentration of residual hydroxyl groups remains in the polyester (meth)acrylate, or such that all or substantially all of the hydroxyl groups of the polyester polyol are (meth)acrylated. The polyester polyol can be prepared by a polycondensation reaction of a polyhydroxyl-functional component (especially a diol) and a polycarboxylic acid-functional compound (especially a dicarboxylic acid or anhydride). To prepare the polyester (meth)acrylate, the hydroxyl groups of the polyester polyol are then partially or completely esterified by reacting with a (meth)acrylation agent. The polyester (meth)acrylate can also be synthesized by reacting a hydroxyl-containing (meth)acrylate such as a hydroxyalkyl (meth)acrylate (e.g., hydroxyethyl acrylate) with a polycarboxylic acid. The polyhydroxyl-functional component and the polycarboxylic acid-functional component can each have a linear, branched, alicyclic, or aromatic structure and can be used individually or as a mixture.

[0177] Non-limiting examples of polyether (meth)acrylates are condensation reaction products of polyetherols, which are polyether polyols, with (meth)acrylation agents (e.g., (meth)acrylic acid, (meth)acrylic anhydride, (meth)acryloyl chloride, or combinations thereof). Suitable polyetherols can be linear or branched substances containing ether bonds and terminal hydroxyl groups. Polyetherols can be prepared by ring-opening polymerization of epoxides and other oxygen-containing heterocyclic compounds (e.g., ethylene oxide, 1,2-propylene oxide, butene oxide, tetrahydrofuran, and combinations thereof) with starter molecules. Suitable starter molecules include water, hydroxyl-functional substances, polyester polyols, and amines. Polyetherols can also be obtained by condensation of diols such as glycols.

[0178] Non-limiting examples of urethane (meth)acrylates are condensation reaction products of at least one polyisocyanate (e.g., diisocyanate, triisocyanate), at least one polyol (e.g., polyether polyol or polyester polyol), and a hydroxyl-functionalized (meth)acrylate (e.g., 2-hydroxyethyl (meth)acrylate or 3-hydroxypropyl (meth)acrylate), resulting in terminal (meth)acrylate groups. For example, urethane (meth)acrylates can contain 2, 3, 4, or more (meth)acrylate groups per molecule. The order of addition of components for preparing urethane (meth)acrylates is well known in the art. For example, the hydroxyl-functionalized (meth)acrylate can first be reacted with the polyisocyanate to obtain an isocyanate-functionalized (meth)acrylate, which can then be reacted with the polyol. In yet another embodiment, the polyisocyanate can first be reacted with the polyol to obtain an isocyanate-functionalized polyol, which can then be reacted with the hydroxyl-functionalized (meth)acrylate. Alternatively, all the components can be combined and reacted simultaneously.

[0179] (Meth)acrylated poly(meth)acrylate non-limiting examples are substances having an (oligomer) (meth)acrylic backbone functionalized with one or more (meth)acrylate groups which can be at the ends of the oligomer or pendant on the acrylic backbone. The (meth)acrylic backbone can be a homopolymer, random copolymer or block copolymer consisting of repeating units of (meth)acrylic monomers. The (meth)acrylic monomers can be any monomer (meth)acrylate such as C1-C6 alkyl (meth)acrylate, as well as functionalized (meth)acrylates such as (meth)acrylates having hydroxyl, carboxylic acid and / or epoxy groups. The (meth)acrylated poly(meth)acrylate can be prepared using any procedure known in the art, for example, by oligomerizing a (meth)acrylic monomer (e.g., hydroxyalkyl (meth)acrylate, (meth)acrylic acid, glycidyl (meth)acrylate) at least partially functionalized with hydroxyl, carboxylic acid and / or epoxy groups to obtain a functionalized poly(meth)acrylate, which is then reacted with one or more (meth)acrylate-containing reactants to introduce the desired (meth)acrylate functional groups.

[0180] The curable composition can contain from 0 to 80% by weight, particularly from 5 to 75% by weight, more particularly from 10 to 70% by weight, even more particularly from 15 to 60% by weight, still more particularly from 20 to 50% by weight of (meth)acrylate-functionalized oligomer, based on the total weight of the curable composition. In particular, the curable composition can contain from 0 to 50% by weight, 1 to 45% by weight, 5 to 40% by weight, 10 to 35% by weight or 15 to 30% by weight of (meth)acrylate-functionalized oligomer, based on the total weight of the polymerizable components.

[0181] In an embodiment, the curable composition has a glass transition temperature T of about 20 °C or higher upon curing, or about 30 °C or lower upon curing gIt may have. In an embodiment, the curable composition may be liquid at a temperature of 25°C ± 2°C. In an embodiment, when the curable composition is measured with a Brookfield DV-III viscometer using spindle SC-27 at 60°C, it may have a viscosity of 50,000 cP or less, for example 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. Such viscosity characteristics facilitate spreading the composition onto a substrate for film formation.

[0182] In a preferred embodiment, when the curable composition is measured with a Brookfield DV-III viscometer using spindle SC-27 at 25°C, it may have a viscosity of 50,000 cP or less, for example 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 10,000 cP or less.

[0183] In an embodiment, the curable composition may contain less than 1 wt% of a solvent and less than 1 wt% of water, or may contain no solvent and no water. In an embodiment, a film or coating can be formed by curing the curable composition.

[0184] [Method for preparing and curing a curable composition] 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: - Preparing an oligomer according to the present invention dissolved in a non-reactive solvent; - Adding a reactive diluent and diluting to obtain a diluted curable composition; - Removing at least a part of the non-reactive solvent from the diluted curable composition to obtain a curable composition according to the present invention and includes.

[0185] The oligomer dissolved in the non-reactive solvent can be prepared by solution polymerization as described above. The oligomer, non-reactive solvent and reactive diluent can be as defined above. The non-reactive solvent can be at least partially removed by heating the diluted curable composition at a temperature of, for example, 40 °C or higher, particularly 50 °C or higher, more particularly 60 °C or higher. The amount of the non-reactive solvent after the removal step can be less than 1%, less than 0.5%, or even 0% by weight of the non-reactive solvent based on the weight of the curable composition.

[0186] The present invention also relates to a method for curing the curable composition according to the present invention. The method for curing the curable composition includes curing the curable composition.

[0187] The curing step can be carried out at ambient temperature (i.e., 10 to 30 °C).

[0188] 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%, particularly less than 0.05%, more particularly less than 0.001%, and even more particularly 0% by weight of a photoinitiator other than the oligomer of the present invention based on the weight of the curable composition.

[0189] The method for curing the curable composition of the present invention may not include a pre-curing step, particularly a step of curing at least a part of the reactive diluent by irradiating the curable composition with a long-wavelength and / or low-intensity light source, for example, in the presence of a photoinitiator other than the oligomer of the present invention, before crosslinking the oligomer of the present invention. When used herein, the long-wavelength and / or low-intensity light source is a light source that cannot activate the polymerized chromophore monomer units of the oligomer of the present invention and cannot cause crosslinking of the oligomer and / or the reactive diluent. Examples of long-wavelength and / or low-intensity light sources are black lights (in contrast to mercury lamps that can activate chromophores containing benzophenone moieties or LED-UV lamps that can activate chromophores containing thioxanthone moieties). Preferably, the method for curing the curable composition of the present invention includes a curing step of simultaneously curing at least a part of the reactive diluent and at least a part of the oligomer of the present invention. Without being bound by theory, such a curing method is considered to enable grafting at least a part of the reactive diluent onto at least a part of the oligomer of the present invention.

[0190] [Coating] In an embodiment, a coating can be formed by curing the curable composition. The method for preparing a cured coating according to the embodiment includes curing the curable composition. In particular, the curable composition can be cured by exposing the composition to radiation (such as visible radiation, ultraviolet radiation, LED radiation, laser radiation, electron beam radiation, peroxides, accelerators, and heat). More specifically, the curable composition can be completely cured by exposing the composition to ultraviolet (UV) radiation. The ultraviolet-curable composition can advantageously be cured by exposing the composition to an LED light source.

[0191] Before curing, the ultraviolet curable composition can be applied to the surface of a substrate by any known general method such as, for example, spraying, jetting, knife coating, roller coating, casting, drum coating, dipping, and combinations thereof. Indirect coating using a transfer process can also be used.

[0192] The substrate on which the ultraviolet curable composition is applied and cured can be any kind of substrate. When used as an adhesive, the polymerizable composition is placed between two substrates and then cured, and the cured composition joins the substrates together to obtain an adhered article. The ultraviolet curable composition according to the present disclosure can also be formed or cured in bulk form (for example, the ultraviolet curable composition can be poured into a suitable mold and then cured).

[0193] A plurality of layers of the ultraviolet curable composition according to the present disclosure can be applied to the surface of a substrate; the plurality of layers can be cured simultaneously (for example, by a single radiation exposure), or each layer can be cured sequentially and then an additional layer of the ultraviolet curable composition can be applied.

[0194] In an embodiment, the coating can have a gel content of 30% to 99% as measured by the method “Method A - Gel Content” disclosed herein. For example, the coating can have a gel content of 30% to 95%, 40% to 80%, 50% to 70%, or any and all partial ranges formed from any of these endpoints.

[0195] Without wishing to be bound by any particular theory, it is believed that oligomers containing polymerized high T g monomer units, polymerized low T g monomer units, polymerized chromophore monomer units, and optionally at least one polymerized additional monomer unit can cure to form a coating with a high gel content and thus a high degree of crosslinking. Further, oligomers having a T g of 0 °C or higher can cure to also have a T gIt is considered that a coating with a higher gel content than conventional oligomers having [this] can be formed. The polymerized high-T g Oligomers containing monomers are thought to have a higher degree of hydrogen abstraction and cross-linking during curing, which can improve the strength of the coatings formed from the oligomers described herein.

Examples

[0196] The various embodiments disclosed herein are further clarified by the following examples. The examples are illustrative in nature and should not be understood as limiting the embodiments disclosed herein.

[0197] [Materials] The following materials were used in the examples: TIFF2025523911000015.tif168170

[0198] [Formulations] Table 2 shows the components (weight percentages) used in the formation of the oligomers and the specified properties of Comparative Examples C1 to C26 and Examples E1 to E21.

[0199] The monomers shown in Table 2 were solution polymerized using the amount of MEK shown in Table 2 as a solvent to obtain oligomers. The solvent and monomers were added to a 60 mL vial. In a separate vial, a Vazo52 initiator solution in the solvent was prepared and added to the monomer solution (total monomer:initiator weight ratio was 400:1). Then, the vial was placed in a water bath at 65 °C and gently shaken for 11 hours. By adjusting the type of solvent, solids content, reaction temperature, reaction time, and initiator:monomer ratio, oligomers of various molecular weights can be prepared using experimental conditions well known to those skilled in the art. A monomer:Vazo52 ratio between 100:1 and 1000:1 was typically used to produce relatively low molecular weight oligomers as described and used in the following examples.

[0200] To prepare a formulation for evaluating the curing rate according to Method B below, the components listed in Table 2 were added to SR355 in a Flacktek® polypropylene cup and mixed using a Flacktek® DAC400.2VAC high-speed mixer at 1500 rpm for 2 minutes until homogeneous. TIFF2025523911000016.tif253170TIFF2025523911000017.tif255170TIFF2025523911000018.tif255170TIFF2025523911000019.tif20170

[0201] [Method] The following methods were used in this application: [Molecular weight] The number average molecular weight (Mn) and weight average molecular weight (Mw) of the oligomer were quantified using size exclusion chromatography (SEC) with poly(methyl methacrylate) reference standards and tetrahydrofuran as the solvent under the following conditions: - Columns: Agilent PLgel 5 micron 100A, 250×4.6 mm; Agilent PLgel 3 micron MiniMix E, 250×4.6 mm; Agilent PLgel 5 micron MiniMix D, 250×4.6 mm, - Detector: Refractive index detector - Solvent flow rate: 0.45 μL / min - Temperature: 40 °C - Sample injection volume: 25 μL

[0202] [Method A - Gel content] The gel content of the neat oligomer was measured by curing a 3 MIL wet coating using an H valve (mini Fusion LC6, 15 fpm, 3 passes). The drawdown thickness was dependent on the final percentage of MEK in the oligomer. For example, if the examples were provided as either 60% monomer and 40% MEK, or 50% monomer and 50% MEK, the example with 40% MEK was drawn down from a thickness of 5 MIL and the example with 50% MEK was drawn down from a thickness of 6 MIL so that the film thickness after evaporation of the MEK would be 3 MIL. After drawdown, the glass slides were placed in an oven at 60 °C for 1 hour to remove the solvent. The samples were cured in air or nitrogen. After curing, the samples were removed from the glass slides and placed in MEK solution for 24 hours. The gel content was given as the percentage of the residual weight of the sample after immersion in MEK for 24 hours compared to the initial weight of the sample, as given by the following formula. TIFF2025523911000020.tif16170

[0203] Here in Figure 1, the environment (i.e., air (shown by the grey bar) or nitrogen (shown by the black bar)) had a minimal effect on the gel content. Example E1 (an oligomer containing 54.5 wt% BA, 44.5 wt% MMA, and 1 wt% BENZO) had a gel content of less than 5 wt% when cured in air and nitrogen. On the other hand, Comparative Example C7 (an oligomer containing 69.5 wt% BA, 26.5 wt% MMA, and 1 wt% BENZO) had a gel content of 67 wt% (air) and 79% (nitrogen). As illustrated in Figure 1 and Table 1, as the MMA, which is a high T monomer unit, increases, the gel content decreases and the T increases. Thus, the amount of polymerized high T monomer units and polymerized low T monomer units in the oligomer can be adjusted to achieve both the desired crosslink amount and T such as the indicated gel content. g As the MMA, which is a high T monomer unit, increases, the gel content decreases and the T increases. g Thus, the amount of polymerized high T monomer units in the oligomer g and polymerized low T monomer units g can be adjusted to achieve both the desired crosslink amount and T g such as the indicated gel content.

[0204] Next in Figures 2 and 3, the MMA was replaced with another high Tg When the monomer unit IBOMA is substituted, the predicted T g When normalized to 0.01%, improved gel content was observed whether cured in air (Figure 2) or nitrogen (Figure 3). For example, Example E2, an oligomer containing 38.5 wt% BA, 60.4 wt% MMA, and 1 wt% BENZO, exhibited improved gel content compared to the predicted T g The temperature was 25° C. and the gel content was 5 wt % (air and nitrogen). Example E4, an oligomer containing 38.5 wt % BA, 50.4 wt % IBOMA, and 1 wt % BENZO, exceeded the expected T g The temperature was 24°C, and the gel content was 40 wt% (air) and 51 wt% (nitrogen). As illustrated in Figures 2, 3 and Table 1, the selected polymerized high T g Selection of monomer units and polymerized high T g By adjusting the amount of monomer units and polymerized low Tg monomer units, the desired amount of crosslinking, such as the gel content shown, and higher T g Both can be achieved.

[0205] Next, in Fig. 4 and Fig. 5, MMA is replaced with SR506A and tBMA, etc., which are high-T g When substituted into monomer units, the predicted T g When normalized at 0.05°C, the gel content improved whether cured in air (Figure 4) or nitrogen (Figure 5). Furthermore, the replacement of IBOMA with other cycloaliphatic moieties such as SR421A and SR218 improved the T g The gel content was higher at copolymer ratios where the cycloaliphatic moiety is 0.01 to 0.01. Without wishing to be bound by theory, it is possible that the incorporation of the cycloaliphatic moiety allows adjacent acrylic copolymer chains to initiate hydrogen abstraction more quickly and efficiently due to the availability of tertiary protons on the cycloaliphatic ring, unlike copolymers containing MMA. Furthermore, the size of the cycloaliphatic comonomer and the availability of multiple sites for hydrogen abstraction may provide more available protons for adjacent chains and less steric hindrance compared to small aliphatic comonomers such as MMA.

[0206] As illustrated in FIGS. 2 to 5 and Table 1, the high T g monomer units can be adjusted to achieve the desired degree of crosslinking at a given copolymer ratio, as indicated by the gel content.

[0207] [Method B - Photo Differential Scanning Calorimetry (PhotoDSC)] In the examples, the oligomers were mixed with SR355 at an initial weight ratio of oligomer:SR355, placed in Tzero pans, and the residual solvent was evaporated off in an oven. The initial weight ratio of oligomer:SR355 was selected such that the weight ratio of oligomer:SR355 after evaporation of the solvent was 1:1. The samples were exposed to broad-spectrum UV light (100 mW / cm 2 ) for 2 minutes.

[0208] Here in FIG. 6, the time to reach the peak maximum was recorded (shown by the gray bars in FIG. 6), and the curing rate of each oligomer was determined. The heat flow under each curve was measured during curing (shown by the black bars in FIG. 6). As illustrated in FIG. 6, the curing rate increased as the amount of MMA increased. Thus, the amount of polymerized high T g monomer units and polymerized low T g monomer units in the oligomer can be adjusted to achieve the desired curing rate. Further, all the examples in FIG. 6 induced crosslinking with SR355.

[0209] Next in FIG. 7, the time taken to reach the peak maximum was recorded, and the curing rate of each oligomer was determined. As illustrated in FIG. 7, all the examples had a similar curing rate. As the T g of the oligomer increased, the curing rate tended to decrease. Thus, the amount of polymerized high T g monomer units and polymerized low T g monomer units in the oligomer can be adjusted by adjusting the T g of the oligomer to achieve the desired curing rate.

[0210] An oligomer of the resulting composition and SR355 were added to the ditrimethylolpropane tetraacrylate (SR355) such that the weight ratio became 1:1 after MEK evaporation, thereby preparing a UV-curable coating composition. The UV-curable coating composition was mixed using a Flacktek® DAC400.2VAC high-speed mixer at 1500 rpm for 2 minutes until homogeneous.

[0211] The gel content was measured by curing a 4MIL wet coating of the UV-curable coating composition on a glass slide. After drawdown, the glass slide was placed in an oven at 60 °C for 1 hour to remove the solvent. The sample was cured in air or nitrogen. For air: After drying in the oven, the sample was cured using a small Fusion LC6 microwave bulb at 15 feet / minute for 3 passes. For nitrogen: After drying in the oven, the sample was placed in a nitrogen chamber and a nitrogen flow was applied for 5 minutes. The nitrogen chamber with a quartz window was passed under the Fusion LC6 microwave bulb at 15 feet / minute for 3 passes. After curing, the sample was removed from the glass slide and placed in MEK solution for 24 hours. The gel content was given as the percentage of the residual weight of the sample after 24 hours of immersion in MEK compared to the initial weight of the sample, as given by the following formula. 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.

[0212] [Aspect] A further aspect of the present invention is provided by the subject matter of the following clauses: Clause 1 1% to 95% by weight of polymerized high T based on the total weight of the oligomer g monomer units, 0.1% to 98.9% by weight of polymerized low T gcomprising monomer units, 0.1% to 40% by weight of polymerized chromophore monomer units, and 0 to 20% by weight of at least one polymerized additional monomer unit; having a high T g wherein the monomer units are (meth)acrylate monomers having a Fox equation average glass transition temperature (T g ) of 25 °C or higher, and the low T g monomer units are monovalent (meth)acrylate monomers having a Fox equation average T g of less than 25 °C, and the Fox equation average T g of the high T g monomer units is at least 20 °C higher than the Fox equation average T g of the low T g monomer units, and the chromophore monomer units are (meth)acrylate monomers having a pendant Norrish type II chromophore, and the oligomer has a weight average molecular weight of at least 10,000 grams / mol (g / mol); and has a T g of 0 °C or higher.

[0213] Item 2. The following formula (I): TIFF2025523911000022.tif56170(In the above formula, - Each A 1 is independently a (C1-C 30 ) hydrocarbyl or a (C1-C 30 ) heterohydrocarbyl, preferably a (C1-C 30 ) hydrocarbyl, and more preferably at least a part of the A 1 moiety is selected from isobutyl, tert-butyl or cyclic (C1-C 30 ) hydrocarbyl; - Each A 2 is independently a (C2-C 30 ) hydrocarbyl or a (C2-C 30 ) heterohydrocarbyl, preferably a (C4-C 30 ) hydrocarbyl; - Each A 3 is independently a monovalent residue containing a Norrish type II chromophore, preferably a monovalent residue containing benzophenone; - Each A 4is independently a (C1-C 30 ) hydrocarbyl or a (C1-C 30 ) heterohydrocarbyl, preferably a functional group selected from acidic groups, nitrogen-containing groups, 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, and combinations thereof, having a -(C1-C 30 ) heterohydrocarbyl; - Z 1 , Z 2 , Z 3 , and Z 4 are independently -H or -CH3; - m is the weight fraction of polymerized high-T g monomer units, and in particular m is from 0.01 to 0.95; - n is the weight fraction of polymerized low-T g monomer units, and in particular n is from 0.001 to 0.989; - p is the weight fraction of polymerized chromophore monomer units, and in particular p is from 0.001 to 0.4; - q is the weight fraction of at least one polymerized additional monomer unit, optionally 0, and in particular q is from 0 to 0.20; and - m + n + p + q equals 1) An oligomer according to the preceding paragraph, according to.

[0214] Item 3 A 1 At least a part of the part is selected from isobutyl, tert-butyl, a substituted or unsubstituted (C6-C 12 ) cycloalkyl which may be bonded to an alkylene part, a substituted or unsubstituted (C6-C 12 ) aryl which may be bonded to an alkylene or oxyalkylene part, or a combination thereof, A 2 is a straight-chain or branched (C4-C 30 ) alkyl or a combination thereof, and A 3 is X or -L-X, where L is a (C1-C 10The oligomer according to any one of the preceding paragraphs, which is a hetero hydrocarbylene linker, and X is a monovalent residue of a Norrish type II chromophore.

[0215] Item 4 A 1 At least a part of the moiety 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, 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 is a monovalent residue of a Norrish type II chromophore, the oligomer according to the preceding paragraph.

[0216] Item 5 The oligomer according to any one of the preceding paragraphs, wherein the Norrish type II chromophore is selected from benzophenone, thioxanthone, or titanocene.

[0217] Item 6 A 3 is -L-X, L is a (C1-C 10 ) hetero hydrocarbylene linker, and X is a monovalent group of benzophenone, the oligomer according to any one of the preceding paragraphs.

[0218] Item 7 A 1 At least a part of the moiety 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, A 2 is n-butyl, and A 3 is a monovalent residue of benzophenone, the oligomer according to any one of the preceding paragraphs.

[0219] Item 8 A 3 is the formula (IVa) disclosed below: The oligomer according to any one of the preceding items, having TIFF2025523911000023.tif48170.

[0220] Item 9 q is from 0.001 to 0.20, preferably from 0.001 to 0.10, and the additional monomer unit contains a functional group selected from an acidic group, a heterocyclic ring having one or more nitrogen ring atoms, a tertiary amine functional group, an alkyleneoxy functional group or a mercaptan group, preferably, the additional monomer unit is selected from (meth)acrylic acid, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, N-vinylpyrrolidone, N-vinylcaprolactam, acryloxymorpholine, dimethylacrylamide, poly(ethylene oxide) mono(meth)acrylate, hydroxyethyl ethyleneurea (meth)acrylate, the reaction product of a cyclic anhydride and a hydroxy-functional (meth)acrylate, and combinations thereof, the oligomer according to any one of the preceding items.

[0221] Item 10 Formula (V): TIFF2025523911000024.tif52170 (in the above formula, - Each A 1a is independently selected from isobutyl, tert-butyl or cyclic (C1-C 30 ) hydrocarbyl; - Each A 1b is independently selected from (C1-C 30 ) hydrocarbyl other than isobutyl, tert-butyl or cyclic (C1-C 30 ) hydrocarbyl; - Each A 2 is independently (C2-C 30 ) hydrocarbyl or (C2-C 30 ) heterohydrocarbyl; - Each A 3 is independently a monovalent residue containing a Norrish type II chromophore, preferably a monovalent residue containing benzophenone; - Each A 4 is independently a (C1-C 30 ) hydrocarbyl or a (C1-C 30 ) heterohydrocarbyl, preferably having a functional group selected from an acidic group, a nitrogen-containing group, a hydroxyl group, an epoxy group, a carbonyl group, an acetoacetoxy group, an acetoacetamide group, a 1,1-dimethyl-3-oxobutyl (diacetone) group, a thiol group, a silane group, an ether bond, an ester bond, and combinations thereof, and being a -(C1-C 30 ) heterohydrocarbyl; - Z 1 , Z 2 , Z 3 , and Z 4 are independently -H or -CH3; - m1 is from 0.01 to 0.95, particularly from 0.20 to 0.90, more particularly from 0.25 to 0.85, even more particularly from 0.30 to 0.80, still more particularly from 0.35 to 0.75, and yet more particularly from 0.40 to 0.75; - m2 is from 0 to 0.94, particularly from 0 to 0.90, more particularly from 0 to 0.80, even more particularly from 0 to 0.70, still more particularly from 0 to 0.60, and yet more particularly from 0 to 0.50; - n is from 0.001 to 0.989, particularly from 0.10 to 0.80, more particularly from 0.15 to 0.75, even more particularly from 0.20 to 0.70, still more particularly from 0.25 to 0.65, and yet more particularly from 0.25 to 0.60; - p is from 0.001 to 0.40, particularly from 0.005 to 0.30, more particularly from 0.005 to 0.20, even more particularly from 0.005 to 0.15, still more particularly from 0.005 to 0.10, and yet more particularly from 0.01 to 0.10; - q is from 0 to 0.20, particularly from 0 to 0.10; and - m1 + m2 + n + p + q is equal to 1; - The oligomer according to any one of the preceding paragraphs, wherein m1 + m2 has a value from 0.01 to 0.95, particularly from 0.20 to 0.90, more particularly from 0.25 to 0.85, even more particularly from 0.30 to 0.80, still more particularly from 0.35 to 0.75, and yet more particularly from 0.40 to 0.75).

[0222] Item 11 The following formula (V): TIFF2025523911000025.tif115170(In the above formula, m is from 0.2 to 0.8, n is from 0.1 to 0.8, and p is from 0.001 to 0.2; Z of formula (V) 1 、Z 2 、and Z 3 is independently -H or -CH3), and has a weight average molecular weight of at least 20000 g / mol, the oligomer according to any one of the preceding paragraphs).

[0223] Item 12 When Z 1 is H or -CH3, Z 2 and Z 3 are -H, and q is greater than 0, Z 4 is -H, the oligomer according to any one of the preceding paragraphs).

[0224] Item 13 The T of the oligomer g is from 0 °C to 100 °C, particularly from 20 °C to 100 °C, more particularly from 30 °C to 100 °C, the oligomer according to any one of the preceding paragraphs).

[0225] Item 14 The additional monomer unit is a (meth)acrylate monomer, the oligomer according to any one of the preceding paragraphs).

[0226] Item 15 The additional monomer unit is a (meth)acrylate monomer having a pendant amine functional group, the oligomer according to any one of the preceding paragraphs).

[0227] Item 16: The oligomer according to any one of the preceding items, 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, morpholino (meth)acrylate, dimethylamino (meth)acrylate, or a combination thereof.

[0228] Item 17: The oligomer according to any one of the preceding items, 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.

[0229] Item 18: The oligomer according to any one of the preceding items, 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.

[0230] Item 19: The oligomer according to any one of the preceding items, 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.

[0231] Item 20: The oligomer according to any one of the preceding items, having a gel content of at least 10% after curing.

[0232] Item 21: The oligomer according to any one of the preceding items, having a gel content of at least 20% after curing.

[0233] Item 22: A curable composition comprising the oligomer according to any one of the preceding items and one or more of the following compounds: (meth)acrylate monomer, diluent, (meth)acrylate oligomer, filler, photoinitiator, slip agent, thickener, slip agent, hindered amine light stabilizer, ultraviolet absorber monomer, or other auxiliary additives.

[0234] Item 23: The curable composition according to Item 22, comprising a reactive diluent.

[0235] Item 24. The curable composition according to Item 23, wherein the reactive diluent is a monofunctional (meth)acrylate monomer having a Tg higher than 25°C, particularly 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, 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, a substituted or unsubstituted (C6-C 12 ) cycloalkyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentanyl (meth)acrylate, tricyclodecanemethanol mono(meth)acrylate, 2-phenoxyethyl methacrylate, or a monofunctional (meth)acrylate monomer selected from combinations thereof.

[0236] Item 25: The reactive diluent is a polyfunctional (meth)acrylate, particularly bisphenol A di(meth)acrylate; hydrogenated bisphenol A di(meth)acrylate; ethylene glycol di(meth)acrylate; diethylene glycol di(meth)acrylate; triethylene glycol di(meth)acrylate; tetraethylene glycol di(meth)acrylate; polyethylene glycol di(meth)acrylate; propylene glycol di(meth)acrylate; dipropylene glycol di(meth)acrylate; tripropylene glycol di(meth)acrylate; tetrapropylene glycol di(meth)acrylate; polypropylene glycol di(meth)acrylate; polytetramethylene glycol di(meth)acrylate; 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-decanediol 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; pentaerythritol di(meth)acrylate; pentaerythritol tri(meth)acrylate; pentaerythritol tetra(meth)acrylate; di(trimethylolpropane) diacrylate; di(trimethylolpropane) triacrylate;A curable composition according to item 23 or 24, comprising a polyfunctional (meth)acrylate selected from 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.

[0237] Item 26. The curable composition substantially does not contain a photoinitiator other than the oligomers described in any one of Items 1 to 21. In particular, the curable composition contains less than 0.1% by weight, particularly less than 0.05% by weight, more particularly less than 0.001% by weight, and even more particularly 0% of a photoinitiator other than the oligomers described in any one of Items 1 to 21. A curable composition according to any one of Items 23 to 25.

[0238] Item 27. A coating formed by curing an ultraviolet curable composition according to any one of Items 22 to 26.

[0239] Item 28. A coating according to Item 27, having a gel content of at least 30%.

[0240] Item 29. A coating according to Item 27 or 28, having a gel content of at least 50%.

[0241] Item 30. A coating according to any one of Items 27 to 29, having a gel content of at least 70%.

[0242] Item 31. A method for preparing a curable composition according to any one of Items 23 to 26, comprising: - a step of preparing by dissolving an oligomer according to any one of Items 1 to 21 in a non-reactive solvent; - a step of adding a reactive diluent to obtain a diluted curable composition; - A step of removing at least a part of the non-reactive solvent from the diluted curable composition to obtain the curable composition according to the present invention A method comprising the above.

[0243] A method for curing the curable composition described in any one of Items 23 to 26 of Item 32 or the curable composition prepared by the method described in Item 31, comprising activating the polymerized chromophore monomer unit of the oligomer and irradiating the curable composition with a light source having a wavelength and / or intensity capable of causing crosslinking of the oligomer and / or the reactive diluent to cure the curable composition.

[0244] It is obvious to those skilled in the art that various modifications and changes can be made without departing from the scope disclosed herein. Modifications, combinations, sub-combinations, and changes of the embodiments of the present disclosure incorporating the spirit and content disclosed herein may occur to those skilled in the art, so the scope disclosed herein should be construed to include all within the scope of the appended claims and their equivalents.

[0245] For the purpose of defining the present technology, a transitional phrase "consisting of" can be introduced into the claims to make it a closed preamble term that limits the scope of the claims to the described components or steps and naturally occurring impurities. For the purpose of defining the present technology, a transitional phrase "essentially consisting of" can be introduced into the claims to limit the scope of one or more claims to the described elements, components, materials, or method steps, and elements, components, materials, or method steps not described that do not substantially affect the novel characteristics of the subject matter of any claim.

[0246] As used in the specification and the appended claims, the singular forms "a", "an", and "the" include plural references unless the context clearly dictates otherwise. The verb "comprises" and its cognates are to be construed as referring to elements, components, or steps in a non-exclusive manner. The recited elements, components, or steps may be present, utilized, or combined with other elements, components, or steps not expressly recited.

[0247] Any two quantitative values assigned to a characteristic may form a range of that characteristic, and it is to be understood that all combinations of ranges formed from all of the recited quantitative values of a given characteristic are contemplated in this disclosure. The subject matter disclosed herein has been described in detail with reference to specific embodiments. It is to be understood that any detailed description of components or features of an embodiment is not necessarily meant to imply that such components or features are essential to that embodiment or to other embodiments.

Claims

1. Based on the total weight of the oligomer, 1% to 95% by weight of polymerized high-T ｇ monomer units; From 0.1% by weight to 98.9% by weight of polymerized low-T ｇ monomer units; 0.1% to 40% by weight of polymerized chromophore monomer units; and 0 to 20% by weight of at least one polymerized additional monomer unit comprising; High T ｇ The monomer unit is a (meth)acrylate monomer having a Fox formula average glass transition temperature (T ｇ ) of 25 °C or higher; Low T ｇ The monomer unit is a monovalent (meth)acrylate monomer having a Fox formula average T of less than 25 °C ｇ and; High T ｇ Fox formula average T of monomer units ｇ is low T ｇ Fox formula average T of monomer units ｇ is at least 20 °C higher than; The chromophore monomer unit is a (meth)acrylate monomer having a pendant Norrish II type chromophore, an oligomer; having a weight average molecular weight of at least 10,000 grams / mole (g / mol); and T of 0 °C or higher ｇ An oligomer having

2. Formula (I): (In the above formula, - Each A １ is independently (C １ -C ３０ ) hydrocarbyl or (C １ -C ３０ ) heterohydrocarbyl, preferably (C １ -C ３０ ) hydrocarbyl, more preferably at least a part of the A １ moiety is selected from isobutyl, tert-butyl or cyclic (C １ -C ３０ ) hydrocarbyl; - Each A ２ is independently (C ２ - C ３０ ) hydrocarbyl or (C ２ - C ３０ ) heterohydrocarbyl, preferably (C ４ - C ３０ ) hydrocarbyl; - each A ３ is a monovalent residue independently containing a Norrish type II chromophore, preferably a monovalent residue containing benzophenone; - Each A ４ is independently (C １ -C ３０ ) hydrocarbyl or (C １ -C ３０ ) heterohydrocarbyl, preferably a functional group selected from an acidic group, a nitrogen-containing group, a hydroxyl group, an epoxy group, a carbonyl group, an acetoacetoxy group, an acetoacetamide group, a 1,1-dimethyl-3-oxobutyl (diacetone) group, a thiol group, a silane group, an ether bond, an ester bond, and combinations thereof -(C １ -C ３０ ) heterohydrocarbyl; -Z １ 、Z ２ 、Z ３ 、and Z ４ are each independently -H or -CH ３ ; - m is the weight fraction of the polymerized high T ｇ monomer units; - n is the weight fraction of the polymerized low T ｇ monomer units; - p is the weight fraction of the polymerized chromophore monomer unit; - q is the weight fraction of at least one polymerized additional monomer unit, optionally 0; and - m + n + p + q is equal to 1) The oligomer according to claim 1, according to.

3. A １ at least a part of which is selected from substituted or unsubstituted (C ６ -C １２ ) cycloalkyl optionally bonded to an isobutyl, tert-butyl, alkylene moiety, substituted or unsubstituted (C ６ -C １２ ) aryl, or a combination thereof; A ２ is a linear or branched (C ２ -C ３０ ) alkyl, or a combination thereof; and A ３ is X or -L-X, where L is a (C １ -C １０ ) heterohydrocarbylene linker and X is a monovalent residue of a Nolish II type chromophore, the oligomer according to claim 2.

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

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

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

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

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

9. q is from 0.001 to 0.20, preferably from 0.001 to 0.10; and The additional monomer unit contains a functional group selected from an acidic group, a heterocycle having one or more nitrogen ring atoms, a tertiary amine functional group, an alkyleneoxy functional group or a mercaptan group, preferably the additional monomer unit is (meth)acrylic acid, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, N - vinylpyrrolidone, N - vinylcaprolactam, acryloxymorpholine, dimethylacrylamide, poly(ethylene oxide) mono(meth)acrylate, hydroxyethyl ethyleneurea (meth)acrylate, a reaction product of a cyclic anhydride and a hydroxy - functional (meth)acrylate, and combinations thereof, the oligomer according to any one of claims 2 to 8.

10. Formula (V): (In the above formula, - each A １ａ is independently selected from isobutyl, tert-butyl or cyclic (C １ -C ３０ ) hydrocarbyl; - each A １ｂ is independently selected from (C １ - C ３０ ) hydrocarbyl other than isobutyl, tert-butyl or cyclic (C １ - C ３０ ) hydrocarbyl; - each A ２ is independently (C ２ - C ３０ ) hydrocarbyl or (C ２ - C ３０ ) heterohydrocarbyl; - each A ３ is a monovalent residue independently containing a Norrish type II chromophore, preferably a monovalent residue containing benzophenone; - each A ４ is independently (C １ -C ３０ ) hydrocarbyl or (C １ -C ３０ ) heterohydrocarbyl, preferably a functional group selected from acidic groups, nitrogen-containing groups, 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, and combinations thereof - (C １ -C ３０ ) heterohydrocarbyl; -Z １ , Z ２ , Z ３ , and Z ４ are independently -H or -CH ３ ; -m １ is from 0.01 to 0.95, particularly from 0.20 to 0.90, more particularly from 0.25 to 0.85, even more particularly from 0.30 to 0.80, still more particularly from 0.35 to 0.75, and yet more particularly from 0.40 to 0.75; -m ２ is from 0 to 0.94, particularly from 0 to 0.90, more particularly from 0 to 0.80, even more particularly from 0 to 0.70, still more particularly from 0 to 0.60, and yet more particularly from 0 to 0.50; - n is from 0.001 to 0.989, particularly from 0.10 to 0.80, more particularly from 0.15 to 0.75, still more particularly from 0.20 to 0.70, even more particularly from 0.25 to 0.65, yet more particularly from 0.25 to 0.60; - p is from 0.001 to 0.40, particularly from 0.005 to 0.30, more particularly from 0.005 to 0.20, even more particularly from 0.005 to 0.15, still more particularly from 0.005 to 0.10, and yet more particularly from 0.01 to 0.10; - q is from 0 to 0.20, particularly from 0 to 0.10; and -m １ +m ２ +n + p + q equals 1; -m １ +m ２ is from 0.01 to 0.95, particularly from 0.20 to 0.90, more particularly from 0.25 to 0.85, even more particularly from 0.30 to 0.80, still more particularly from 0.35 to 0.75, and yet more particularly from 0.40 to 0.75) An oligomer according to any one of claims 2 to 9, which follows.

11. Formula (VI): (In the above formula, m is from 0.2 to 0.8; n is from 0.1 to 0.8; and p is from 0.001 to 0.2) According to An oligomer according to any one of claims 2 to 10, having a weight average molecular weight of at least 20,000 g / mol.

12. Z １ is -CH ３ and; Z ２ and Z ３ is -H; and When q is greater than 0, Z ４ is -H, the oligomer according to any one of claims 2 to 11.

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

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

15. The reactive diluent contains a monofunctional (meth)acrylate monomer having a Tg higher than 25°C, in particular, 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, 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, a substituted or unsubstituted (C ６ -C １２ ) cycloalkyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentanyl (meth)acrylate, tricyclodecanemethanol mono(meth)acrylate, 2-phenoxyethyl methacrylate, or a combination thereof, and the curable composition according to claim 14.

16. The reactive diluent is a polyfunctional (meth)acrylate, particularly bisphenol A di(meth)acrylate; hydrogenated bisphenol A di(meth)acrylate; ethylene glycol di(meth)acrylate; diethylene glycol di(meth)acrylate; triethylene glycol di(meth)acrylate; tetraethylene glycol di(meth)acrylate; polyethylene glycol di(meth)acrylate; propylene glycol di(meth)acrylate; dipropylene glycol di(meth)acrylate; tripropylene glycol di(meth)acrylate; tetrapropylene glycol di(meth)acrylate; polypropylene glycol di(meth)acrylate; polytetramethylene glycol di(meth)acrylate; 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-decanediol 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; pentaerythritol di(meth)acrylate; pentaerythritol tri(meth)acrylate; pentaerythritol tetra(meth)acrylate; di(trimethylolpropane) diacrylate; di(trimethylolpropane) triacrylate;The curable composition according to claim 14 or 15, comprising a polyfunctional (meth)acrylate selected from 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. Substantially free of photoinitiators other than the oligomers according to any one of claims 1 to 21, particularly containing less than 0.1% by weight, particularly less than 0.05% by weight, more particularly less than 0.001% by weight, and even more particularly 0% of photoinitiators other than the oligomers according to any one of claims 1 to 21, A curable composition according to any one of claims 14 to 16.

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

19. A coating according to claim 18, having a gel content of at least 30%.

20. A method for preparing a curable composition according to any one of claims 14 to 17, - A step of preparing by dissolving an oligomer according to any one of claims 1 to 13 in a non-reactive solvent; - A step of adding a reactive diluent to obtain a diluted curable composition; - A step of removing at least a part of the non-reactive solvent from the diluted curable composition to obtain a curable composition Including, the method.

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

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